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Optimization of Hydrogen Generation by Catalytic Hydrolysis of NaBH4 with Halloysite-Supported CoB Catalyst Using Response Surface Methodology

Published online by Cambridge University Press:  01 January 2024

Seda Hosgun Open the ORCID record for Seda Hosgun [Opens in a new window] ,
Mine Ozdemir  and
Yeliz Buruk Sahin
Seda Hosgun*
Affiliation:
Department of Chemical Engineering, Eskişehir Osmangazi University, Eskişehir 26480, Turkey
Mine Ozdemir
Affiliation:
Department of Chemical Engineering, Eskişehir Osmangazi University, Eskişehir 26480, Turkey
Yeliz Buruk Sahin
Affiliation:
Department of Industrial Engineering, Eskişehir Osmangazi University, Eskişehir 26480, Turkey
*
*E-mail address of corresponding author: serol@ogu.edu.tr
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Abstract

The hydrolysis of sodium borohydride (NaBH4) is a promising reaction with a possible practical application as a means of generating hydrogen. The efficiency of hydrogen production can be enhanced significantly by use of a catalyst during the reaction. Cobalt borides show significant catalytic activity, but unsupported CoB particles aggregate easily and are difficult to separate from the reaction medium for re-use. The objectives of the present study were to use halloysite (Hly) as a support material to increase the catalytic activity and reusability of a Co metal-based system and to investigate the binary effect of metal loading and reaction parameters on the hydrolysis of NaBH4. Catalysts were prepared by wet impregnation and chemical reduction. The surface morphology and structural properties of the prepared catalysts were characterized using N2 adsorption-desorption and the Brunauer-Emmet-Teller (BET) method, field emission scanning electron microscopy (FE-SEM), with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma mass spectrometry (ICP-MS). Response surface methodology (RSM) was used to optimize metal loading and reaction conditions for the hydrogen-generation rate. Optimum reaction conditions were determined (using Design Expert 7.0 software) as 5.01 wt.% Co loading using a Co-B/Hly-supported catalyst, 0.44 M NaBH4, 10.66 mg catalyst, and at a reaction temperature of 39.96°C. The maximum hydrogen generation rate was 33,854 mL min−1 gCo−1 under these conditions.

Keywords

Box Behnken designCoBHalloysiteHydrogen generationHydrolysisNaBH4

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Type
Article
Information
Clays and Clay Minerals , Volume 69 , Issue 1 , February 2021 , pp. 128 - 141
Copyright
Copyright © The Clay Minerals Society 2021

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References

Acar, C., & Dincer, I. (2019). Review and evaluation of hydrogen production options for better environment. Journal of Cleaner Production, 218, 835–849.CrossRefGoogle Scholar
Ayodele, B. V., Ghazali, A. A., Yassin, M. Y. M., & Abdullah, S. (2019). Optimization of hydrogen production by photocatalytic steam methane reforming over lanthanum modified Titanium (IV) oxide using response surface methodology. International Journal of Hydrogen Energy, 44(37), 20700–20710.CrossRefGoogle Scholar
Aytar, P., Gedikli, S., Buruk, Y., Cabuk, A., & Burnak, N. (2014). Lead and nickel biosorption with a fungal biomass isolated from metal mine drainage: Box-Behnken experimental design. International Journal of Environmental Science and Technology, 11(6), 1631–1640.CrossRefGoogle Scholar
Box, G. E., & Behnken, D. W. (1960). Some new three level designs for the study of quantitative variables. Technometrics, 2(4), 455–475.CrossRefGoogle Scholar
Chen, D., Liu, C., Mao, Y., Wang, W., & Li, T. (2020). Efficient hydrogen production from ethanol steam reforming over layer-controlled graphene-encapsulated Ni catalysts. Journal of Cleaner Production, 252, 119907.CrossRefGoogle Scholar
Dai, H. B., Kang, X. D., & Wang, P. (2010). Ruthenium nanoparticles immobilized in montmorillonite used as catalyst for methanolysis of ammonia borane. International Journal of Hydrogen Energy, 35(19), 10317–10323.CrossRefGoogle Scholar
Daza-Gomez, L. C., Ruiz-Ruiz, V. F., Mendoza-Nieto, J. A., Pfeifer, H., & Diaz, D. (2020). Co3O4 nanostructures and Co3O4 supported on halloysite nanotubes: New highly active and thermally stable feasible catalysts for CO oxidation. Applied Clay Science, 190, 105590.CrossRefGoogle Scholar
Derringer, G., & Suich, R. (1980). Simultaneous optimization of several response variables. Journal of Quality Technology, 12, 214–219.CrossRefGoogle Scholar
Elliott, E. P., Barrett, E. P., Joyner, L. G., & Halenda, P. P. (1951). The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. Journal of the American Chemical Society, 73(1), 373–380.Google Scholar
Erol, S., & Özdemir, M. (2017). Development of Co-B/Magnesite catalyst for hydrogen generation by Hydrolysis of sodium borohydride. Journal of The Turkish Chemical Society: Section B Engineering, 1, 69–76.Google Scholar
Fernandes, R., Patel, N., Miotello, A., & Filippi, M. (2009). Studies on catalytic behavior of Co-Ni-B in hydrogen production by hydrolysis of NaBH4. Journal of Molecular Catalysis A: Chemical, 298, 1–6.CrossRefGoogle Scholar
Guo, W. Q., Ren, N. Q., Wang, X. J., Xiang, W. S., Ding, J., You, Y., & Liu, B. F. (2009). Optimization of culture conditions for hydrogen production by EthanoligenensharbinenseB49 using response surface methodology. Bioresource Technology, 100(3), 1192–1196.CrossRefGoogle ScholarPubMed
Guo, J., Hou, Y., Li, B., & Liu, Y. (2018). Novel Ni-Co-B hollow nanospheres promote hydrogen generation from the hydrolysis of sodium borohydride. International Journal of Hydrogen Energy, 43, 15245–15254.CrossRefGoogle Scholar
Hitit, Z. Y., Lazaro, C. Z., & Hallenbeck, P. C. (2017). Hydrogen production by co-cultures of Clostridium butyricum and Rhodospeudomonas palustris: Optimization of yield using response surface methodology. International Journal of Hydrogen Energy, 42(10), 6578–6589.CrossRefGoogle Scholar
Hosgun, H. L., Ture, A. G., Hosgun, E. Z., & Bozan, B. (2020). Synthesis 5-hydroxymethylfurfural (5-HMF) from fructose over cetyl trimethylammonium bromide-directed mesoporous alumina catalyst: effect of cetyl trimethylammonium bromide amount and calcination temperature. Reaction Kinetics, Mechanisms and Catalysis, 129, 337–347.CrossRefGoogle Scholar
Ingersoll, J. C., Mani, N., Thenmozhiyal, J. C., & Muthaiah, A. (2007). Catalytic hydrolysis of sodium borohydride by a novel nickel–cobalt–boride catalyst. Journal of Power Sources, 173(1), 450–457.CrossRefGoogle Scholar
Jeong, S. U., Cho, E. A., Nam, S. W., Oh, I. H., Jung, U. H., & Kim, S. H. (2007). Effect of preparation method on Co-B catalytic activity for hydrogen generation from alkali NaBH4 solution. International Journal of Hydrogen Energy, 32, 1749–1754.CrossRefGoogle Scholar
Jitrwung, R., & Yargeau, V. (2011). Optimization of media composition for the production of biohydrogen from waste glycerol. International Journal of Hydrogen Energy, 36(16), 9602–9611.CrossRefGoogle Scholar
Kaze, C. R., Alomayri, T., Hasan, A., Tome, S., Lecomte-Nana, G. L., Nemaleu, J. G. D., Tchakoute, H. K., Kamseu, E., Melo, U. C., & Rhaier, H. (2020). Reaction kinetics and rhelogical behaviour of meta-halloysite based geopolymer cured at room temperature: Effect of thermal activation on physiochemical and microstructural properties. Applied Clay Science, 196, 105773.CrossRefGoogle Scholar
Kim, C., Lee, S. S., Li, W., & Fortner, J. D. (2020). Towards optimizing cobalt based metal oxide nanocrystals for hydrogen generation via NaBH4 hydrolysis. Applied Catalysis A: General, 589, 117303.CrossRefGoogle Scholar
Krasilin, A. A. (2020). Energy modeling of competition between tubular and platy morphologies of chrysotile and halloysite layers. Clays and Clay Minerals, 68, 436–445.CrossRefGoogle Scholar
Krishnan, P., Advani, S. G., & Prasad, A. K. (2008). Cobalt oxides as Co2B catalyst precursors for the hydrolysis of sodium borohydride solutions to generate hydrogen for PEM fuel cells. International Journal of Hydrogen Energy, 33(23), 7095–7102.CrossRefGoogle Scholar
Li, X., Fan, G., & Zeng, C. (2014). Synthesis of ruthenium nanoparticles deposited on graphene-like transition metal carbide as an effective catalyst for the hydrolysis of sodium borohydride. International Journal of Hydrogen Energy, 39(27), 14927–14934.CrossRefGoogle Scholar
Li, Z., Wang, L., Zhang, Y., & Xie, G. (2017). Properties of Cu-Co-P/γ-Al2O3 catalysts for efficient hydrogen generation by hydrolysis of alkaline NaBH4 solution. International Journal of Hydrogen Energy, 42, 5749–5757.CrossRefGoogle Scholar
Lim, S., Park, S., & Sohn, D. (2020). Modification of halloysite nanotubes for enhancement of gas-adsorption capacity. Clays and Clay Minerals, 68, 189–196.CrossRefGoogle Scholar
Liu, B. H., Li, Z. P., & Suda, S. (2006). Nickel- and cobalt-based catalysts for hydrogen generation by hydrolysis of borohydride. Journal of Alloys and Compounds, 415, 288–293.CrossRefGoogle Scholar
Lu, A., Chen, Y., Jin, J., Yue, G. H., & Peng, D. L. (2012). CoO nanocrystals as a highly active catalyst for the generation of hydrogen from hydrolysis of sodium borohydride. Journal of Power Sources, 220, 391–398.CrossRefGoogle Scholar
Manna, J., Ror, B., Vasthistha, M., & Sharma, P. (2014). Effect of Co+2/BH4- ratio in the synthesis of Co-B catalysys on sodium borohydride hydrolysis. International Journal of Hydrogen Energy, 39, 406–413.CrossRefGoogle Scholar
Mishra, P., Ameen, F., Zaid, R. M., Singh, L., Ab Wahid, Z., Islam, M. A., & Al Nadhari, S. (2019). Relative effectiveness of substrate-inoculum ratio and initial pH on hydrogen production from palm oil mill effluent: Kinetics and statistical optimization. Journal of Cleaner Production, 228, 276–283.CrossRefGoogle Scholar
Montgomery, D. C. (2017). Design and analysis of experiments. John Wiley and Sons.Google Scholar
Myers, R.H., Montgomery, D.C., & Anderson-Cook, C.M. (2016). Response Surface Methodology: Process and Product Optimization using Designed Experiments. John Wiley & Sons, Hoboken, New Jersey, USA.Google Scholar
Ozkan, G., Akkus, M. S., & Ozkan, G. (2019). The effects of operating conditions on hydrogen production from sodium borohydride using Box-Wilson optimization technique. International Journal of Hydrogen Energy, 44(20), 9811–9816.CrossRefGoogle Scholar
Patel, N., & Mitello, A. (2015). Progress in Co–B related catalyst for hydrogen production by hydrolysis of boron-hydrides: A review and the perspectives to substitute noble metals. International Journal of Hydrogen Energy, 40(3), 1429–1464.CrossRefGoogle Scholar
San, F. G. B., Karadag, C. I., Okur, O., & Okumus, E. (2016). Optimization of the catalyst loading for the direct borohydride fuel cell. Energy, 114, 214–224.Google Scholar
Sarac, N., Uğur, A., Simsek, Ö., Aytar, P., Toptas, Y., Buruk, Y., Cabuk, A., & Burnak, N. (2017). Phenol Tolerance and Bio-degradation Optimization of Serratia Marcescens NS09-1 Using Plackett-Burman and Box-Behnken Design. Environmental Engineering and Management Journal, 16(11), 2637–2645.Google Scholar
Sahin, Ö., Kιlιnc, D., & Saka, C. (2016). Bimetallic Co-Ni based complex catalyst for hydrogen production by catalytic hydrolysis of sodium borohydride with an alternative approach. Journal of Energy Institute, 89, 617–626.CrossRefGoogle Scholar
Sahiner, N., & Sengel, S. (2017). Environmentally benign halloysite clay nanotubes as alternative catalyst to metal nanoparticles in H2 production from methanolysis of sodium borohydride. Fuel Processing Technology, 158, 1–8.CrossRefGoogle Scholar
Sahiner, N., & Sengel, S. (2017). Various amine functionalized halloysite nanotube as efficient metal free catalyst for H2 generation from sodium borohydride methanolysis. Applied Clay Science, 146, 517–525.CrossRefGoogle Scholar
Tian, H., Guo, Q., & Xu, D. (2010). Hydrogen generation from catalytic hydrolysis of alkaline sodium borohydride solution using attapulgite clay-supported Co-B catalyst. Journal of Power Sources, 195, 2136–2142.CrossRefGoogle Scholar
Vinokurov, V., Sitavitskaya, A., Gulatov, A., Ostudin, A., Sosna, M., Gushchin, P., Darrat, Y., & Lvov, Y. (2018). Halloysite nanotube-based cobalt mesocatalysts for hydrogen production from sodium borohydride. Journal of Solid State Chemistry, 268, 182–189.CrossRefGoogle Scholar
Wang, J., & Wan, W. (2009). Application of desirability function based on neural network for optimizing bio hydrogen production process. International Journal of Hydrogen Energy, 34(3), 1253–1259.CrossRefGoogle Scholar
Wang, Y., Li, T., Bai, S., Qi, K., Cao, Z., Zhang, K., Wu, S., & Wang, D. (2016). Catalytic hydrolysis of sodium borohydride via nanostructured cobalt–boron catalysts. International Journal of Hydrogen Energy, 41(1), 276–284.CrossRefGoogle Scholar
Wang, L., Li, Z., Zhang, Y., Zhang, T., & Xie, G. (2017). Hydrogen generation from alkaline NaBH4 solution using electroless-deposited Co-Ni-W-P/γ-Al2O3 as catalysts. Journal of Alloys and Compounds, 702, 649–658.CrossRefGoogle Scholar
Watts, C. F., & Wolstenholme, J. (2003). An Introduction to Surface Analysis by XPS and AES. Wiley-Blackwell, Oxford, UK.CrossRefGoogle Scholar
Wu, C., Bai, Y., Liu, D. X., Wu, F., Pang, M. L., & Yi, B. L. (2011) Ni–Co–B catalyst-promoted hydrogen generation by hydrolyzing NaBH4 solution for in situ hydrogen supply of portable fuel cells. Catalysis Today, 170(1), 33–39.CrossRefGoogle Scholar
Wu, C., Wu, F., Bai, Y., Yi, B., & Zhang, H. (2005). Cobalt boride catalysts for hydrogen generation from alkaline NaBH4 solution. Materials Letter, 33, 7385–7391.Google Scholar
Xu, D., Zhang, H., & Ye, W. (2007). Hydrogen generation from hydrolysis of alkaline sodium borohydride solution using Pt/C catalyst. Catalysis Communications, 8(11), 1767–1771.CrossRefGoogle Scholar
Xu, D., Dai, P., Liu, X., Cao, C., & Guo, Q. (2008). Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution. Journal of Power Sources, 182(2), 616–620.CrossRefGoogle Scholar
Xu, D., Wang, H., Guo, Q., & Ji, S. (2011). Catalytic behavior of carbon supported Ni-Bi Co-B and Co-Ni-B in hydrogen generation by hydrolysis of KBH4. Fuel Processing Technology, 92, 1606–1610.CrossRefGoogle Scholar
Yang, C. C., Chen, M. S., & Chen, Y. W. (2011). Hydrogen generation by hydrolysis of sodium borohydride on CoB/SiO2 catalyst. International Journal of Hydrogen Energy, 36(2), 1418–1423.CrossRefGoogle Scholar
Yin, Y., & Wang, J. (2019). Optimization of fermentative hydrogen production by Enterococcus faecium INET2 using response surface methodology. International Journal of Hydrogen Energy, 44(3), 1483–1491.CrossRefGoogle Scholar
Zhang, H., Ling, T., & Du, X. W. (2015). Gas-Phase cation exchange toward porous single-crystal CoO nanorods for catalytic hydrogen production. Chemistry of Materials, 27(1), 352–357.CrossRefGoogle Scholar
Zhang, H., Feng, X., Cheng, L., Hou, X., Li, Y., & Han, S. (2019). Non-noble Co-anchored on nanoporous graphene oxide, as an efficient and long-life catalyst for hydrogen generation from sodium borohydride. Colids and Surfaces A: Physicochemical and Engineering Aspect, 563, 112–119.CrossRefGoogle Scholar