Journal of CO2 Utilization 1 (2013) 17

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Journal of CO2 Utilization

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Organoamines-grafted on nano-sized silica for carbon dioxide capture

Miklos Czaun, Alain Goeppert, Robert B. May, Drew Peltier, Hang Zhang, G.K. Surya Prakash *, George A. Olah *
Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park Campus, Los Angeles, CA 90089-1661, USA

A R T I C L E I N F O

A B S T R A C T

Article history: Received 2 February 2013 Received in revised form 26 March 2013 Accepted 26 March 2013 Available online 24 April 2013 Keywords: Nanosilica Chemically grafted organoamines Carbon dioxide capture

Organoamineinorganic hybrid adsorbent materials were synthesized by covalent immobilization of alkylaminotrimethoxysilanes and polyethyleneiminetrimethoxysilane onto fumed silica (nanosilica). The obtained silicaorganic hybrid materials were characterized by thermogravimetry and diffuse reectance infrared Fourier transform spectroscopy (DRIFT) conrming the successful grafting of the amine derivatives to silica and their surface area measured using BrunauerEmmettTeller method (BET). The inuence of reaction conditions on the graft density of organoamines was investigated and it was found that the saturation of the silane coupling agents with carbon dioxide prior to surface modication resulted in higher graft densities. Carbon dioxide uptake of the obtained hybrid materials were determined by thermogravimetric analysis at room temperature as well as higher temperatures resulting in CO2 adsorption capacities from 32.4 to 69.7 mg g1 adsorbent. 2013 Elsevier Ltd. All rights reserved.

1. Introduction The ever increasing consumption of fossil fuels by humankind has resulted in a rapid increase of carbon dioxide concentration in the atmosphere from 270 ppm at the dawn of the industrial revolution to the present 395 ppm. It is generally accepted that this higher atmospheric carbon dioxide concentration is one of the major contributors to global warming. However, global warming is not the only effect of the increasing anthropogenic emission of CO2. The oceans of our planet are net sinks of CO2 but their absorption capacity is also nite. Furthermore, the dissolution of CO2 in the oceans lowers the pH of seawater resulting in a reduction in the abundance and/or size of shellsh, corals and crustaceans [1]. In order to avoid further increase in CO2 concentration, the management of this greenhouse gas has to gain more attention and we believe that the reduction of anthropogenic CO2 emission should be among the highest priorities of this century. Various sequestration techniques that have been suggested may provide only a temporary answer to our CO2 management problem. For example pumping CO2 to deep aquifers, coal bed, depleted oil or natural gas elds are promising solutions [2,3] but these methods need to be validated on a large scale to ensure the long term safe storage of CO2. As an alternative to sequestration, the capture, recycling and utilization of CO2 promises an ultimate solution. An

elegant way to recycle CO2, for example, is to use it in reforming reactions such as dry reforming or bi-reforming to produce syngas, a mixture of carbon monoxide and hydrogen [4]. Presently, approximately 130 million tonnes per year [5] of CO2 are used in the energy and chemical industries and the majority is converted to urea. This is still a drop in the bucket considering that humanity now emits more than 30 billion tonnes of CO2 per year. Fortunately, there are an increasing number of scientic projects [57] that consider CO2 as a valuable industrial feedstock rather than just a greenhouse gas harmful for the Planets ecosystem. As a result of the predicted improvements, the amount of CO2 utilized in the industry may grow to 300 million tonnes per year [8] in the short term and higher in the following decades. The most widely used post-combustion capture technologies are based on the chemisorption of CO2 (Scheme 1) in aqueous alkanolamine solutions such as monoethanolamine (MEA) [9], diethanolamine (DEA) and methyldiethanolamine (MDEA). The continuous regeneration of alkanolamine solutions (recovery of CO2) is a very energy intensive process due to high heating and pumping costs. While for example an aqueous solution of DEA/ MDEA has a heat capacity of approximately 4.50 J g1 8C1 (xH2 O 0:6, xDEA/xMDEA = 0.24/0.16, t = 50 8C) [10], silica based adsorbents show signicantly lower heat capacities (0.73 J g1 8C1)1 making this kind of adsorbents more energetically efcient candidates for large scale CO2 capture and recycling.

* Corresponding authors. Tel.: +1 213 740 5984; fax: +1 213 740 6679. E-mail addresses: gprakash@usc.edu (G.K. Surya Prakash), olah@usc.edu (G.A. Olah). 2212-9820/$ see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jcou.2013.03.007

1 Average heat capacity of Sil-N2 determined by DSC in the temperature range from 50 to 110 8C.

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(Mallinckrodt, 99.5%), methanol (Mallinckrodt, 99.8%), 3-aminopropyl-trimethoxysilane (N1, Acros, 95%), 3-(2-aminoethylamino)propyltrimethoxy-silane (N2, Acros, 97%), 3-[2-(2-aminoethylamino)ethylamino]-propyl-trimethoxysilane (N3, Acros, technical grade), trimethoxysilylpropyl-polyethyleneimine (PEI, Gelest, 50% in iPrOH) were used without further purication. 2.2. Preparation of adsorbents Aerosil-380 (7.0 g) was mixed in 280 mL toluene and N2 was bubbled through the vigorously stirred suspension for 30 min. 19.95 mmol of silane coupling agent was added dropwise and the reaction mixture was stirred at room temperature for 10 min before heating to 110 8C. The suspension was stirred at this temperature under a nitrogen atmosphere for 12 h. The cold reaction mixture was separated by centrifugation and the obtained solid was resuspended in cold toluene. This suspension was again separated by centrifugation. The above described purication steps were repeated three times using cold methanol as a solvent. Finally, the solid was transferred to a round bottom ask and the solvent was removed by heating at 50 8C under vacuum on a rotovapor followed by vacuum treatment overnight (65 mTorr). A small sample of the obtained white solid material was placed in a sealable glass tube and kept under vacuum at 85 8C for 3 h and then used either for characterization or for measuring the adsorption capacity. 2.3. Thermogravimetric analysis to determine the organic content of the prepared adsorbent Thermogravimetric measurements were carried out on a Shimadzu TGA-50 thermogravimetric analyzer under an air ow of 30 mL min1 in a temperature range from 25 to 800 8C with a heating rate of 10 8C min1. 2.4. FTIR Diffuse reectance infrared Fourier transform spectroscopic measurements were conducted under vacuum on a Bruker Vertex 80v FTIR spectrometer using KBr as a reference. Samples were diluted with KBr, placed into a Praying MantisTM DRP-SAP diffuse reection accessory and scanned from 4000 to 500 cm1 (number of scans = 32). 2.5. Surface area and pore volume analysis The supports were characterized by N2 adsorption/desorption isotherm measurements on a Quantachrome NOVA 2200e instrument. The surface area was determined by the multipoint BET method. The total pore volume was evaluated at a P/P0 close to 0.995. 2.6. Heat capacity Heat capacity of the solid adsorbent was measured on a Perkin Elmer DSC 7 differential scanning calorimeter. In a typical experiment, about 5 mg of the adsorbent (measured precisely with a microbalance) was placed in an aluminium pan and inside the sample cell of the DSC under a ow of nitrogen (20 mL min1). Temperature programme: heating from 0 to 120 8C with a heating rate of 5 8C min1; cooling from 120 to 0 8C with a rate of 20 8C min1. This temperature programme was repeated two times. The heat ow measured in the second cycle was considered to determine the heat capacity. 2.7. Measurement of CO2 adsorption capacity 613 mg of solid adsorbent was loaded in a platinum crucible and placed into a Shimadzu TGA-50 thermogravimetric analyzer.

Scheme 1. Chemisorption of CO2 with amines.

Substituting aqueous adsorbents by solid analogues offers therefore a potentially lower cost solution. Developing more economical alternatives for CO2 adsorption is part of our ongoing efforts (Methanol Economy1) [11] on CO2 capture and its conversion to value added products such as methanol [1113], dimethyl ether, [12] formic acid [14,15], methyl formate and eventually to most of the important petrochemical intermediates such as ethylene and propylene, which are presently produced from natural gas or petroleum oil. Various approaches have been utilized to prepare inorganic organoamine hybrid materials. Based on the interactions that occur between the organic compounds and the inorganic supports, the synthetic techniques can be divided into two main groups. Materials in which there is physical interaction between the amines and the supports fall into the rst group (a), e.g. amine impregnated supports [16,17]. In order to increase the stability of the adsorbents, amines can be chemically attached to the support giving grafted organic inorganic hybrids constituting the second group (b). Functionalization of surface accessible OH groups of inorganic materials using silane coupling agents is a widely used technique to fabricate hybrid materials for a variety of applications [18]. Chemically attached thin lms can be prepared via grafting from techniques (b1) where the organic coating is prepared by surface-initiated oligomerization/ polymerization [19]. They can also be prepared by immobilization of an organic compound (e.g. polymeric) bearing anchoring groups reacting with the OH groups of the support. This latter technique is often referred to as the grafting to approach (b2) [2023]. While inorganicorganoamine adsorbents in which the organic compound is physically adsorbed often suffer from leaching of the amine component [16,17], chemically grafted amines usually show a better stability, that helps to maintain the adsorption capacity over many adsorption/desorption cycles. The application of silicaamine hybrid materials for CO2 capture has been reviewed [2325] and it can be observed that a majority of the reported adsorbent materials are based on porous (high surface area) supports. Although, the high porosity and high surface area are advantageous for gas adsorption, very often impregnation or grafting of organic compounds to porous supports results in a signicant drop in the surface area indicating the necessity to develop new adsorbent materials using more cost effective non-porous supports such as fumed silica. It should be added here that we use the term adsorption in this manuscript to indicate the reversible capture of CO2 molecules as a surface phenomenon rather than a bulk one. Since a chemical reaction takes place between CO2 and organoamines, in fact here we deal with the phenomenon of chemisorption. 2. Experimental 2.1. Materials Fumed silica Aerosil1 380 (average primary particle size 7 nm) was obtained from Evonik (formerly Degussa). Toluene

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Scheme 2. Immobilization of N1, N2, N3 and PEI onto Aerosil-380.

The sample was rst heated to 110 8C under N2 atmosphere (ow = 60 mL/min) and this temperature was maintained for 30 min for desorbing water and CO2 from the surface. The adsorbent was exposed to pure CO2 (ow = 60 mL min1) at 25 8C for 3 h, and then the sweeping gas was replaced with N2 at 85 8C for 90 min for desorption. The second adsorption cycle was carried out under CO2 at 55 8C for 3 h followed by desorption under N2 for 90 min at 85 8C. The third adsorption cycle was carried out at 85 8C for 3 h. Finally 10 adsorption/desorption cycles were carried out isothermally at 85 8C. 15 min adsorption under pure CO2 was followed by 25 min desorption under N2. For the 100 cycle experiment, adsorption (10 min, 85 8C) was followed by desorption (15 min, 85 8C). Otherwise the experimental conditions were similar to those described earlier. 3. Results 3.1. Preparation and characterization of adsorbent materials Herein, we report on the facile synthesis of alkylamine-fumed silica hybrid materials from commercially available and relatively inexpensive starting materials. We have selected Aerosil-380 (fumed silica, average primary particle size 7 nm [26], surface area 329 m2 g1) as a support for the amine containing adsorbents. It is generally accepted and widely practiced that surface hydroxyls of inorganic substrates can be functionalized with reactive groups such as chlorosilanes [18,27], alkoxysilanes [18], and phosphonic acid derivatives [28], establishing chemically attached organic layers on the inorganic materials. Primary and secondary trialkoxysilylalkylamines such as 3-aminopropyl-trimethoxysilane (N1), 3-(2-aminoethylamino)propyltrimethoxysilane (N2), 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (N3), and trimethoxysilylpropyl-polyethyleneimine (PEI) were immobilized onto Aerosil-380 by the reaction of alkoxysilyl anchoring groups and surface silanol groups of the support giving siloxane linkages (Scheme 2). The obtained suspension was separated by centrifugation and the adsorbent particles were washed repeatedly with toluene and methanol and dried under reduced pressure (65 mTorr) at 85 8C. Hybrid materials were characterized by thermogravimetric analysis (TGA) and diffuse reectance infrared Fourier transform spectroscopy (DRIFT). The surface area was determined by the BrunauerEmmettTeller method (BET). Graft density and nitrogen content of adsorbent-grafted silica particles were calculated on the basis of weight losses indicated by the thermograms. Representative thermograms of bare Aerosil-380 (a), Sil-N3 (b), Sil-N3-CO2 (c), Sil-PEI (d) (heating rate 10 8C min1, 30 mL min1 air) are shown in Fig. 1. Weight losses (WL) were recorded in the temperature range from 25 to 800 8C and nitrogen contents (NC) are summarized in Table 1.

Grafting of N1 onto Aerosil-380 resulted in Sil-N1 adsorbent, which contained 1.89 mmol N atom g1 silica while immobilization of N2 containing two nitrogen atom per molecule resulted in an almost double amine loading (3.42 mmol N atom g1 silica). Immobilization of N3 did not follow the same trend and resulted only in slightly higher amine content (3.56 mmol N atom g1 silica) compared with Sil-N2. Not surprisingly, covalent immobilization of alkylaminotrimethoxysilanes onto Aerosil-380 resulted in signicant decrease in surface area compared to the bare support. While Aerosil-380 had a surface area of 329 m2 g1, Sil-N1, Sil-N2 and Sil-N3 were found to have 159, 148 and 157 m2 g1, respectively, indicating a 5457% drop in surface area. It can also be observed that the surface area of the grafted silica particles are very similar regardless of the silane coupling agent applied. Diffuse reectance infrared Fourier transform spectroscopy is a very powerful method to gain structural information about the molecules immobilized on the surface of inorganic materials. Successful grafting of the silane coupling agents N13 is indicated by the antisymmetric (yasNH2) and symmetric stretching vibrations (ysNH2) of hydrogen bonded NH2 groups (3366 and 3302 cm1) [29,30], respectively, and the corresponding vibrations of CH2 groups (yasCH2 at 2928 and ysCH2 at 2856 cm1) [31]. Deformation vibration of amino groups (dNH2) could also be detected at 1595 cm1 in Sil-N13 while CH2 deformations were observed at 1475 and 1449 cm1 [31] in Sil-N1. These peaks are overlapped in Sil-N23 giving a relatively broad band at 1458 cm1. The disappearance of the signal in the DRIFT spectrum of Aerosil-380 at 3745 cm1 attributed to surface OH groups [32]

Fig. 1. TGA curves of bare Aerosil-380 (a), Sil-N3 (b), Sil-N3-CO2 (c), and Sil-PEI (d).

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Table 1 Weight loss (WL), nitrogen content (NC), surface area (ABET) and pure CO2 adsorption capacity of silicaorganic hybrids. Hybrid WL (%) NCa (mmolN g1) Adsorption capacityb (mg g1) 25 8C Sil-N1 Sil-N2 Sil-N3 Sil-N1-CO2 Sil-N2-CO2 Sil-N3-CO2 Sil-PEI Sil-PEI-CO2
a b

Ads. CO2 per N at 25 8C

ABET (m2 g1)

Total pore volume (mL g1)

55 8C 26.2 27.2 33.2 31.5 39.3 42.9 50.2 58.8

85 8C 19.7 18.3 24.6 24.5 30.1 33.7 68.0 69.7 0.43 0.28 0.31 0.42 0.29 0.26 0.05 0.06 159 148 157 149 132 127 43.0 19.6 1.66 1.61 1.63 1.75 1.47 1.26 0.76 0.31

9.9 14.7 14.6 11.8 18.6 21.0 47.0 46.3

1.89 3.42 3.56 2.29 4.51 5.52 20.6 20.0

32.4 35.6 41.3 37.4 47.3 49.8 24.0 30.1

Millimoles of NH2 and NH groups per gram silica support. Milligrams of adsorbed CO2 per gram adsorbent.

further conrmed the surface modication of surface OH groups using methoxysilanes (Fig. 2). 3.2. Measurement of adsorption capacities Adsorption capacities of the silicaalkylamine hybrids were measured with a Shimadzu TGA-50 thermogravimetric analyzer at room temperature, 55 8C and 85 8C using instrument grade CO2 under ow conditions. Adsorbents were heated at 110 8C for 30 min under N2 atmosphere prior to the measurements. The weight increases were determined after an exposure to CO2 (3 h) at each temperature. The adsorption and desorption cycles were repeated ten times at 85 8C showing insignicant changes in the adsorption capacities (Figs. 3 and 4). For two selected adsorbents (Sil-N1 and Sil-PEI) the adsorption/desorption cycles were repeated 100 times at the same temperature conrming the good stability of the hybrid adsorbents (Fig. 5). It should be noted here that slightly lower adsorption capacities were measured in the course of 100 cycles due to shorter adsorption (10 min) and desorption (15 min) times. The monoamino derivative (Sil-N1) showed moderate CO2 uptake at room temperature (32.4 mg CO2 g1 adsorbent), but as expected the adsorbents with higher nitrogen content (3.42 for SilN2 and 3.56 mmol N g1 for Sil-N3) exhibited a higher CO2

Fig. 2. DRIFT spectra of bare Aerosil-380 (a), Sil-N1 (b), Sil-N2 (c), Sil-N3 (d), and SilPEI (e).

Fig. 3. A typical thermogram of adsorption/desorption measurements for Sil-N1.

M. Czaun et al. / Journal of CO2 Utilization 1 (2013) 17

Fig. 4. Adsorption capacities of functionalized silica particles at 25/55/85 8C followed by 10 cycles of adsorption/desorption at 85 8C.

adsorption capacities at 35.6 and 41.3 mg CO2 g1 adsorbent, respectively. CO2 adsorption was also measured at 55 and 85 8C showing decreasing adsorption capacity, 26.2 and 19.7 mg g1 for Sil-N1, respectively, as the temperature increased. A trend could be observed for the diamine and triamine functionalized silica giving

lower adsorption capacities, 27.2/18.3 mg g1and 33.2/ 1 24.6 mg g at 55 and 85 8C respectively. In order to further increase the adsorption capacities of the hybrid materials, we attempted to achieve higher graft densities by following a different grafting procedure. It was shown that H-

Fig. 5. Adsorption capacity of Sil-N1 and Sil-PEI in repeated adsorption and desorption cycles at 85 8C. Inset: Adsorbent weight versus time diagram for Sil-PEI.

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bonded aminopropylsilanes are less reactive and only a small portion of alkoxysilane groups participates in SiOSi bond formation [29]. It was also suggested that the saturation of alkylaminotrimethoxysilane solutions with CO2 prior to introducing the solid support facilitates covalent immobilization preventing the interaction of amine nitrogens of silane coupling agents with surface silanols through hydrogen bonding [33]. Following these leads, toluene solutions of N13 were evacuated and then exposed to CO2 for 15 min before silica particles were added. The suspension was then slowly heated to 60 8C and the temperature was maintained for 30 min. After that, the reaction mixture was heated and kept at 110 8C for 12 h. In accordance with the results of Knowles et al. [33], we obtained alkylamino-grafted silica with higher graft densities (Sil-N1-CO2: 2.29; Sil-N2-CO2: 4.51; Sil-N3-CO2: 5.52 mmol N atom g1 silica) which corresponds to a 21, 32 and 55% increase compared to the adsorbents prepared in the absence of CO2. Interestingly the increase in graft density is higher when the silane coupling agent contains more nitrogen which seems to conrm that the reaction of amino groups with CO2 makes the formation of hydrogen bond with surface silanol groups less favourable. The higher graft densities resulted in higher CO2 adsorption capacities of 37.4, 47.3 and 49.8 mg CO2 g1 adsorbent at 25 8C, respectively, and similar trend could be observed at 55 and 85 8C as well (Table 1). Similarly to the adsorbents prepared from practically CO2 free silane coupling agents and silica suspension these hybrid materials also showed lower adsorption capacity at higher temperature (Table 1). Immobilization of N1, N2 and N3 using solutions saturated with CO2 resulted in slightly lower surface areas (149, 132 and 127 m2 g1) than those we obtained for Sil-N1, Sil-N2 and Sil-N3 but signicantly lower than that of bare Aerosil-380. As the increasing number of secondary amino groups in the grafted layer resulted in better CO2 adsorption capacity per g adsorbent, we attempted to immobilize polyethyleneimine bearing trimethoxysilyl (PEI) anchoring groups. (The average number of ethyleneimine groups in the PEI chain was 18 based on 1 H NMR measurements).2 The high organic content of the hybrid materials was reected by the signicant weight losses in TGA experiments. Sil-PEI showed a weight loss of 47.0% (20.6 mmolN g1) between 200 and 800 8C. DRIFT study of PEI-grafted silica revealed stretching vibration of NH groups at 3255 cm1 and a group of signals from 2947 to 2825 cm1 due to antisymmetric and symmetric CH2 stretching vibrations. Moreover the CH2 deformation bands overlapped showing an intense and broad peak at 1450 cm1. Impregnation or covalent grafting of polymers onto supports usually causes dramatic decrease of the surface area as it was observed in the case of Sil-PEI. Surface area of Sil-PEI (43 m2 g1) showed a 87% decrease compared to that of Aerosil-380. Regardless, the low surface area PEI-grafted silica exhibited remarkable adsorption capacities of 68.0 mg CO2 g1 at 85 8C compared with mono-, di- and triamine functionalized silica. We also attempted to obtain a higher graft density of amine adsorbents on silica by saturating the toluene solution of silane coupling agents with CO2 prior to the addition of Aerosil-380 using PEI. Although the saturation of the silane coupling agent with CO2 resulted in higher graft density for the mono-, di- and triamine derivatives it did not increase the graft density for PEI. (N content of 20.0 mmolN g1) compared to what we obtained under a nitrogen atmosphere (20.6 mmolN g1). Furthermore, while all the mono-, di- and triamine-functionalized silica showed lower adsorption capacity at higher temperature a reverse trend could
Number of ethyleneimine groups were determined based on the integrals of methoxide- and ethylene protons in the 1H NMR spectrum.
2

be observed in the adsorption capacity in the case of Sil-PEI and Sil-PEI-CO2. Although the graft density of Sil-PEI-CO2 was somewhat lower than for Sil-PEI, its CO2 adsorption was however slightly higher. This hybrid material exhibited an adsorption capacity of 24.0/50.2/68.0 mg g1 and 30.1/58.8/69.7 mg g1 at 25, 55 and 85 8C, respectively. As reected by a large number of publications, a variety of supports such as mesoporous [34] or delaminated [35] materials, and metal organic frameworks (MOFs) [36] were functionalized with organoamine derivatives in order to develop high performance CO2 adsorbent materials. If one intends to make a detailed comparison of present results with those reported in the literature, one should refer to a comprehensive review by Jones et al. [23] Furthermore, the comparison of the adsorption capacity and surface area of some hybrid materials with present aminopropylfunctionalized fumed silica is also given in the supplementary information (Table S1). Supplementary material related to this article found, in the online version, at doi:10.1016/j.jhazmat.2012.10.056.

4. Conclusions Silicaorganoamine hybrid materials were prepared by covalent grafting of alkylamines (with one, two or three amino groups) and polyethyleneimine bearing reactive methoxysilane groups. The characterization of the grafted silica particles was carried out by thermogravimetry, DRIFT and BET methods. Both the nitrogen contents and the adsorption capacities of hybrid materials increased (although not linearly) as the molecular weight of the organic component increased. However the CO2/N ratio decreased, indicating that less amino functional groups were accessible or/ and active for adsorption. Higher graft densities and higher CO2 adsorption capacities could be obtained when silane coupling agents containing one, two or three amino groups were saturated with CO2 prior to the reaction with surface silanol groups. Mono-, di- and triamine-functionalized silica sorbents showed decreasing adsorption capacities as a function of temperature while the polyamine-functionalized ones exhibited increasing adsorption capacity at higher temperatures. Organoamine functionalized fumed silica adsorbents are easy to prepare, high performance adsorbents and more cost effective alternatives to other aminegrafted porous adsorbents based on supports for carbon dioxide capture. To the best of our knowledge it is also the rst time that trimethoxysilylpropyl-polyethyleneimine has been used to prepare materials for CO2 adsorption. Acknowledgement Support of our work by the Loker Hydrocarbon Research Institute and the United States Department of Energy is gratefully acknowledged. References
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