water-resistant porous coordination polymers for gas separation · 2018. 1. 2. · porous...

Accepted Manuscript

Review

Water-resistant porous coordination polymers for gas separation

Jingui Duan Wanqin Jin Susumu Kitagawa

PII S0010-8545(16)30385-XDOI httpdxdoiorg101016jccr201611004Reference CCR 112337

To appear in Coordination Chemistry Reviews

Received Date 19 September 2016Revised Date 7 November 2016Accepted Date 7 November 2016

Please cite this article as J Duan W Jin S Kitagawa Water-resistant porous coordination polymers for gasseparation Coordination Chemistry Reviews (2016) doi httpdxdoiorg101016jccr201611004

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1


Jingui Duana c Wanqin Jina and Susumu Kitagawab

a State Key Laboratory of Materials-Oriented Chemical Engineering College of Chemical engineering Nanjing Tech

University Nanjing 210009 China E-mail duanjinguinjtecheducn

b Institute for Integrated Cell-Material Sciences (WPI-iCeMS) Kyoto University Yoshida Sakyo-ku Kyoto

606-8501 Japan E-mail kitagawaicemskyoto-uacjp

c Jiangsu National Synergetic Innovation Center for Advanced Materials Nanjing Tech University Nanjing 210009

China

Received Sep XX 2016

Contents

1 Introduction 2 2 Factors influencing the water stability of PCPs 4

21 Stronger coordination bonds 5 211 Ligands with high pKa values 5 212 Metals with high oxidation states 10

22 Imparting protection for the coordination bond 18

221 Ligands with hydrophobic units 18 223 Coating hydrophobic units for enhanced stability 21

224 Catenation for improved stability 23

3 Gas separations by stable PCPs 24 31 Adsorptive separations in water stable PCPs 25

32 Membrane-based gas separation 33

4 Conclusion and outlook 40 Acknowledgement 41

References 44

Abstract Porous coordination polymer (PCP) chemistry has a promising future because of the tunable structures

and excellent properties of polymers However the strategy for designing and preparing water-resistant PCPs is a

considerable challenge This review surveys and investigates the factors governing water resistance in a hierarchy

sequence Subsequently representative studies are provided with an emphasis on their adsorptive- and

membrane-based gas separations This review is intended to be useful for researchers who are interested in

designing water-resistant PCPs and exploring promising applications for gas separation

Keywords Porous coordination polymer water-resistance adsorptive gas separation membrane-based gas

separation

2

1 Introduction

Porous coordination polymers (PCPs) [1-3] also called metal-organic frameworks (MOFs) [4-6] are a new

type of hybrid material that has been thoroughly investigated over the last decade PCPs materials which are

prepared by means of assembling inorganic metal ionsclusters and organic ligands exhibit intriguing advantages

in structural design PCPs are distinct from zeolites silica and carbon materials and with their high surface area

and functional sites PCPs are thought to be ideal platforms for various promising applications [1-15]

To date the most popular investigations on PCPs have centred on their abilities for improved gas uptake and

separation that is methane storage [12 16 17] and carbon dioxide selective capture [11 18-20] However for

feasible applications careful consideration of the stability profile of PCPs in the presence of water vapour or liquid

water is important particularly if the material is to be recovered or reused [7 21-23] Generally almost saturated

water vapour is included in the transportation and storage of geochemical gas streams Water vapour is also

present in the selective carbon dioxide capture from flue gas systems While moisture can be removed prior to

storage and separation using PCP materials it is impossible to avoid corrosion from trace moisture during sample

loading activation and regeneration processes for long-term usage

Currently more than twenty thousand frameworks with rationally controlled pore properties have been

reported but most of the frameworks are highly sensitive to watermoisture and some chemical solutions [4-6 24

25] Subsequently the rational design and preparation of watermoisture resistant PCPs is a major challenge for

prospective applications [26 27] Before 2012 only a few work reported on the water adsorption of typical

materials such as HKUST-1 MIL-series UiO-66 ZIF-8 and MAF-6 [28-35] Since 2012 more researchers have begun

to explore water adsorption andor water and chemical stability in PCPs Based on those studies several factors

eg ligands with high pKa values metals with high oxidation states and the shielding of coordination sites by

functional groups are central contributors to PCP stability [7 36-46] Therefore a series of PCPs with remarkable

water stability were well-established and explored for a wide range of applications Water stable PCPs were

studied in adsorptive gas separations with humidity [18 45-47] Additionally stable PCP-based membranes for

efficient gas separations have also attracted a great deal of attention [48-50]

Meanwhile it is very important to understand the evaluation methods for PCP materials with good water

stability [45 46 51-53] First the water stability of PCPs can be simply identified via a comparison of the powder

3

X-ray diffraction patterns (PXRD) of the samples before and after water treatment This technology works well for

unstable PCPs because their X-ray diffraction patterns change considerably However for some other frameworks

the PXRD patterns are not reflective of the true framework integrity The porosity of these samples should be

further evaluated via gas adsorption and BET calculations NMR or UV analyses should be performed on treatment

solutions to confirm if ligands partially dissolve from the PCPs if the PCPs are going to be used in a liquid phase

Water stability is one of the crucial factors in determining real-world applications and it has led to intense

interest in PCP materials A considerable number of PCPs with good stability and functional sites should exist

based on the selection of inorganic metal ionsclusters and infinite organic ligands [54] However it is necessary to

establish potential guidelines that may be helpful in preparing water and chemically stable PCPs On the basis of a

comprehensive survey of water stability tests and the structural factors of the tested PCPs the most powerful

strategies for preparing stable PCPs can be divided into two main groups 1) introducing strong coordination bonds

is the most powerful strategy to prepare water-resistant PCPs [55] 2) installing a hydrophobic moiety around the

coordination sites or on the surface of the crystals works to prevent corrosion from water molecules [56-58]

Meanwhile a series of sub-factors such as metal coordination ligand rigidity and interpenetration are included

for each group Therefore a better understanding of the relationships of the two methods with a hierarchy

sequence will significantly help in designing the next generation of stable PCPs If the coordination bond is formed

via the reaction between ligands with high pKa values and metal ions with high oxidation states the generated

PCPs have good stability and other factors are not considered However if a stronger connection is not formed

planting a hydrophobic moiety andor combining relevant structural factors works for the preparation of stable

PCPs

This review is intended to provide readers with a comprehensive overview of the strategies for constructing

stable PCPs and the applications of PCPs for gas separation (Fig 1) In section 1 we will discuss factors that are

related to the synthesis of stable PCPs On the basis of those examples we will define the characterization

methods used to quantify their water stability The gas separations of stable PCPs via static adsorption (simulation

of ideal adsorbed solution theory IAST) dynamic adsorption (breakthrough experiment) and membrane

technologies are surveyed and summarized in section 2 Despite our best efforts we cannot cover all the results

in this promising area In addition the predicted structures for stable PCPs and their gas separations from

4

computational simulations will not be covered in this review Overall this review will provide an important

reference for researchers interested in designing and preparing stable PCPs and applying them to gas separations

Fig 1 Water and moisture with chemically stable PCPs with tunable and versatile pore properties show

promising applications for gas separation

2 Factors influencing the water stability of PCPs

In this section we present factors for understanding PCP materials with varied water stability If the

nucleophile oxygen from a water molecule can coordinate to a metal cluster the corresponding PCP will

decompose and lose its original porosity due to the breakdown of the coordination bonds Based on this many

important factors such as the pKa value of the ligands coordination number coordination geometry oxidation

state of the metal centres hydrophobicity group modifications ligand rigidity and polymercarbon coating can

govern the stability of PCPs However despite the above classification the stability of PCPs is usually governed by

5

two or more factors For instance La(BTB)H2O and La(BTB)-(H2O) which were discovered by Kitagawa and Walton

exhibit the same coordination number with the same ligand but they have different organic linker assemblies

which cause them to have different structural rigidities and water stabilities [46 59] To achieve a better

understanding of the complex interplay of those factors we will introduce them with typical examples in the

following sections

21 Stronger coordination bonds

In porous coordination polymers the word ldquoporousrdquo was believed to be the most important character of the

material but the word ldquocoordinationrdquo indicates the connections of the hybrid components and is used to

distinguish PCPs from other porous materials Thus the strength of the coordination bonds can be used to predict

and evaluate the stability of PCPs In this section we will summarize them based on different mechanisms

211 Ligands with high pKa values

As Lewis adducts PCP materials are formed via the reactions of Lewis acid metal species and Lewis base

organic ligands A higher pKa value of the coordination site of the involved ligands provides stronger

metal-organic bonds for the target PCPs (Table 1) The Long group reported a family of PCPs with pyrazolate (pKa

198) imidazole (pKa 186) and 123-triazole (pKa 139) moieties [60-62] The generated frameworks of Cu(BTTri)

with exposed metal sites adopted a classical Mn(BTT) structure The chemical stabilities of the frameworks were

tested in water (boiling for 3 days) and acidic media (pH = 3 room temperature (RT) and 1 day) The PXRD results

showed that the treated samples had the same diffractions as the untreated sample which indicated good

stability However no further adsorption experiments were conducted to confirm the integrity of the PCPs Then

an additional two PCPs of Cu(BTP) and Ni(BTP) were designed and synthesized The PXRD and gas adsorption data

revealed that Cu(BTP) possessed a greater chemical and thermal stability compared to its carboxylate-based

counterparts (Fig 2)

6

Fig 2 Structure of the pyrazole-based ligand H3BTP (a) structure of Ni3(BTP)2 (b) X-ray diffraction patterns after

treatment in water acid or base for two weeks at 100 Reproduced with permission from ref [60-62]

Recently the Zhou group reported a ftw-a topology framework ([Ni8(OH)4(H2O)2TPP12]) PCN-601 using a Ni8

cluster with a pyrazolate-based porphyrinic ligand [53] The framework exhibits excellent stability and porosity in

a saturated sodium hydroxide solution (20 molLminus1) at RT and 100 and features a good surface area (1309

m2gminus1) In addition to the PXRD and gas adsorption results UV spectra were used to confirm the presence of

dissolved ligands from the PCPs during chemical treatment No peaks were seen for the H4TTP ligand in the UV

spectra which confirmed robustness of the PCP Additional investigations from thermodynamic and kinetic

perspectives showed that the higher crystal field stabilization energy and stiffer coordination connection between

the Ni8 cluster and the ligands allow PCN-601 to have a strong resistance to attack from H2O and OHminus even under

extremely basic conditions (Fig 3)

7

Fig 3 Structure of the pyrazole-based porphyrinic ligand (a) structure of PCN-601 (b) X-ray diffraction patterns

and N2 gas adsorption confirm the integrity of PCN-601 after treatment in harsh conditions (c and d) Reproduced

with permission from ref [53]

Unlike the above high symmetry ligands our group designed a new C2v symmetry linker featuring

heterocoordination sites to address the sensitivity of PCP materials [52] Eight ligands coordinated to the

chloride-centred square-planar [Cu4Cl] units to form a cubic SOD-type framework with a good surface area (1248

m2gminus1) and suitable pore size distribution As expected with the rigid ligand high cluster connection and stronger

strength of the CuminusN coordination bonds PCP-33 demonstrated good water- and chemical-resistance at increased

temperatures This is the first time to report an anionic (NH2(CH3)2+) charged framework with good water stability

and increased gas uptakes This unique phenomenon cannot be achieved by neutral PCPs (Fig 4)

8

Fig 4 Structure of the H3BTBA ligand (a) the eight connected [Cu4Cl] unit (b) topology structure of PCP-33 with

two types of cages (c) PXRD and N2 gas adsorption results show the high stability of PCP-33 after treatment (d and

e) Reproduced with permission from ref [52]

As another important class of PCPs zeolitic imidazolate frameworks (ZIF) present various promising structural

characteristics and properties [31 32 63 64] With a unique M-IM-M angle (~145deg) which is similar to the Si-O-Si

angle this series of PCPs displays unique connections that are preferred and commonly found in zeolites In

addition some hydrophobic groups eg ndashF -NO2 and -CH3 were used to modify the pore surface Thus a few of

the PCPs showed good water-resistance For instance by possessing large pores (116 Aring) connected via small

window apertures (34 Aring) ZIF-8 maintained its integrity in boiling benzene methanol water and other chemical

conditions for 7 days The stronger bonding of Zn2+ with the N-donor ligand and the hydrophobic pore structure

were thought to both contribute to the superior water-resistance (Fig 5) Similarly ZIF-60 -61 -62 -68 -69 and

-70 showed water-resistance under varied conditions

9

Fig 5 Structure of the 2-methylimidazole ligand (a) a cage of ZIF-8 (b) X-ray diffraction patterns after treatment

in water and basic conditions at 100 Reproduced with permission from ref [9d]

Table 1 Water resistant PCPs with stronger coordination bonds from ligand contributions (mainly)

Name Metal

Cluster Ligand BET (m2g) Stable condition

Gas Selectivity and

Separation ref

Cu(BTTri) Cu(II) 135-tris(1H-123-triazol-5-yl)benz

ene 1770

Boiling water 3 days

HCl (pH = 3) RT 24 h CO2N2 19 [61 65]

en-Cu(BTTri) Cu(II) 135-tris(1H-123-triazol-5-yl)benz

ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)

135-tris(1H-123-triazol-5-yl)benz

ene 870 ND CO2N2 165 327 [65 66]

Cu(BTT) Cu(II) 135-benzenetristetrazolate 701 Water 24h RT CO2N2 697

CO2H2 5772 [47]

Cu(BTBA) Cu(II) 135-tris(1H-pyrazol-4-yl)benzene 1248 HCl (pH = 2) NaOH

(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]

Co(BDP) Co(II) 13-benzenedi(40-pyrazolyl) 1710 Boil water 72h ND [44]

Cu(BTP) Cu(II) 135-tris(1H-pyrazol-4-yl)benzene 1860 Boiling water 10 days ND [60]

Cu(pcn) Cu(II) 4-pyridinecarboxylic acid ND RT 78RH 3 days CO2N2 8-147 [67]

Cu(ttbl) Cu(II) 33rsquo55rsquo-tetraethyl-44rsquo-bipyrazolat

e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)

NNrsquoNrsquorsquo-tris(carboxymethyl)-135-

benzenetricarboxamide

13-bis(4-pyridyl)propane

808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]

Co(tapp) Co(II) 4-(4H-124-triazol-

4-yl)-phenyl phosphonate ND

95 RH for

12 h at 90 degC ND [70]

Ni(BTP) Ni(II) 135-tris(1H-pyrazol-4-yl)benzene 1650

Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10

PCN-601 Ni(II) 5101520-tetra(1H-pyrazol-4-yl)-p

orphyrin 1309

Boiling in 20 M NaOH

24h RT 01mM HCl

24h

ND [53]

Ni-L1 Ni(II) L1 1H-pyrazole-4-carboxylic acid 205 RT basic 1d ND [71]

Ni-L2 Ni(II) L2 4-(1H-pyrazole-4-yl)benzoic acid 990 RT basic 1d ND [71]

Ni-L3 Ni(II) L3 44rsquo-benzene-14-diylbis(

1H-pyrazole) 1770 RT basic 1d ND [71]

Ni-L4 Ni(II)

L4

44rsquo-buta-13-diyne-14-diylbis(1H-p

yrazole)

1920 RT basic 1d Diethylsulfide(DES)

(ArN2) [71]

Ni-L5 Ni(II)

L5

44rsquo-(benzene-14-diyldiethyne-21-

diyl)bis(1H-pyrazole)


(ArN2) with RH [71]

Ni-L5-CH3 Ni(II) L5-CH3 1985 RT basic 1d Diethylsulfide(DES)

(ArN2) [71]

Ni-L5-CF3 Ni(II) L5-CF3 2195 RT basic 1d

Diethylsulfide(DES)

(ArN2)

with RH

[71]

Ni(NIC) Ni(II) Nicotinate Negligible

area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]

Ni(hptz) Ni(II) 4-(124-triazol-4-yl)

phenylphosphonic acid 434


Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]

Zn(BTP) Zn(II) 135-tris(1H-pyrazol-4-yl)benzene 930 Boiling water 1 day ND [60]

ZIF-8 Zn(II) N-methylimidazole 1630

Boiling Water 7 days

8M NaOH boiling

24h

CO2CO BK [31 32]

ZIF-11 Zn(II) Imidazolate ND Water 7 days 50 N2H2 [32]

ZIF-68 Zn(II) Benzoimidazole and

2-Nitro-2H-imidazole 1090 Boiling water 7 days

CO2N2 187

CO2CH4 4 [32]

ZIF-69 Zn(II) 5-Chloro-2H-benzoimidazole and


CO2N2 199

CO2CH4 5 [32]

ZIF-70 Zn(II) Imidazolate and


CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri

azol-3-yl]pyridin-2-yl-1H-124-triaz

ol-3-yl)pyrazine

ND Boiling water 24h ND [75]

Pb-(o-PDA) Pb(II) Phenylenediacetic acid ND Boiling water 24h ND [75]

JUC-110 Cd(II) (S)-4567-tetrahydro-1H-imidazo[

45-c]pyridine-6-carboxylate ND Boiling water 7 days WaterEtOH [76]

Tb-(ftzb) Tb(III) 2-fluoro-4-(1H-tetrazol-5-yl)

benzoic acid 1220 RT water 24h CO2N2 BK [77]

ND no data

212 Metals with high oxidation states

Inorganic building blocks are another component of PCP materials that play a critical role in creating stronger

coordination bonds Ti Zr and Hf with a +4 oxidation state and some trivalent metals such as Cr Al and La were

selected to prepare water-resistant PCPs with ligands with lower pKa values [55 78-80] The high charge density

(Zr) of the metals will polarize the O atoms of the carboxylate groups to form stronger M-O bonds that will be

11

similar to the strength of a covalent bond

In 2006 the Schubert group first reported on a Zr6 cluster in its isolated phase [81] The cluster consists of an

inner Zr6O4(OH)4 core in which the triangular faces of a Zr6 octahedron are alternatively capped by μ3-O and μ3-OH

groups Each zirconium atom is eight-coordinated by eight oxygen atoms Compared to clusters of Cu2(OH)2(CO2)4

and Zn4O(CO2)6 the connectivity number in the Zr6-cluster significantly increases to 12 Thus the geometry of the

Zr6 cluster is fully covered by coordinated oxygen atoms which is similar to closed packed metal structures The

Lillerud group reported three PCPs (UiO-66 UiO-67 and UiO-68) based on three dicarboxylate linkers with varied

lengths [34] The X-ray reflections of the treated samples completely overlap with the results of the as-synthesized

samples which indicated the potential for water and chemical stability

Since the discovery of this node and the stability of the UiO-66 series a number of stable PCPs were designed

with Zr6 centres Importantly some of them demonstrated high surface areas and functional open metal sites For

instance PCN-224 had 3-D nanochannels and a high surface area (2600 m2g-1) and was obtained from a

six-connected Zr6 cluster (Fig 6) [82] Here the D4h symmetry ligands reduce the 12 connections of Zr6 cluster to 6

Meanwhile six terminal OH- bridging species complete the coordination geometry and provide available open

metal sites Additionally the introduction of the OH groups improves the hardness of the Zr6 core which

strengthens the bonding between the ligands and the Zr6 units Further stability tests revealed that the framework

can maintain its integrity in chemical solutions with a wide pH range (from 0 to 11)

12

Fig 6 View of the 6-connected D3d symmetric Zr6 unit in PCN-224 (a) Tetratopic TCPP ligands (b) framework of

PCN-224 (c) PXRD and gas adsorption of PCN-224 before and after treatment (d and e) Reproduced with

permission from ref [82]

Although it is difficult to prepare PCPs with highly reactive M4+ ions a group of PCPs such as UiO-66 (Zr and

Hf)[83-85] MOF-525 [86] MOF-801 [64] PCN-222 [87] PCN-225 [88] PCN-777 [89] FJI-H6 [38] DUT-51 [90]

NU-1000 [91] and MIL-140 [92] have been synthesised However the water stability of some of the Zr-based

materials has recently come into question For example as the ldquoarmrdquo of the ligand increases from one benzene

ring (UiO-66) [34] to seven or more (NU-1105) [41] the structures become more fragile (collapsing during the

activation or flexible framework) Lillerud thought the analogues of UiO-66 UiO-67 and UiO-68 were stable in

aqueous and acidic conditions However there is a lack of experimental evidence to support this claim Recently

the Hupp and DeCoste group explored the degradation mechanisms of PCPs with the Zr6 building unit [93 94]

Based on the IR and PXRD analysis results the new adsorption bands and decreased peak intensities was found

and which confirmed the transformation of the carboxylate groups to their protonated analogues of HCl in the

treated UiO-66 However the high connectivity of the Zr6 cluster led to a tolerance for a total framework collapse

because other partial coordination bonds can support the framework integrity However the amorphous PXRD

13

and FTIR results characterize the breakdown of UiO-66 and UiO-66-NH2 in a solution of 01 M NaOH Further

UiO-67 with a longer ldquoarmrdquo shows a decrease in stability in comparison to the UiO-66 It is not stable in water

(new PXRD peaks) 01 M HCl (new PXRD peaks) or 01 M NaOH (amorphous) The researchers believed that the IR

data should show a difference in the water treated UiO-67 compared to its parent phase because the ligand

hydrolysis from the clustering of H2O near the Zr6-based centre should exist but the IR results failed to further

elucidate this question Later using rational design experiments the Hupp group gave a clear answer to this issue

Indeed UiO-67 and NU-1000 are stable against linker hydrolysis However both frameworks are susceptible to

channel collapse via capillary force when activated directly from the H2O (Fig 7) Once the treated samples were

washed and exchanged with acetone their crystallinity and gas uptake could be recovered with a significant

decrease in surface tension

Fig 7 Molecular representations and DFT free energies (in kcal mol-1) associated with the hypothetical hydrolytic

degradation of UiO-67 Reproduced with permission from ref [94]

In addition to group IV elements metals with a +3 oxidation state can also provide strength to coordination

bonds At a molecule level metal centres with a high inertness will bring a bigger difference in the frontier orbitals

to the water and metal centres which results in good stability [95] For instance MIL-101 is bridged by the

remarkable μ3-oxocentered tri-nuclear chromium motif and possesses a very large pore cavity [30] Its high water

14

resistance made it a famous material in the PCP area Thus more and more studies have been conducted to

identify stable PCPs containing metals with a +3 oxidation state

Our group reported a water and chemically stable microporous framework (La-BTB) with La-O chains [46 51]

The overall structure possesses a 1D hexagonal channel (10 Aring) The coordination geometry of La3+ was completed

with nine oxygens Eight of the oxygens come from the carboxylate groups of the involved BTB ligands

Interestingly the adjacent ligands packed together without any space even for a single hydrogen molecule This

PCP was carefully tested It has a good surface area and water and chemical stability The as-synthesized phase

was soaked in chemical solutions over a broad pH range (from 2 to 14) at increased temperatures The PXRD

patterns indicated the robustness of the solution treated frameworks Further the samples treated with moisture

at high temperatures also showed good stability which was confirmed via PXRD and gas adsorption experiments

(Fig 8)

Fig 8 View of the La-O infinite chain in La-BTB (a) BTB ligand structure (b) the framework of La-BTB (c)

comparison of PXRD and gas adsorption before and after treatment (d and e) Reproduced with permission from

ref [10k]

To expand the chemistry of stable PCPs with La3+ ions we proposed and validated another framework

(La-BTN) with a new tricarboxylate ligand with a large aromatic organic surface [45] The 3D framework crystallizes

15

into a rare chiral P65 space group The adjacent and nine coordinated La3+ ions were bridged by three carboxylate

groups which led to edge-shared polyhedrons and an inorganic helical chain Because it had the similar infinite

La-O chains and rigid ligands a high stability was expected for the framework The PXRD and gas adsorption

results of the treated samples showed that La-BTN had good stability against moisture water and chemical

conditions at increased temperatures Compare with performance of La-BTB (~4 gas uptake decrease after

treatment towards its original phase) almost ~20 decrease in the gas adsorption of treated La-BTN indicated a

relative weaker framework This can be explained by a difference in their structural effect The distance of the

adjacent organic ligands was increased to ~62 Aring (La-BTB ~38 Aring) which provides more space for water molecules

to approach and corrode the La-O coordination bonds [51] In addition there are groups of stable PCPs with

trivalent metal centres such as Al3+ Cr3+ Eu3+ and In3+ ions

Table 2 Water resistant PCPs with stronger coordination bonds from metal contributions (mainly)

Name Metal

Cluster Ligand

BET

(m2g) Stable condition Gas separation ref

UiO-66 Zr(IV) 1 4-benzenedicarboxylic acid 1187

(LSA) Boiling water 4h

CO2CH4 32

CO2N2 134

[34 94

96-98]

UiO-66-NH2 Zr(IV) 1 4-benzenedicarboxylic acid (NH2) 9301630 RT 48 h water RT

2h pH = 1-9 CO2CH4 9

[21

99-102]

UiO-66-Br Zr(IV) 1 4-benzenedicarboxylic acid (Br) 640 RT 48 h water pH

= 14

CO2CH4 47

CO2N2 251 [98-100]

UiO-66-I Zr(IV) 1 4-benzenedicarboxylic acid (Br) 799 (LSA) RT 12 h water pH

= 14 CO2CH4 47

[97 99

100]

UiO-66-NO2 Zr(IV) 1 4-benzenedicarboxylic acid (NO2) ND RT pH = 1 pH = 14 CO2CH4 51

CO2N2 264 [98 100]

UiO-66-CF3 Zr(IV) 1 4-benzenedicarboxylic acid (CF3) 739 (LSA) RT water 12h RT

1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)

1 4-benzenedicarboxylic acid

(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]

UiO-67 Zr(IV) 44-biphenyl-dicarboxylate 21453000

(LSA) RT water 24h ND [34 94]

DUT-51-Zr Zr(IV) dithieno[32-b2rsquo3rsquo-d]-thiophene-2

6-dicarboxylate 2671 RT water 12h ND [104]

DUT-51-Hf Hf(IV) dithieno[32-b2rsquo3rsquo-d]-thiophene-2


DUT-67 Zr(IV)H

f(IV) 25-Thiophenedicarboxylic acid 1064810

RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1

M HCl 3 days ND [105]

DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH

2 (Ti) Ti(IV) 14-benzenedicarboxylic acid-(NH2) 1550 Moisture 373 K

CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]

MIL-140 Zr(IV) 14-benzenedicarboxylic acid 415 Boiling water 12 h ND [92]

16

(Zr)

MIL-163

(Zr) Zr(IV)

55rsquo-(1245-tetrazine-36-diyl)bis(b

enzene-123-triol) 90170

Boiling water 7

days pH = 74 310

K 14 days

ND [90]

BUT-10 Zr(IV) 9-fluorenone-27-dicarboxylic acid 2505 Similar as UIO-67 CO2CH4 51-52

CO2N2 186-229 [108]

BUT-11 Zr(IV) dibenzo[bd]-thiophene-37-dicarb

oxylic acid 55-dioxide 1848 Similar as UIO-67

CO2CH4 90-92

CO2N2 315-431 [108]

PCN-56 Zr(IV) 2rsquo5rsquo-dimethylterphenyl-44rdquo-dicarb

oxylic acid 3741 RT pH = 2 48 h

Normalized

selectivity

(CO2N2 ~018)

[109]


oxylic acid-(2CH2N3) 2185

RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]

PCN-222 Zr(IV) Porphyrin ligand (See ref ) 2600 RT pH = 1 ndash 11 24h ND [82 110]

PCN-225 Zr(IV) Porphyrin ligand (See ref ) 1902 Boiling pH = 0-12

24h ND [88]

PCN-228 Zr(IV) Porphyrin ligand (See ref ) 4510 RT 1 M HCl 24h ND [111]


PCN-230 Zr(IV) Porphyrin ligand (See ref ) 4455 RT pH = 0 ndash 12 24h ND [111]

PCN-521 Zr(IV) 4rsquo4rsquorsquo4rsquorsquorsquo4rsquorsquorsquorsquo-methanetetrayltetra

biphenyl- 4-carboxylate 3411 RT in air 24h ND [112]

PCN-777 Zr(IV) 44rsquo4rsquorsquo-s-triazine-246-triyl-tribenz

oate 2008 RT pH = 3 ndash 11 12h ND [89]

Zr-BTBA Zr(IV)

44rsquo4rsquorsquo4rsquorsquorsquo-([11rsquo-biphenyl]-33rsquo55rsquo

-tetrayltetrakis(ethyne-21-diyl))

tetrabenzoic acid

4342 RT water 48 h ND [113]

Zr-(dmbd) Zr(III) 25-dimercapto-14-benzenedicarb

oxylic acid 513 RT water 12h CO2N2 187 [114]

MOF-525 Zr(IV) tetrakis(4-carboxyphenyl)porphyrin 2620 RT Water pH = 5

24 h ND [86]


24 h ND [86]

MOF-801-P Zr(IV) Fumaric acid 990 RT Moisture ND [64]

MOF-802 Zr(IV) 1Hpyrazole-35-dicarboxylic acid 1145 RT Moisture ND [64]

MOF-841 Zr(IV) 44rsquo4rsquorsquo4rsquorsquorsquo-Methanetetrayltetraben

zoic acid 1390 RT Moisture ND [64]

NU-1100 Zr(IV)

4-[2-[368-tris[2-(4-carboxyphenyl)

-ethynyl]-pyren-1-yl]ethynyl]-benzo

ic acid

4020 RT water 24h ND [115]

NU-1105 Zr(IV) Py-TP (See ref) 5645 RT in air a year ND [41]

FJI-H6 Zr(IV)

4rsquo4rsquorsquo4rsquorsquorsquo4rsquorsquorsquorsquo-(porphyrin-5101520

-tetrayl)tetrakis([110-biphenyl]-4-c

arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]

La-BTB La(III) 135-tris(4-carboxyphenyl)benzene

) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]

La-BTN La(III) 135-Tri(6-hydroxycarbonylnaphth

alen-2-yl)benzene 240

Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17

La(pyzdc) La(III) pyrazine-25-dicarboxylate ND Boiling water and

Tuluene 72 h

H2OCH3OH BK

simulation [116]

PCMOF-5 La(III) 1245-tetrakisphosphonomethylb

enzene 0

Boiling water 7

days ND [117]

La-Cu(nic) La(III) Nicotinate Negligible

area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)

444-Tricarboxyltriphenylamine

246-tri-p-carboxyphenylpyridine

135-tris(4-carboxyphenylethynyl)

benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]

Eu-Cu(nic) Eu(III) Nicotinate Negligible

area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)

35-di(24-dicarboxylphenyl)pyridin

e ND

RT water 30d

Boiling water 3d ND [119]

Eu(bpydb) Eu(III) 44prime-(44prime-bipyridine-26-diyl)

dibenzoic acid 316 Water 353 K 20 h ND [120]

Eu-(NDC) Eu(III) 14-naphthalenedicarboxylate 465

Boiling water

24hBoiling

solution pH = 35 ndash

10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]

Tb-(FTZB) Tb(III) 2-fluoro-4-(1H-tetrazol-5-

yl)benzoic acid 1220 RT water 24h BK CO2N2 [77]

Tb-(dsoa) Tb(III) disodium-220-disulfonate-440-oxy

dibenzoic acid ND

RT water 28 days

Boiling water 24h ND [122]

Tb-(cppc) Tb(III) 5-(4-carboxyphenyl)pyridine-2-carb

oxylate ND RT water weeks ND [123]

Dy (cmdcp) Dy(III) N-carboxymethyl-(35-dicarboxyl)-p

yridinium bromide ND RT water 30 days ND [37]

MIL-53 Al(III) 1 4-benzenedicarboxylic acid ~900

353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]

MIL-96 Al(III) 135-benzenetricarboxylic acid ND RT pH = 1- 8 24h CO2CH4 23 [127

128]

MIL-121 Al(III) 1245-benzenetetracarboxylic acid 180 RT Water several

days ND [129]

NOTT-300 Al(III) biphenyl-33rsquo55rsquo-tetracarboxylic

acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]

CAU-6 Al(III) 2-aminoterephthalate 620760 303K 100 mgL

fluoride solution ND

[131

132]

CAU-10-R Al(III) Isophthalic acid-R (R CH3 NH2

NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]

Al-PMOF Al(III) meso-tetra(4-carboxyl-phenyl)

porphyrin 1400 RT 7 days ND [22]

MIL-53 Fe(III) 1 4-benzenedicarboxylic acid ND

303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]

MIL-100 Fe(III) 135-benzenetricarboxylic acid 2800

(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18

MIL-127 Fe(III) 33rsquo55rsquo-azobenzenetetracarboxyla

te ND

310 K pH = 74 24

h ND [99]

Fe-(bdp) Fe(III) 14-benzenedipyrazolate 1230 373K pH = 2 to 10

14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]

MIL-100 (Cr) 135-benzenetricarboxylic acid 1900 323 K Water 24 h C3H8C3H6 [28 30]

MIL-53 Cr(III) 1 4-benzenedicarboxylic acid ~800

353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]

MIL-101 Cr(III) 1 4-benzenedicarboxylic acid 2800-423

0 323 K Water 24 h CO2CH4 31 [30 139]

InPCF-1 ln(III) 4rsquo-phosphonobiphenyl-35-dicarbo

xylate 246 RT water 1-7 days

CO2N2 22

CO2O2 32 [140]

LSA Langmuir surface area BK breakthrough experiments

22 Imparting protection for the coordination bond

Generally a collapse or decomposition of PCPs is a result of ligand displacement by atmospheric water

molecules Therefore once water molecules are prevented from attacking the coordination bonds the porosity of

PCPs should be maintained Based on this opinion a number of PCPs with good stability have been prepared by

imparting some hydrophobic groups around the coordination sites ie using ligands with incorporated F or alkyl

moieties or coating carbon or polymers on the surface of the crystals However those strategies possess varied

stable mechanisms In the first case each porecage is modified periodically with functional groups and water

molecules cannot enter the pore or approach the metal centres In the second case moisture and water are

restrained from going inside the crystals which prevents the hydrolysis reaction with the coordination bonds

221 Ligands with hydrophobic units

The Omary group reported two PCPs FMOF-1 and FMOF-2 based on the association of the

35-is(trifluoromethyl)-124-triazolate ligand bridged by three or four coordinated silver cations [56 141] PXRD

and IR analyses confirmed that FMOF-1 does not suffer from degradation upon long-term exposure to boiling

water This is because the alignment of the dense fluorinated groups can block watermoisture from breaking the

coordination bonds (Fig 9) Based on a similar idea the alkyl group modified MOF-5 and polymer ligand involved

polyMOFs exhibited improved water stability [142 143]

19

Fig 9 Structure of the 35-is(trifluoromethyl)-124-triazolate ligand (a) structure of FMOF-1 (b) water adsorption

of FMOF-1 zeolite and activated carbon (c) Reproduced with permission from ref [139]

In addition to ligands with modified F or alkyl groups phosphonate monoesters were reported by the Shimizu

group to be a good alternative to carboxylates for stabilizing PCPs [117 144-148] They have the potential to offer

carboxylate-like coordination modes with the added variable of organic tethers on ester groups The monoanionic

charge of a phosphonate monoester can moderate self-assembly and allow for stable yet crystalline products with

strong coordination bonds between the metal and phosphonate oxygen Further hydrophobic ester tether groups

could provide shielding for the coordination bonds through kinetic blocking CALF-25 which is lined with the ethyl

ester groups in its pore is one such example Following treatments with water vapour (high relative humidity at

3129 and 353 K) no changes in the PXRD patterns and only a few reductions in the gas adsorption were seen (Fig

10)

20

Fig 10 Structure of the phosphonate monoesters in CALF-25 (a) structure of CALF-25 (b) comparison of PXRD and

gas adsorption before and after treatment (d and e) Reproduced with permission from ref [148]

222 Postsynthetic modification of hydrophobic units

Meanwhile postsynthetic modification (PSM) incorporation of desired functionality within a given PCP

structure has been used to stabilize sensitive PCPs [149-151] Introducing functionalization at the metal node

covalent modification of the organic linker and solvent-assisted ligand incorporation were believed as the most

attractive strategies The Cohen group systemically investigated the physical properties of a series IRMOFs

comprised of Zn4O clusters and dicarboxylate ligands [152] Through the contact angle SEM and PXRD

experiments IRMOF-3-AM6 and IRMOF-3-AM15 with longer alkyl chains maintained their crystallinity after water

treatment In this case the alkyl chain monomers can go inside the pore and react with the active sites to form a

hydrophobic pendant for blocking water vapours The modified PCPs show good stability but decreased porosity

Similarly stable PCPs were built up by using a polymer co-ligand strategy along with incorporation of pendant

hydrophobic groups [58 153] Furthermore through the technique of solvent-assisted ligand incorporation series

of perfluoroalkane carboxylates with various chain lengths (C1-C9) were attached to Zr6 nodes of NU-1000 by Hupp

group The fluoroalkane-functionalized mesoporous PCPs show enhanced framework stability as well as increased

adsorption selectivity of CO2 at room temperature[154]

21

223 Coating hydrophobic units for enhanced stability

Inspired by the above ideas some hydrophobic organic polymers with larger molecular weights and longer

chains were used to stabilize PCP frameworks The polymers formed a thin protective layer on the surface of the

crystals [155] This technique enhances the stability of PCP surface while the inner part of the crystals remains

unchanged It may only change the kinetics of water diffusion (through the layer of coating) but not improve the

stability of PCP itself Thus thin and flexible as well as good hydrophobicity were believed as necessary characters

for optimizing protective layers More importantly the pore size of protective layers should be finely controlled for

target gas entering while keeping outside or decreasing the diffusion speed of water molecules Despite the

difficulty for balancing those factors this technology demonstrated high potential for creating more and more

stable PCPs The Jiang group deposited polydimethysiloxane (PDMS) on HKUST-1 to form a protective layer on the

surface of the crystals (Fig 11) [156] As expected the colour morphology and crystallinity of the crystals did not

change even when they were treated in water for 3 months Further porosity characterization revealed that the

BET of the coated crystals was the same as the pristine crystals This promising method was again verified by

coating polymers onto a more sensitive MOF-5 In addition a similar method for chemical vapour deposition of

perfluorohexane on PCP crystals was developed by the Decoste group The generated materials also showed good

water resistance

Fig 11 PDMS-coated HKUST-1 shows improved water stability Reproduced with permission from ref [156]

Carbon another hydrophobic material was also used as a protection regent to enhance the stability of

22

sensitive PCPs [157 158] Previously carbonaceous grease was incorporated into frameworks to prevent attacks

from water molecules Moreover a group of nanoporous carbon materials was prepared via thermal pyrolysis of

PCP which acts as a porous template and a carbon resource Inspired by those materials the Park group

developed a simple method for painting a carbon film on PCP crystals Through careful control of the temperature

a thin carbon layer was generated on the outer surface of the MOF-5 crystal After exposing the coated crystals to

humidity for two weeks the PXRD results including peak diffractions and peak intensity were the same as that of

the fresh MOF-5 Additionally the crystals are also stable in liquid water but the carbon modified crystals showed

a decreased pore volume (Fig 12)

Fig 12 Schematic representations of the thermal modification of carbon-coated PCPs (a) (from crystal to

MOF-5amorphous carbon then to ZnO nanoparticlesamorphous carbon) The corresponding XRD patterns (b)

BET and BET loss (c) pore size distributions of treated samples (d) Reproduced with permission from ref [157]

Furthermore covering a stable shell PCP on a water sensitive core PCP is another important method for

obtaining stable materials However for continuous coverage it is better to have the same node for the core and

the shell structures The Rosi group developed a core-shell structure by encapsulating the unstable Bio-MOF-11

structure with a stable Bio-MOF-14 [153] The core-shell structure demonstrated improved water stability and

separation ability Similarly by using shell ligand exchange reactions the Yang group prepared a series of stable

core-shell structures by exchanging the 5 6-dimethylbenzimidazole ligand on the surface of the ZIF-7 ZIF-8 and

23

ZIF-93 crystals [159]

224 Catenation for improved stability

Catenation has been common in the PCP field once longer ligands were selected as options for structure

preparation [160-163] Two or more identical and independent frameworks interpenetrate or interweave together

which offers protection and stability to each framework The Walton group developed stable PCPs using the

catenation strategy in combination with ligand pillaring [161] In contrast to the non-catenated and unstable

isostructures (Zn-TMBDC-DABCO and Zn-TMBDC-BPY Zn-BDC-BPY) Zn-BDC-BPY (MOF-508) is stable under 90

relative humidity (RH) exposure This is because the two-fold interpenetration results in a reduction in the pore

volume and creates a hydrophobic environment to prevent water adsorption

Table 3 Steric structure and hydrophobic units contribute for water stability of PCPs

Name Metal

Cluster Ligand

BET

(m2

g)

Stable condition Gas separation ref

Ni(bpe)(MoO4) Ni(II) 12-bis(4-pyridyl)ethene 456

RT AirWater 30 days

boiling water 24 h RT

01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]

Zn(idc)(hprz) Zn(II) imidazole-45-dicarboxylate

piperazine ND

RT waterseries

organic solvents 24 h ND [165]

CALF-25 Ba(II) 1368-pyrenetetraphosphon

ate 385 353K 80 RH ND [148]

UTSA-16 Co(II) K(I) citric acid 628 RT air 3 days CO2N2 3147

CO2CH4 298 [166]

Ni(dppz) Ni(II) 35-di(pyridine-4-yl) benzoate 321 RT Moisture CO2N2 113 [167]

Bio-MOF-14 Zn(II) adeninate ND RT water 30 days CO2N2 selectivity [153]

FMOF-1 Ag(I) 35-bis(trifluoromethyl)-124-

triazolate ND

Boiling water

long-term n-HexaneH2O

[56

141]

MOF-508 Zn(II) 1 4-benzenedicarboxylic

acid 44rsquo-bipyridine 800

90

RH exposure ND [161]

MOF-508-TM Zn(II)

356-tetramethyl-14-

benzenedicarboxylic acid

14-diazabicyclo[222]octane

105

0

90


SCUTC-18 Zn(II) 14-benzenedicarboxylate

220-dimethyl-440-bipyridine 523 Rt Air 14days

CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)

poly(14-benzenedicarboxylat

e) ND RTBoiling water 24h CO2N2 separations [142]

SIFSIX-3-Cu Cu(II) pyrazine ND RH 74 CO2N2 26000 BK [18]

SIFSIX-3-Zn Zn(II) pyrazine 250 RH 74 CO2N2 2500 BK [8]

3 Gas separations by stable PCPs

Gas separations especially for the production of pure hydrogen and light hydrocarbons are amongst the most

24

important industrial processes As starting materials their phase purity will influence the conversion of value

added chemicals However the current approach of cryogenic distillation demands a great deal of energy

Moreover distillation does not work for materials that decompose at high temperatures Thus developing

effective separation and purification technologies that require less energy consumption is necessary and

important Adsorptive and membrane separations are good alternatives and a material with a suitable pore size is

required for gas separations Therefore a group of porous materials such as zeolites porous carbon and porous

metal oxide etc have been investigated for use in the above technologies for various separations [170 171]

Clearly designable and robust PCP materials have demonstrated significant promise for those efficient separations

Until now a great deal of research has focused on pore design and adsorptive separation [8 49 170-172] and the

review of stable PCP-based separations has not been well-organized

Based on a survey of the reports gas separations are usually studied by two prodedures One is adsorptive

separation [65 170 171] and the other is membrane-based separation [49 173-175] However no matter what

the type of technology the crucial problem is material selection This is because the material will decide the target

separation performance working time and potential cost Because of the ability to tune pore properties at a

molecular level we can expect that some PCPs would be good candidates for gas separations [8 21] For

adsorptive separations most reports have focused on selective adsorptions derived from the static

single-component measurements from the Henry constant and ideal adsorbed solution theory (IAST) calculations

However to evaluate the gas separation ability of adsorbents under flowing gas conditions the pressure swing

adsorption (PSA) process is a powerful approach that will fully utilize the fixed-bed space and minimize the energy

regeneration cost Only a few typical structures (such as ZIF-8 and UiO-66) were investigated for membrane

separation even though many other members are highly desirable However practical separations of a mixture

involve more complex systems which might include varied working pressures stream components diffusion

speeds long term usage and the degree of humidity [176] Therefore gas separation with PCPs has not reached

the level of feasible application In terms of issues well-designed stable PCPs with functional pore properties are

the most promising option Thus in this section we would like to summarize the separation behaviours of stable

PCPs in regards to adsorptive separation and membrane separation The relationships between the PCP

structures and their separation performances will also be discussed

25

31 Adsorptive separations in water stable PCPs

Adsorptive separations which depend on the differences in adsorption capacity were widely studied in various

materials With the advantages of easy operation high efficiency and low energy cost this technology requires

materials with outstanding pore characters such as specific interaction sites and a suitable pore size

Conventionally zeolite and activated carbon materials have been used as the absorbent for impurities removal in

mixed gas systems [177 178] However PCP materials especially water stable PCPs are believed to be the most

promising candidates for adsorptive separation Generally the water resistance of PCP materials has not been

considered in lab investigations However if PCP materials are selected as absorbents for feasible applications the

weak stability of the frameworks becomes one of the most important obstacles Moisture even a trace amount

cannot be fully removed from the mixture systems such as selective capture of CO2 from air or natural gas

Therefore rationally designed stable PCPs with ideal pore sizes and surface area are an optimal media for water

included separations

With the promising advantages of their structural design PCP materials were studied for the selective capture

of CO2 from air or plant emissions [11] Based on the smaller kinetic diameter (33 Aring) and larger quadrupole

moment (43 times 10-27 esu-1cm-1) of the CO2 molecule the strategies of pore size tuning and polar surface

modification work well for CO2 separations Following the discovery of the ZIF-8 framework (window apertures

34 Aring) the Yaghi group reported a dozen stable zeolitic frameworks [32] ZIF-68 69 and 70 have large pores (72

102 and 159 Aring in diameter) connected through tunable apertures (44 75 and 131 Aring respectively) Their

frameworks show high thermal stabilities and exceptional waterchemical stabilities Thus they were used to

conduct the difficult separation of CO2CO Single gas isotherms showed that all of the frameworks have a high

affinity and capacity for CO2 and ZIF-69 outperformed ZIF-68 and ZIF-70 The breakthrough experiments showed a

different retention time for CO2 from the binary mixture of CO2CO (5050 vv) on the fixed bed absorber of ZIF-68

69 and 70 Thus the adsorptive CO2 selectivity and separation were determined based on their surface area and

pore metric attributions (Fig 13)

26

Fig 13 View of the systemically tuned pore size in ZIF-68 69 and 70 (a) single gas adsorption isotherms of CO2

and CO for ZIF-69 at 273 K (b) Breakthrough curves of a CO2CO mixture stream passed through the sample bed

of ZIF-68 Reproduced with permission from ref [32]

To further enhance the polarity of the pore surface the Long group developed a new strategy of grafting

alkylamine functionality onto the open metal sites of PCPs The highly porous CuBTTri with good stability in water

and under chemical conditions was modified by the ethylenediamine (en) functionality [61 66] When comparing

CO2 uptakes in the low pressure area the en-CuBTTri material shows a greater amount of CO2 compared to its

original phase The calculated selectivity for CO2 over N2 increased from 10 to 13 at 009 bar and from 21 to 25 at

1 bar despite the reduction in CO2 capacity upon en grafting This phenomenon should be assigned as the

enhanced host-guest interaction which was further confirmed by calculating the adsorption heats (from 21 to 90

kJmol-1) The dynamic adsorption of the CO2N2 (15 85) mixtures showed that a 075 wt weight increase was

achieved over 30 cycles with no capacity loss on en-CuBTTri which suggested a better affinity for CO2 molecules

Inspired by this investigation the grafted ethylenediamine was changed to NNrsquo-dimethylethylenediamine (mmen)

for further pore surface modification in Cu-BTTri As expect a significant increase in the gravimetric capacity for

CO2 and the calculated CO2N2 selectivity was achieved in mmen-Cu-BTTri Moreover this modified material

adsorbed nearly 7 wt CO2 from a 15 CO2 in N2 mixture over 72 cycles However because of the higher

27

adsorption heat regeneration with a N2 purge should be performed at 60 Based on the above observations

well modified amide groups in PCPs can increase the binding energy of the host and guest to improve the ability

for selective CO2 capture However there are some drawbacks decreased pore volume the high energy costs

associated with activation regeneration and recycling of sorbent material impeding CO2 sorption via the

hygroscopic properties of amines under feasible conditions (Fig 14)

Fig 14 Stable framework of CuBTTri with grafted ethylenediamine and NNrsquo-dimethylethylenediamine on open Cu

sites (a) gas cycling experiment for amide modified Cu-BTTri under a mixture of CO2N2 (15) followed by a flow

of pure N2 at ambient temperature (b and c) Reproduced with permission from ref [61] and [66]

Meanwhile our group reported two water and chemical stable PCPs (La-BTB and La-BTN) [45 46] Their

structure and stabilities were discussed in a previous section Here the performances of their related gas

separations were evaluated With a rigid framework and rich open metal sites the surface area of La-BTB is 1024

m2middotg-1 Single-component adsorption isotherms for CH4 CO2 C2H4 and C2H6 indicated that La-BTB is a potential

candidate for the purification of CH4 from natural gas The predicted (IAST) selectivity of the C2 hydrogen carbons

relative to CH4 has an unprecedented value (ca 242-48) at 195 K in the region of 100 kPa At 273 K the predicted

selectivity of the C2 hydrogen carbons to CH4 (C2H6CH4 22 C2H4CH4 12) remains larger than 8 which suggests

practical application Further the breakthrough experiments showed that La-BTB has a good capacity to purify CH4

28

The concentration of the outflowing gas was almost 0 for C2H6 or CO2 and 100 for CH4 which is consistent with

the equilibrium adsorption behaviours and IAST results Thus without any post-modification the high stability and

high capacity of La-BTB show a promising future for gas separation under both equilibrium and flow conditions To

improve the separation ability we designed and validated another water and chemical stable PCP La-BTN

Featuring a larger organic surface and higher density the volumetric storage capacity of CO2 in La-BTN one of the

important adsorbent standards for feasible applications reached 1671 gL-1 at 195 K with a capacity of 565 gL-1

(273 K 1 bar) This value is higher than that of some important porous materials (La-BTB 548 gL MOF-5 399

gL and MOF-177 507 gL (at 298 K 31 bar) However the uptakes of N2 O2 and CO in La-BTN increase very

slowly with the pressure IAST and breakthrough simulations of an equimolar four-component mixture

demonstrated that the La-BTN can selectively capture CO2 from the mixture of CO2N2O2CO The significant time

interval between the breakthroughs of CO O2 N2 and CO2 showed the possibility for CO2 separation from a flue

gas system (Fig 15)

Fig 15 Structures of La-BTB and La-BTN (a and b) breakthrough experiment (CO2CH4) and simulation

(CO2N2O2CO) for an absorber packed with La-BTB and La-BTN at 273 K Reproduced with permission from ref

[46] and [45]

29

Although several groups of PCPs are stable in water and moisture systems their gas separations were

evaluated with dry gas only For practical applications it is necessary to investigate their gas separation in the

presence of moisture because so many industrial gas streams contain water vapour Thus to assist in our

understanding the gas uptake and stability of HKUST-1 in the presence of water was explored [179] In this work

the CO2 sorption isotherms of HKUST-1 were measured before and after three successive water sorption

experiments in which the humidity was limited to 30 at 298 K The CO2 adsorption capacity of HKUST-1 declined

after each water sorption and appeared to level out at 75 of its original level after three water

adsorptiondesorption cycles This is due to the loss of crystallinity which is indicated by the disappearance of the

PXRD peaks of HKUST-1 (Fig 16)

Fig 16 Crystal structure of HKUST-1 (a) PXRD patterns of HKUST-1 after water sorption experiments (b) H2O

vapour sorption isotherms of HKUST-1 at 298 and 302 K (c) CO2 isotherms at 298 K and 0 to 5 bar before and

after each H2O isotherm at 298 K in the relative vapour pressure range of 0 to 30 before the first H2O isotherm

Reproduced with permission from ref [179]

For further understanding regarding the effect of water under dynamic conditions the Matzger group

compared the CO2 capture ability of the MDOBDC series (where M = Zn Ni Co and Mg DOBDC =

25-dioxidobenzene 14-dicarboxylate) at varied humidities [180] Compared to the performance of MgDOBDC

(16) the breakthrough curves of N2CO2H2O at a relative humidity (RHs) in the feed of 9 36 and 70 were

30

collected The results showed the CO2 capacity of MgDOBDC in the surrogate flue gas is drastically reduced after

moisture treatment and regeneration However CoDOBDC exhibits high capacities for CO2 compared to the

pristine materials The capacity of the regenerated CoDOBDC sample is approximately 85 of that of the pristine

material In addition the PXRD of the regenerated materials did not indicate a phase change The data clearly

suggested that the unstable PCPs are not suitable adsorbents for repetitive CO2 capture from a humid flue gas

because the performance drastically degrades after a single regeneration treatment In addition the kinetic and

thermodynamic factors of H2O can also influence the CO2 capacity of PCP materials

Based on those problems and the previous material [Cu(44rsquo-bipyridine)2(SiF6)]n [181] the Zaworotko group

created another three PCPs via a reticular chemistry approach SIFSIX-2-Cu SIFSIX-2-Cu-i and SIFSIX-3-Zn (Fig 17)

[8] The CO2 measurements and single-crystal x-ray diffraction studies showed that SIFSIX-2-Cu-i and SIFSIX-3-Zn

uniformly adsorb CO2 over a range of CO2 loading The adsorption is efficient and reversible which means that the

CO2 is easily captured and easily removed from the SIFSIX material From the single gas isotherms the simulated

IAST results confirmed the high CO2 capture ability of those PCPs Further the breakthrough tests of binary

CO2N21090 and CO2CH45050 gas mixtures with the SIFSIX-3-Zn sample beds showed longer CO2 retention

times and seconds time for N2 and CH4 which indicated a much higher CO2 selectivity Because of the lack of open

metal sites and amide groups those unique adsorption behaviours can be explained as favourable interactions of

the SiF62- moieties for the CO2 molecules Moreover water did not affect the ability of SIFSIX-3-Zn to

preferentially selectively capture CO2 This is because the interaction between the strongly polarized CO2 and

SiF62minus anion make the SIFSIX-3-Zn hydrophobic These characteristics make them promising candidates for real

world applications such as efficient and selective CO2 capture in a power plants post-combustion chamber

31

Fig 17 Structure of SIFSIX-2-Cu (a) SIFSIX-2-Cu-i (b) and SIFSIX-3-Zn (c) breakthrough experiments for a

CO2N21090 and CO2CH45050 gas mixtures performed with SIFSIX-2-Cu-I and SIFSIX-3-Zn (d and e) kinetics of

adsorption for SIFSIX-3-Zn in pure gases and gas mixtures containing various compositions of CO2 (f) PXRD

patterns of SIFSIX-2-Cu-i after multiple cycles of breakthrough tests high-pressure sorption and water sorption

experiments Reproduced with permission from ref [8]

Based on the previous results the Eddaoudi group reported a framework SIFSIX-3-Cu based on the

hydrophobic silicon hexafluoride anion and pyrazinecopper(II) two-dimensional periodic 44 square grids (Fig 18)

[18] The pore size distribution of this material reached 35 Aring (larger than the kinetic parameters of CO2 33 Aring)

which allows for steeper variable temperature adsorption isotherms at low pressure Typically gas uptakes are

32

influenced by the working temperature however the CO2 uptakes of SIFSIX-3-Cu are almost the same as the

temperature was increased from 298 to 328 K Together with a higher adsorption heat (54 kJmol-1) SIFSIX-3-Cu

can strongly and rapidly adsorb CO2 but not N2 O2 CH4 and H2 Because of its stability the CO2 selectivity of this

material was tested using breakthrough experiments By varying the humidity the results showed that strong

electrostatic interactions and suitable pore size distributions drive the high selectivity of CO2N2 Additionally the

significant selectivity of SIFSIX-3-Cu at 1000 ppm CO2 was not affected by the presence of humidity (RH) at 74

This unique material shows that PCPs with the ability for rational pore size modification and inorganic-organic

moiety substitutions offer a remarkable ability for CO2 removal from highly diluted gas streams

Fig 18 Structure of SIFSIX-3-Cu (a) CO2 adsorption isotherms at variable temperatures for SIFSIX-3-Cu (b) Column

breakthrough test of CO2N21000 ppm999 for SIFSIX-3-Cu SIFSIX-3-Zn in dry conditions (c) Column

breakthrough test of CO2N21000 ppm999 for SIFSIX-3-Cu in dry conditions and at 74 RH (d) Reproduced


33

32 Membrane-based gas separation

As another energy-saving and high efficiency strategy for gas separation membrane technology has received a

great deal of attention in the last few decades [173 176 177 182-185] However for gas separation the

mechanism of the molecule sieve requires ultra-high standards for the permeated channels of the membrane

materials Inorganic zeolites and organic polymer membranes have been explored and used for separations in

industry However the removal (thermal burning) of the organic template used for higher crystalline zeolite

fabrication usually produces membrane cracks which results in lower separations especially for gas streams

[177] Meanwhile the fundamental trade-off between selectivity and throughput by non-uniform pores in

polymeric membranes was often observed [186] With well-defined and highly regular pore system PCP-based

membranes are expected to offer unique opportunities for advanced applications even with the difficulty of

fabricating perfect and continuous PCP-based membranes Generally membrane-based separations include two

types of thin PCP films on some porous supports and porous fillers in mixed-matrix membranes Along with the

discovery of new PCPs potential candidates for membrane preparation also show a promising future In 2007 the

Caro group reported a pioneering membrane work by crystalizing Mn(HCO2)2 crystals on porous supports which

showed that the density of the crystals can influence the surface property [187] In 2009 the Zhu group reported

the HKUST-1 membrane which was prepared via means of a lsquolsquotwin copper sourcersquorsquo technique using an oxidized

copper net to provide homogeneous nucleation sites for continuous crystal film growth in a solution containing

Cu2+ ions and the organic ligand [188] This special membrane has a high H2 permeation flux and good permeation

selectivity that are better than those of conventional zeolite membranes Then research on PCP membranes

witnessed a quick development through different strategies such as direct growth second growth layer-by-layer

growth post-synthesis modification and mixed-matrix membranes (MMMs) Despite these developments

fabricating a continuous and defect free PCP membrane remains difficult Furthermore once the lab scale work is

moved to feasible conditions the water stability and membrane performance repeatability became critical issues

Here we will summarize the membrane work with stable PCP frameworks

Inspired by the ideal pore size and good stability the Caro group reported a series of membranes based on

ZIF-8 (Fig 19) [189] Firstly they synthesized the ZIF-8 membrane on a porous titania support via a

microwave-assisted solvothermal method The cross section of the membrane showed a continuous

34

well-intergrown layer of ZIF-8 crystals on top of the support Using the Wicke-Kallenbach technique the

volumetric flow rates of a series of single gases and a group of mixtures were explored The permeabilities of the

membrane which were calculated from the volumetric flow rates depended on the pore size and the kinetic

diameters of the guest molecules Importantly the separation factors for H2CH4 reached 112 at 298 K and 1 bar

This work clearly shows the feasibility of gas separations using PCP membranes

Fig 19 SEM image of the cross section of a simply broken ZIF-8 membrane (right) EDXS mapping of the sawed and

polished ZIF-8 membrane (colour code orange Zn cyan Ti) Reproduced with permission from ref [189]

After this they systemically investigated the fabrication methods and separation performance of ZIF-8

membranes [190-195] For instance by modification of the polydopamine on the aluminium support the weak

connection of the ZIF-8 crystals and support was improved via the associated covalent bonds The corresponding

membrane showed good thermal stability good H2 selectivity and improved H2 permeability which were

promising for H2 separation and purification Additionally by depositing a graphene oxide (GO) suspension on a

semi-continuous ZIF-8 layer a novel hybrid ZIF-8GO membrane was developed and it showed attractive

separation factors and permeability for H2 toward CO2 N2 CH4 and C3H8 (Fig 20) Meanwhile a series of

membranes with stable ZIFs (ZIF-7 ZIF-22) have been reported for promising gas separations [196-199]

35

Fig 20 Scheme of ZIF-8 membrane preparation using PDA as a covalent linker between the ZIF-8 layer and Al2O3

support (a) preparation of bicontinuous ZIF-8GO membranes through layer-by-layer deposition of graphene

oxide on the semi-continuous ZIF-8 layer (b) Reproduced with permission from ref [194 195]

Using the porous materials of ZIF-90 the Huang group investigated the membrane performance and membrane

stability during H2 purification (Fig 21) [200-202] They first synthesized the continuous ZIF-90 membrane with a

covalent connection between the ZIF-90 and Al2O3 support The prepared membrane demonstrated a high

performance for H2CH4 separation in the temperature range from 298 to 498 K More importantly the membrane

performance for the H2CH4 mixture containing 3 mol steam at 473 K showed good stability for the H2

permeability and H2CH4 selectivity over one day Encouraged by those results the group post-modified the

membrane with an ethanol amine The shrinking window apertures and unique interactions with CO2 molecules

created an efficient H2CO2 separation from 298 to 498 K The selectivity improved from 72 to 162 via this

covalent modification and those values were not influenced by moisture steam Similar to this approach the

organosilica-APTEs modified ZIF-90 membrane also showed a good ability for H2 purification in the presence of 3

mol steam Thus stable PCP-based membranes have been suggested for gas separations even in the presence

of moisture

36

Fig 21 Preparation scheme for ZIF-90 membranes using 3-ami-nopropyltriethoxysilane (APTES) as a covalent linker

between the ZIF-90 membrane and Al2O3 support via an imine condensation reaction Reproduced with

permission from ref [200-202]

In addition to the ZIF-series the MIL-series frameworks have also been explored for membrane preparation

[196 198 203] In 2011 our group reported the MIL-53 membrane created using the novel and facile technique

of reactive seeding (RS)[126] Similar to direct synthesis the seeding step was performed during in situ growth

Then a continuous MIL-53 membrane on alumina porous supports was prepared via second growth Because of

the larger channel size (73 Aring) the MIL-53 membrane demonstrated normal H2CO2 gas separation Whereas

upon passing waterndashethyl acetate mixtures (7 wt water) the concentration of the permeated water increased to

99 wt with a high flux (Fig 22)

Fig 22 Schematic diagram of the preparation of stable MIL-53 membranes on alumina supports via the RS method

37


Very recently high porous Zirconium-based PCPs were also investigated as membranes for gas and ion

separation Due to high reaction activity of Zr4+ ion it is a challenge to fabricate continuous Zr-PCP polycrystalline

membranes After sufficient optimization of the preparation parameters and conditions the UiO-66 membrane

was synthesized on the outer surface of porous ceramic hollow fibers by Li group (Fig 23) [204] H2 permeability of

UiO-66 membrane was 72times10-7 molmiddotm-2middots-1middotPa-1 and the gas selectivity of H2N2 and H2CH4 reached to 224 and

64 respectively In addition high permeability of CO2 leaded to good selectivity of CO2N2 (297) at room

temperature Importantly the UiO-66 membrane with suitable pore size (sim60 Aring) exhibited moderate K+ and Na+

while high Ca2+ Mg2+ and Al3+ ions rejection indicating high potential usage in real industrial separation process

such as gas separation and water treatment

Fig 23 SEM images (aminusc and e cross section d top view) and (f) EDXS mapping (corresponding to e) of the

alumina hollow fiber supported UiO-66 membranes Reproduced with permission from ref [204]

To improve gas separation in permeation and selectivity the Yang group reported ultra-thin molecular sieve

membranes via fabrication of high crystalline and stable Zn2(bim)4 nanosheets on aluminium support [205] The

pore size of Zn2(bim)4 is approximately 021 nm The layered and large area PCP nanosheets were exemplified

38

from two dimensional crystals via wet ball milling and ultrasonication To avoid ordered restacking of nanosheets

the hot drop coating process was used to prepare an ultra-thin membrane Gas separation experiments at

different temperatures clearly showed H2CO2 separation via a size exclusion mechanism Surprisingly the

anomalous proportional relationship of high permeability and high selectivity for this ultra-thin membrane was

achieved by suppressing the lamellar stacking of the nanosheets More importantly the stable separation

performance in a gas mixture with 4 steam demonstrated its high hydrothermal stability and indicated a

significant possibility for practical usage (Fig 24)

Fig 24 SEM image of a bare porous a-Al2O3 support (a) SEM top view (b) and cross-sectional view (c) of a

Zn2(bim)4 nanosheet layer on an a-Al2O3 support Scatterplot of H2CO2 selectivities with an average selectivity

(red line) measured from 15 membranes (d) Anomalous relationship between the selectivity and permeability

measured from 15 membranes (e) Reproduced with permission from ref [205]

In parallel to the development of PCP film membranes efforts were also devoted to developing mixed matrix

membranes (MMMs) [198 206 207] As a type of polymeric membrane composed of porous fillers MMM

technology combines the advantages of polymers and particle fillers and MMMs show the potential to exceed

the Robenson upper bound for gas separations Additionally it is easy to prepare large scale MMMs with low cost

and without defects Generally the porous fillers include silicalite zeolite and silica particles However because

of their excellent performance in adsorption-based gas separations PCPs show promise as new fillers for MMM

39

preparation and application Usually the void spaces between the zeolite crystals and the polymeric matrix is

displayed and guest molecules can bypass the filler particles which results in a loss of selectivity However the

nature of the well-designed organic ligands in PCP materials will allow for good compatibility and will avoid the so

called ldquosieve in cage morphologyrdquo Additionally the involved polymers with a good hydrophobicity can provide a

type of protection for PCP fillers

As a pioneering work with MMMs and PCP fillers Cu-based PCP with a biphenyl

dicarboxylate-triethylenediamine ligand was embedded in the polymer of poly(3-acetoxyethylthiophene) for

MMMs in 2004 [208] The increased hydrophobicity of the MMM resulted in an increased CH4 permeability at 20

and 30 wt PCP loading Since then a number of MMMs with different PCPs fillers such as HKUST-1 ZIF-8

UiO-66 and MIL-53 have been explored Despite the hydrophobic protection from polymers not all of the PCPs

can be used as porous filler in MMMs even if they have a suitable pore size and capability for discrimination

adsorption For long-life time and highly effective PCP-based MMMs water stable PCPs are the premier choice

For CO2CH4 separation the Nair group reported the high performance of an MMM that incorporated a stable

nanaocrystal of ZIF-90 with three different poly(imide)s [209] With uniform and nano-sized crystals the ZIF-90

filler separated well and adhered with the poly(imide)s without any interfacial voids Thus ZIF-906FDA-DAM

membranes with a 15 wt loading showed a high performance for CO2CH4 separation and promising CO2N2

separation properties surpassing the Robenson limit of 2008 Furthermore when the Yampolskii group fabricated

a MMM with ZIF-8 crystals the corresponding behaviour for the CO2CH4 separation also exceed the Robertson

limit The self-supported membrane with ZIF-8 content showed an increase in the permeability and diffusion

coefficients as well as the separation factors as the ZIF-8 loading increased This can be explained by the

increased free volume after the introduction of ZIF-8 nanoparticles into the PIM-1 matrix (Fig 25)

40

Fig 25 SEM images of the cross-sections of mixed-matrix membranes containing ZIF-90 crystals a) ZIF-90AUltem

b) ZIF-90AMatrimid c) ZIF-90A6FDA-DAM and d) ZIF-90B6FDA-DAM Reproduced with permission from ref

[209]

As a water stable PCP UiO-66 was successfully separated in PCDF polymers and established a homogenous

MMM These durable large area and free standing membranes with good stability and flexibility can be prepared

on various supports Interestingly with the tunable functional groups in the PCP framework post modification of

MMMs can be performed in-situ to improve functions Meanwhile the Janiak group developed another MMM

with MiL-101 that exhibits significantly improved O2 permeability without a loss in the O2N2 separation [210]

They believed that the intersegmental spacing between the two polymer chains of the membrane enhanced the

diffusion speed of the O2 gas However a separation of gas mixtures with steam was not studied in this work

4 Conclusion and outlook

Dramatic advances have been achieved in the chemistry of water stable PCPs PCPs have been a hot topic in the

last few decades but their stability has always posed a challenge This is because the coordination bonds involved

are not strong enough when attacked by water molecules especially compared to the strong Si-O bonds in zeolite

materials From reported literature selected ligands metal clusters coordination geometries and protections

from hydrophobic units can offer a significant chance for design and synthesis of a stable PCP In addition to their

intriguing structures water stable PCPs also have the potential for significant applications for adsorptive-based

41

and membrane-based gas separations Therefore in this review we highlighted the crucial advances for stable PCP

preparations and their applications for gas purification PCPs with good stability were summarized in three tables

with different strategies (Table 1-3) These data can act as databases for the desired references

Tremendous progress has already been made in gas separation with stable PCPs and more frameworks with

better performance will be developed by selection of ligands and metal centres Some researchers and companies

have begun to develop cheap stable and functional structures that can be easily obtained on a large scale The

total processes for separations were evaluated both technologically and economically By learning about the

success of the zeolite industry we strongly believed that PCP materials are capable of serving as effective

adsorbents or molecular sieves for effective gas separation with continued investigations in the field

Acknowledgement

The authors gratefully acknowledge financial support from National Science Foundation of China (21301148

21671102) National Science Foundation of Jiangsu Province (BK20161538) Six talent peaks project in Jiangsu

Province (JY-030) Innovative Research Team Program by the Ministry of Education of China (IRT13070) State Key

Laboratory of Coordination Chemistry (SKLCC1616) State Key Laboratory of Materials-Oriented Chemical

Engineering (ZK201406) ACCEL project of the Japan Science and Technology Agency (JST) and JSPS KAKENHI

Grant-in-Aid for Challenging Exploratory Research (Grant No 25620187) iCeMS is supported by the World Premier

International Research Initiative (WPI) of the Ministry of Education Culture Sports Science and Technology Japan

(MEXT)

42

Author information

Jingui Duan received his PhD from the Department of Chemistry Nanjing University in

2011 He was a JSPS postdoc at Kyoto University under the supervision of Prof S

Kitagawa from 2011 to 2014 and then joined Nanjing Tech University in 2015 as an

associate professor His current research interest is in the design synthesis porous

coordination polymersporous coordination polymers membrane for their application

in gas separation

Wanqin Jin is a professor of Chemical Engineering at Nanjing Tech University He

received his PhD from Nanjing University of Technology in 1999 He was a

research associate at the Institute of Materials Research amp Engineering of

Singapore (2001) an Alexander von Humboldt Research Fellow (2001ndash2003) and

visiting professor at the Arizona State University (2007) and Hiroshima University

(2011 JSPS invitation fellowship) His current research focuses on membrane

materials and membrane processes He has published over 200 SCI tracked

publications and is now on several Editorial Boards such as the Journal of

Membrane Science and a council member of the Aseanian Membrane Society

Susumu Kitagawa received his PhD from Kyoto University in 1979 He was promoted to

a full professor at Tokyo Metropolitan University in 1992 and he moved to Kyoto

University as a professor of Inorganic Chemistry in 1998 Presently he is also the

Director of the Institute for Integrated Cell-Material Sciences (WPI-iCeMS) at Kyoto

University His current research interests include the chemical and physical properties

of porous coordination polymersmetal organic frameworks

43

Abbreviations

PCPs Porous coordination polymers MOFs Metal organic frameworks PCN Porous coordination networks ZIF Zeolite imidazole framework MAF Metal azolate framework LSA Langmuir surface area BK Breakthrough experiments HKUST Hong Kong University of Science and

Technology UiO University of Oslo MIL Mateacuterial Institut Lavoisier DUT Durban University of Technology BUT Beijing University of Technology NU Northeast University FJI Fujian Institute CAU Christian-Albrechts-Universitt NOTT Nottingham university CALF Calgary Framework USTA University of Texas at San Antonio MMM Mixed matrix membrane DMF NNrsquo-Dimethylformamide BTTri 135-tris(1H-123-triazol-5-yl)benzene BTT 135-benzenetristetrazolate BTBA 135-tris(1H-pyrazol-4-yl)benzene BDP 13-benzenedi(40-pyrazolyl) BTP 135-tris(1H-pyrazol-4-yl)benzene pcn 4-pyridinecarboxylic acid ttbl 33rsquo55rsquo-tetraethyl-44rsquo-bipyrazolate

TCMBT NNrsquoNrsquorsquo-tris(carboxymethyl)-135-benzenetricarboxamide

bpp 13-bis(4-pyridyl)propane tapp 4-(4H-124-triazol-4-yl)-phenyl phosphonate L1 1H-pyrazole-4-carboxylic acid L2 4-(1H-pyrazole-4-yl)benzoic acid

L3 44rsquo-benzene-14-diylbis( 1H-pyrazole)

L4 44rsquo-buta-13-diyne-14-diylbis(1H-pyrazole)

L5 44rsquo-(benzene-14-diyldiethyne-21-diyl)bis(1H-pyrazole)

NIC Nicotinate hptz 4-(124-triazol-4-yl) phenylphosphonic acid

ptptp 2-(5-6-[5-(pyrazin-2-yl)-1H-124-triazol-3-yl]pyridin-2-yl-1H-124-triazol-3-yl)pyrazine

o-PDA Phenylenediacetic acid ftzb 2-fluoro-4-(1H-tetrazol-5-yl) benzoic acid BTB 135-tris(4-carboxyphenyl)benzene)

BTN 135-Tri(6-hydroxycarbonylnaphthalen-2-yl)benzene

pyzdc pyrazine-25-dicarboxylate dbpp 35-di(24-dicarboxylphenyl)pyridine bpydb 44prime-(44prime-bipyridine-26-diyl) dibenzoic acid

44

NDC 14-naphthalenedicarboxylate

FTZB 2-fluoro-4-(1H-tetrazol-5- yl)benzoic acid

dsoa disodium-220-disulfonate-440-oxydibenzoic acid

cppc 5-(4-carboxyphenyl)pyridine-2-carboxylate

cmdcp N-carboxymethyl-(35-dicarboxyl)-pyridinium bromide

bdp 14-benzenedipyrazolate bpe 12-bis(4-pyridyl)ethene idc imidazole-45-dicarboxylate hprz piperazine dppz 35-di(pyridine-4-yl) benzoate PDMS Polydimethylsiloxane 6FDA 44prime-(Hexafluoroisopropylidene)diphthalicanhyd

ride RH relative humidity Ultem Polyetherimide PVDF Polyvinylidene fluoride

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52

53

Factors of governing water resistance of porous coordination polymers were surveyed and discussed

Representative studies were given with emphasis on adsorptive- and membrane-based gas separations by

water resistent porous coordination polymers

1


Jingui Duana c Wanqin Jina and Susumu Kitagawab

a State Key Laboratory of Materials-Oriented Chemical Engineering College of Chemical engineering Nanjing Tech

University Nanjing 210009 China E-mail duanjinguinjtecheducn

b Institute for Integrated Cell-Material Sciences (WPI-iCeMS) Kyoto University Yoshida Sakyo-ku Kyoto

606-8501 Japan E-mail kitagawaicemskyoto-uacjp

c Jiangsu National Synergetic Innovation Center for Advanced Materials Nanjing Tech University Nanjing 210009

China

Received Sep XX 2016

Contents

1 Introduction 2 2 Factors influencing the water stability of PCPs 4

21 Stronger coordination bonds 5 211 Ligands with high pKa values 5 212 Metals with high oxidation states 10

22 Imparting protection for the coordination bond 18

221 Ligands with hydrophobic units 18 223 Coating hydrophobic units for enhanced stability 21

224 Catenation for improved stability 23

3 Gas separations by stable PCPs 24 31 Adsorptive separations in water stable PCPs 25

32 Membrane-based gas separation 33

4 Conclusion and outlook 40 Acknowledgement 41

References 44

Abstract Porous coordination polymer (PCP) chemistry has a promising future because of the tunable structures

and excellent properties of polymers However the strategy for designing and preparing water-resistant PCPs is a

considerable challenge This review surveys and investigates the factors governing water resistance in a hierarchy

sequence Subsequently representative studies are provided with an emphasis on their adsorptive- and

membrane-based gas separations This review is intended to be useful for researchers who are interested in

designing water-resistant PCPs and exploring promising applications for gas separation

Keywords Porous coordination polymer water-resistance adsorptive gas separation membrane-based gas

separation

2

1 Introduction



























3




















PCPs








4












5





following sections


















6












7











8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




2

1 Introduction



























3




















PCPs








4












5





following sections


















6












7











8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




3




















PCPs








4












5





following sections


















6












7











8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




4












5





following sections


















6












7











8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




5





following sections


















6












7











8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




6












7











8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




7











8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




8













9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




9




Name Metal


Gas Selectivity and

Separation ref


ene 1770


HCl (pH = 3) RT 24 h CO2N2 19 [61 65]


ene 345 ND CO2N2 10-21 [61 65]

mmen-Cu(BT

Tri) Cu(II)


ene 870 ND CO2N2 165 327 [65 66]


CO2H2 5772 [47]


(pH = 12) 24 h

C2H2CH4 40minus65

CO2CH4 and

C2H2CO2 6-10

[52]





e 576

0001M NaOH and

0001M HCl boiling

24h

ND [68]

Cu(TCMBT)(b

pp) Cu(II)




808 Boiling water 2

months

CO2N220

CO2CH4 4 [69]



95 RH for

12 h at 90 degC ND [70]


Boiling in HCl HNO3

(pH = 2) NaOH (pH =

14) 14 days

ND [60]

10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




10


orphyrin 1309


24h RT 01mM HCl

24h

ND [53]





Ni-L4 Ni(II)

L4


yrazole)


(ArN2) [71]

Ni-L5 Ni(II)

L5




(ArN2) with RH [71]


(ArN2) [71]


Diethylsulfide(DES)

(ArN2)

with RH

[71]


area

15 ppm SO2 2 days

RT Water 48 h CO2N2 13 [72 73]




Boiling 01M HCl 7

days

CO2N2 114

CO2CH4 298 [74]




8M NaOH boiling

24h

CO2CO BK [31 32]




CO2N2 187

CO2CH4 4 [32]



CO2N2 199

CO2CH4 5 [32]



CO2N2 173

CO2CH4 52 [32]

Pb- (ptptp) Pb(II)

2-(5-6-[5-(pyrazin-2-yl)-1H-124-tri


ol-3-yl)pyrazine







ND no data






11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




11


















12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




12
















13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




13

















14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




14











(Fig 8)



ref [10k]



15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




15












Name Metal

Cluster Ligand

BET




CO2CH4 32

CO2N2 134

[34 94

96-98]


2h pH = 1-9 CO2CH4 9

[21

99-102]


= 14

CO2CH4 47

CO2N2 251 [98-100]


= 14 CO2CH4 47

[97 99

100]


CO2N2 264 [98 100]


1 M HCl 12h CO2CH4 75 [21 103]

UiO-66-CO

OH Zr(IV)


(COOH) 217 (LSA)

RT water 12h RT

1 M HCl 12h CO2CH4 52 [21 103]







DUT-67 Zr(IV)H


RT Water 24 h 1

M HCl 3 days

CO2CH4 27-29

CO2N2 94-99 [105]

DUT-68 Zr(IV)H


RT Water 24 h 1


DUT-69 Zr(IV)H


RT Water 24 h 1


MIL-125-NH


CO2N2 27 BK

CO2CH4 7

H2SCH4 70

[80 106

107]


16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




16

(Zr)

MIL-163

(Zr) Zr(IV)



Boiling water 7

days pH = 74 310

K 14 days

ND [90]


CO2N2 186-229 [108]



CO2CH4 90-92

CO2N2 315-431 [108]



Normalized

selectivity

(CO2N2 ~018)

[109]



RT pH = 2-11 15-24

h

Normalized

selectivity

(CO2N2 ~07)

[109]



RT water 72 h pH

= 2-11 20-24 h

Normalized

selectivity

(CO2N2~10)

[109]



24h ND [88]








Zr-BTBA Zr(IV)



tetrabenzoic acid

4342 RT water 48 h ND [113]




24 h ND [86]


24 h ND [86]





NU-1100 Zr(IV)



ic acid

4020 RT water 24h ND [115]


FJI-H6 Zr(IV)



arboxylicacid)

5007 RT pH = 0-10 24h ND [38]

FJI-H7 Hf(IV)



arboxylicacid)

3831 RT pH = 0-10 24h ND [38]


) 1024

Boiling system pH

= 7 and 14 3 days

80RH 353K 3

days

C2H6CH4 21

C2H4CH4 12

CO2CH4 8 BK

for C2H6CH4

CO2CH4

[46]



Boiling system pH =

2- 12 24 h

CO2N2 93-38

CO2O2 78-20

CO2CO 68-18

[45]

17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




17


Tuluene 72 h

H2OCH3OH BK

simulation [116]


enzene 0

Boiling water 7

days ND [117]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

SUMOF-7I-

7II-7III La(III)




benzene

780

1002

1489

Boiling water and

DMF 30 days RT

pH = 2-11 24 h

ND [118]


area

15 ppm SO2 2 days

80 RH 72h RT

Water 48h

CO2N2 3-4 [72]

Ln(dbpp)

Eu(III)L

a(III)

Nd(III)S

m(III)


e ND

RT water 30d





Boiling water

24hBoiling


10 24 h

BK CH4n-C4H10

CO2N282

CO2CH4 16

[121]




dibenzoic acid ND

RT water 28 days







353 K water 6h

007 M NaOH 007

HCl 2h

Membrane

Separation for

H2CO2

[124-126

]


128]


days ND [129]


acid 1370

RT airmoisture 30

days

CO2CH4 100

CO2N2 180

CO2H2 105

SO2CH4 3620

SO2N2 6522

SO2H2 105

[130]



[131

132]


NO2 OCH3OH) 635440

RT pH = 2-8

stirring 403K

water 3 h

CO2H2 59-121 [133]




303 K 100 mgL

fluoride 24 h

solution

ND [99 125

131]


(LSA)

310 K pH = 74 24

h 323 K Water 24

h

CO2CH4 585

C3H8C3H6 BK S =

289

[99

134-136]

18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




18


te ND

310 K pH = 74 24

h ND [99]


14 days

BK of

22-dimethylbuta

ne

23-dimethylbuta

ne

3-methylpentane

2-methylpentane

andn-hexane

[137]



353 K water 6h

007 M NaOH 007

HCl 2h

CO2CH4 23 [125

138]


0 323 K Water 24 h CO2CH4 31 [30 139]



CO2N2 22

CO2O2 32 [140]


















19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




19











10)

20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




20

















21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




21
















water resistance



22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



(2010) 195-199




52

53




22


















23











Name Metal

Cluster Ligand

BET

(m2

g)



RT AirWater 30 days


01M NaOH 7 days

CO2N2 1820

CO2CH4 [164]


piperazine ND

RT waterseries



ate 385 353K 80 RH ND [148]


CO2CH4 298 [166]




triazolate ND

Boiling water


[56

141]



90


MOF-508-TM Zn(II)

356-tetramethyl-14-



105

0

90




CO2N2 398 CO2CH4

46 CO2O2 235

[168

169]

Poly-Zn(bpdc)(

bpy) Zn(II)







24




























25

























26

















27

















28












gas system (Fig 15)



[46] and [45]

29


















30





















31










32













33




























34
















35















of moisture

36












37
















38


















39






















40



[209]















41










Acknowledgement








(MEXT)

42

Author information






in gas separation
















43

Abbreviations













44








References





343 (2014) 167-170


Yaghi Science 329 (2010) 424-428













303-308






45





4228-4235







Chem Int Ed 51 (2012) 7440-7444


Soc 136 (2014) 8863-8866


Chem Int Ed 49 (2010) 8489-8492







Angew Chem Int Ed 45 (2006) 8227-8231


2040-2042


Natl Acad Sci U S A 103 (2006) 10186-10191




(2008) 13850-13851



Society 138 (2016) 6204-6216





Soc 137 (2015) 7169-7177





Mater 22 (2010) 3316-3322

46



5 (2014) 660-666


23 (2013) 3525-3530








(2016) 914-919




18094-18097





1311-1319





(2014) 4369-4381


112 (2012) 724-781



(2012) 263-267







Mater 173 (2013) 86-91






47

(2013) 7660-7667


221-227


8775-8778




3283-3293


Soc 135 (2013) 17105-17110





Inorg Chem 51 (2012) 6443-6445



13934-13938


Chem Int Ed 54 (2015) 149-154







8944-8946


5642-5650



J Am Chem Soc 134 (2012) 10174-10181


4730-4737



Mater 25 (2013) 2767-2776







48




10857-10859





Chem Soc 137 (2015) 413-419


Ed 53 (2014) 815-818




7795-7798










4034-4041


(2015) 5034-5040




15834-15842










(2014) 72-78



17-26

49


120 (2009) 325-330





5949-5952





359-368




(2016) 920-925







132 (2010) 14055-14057




[151] SM Cohen Chem Rev 112 (2012) 970-1000




135 (2013) 16801-16804






9140-9142






Soc 134 (2012) 19556-19559


50













Commun 51 (2015) 17672-17675










(2015) 2421-2454



8041-8047



















51



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water-resistant porous coordination polymers for gas separation · 2018. 1. 2. · porous...

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