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Nickel nanoparticles catalyse reversible hydration of carbon dioxide for mineralization carbon capture and storage
iller* Gaurav A. Bhaduri and Lidija S
The separation and storage of CO2 in geological form as mineral carbonates has been seen as a viable method to reduce the concentration of CO2 from the atmosphere. Mineralization of CO2 to mineral salts like calcium

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Received 15th November 2012, Accepted 16th January 2013 DOI: 10.1039/c3cy20791a www.rsc.org/catalysis

carbonate provides a stable storage of CO2. Reversible hydration of CO2 to carbonic acid is the rate limiting step in the mineralization process. We report catalysis of the reversible hydration of CO2 using nickel nanoparticles (NiNPs) at room temperature and atmospheric pressure. The catalytic activity of the NiNPs is pH independent and as they are water insoluble and magnetic they can be magnetically separated for reuse. The reaction steps were characterized using X-ray photoemission spectroscopy and a possible reaction mechanism is described.

Introduction
Since the identification of carbon dioxide as an anthropogenic green house gas, there has been extensive research devoted to carbon dioxide capture and storage (CCS) which has been extensively reviewed.110 Of the various propositions for storage of carbon dioxide, that which has gained the greatest interest of governments and industries is storage of carbon dioxide in geological form.2,4,5,10 CCS is generally divided into two dierent forms: (a) geological storage in saline aquifers or enhanced oil recovery (terrestrial or oceanic);10 or (b) mineral sequestration4,11 either as an in situ12 or ex situ13 process. The former approach requires there to be a continuous monitoring of the oil well for possible leaks5 (especially in oceanic storage) while the latter provides a more reliable maintenance-free solution to the problem of carbon dioxide storage. Calcium carbonate is an abundant thermodynamically stable material.1 The current calcium carbonate present on Earth acts as a carbon reservoir estimated to be equivalent to 1.5 1017 metric tons of carbon dioxide.14 Therefore conversion of carbon dioxide to mineral carbonates has been proven environmentally and geologically safe for long-term storage of carbon dioxide.1,11,14 The two major steps in the mineralization of carbon dioxide to calcium carbonate are conversion of carbon dioxide to carbonic acid followed by neutralization of the acid; the rate limiting step being the hydration of carbon dioxide to carbonic acid. At present the Carbonic Anhydrase (CA) enzyme is the most promising candidate for this process as it catalyses the reversible hydration of carbon
School of Chemical Engineering and Advanced Material, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK. E-mail: lidija.siller@newcastle.ac.uk

dioxide at mild pH values (pH between 7 and 5), the fastest rate being that of human CA II.14 CA is water soluble and there has been intensive research for the use of CA immobilized on various supports.1522 The limitations with the use of enzyme are cost of extraction and specific operating parameters i.e. pH (pH between 7 and 10) and temperature (430 1C).1418 CA catalyses the hydration reaction at a pH > 7 and the dehydration of the bicarbonate ion at a pH o 7.12 Thus it is important to maintain the pH of the solution above 7 at all times and all the research is focused at pH above 7.1418 There have been few reports on other organic catalysts for the reversible hydration of carbon dioxide.2325 Kiese and Hastings26 and Caplow27 have reported the catalysis of the hydration of carbon dioxide using halogens whereas Guo et al.28 and Thee et al.29 reported the use of borate. In the present work we report the catalysis of the reversible hydration of carbon dioxide by an inorganic metal catalyst, nickel nanoparticles [NiNPs] for application in ex situ mineralization of carbon dioxide. NiNPs are water insoluble and magnetic, hence can be magnetically separated and reused in the process. The catalytic activity of the nanoparticles is pH independent and there is no requirement for any additional reagents for the process [such as buers required for the use of CA]. Moreover, the catalyst is active at room temperature [RT] and atmospheric pressure.

Experimental
Materials The nickel nanoparticles were purchased from Nano Technologies (Korea) and 99% pure CO2 from BOC (UK). Sodium hydroxide and hydrochloric acid (0.1 M) were bought from Sigma Aldrich (UK)

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Fig. 1

HRTEM images of the Ni nanoparticles.

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and used as-received without further purification. Water used in the process and chemical preparation was distilled and filtered and had a low conductivity of 2 mS cm1. 0.1 M NaOH solution was prepared by dissolving NaOH in DI water and was standardised using 0.1 M HCl solution. The NiNP suspensions were prepared by adding the required amount of NiNPs in distilled water and ultrasonicated for 5 min in an Ultra-sonicator (Hilsonic). CO2 uptake Determination of the concentration of CO2 was performed in a 20 ml jacketed vessel purchased from Soham Scientific. CO2 gas (at 1 atm, flow rate 1.69 mM min1) was bubbled in 10 ml of DI water or NiNPs suspension for 30 min and then titrated with 0.1 M NaOH solution. There was a CO2 environment over the surface of the water/NiNPs suspension. The temperature of the reaction chamber was kept constant at 20 1C, by circulating water through the jacket using a constant temperature water bath (BS5, Fisher Scientific). Reaction kinetics CO2 absorption rate experiments were undertaken with a fixed volume flask of water (200 ml) in a 250 ml glass reactor, (LS Industries) and CO2 was sparged at 1 atm (0.01 MPa, flow rate 1.69 mM min1) pressure using a sinter. The pH and conductivity were measured using a pH 209 bench top pH meter (Hanna Instruments) and pIONneer30 (Radiometer analytical). The temperature was maintained by immersing the reactor in a constant temperature water bath (BS5, Fisher Scientific). The conductivity of the aqueous suspension of NiNPs was measured after ultrasonication for 10 minutes, using the pIONneer30 (Radiometer analytical). Characterization techniques Specimens for HRTEM measurements were prepared on Cu grids with lacey carbon films (300 mesh, Agar Scientific). The size distribution of the NiNPs was analyzed by HRTEM using a JEOL 2100F field emission gun instrument operating at 200 keV located in Durham University, UK. The samples for XPS analysis were prepared by separating the Ni nanoparticles from the solution after they had precipitated. The nanoparticles were removed from the solution using a micropipette (Eppendorf), dropped on a Si wafer and dried for a day before analysis. The XPS analysis was carried out in an X-ray Photoemission Spectrometer (Kartos Axis Ultra 165) equipped with a monochromatic

Al Ka X-ray source. The pass energy used was 20 eV. The XPS results were fitted using a Shirley background30 and Gaussian Lorentzian (mixed) singlet peak shapes. For calibration the first component of the C 1s line was aligned to 284.8 eV corresponding to the binding energy of amorphous carbon.31 All the other peaks were fitted using mixed singlets.32 For the Ni spectra a Shirley background was subtracted from the original data and the background subtracted data fitted using mixed singlets.

Results and discussion

Commercially purchased NiNPs [NanoTechnolgy, Korea] were characterized using high resolution transmission electron microscopy [HRTEM] to determine their size distribution [Fig. 1]. The majority of the particles have characteristic lengths below 100 nm. The presence of nickel was confirmed using energy dispersive X-ray spectroscopy (EDX) [Fig. 2]. The crystal planes of the nanoparticles can be seen in the Selected Area

Fig. 2

Energy dispersive X-ray spectroscopy from Ni nanoparticles.

Fig. 3

Selected area electron diraction from Ni nanoparticles.

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Paper Brownian motion of the particles that might change the equilibrium dissolution state. Based on this result all further analysis were performed with a NiNP concentration of 30 ppm. Since the pH drop of the solution is a function of the formation of carbonic acid, the rate of pH change can be related to the rate of the overall reaction [rA]14 i.e. reactions (13). Similar approaches have been reported for the study of the catalytic activity of CA.14 The rate of change of pH and conductivity are shown in Fig. 5. Two sets of experiments were performed at dierent initial pH values to test the catalytic activity of Ni nanoparticles at pH values above and below 6. CA is not stable at low pH values [below pH of 5]14,35 and thus study of the catalytic activity of NiNPs becomes important at low pH values. It can be seen from Fig. 5a and c that the change in pH in the presence of the catalyst [filled circles] is significantly more rapid than that without the catalyst [filled squares] for the two dierent initial pH values [at pH 6.2 and 5.5]. The reactions associated with this process are20 CO2(gas) ) CO2(aq) CO2(aq) + H2O ) H2CO3 H2CO3 3 H+ + HCO3 (1) (2) (3)

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Fig. 4 Increase in the amount of carbon dioxide absorbed in aqueous solution of Ni nanoparticles as a function of particle concentration, at RT and at atmospheric pressure.

Electron Diraction [SEAD] pattern [Fig. 3] and correspond to the [220], [222], [311], [400], [422] and [531] lattice planes respectively.33 Fig. 4 shows the enhancement of CO2 solution concentration (all species of CO2, i.e. CO2(aq), H2CO3 and H+ and HCO3, present in water) as a function of the NiNP concentration. The concentration of dissolved CO2 was determined by titrating the CO2 solution with 0.1 M NaOH solution. The amount of CO2 dissolved in water (without the NiNPs) was similar to that reported in the literature34 (lit.,34 B39 mM). A maximum is observed at 30 ppm [three times the capacity of de-ionized water], as compared to that of water without NiNPs. By further increasing the particle concentration a decrease in the CO2 dissolution was observed, and it can be attributed to the

As there are no additional ions generated in the reaction the change in conductivity of the solution is a measure of the formation of bicarbonate ions from CO2. CO2(aq) being neutral in charge would not be responsible for the increase in conductivity of the solution. Thus the increase in the conductivity of the

Fig. 5 pH and conductivity changes during bubbling of carbon dioxide through DI water and aqueous Ni nanoparticle suspension. (a) pH change starting from pH above 6, (b) conductivity change corresponding to pH change from above 6, (c) pH change starting at pH value below 6, (d) conductivity change corresponding to pH change from below 6. Experiments are performed at RT and atmospheric pressure.

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Fig. 6 Conductivity change of the Ni nanoparticle suspension compared to that of the blank and Ni suspension when bubbled with CO2 for (a) pH above 6 and (b) pH below 6.

Fig. 7

XPS spectra of NiNPs before bubbling carbon dioxide; (a) O 1s line and (b) Ni 2p line.

solution is due to the generation of carbonic acid, providing proof of the catalytic activity. It can be observed from Fig. 5b and d that the initial rate of increase in the conductivity of the solution is higher in the presence of the NiNPs than in their absence. Thus the NiNPs act as a catalyst until the solution is saturated with bicarbonate ions and the surface of the NiNPs adsorbs some of those bicarbonates [see XPS analysis below] and/or CO2 gas. In order to confirm that the increase in ion conductivity is not purely due to the ions leached into the water from the NiNPs themselves, changes in conductivity of solutions which only contains NiNPs were analysed (Fig. 6a and b). It could be seen that this contribution to the ionic conductivity is negligible. Therefore, we can conclude that the increase in conductivity of the solution is purely due to an increase in the amount of bicarbonate ions alone. It was also observed that there was an initial immediate increase in the pH of DI water by 0.40.5 (Fig. 5a and b, observe the pH drop at 0 min) due to the addition of NiNPs and we suggest on the basis of our X-ray photoemission spectroscopy (XPS) analysis (see below) that this is likely due to the dissociation of water and formation of OH groups on the NiNP surface. This assertion is supported by the observation of OH species on the [111]36 and [110]37 surfaces of single crystal Ni when exposed to H2O at 300 K.36,37 In order to have an insight into the reaction mechanism and the species present on the nanoparticle surface, X-ray

photoelectron spectroscopy [XPS] was performed on the Ni nanoparticles before [Fig. 7] and after carbon dioxide bubbling [Fig. 7]. All errors in energy position are 0.1 eV. An insight into the chemical state of the NiNPs after dissolution in DI water without carbon dioxide exposure can be obtained by examination of the Ni 2p3/2 and O 1s core lines (Fig. 7). The Ni 2p3/2 line can be decomposed into peaks located at binding energies of 852.6 eV, 854.0 eV, 855.7 eV and a plasmon peak at 861.0 eV.31,38 The O 1s line was fitted by three peaks located at 529.8 eV, 531.3 eV and 532.2 eV. The Ni 2p3/2 peak at 852.6 eV binding energy is associated with Ni0 (ref. 39) while that at 855.7 eV corresponds to nickel in the Ni2+ oxidation state and has a binding energy corresponding to that of Ni(OH)2.31,40 Moreover, the O 1s peak at 531.3 eV corresponds to oxygen in the hydroxyl (OH) group associated with Ni(OH)2.31 The binding energy of the O 1s in multilayers of H2O (532.4 eV)36 is at a higher binding energy than that of the OH group (530.9 eV)36 thus the peak observed at 532.1 eV can be assigned to water adsorbed at the surface of the Ni nanoparticles.36,37 The Ni 2p3/2 peak at 854.0 eV corresponds to NiO which is confirmed by the presence of the O 1s peak at 529.8 eV.31,38 XPS of the NiNPs after carbon dioxide bubbling is shown in Fig. 8. The Ni 2p3/2 is again fitted using three peaks, which are located at binding energies of 852.9 eV, 854.4 eV, and 855.9 eV, respectively, and a plasmon peak at 861.5 eV.31,38 The Ni peak at 852.9 eV corresponds to Ni0 (ref. 38) whereas the peaks at

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Fig. 8

XPS spectra of NiNPs after bubbling with carbon dioxide; (A) O 1s, (B) Ni 2p3/2 and (C) C 1s.

854.4 eV and 855.9 eV correspond to the Ni2+ oxidation state.38 The carbon C 1s line is also fitted with three peaks located at 284.8 eV, 286.0 eV, and 288.1 eV. The C 1s component at 284.8 eV binding energy is assigned to adventitious carbon.31 The C 1s peak at 286.0 eV corresponds to carbon in alcohol groups and that at 288.1 eV to carbon in ester groups.31 The O 1s line is fitted with four peaks located at 530.1 eV, 531.7 eV, 532.5 eV and 533.2 eV. The peak for O 1s at 530.0 eV and the Ni 2p3/2 peak at 854.4 eV are assigned to NiO on NiNPs.38 The O 1s peaks at 531.7 eV and 533.2 eV correspond to the two dierent oxygen sites in the ester (COO) group (the first corresponding to the oxygen double bonded to carbon and the second to the oxygen single bonded to carbon) and the O 1s peak at 532.5 eV corresponds to the alcohol group (COH).31,41 Bicarbonate molecules contain both an ester and an alcoholic carbon, therefore we interpret the presence as a signature of bicarbonate species present on the nickel surface. We suggest that the Ni 2p3/2 peak at 855.9 eV corresponds to Ni(HCO3)X adsorbed at the Ni surface. Based on the interpretation of the XPS results we can derive a possible reaction mechanism which is presented in Fig. 9. In the aqueous environment there is the generation of hydroxyl groups on the surface of the Ni nanoparticles. These hydroxyl groups are then attacked by the carbon dioxide molecule to form bicarbonate ions on the Ni surface which are then displaced by water molecules, which then lose hydrogen ions and regenerate the hydroxyl ions on the Ni surface. The absence of the OH group on the surface of NiNPs [Fig. 8] in the XPS results suggests a possible conversion of OH groups to HCO3 groups when CO2 is bubbled in the NiNPs aqueous suspension. There were no hydroxyl groups observed in the XPS results of the Ni

Fig. 9

Schematic of the reaction mechanism of hydrogenation of CO2 by NiNPs.

nanoparticles after CO2 bubbling, indicating the conversion of the hydroxyl groups to bicarbonate groups in the reaction. It can be expected that other nano-forms of nickel and its alloys alone or on the support will also be catalytically active for the hydration reaction of CO2 and therefore finding the optimal inorganic catalyst for mineral storage of CO2 is worthy of future studies. It should also be noted that NiNPs are toxic and there have been recent studies that have been reported on their toxicity.4245 Thus NiNPs cannot be used for underground injection of CO2, but should be retailed and reused in the reactor (or process) with minimal exposure to the environment. Considering 99% recovery of the catalyst (NiNP) in the above

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Paper mentioned process the cost incurred per ton capture of CO2 would be B7.9 (USD), considering the current price of Ni metal being 16605 USD pre ton.46

Catalysis Science & Technology 17 C. Prabhu, S. Wanjari, S. Gawande, S. Das, N. Labhsetwar, S. Kotwal, A. K. Puri, T. Satyanarayana and S. Rayalu, J. Mol. Catal. B: Enzym., 2009, 60, 1321. 18 S. Wanjari, C. Prabhu, R. Yadav, T. Satyanarayana, N. Labhsetwar and S. Rayalu, Process Biochem., 2011, 46, 10101018. 19 R. Yadav, N. Labhsetwar, S. Kotwal and S. Rayalu, J. Nanopart. Res., 2011, 13, 263271. 20 M. Vinoba, D. H. Kim, K. S. Lim, S. K. Jeong, S. W. Lee and M. Alagar, Energy Fuels, 2011, 25, 438445. 21 E. Ozdemir, Energy Fuels, 2009, 23, 57255730. 22 L.-H. Cheng, L. Zhang, H.-L. Chen and C.-J. Gao, J. Membr. Sci., 2008, 324, 3343. 23 D. Huang, O. V. Makhlynets, L. L. Tan, S. C. Lee, E. V. Rybak-Akimova and R. H. Holm, Inorg. Chem., 2011, 50, 1007010081. 24 D. Huang, O. V. Makhlynets, L. L. Tan, S. C. Lee, E. V. RybakAkimova and R. H. Holm, Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 12221227. 25 M. J. Medeiros, D. Pletcher and D. Sidorin, J. Electroanal. Chem., 2008, 619620, 8386. 26 M. Kiese and A. B. Hastings, J. Biol. Chem., 1940, 132, 267280. 27 M. Caplow, J. Am. Chem. Soc., 1971, 93, 230235. 28 D. Guo, H. Thee, G. da Silva, J. Chen, W. Fei, S. Kentish and G. W. Stevens, Environ. Sci. Technol., 2011, 45, 48024807. 29 H. Thee, K. H. Smith, G. da Silva, S. E. Kentish and G. W. Stevens, Chem. Eng. J., 2012, 181182, 694701. 30 D. A. Shirley, Phys. Rev. B: Solid State, 1972, 5, 47094714. 31 B. P. Payne, M. C. Biesinger and N. S. McIntyre, J. Electron Spectrosc. Relat. Phenom., 2009, 175, 5565. 32 J. Yu, Q. Xiang and M. Zhou, Appl. Catal., B, 2009, 90, 595602. glund and A. FernA ndez Guillermet, Phys. 33 G. Grimvall, J. HA Rev. B: Condens. Matter Mater. Phys., 1993, 47, 1533815341. 34 N. Favre, M. L. Christ and A. C. Pierre, J. Mol. Catal. B: Enzym., 2009, 60, 163170. 35 J. C. Kernohan, Biochim. Biophys. Acta, Nucleic Acids Protein Synth., 1965, 96, 304317. 36 M. Schulze, R. Reiner, K. Bolwin and W. Kuch, Fresenius J. Anal. Chem., 1995, 353, 661665. 37 H. Guo and F. Zaera, Catal. Lett., 2003, 88, 95104. 38 M. C. Biesinger, B. P. Payne, L. W. M. Lau, A. Gerson and R. S. C. Smart, Surf. Interface Anal., 2009, 41, 324332. 39 R. J. Behm and C. R. Brundle, Surf. Sci., 1991, 255, 327343. 40 S. Chou, F. Cheng and J. Chen, Eur. J. Inorg. Chem., 2005, 40354039. 41 A. B. Christie, I. Sutherland and J. M. Walls, Vacuum, 1981, 31, 513517. 42 Z. X. Zhuang, J. Z. Zhang, H. X. Huang, P. T. Tang and B. Y. Zhang, Toxicol. Lett., 1998, 95(supp. 1), 56. 43 Q. Zhang, Y. Kusaka, X. Zhu, K. Sato, Y. Mo, T. Kluz and K. Donaldson, J. Occup. Health, 2003, 45, 2330. 44 J. I. Phillips, F. Y. Green, J. C. A. Davies and J. Murray, Am. J. Ind. Med., 2010, 53, 763767. 45 M. Ahamed, Toxicol. In Vitro, 2011, 25, 930936. 46 www.indexmundi.com/commodities/?commodity=nickel, (accessed 29/01/2013).

Conclusion
Here we report the catalytic activity of the NiNPs for the reversible hydration of carbon dioxide. The catalyst showed activity independent of the pH of the solution, at room temperature and atmospheric pressure. A threefold enhancement in the dissolution of CO2 in water was observed in the presence of NiNPs (30 ppm). There was also an initial increase in the pH of water by addition of NiNPs, which was due to the formation of Ni(OH)x on the NiNP surface as seen from the XPS analysis. The XPS analysis provided the reaction steps on the basis of which the reaction mechanism was suggested.

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Acknowledgements
GAB would like to thank Newcastle University for a Teaching Scholarship. We would like to thank Dr B. G. Mendis for the HRTEM analysis and Dr M. R. C. Hunt for critical reading of the manuscript. We thank the EPSRC (SECURE, EP/K004689/1) for funding.

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