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www.sciencemag.org/content/350/6258/302/suppl/DC1
Supplementary Materials for
CO2 capture from humid flue gases and humid atmosphere using a
microporous coppersilicate
Shuvo Jit Datta, Chutharat Khumnoon, Zhen Hao Lee, Won Kyung Moon, Son Docao, Thanh Huu Nguyen, In Chul Hwang, Dohyun Moon, Peter Oleynikov, Osamu Terasaki,
Kyung Byung Yoon* *Corresponding author. E-mail: [email protected]
Published 16 October 2015, Science 350, 302 (2015) DOI: 10.1126/science.aab1680
This PDF file includes:
Materials and Methods
Figs. S1 to S19
Tables S1 to S5
References
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Materials and Methods
Materials
Sodium silicate solution (Na2SiO3, 10.6 % Na2O, and ~26.5% SiO2, Sigma-Aldrich), sodium silicate solution (Na2SiO3, 17-19% Na2O, and 35-38%, SiO2, Kanto), copper sulfate pentahydrate (CuSO4. 5H2O, 99%, Alfa-Aesar), titanium isopropoxide [TIP, 98%, Junsei], vanadium oxide (V2O5, 99%, Aldrich), sulfuric acid (H2SO4, 95%, Duksan), hydrofluoric acid (HF, 48-51%, Baker), sodium hydroxide (NaOH, 93%, Duksan), sodium chloride (99.5%, Samchun), potassium fluoride (KF, 95%, Samchun), potassium hydroxide (KOH, 95%, Samchun), potassium chloride (KCl, 99%, Oriental), magnesium nitrate hexahydrate (Mg(NO3)2·6H2O, 99%, Sigma-Aldrich), nickel (II) acetate tetrahydrate (Ni(OCOCH3)2· 4H2O, 98%, Aldrich), cobalt (II) acetate tetrahydrate (Co(OCOCH3)2· 4H2O, 98.5%, Junsei), zinc carbonate basic ([ZnCO3]2· Zn(OH)2]3, 58% Zn basis, Sigma-Aldrich), zinc nitrate tetrahydrate (Zn(NO3)2· 4H2O, 98%, Samchun), copper nitrate trihydrate (Cu(NO3)2· 3H2O, 99-104%, Sigma-Aldrich), chromium nitrate nonahydrate (Cr(NO3)3· 9H2O, 99%, Sigma-Aldrich), zinc hexafluorosilicate hydrate (ZnSiF6· xH2O, 99%, Aldrich), copper hexafluorosilicate hydrate (CuSiF6· xH2O, Fluorochem), vanadium (III) chloride (VCl3, 97%, Aldrich), 2,5-dihydroxyterephthalic acid (H4DOBDC, 98%, Aldrich), pyrazine (C4H4N2, 98% TCI), citric acid monohydrate (C6H8O7·H2O, 99.5%, Sigma-Aldrich), 3-amino-1,2,4-triazole (C2H4N4, 95%, Sigma), 3,3´,5,5´-biphenyltetracarboxylic acid (C16H10O8, Aldrich), 1,3,5-Tris(4-carboxyphenyl)benzene (H3BTB, 98%, Aldrich), Benzene-1,3,5-tricarboxylic acid (Aldrich), terephthalic acid (C8H6O4, 98%, Aldrich), 2-Methylimidazole (C4H6N2, 98%, Fluka), N,N-dimethylformamide (DMF, 99%, Samchun), N,N-diethylformamide (DEF, 99%, Samchun), tetrahydrofuran (THF, 99.8%, SK), methanol (CH3OH, 99.9%, Sigma-Aldrich), ethanol (C2H5OH, 99.9%, Samchun), were purchased and used without further purification.
CO2 (99.999%), N2 (99.999%), O2 (99.999%) and mixed gases consisting of CO2:N2 = 10:90 and CO2:O2 = 10:90, simulated flue gases consisting of CO2, O2, and N2 with the volume ratio of 10:19:71, 11:19:70, and 12.5:18.5:69 and simulated air (400 ppm CO2, in O2 and N2) were purchased from RIGAS, Sam Jung, and Air Products Korea.
Methods
Synthesis of ETS-10 (Titanosilicate, Na1.11K0.83TiSi5O13· xH2O) A Si source solution was first prepared by dissolving Na2SiO3 (18.4 g, 17-19% Na2O, and
35-38%, SiO2, Kanto) in H2O (60 g). Into this, a NaOH solution (2.4 g of NaOH and 20 g of H2O) was added with vigorous stirring, and the mixture was stirred for 2 h. For the preparation of Ti source solution, titanium isopropoxide (5.7 g), H2SO4 (4.5 g), and H2O (35 g) were mixed
together and boiled at 100˚C for 90 min, 10 ml H2O was finally added into the mixture and
allowed to cool at room temperature. The Ti source solution was added drop wise into the Si source solution, and the mixture was stirred for 1 h. A dilute KF solution (1.2 g of KF and 15 g of H2O) was added into the above mixture. The mixture was aged for 16 h at room temperature and transferred into a Teflon-lined autoclave, and heated at 200°C for 22 h under a static condition. After cooling the autoclave to room temperature, the crystals were collected by centrifugation, and washed with copious amounts of distilled deionized water. The scanning
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electron microscopy (SEM) shows the typical crystal size 200-300 nm, and those crystal could be used as the seed for AM-6 and SGU-29 synthesis.
Synthesis of AM-6 (Vanadosilicate, Na1.12K0.85VSi5O13· xH2O) Preparation of Si source solution: A NaOH solution (3 g NaOH and 20 g of H2O) was added
into the sodium silicate solution composed of 12.2 g of Na2SiO3 (17-19% Na2O, and 35-38%, SiO2, Kanto) and 40 g of H2O. A dilute KCl solution (3 g of KCl and 10 g of H2O) was added into the above mixture and the mixture was vigorously stirred.
Preparation of vanadium source solution: A required amount of H2SO4 (4.9 g) was added into a 100-mL round bottom flask containing H2O (10 g). Subsequently, V2O5 (1.7 g) and EtOH (4 g) were sequentially added into the flask. The mixture was refluxed for 40 min, during the heterogeneous mixture was turned into blue solution. The blue V source solution was added into the Si source solution in a dropwise manner. The mixture was aged for 15 h at room temperature; seed ETS-10 (50 mg) was added into the gel and the gel was transferred into a 50 ml Teflon-lined autoclave, and placed in a preheated oven at 230 °C for 48 h, under a static condition. The precipitated pale yellow crystals were collected, washed, dried at 100 °C for 1 h.
Synthesis of SGU-29 (Coppersilicate, Na1.15K0.84CuSi5O12· xH2O) The silicon source solution was prepared by mixing of sodium silicate (40 g, 10.6 % Na2O,
and ~26.5% SiO2, Sigma-Aldrich), 1.3 g of NaOH, 12 g of KCl, 18.5 g of NaCl, and 60 g of DDW. The mixture was vigorously stirred (800 rpm) at room temperature for 3 h. The copper source solution was prepared by dissolving CuSO4 (9 g) in 30 g of DDW containing 1.2 g of H2SO4. The copper source solution was then added into the sodium silicate solution in a dropwise manner. The mixture was aged for 15 h at room temperature, and the pH was adjusted to 10.66 (if required) by adding diluted H2SO4 in water. The seed ETS-10 (100 mg) was added into the gel and the gel was transferred into the 50 ml Teflon-lined autoclaves, and placed in a preheated oven at 215 °C for 24 h under a static condition. The precipitated light purple crystals were collected by centrifugation at 8000 rpm, and washed with copious amounts of water. The sample was dried at 100 °C for 1 h, and analyzed by X-ray powder diffraction. Preparation of Na+-exchanged SGU-29, AM-6 and ETS-10
The ion exchange was conducted at 70 C for 120 min and repeated for three times. First, 1 g of pristine (SGU-29, AM-6 or ETS-10) powder was introduced into a glass vial containing 45 mL of 1 M NaCl solution and subsequently the heterogeneous mixture was magnetically stirred and washed with copious amount of water. The ion exchange proceeded up to 85%. The chemical composition was determined by ICP-MS and X-ray fluorescence. The compositions were found to be Na1.69K0.3CuSi5O12•xH2O, Na1.65K0.33VSi5O13•xH2O, and Na1.61K0.35TiSi5O13•xH2O for SGU-29, AM-6 and ETS-10, respectively. Synthesis of Mg-DODBC (Mg2(dhtp)(H2O)2·8H2O)
Mg-DOBDC was synthesized according to reported procedure (11). Briefly, H4DOBDC (2,5-dihydroxyterephthalic acid, 0.11g, 0.555 mmol, 1 equiv) was dissolved in 25 mL of 15:1:1 (v/v/v) mixture of DMF-ethanol-water. Separately, Mg(NO3)2·6H2O (0.47 g, 1.83 mmol, 3.3 equivalent) was dissolved in 25 ml of 15:1:1 (v/v/v) mixture of DMF-ethanol-water. These two solutions were mixed together and stirred for 15 min at RT. The solution was then transferred into a 65 mL Teflon lined autoclave and the autoclave was placed in a preheated oven at 125 C for 20 h.
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After reaction the autoclave was removed from the oven and allowed to cool to RT. The yellow microcrystalline product was collected by centrifugation and placed in methanol (10 mL). The methanol was decanted and the yellow product was placed in fresh methanol. This procedure was repeated for four times in two days. A dark yellow crystalline material was obtained. Synthesis of SIFSIX-3-Cu, [Cu(SiF6)(pyz)]·2H2O]n
SIFSIX-3-Cu was synthesized according to the reported procedure (14). Pyrazine (1.20 g, 15 mmol) was dissolved in 20 ml of methanol. Separately, CuSiF6·H2O (1.3 g, 6.32 mmol) dissolved in 20 mL of methanol. The pyrazine solution was carefully layered onto CuSiF6·H2O solution and the solution was kept at 40 ºC for 1 days. The turquoise color microcrystalline sample was collected by methanol decantation and placed in 40 ml methanol. The methanol was decanted and refill three times over three days and dried at RT. Synthesis of SIFSIX-3-Zn, [Zn(SiF6)(pyz)]·2H2O]n
SIFSIX-3-Zn was synthesized according to the reported procedure (13) with a slight modification. Pyrazine (1.04 g, 13 mmol) was dissolved in 20 ml of methanol. Separately, ZnSiF6·H2O (1.3 g, 6.26 mmol) was dissolved in 20 ml of methanol. The pyrazine solution was carefully layered onto ZnSiF6·H2O solution and the solution was kept at 40 C for 3 days. The rest of the procedure is the same with that for the synthesis of SIFSIX-3-Cu. Synthesis of Ni-DOBDC, (Ni2(dhtp)(H2O)2·8H2O)
Ni-DOBDC was synthesized according to the reported procedure (31). Briefly, H4DOBDC (2,5-dihydroxyterephthalic acid, 0.298 g, 1.5 mmol) was dissolved in 20 ml THF by sonication. Separately, nickel acetate tetrahydrate (Ni(OCOCH3)2·4H2O, 0.746 g, 3 mmol) was dissolved in 20 ml of water by sonication. These two solutions were mixed together and stirred for 15 min at RT. The solution was then transferred in 65 ml Teflon lined autoclave and placed in preheated oven at 110 C for 72 h. After the reaction the autoclave was removed and allowed to cool to RT. The deep-yellow microcrystalline product was collected and washed with methanol (10 ml) by placing it in methanol for 15 h and decanting the supernatant solution. This procedure was repeated for two times and the product was dried at 50 C. NaX, [Na88(Al88Si104O384)·xH2O]
Commercially available zeolite X (Lot no 943196110142 from UOP) was ion exchanged with Na+ by placing 1 g of zeolite X powder in a glass vial containing 90 mL of 1 M NaCl solution and subsequently stirred at 70ºC for 120 min. This procedure was repeated twice. After ion-exchange the sample was washed with copious amount of water until the chloride test with AgNO3 solution was negative. Synthesis of UTSA-16, {[KCo3(C6H4O7)(C6H5O7)(H2O)2]•8H2O}n)
UTSA-16 was synthesized according to the reported procedure (15). Citric acid (C6H8O7·H2O, 0.63 g, 3.28 mmol) was dissolved in 7.5 ml of 1:1 (v/v) mixture H2O-ethanol. Subsequently, KOH (0.504 g, 9 mmol) was added into the above solution and the solution was sonicated for 3 min. Separately, cobalt acetate tetrahydrate (Co(OCOCH3)2·4H2O, 0.75 g, 3 mmol) was dissolved in 7.5 ml of 1:1 (v/v) mixture H2O-ethanol. Upon mixing these two solutions a violet sticky gel was formed. The hydrothermal reaction was carried out at 120 C for
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48 h. The violet prismatic crystals were collected by filtration, washed with diethyl ether, and dried at RT. Synthesis of Zn2(Atz)2(ox)
Zn2(Atz)2(ox) was synthesized according to the reported procedure (27). Zinc carbonate basic [ZnCO3]2·[Zn(OH)2]3 (0.5 g) was dispersed in 25 ml of 1:1 (v/v) mixture of methanol-water by sonication. Subsequently, oxalic acid (0.5 g) was added into the solution and sonicated for 5 minutes. Separately, 3-amino-1,2,4-triazole (2 g) was dissolved in 25 ml of 1:1 (v/v) mixture of methanol-water. These two solutions were mixed together and stirred for 15 min at RT. The mixture was transferred into a 65 ml Teflon lined autoclave and the autoclave was placed in a preheated oven at 180 ºC for 72 h. The white aggregated cubic crystals were collected by filtration and soaked in dry acetone for 3 days. The sample was heated under vacuum at 60 C for 2 h and at 100 C for 12 h before use. Synthesis of Co-DOBDC, Zn-DOBDC, HKUST-1, MOF-505, MOF-14, MIL-47, MIL-101 (Cr), ZIF-8, IRMOF-1, and MOF-177
The above materials were synthesized according to the reported procedures: Co-DOBDC (32), Zn-DOBDC (33), HKUST-1 (35), MOF-505 (36), MOF-14 (37), MIL-47 (39), MIL-101 (41), IRMOF-1 (44), MOF-177 (45). ZIF-8 (46), X-ray powder diffraction analysis
Powder X-Ray diffraction patterns were collected on a Rigaku D/MAX-2500/pc diffractometer (Cu K =1.54056 Ǻ) with an operating power of 50kV/200mA and automatic divergence slit (irradiated length = 10 mm), a progressive receiving slit (slit height = 0.3 mm), and a flat plate sample holder. The data were collected by the step-counting method (step = 0.02º, time = 4 s) in the range 2 = 3-50º. In-situ powder X-ray diffraction patterns were collected on a Rigaku Ultima IV X-ray diffractometer (Cu K =1.54056 Ǻ, dual position graphite diffracted beam monochromator) with an operated power 40kV/50mA. The temperature was varied between 25 and 600 ºC under air. The heating rate was 5 ºC/min and the holding time at each temperature was 30 min so that the temperature of the sample can reach the equilibrium.
Single crystal X-ray diffraction structure analysis Data collection The single crystal diffraction data of SGU-29 was recorded at room temperature on an ADSC
Quantum 210 CCD diffractometer using synchrotron radiation (λ = 0.7000 Å), a scan width of 1.00 in , a measuring time of 10~30 sec per frame, and detector distance of 63.00 mm in Macromolecular Crystallography Wiggler Beamline 2D, Pohang Accelerator Laboratory (PAL). The diffraction patterns were processed and scaled using the HKL3000 program. The structure was solved by the direct methods. The collected data was refined in the tetragonal (polymorph type-A, SGU-29 T) and the monoclinic (polymorph type-B, SGU-29 M) crystal systems derived from the original triclinic system. The refinement was carried out with full-matrix least-squares on F2 in the SHELXTL program package.
For the measurement of a single crystal synchrotron X-ray diffraction, a suitable piece was obtained by cutting a large single crystal along three directions (fig. S4). The reason for dissecting the crystal was in the polycrystalline nature of the single crystal diffraction data that
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was initially collected from the whole piece. The data collection was performed in the primitive triclinic crystal system setting (Table S1).
Crystal structure solution and refinement The crystal structure of SGU-29 was solved using the direct methods in 3 different space
groups: (i) C-centered monoclinic (C2/c) for monoclinic SGU-29 (M) which corresponds to the polymorph type-B of ETS-10 proposed by Anderson et al. (22); (ii) primitive tetragonal (P41/P43) for tetragonal SGU-29 (T) which resembles the polymorph type-A of ETS-10 proposed by Anderson et al. (22); and (iii) I-centered tetragonal (I41/amd) that counterfeit the T1 type derived by Wang and Jacobson (23). The structure solution converged to low R-factors for the SGU-29 T1 and M types. The single crystal structural data of SGU-29 (M) and (T1) are summarized in the Table S1. The comparison of SGU-29 structure data with that of ETS-10 can be found in Table S2.
SGU-29 (monoclinic type M, s.g. C2/c) The centrosymmetric monoclinic space group C2/c (no. 15) was used for the structure
solution of the monoclinic SGU-29 (M). The unit cell parameters and the volume were determined as a = 20.820(4), b = 20.819(4), c = 14.697(3) Å, β = 110.73(3)o and V = 5958(2) Å3. The initial refinement of the structure model revealed high anisotropy of several atoms in the unit cell (all Cu atoms, eight Si atoms and twelve O atoms). In order to resolve the presence of severe disorder a new average structure (fig. S5A) was introduced into the refinement procedure by combining two independent parts, namely part-1 and part 2 (fig. S5B and fig S5C respectively) with the refined content of 72.75% for part-1. The final coppersilicate framework structure (M) is consistent with the titanosilicate ETS-10 polymorph type-B structure (22). The information for the basic building units, the average bond lengths and angles of SGU-29(M) is show in (fig. S6). The unit cell of SGU-29 (M) contains five crystallographically independent sodium atoms (Na+). Their positions are shown in fig. S7, together with the data for interatomic distances and ionic coordination numbers (fig. S8).
SGU-29 (tetragonal type T1, s.g. I41/amd) Besides the monoclinic structural model, the single crystal data of SGU-29 can be described
and refined using higher symmetry, e.g. in the I-centered tetragonal Bravais lattice system following Wang and Jacobson (23) with the unit cell parameters a = b = 7.361(1) and c = 27.492(6) Å. The initial refinement resulted in high anisotropy of some atoms (one Cu atom, two Si atoms, five O atoms and two Na atoms) in the unit cell. The final structure of T1 coppersilicate framework has average bond lengths and angles of the monoclinic SGU-29(M).
Analysis of electron microscopy data Scanning electron microscopy (SEM) images were obtained using a field-emission scanning
electron microscopes (FE-SEM, JEOL JEM 7600 and Hitachi S-4300) operated at 15 kV. Transmission electron microscopy (TEM) images were collected on a JEOL JEM 4010 microscope operated at 400 kV. High resolution transition electron microscopy (HRTEM) image of SGU-29 is shown in fig. S9A and is similar to that of ETS-10 reported previously by Anderson et al. (22). The single crystal precession electron diffraction (PED) patterns were acquired and processed with the EDT-COLLECT and EDT-PROCESS software packages (47). The selected area PED pattern taken along [1-10] zone axis from the edge of an individual SGU-29 crystal (fig. S9B) reveals presence
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of diffuse lines along c* direction. These lines are due to severe stacking disorder in the structure. The 2mm plane symmetry of the PED pattern (fig. S9B) can be explained by both monoclinic (M) and tetragonal (T) structure models as follows. A diffraction pattern from a tetragonal crystal taken along [010]T will be similar to that shown in fig. S9C. Simultaneously, a crystal with two monoclinic parts (50% each) of monoclinic M and mirrored monoclinic Mm will produce an average ED pattern along [110]M (fig. S9D) with 2mm plane symmetry that is the sum of 2 individual ED patterns from both monoclinic parts (fig. S9D to E) having only 2-fold symmetry. The significant similarity between fig. S9C and fig. S9F suggests that the structure of SGU-29 can be described by either M + Mm or T models.
Magnetic susceptibility and ESR spectra measurement Zero-field cooled (ZFC) susceptibility was measured on a SQUID magnetometer (MPMS5)
at Pusan National University at 1000 Oe between 2 to 300 K. Electron spin resonance (ESR) spectra were measured at room temperature on a Bruker A200 electron spin resonance spectrometer.
Chemical composition determination Elemental analyses of SGU-29 for the ratio of Na+, K+, Si, and Cu were carried out using
ICP-MS (Agilent Technologies, 7700 series ICP-MS) and X-ray fluorescence (XRF) analysis.
Gas sorption measurements The low-pressure gas sorption isotherms were collected on a BELSORP-max surface area
and pore size distribution analyzer. SGU-29 was evacuated under vacuum at 250 C for 12 h. Other CO2 sorbents employed in this work for comparison were dehydrated under the conditions described in the original references. The exchanging solvents, durations, evacuation temperatures and times are listed in the table S3.
The surface area of SGU-29 was determined from the N2 adsorption isotherm at 77 K, by applying Brunauer-Emmett-Teller (BET) method. The isosteric heats of adsorption (Qst) for CO2, N2, and O2 in Fig. 2H were calculated from the corresponding sorption isotherms measured at the temperatures between 298 and 338 K using the Clausius-Clapeyron expression. The bath temperature was accurately controlled with the temperature accuracy of ±0.2 ºC using a temperature control system (CWB-13G, Hanyang Scientific Equipment) containing a mixture of ethylene glycol and water as the heat transfer fluid.
Adsorption selectivity The ideal adsorbed solution theory (IAST) was used to calculate the selectivity (48). Using
the pure component isotherms, the adsorption selectivity is given as
Selectivity = //
(1)
where qi and pi are the uptake and the partial pressure of component i, respectively. Dynamic column CO2 breakthrough experiments
The gas separation capabilities of SGU-29 and other sorbents were tested using a standard dynamic CO2 breakthrough set up (fig. S10). Through one port pure CO2 or a premixed gas with a known composition was introduced into the set up and the flow rate was controlled by mass
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flow controllers (MFC). The introduced gas was passed through a water bath to include water vapor into the mixed gas. The amount of moisture into a gas mixture was controlled by controlling water bath temperature. Using a high precision humidity sensor the humidity of a gas mixture was monitored. Into a stainless steel sample bed 0.5 mL of a CO2 sorbent (typically, 0.5-1 g) was packed. The dimension of the stainless steel sample bed was, inner diameter = 4 mm, outer diameter = 6.5 mm, and length = 14 cm. Argon was initially purged into the sample column. The experiments were performed under isothermal conditions with the temperature ranging between 298 and 378 K and the pressure of 1013 mbar (negligible pressure drop or increase) and the mixed gas flow rate was 3 mL/min. The sample bed, humidity sensor, and the pressure transducer were placed within an oven to control the temperature of the sorbent and system. The flow rate of the gas was further confirmed using a bubble flow meter.
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Table S1 to S5
Table S1. Crystal data and structural refinement of SGU-29. SGU-29(T1) (polymorph A) SGU-29(M) (polymorph B) Chemical formula Na2[CuSi5O12] Na2[CuSi5O12] Formula weight 441.97 441.97 Temperature 297(2) K 297(2) K Wavelength 0.70000 Å 0.70000 Å Crystal system Tetragonal Monoclinic Space group I4(1)/amd C2/c Unit cell dimensions a = 7.3608(10) Å a = 20.820(4) Å, b = 7.3608(10) Å b = 20.819(4) Å, c = 27.492(6) Å c = 14.697(3) Å,
β = 110.73(3)°. Volume 1489.6(4) Å3 5958(2) Å3 Z 4 16 Density (calculated) 1.971 Mg/m3 1.971 Mg/m3 Absorption coefficient 1.897 mm-1 1.897 mm-1 F(000) 868 3472 Crystal size 0.010 x 0.010 x 0.005 mm3 0.010 x 0.010 x 0.005 mm3 θ range for data collection 2.82 to 29.54°. 1.75 to 29.54°. Index ranges -10 ≤ h ≤ 10,
-10 ≤ k ≤ 10, -38 ≤ l ≤ 38
-29 ≤ h ≤ 29, -29 ≤ k ≤ 29, -20 ≤ l ≤ 20
Reflections collected 7369 31334 Independent reflections 622 [R(int) = 0.0353] 8716 [R(int) = 0.0760] Completeness to θ = 29.54°
98.1 % 99.5 %
Absorption correction Empirical Empirical Max. and min. transmission 0.9986 and 0.9813 0.9906 and 0.9813 Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints / parameters 622 / 0 / 51 8716 / 0 / 481 Goodness-of-fit on F2 1.051 1.041 Final R indices [I>2sigma(I)] R1 = 0.0448, wR2 = 0.1562 R1 = 0.0837, wR2 = 0.2698 R indices (all data) R1 = 0.0449, wR2 = 0.1564 R1 = 0.0964, wR2 = 0.2861 Extinction coefficient - 0.0048(5) Largest diff. peak and hole 0.638 and -0.608 e.Å-3 1.434 and -2.450 e. Å-3
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Table S2. Comparison of structural parameters of SGU-29 and ETS-10. Name SGU-29 ETS-10
References This work Ref (22) Ref (23)
Analysis technique
Single crystal X-ray diffraction and HRTEM
Powder XRD, NMR and HRTEM
Single crystal X-ray diffraction
Chemical formula
Na2[CuSi5O12] Na2[TiSi5O13]
Crystal system Monoclinic Tetragonal Monoclinic Tetragonal Tetragonal
Space group C2/c (no. 15) I41/amd (141) C2/c (15) P41(76) or P43 (78)
I41/amd (141)
Unit cell a = 20.820(4) Å a = 7.361(1) Å a = 21.00 Å a = 14.58 Å a = 7.487(1) Å
b = 20.819(4) Å b = 7.361(1) Å b = 21.00 Å b = 14.58 Å
b = 7.487(1) Å
c = 14.697(3) Å c = 27.492(6) Å c = 14.51 Å c = 27.08 Å c = 27.407(5) Å
β = 110.73(3)° β= 111.12(3)°
Volume[Å3] 5958(2) 1489.6(4) 5969.08 5756.57 1536.2(4)
Z 16 4 16 16 4
R1 [I>2Σ(I)] 0.0848 0.0448 - - 0.119
R1 (all data) 0.0975 0.0449 0.1578
Occupancies for disorder atoms Na+ coordination
Part I = 72.6 %, Part II = 27.4 % Yes
Half occupancies of independent atoms Yes
-
No
- No
Half occupancies of independent atoms Yes
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Table S3. Exchanging solvent, activation temperature and time, and comparisons of obtain and reference BET surface areas (m2/g).
Sorbents Exchanging Solvent Activation Surface Area (m2/g)
ref solvent time (h) temp (ºC) time (h) obtained ref
SGU-29 -- -- 250 12 457 -- this work
AM-6 -- -- 250 12 430 -- this work
ETS-10 -- -- 250 12 440 -- 8
SIFSIX-3-Cu methanol 72 RT/50 12/12 318 300 14
SIFSIX-3-Zn methanol 72 RT 25 239 250 13 Mg-DOBDC methanol 48 250 5 1522 1495 11 Ni-DOBDC methanol 48 250 5 1189 1070 31
Co-DOBDC methanol 24 250 5 1045 1080 32
Zn-DOBDC methanol 72 250 5 856 816 33
UTSA-16 -- -- 90 24 636 628 15
NaX -- -- 250 12 635 -- 9
Cs-CHA -- -- 250 12 -- -- 10
Zn-Atz acetone 72 100 12 764 782 27
HKUST-1 -- -- 250 12 1558 1663 35
MOF-505 acetone 72 120 12 1608 1830 36
MOF-14 -- -- 100 12 1539 1502 37
MIL-47 -- -- 100 12 1007 930 39
MIL-101(Cr) -- -- 250 12 3688 3870 41
IRMOF-1 chloroform 5 100 5 3869 3800 44
MOF-177 chloroform 72 100 5 3280 4500 45
ZIF-8 methanol 48 100 5 1709 1630 46 The surface areas for SIFSIX-3-Cu, SIFSIX-3-Zn, and Zn-Atz were obtained from CO2 adsorption isotherms at 298 K and others from N2 sorption isotherms at 77 K.
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Table S4. CO2 uptake (cm3/cm3) from CO2 sorption isotherms at various pressure and calculated crystal density (g/cm3) for various CO2 sorbents used in this study.
Sorbents CO2 uptake (cm3/cm3) Framework
density g/cm3
Reference 0.4 mbar 50 mbar 100 mbar 1000 mbar
SGU-29 26.0 114.6 125.5 156.0 1.97 this work
AM-6 12.2 98.3 110.2 143.7 2.01 this work
Mg-DOBDC 1.8 74.8 101.2 161.9 0.91 11
ETS-4 3.7 89.8 100.1 127.9 2.20 8
ETS-10 8.4 80.8 94.4 134.9 1.93 8
SIFSIX-3-Cu 43.1 84.1 85.0 88.2 1.58 14
SIFSIX-3-Zn 5.2 75.9 81.2 89.7 1.57 13
Ni-DOBDC 0.9 51.5 80.2 160.7 1.19 31
NaX 6.2 51.7 75.1 144.9 1.42 9
Na-Rho -- 64.6 71.1 99.7 1.04 7
UTSA-16 -- 28.2 64.9 152.9 1.66 15
Zn-Atz -- 33.4 54.9 136.0 1.71 27
Co-DOBDC -- 26.3 50.9 154.6 1.18 32
Na-A -- 34.2 50.1 104.9 1.51 6
Cs-CHA -- 30.7 46.0 75.4 2.25 10
UiO-66(Zr)-COOH -- 22.3 42.0 67.2 1.42 16
Zn-DOBDC -- 13.1 26.2 141.7 1.22 33
ZIF-20 -- 14.0 24.1 89.5 1.27 34
ZIF-69 -- 10.4 19.1 83.0 1.30 17
HKUST-1 -- 5.0 10.5 95.4 0.88 35
MOF-505 -- 4.7 10.3 81.1 0.99 36
MOF-14 -- 4.1 8.4 58.1 0.89 37
ZIF-300 -- 3.6 8.4 40.0 1.45 18
PCN-88 -- 4.6 7.9 61.9 0.66 38
MIL-47 -- 3.1 6.4 45.0 1.00 39
ZIF-100 -- 2.3 2.9 19.1 0.86 40
MIL-101 -- 1.1 2.6 21.3 0.44 41
NOTT-202a -- 1.1 2.5 18.1 0.63 42
NU-100 -- 1.1 1.8 18.3 0.30 43
IRMOF-1 -- 0.8 1.7 11.8 0.59 44
MOF-177 -- 0.8 1.5 8.6 0.43 45 ZIF-8 -- 0.5 1.2 26.2 1.14 46 CO2 uptake of ZIF-20 and ZIF-69 at 273 K, PCN-88 at 296 K, NOTT-202a at 293 K and remained data at 298 K.
12
Table S5. Comparison of the performance of SGU-29 and AM-6 with eight of the best currently available CO2 adsorbing materials.
Sorbents (Qst)CO2 at low
loading (kJ mol-1)
H2O uptake at 31.6
mbar [*]
Selectivity at 1 bar (10/90)
Static CO2 uptake at 100
mbar [*]
Dynamic CO2 uptake from breakthrough exp [*]
CO2/N2 CO2/O2 F0 F29
SGU-29 51.30 393 3515 4569 125.5 117 115
AM-6 NM 419 1579 2217 110.2 101 99
Mg-DOBDC 47 875 235 350 101.2 86 30
ETS-4 NA 507 NA NA 100.1 91 87
ETS-10 NA 420 879 988 94.4 87 84
SIFSIX-3-Cu 54 368 6897 9780 85.0 77 72
SIFSIX-3-Zn 45 411 1680 2015 81.2 56 54
Ni-DOBDC 41 870 44 81 80.2 68 53
NaX 48.2 681 541 957 75.1 63 51
UTSA-16 34.6 607 58 93 64.5 42 38
[*] cm3/cm3, Water sorption isotherms performed at 298 K, selectivity calculated using IAST from pure (CO2, N2 and O2) component sorption isotherms measured at 298 K, static and dynamic CO2 uptake obtained from pure CO2 sorption isotherms and column breakthrough experiment using a simulate dry (F0) and 90% RH flue gas (F29), respectively at 298 K. Not measured (NM), Not available (NA).
13
Figs. S1 to S19
Fig. S1. X-ray powder diffraction patterns of ETS-10, AM-6, SGU-29, and the simulated diffraction pattern for the monoclinic lattice system of SGU-29 single crystal with Cu Kα1 as the X-ray source. The vertical pink dot lines represent the family of 110, 220, and 440 planes that include the centers of the open channels and quantum wires (ETS-10, AM-6) or open channels and columns of [CuO4]-units (SGU-29) packed perpendicular to c-axis.
14
Fig. S2. In situ X-Ray powder diffraction patterns of SGU-29 at mentioned temperature under air.
5 10 15 20 25 30 35 40 45
450
350
250
150
50
2 Theta degree
oC
600550
500
400
300
100
25
Inte
nsi
ty (
a.u
.)
200
15
Fig. S3. (A) Plots of magnetic susceptibility () and inverse magnetic susceptibility (1/) of SGU-29 with respect to temperature (T) from 2 to 300 K. The calculated effective magnetic moment (eff) is 1.71 BM. The linear relationship established between 1/ and T demonstrates that the Cu ions in SGU-29 are Curie-like purely paramagnetic. (B) The X-band ESR spectrum of SGU-29 at room temperature.
0 50 100 150 200 250 3000.00
0.02
0.04
0.06
0.08
Temperature (K)
(em
u/m
ol)
C= 0.3656
eff=1.71 BM
(e
mu
/mo
l)
0
200
400
600
800
A
2100 2900 3700 4500
B
g = 2.15H
pp=202
Inte
nsi
ty
Magnetic field (G)
16
Fig. S4. A single crystal of SGU-29. (A) SEM image with three cutting directions (red, green and blue dashed lines). (B) Optical (confocal) microscopy image with the corner that was cut for a single crystal X-ray diffraction experiment (yellow dashed lines).
17
Fig. S5. (A) The average crystal structure of monoclinic SGU-29 shown along the [110] zone axis representing the overlap of 2 independent parts (shown as polyhedral and ball-and-stick models). (B) part 1 ( polyhedra), and (C) part 2 ( ball-and-stick). See supplementary methods for details.
18
Fig. S6. (A to C) The basic building units, the average bond lengths and angles in monoclinic SGU-29.
ab
c
Oa
Ob
Oc
Od
Od Si
a
Sib
Sib
Cu
C. (001) plane
a/b
c
Oc
Oa
Oa
Ob
Od
Ob O
d
Sia
Sib
Sia
Sib
B. [1-10] axis
a b
c
Oa
Ob
Oc
Od
Od
Sia
Oa
Sia
Ob
Sib
Cu
α
β
A. [-1-10] axis
1. Cu Oa Si
a:
d(Sia O
a) 1.580(4) Å
d(Cu Oa) 1.934(4) Å
(Cu Oa Sia) 129.26(2)
o
2. Sia O
b Si
a:
d(Sia O
b) 1.619(4) Å
(Sia O
b Si
a) 145.10(3)
o
3. Sia O
c Si
a:
d(Sia O
c) 1.657(3) Å
(Sia O
c Si
a) 123.7(2)
o
4. Sia O
d Si
b:
d(Sia O
d) 1.623(3) Å
d(Sib O
d) 1.603(3) Å
(Sia O
d Si
b) 142.1(2)
o
19
Fig. S7. Views of the [CuO4]-units and Na+ ions along various axes.
20
A. Na1: CN = 12 B. Na2: CN = 6 Fig. S8. (A to D) The positions, coordination and bond distances for Na+ ions, (A) Na1, (B) Na2, (C) Na3, and (D) Na4 and Na5.
Na(1) O(18A) = 3.1110(6) Na(1) O(15A) = 3.1110(5) Na(1) O(23A) = 3.0960(6) Na(1) O(22A) = 3.0931(11) Na(1) O(24A) = 3.3976(5) Na(1) O(19A) = 3.3966(8) Na(1) Na(1b) = 0.5507(2) Na(1b) O(18A) = 2.7836(6) Na(1b) O(15A) = 2.7917(4) Na(1b) O(23A) = 2.7719(5) Na(1b) O(22A) = 2.7764(9) Na(1b) O(24A) = 3.1689(5) Na(1b) O(19A) = 3.1840(6) Na(1b) Na(1b) = 1.1014(3)
Na(2)O(8) = 4.4389(9) Na(2)O(9) = 4.3941(8) Na(2) O(5) = 4.4001(8) Na(2) O(2) = 4.3852(9) Na(2)O(14A) = 4.3248(8) Na(1)O(16A) = 4.3258 (7)Na(2)Na(2) = 1.1239(3)
21
C. Na3: CN = 6 D. Na4 and Na5: CN = 7(11)
Fig. S8. (A to D) The positions, coordination and bond distances for Na+ ions, (A) Na1, (B) Na2, (C) Na3, and (D) Na4 and Na5.
Na(3) O(13A) = 2.6225(8) Na(3) O(17A) = 2.6208(5)
Na(3) O(20A) = 2.5881(6)
Na(3) O(21A) = 2.5953(4) Na(3) O(14A) = 3.2173(5)
Na(3) O(16A) = 3.2654(6)
Na(4A) O(13A) = 2.4365(4) Na(4A) O(17A) = 2.4451(5) Na(4A) O(18A) = 2.4818(4) Na(4A) O(15A) = 2.4821(8) Na(4A) O(19A) = 2.5718(5) Na(4A) O(7) = 2.8975(8) Na(4A) O(3) = 2.9105(5) Na(4A) O(9) = 3.8790(6) Na(4A) O(3A) = 3.9658(7) Na(4A) O(6) = 3.9578(7) Na(4A) O(8) = 3.8738(6) Na(5) O(20A) = 2.4493(4) Na(5) O(22A) = 2.4950(4) Na(5) O(6) = 2.8955(5) Na(5) O(4a) = 3.9646(7) Na(5) O(21A) = 2.4498(8) Na(5) O(24A) = 2.5470(8) Na(5) O(2) = 3.8775(6) Na(5) O(7) = 3.9699(7) Na(5) O(23A) = 2.4925(6) Na(5) O(4) = 2.8746(8) Na(5) O(5) = 3.8707(6)
22
Fig. S9. (A) HRTEM image of SGU-29. (B) The electron diffraction (ED) pattern of SGU-29 with the axes of the monoclinic and tetragonal lattices. (C) Simulated electron diffraction pattern along the [010] (T). (D, E) Simulated electron diffraction patterns of [110]M (D) and [-1-10]Mm (E). (F) Overlap of the simulated electron diffraction patterns of M and Mm.
23
Fig. S10. Schematic illustration of a set-up for the dynamic column CO2 separation.
24
Fig. S11. Three different types of tilted elliptical 12-mebered rings running along [110] direction. The tilted angles are as indicated.
25
Fig. S12. (A, B) Bar graphs comparison of CO2 uptake from CO2 sorption isotherms of the indicated sorbents at (A) 1000 and (B) 100 mbar. The CO2 uptake of Na-A (6), Na-Rho (7), ZIF-20 (34), ZIF-69 (17), UiO-66(Zr)-COOH (16), PCN-88 (38), ZIF-300 (18), ZIF-100 (40), and NU-100 (43) were taken from the literature with the reference shown in the corresponding parenthesis.
0
20
40
60
80
100
120
140
ETS
-10
AM
-6
SG
U-2
9
NU
-100
ZIF-
100
Cs-
CH
A
PC
N-8
8
SIF
SIX
-3-Z
n
Na-
A
Zn-A
tz
B
ZIF-
300
ZIF-
69100 mbar
UiO
-66(
Zr)
MIL
-101
MIL
-47
MO
F-14
NO
TT-2
02
MO
F-50
5
ZIF-
20
Zn-D
OB
DC
HK
US
T-1
Ni-D
OB
DC
Na-
Rho
NaX
Mg-
DO
BD
C
SIF
SIX
-3-C
u
CO
2 u
pta
ke (
cm3/c
m3)
UTS
A-1
6
ETS
-4
Co-
DO
BD
C0
30
60
90
120
150
180
ETS
-10
Zn-A
tz
UTS
A-1
6
NU
-100
ZIF-
100
ZIF-
8
Cs-
CH
AP
CN
-88
SIF
SIX
-3-Z
n
Na-
A
ETS
-4
A
ZIF-
300
ZIF-
69
1000 mbar
UiO
-66(
Zr)
MIL
-101
MIL
-47
MO
F-14
MO
F-50
5
ZIF-
20
Zn-D
OB
DC
HK
US
T-1
Ni-D
OB
DC
Na-
Rho
NaX
Mg-
DO
BD
C
SIF
SIX
-3-C
u
CO
2 up
take
(cm
3 /cm
3 )
AM
-6
SG
U-2
9C
o-D
OB
DC
26
Fig. S13. The CO2 uptake from CO2 adsorption isotherms at PCO2 = 0.4 mbar.
0
10
20
30
40
50
ETS
-10
SG
U-2
9
ETS
-4
SIF
SIX
-3-Z
n
0.4 mbar
Ni-D
OB
DC
NaX
Mg-
DO
BD
C
SIF
SIX
-3-C
u
CO
2 u
pta
ke (
cm3/c
m3 )
AM
-6
27
Fig. S14. (A, B) A comparison of water adsorption isotherms on SGU-29, AM-6, ETS-10, ETS-4, NaX and NaA at 298 K in two different units (A) cm3/cm3 and (B) cm3/g. Note that P/P0 is the relative pressure of water with P0 of 3.16 kPa is the saturated vapor pressure of water at 298 K.
0.0 0.2 0.4 0.6 0.8 1.0
0
100
200
300
400
500
600
700NaX
ETS-10
NaA
AM-6
ETS-4
SGU-29
Relative pressure (P/P0)
H2O
up
take
(cm
3 /cm
3 )
A
0.0 0.2 0.4 0.6 0.8 1.0
0
100
200
300
400
500NaX
ETS-10
NaA
AM-6
ETS-4
SGU-29
Relative pressure (P/P0)
H2O
up
take
(cm
3 /g)
B
28
Fig. S15. (A, B) A comparison of water adsorption isotherms of Mg-DOBDC, Ni-DOBDC, NaX, UTSA-16, SIFSIX-3-Cu, SIFSIX-3-Zn, and SGU-29 measured at 298K in two different units (A) cm3/cm3, and (B) cm3/g. P/P0 is the relative pressure of water with P0 = 3.16 kPa, which corresponds to the saturated vapor pressure of water at 298 K.
0.0 0.2 0.4 0.6 0.8 1.0
0
200
400
600
800
1000
UTSA-16
Ni-DOBDC
Mg-DOBDCNaX
Relative pressure (P/P0)
H2O
up
take
(cm
3 /cm
3 )
A
SIFSIX-3-ZnSGU-29SIFSIX-3-Cu
0.0 0.2 0.4 0.6 0.8 1.0
0
200
400
600
800
1000
UTSA-16
Ni-DOBDC
Mg-DOBDC
NaX
SGU-29
Relative pressure (P/P0)
H2O
up
take
(cm
3 /g)
B
SIFSIX-3-ZnSIFSIX-3-Cu
29
Fig. S16. (A, B) In situ FTIR spectra of SGU-29 in the region of (A) adsorbed water and (B) adsorbed CO2 taken at various times (0-180 sec) under the flow of a humid flue gas (F29) at 298 K. The F29 gas was passed through water whose temperature was maintained 40 ºC. The flow rate was 50 ml/min.
3800 3600 3400 3200 3000 28000.0
0.5
1.0
1.5
2.0
2.5
3.0
180 sec 120 60 30 0 A
bso
rban
ce
Wavenumber (cm-1)
A
2450 2400 2350 2300 22500.0
0.5
1.0
1.5
2.0
2.5
3.0
Ab
sorb
ance
180 sec 120 60 30 0
Wavenumber (cm-1)
BF29
30
Fig. S17. (A, B) Schematic illustrations showing the presence of only H2O-specific and CO2-specific sites but not H2O/CO2 sharing sites in SGU-29 (A) and H2O-specific, CO2-specific, and H2O/CO2 sharing sites in NaX (B).
31
Fig. S18. (A, B) Progressive change of the FTIR spectra of dried AM-6 with time (as indicated) under the flow of (A) dry flue gas F0 and (B)humid flue gas F29 at 298 K. Flow rate = 5 ml/min.
40 min2510 530
4000 3600 3200 2800 2400 20000.0
0.5
1.0
1.5
2.0
2.5
3.0
0
40 min
F29B
2450 2400 2350 2300 2250
40 min2510 530
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0
40 min
F0A
Wavenumber (cm-1)
32
Fig. S19. (A) Comparison of CO2 adsorption capacities of SGU-29 and other reported CO2 sorbents from humid F29 flue gas at 298 K, the sorbents are regenerated using a vacuum swing regeneration mode at 403 K for 30 min. (B) CO2 adsorption of SGU-29 from F29 flue gas, the samples regenerated at mentioned temperature under vacuum for 30 min.
1 2 3 4 5 6 7 8 9 500
20
40
60
80
100
120
140
Mg-DOBDCSIFSIX-3-Cu
NaX
F29
SIFSIX-3-Zn
UTSA-16
Ni-DOBDC
SGU-29
No. of cycles
UC
O (
cm3/c
m3)
2
A
1 2 3 4 5 6 7 8 9 500
20
40
60
80
100
120
140
353 K
373 K
F29
298 K
B
No. of cycles
403 K
UC
O
(cm
3/c
m3)
2
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