Microporous and Mesoporous Materials 151 (2012) 474480

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Microporous and Mesoporous Materials

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Hydrolysis controlled synthesis of amine-functionalized hollow ethanesilica nanospheres as adsorbents for CO2 capture
Shiyang Bai a,b, Jian Liu a,c, Jinsuo Gao a, Qihua Yang a,, Can Li a,
a

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China Graduate School of the Chinese Academy of Sciences, Beijing 100049, China c ARC Centre of Excellence for Functional Nanomaterials, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, QLD 4072, Australia
b

a r t i c l e

i n f o

a b s t r a c t
Bifunctionalized organosilica hollow nanospheres with bridging ethane group and protruding amine group have been successfully synthesized through prehydrolysis strategy using 3-(aminopropyl)triethoxysilane (APTES) and 1,2-bis(trimethoxysilyl)ethane (BTME) as precursor and F127 (EO106PO70EO106) as a single micelle template in a neutral medium. It was found that prehydrolysis of BTME could efciently decrease the interruption of amine group on the assembly process and result in the formation of uniform hollow nanospheres with particle size in 1518 nm. This general synthetic strategy has been extended to the preparation of functionalized hollow nanospheres with different functional groups, such as N-propyl4,5-dihydroimidzole and di-propyl-amine group. These amine-functionalized hollow nanospheres are efcient adsorbents for CO2. The controlling experiments suggest that both the hollow structure and amine group are responsible for obtaining high CO2 adsorption capacity. 2011 Elsevier Inc. All rights reserved.

Article history: Received 28 June 2011 Received in revised form 16 August 2011 Accepted 7 September 2011 Available online 13 September 2011 Keywords: Amine-functionalized Hollow nanospheres Prehydrolysis CO2 adsorption

1. Introduction Recently, silica hollow nanospheres have attracted much research attention because of their potential applications in catalysis, drug delivery, and protection materials for biomolecules [14]. Thanks to the recent advancement in materials synthesis, the hollow nanospheres with tunable particle size and shell structure have been successfully synthesized using strategies such as hard templating method [57], sonochemical [8], surfactant/vesicle templates [1,913], and emulsion templating technology [1416]. However, most reported hollow nanospheres are rather large, with their sizes ranging from at least 50 nm to micrometers, and often have thick walls. And especially they are usually composed of pure silica, lack of functionalities, which limits their application scope. The direct synthesis of functionalized hollow nanospheres has aroused much research attention [14,1719]. Due to the unique hollow structure, the functional moiety can be introduced in the hollow interior. For example, yolkshell [20] nanostructures with interior functionalities have been reported. Another alternative is to incorporate the functional group on the shell of the hollow nanospheres. These hollow nanospheres embody the advantages of organicinorganic materials, nanomaterials, and hollow structures and permit the maximum accommodation of elementary
Corresponding authors. Tel.: +86 411 84379552; fax: +86 411 84694447 (Q. Yang), tel.: +86 411 84379070 (C. Li). E-mail addresses: yangqh@dicp.ac.cn (Q. Yang), canli@dicp.ac.cn (C. Li).
1387-1811/$ - see front matter 2011 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2011.09.014

functions in a small entity, which will widen the application range of hollow nanospheres and allow the manipulation of the surface properties to control the interactions with various guest species. However, due to the complicated assembly steps involving hard template method and limited soft template method, only a few works were reported on the synthesis of functionalized silica hollow nanospheres. The silica hollow nanospheres (particle size in the range 300800 nm) with ethane-bridging group and highly ordered mesoporous structure in the shell were reported by Lus group through a vesicle and a liquid crystal dual templating approach [2]. Recently, our group reported a facile method for the synthesis of hollow organosilica nanospheres using F127 as a single micelle template [1,21]. This method has been successfully extended for the synthesis of thiol- and L-prolinamide-functionalized hollow-nanospheres with particle sizes of 1620 nm [18]. An important aspect yet to be developed is to extend the functional groups in the hollow spheres for their versatile applications. Among various functional groups, amine is very attractive, due to the various applications provided by the rich amine chemistry, including base-catalysis [2227], coupling and immobilization of functional molecules and biomolecules [28,29], drug delivery device [17,30], chemical sensors [31], conned synthesis of nanoparticle [32,33], adsorption and sequestration of heavy metal ions [34,35], acidic gas [36], and polyanions [37], and even growth of dendritic macromer [38]. The CO2 capture and sequestration is a big issue nowadays because it is believed to cause global warming. Among various

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methods for removing CO2 [39], chemisorption of CO2 on oxide surfaces or adsorption within porous silicates, carbons, and membranes has attracted much research attention due to the easy manipulation and economic efciency. With an aim to increase the CO2 adsorption capacity, the amine was incorporated in the adsorbents, for example, mesoporous silica materials [40,41]. To date, the CO2 adsorption capacities of the amine-functionalized mesoporous silicas are in the range of 13 mmol/g [4045]. Many inuence for the adsorption of CO2 have been discussed in some previous reports. For example, the comparison of the materials with different structure, such as MCM-41, SBA-12 and SBA-15, and their inuence of carbon dioxide sorption are investigated [44]. However, the investigation of the inuence of the adsorbents morphology on CO2 adsorption capacity is not investigated in details, such as hollow interiors, which may also play an important role in CO2 adsorption efciency. In this paper, we described the synthesis of amine-functionalized ethanesilica hollow nanospheres through the hydrolysis controlled direct synthesis method using F127 as a single micelle template. This method is very efcient and can be extended for the synthesis of ethanesilica hollow nanospheres functionalized with organic groups containing basic functionality. The CO2 adsorption capacity of the functionalized ethanesilica hollow nanospheres was investigated and compared. 2. Experimental section 2.1. Chemicals and reagents All materials are of analytical grade and used without any further purication. Triblock poly(ethylene oxide)poly(propylene oxide) poly(ethylene oxide) copolymer Pluronic F127 (MW = 12,600, EO106PO70EO106) and 1,2-bis(trimethoxysilyl)ethane (BTME, 97%) were purchased from SigmaAldrich Company Ltd. (USA). Bis(trimethoxysilypropyl)amine (BTMSPA), 3-(aminopropyl)triethoxysilane (APTES) and N-(3-triethoxysilylpropyl)-4,5-dihydroimidzole (TESPHI) were purchased from Gelest, Inc. (Germany). Other reagents were obtained from Shang Hai Chemical Reagent Inc. of Chinese Medicine Group. 3-Tert-butyloxycarbonylaminopropyltriethoxysilan (Boc-APTES) was synthesized according to published method [46]. 2.2. Synthesis In a typical synthesis, F127 (0.8 g) and sodium acetate (16.8 mmol) were dissolved in 28 mL of deionized water at 20 C under vigorous stirring. When the copolymer was dissolved, BTME (8 mmol) was added under stirring. After pre-hydrolysis of BTME for desired time (2 or 6 h), APTES (29 mmol) were added. The molar composition of the mixture was BTME/APTES/F127/NaAc/ H2O = 1:0.251.12:0.0079:2.1:194.5. The resultant mixture was stirred at 20 C for 24 h and aged at 100 C under static conditions for an additional 24 h. The solid product was recovered by ltration and air-dried at room temperature overnight. The surfactant was extracted by reuxing 1.0 g of as-synthesized material in 200 mL of ethanol containing 1.5 g of HCl (36.5 wt%) for 24 h. Deprotonation was performed by stirring 0.5 g of extracted samples in 20 mL triethylamine for 20 min. After ltration and washed thoroughly with ethanol and water, the samples were denoted as NH2-HNs-n. NH2-HNs is the abbreviation of amine-functionalized hollow nanospheres and n is the molar percent of APTES/BTME (Scheme 1). Using similar method mentioned above, BisNH-HNs-x and lmiHNs-x were also synthesized using bis(trimethoxysilypropyl)amine (BTMSPA) and N-(3-triethoxysilylpropyl)-4,5-dihydroimidzole

(TESPHI) as organosilane precursor, respectively (x is the molar percent of xx/BTME, xx is BTMSPA and TESPHI). For comparison, the ethanesilica hollow nanospheres (HNs) were synthesized using similar method without adding APTES. Amine-functionalized materials were also prepared using APTES or Boc-APTES as organosilane presursor without prehydrolysis of BTME. 2.3. Characterization Transmission electron microscopy (TEM) was performed using a FEI Tecnai G2 Spirit at an acceleration voltage of 120 kV. Before examination, the samples were dispersed in anhydrous ethanol and deposited on a holey carbon lm on a Cu grid. The nitrogen sorption experiments were performed at 196 C on a Micromeritics ASAP 2020 system. Prior to the measurement, the samples were out-gassed at 120 C for 6 h. The BET (BrunauerEmmettTeller) specic surface areas were calculated using adsorption data in a relative pressure range of P/P0 = 0.050.25. Pore size distribution curve was calculated from the desorption branch using BJH (BarrettJoynerHalenda) method. The total pore volumes were estimated from the amounts adsorbed at a relative pressure (P/P0) of 0.99. The X-ray photoelectron spectroscopy (XPS) was performed using a VG ESCALAB MK2 spectrometer equipped with a monochromated Al Ka X-ray source. FT-IR spectra were collected with a Nicolet Nexus 470 IR spectrometer with KBr pellet. The element analysis of C, H, and N was performed on varioEL III Elemental analyzer. The CO2 uptake was measured by Micromeritics ASAP 2020 system at 0 C. 3. Results and discussion 3.1. Synthesis of amine-functionalized hollow nanospheres (NH2-HNs-n) Using BTME as pure silane precursor, the ethanesilica hollow nanospheres (HNs) with particle size of 1318 nm and shell thickness of 34 nm can be easily synthesized with F127 triblock copolymer as template under near neutral conditions (pH = 7.92) as evidenced by the TEM characterization (Fig. 1a). However, only aggregated irregularly shaped nanoparticles were observed in the TEM image of the sample prepared using mixture of APTES and BTME as the silane source under similar synthesis conditions (Fig. 1b). The hollow nanospheres can be obtained by using Boc-APTES (NH2 was protected by butyloxycarbonyl) as organosilane precursor (Fig. 1c). The particle size mainly distributed at 13 18 nm, although some large particles with size of 3050 nm were also observed. The fact that hollow nanospheres can be obtained using Boc-APTES rather than APTES suggests the unmatched hydrolysis rate of BTME and APTES. The basic amine group at APTES can catalyze the hydrolysis of APTES. Moreover, it was reported that the strong interference of amine groups on the co-assembly process is due to the electrostatic and hydrogen bond interactions among the amine groups, the block copolymer and the silicate species [47]. The synthesis of amine functionalized hollow nanospheres using Boc-APTES as precursor is tedious and not economic efciency because the protect groups need to be introduced into APTES rst, and then to be removed from the solid product. The prehydrolysis method is generally used for the synthesis of mesoporous silicas when two precursors have quite different hydrolysis and condensation rates [23,48]. Therefore, we used the prehydrolysis strategy of BTME for the synthesis of amine-functionalized ethanesilica hollow nanospheres with APTES/BTME molar ratio of 0.25. The preformed organosilicate and surfactant micelle composite may prevent the interference of amine groups on the

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Scheme 1. The prehydrolysis synthesis process of aminopropyl-functional hollow nanospheres and the structure of the organosiliane precursors.

Fig. 1. TEM images of amino functional hollow nanosphere (a) HNs, (b) NH2-HNs-0.25 without the prehydrolysis of BTME, (c) NH2Boc-HNs-0.25, (d) NH2-HNs-0.25 with BTME prehydrolysis time of 2 h, (e) NH2-HNs-0.25 before deprotonation and (f) NH2-HNs-0.25.

Table 1 Physical and textural properties and CO2 sorption capacities of amino-functionalized hollow nanospheres. Sample BET surface area (m2/g) 604 404 332 164 361 503 445 Pore volume (cm3/g)a 2.24 1.27 0.55 0.29 1.30 0.96 1.23 Cage size (nm)b 6.5 5.5 5.5 5.18.8d 5.0 5.5 7.9 Nitrogen content (mmol/g)c 1.9 3.1 3.7 1.9 5.1 3.92 CO2 capacity (760 mmHg) (mmol/g) 0.72 1.3 1.7 1.5 0.75 1.3 2.23 Molar ratio of CO2/N 0.68 0.55 0.40 0.39 0.25 0.56

HNs NH2-HNs-0.25 NH2-HNs-0.88 NH2-HNs-1.12 BisNH-HNs-0.25 Imi-HNs-0.25 0.3-SBA-15-NH2e

a b c d e

The total pore volume determined at the relative pressure of 0.99. The pore size distribution calculated from the N2 adsorption branch using the BJH method. The result were given by element analysis. Pore size distribution. The data were from Ref. [45].

co-assembly process. The sample synthesized with BTME prehydrolysis time of 2 h is composed of irregularly shaped nanoparticles with some hollow nanospheres scattering among them, suggesting the amine-functionalized hollow nanospheres can be obtained with prehydrolysis of BTME by using APTES as precursor (Fig. 1d). Further

prolonging the prehydrolysis time of BTME to 6 h, uniform aminefunctionalized hollow nanospheres with particle size of 1518 nm and wall thicknesses of 34 nm were obtained (Fig. 1e). Due to the acidic medium for removal of the template, most of the aminopropyl groups in the hollow nanospheres were protonated. To

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Fig. 2. TEM images of amino functional hollow nanosphere with different APTES/BTME ratio in initial mixture, (a) NH2-HNs-0.88 and (b) NH2-HNs-1.12.

obtain the free amine groups, the extracted samples were treated with triethylamine to neutralize the protonated amine groups. The TEM image of the deprotonated sample, NH2-HNs-0.25, shows that the hollow spherical morphology is maintained, suggesting that the hollow spherical morphology survives the deprotonation process (Fig. 1f). The N2 sorption isotherms of the samples before and after the deprotonation show type IV isotherm pattern. Similar to that of HNs, the isotherm curves of NH2-HNs-0.25 exhibits two capillary condensation steps. The rst hysteresis loop at relative pressure 0.45 < P/P0 < 0.70 is from the void space of the hollow interior, and the second capillary condensation at relative pressure 0.70 < P/ P0 < 1.0 is from the void space of the aggregated nanospheres, further conrming the TEM results that the samples have hollow nanospherical morphology. Correspondingly, two sets of pore size distribution were observed with the primary pore size at 5.5 nm and secondary pore size at 21 nm. The BET surface area and pore volume of the samples before and after deprotonation are almost the same, further conrming that the morphology and structure of the sample are stable during the deprotonation process in base medium (Table 1). The above results show that prehydrolysis of BTME is an efcient method for the synthesis of amine-functionalized hollow nanospheres. Using BTME hydrolysis time of 6 h, NH2-HNs-n with different amine content was synthesized by adjusting the quantities of APTES in the initial mixture. With the molar ratio of APTES/BTME increasing from 0.25 to 1.12, the particle transforms from uniform hollow nanosphere to aggregated hollow nanosphere, then to mixture of hollow nanosphere and solid silica nanosphere as shown in Fig. 2. The N2 sorption isotherms of NH2-HNsn (n = 0.88, 1.12) are of type IV (Fig. 3A) similar to NH2-HNs-0.25. However, the secondary mesopore from the void space formed by nanospheres packing decreased with increasing of n, suggesting that the aggregation degree of the hollow nanospheres increases. NH2-HNs-1.12 only shows one capillary condensation step at 0.5. The disappearance of the capillary condensation step at 0.7 < P/ P0 < 1.0 conrms that this sample has no hollow interior, which is in consistent with the TEM results. The above results show the successful synthesis of aminefunctionalized hollow nanospheres through prehydrolysis of BTME. The versatility of this method was investigated for the synthesis of different kinds of functionalized hollow nanospheres containing base functionality. BisNH-HNs-0.25 and Imi-HNs-0.25 were synthesized respectively using bis(trimethoxysilypropyl)amine and N-(3-triethoxysilylpropyl)-4,5-dihydroimidzole instead of APTES under similar conditions to NH2-HNs-0.25. Fig. 4 shows the TEM images of BisNH-HNs-0.25 and Imi-HNs-0.25. Both samples are composed of hollow nanosphere with particle

Adsorportion Dv (d) [cc/nm/g STP]

(A)
Volume Adsorbed (cc/g STP)

+800

(B)

5.5nm

+600 +400

(a) (b) (c) (d) (e)

+200

(a) (b) (c) (d) (e)

1 10 100

0.0 0.2 0.4 0.6 0.8 1.0 1.2 Relative Pressure P/P0

Pore Diameter (nm)

Volume Adsorbed (cc/g STP)

+200

(f) (g) 0.0 0.2 0.4 0.6 0.8 1.0 Relative Pressure P/P0

Adsorportion Dv (d) [cc/nm/g STP]

(C)

(D)

(g) (f)
1 10 Pore Diameter (nm)

Fig. 3. (A) and (C) N2 sorption isotherm and (B) and (D) pore size distribution of amino functional hollow nanosphere, (a) HNs, (b) NH2-HNs-0.25 before deprotonation, (c) NH2-HNs-0.25, (d) NH2-HNs-0.88, (e) NH2-HNs-1.12, (f) BisNH-HNs-0.25 and (g) Imi-HNs-0.25.

size of 1518 nm and shell thickness of 34 nm. The hollow nanospherical morphology of BisNH-HNs-0.25 and Imi-HNs-0.25 is also conrmed by the existence of two types of capillary condensation step in the N2 sorption isotherms (Fig. 3). The above results prove the prehydrolysis method is a general approach for the preparation of hollow nanospheres with different chemical compositions.

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Fig. 4. TEM images of functionalized hollow nanospheres of (a) BisNH-HNs-0.25 and (b) Imi-HNs-0.25.

(A)

(B)
1568

1412 14 1448 1470 0

e (e)

Intensity (a.u.)

2800-3000

Intensity (a.u.)

(e) (d) ) (c) (b) ) (a)

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1448 8 0 1510 1470

4000

3000

2000
-1

1000

1600

1500

1400

1300
-1

1200

Wavenumber cm v

Wavenumber cm

Fig. 5. (A) IR spectra of the hollow nanospheres of (a) HNs, (b) NH2-HNs-0.25 before the deprotonation, (c) NH2-HNs-0.25, (d) BisNH-HNs-0.25 and (e) Imi-HNs-0.25, and (B) the corresponding enlargement of region of 16001200 cm1.

3.2. Composition characterization To verify the successful incorporation of the organic components, all the samples were characterized by FT-IR and elemental analysis. Fig. 5 show the FT-IR spectra of HNs, NH2-HNs-n, BisNH-HNs0.25 and Imi-HNs-0.25. The bands between 2800 and 3000 cm1 can be ascribed to the stretching of CH of the propyl as well as the bridging ethylene groups. The bands at 1470 and 1448 cm1 can be ascribed to the bending vibrations of CH of the propyl group of APTES, BTMPA or TEPHI. The incorporation of the amine moiety is further conrmed by the appearance of the broad band around 3050 and 3250 cm1, which can be attributed to the NH stretching vibration [49]. For NH2-HNs-n samples, the appearance of the band at 1495 and 1567 cm1 corresponding to the symmetric and asymmetric vibration of NH2 conrms the successful incorporation of amine group. In the spectrum of Imi-HNs-0.25, the band at 1568 cm1 was attributed to the vibration of C=N, which proved the incorporation of 4,5-dihydroimidzole. The band at 1412 cm1 is related to the CH vibrations of the bridging ethane groups [50]. But HNs sample only shows the bands at 2800 3000, 1412 and 1630 cm1, which ascribed to the CH vibrations of bridging ethane groups and water, respectively. The XPS measurements were conducted on the extracted and the deprotonated NH2-HNs-0.25. The N1s spectra of NH2-HNs before and after the deprotonation are shown in Fig. 6. The standard

binding energy for the free amine group (NH2) falls in the region of 399401 eV, while the protonated amine NH has a higher 3 binding energy of 1.5 eV than the free amine [49,51]. Thus, the peak at 400 eV and 402 eV is assigned to the NH2 and protonated amine groups, respectively. After deprotonation, the peak area ratio of S400:S402 changes from 1.2 to 2.5, indicating that most of the NH groups have been deprotonated. This also suggests that 3 most organic groups in the hollow nanospheres could be accessed by the guest molecules. The content of amine group incorporated into the nal samples varied in the range of 1.95.1 mmol g1 based on the N elemental analysis (Table 1). With the increase of APTES in the initial mixture, the loading of amino group in the nal products increased as expected. 3.3. Adsorption of CO2 CO2 capture plays an important role for reducing greenhousegas emissions. The cavity of hollow nanospheres combined with amino functional group may offer potentially efcient CO2 adsorbents. Therefore, the CO2 adsorption behavior of the hollow nanospheres with different kind of composition was investigated. The adsorption isotherms of CO2 on HNs and functionalized-HNs at 0 C are shown in Fig. 7. A linear relationship of the CO2 adsorption amount as a function of pressure was observed on HNs and BisNH-HNs, indicating that the physical adsorption occurs. The

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(a)

(b)

Intensity (a.u.)

410 408 406 404 402 400 398 396 394

Intensity (a.u.)
410 408 406 404 402 400 398 396 394

Binding Energy (eV)

Binding Energy (eV)

Fig. 6. XPS N1s spectra of NH2-HNs-0.25 before (a) and after (b) the deprotonation.

(c) 1.5 (d) (b) (e) 1.0 (f) (a) 0.5

nanostructure favors the accessibility of the functional group to guest molecules. 4. Conclusion In summary, amine-functionalized organosilica hollow nanospheres with uniform particle size have been successfully synthesized for the rst time through prehydrolysis co-condensation strategy. The amino contents can be controlled by tuning the molar ratio of APTES/BTME in the initial mixture. The CO2 adsorption isotherms of NH2-HNs-n suggest that at low pressure range the CO2 adsorption was mainly driven by chemical adsorption, and at high pressure range the physical adsorption plays important roles. This result suggests that both amine loading and hollow interiors have a cooperative action in the sorption of CO2. It should be also mentioned that the prehydrolysis synthesis method is very general and can be extended for the synthesis of various functionalized hollow nanospheres. Acknowledgments

Uptake (mmol/g )

0.0 0 100 200 300 400 500 600 700 800

Pressure (mmHg)
Fig. 7. CO2 adsorption isotherms of (a) HNs, (b) NH2-HNs-0.25, (c) NH2-HNs-0.88, (d) NH2-HNs-1.12, (e) Imi-HNs-0.25 and (f) BisNH-HNs-0.25 at 0 C and under pressure of 0760 mmHg.

isotherms of CO2 on NH2-HNs and Imi-HNs are of type I and a sharp increase in CO2 adsorption amount was observed at pressure range from about 0 to 20 mmHg. This suggests the chemical adsorption behavior between CO2 and adsorbents [52]. CO2 adsorption amount is much higher on NH2-HNs and Imi-HNs than on HNs and BisNHHNs, showing the NH2 and dihydroimidzole play important roles in CO2 capture (Table 1). The CO2 adsorption amount increases as the content of NH2 in NH2-HNs increasing in the pressure range of 0200 mmHg, despite the fact that the BET surface area and pore volume of NH2-HNs decrease as the NH2 content increase. However, NH2-HNs-0.88 shows higher CO2 adsorption amount than NH2-HNs-1.12 in the pressure range of 200760 mmHg. The above results suggest that chemical adsorption mainly determines the CO2 adsorption amount at low pressure range and physical adsorption plays more and more important roles at high pressure range. The sample of NH2-HNs-0.88 gave the CO2 adsorption capacity of 1.7 mmol/g under the pressure of 760 mmHg. This was competitive with the capacity of amino-functionalized mesoporous adsorbents reported so far [4045] (Table 1). The total CO2 adsorption capacities were also estimated based on the N content in the functionalized hollow ethane silica nanospheres (Table 1). N/CO2 decreases in the order of NH2-HNs-1.12 < NH2-HNs-0.88 < NH2-HNs-0.25, which was almost in the same trend with the quality of the hollow nanostructure. These suggest that the high BET surface area and perfect hollow

This work was nancially supported by the National Basic Research Program of China (2009CB623503) and the Program Strategic Scientic Alliances between China and the Netherlands (2008DFB50130). References
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