SavedAdd your journal

Journals / Middle East Journal of Science / 2025 / Volume: 11 Issue: 2

PREPARATION AND CHARACTERIZATION OF ACTIVATED CARBON FROM ACORN CUPS VIA HCl-FeCl2 CO-ACTIVATION FOR HYDROGEN GENERATION THROUGH NaBH4 SOLVOLYSIS

Uğur Işık(ARTVİN ÇORUH ÜNİVERSİTESİ)0000-0003-1010-9563
Pages
—
Publication Date
2025-12-30
🏛️Bibliographic metadata and full text access for this article are provided via DergiPark.
DergiPark Record ↗
✨

AI Summary & Key Takeaways

AI Insight
⚡ TL;DR(Too Long; Didn't Read)

Overall, the results show that Ac-HCl-Fe is a promising, efficient, and sustainable catalyst for hydrogen generation by solvolysis of NaBH4, especially in binary solvent systems.

📌 3 Key Takeaways

🎯
Objective & Hypothesis:This current study reports the synthesis, characterization, and optimization of a novel catalyst (Ac-HCl-Fe) derived from Acorn cups biomass waste for hydrogen production via sodium borohydride (NaBH4) solvolysis.
📊
Key Findings & Data:Catalytic performance tests showed the efficiency of Ac-HCl-Fe in hydrogen generation, with parameters including catalyst loading, NaBH4 quantity, and reaction temperature significantly influencing the kinetics.
💡
Conclusion & Impact:Overall, the results show that Ac-HCl-Fe is a promising, efficient, and sustainable catalyst for hydrogen generation by solvolysis of NaBH4, especially in binary solvent systems.
🔬Design:Modeling & Simulation
📍Scope:Comprehensive Sample
⚙️Variables:Hydrogen generation · Sodium borohydride · Solvolysis

Abstract

This current study reports the synthesis, characterization, and optimization of a novel catalyst (Ac-HCl-Fe) derived from Acorn cups biomass waste for hydrogen production via sodium borohydride (NaBH4) solvolysis. The catalyst characterization was conducted using FTIR, SEM, and SEM-EDX techniques. Catalytic performance tests showed the efficiency of Ac-HCl-Fe in hydrogen generation, with parameters including catalyst loading, NaBH4 quantity, and reaction temperature significantly influencing the kinetics. Remarkably, the NaBH4 methanolysis reaction catalyzed by Ac-HCl-Fe was completed in 4.0 minutes, while the NaBH4 solvolysis in a binary propylene glycol/methanol (1:1, v/v) solvent system reached completion within just 0.9 minutes, producing a similar volume of hydrogen (~670 mL). The HGR was determined to be 68,300 mL min⁻1gcat⁻1 for the NaBH4 solvolysis reaction conducted in a binary propylene glycol/methanol (1:1, v/v) solvent system at 30 °C. In addition, the effective activation energy was calculated to be 32.36 kJ/mol, that is relatively low compared to other activated carbon-based catalysts reported for similar applications. Overall, the results show that Ac-HCl-Fe is a promising, efficient, and sustainable catalyst for hydrogen generation by solvolysis of NaBH4, especially in binary solvent systems.

🔖

Cite This Article

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, Volume: 11 Issue: 2. https://doi.org/10.51477/mejs.1805593

📄 Full Text PDF Viewer

📄

PDF görüntüleyici hazırlanıyor...

References (66)

  1. Chamoun, R., Demirci, U. B., and Miele, P., "Cyclic dehydrogenation–(re) hydrogenation with hydrogen‐storage materials: An overview," Energy Technology, 3(2), 100-117, 2015. https://doi.org/10.1002/ente.201402136
  2. Rusman, N. A. A., & Dahari, M., "A review on the current progress of metal hydrides material for solid-state hydrogen storage applications," International Journal of Hydrogen Energy, 41(28), 12108-12126, 2016. https://doi.org/10.1016/j.ijhydene.2016.05.244
  3. Veziroğlu, T. N., & Şahi, S., "21st Century's energy: Hydrogen energy system," Energy conversion and management, 49(7), 1820-1831, 2008. https://doi.org/10.1016/j.enconman.2007.08.015
  4. Veziroglu, T. N., "Conversion to hydrogen economy," Energy Procedia, 29, 654-656, 2012.
  5. Sahaym, U., & Norton, M. G., "Advances in the application of nanotechnology in enabling a ‘hydrogen economy’," Journal of Materials Science, 43(16), 5395-5429, 2008. https://doi.org/10.1007/s10853-008-2749-0
  6. Durbin, D. J., & Malardier-Jugroot, C., "Review of hydrogen storage techniques for on board vehicle applications," International journal of hydrogen energy, 38(34), 14595-14617, 2013. https://doi.org/10.1016/j.ijhydene.2013.07.058
  7. Midilli, A., Ay, M., Dincer, I., & Rosen, M. A., "On hydrogen and hydrogen energy strategies: I: current status and needs," Renewable and sustainable energy reviews, 9(3), 255-271, 2005. https://doi.org/10.1016/j.rser.2004.05.003
  8. Ibrahim, A., Paskevicius, M., & Buckley, C. E., "Chemical compression and transport of hydrogen using sodium borohydride," Sustainable Energy & Fuels, 7(5), 1196-1203, 2023. https://doi.org/10.1039/D2SE01334G
  9. Council, H., "Hydrogen for net zero-A critical cost-competitive energy vector," 2021. https://hydrogencouncil.com/en/hydrogen-for-net-zero/
  10. Jorgensen, S. W., "Hydrogen storage tanks for vehicles: Recent progress and current status," Current Opinion in Solid State and Materials Science, 15(2), 39-43, 2011. https://doi.org/10.1016/j.cossms.2010.09.004
  11. Kılınç, D., Şahi̇n, Ö., & Saka, C., "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, 2018. https://doi.org/10.1016/j.ijhydene.2017.10.151
  12. Saka, C., Yıldız, D., Kaya, S., Caglar, A., Elitok, D., Yaylı, E.,. & Kivrak, H., "A novel hazelnutt bagasse based activated carbon as sodium borohydride methanolysis and electrooxidation catalyst," International Journal of Hydrogen Energy, 48(65), 25339-25353, 2023. https://doi.org/10.1016/j.ijhydene.2023.03.261
  13. Saka, C., "Phosphorus and oxygen doped carbon-based on Spirulina microalgae as efficient metal-free catalysts to obtain H2 from methanolysis of NaBH4," International Journal of Hydrogen Energy, 46(5), 3753-3762, 2021. https://doi.org/10.1016/j.ijhydene.2020.08.222
  14. Sahiner, N., & Demirci, S., "Natural microgranular cellulose as alternative catalyst to metal nanoparticles for H2 production from NaBH4 methanolysis," Applied Catalysis B: Environmental, 202, 199-206, 2017. https://doi.org/10.1016/j.apcatb.2016.09.028
  15. Sahiner, N., Yasar, A. O., & Aktas, N., "H2 generation from NaBH4 methanolysis via magnetic field sensitive ionic liquid coated silica particles as catalyst," Surfaces and Interfaces, 8, 36-44, 2017. https://doi.org/10.1016/j.surfin.2017.04.006
  16. Ould-Amara, H., Alligier, D., Petit, E., Yot, P. G., & Demirci, U. B., "Sodium borohydride and propylene glycol, an effective combination for the generation of 2.3 wt% of hydrogen," International Journal of Hydrogen Energy, 43(15), 7237-7244, 2018. https://doi.org/10.1016/j.ijhydene.2018.02.169
  17. Demirci, U. B., Akdim, O., Andrieux, J., Hannauer, J., Chamoun, R., & Miele, P., "Sodium borohydride hydrolysis as hydrogen generator: issues, state of the art and applicability upstream from a fuel cell," Fuel Cells, 10(3), 335-350, 2010. https://doi.org/10.1002/fuce.200800171
  18. F Abdulaziz, F., El-Tantawy, A. I., Humaidi, J. R., Aljaloud, A. S., Azhary, A., Alanazi, A. A.,. & Taha, T. A. M., "Structure-performance relationship of SrTiO3/S@ g-C3N4 nanocomposites for highly active hydrogen production via NaBH4 methanolysis," Diamond and Related Materials, 148, 111389, 2024. https://doi.org/10.1016/j.diamond.2024.111389
  19. Işik, U., Namli, M., Kantar, C., & Karakaş, D. E., "Zinc phthalocyanine as a heterogeneous catalyst for efficient H2 generation from NaBH4 methanolysis," International Journal of Hydrogen Energy, 176, 151497, 2025. https://doi.org/10.1016/j.ijhydene.2025.151497
  20. Isik, U., Gultekin, E., Karakas, D. E., & Kaya, M., "Synthesis and characterization of triazole-based schiff bases as novel highly efficient organocatalysts for rapid H2 generation via NaBH4 methanolysis," Fuel, 406, 137052, 2026. https://doi.org/10.1016/j.fuel.2025.137052
  21. Karakaş, D. E., "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, 2022. https://doi.org/10.1016/j.ijhydene.2021.09.102
  22. Schlesinger, H. I., Brown, H. C., Finholt, A. E., Gilbreath, J. R., Hoekstra, H. R., & Hyde, E. K., "Sodium borohydride, its hydrolysis and its use as a reducing agent and in the generation of hydrogen1," Journal of the American Chemical Society, 75(1), 215-219, 1953. https://doi.org/10.1021/ja01097a057
  23. Xu, D., Dai, P., Guo, Q., & Yue, X., "Improved hydrogen generation from alkaline NaBH4 solution using cobalt catalysts supported on modified activated carbon," International journal of hydrogen energy, 33(24), 7371-7377, 2008. https://doi.org/10.1016/j.ijhydene.2008.09.065
  24. Wang, Y., Liu, J., Wang, K., Chen, T., Tan, X., & Li, C. M., "Hydrogen storage in Ni–B nanoalloy-doped 2D graphene," International Journal of Hydrogen Energy, 36(20), 12950-12954, 2011. https://doi.org/10.1016/j.ijhydene.2011.07.034
  25. Barghi, S. H., Tsotsis, T. T., & Sahimi, M., "Chemisorption, physisorption and hysteresis during hydrogen storage in carbon nanotubes," International journal of hydrogen energy, 39(3), 1390-1397, 2014. https://doi.org/10.1016/j.ijhydene.2013.10.163
  26. Long, J. J., Wu, H. C., Liu, Y. T., Ding, Y. Y., Yao, Q. L., Metin, O., & Lu, Z. H., "Hydrogen production from chemical hydrogen storage materials over copper‐based catalysts," CMat, 1(1), e10, 2024. https://doi.org/10.1002/cmt2.10
  27. Yang, Y. W., Lu, Z. H., & Chen, X. S., "Cu-based nanocatalysts for hydrogen generation via hydrolysis and methanolysis of ammonia borane," Materials Technology, 30(sup2), A89-A93, 2015. https://doi.org/10.1179/17535557A15Y.000000004
  28. Han, Y., Ma, J., Wang, X., Wang, Y., Zhang, K., Cao, Z.,. & Li, G., "Preparation of Co–P–B/foam Ni catalyst and its catalytic performance for hydrogen production by hydrolysis of NaBH4 solution," Fuel, 372, 132262, 2024. https://doi.org/10.1016/j.fuel.2024.132262
  29. Karakaş, D. E., Horoz, S., Durap, F., Orak, C., & Kaya, M., "Integrated catalytic and energy storage performance of grass waste derived ni-based catalyst," Arabian Journal for Science and Engineering, 50(6), 4209-4221, 2025. https://doi.org/10.1007/s13369-024-09564-8
  30. Lam, E., & Luong, J. H., "Carbon materials as catalyst supports and catalysts in the transformation of biomass to fuels and chemicals," ACS catalysis, 4(10), 3393-3410, 2014. https://doi.org/10.1021/cs5008393
  31. Lin, T., Chen, I. W., Liu, F., Yang, C., Bi, H., Xu, F., & Huang, F., "Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage," Science, 350(6267), 1508-1513, 2015. https://doi.org/10.1126/science.aab3798
  32. E. M. Kalkan, " Synthesis of oak acorn cup-supported metal-doped/metal-free catalysts and investigation of catalytic activities in sodium borohydride methanolysis reactions," Master's Thesis, Siirt University, Siirt, Türkiye, 2023.
  33. Asmae, B., Ahmed, B., Benaouda, B., Saleh, Y. S. G., Benderdouche, N., Ali, Ç.,. & Michalkiewicz, B., "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, 2025. https://doi.org/10.1016/j.jtice.2025.106011
  34. Zhang, Y., Zhang, C., Li, W., Xiao, Q., Jiao, F., Xu, S.,. & Cao, W., "Reaction mechanism of stearic acid pyrolysis via reactive molecular dynamics simulation and TG-IR technology," Renewable Energy, 217, 119115, 2023. https://doi.org/10.1016/j.renene.2023.119115
  35. Feng, J., Zhu, H., Xu, Y., Jiang, J., & Pan, H., "Preparation and characterization of high-performance activated carbon from papermaking black-liquor at low temperature," Journal of Analytical and Applied Pyrolysis, 159, 105292, 2021. https://doi.org/10.1016/j.jaap.2021.105292
  36. Aziz, E. K., Abdelmajid, R., Rachid, L. M., & Mohammadine, E. H., "Adsorptive removal of anionic dye from aqueous solutions using powdered and calcined vegetables wastes as low-cost adsorbent," rab Journal of Basic and Applied Sciences, 25(3), 93-102, 2018. https://doi.org/10.1080/25765299.2018.1517861
  37. Tetsuka, H., Nagoya, A., Fukusumi, T., & Matsui, T., "Molecularly Designed, Nitrogen-Functionalized Graphene Quantum Dots for Optoelectronic Devices," Advanced Materials (Deerfield Beach, Fla.), 28(23), 4632-4638, 2016. https://doi.org/10.1002/adma.201600058
  38. Masanizan, A., Lim, C. M., Kooh, M. R. R., Mahadi, A. H., & Thotagamuge, R., "The removal of ruthenium-based complexes N3 dye from DSSC wastewater using copper impregnated KOH-activated bamboo charcoal," Water, Air, & Soil Pollution, 232(9), 388, 2021. https://doi.org/10.1007/s11270-021-05333-7
  39. Das, P., Sreelatha, T., & Ganesh, A., "Bio oil from pyrolysis of cashew nut shell-characterisation and related properties," Biomass and bioenergy, 27(3), 265-275, 2004. https://doi.org/10.1016/j.biombioe.2003.12.001
  40. Rahayu, N. W. S. T., Park, J., Yang, M., Wang, S., & Lee, M., "Cesium removal from a water system using a polysulfone carrier containing nitric acid-treated bamboo charcoal," Journal of Environmental Radioactivity, 225, 106374, 2020. https://doi.org/10.1016/j.jenvrad.2020.106374
  41. Xu, N., Gao, S., Xu, C., Fang, Y., Xu, L., & Zhang, W., "Carbon quantum dots derived from waste acorn cups and its application as an ultraviolet absorbent for polyvinyl alcohol film," Applied Surface Science, 556, 149774, 2021. https://doi.org/10.1016/j.apsusc.2021.149774
  42. Xu, D., Lai, X., Guo, W., Zhang, X., Wang, C., & Dai, P., "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, 2018. https://doi.org/10.1016/j.ijhydene.2018.02.074
  43. Sahiner, N., & Demirci, S., "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, 2017. https://doi.org/10.1002/er.3679
  44. Bekirogullari, M., "Hydrogen production from sodium borohydride by ZnCl2 treated defatted spent coffee ground catalyst," International journal of hydrogen energy, 45(16), 9733-9743, 2020. https://doi.org/10.1016/j.ijhydene.2020.01.244
  45. Saka, C., "Fabrication of protonated chitosan/montmorillonite catalyst for hydrogen production via sodium borohydride in the optimum methanol/propylene glycol mixture," International Journal of Hydrogen Energy, 65, 410-420, 2024. https://doi.org/10.1016/j.ijhydene.2024.03.371
  46. Khan, M. S. J., Alkhadher, S. A. A., Sidek, L. M., Kamal, T., Asiri, A. M., Khan, S. B.,. & Ahmed, A. N., "Metal nanoparticles entrapment in chitosan-carbon black composite hydrogel towards sustainable environmental solutions," International Journal of Biological Macromolecules, 296, 139717, 2025. https://doi.org/10.1016/j.ijbiomac.2025.139717
  47. Elma Karakaş, D., Kaya, M., & Horoz, S., "Efficient hydrogen generation from the NaBH4 methanolysis by waste material: banana peel," Carbon Letters, 32(6), 1593-1601, 2022. https://doi.org/10.1007/s42823-022-00391-1
  48. Kaya, M., Bekiroğullari, M., & Saka, C., "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, 2019. https://doi.org/10.1002/er.4548
  49. Saka, C., "Facile fabrication of P-doped g-C3N4 particles with nitrogen vacancies for efficient dehydrogenation of sodium borohydride methanolysis," Fuel, 313, 122688, 2022. https://doi.org/10.1016/j.fuel.2021.122688
  50. Saka, C., "Use of two-component methanol/glycerol solvent system as an alternative to single-component solvent systems in hydrogen production with sodium borohydride and design of phosphorus, nitrogen co-doped chitosan/kaolin composite with heterojunction as metal-free catalyst," International Journal of Hydrogen Energy, 98, 1007-1019, 2025. https://doi.org/10.1016/j.ijhydene.2024.12.134
  51. Karakaş, D. E., Kaya, M.,, & Horoz, S., "Catalytic activites of a biomaterial (sumac) catalyst in sodium borohyride methanolysis reactions," Journal of Molecular Structure, 1273, 134276, 2023. https://doi.org/10.1016/j.molstruc.2022.134276
  52. Ekinci, S., & Onat, E. "Activated carbon assisted cobalt catalyst for hydrogen production: synthesis and characterization." Balıkesir Üniversitesi Fen Bilimleri Enstitüsü Dergisi, 26(2), 455-471, 2024. https://doi.org/10.25092/baunfbed.1297146
  53. Onat, E., Ekinci, S., Izgi, M. S., Erkan, E., Atiç, S., Kocaman, B., & Tümen, V. "Sustainable hydrogen production from NaBH4 using Co@CHE Catalyst: Experimental and MLP-Based modeling for autonomous fuel systems." Fuel, 406, 136999, 2026. https://doi.org/10.1016/j.fuel.2025.136999
  54. Onat, E., Alan, Y., Savcı, A., Ekinci, S., & İzgi, M. S. "Green-synthesized Co@VHE nanocatalyst from Verbascum insulare for enhanced hydrogen generation and biological applications." Biomass and Bioenergy, 204, 108435, 2026. https://doi.org/10.1016/j.biombioe.2025.108435
  55. Onat, E., İzgi, M. S., Şahin, Ö., & Ekinci, S. "Enhanced Hydrogen Production from Sucrose-Derived Carbon Quantum Dots-Supported Ru Catalysts: A Comparative Study of KBH4 and NaBH4 Hydrolysis." Renewable Energy, 123692, 2025. https://doi.org/10.1016/j.renene.2025.123692
  56. Gokkus, K., Ozbal, A., Senturan, U. M., Gür, M., & Bütün, V., "Synthesis of azo polymers and their catalytic performance in hydrogen production via NaBH4 methanolysis," Materials Research Bulletin, 180, 113009, 2024. https://doi.org/10.1016/j.materresbull.2024.113009
  57. Gao, Z., Ding, C., Wang, J., Ding, G., Xue, Y., Zhang, Y.,. & Gao, X., "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, 2019. https://doi.org/10.1016/j.ijhydene.2019.02.008
  58. Sahaym, U., & Norton, M. G., "Advances in the application of nanotechnology in enabling a ‘hydrogen economy’," Journal of Materials Science, 43(16), 5395-5429, 2008. https://doi.org/10.1007/s10853-008-2749-0
  59. Saka, C., Yıldız, D., Kaya, S., Caglar, A., Elitok, D., Yaylı, E.,. & Kivrak, H., "A novel hazelnutt bagasse based activated carbon as sodium borohydride methanolysis and electrooxidation catalyst," International Journal of Hydrogen Energy, 48(65), 25339-25353, 2023. https://doi.org/10.1016/j.ijhydene.2023.03.261
  60. F Abdulaziz, F., El-Tantawy, A. I., Humaidi, J. R., Aljaloud, A. S., Azhary, A., Alanazi, A. A.,. & Taha, T. A. M., "Structure-performance relationship of SrTiO3/S@ g-C3N4 nanocomposites for highly active hydrogen production via NaBH4 methanolysis," Diamond and Related Materials, 148, 111389, 2024. https://doi.org/10.1016/j.diamond.2024.111389
  61. Han, Y., Ma, J., Wang, X., Wang, Y., Zhang, K., Cao, Z.,. & Li, G., "Preparation of Co–P–B/foam Ni catalyst and its catalytic performance for hydrogen production by hydrolysis of NaBH4 solution," Fuel, 372, 132262, 2024. https://doi.org/10.1016/j.fuel.2024.132262
  62. Asmae, B., Ahmed, B., Benaouda, B., Saleh, Y. S. G., Benderdouche, N., Ali, Ç.,. & Michalkiewicz, B., "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, 2025. https://doi.org/10.1016/j.jtice.2025.106011
  63. Zhang, Y., Zhang, C., Li, W., Xiao, Q., Jiao, F., Xu, S.,. & Cao, W., "Reaction mechanism of stearic acid pyrolysis via reactive molecular dynamics simulation and TG-IR technology," Renewable Energy, 217, 119115, 2023. https://doi.org/10.1016/j.renene.2023.119115
  64. Khan, M. S. J., Alkhadher, S. A. A., Sidek, L. M., Kamal, T., Asiri, A. M., Khan, S. B.,. & Ahmed, A. N., "Metal nanoparticles entrapment in chitosan-carbon black composite hydrogel towards sustainable environmental solutions," International Journal of Biological Macromolecules, 296, 139717, 2025. https://doi.org/10.1016/j.ijbiomac.2025.139717
  65. Karakaş, D. E., Kaya, M.,, & Horoz, S., "Catalytic activites of a biomaterial (sumac) catalyst in sodium borohyride methanolysis reactions," Journal of Molecular Structure, 1273, 134276, 2023. https://doi.org/10.1016/j.molstruc.2022.134276
  66. Gao, Z., Ding, C., Wang, J., Ding, G., Xue, Y., Zhang, Y.,. & Gao, X., "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, 2019. https://doi.org/10.1016/j.ijhydene.2019.02.008