DOI: https://doi.org/10.9767/bcrec.20634

Effect of Sodium Borohydride to Ferric Chloride Molar Ratios on Nanoscale Zero-Valent Iron for Hydrogen Generation from Formic Acid

1Waste Management and Resources Recovery (WeResCue) Group, Faculty of Chemical Engineering, Universiti Teknologi MARA, Cawangan Pulau Pinang, 13500 Permatang Pauh, Pulau Pinang, Malaysia

2Graphite Signature Sdn Bhd, 31650 Ipoh, Malaysia

Received: 13 Jan 2026; Revised: 4 Mar 2026; Accepted: 5 Mar 2026; Available online: 9 Mar 2026; Published: 30 Aug 2026.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2026 by Authors, Published by BCREC Publishing Group
Creative Commons License This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.
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Abstract

Hydrogen generation from formic acid using nanoscale zero-valent iron (nZVI) represents a promising route for low-cost and sustainable hydrogen production. However, the effect of sodium borohydride (NaBH₄) to ferric chloride (FeCl₃) molar ratio on nZVI synthesis and performance remains insufficiently explored. This study investigated how varying NaBH₄:FeCl₃ molar ratios affect nZVI synthesis characteristics and its hydrogen generation efficiency from formic acid, which acts as a safe and easily handled hydrogen carrier. nZVI was synthesized through a one-step liquid-phase chemical reduction method using NaBH₄:FeCl₃ ratios ranging from 4.4:1 to 8.8:1. UV–Vis spectroscopy indicated that the 4.4:1 ratio yielded the highest nZVI formation, reflecting optimal reduction efficiency and particle formation. Hydrogen generation experiments conducted in a closed reactor equipped with a water displacement system revealed that nZVI synthesized at the 4.4:1 ratio achieved the maximum hydrogen volume (98 mL), which progressively declined to 53 mL at the 8.8:1 ratio. These findings demonstrate that precursor molar ratios significantly influence nZVI formation, stability, and reactivity toward hydrogen evolution. An optimal NaBH₄:FeCl₃ ratio of 4.4:1 was identified for maximizing nZVI formation and hydrogen volume, providing valuable insights for developing scalable formic acid–based hydrogen generation systems. Copyright © 2026 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Keywords: Hydrogen; Nanoscale Zero-Valent Iron; Formic acid; Sodium borohydride; Molar Ratio
Funding: Ministry of Higher Education (MOHE), Malaysia under contract FRGS/1/2022/TK08/UITM/02/5; Ministry of Higher Education (MOHE), Malaysia under contract FRGS/1/2023/TK08/UITM/02/10

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Section: 3rd International Symposium of Reaction Engineering, Catalysis and Sustainable Energy 2025 (RECASE 2025)
Language : EN
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  1. Ramachandran, R., Menon, R.K. (1998). An overview of industrial uses of hydrogen. Int. J. Hydrogen Energy, 23, 593–598. DOI: 10.1016/s0360-3199(97)00112-2
  2. Liu, W., Zuo, H., Wang, J., Xue, Q., Ren, B., Yang, F. (2021). The production and application of hydrogen in steel industry. Int. J. Hydrogen Energy, 46, 10548–10569. DOI: 10.1016/j.ijhydene.2020.12.123
  3. Mozakka, M., Salimi, M., Hosseinpour, M. (2024). Determining the challenges of transition to a hydrogen economy through developing a quantitative index. International Journal of Hydrogen Energy, 56, 1301–1308. DOI: 10.1016/j.ijhydene.2023.12.297
  4. Gunawardane, K. (2023). Evolution of hydrogen energy and its potential opportunities around the globe. In: Hydrogen Energy Conversion and Management. Elsevier, pp. 3–33. DOI: 10.1016/B978-0-443-15329-7.00007-7
  5. Chang, S.H., Rajuli, M.F. (2024). An overview of pure hydrogen production via electrolysis and hydrolysis. Int. J. Hydrogen Energy, 84, 521–538. DOI: 10.1016/j.ijhydene.2024.08.245
  6. Chang, S.H. (2017). Parametric studies on an innovative waste vegetable oil-based continuous liquid membrane (WVCLM) for Cu(II) ion separation from aqueous solutions. Journal of Industrial and Engineering Chemistry, 50, 102–110. DOI: 10.1016/j.jiec.2017.01.037
  7. Chang, S.H., Jampang, A.O.A. (2021). Green extraction of gold(III) and copper(II) from chloride media by palm kernel fatty acid distillate. Journal of Water Process Engineering, 43. DOI: 10.1016/j.jwpe.2021.102298
  8. Halim, S.F.A., Chang, S.H., Morad, N. (2020). Extraction of Cu(II) ions from aqueous solutions by free fatty acid-rich oils as green extractants. Journal of Water Process Engineering, 33. DOI: 10.1016/j.jwpe.2019.100997
  9. Eppinger, J., Huang, K.W. (2017). Formic Acid as a Hydrogen Energy Carrier. ACS Energy Lett., 2, 188–195. DOI: 10.1021/acsenergylett.6b00574
  10. Wang, X., Meng, Q., Gao, L., Jin, Z., Ge, J., Liu, C., Xing, W. (2018). Recent progress in hydrogen production from formic acid decomposition. Int. J. Hydrogen Energy, 43, 7055–7071. DOI: 10.1016/j.ijhydene.2018.02.146
  11. Singh, A.K., Singh, S., Kumar, A. (2016). Hydrogen energy future with formic acid: A renewable chemical hydrogen storage system. Catal. Sci. Technol. 6, 12–40. DOI: 10.1039/c5cy01276g
  12. Singh, A.K., Rarotra, S., Pasumarthi, V., Mandal, T.K., Bandyopadhyay, D. (2018). Formic acid powered reusable autonomous ferrobots for efficient hydrogen generation under ambient conditions. Journal of Materials Chemistry A, 6(19), 9209–9219. DOI: 10.1039/c8ta02205d
  13. Jamei, M.R., Khosravi, M.R., Anvaripour, B. (2014). A novel ultrasound assisted method in synthesis of NZVI particles. Ultrasonics Sonochemistry, 21(1), 226–233. DOI: 10.1016/j.ultsonch.2013.04.015
  14. Zhang, Y., Tang, Y., Yan, R., Liang, S., Liu, Z., Yang, Y. (2024). Green-synthesized, biochar-supported nZVI from mango kernel residue for aqueous hexavalent chromium removal: Performance, mechanism and regeneration. Chinese Journal of Chemical Engineering, 71, 91–101. DOI: 10.1016/j.cjche.2024.04.009
  15. Sathish, T., Masih, J., Gupta, A., Kumar, A., Raja, L., Singh, V., Al-Enizi, A.M., Pandit, B., Gupta, M., Senthilkumar, N., Yusuf, M. (2024). Sustainable nanoparticles of Non-Zero-valent iron (nZVI) production from various biological wastes. Journal of King Saud University - Science, 36(11), 103553. DOI: 10.1016/j.jksus.2024.103553
  16. Bounab, N., Duclaux, L., Reinert, L., Oumedjbeur, A., Boukhalfa, C., Penhoud, P., Muller, F. (2021). Improvement of zero valent iron nanoparticles by ultrasound-assisted synthesis, study of Cr(VI) removal and application for the treatment of metal surface processing wastewater. Journal of Environmental Chemical Engineering, 9(1), 104773. DOI: 10.1016/j.jece.2020.104773
  17. Pandey, K., Sharma, S., Saha, S. (2022). Advances in design and synthesis of stabilized zero-valent iron nanoparticles for groundwater remediation. Journal of Environmental Chemical Engineering, 10(3), 107993. DOI: 10.1016/j.jece.2022.107993
  18. Yuvakkumar, R., Elango, V., Rajendran, V., Kannan, N. (2011). Preparation and characterization of zero valent Iron nanoparticles. Digest Journal of Nanomaterials and Biostructures, 6(4), 1771–1776
  19. Pasinszki, T., Krebsz, M. (2020). Synthesis and application of zero-valent iron nanoparticles in water treatment, environmental remediation, catalysis, and their biological effects. Nanomaterials, 10. DOI: 10.3390/nano10050917
  20. Boonruam, P., Soisuwan, S., Wattanachai, P., Morillas, H., Upasen, S. (2020). Solvent effect on zero-valent iron nanoparticles (nZVI) preparation and its thermal oxidation characteristic. ASEAN Engineering Journal, 10(2), 1–12. DOI: 10.11113/aej.v10.16525
  21. Song, H.-C., Carraway, E.R., Kim, Y.-H. (2005). Synthesis of Nano-Sized Iron for Reductive Dechlorination. 2. Effects of Synthesis Conditions on Iron Reactivities. Environmental Engineering Research, 10(4), 174–180. DOI: 10.4491/eer.2005.10.4.174
  22. Hwang, Y.H., Kim, D.G., Shin, H.S. (2011). Effects of synthesis conditions on the characteristics and reactivity of nano scale zero valent iron. Applied Catalysis B: Environmental, 105 (1–2), 144–150. DOI: 10.1016/j.apcatb.2011.04.005
  23. Turabik, M., Simsek, U.B. (2017). Effect of synthesis parameters on the particle size of the zero valent iron particles. Inorganic and Nano-Metal Chemistry, 47(7), 1033–1043. DOI: 10.1080/15533174.2016.1219869
  24. Yusuf, S.A., Ismail, S.N.S., Zubairi, M.S.R.M.A., Muthuraman, G., Halim, S.F.A., Chang, S.H. (2025). Hydrogen Production by Formic Acid Decomposition with Nanoscale Zero-Valent Iron (nZVI): Effects of nZVI Dosage, Temperature and Time. Journal of Advanced Research in Fluid Mechanics and Thermal Sciences, 125(1), 158–166. DOI: 10.37934/arfmts.125.1.158166
  25. Bae, S., Collins, R.N., Waite, T.D., Hanna, K. (2018). Advances in Surface Passivation of Nanoscale Zerovalent Iron: A Critical Review. Environmental Science and Technology, 52(21), 12010–12025. DOI: 10.1021/acs.est.8b01734
  26. Visentin, C., Trentin, A.W. da S., Braun, A.B., Thomé, A. (2021). Nano scale zero valent iron production methods applied to contaminated sites remediation: An overview of production and environmental aspects. J. Hazard. Mater. 410, 124614. DOI: 10.1016/j.jhazmat.2020.124614
  27. Rahman, N., Nasir, M., Bharti, M., Samdani, M.S. (2023). Fabrication of Zero-Valent Iron Nanoparticles Impregnated Cross-Linked Chitosan Grafted β-Cyclodextrin for Removal of Cloxacillin from Aqueous Environment. Journal of Inorganic and Organometallic Polymers and Materials, 34(4), 1654–1677. DOI: 10.1007/s10904-023-02907-2
  28. Tang, H., Wang, J., Zhang, S., Pang, H., Wang, X., Chen, Z., Li, M., Song, G., Qiu, M., Yu, S. (2021). Recent advances in nanoscale zero-valent iron-based materials: Characteristics, environmental remediation and challenges. J. Clean. Prod. 319, 128641. DOI: 10.1016/j.jclepro.2021.128641
  29. Chen, K.F., Li, S., Zhang, W.X. (2011). Renewable hydrogen generation by bimetallic zero valent iron nanoparticles. Chemical Engineering Journal, 170(2–3), 562–567. DOI: 10.1016/j.cej.2010.12.019
  30. Shamsuri, S.R.S., Saifudin, K.N., Othman, I.S., Ismail, S., Rashid, M.W.A., Moriga, T. (2024). Synthesis of Ni Nanoparticle with Controlled Morphology via Liquid Phase Reduction Method. Journal of Advanced Research in Micro and Nano Engineering, 24(1), 46–51. DOI: 10.37934/ARMNE.24.1.4651
  31. Gao, Y., Gao, X., Zhang, X. (2023). Hydrogen generation by soluble CO2 reaction with zero-valent iron or scrap iron and the role of weak acids for controlling FeCO3 formation. Sustainable Energy Technologies and Assessments, 56(2), 103061. DOI: 10.1016/J.ENG.2017.01.022
  32. Zhu, S., Zhang, Y., Zhang, Z., Ai, F., Zhang, H., Li, Y., Wang, Y., Zhang, Q. (2023). Ascorbic acid-mediated zero-valent iron enhanced hydrogen production potential of bean dregs and corn stover by photo fermentation. Bioresource Technology, 374, 128761. DOI: 10.1016/j.biortech.2023.128761
  33. Chang, S.H., Jampang, A.O.A., Din, A.T.M. (2025). Adsorption isotherms, kinetics, and thermodynamics of Au(III) on chitosan/palm kernel fatty acid distillate/magnetite nanocomposites. International Journal of Biological Macromolecules, 304. DOI: 10.1016/j.ijbiomac.2025.140913
  34. Chang, S.H., Jampang, A.O.A. (2023). Enhanced adsorption selectivity of Au(III) over Cu(II) from acidic chloride solutions by chitosan/palm kernel fatty acid distillate/magnetite nanocomposites. International Journal of Biological Macromolecules, 252. DOI: 10.1016/j.ijbiomac.2023.126491
  35. Huang, Y.X., Guo, J., Zhang, C., Hu, Z. (2016). Hydrogen production from the dissolution of nano zero valent iron and its effect on anaerobic digestion. Water Research, 88(2), 475–480. DOI: 10.1016/j.watres.2015.10.028

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