Download PDF
Open Access
CC BY 4.0 · Sustainability & Circularity NOW 2025; 02: a25082332
DOI: 10.1055/a-2508-2332
Rapid Communication

Beyond Hydrolysis: Scalable, On-Demand Dihydrogen Release from NaBH4 Enables Circular and Sustainable Process Design

Authors

  • Pier W. Wessels

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

  • Caroline J. Verhoef

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

  • Florenz Buß

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

  • Valentin Geiger

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

  • G. Bas de Jong

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

  • Tim Wesselingh

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

  • Philip Germanacos

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

  • J. Chris Slootweg 

    1   Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD Amsterdam, the Netherlands

Funding Information This research is supported financially by the project Sustainable Hydrogen Integrated Propulsion Drives (SH2IPDRIVE), which has received funding from RvO (reference number MOB21013) through the RDM regulation of the Ministry of Economic Affairs and Climate Policy, as well as H2Fuel B.V. and a RVO/TKI Chemistry PPS-project subsidy (CHEMIE.PJT.2022.001).
Further Information
  Permissions and Reprints All articles of this category


Graphical Abstract

Preview

Abstract

Hydrogen storage in its elemental form poses significant safety and economic challenges. Metal hydrides, particularly sodium borohydride, offer a promising alternative because of their superior safety profiles and enhanced transportability. This study presents a scalable hydrogen release system based on sodium borohydride and commercially available alcohols and acids. The system enables rapid, controlled hydrogen generation, achieving quantitative yields. Quantum chemical calculations were performed to propose a mechanism for the alcoholysis of NaBH4 with isopropyl alcohol (IPA) and acid present. It was demonstrated that the reaction proceeds via isopropoxy-substituted borane derivatives BH(3−n)(O i Pr) n (for n = 0, 1, 2, 3), which can form Lewis acid–base adducts with IPA. These Lewis acid–base adducts serve as reaction complexes for σ-bond metathesis, upon which an equivalent of hydrogen gas is released. Notably, the spent fuel can be regenerated to sodium borohydride using established chemical reactions, ensuring the system's sustainability and applicability for larger-scale hydrogen production.

Keywords

Hydrogen storage - NaBH4 - Energy transition - Alcoholysis - Semi-alcoholysis

Supplementary Material



Publication History

Received: 25 November 2024

Accepted after revision: 23 December 2024

Accepted Manuscript online:
24 December 2024

Article published online:
07 February 2025

© 2025. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting unrestricted use, distribution, and reproduction so long as the original work is properly cited. (https://creativecommons.org/licenses/by/4.0/).

Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany

Bibliographical Record
Pier W. Wessels, Caroline J. Verhoef, Florenz Buß, Valentin Geiger, G. Bas de Jong, Tim Wesselingh, Philip Germanacos, J. Chris Slootweg. Beyond Hydrolysis: Scalable, On-Demand Dihydrogen Release from NaBH4 Enables Circular and Sustainable Process Design. Sustainability & Circularity NOW 2025; 02: a25082332.
DOI: 10.1055/a-2508-2332
 

  • References

  • 1 Rasul MG, Hazrat MA, Sattar MA, Jahirul MI, Shearer MJ. The Future of Hydrogen: Challenges on Production, Storage and Applications. Energy Convers. Manag. 2022; 272: 116326
    Search in Google Scholar
  • 2 Zhang T, Uratani J, Huang Y, Xu L, Griffiths S, Ding Y. Hydrogen Liquefaction and Storage: Recent Progress and Perspectives. Renewable Sustainable Energy Rev. 2023; 176: 113204
    Search in Google Scholar
  • 3 Li H, Niu R, Li W, Lu H, Cairney J, Chen Y.-S. Hydrogen in Pipeline Steels: Recent Advances in Characterization and Embrittlement Mitigation. J. Nat. Gas Sci. Eng. 2022; 105: 104709
    Search in Google Scholar
  • 4 Hormaza Mejia A, Brouwer J, Mac Kinnon M. Hydrogen Leaks at the Same Rate as Natural Gas in Typical Low-Pressure Gas Infrastructure. Int. J. Hydrogen Energy 2020; 45 (15) 8810-8826
    Search in Google Scholar
  • 5 Yang M, Hunger R, Berrettoni S, Sprecher B, Wang B. A Review of Hydrogen Storage and Transport Technologies. Clean Energy 2023; 7 (01) 190-216
    Search in Google Scholar
  • 6 Züttel A. Hydrogen Storage Methods. Naturwissenschaften 2004; 91 (04) 157-172
    Search in Google Scholar
  • 7 Schlapbach L, Züttel A. Hydrogen-Storage Materials for Mobile Applications. Nature 2001; 414: 353
    Search in Google Scholar
  • 8 Aziz M, Wijayanta AT, Nandiyanto A. BD. Ammonia as Effective Hydrogen Storage: A Review on Production, Storage and Utilization. Energies 2020; 13 (12) 3062
    Search in Google Scholar
  • 9 Chu C, Wu K, Luo B, Cao Q, Zhang H. Hydrogen Storage by Liquid Organic Hydrogen Carriers: Catalyst, Renewable Carrier, and Technology – A Review. Carbon Resour. Convers. 2023; 6 (04) 334-351
    Search in Google Scholar
  • 10 Negro V, Noussan M, Chiaramonti D. The Potential Role of Ammonia for Hydrogen Storage and Transport: A Critical Review of Challenges and Opportunities. Energies 2023; 16 (17) 6192
    Search in Google Scholar
  • 11 Spatolisano E, Pellegrini LA, De Angelis AR, Cattaneo S, Roccaro E. Ammonia as a Carbon-Free Energy Carrier: NH3 Cracking to H2 . Ind. Eng. Chem. Res. 2023; 62 (28) 10813-10827
    Search in Google Scholar
  • 12 Makepeace JW, He T, Weidenthaler C, Jensen TR, Chang F, Vegge T, Ngene P, Kojima Y, De Jongh PE, Chen P, David W. IF. Reversible Ammonia-Based and Liquid Organic Hydrogen Carriers for High-Density Hydrogen Storage: Recent Progress. Int. J. Hydrogen Energy 2019; 44 (15) 7746-7767
    Search in Google Scholar
  • 13 Modisha PM, Ouma C. NM, Garidzirai R, Wasserscheid P, Bessarabov D. The Prospect of Hydrogen Storage Using Liquid Organic Hydrogen Carriers. Energy Fuels 2019; 33 (04) 2778-2796
    Search in Google Scholar
  • 14 Klopčič N, Grimmer I, Winkler F, Sartory M, Trattner A. A Review on Metal Hydride Materials for Hydrogen Storage. J. Energy Storage 2023; 72: 108456
    Search in Google Scholar
  • 15 Dematteis EM, Amdisen MB, Autrey T, Barale J, Bowden ME, Buckley CE, Cho YW, Deledda S, Dornheim M, De Jongh P, Grinderslev JB, Gizer G, Gulino V, Hauback BC, Heere M, Heo TW, Humphries TD, Jensen TR, Kang SY, Lee Y.-S, Li H.-W, Li S, Møller KT, Ngene P, Orimo S, Paskevicius M, Polanski M, Takagi S, Wan L, Wood BC, Hirscher M, Baricco M. Hydrogen Storage in Complex Hydrides: Past Activities and New Trends. Prog. Energy 2022; 4 (03) 032009
    Search in Google Scholar
  • 16 Song M, Zhang L, Wu F, Zhang H, Zhao H, Chen L, Li H. Recent Advances of Magnesium Hydride as an Energy Storage Material. J. Mater. Sci. Technol. 2023; 149: 99-111
    Search in Google Scholar
  • 17 Chen Z, Ma Z, Zheng J, Li X, Akiba E, Li H.-W. Perspectives and Challenges of Hydrogen Storage in Solid-State Hydrides. Chin. J. Chem. Eng. 2021; 29: 1-12
    Search in Google Scholar
  • 18 Schlesinger HI, Brown HC, Finholt AE, Gilbreath JR, Hoekstra HR, Hyde EK. Sodium Borohydride, Its Hydrolysis and Its Use as a Reducing Agent and in the Generation of Hydrogen1. J. Am. Chem. Soc. 1953; 75 (01) 215-219
    Search in Google Scholar
  • 19 Berger A, Ibrahim A, Hales TA, D’Angelo AM, Buckley CE, Paskevicius M. Alkali Metal Alkoxyborate Ester Salts; a Contemporary Look at Old Compounds. Dalton Trans. 2024; 53 (08) 3638-3653
    Search in Google Scholar
  • 20 Go No-Go Recommendation for Sodium Borohydride for On-Board Vehicular Hydrogen Storage. NREL/MP–150-42220, 1219597, 5642; 2007; p NREL/MP–150-42220, 1219597, 5642
  • 21 Dragan M. Hydrogen Storage in Complex Metal Hydrides NaBH4: Hydrolysis Reaction and Experimental Strategies. Catalysts 2022; 12: 356
    Search in Google Scholar
  • 22 Kolodziejski M. Review of Hydrogen-Based Propulsion Systems in the Maritime Sector. Arch. Thermodyn. 2024; 44: 335-380
    Search in Google Scholar
  • 23 Kwon S, Kang S, Kim T. Development of NaBH4-Based Hydrogen Generator for Fuel Cell Unmanned Aerial Vehicles with Movable Fuel Cartridge. Energy Procedia 2019; 158: 1930-1935
    Search in Google Scholar
  • 24 Hayouk E, Schechter A, Avrahami I. A Novel Micro-Reactor for Hydrogen Production from Solid NaBH4 Hydrolysis in a Dual-Cycle Methodology. Heliyon 2024; 10 (04) e25744
    Search in Google Scholar
  • 25 Abdelhamid HN. A Review on Hydrogen Generation from the Hydrolysis of Sodium Borohydride. Int. J. Hydrogen Energy 2021; 46 (01) 726-765
    Search in Google Scholar
  • 26 Andrieux J, Laversenne L, Krol O, Chiriac R, Bouajila Z, Tenu R, Counioux JJ, Goutaudier C. Revision of the NaBO2–H2O Phase Diagram for Optimized Yield in the H2 Generation through NaBH4 Hydrolysis. Int. J. Hydrogen Energy 2012; 37 (07) 5798-5810
    Search in Google Scholar
  • 27 Hannauer J, Demirci UB, Pastor G, Geantet C, Herrmann JM, Miele P. Hydrogen Release through Catalyzed Methanolysis of Solid Sodium Borohydride. Energy Environ. Sci. 2010; 3 (11) 1796-1803
    Search in Google Scholar
  • 28 Retnamma R, Novais AQ, Rangel CM. Kinetics of Hydrolysis of Sodium Borohydride for Hydrogen Production in Fuel Cell Applications: A Review. Int. J. Hydrogen Energy 2011; 36 (16) 9772-9790
    Search in Google Scholar
  • 29 Xueping Z, Maowen G, Chunrong L, Chao L, Shenglin L, Ping L, Zhuorui L, Zengqiang T. Effect of Catalysts on Hydrolysis Hydrogen Release of Sodium Borohydride. Rare Met. Mater. Eng. 2018; 47 (03) 754-758
    Search in Google Scholar
  • 30 Demirci UB. Exploring the Technological Maturity of Hydrogen Production by Hydrolysis of Sodium Borohydride. Int. J. Hydrogen Energy 2023; 48 (76) 29682-29698
    Search in Google Scholar
  • 31 Ramya K, Dhathathreyan KS, Sreenivas J, Kumar S, Narasimhan S. Hydrogen Production by Alcoholysis of Sodium Borohydride: H2 by Alcoholysis of NaBH4 . Int. J. Energy Res. 2013; 37 (14) 1889-1895
    Search in Google Scholar
  • 32 Saka C. Highly Active and Durable Hydrogen Release in NaBH4 Methanolysis Reaction with Sulphur and Phosphorus-Doped Metal-Free Microalgal Carbon Nanoparticles. Appl. Catal., B 2021; 292: 120165
    Search in Google Scholar
  • 33 Uceda RG, Roldan-Molina E, Navarro J. AR, Oltra JE. The Aza Diels-Alder Reaction on Brominated Conjugated Dienes. Eur. J. Org. Chem. 2021; 2021 (13) 2003-2005
    Search in Google Scholar
  • 34 Schopper N, Sprenger J. AP, Zapf L, Reiss GJ, Ignat’ev NV, Finze M. Alkoxycyanoborates: Metal Salts and Low-Viscosity Ionic Liquids. New J. Chem. 2021; 45 (33) 14973-14987
    Search in Google Scholar
  • 35 General Procedure: In an RBF equipped with a stirring bar, NaBH4 (1.00 equiv) was added to alcohol (12.0 eq.). The reaction mixture was stirred for x min at x °C and the solvent was removed in vacuo. The residue was dried in a vacuum oven at 80 °C for 24 h.
  • 36 The Economics of Sodium Sulphate. 8th ed. Roskill Information Services. Ed. Roskill Information Services; London: 1999
    Search in Google Scholar
  • 37 To a solution of isopropanol (34.5 g, 43.9 mL, 24.0 equiv, 574 mmol) and NaBH4 (1.81 g, 2.00 equiv, 47.8 mmol), a solution of isopropanol (1 mL) and H2SO4 (2.39 g, 1.30 mL, 98 wt %, 23.9 mmol, 1.00 equiv) was added dropwise over 30 min. The reaction was stirred at RT for 1 h. Gas evolution was measured modified setup of Chen et al. The resolution suspension was attached to a fractional distillation setup, and triisopropyl borate was obtained as an azeotropic mixture with IPA in a ratio of 1:0.12 IPA:B(OiPr)3. The analytical data are in accordance with previous publications.
  • 38 Zheng F, Rassat SD, Helderandt DJ, Caldwell DD, Aardahl CL, Autrey T, Linehan JC, Rappé KG. Automated Gas Burette System for Evolved Hydrogen Measurements. Rev. Sci. Instrum. 2008; 79 (08) 084103
    Search in Google Scholar
  • 39 Saka C, Balbay A. Influence of Process Parameters on Enhanced Hydrogen Evolution from Alcoholysis of Sodium Borohydride with a Boric Acid Catalyst. Int. J. Hydrogen Energy 2020; 45 (32) 16193-16200
    Search in Google Scholar
  • 40 Balbay A. The Effect of the Concentration of Hydrochloric Acid and Acetic Acid Aqueous Solution for Fast Hydrogen Production from Methanol Solution of NaBH4. Int. J. Hydrogen Energy 2018; 43 (31) 14265-14272
    Search in Google Scholar
  • 41 Avci Hansu T. Study of the Activity of a Novel Green Catalyst Used in the Production of Hydrogen from Methanolysis of Sodium Borohydride. MANAS J. Eng. 2021 9 (2) 115-121
  • 42 Jin Liangyu, Zhang Wenxu. Production Method of High Purity Triisopropyl Borate. CN103204866A, July 17, 2013 https://patents.google.com/patent/CN103204866A/en
  • 43 Adams L, Hosmane SN, Eklund JE, Wang J, Hosmane NS. A New Synthetic Route to Boron-10 Enriched Pentaborane(9) from Boric Acid and Its Conversion to Anti – 10B18H22 . J. Am. Chem. Soc. 2002; 124 (25) 7292-7293
    Search in Google Scholar
  • 44 Schlesinger HI, Brown HC, Finholt AE. The Preparation of Sodium Borohydride by the High Temperature Reaction of Sodium Hydride with Borate Esters1 . J. Am. Chem. Soc. 1953; 75 (01) 205-209
    Search in Google Scholar
  • 45 In a glovebox, a Schlenk tube was filled with a suspension of white oil (3 mL) and NaH (0.140 g, 5.85 mmol, 4.40 equiv), and triisopropyl borate (0.250 g, 1.33 mmol, 0.30 mL) was added. The Schlenk tube was buried in a sand bath and stirred at 270 °C for 4 h. The reaction was cooled to room temperature and extracted with isopropanol (3 × 10 mL). A second extraction with isopropylamine (3 × 3 mL) was performed, and the resulting solution was evaporated in vacuo. The residue was dried in a vacuum oven at 80 °C for 24 h and NaBH4 was obtained as a colorless solid (0.03 mg, 0.64 mmol, 48%). The analytical data are in accordance with previous publications.
  • 46 Chen Z, Ma Z, Zheng J, Li X, Akiba E, Li H.-W. Perspectives and Challenges of Hydrogen Storage in Solid-State Hydrides. Chin. J. Chem. Eng. 2021; 29: 1-12
    Search in Google Scholar
  • 47 Schlesinger HI, Brown HC, Finholt AE. The Preparation of Sodium Borohydride by the High Temperature Reaction of Sodium Hydride with Borate Esters1 . J. Am. Chem. Soc. 1953; 75 (01) 205-209
    Search in Google Scholar
  • 48 Song M, Zhang L, Wu F, Zhang H, Zhao H, Chen L, Li H. Recent Advances of Magnesium Hydride as an Energy Storage Material. J. Mater. Sci. Technol. 2023; 149: 99-111
    Search in Google Scholar