Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation

Uğur Işık

doi:10.58692/jotcsb.1836937

Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation

Abstract

In this study, a novel catalyst (Ac-Co-500) derived from acorn cup biomass waste was synthesized, characterized, and optimized for hydrogen generation via sodium borohydride (NaBH4) methanolysis. The elemental and structural properties of the catalyst were investigated using FT-IR, SEM, and SEM-EDX analyses. Hydrogen generation efficiencies were evaluated, showing that catalyst loading, NaBH4 amount, and reaction temperature substantially influenced the reaction kinetics. Remarkably, the NaBH4 methanolysis reaction catalyzed by Ac-Co-500 exhibited a hydrogen generation rate of 6796 mLmin-1gcat-1 and was completed within 2.33 minutes, yielding approximately 670 mL of hydrogen. The activation energy was measured at 14.09 kJ/mol, which is comparatively low relative to both metal-free and metal-based catalysts noted for similar applications. The reusability of Ac-Co-500 was also assessed over four cycles, with hydrogen generation time gradually increasing with each cycle. Overall, the results indicate that Ac-Co-500 is a promising, efficient, and sustainable catalyst for hydrogen production through NaBH4 methanolysis.

Keywords

Supporting Institution

Artvin Coruh University Scientific Research Project Coordination (Project Number: 2023.TAB.F65.02.01).

Project Number

2023.TAB.F65.02.01

Ethical Statement

The author declares that this document does not require ethics committee approval or any special permission. This study does not cause any harm to the environment.

References

Akhtar, K., Khan, M. S. J., Bakhsh, E. M., Kamal, T., Asiri, A. M., & Khan, S. B. (2023). Chitosan hydrogel anchored phthalocyanine supported metal nanoparticles: Bifunctional catalysts for pollutants reduction and hydrogen production. Environmental Pollution, 327, 121524.
Asmae, B., Ahmed, B., Benaouda, B., Saleh, Y. S. G., Benderdouche, N., Ali, Ç., Sreńscek-Nazzal, J., & Michalkiewicz, B. (2025). Selected pharmaceutical pollutant recovery from wastewater by an agro-byproduct Laurus nobilis-based adsorbent: Theoretical and experimental studies. Journal of the Taiwan Institute of Chemical Engineers, 170, 106011.
Caglar, A., Kaya, S., Saka, C., Yildiz, D., & Kivrak, H. (2024). Investigation of electrooxidation and methanolysis of sodium borohydride on activated carbon supported Co catalysts from poplar sawdust. International journal of hydrogen energy, 75, 171-178.
Crisafulli, C., Scirè, S., Zito, R., & Bongiorno, C. (2012). Role of the support and the Ru precursor on the performance of Ru/carbon catalysts towards H2 production through NaBH4 hydrolysis. Catalysis letters, 142(7), 882-888.
Demirci, U. B., Akdim, O., Andrieux, J., Hannauer, J., Chamoun, R., & Miele, P. (2010). Sodium borohydride hydrolysis as hydrogen generator: issues, state of the art and applicability upstream from a fuel cell. Fuel Cells, 10(3), 335-350.
Feng, J., Zhu, H., Xu, Y., Jiang, J., & Pan, H. (2021). Preparation and characterization of high-performance activated carbon from papermaking black-liquor at low temperature. Journal of Analytical and Applied Pyrolysis, 159, 105292.
Gao, Z., Ding, C., Wang, J., Ding, G., Xue, Y., Zhang, Y., Zhang, K., Liu, P., & Gao, X. (2019). Cobalt nanoparticles packaged into nitrogen-doped porous carbon derived from metal-organic framework nanocrystals for hydrogen production by hydrolysis of sodium borohydride. International journal of hydrogen energy, 44(16), 8365-8375.
Gokkus, K., Ozbal, A., Senturan, U. M., Gür, M., & Bütün, V. (2024). Synthesis of azo polymers and their catalytic performance in hydrogen production via NaBH4 methanolysis. Materials Research Bulletin, 180, 113009.

Inger, E., Sunol, A. K., & Sahiner, N. (2020). Catalytic activity of metal‐free amine‐modified dextran microgels in hydrogen release through methanolysis of NaBH4. International Journal of Energy Research, 44(7), 5990-6001.
Isik, U., Gultekin, E., Karakas, D. E., & Kaya, M. (2026). Synthesis and characterization of triazole-based schiff bases as novel highly efficient organocatalysts for rapid H2 generation via NaBH4 methanolysis. Fuel, 406, 137052.
Işık, U. (2025). PREPARATION AND CHARACTERIZATION OF ACTIVATED CARBON FROM ACORN CUPS VIA HCl-FeCl2 CO-ACTIVATION FOR HYDROGEN GENERATION THROUGH NaBH4 SOLVOLYSIS. Middle East Journal of Science, 11(2), 228-246.
Işik, U., Namli, M., Kantar, C., & Karakaş, D. E. (2025). Zinc phthalocyanine as a heterogeneous catalyst for efficient H2 generation from NaBH4 methanolysis. International journal of hydrogen energy, 176, 151497.
Jacobson, M. Z., Colella, W., & Golden, D. (2005). Cleaning the air and improving health with hydrogen fuel-cell vehicles. Science, 308(5730), 1901-1905.
Kalkan, E. M. (2023). Meşe Palamudu Çanağı Destekli Metalli/Metalsiz Katalizörlerin Sentezi ve Sodyum Borhidrürün Metanoliz Reaksiyonlarındaki Katalitik Etkinliklerinin İncelenmesi Siirt Üniversitesi].
Karakaş, D. E. (2022). A novel cost-effective catalyst from orange peel waste protonated with phosphoric acid for hydrogen generation from methanolysis of NaBH4. International journal of hydrogen energy, 47(24), 12231-12239.
Karakaş, D. E., Akdemir, M., Atelge, M., Kaya, M., & Atabani, A. (2023). Defatted spent coffee grounds-supported cobalt catalyst as a promising supercapacitor electrode for hydrogen production and energy storage. Clean Technologies and Environmental Policy, 25(2), 483-493.
Karakaş, D. E., Horoz, S., Durap, F., Orak, C., & Kaya, M. (2025). Integrated catalytic and energy storage performance of grass waste derived ni-based catalyst. Arabian Journal for Science and Engineering, 50(6), 4209-4221.
Karakaş, D. E., Mustafa, K., & Horoz, S. (2023). Catalytic activites of a biomaterial (sumac) catalyst in sodium borohyride methanolysis reactions. Journal of Molecular Structure, 1273, 134276.
Kaya, M. (2020). Production of metal-free catalyst from defatted spent coffee ground for hydrogen generation by sodium borohyride methanolysis. International journal of hydrogen energy, 45(23), 12731-12742.
Kaya, M., Bekiroğullari, M., & Saka, C. (2019). Highly efficient CoB catalyst using a support material based on Spirulina microalgal strain treated with ZnCl2 for hydrogen generation via sodium borohydride methanolysis. International Journal of Energy Research, 43(9), 4243-4252.
Khan, M. S. J., Alkhadher, S. A. A., Sidek, L. M., Kamal, T., Asiri, A. M., Khan, S. B., Zawawi, M. H., Basri, H., & Ahmed, A. N. (2025). Metal nanoparticles entrapment in chitosan-carbon black composite hydrogel towards sustainable environmental solutions. International Journal of Biological Macromolecules, 296, 139717.
Kılınç, D., Şahi̇n, Ö., & Saka, C. (2018). Salicylaldimine-Ni complex supported on Al2O3: Highly efficient catalyst for hydrogen production from hydrolysis of sodium borohydride. International journal of hydrogen energy, 43(1), 251-261.
Lin, T., Chen, I.-W., Liu, F., Yang, C., Bi, H., Xu, F., & Huang, F. (2015). Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science, 350(6267), 1508-1513.
Liu, B., & Li, Z. (2009). A review: hydrogen generation from borohydride hydrolysis reaction. Journal of Power Sources, 187(2), 527-534.
Liu, M., Liu, H., Chen, K., Sun, J., Wang, H., Liu, J., & Ouyang, L. (2021). An Al–Li alloy/water system for superior and low-temperature hydrogen production. Inorganic Chemistry Frontiers, 8(14), 3473-3481.
Ma, M., Yang, L., Ouyang, L., Shao, H., & Zhu, M. (2019). Promoting hydrogen generation from the hydrolysis of Mg-Graphite composites by plasma-assisted milling. Energy, 167, 1205-1211.
Meda, U. S., Rajyaguru, Y. V., & Pandey, A. (2023). Generation of green hydrogen using self-sustained regenerative fuel cells: Opportunities and challenges. International journal of hydrogen energy, 48(73), 28289-28314.
Moreno-Castilla, C., López-Ramón, M., & Carrasco-Marın, F. (2000). Changes in surface chemistry of activated carbons by wet oxidation. Carbon, 38(14), 1995-2001.
Niu, W., Ren, D., Han, Y., Wu, Y., & Gou, X. (2012). Optimizing preparation of carbon supported cobalt catalyst for hydrogen generation from NaBH4 hydrolysis. Journal of alloys and compounds, 543, 159-166.
Ozturk, O. F., Demirci, S., Sengel, S. B., & Sahiner, N. (2018). Highly regenerable ionic liquid microgels as inherently metal‐free green catalyst for H2 generation. Polymers for Advanced Technologies, 29(5), 1426-1434.
Rahayu, N. W. S. T., Park, J., Yang, M., Wang, S., & Lee, M. (2020). Cesium removal from a water system using a polysulfone carrier containing nitric acid-treated bamboo charcoal. Journal of Environmental Radioactivity, 225, 106374.
Reuß, M., Grube, T., Robinius, M., Preuster, P., Wasserscheid, P., & Stolten, D. (2017). Seasonal storage and alternative carriers: A flexible hydrogen supply chain model. Applied energy, 200, 290-302.
Sahiner, N. (2017). Modified multi-wall carbon nanotubes as metal free catalyst for application in H2 production from methanolysis of NaBH4. Journal of Power Sources, 366, 178-184.
Sahiner, N., & Demirci, S. (2017). Very fast H2 production from the methanolysis of NaBH4 by metal‐free poly (ethylene imine) microgel catalysts. International Journal of Energy Research, 41(5), 736-746.
Sahiner, N., Yasar, A. O., & Aktas, N. (2016). An alternative to metal catalysts: poly (4-vinyl pyridine)-based polymeric ionic liquid catalyst for H2 generation from hydrolysis and methanolysis of NaBH4. International journal of hydrogen energy, 41(45), 20562-20572.
Saka, C. (2022). Facile fabrication of P-doped g-C3N4 particles with nitrogen vacancies for efficient dehydrogenation of sodium borohydride methanolysis. Fuel, 313, 122688.
Saka, C. (2025). Utilization of Co@ CoO nanoparticles incorporated on sulphur-doped activated carbon derived from biomass waste for efficient hydrogen generation from sodium borohydride methanolysis. Biomass and bioenergy, 201, 108038.
Saka, C., Kaya, M., & Bekiroğullari, M. (2020). Spirulina microalgal strain as efficient a metal‐free catalyst to generate hydrogen via methanolysis of sodium borohydride. International Journal of Energy Research, 44(1), 402-410.
Saka, C., Yıldız, D., Kaya, S., Caglar, A., Elitok, D., Yaylı, E., Kaya, M., Atelge, R., & Kivrak, H. (2023). A novel hazelnutt bagasse based activated carbon as sodium borohydride methanolysis and electrooxidation catalyst. International journal of hydrogen energy, 48(65), 25339-25353.
Santos, D., & Sequeira, C. (2011). Sodium borohydride as a fuel for the future. Renewable and sustainable energy reviews, 15(8), 3980-4001.
Stern, N. H. (2007). The economics of climate change: the Stern review. cambridge University press.
Taha, T. A. M., Abouhaswa, A., & Mohamed, W. (2025). Enhanced catalytic performance of magnetic zinc-doped cobalt ferrite nanoparticles in sodium borohydride methanolysis. International journal of hydrogen energy, 112, 133-143.
van der Spek, M., Banet, C., Bauer, C., Gabrielli, P., Goldthorpe, W., Mazzotti, M., Munkejord, S. T., Røkke, N. A., Shah, N., & Sunny, N. (2022). Perspective on the hydrogen economy as a pathway to reach net-zero CO 2 emissions in Europe. Energy & Environmental Science, 15(3), 1034-1077.
Xu, D., Lai, X., Guo, W., Zhang, X., Wang, C., & Dai, P. (2018). Efficient catalytic properties of SO42−/MxOy (M= Cu, Co, Fe) catalysts for hydrogen generation by methanolysis of sodium borohydride. International journal of hydrogen energy, 43(13), 6594-6602.
Xu, N., Gao, S., Xu, C., Fang, Y., Xu, L., & Zhang, W. (2021). Carbon quantum dots derived from waste acorn cups and its application as an ultraviolet absorbent for polyvinyl alcohol film. Applied Surface Science, 556, 149774.

Details

Primary Language

English

Subjects

Catalytic Activity, Chemical Reaction

Journal Section

Research Article

Authors

Uğur Işık ^*
0000-0003-1010-9563
Türkiye

Publication Date

March 4, 2026

Submission Date

December 5, 2025

Acceptance Date

February 6, 2026

Published in Issue

Year 2026 Volume: 2026

DOI

https://doi.org/10.58692/jotcsb.1836937

IZ

https://izlik.org/JA88UX69FY

Cite

RIS / Bibtex

APA

Işık, U. (2026). Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation. Journal of the Turkish Chemical Society Section B: Chemical Engineering, 2026, 1-14. https://doi.org/10.58692/jotcsb.1836937

AMA

1.Işık U. Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation. JOTCSB. 2026;2026:1-14. doi:10.58692/jotcsb.1836937

Chicago

Işık, Uğur. 2026. “Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation”. Journal of the Turkish Chemical Society Section B: Chemical Engineering 2026 (March): 1-14. https://doi.org/10.58692/jotcsb.1836937.

EndNote

Işık U (March 1, 2026) Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation. Journal of the Turkish Chemical Society Section B: Chemical Engineering 2026 1–14.

IEEE

[1]U. Işık, “Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation”, JOTCSB, vol. 2026, pp. 1–14, Mar. 2026, doi: 10.58692/jotcsb.1836937.

ISNAD

Işık, Uğur. “Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation”. Journal of the Turkish Chemical Society Section B: Chemical Engineering 2026 (March 1, 2026): 1-14. https://doi.org/10.58692/jotcsb.1836937.

JAMA

1.Işık U. Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation. JOTCSB. 2026;2026:1–14.

MLA

Işık, Uğur. “Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation”. Journal of the Turkish Chemical Society Section B: Chemical Engineering, vol. 2026, Mar. 2026, pp. 1-14, doi:10.58692/jotcsb.1836937.

Vancouver

1.Uğur Işık. Enhanced Hydrogen Generation via NaBH4 Methanolysis Using Novel Acorn Cup-Derived Activated Carbon through CH3COOH–CoCl2 Co-Activation. JOTCSB. 2026 Mar. 1;2026:1-14. doi:10.58692/jotcsb.1836937