C A R B O N 4 9 ( 2 0 1 1 ) 2 1 1 3 – 2 1 1 9

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Simple hydrothermal synthesis of ordered mesoporouscarbons from resorcinol and hexamine

Dan Liu a, Jia-Heng Lei a,*, Li-Ping Guo a, Ke-Jian Deng b

a Department of Chemistry, School of Science, Wuhan University of Technology, Wuhan 430070, PR Chinab Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education,

South-Central University for Nationalities, Wuhan 430070, PR China

A R T I C L E I N F O

Article history:

Received 3 September 2010

Accepted 18 January 2011

Available online 23 January 2011

0008-6223/$ - see front matter Crown Copyrdoi:10.1016/j.carbon.2011.01.047

* Corresponding author: Fax: +86 27 87756662E-mail address: daniellliu@whut.edu.cn (

A B S T R A C T

Hexamine has been used as a release source of formaldehyde towards the self-assembly

synthesis of resorcinol/formaldehyde (RF) resin-based mesoporous carbons under hydro-

thermal conditions. The obtained mesoporous carbons exhibit the micrometer-sized,

sphere-like morphology and a high surface area. The use of hexamine instead of formalde-

hyde efficiently harnesses the organic–organic self-assembly of RF resin and block copoly-

mer. Ordered mesostructures can be obtained over a wide range of hydrothermal

temperature without the extra addition of inorganic bases or acids as catalysts. The

method described here has the advantage of being a one-pot procedure and only involves

the use of several organic precursors in an aqueous system.

Crown Copyright � 2011 Published by Elsevier Ltd. All rights reserved.

1. Introduction

Since first synthesis of ordered mesoporous carbons (OMCs)

was achieved by using mesoporous silica as the hard tem-

plate, OMCs have attracted great attention because of their

potential applications in catalysis, adsorption, separation, en-

ergy storage/conversion, and so on [1–4]. In recent years, a

soft templating method has been developed to directly pre-

pare OMCs by organic–organic assembly of amphiphilic block

copolymers and phenolic resins, which escapes from a fussy

hard templating process. However, most of reported synthe-

ses resorted to solvent evaporation induced self-assembly

(EISA) pathway in nonaqueous media [5–14]. For example,

Liang et al. has first prepared OMC films by using resorcinol/

formaldehyde (RF) as a carbon source and diblock copolymer

as a template in the N,N 0-dimethylformamide media [5]. Sim-

ilar syntheses might also be achieved under acidic conditions

by using ethanol/H2O mixture as the volatile solvent [8,14].

Ordered mesoporous polymers and carbons with the 2-D hex-

agonal, cubic, and lamellar structures have also been pre-

ight � 2011 Published by

.J.-H. Lei).

pared by using prepolymerized phenol/formaldehyde (PF)

resols as the carbon precursors in ethanol phase under nearly

neutral conditions [6,9–11]. Although EISA pathway is a pow-

erful tool for the preparation of OMCs and other mesoporous

materials, it always involves the evaporation of a large

amount of organic solvents, and the products are generally

obtained in form of thin films or monoliths. Additionally, a

multi-step process is needed: prepolymerization, solvent

evaporation and thermal solidification. These disadvantages

make it industrially unfeasible due to the engineering difficul-

ties. Alternatively, OMCs might also be synthesized by com-

mon dilute aqueous reaction route under atmospheric

pressure at relatively low temperature [15–18]. However, it

takes about 5–7 days to complete the reaction at 60–70 �Cdue to the slow reaction rates, which is highly time- and

energy-consuming.

The hydrothermal pathway is faster and more energy effi-

cient than the nonaqueous EISA method and the dilute aque-

ous route. Unfortunately, to date, there are only two reports

on the hydrothermal syntheses of ordered mesoporous

Elsevier Ltd. All rights reserved.

Fig. 1 – Schematic illustration of the formation of ordered mesostructured RF/F127 composites from resorcinol and hexamine.

2114 C A R B O N 4 9 ( 2 0 1 1 ) 2 1 1 3 – 2 1 1 9

polymer and carbon monoliths, which are based on the self-

assembly of block copolymers and PF oligomers [19,20]. In

the above two cases, the prepolymerization step had to be

performed separately, which virtually leads to a two-step pro-

cess. An underlying reason is that the condensation kinetics

of phenol with formaldehyde is difficult to control in the sur-

factant-directed assembly process. To avoid the occurrence of

fast self-polymerization reactions, the prepolymerized PF

oligomers with weak reactivity instead of molecular precur-

sors were always used as starting units.

Herein, we introduce a simple method to prepare OMCs

under hydrothermal conditions. A schematic representation

of the synthesis is shown in Fig. 1. The crucial difference to

previous work is the use of hexamethylenetetramine (HMT)

instead of formaldehyde during the synthesis. HMT, also

known as hexamine or methenamine, is often used as a pH

buffer or curing agent. It is quite stable in aqueous solution

at moderate pH and temperature, but is subject to hydrolysis

into formaldehyde and ammonia at elevated temperature or

acidity. Our results show that the organic–organic self-assem-

bly can be well controlled when HMT was employed as a re-

lease source of formaldehyde towards the self-assembly

synthesis of RF-based OMCs. It is worth mentioning that no

additional prepolymerization step was necessary in the pres-

ent process as compared with the previous method. Ordered

mesoporous polymers and carbons with high surface areas

can be obtained by the one-pot procedure in an aqueous sys-

tem. Furthermore, no mineral acids or bases as catalysts were

added to the reaction system and thus metal or halide ions

were never introduced into the products, possibly resulting

in the formation of high-purity carbon materials.

2. Experimental

2.1. Materials

Poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene

oxide) triblock copolymer Pluronic F127 (EO106PO70EO106,

Mav = 12,600) was purchased from Sigma–Aldrich Corp. Other

chemicals were purchased from Sinopharm Chemical Re-

agent Corp. All chemicals were used as received without fur-

ther purification.

2.2. Synthesis

In a typical synthesis, 0.55 g resorcinol (R), 0.35 g HMT, 1.00 g

Pluronic F127, and 0.20 g 1,3,5-trimethylbenzene (TMB) were

dissolved in 18 g water after magnetically stirring at room

temperature for 2 h. The resultant homogenous solution

was poured into a 100-mL Teflon-lined autoclave and then

transferred into an oven at 100 �C for 12 h. The orange-red

polymer particles were collected by filtration, washed several

times and dried in air. About 1.6 g products were obtained. Fi-

nally, the as-made F127/RF composite (RF-as) was thermally

treated at 350 or 900 �C for 3 h, with a heating rate 1 �C min�1

under a nitrogen atmosphere, to obtain the mesoporous poly-

mer (RF-350) and carbon (RF-900).

2.3. Characterization

Powder X-ray diffraction (XRD) patternswere recorded on a Rig-

aku D/MAX-RB diffractometer with a CuRa radiation operating

at 40 kV, 50 mA. Transmission electron microscopy (TEM)

1 2 3 4 5

×

Inte

nsi

ty (

a. u

.)

2θ (degree)

×

Fig. 2 – XRD patterns of as-made RF (RF-as), RF calcined at

350 �C (RF-350) and RF calcined at 900 �C (RF-900).

C A R B O N 4 9 ( 2 0 1 1 ) 2 1 1 3 – 2 1 1 9 2115

images were taken with a JEM 2100F electron microscope oper-

ating at 200 kV. Nitrogen sorption data were measured with a

Quantachrome Autosorb-1 analyzer at �196 �C. Prior to the

measurements, the samples were degassed at 300 �C for 4 h.

Thermogravimetric (TG) analysis was carried out on a SDT

Q600 V5.0 Build 63 thermal analyzer with a heating speed of

5 �C min�1 and in a nitrogen flow of 100 mL min�1. Fourier

transform infrared (FT-IR) spectra in the range of 400–

4000 cm�1 were recorded on a Nicolet AVATAR 370 spectrome-

ter in the transmission mode using KBr method. Scanning

electron microscopy (SEM) images were taken using a Hitachi

S-4800 field-emission scanning electron microscope.

2.4. Calculations

The specific surface areas (SBET) were calculated by the Bru-

nauer–Emmett–Teller (BET) method using adsorption data in

a relative pressure range from 0.04 to 0.2. The total pore vol-

umes (Vt) were estimated on the basis of the amount ad-

sorbed at a relative pressure of about 0.99. The micropore

volumes (Vmi) and mesopore volumes (Vme) were calculated

from the as-plot method [21,22], where as denotes the stan-

dard reduced adsorption on the reference solid defined as

the ratio of the amount adsorbed at a given relative pressure

to the amount adsorbed at the relative pressure of 0.4. The

as-plots were obtained using nitrogen adsorption isotherm

for macroporous non-graphitized carbon black Cabot BP280

reported by Kruk et al. [23] as reference data. These plots were

used to obtain the sum of the micropore volume and meso-

pore volume (Vmi + Vme) in the range of as from 1.8 to 3. The

micropore volume (Vmi) was estimated in the range of as from

0.8 to 1.2. The difference between two volumes was used to

determine the mesopore volume (Vme). The pore size distribu-

Table 1 – Textural parameters of mesoporous polymer and carb

Sample d10 (nm) a0 (nm) SBET (m2 g�1) Vt (

RF-350 11.9 13.7 633RF-900 9.9 11.4 1483

a d10: d10-spacing; a0: unit-cell parameter, was calculated using the form

micropore volume; Vme: mesopore volume; Dme: mesopore diameters at th

tions (PSDs) were given with the non-local density functional

theory (NLDFT) method for the slit/cylinder pore model using

the software provided by Quantachrome.

3. Results and discussion

The sample was prepared through simply dissolving resor-

cinol, HMT, TMB and F127 into water, followed by hydrother-

mal treatment and then pyrolysis under an inert gas. XRD

patterns of the as-made and calcined samples are shown in

Fig. 2. The XRD pattern of RF/F127 composite shows only

one poorly resolved shoulder peak, due to too large d-spacing

beyond the low angle cutoff of our instrument. After calcina-

tion under nitrogen atmosphere at 350 �C, the XRD pattern

becomes more resolved and three diffraction peaks with a

d-spacing ratio of 1/(1/p

3)/(1/p

7), which can be indexed as

(10), (11) and (21) reflections of 2D hexagonal p6m mesostruc-

ture [6]. After calcination at 900 �C, the resultant mesoporous

carbon still reveals the reflection peaks of p6m symmetry,

suggesting that a highly ordered hexagonal mesostructure is

preserved, in contrast to the partial collapse of the RF meso-

structure after carbonization, which was prepared by the tra-

ditional prepolymerization and EISA procedure under basic

conditions [12]. Additionally, the three peaks shift to larger

2h angle and the calculated unit-cell parameter (a0) is reduced

from 13.7 to 11.4 nm (Table 1). It represents a significant

shrinkage of the framework, associated with the pyrolysis

and carbonization of the RF frameworks.

TEM images of RF-900 show typical patterns viewed along

[1 1 0] and [0 0 1] directions of 2D hexagonal mesostructures

(Fig. 3A and B). The cell parameter (a0) estimated from the

images is in agreement with the value calculated from XRD

data. SEM image of RF-900 presents the morphology of the

dispersed microspheres with a smooth surface and a broad

size distribution from hundreds of nanometers to a few

micrometers (Fig. 3C). High-resolution SEM (HR-SEM) was also

carried out to directly observe the mesostructure. RF-as with

large cell parameter was selected to meet the sufficient reso-

lution. HR-SEM image (Fig. 3D) reveals that a RF-as particle

consists of many different domains, which are hexagonally

ordered on a relatively short length scale. Terraces are clearly

visible on the edge of the particle. Furthermore, the more

curved (U-shaped) channels can be observed nearer the top

of the microparticle, possibly because the top region can not

‘‘contain’’ too long pore channels. These observations provide

some insight into the growth of the particles.

Nitrogen sorption isotherms and the corresponding NLDFT

pore size distributions for RF-350 and RF-900 are plotted in

Fig. 4. Both of the isotherms are type-IV curves with well-

developed hysteresis loops and distinct condensation steps

on.a

cm3 g�1) Vmi (cm3 g�1) Vme (cm3 g�1) Dme (nm)

0.57 0.11 0.42 5.300.96 0.31 0.62 4.74

ula a0 = 2 d10/p

3; SBET: BET surface area; Vt: total pore volume; Vmi:

e maxima of NLDFT PSD curves.

Fig. 3 – TEM images of RF-900 viewed along [1 1 0] (A) and [0 0 1] (B) directions. SEM image of RF-900 (C) and HR-SEM image of

RF-as (D).

150

200

250

300

350

400

450

500

550

600

650

RF-350

RF-900

Volu

me

Ad

sorb

ed (

cm3 g

-1 S

TP

)

Relative Pressure (P/P0)

0.0 0.2 0.4 0.6 0.8 1.0 0 2 4 6 80.0

0.1

0.2

0.3

0.4

0.5

0.6

RF-350

RF-900

dV

/dD

(cm

3 g-1 n

m-1)

Pore Diameter (nm)

BA

Fig. 4 – Nitrogen sorption isotherms (A) and NLDFT pore size distributions (B) of RF-350 and RF-900.

2116 C A R B O N 4 9 ( 2 0 1 1 ) 2 1 1 3 – 2 1 1 9

(Fig. 4A), which is typical sorption behavior from mesoporous

materials. The adsorption and desorption branches of RF-350

are not close at low pressure, possibly related to the sorption

behavior of polymer materials [16]. Table 1 summarizes the

results of the pore structure analysis for the calcined samples.

Specially, the carbon sample RF-900 possesses a high BET sur-

face area of 1483 m2 g�1 and a total pore volume of

0.96 cm3 g�1. The micropore volume calculated by the as-plot

method is as high as 0.31 cm3 g�1. This result indicates that

high microporosity of RF-900 leads to its high surface area.

The NLDFT PSDs are calculated with a pore model of mixed

cylinder and slit shapes. The PSD curve of RF-900 (Fig. 4B) re-

veals several maxima in the micropore range (<2 nm) except

for the narrow peak from the primary mesopores. Usually,

the phenolic resin-based OMCs prepared from EISA route

shows relatively low microporosity, and the reported values

of surface areas are generally between 300 and 1000 m2 g�1

[6,8,12]. Development of microporosity in these carbons could

be achieved by post-synthesis KOH activation [24,25] or silica-

assisted synthesis [26,27], leading to the significant increase

of the surface areas. The high microporosity of RF-900 has

not been fully understood. However, many previous studies

have shown that mesoporous materials prepared by the EISA

route generally have lower microporosity than those from the

hydrothermal route [28]. It is mainly due to a lower extent of

inclusion of polyethylene oxide (PEO) segments into the pore

1 2 3 4 5

Inte

nsi

ty (

a. u

.)

2θ (degree)

Fig. 6 – XRD patterns of mesoporous polymer (a) and carbon

(b) prepared with a reactant composition of 1.10 g R/0.70 g

HMT/1.00 g F127/0.20 g TMB/27 g H2O/0.12 g NH3. The as-

made sample was hydrothermally prepared at 100 �C, and

then calcined at 350 and 900 �C in a nitrogen atmosphere for

3 h, respectively, to obtain the polymer and carbon sample.

1 2 3 4 5

220°C

150°C

130°C

110°C

90°C

80°C

70°C

Inte

nsi

ty (

a. u

.)

2θ (degree)

Fig. 7 – XRD patterns of mesoporous carbons prepared under

different hydrothermal temperature from 70 to 220 �C. All

samples were prepared with a fixed reactant composition of

C A R B O N 4 9 ( 2 0 1 1 ) 2 1 1 3 – 2 1 1 9 2117

walls in the EISA process [28]. It is known that the micropor-

sity of the soft-templating OMCs is generated by both the

pyrolysis of the resin frameworks and the removal of PEO seg-

ments from the pore walls [9]. Therefore, it can be speculated

that the high microporsity of RF-900 may result from a high

extent of embedding of PEO segments into the resin matrix

under the present conditions.

The pyrolysis behavior of the as-made RF/F127 composite

was monitored by thermal analysis in a nitrogen flow. The

TG curve (Fig. S1) of RF-as shows a sharp weight loss in the

temperature range of 300–400 �C, mainly attributed to decom-

position of F127. FT-IR spectra show that the typical absor-

bance peak of F127 at 1103 cm�1 disappears after calcination

at 350 �C under nitrogen (Fig. S2), confirming the decomposi-

tion of F127. The typical absorbance bands from RF resins

around 2900, 1608, and 1450 cm�1, corresponding to the C–H

stretching vibrations and the stretching skeletal vibrations

of benzene rings, are maintained after calcination at 350 �C.

These observations indicate that RF-350 preserves the poly-

mer frameworks.

We found that the addition of an appropriate amount of

TMB during the synthesis could greatly improve the meso-

scopic ordering of the products. For the case without the addi-

tion of TMB, the product only shows a broad XRD peak with

low intensity (Fig. 5), implying poor ordering. The excessive

addition of TMB also leads to the degradation of structural

ordering from XRD data. A possible reason is that the addition

of TMB increases the hydrophobicity of the surfactants, and

then improves their assembly ability to form the ordered mes-

ostructure. On the other hand, the more TMB molecules

added to the solution might disturb the self-organization of

the block copolymer and result in disordered mesophase. A

comparable effect has also been observed before for the syn-

theses of mesoporous silicas from a relatively concentrated

solution [29]. In fact, the mass ratio of TMB/F127 is one of

the most key factors that affect the mesoscopic ordering of

products in this system, and its favorable value is close to

0.2. When the TMB/F127 mass ratio is fixed at 0.2, the adjust-

ment of the R/F127/H2O mass ratio shows a relatively little

1 2 3 4 5

Inte

nsi

ty (

a. u

.)

2θ (degree)

x = 0.1 g

x = 0.3 g

x = 0 g

Fig. 5 – XRD patterns of mesoporous carbons prepared with

a reactant composition of 0.55 g R/0.35 g HMT/1.00 g F127/

x g TMB/18 g H2O. All samples were prepared under the

fixed hydrothermal temperature (100 �C), and calcined at

900 �C in a nitrogen atmosphere for 3 h.

0.55 g R/0.35 g HMT/1.00 g F127/0.20 g TMB/18 g H2O, and

calcined at 900 �C in a nitrogen atmosphere for 3 h.

influence on the structural ordering. As an example, XRD pat-

tern shown in Fig. 6 reveals that highly ordered hexagonal

p6m mesostructure can be obtained with the doubled mass

ratio of R/F127. It should be noted that, in this case, the aque-

ous ammonia must be added extra to completely dissolve the

reactants.

The effect of the hydrothermal temperature on the struc-

tural ordering of the products was also investigated. At reac-

tion temperature lower than 70 �C, no precipitation was

found in the autoclave, probably because HMT is hard to

hydrolyze blow 70 �C [30]. At 70 and 80 �C, small amounts of

grey colloidal solids were obtained. The corresponding carbo-

naceous products exhibit only a wide XRD peak with week

intensity (Fig. 7), suggesting poor pore regularity. It might be

attributed to the lowly cross-linked RF polymers and the

resulting unstable carbon frameworks. Well-defined XRD pat-

terns, assigned to 2D hexagonal mesostructures, can be ob-

served for the carbonaceous samples synthesized from 90 to

2118 C A R B O N 4 9 ( 2 0 1 1 ) 2 1 1 3 – 2 1 1 9

220 �C. The color of the as-made RF/F127 composites changes

from yellow into red along with the increase of hydrothermal

temperature, possibly related to the enhanced cross-linking

degree of RF frameworks. Although the further temperature

experiments can not be performed due to the temperature

limit of Teflon autoclaves, it can not be excluded that the

higher reaction temperature would also be possible to result

in ordered structures. These results indicate that the synthe-

sis system has good thermal adaptability.

The formation of the strong interactions between the sur-

factants and precursors is the key of self-assembly syntheses

for OMCs [31]. Until now, only several phenols (i.e., phenol,

resorcinol, phloroglucinol, etc.) were successfully used to fab-

ricate mesostructured resins and carbons, able to form hydro-

gen-bondings with hydrophilic PEO blocks of amphiphilies.

The previous methods generally involved a phenol–aldehyde

prepolymerization step, instead of direct use of monomers

during the syntheses. This is a rational choice to meet the

requirements of self-assembly because the oligomers have

plenty of hydroxyl groups that can strongly interact with

amphiphilies by hydrogen bonds. More importantly, the prep-

olymerization also makes the cross-linking and polymerizing

processes of the phenolic resin frameworks stand apart from

the assembly processes, in part or in whole. Therefore, it skill-

fully avoids uncontrollable self-condensation of the mono-

mers in the surfactant-templating assembly processes [31].

The step-by-step strategy has some similarities to the prepa-

ration of non-silicate mesostructured oxide with nanobuild-

ing blocks (NBBs) as precursors due to their less reactivity

than molecular precursors [32].

As mentioned above, the use of the prepolymerized oligo-

mers as starting units favors the individual control of the self-

assembly and polymerization processes. Different from the

strategy, the method described here is based on the indirect

introduction of reactive monomer and catalyst to control

the condensation/polymerization reaction. Fig. 1 illustrates

the formation of mesostructured RF/F127 composite by using

HMT as a release source of formaldehyde. After all four reac-

tants are dissolved in water, the resorcinol can strongly inter-

act with the PEO blocks of F127 by hydrogen-bonding

interactions and the hydrophobic TMB can interact with the

polypropylene oxide (PPO) blocks. Under hydrothermal condi-

tions, HMT will gradually decompose to yield formaldehyde

and ammonia. The released formaldehyde molecules in turn

condensate with the resorcinol molecules associated with the

hydrophilic segments of triblock copolymers under a weak

basic condition (derived from the released ammonia). The

gradual polymerization reactions induce the production and

lengthening of RF resol/F127 micelles, and then the packing

of the micelles and the further polymerization of RF resol re-

sults in the formation of ordered mesostructure. The method

can simplify the synthesis and allow the single-step forma-

tion of ordered mesostructures without an additional prepo-

lymerization step.

We also attempted to use an equivalent amount of formal-

dehyde and ammonia instead of HMT in the present reaction

system. However, when all the reactants were mixed at once,

an insoluble material was formed rapidly. Neither XRD nor

TEM (data not shown) gives any indication of the presence

of ordered mesostructure for the resultant product. Virtually,

resorcinol can rapidly react with formaldehyde at room tem-

perature even without the presence of any catalysts because

of its high electron density at the 2, 4 and 6 reactive positions

[33]. Therefore, when formaldehyde is directly used, the

uncontrolled self-condensation of resorcinol and formalde-

hyde will result in the formation of dense resins instead of

alignment around the surfactants.

4. Conclusions

In brief, we have proposed a simple route to prepare OMCs

under hydrothermal conditions. The crucial difference to pre-

vious work is that the commonly used formaldehyde is re-

placed with hexamine. The strategy efficiently harnesses

both the organic–organic self-assembly and the formation of

the RF frameworks. This method has the advantage of being

a one-pot procedure and only involves the use of several com-

mon organic reactants.

Acknowledgements

This work was supported by the National Natural Science

Foundation of China (50272048). We thank Haolin Tang, Lijun

Liu and Duan Fan for characterization assistance.

Appendix A. Supplementary data

Supplementary data associated with this article can be found,

in the online version, at doi:10.1016/j.carbon.2011.01.047.

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