Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions

doi:10.1016/j.cjche.2025.02.030

Chinese Journal of Chemical Engineering ›› 2025, Vol. 83 ›› Issue (7): 217-228.DOI: 10.1016/j.cjche.2025.02.030

Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions

Yilun Dong^1,2,3, Kang Xue^1,2,3,4, Zexing He^1,2,3, Chongjun Li^1,2,3, Ruijie Gao^1,2,3,4, Zhenfeng Huang^1,2,3,4, Chengxiang Shi^1,2,3,4, Xiangwen Zhang^1,2,3,4, Lun Pan^1,2,3,4, Jijun Zou^1,2,3,4

1 Key Laboratory for Green Chemical Technology of the Ministry of Education, Institute of Molecular Plus, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
2 National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300072, China;
3 Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China;
4 Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China

Received:2024-11-02 Revised:2025-01-21 Accepted:2025-02-19 Online:2025-07-28 Published:2025-07-28
Contact: Kang Xue,E-mail:xuekang@tju.edu.cn;Jijun Zou,E-mail:jj_zou@tju.edu.cn
Supported by:
The authors appreciate the support from the National Natural Science Foundation of China (22222808, 21978200, 22208330), the Postdoctoral Fellowship Program of CPSF (GZC20241204), the China Postdoctoral Science Foundation-Tianjin Joint Support Program (2023T022TJ) and the Haihe Laboratory of Sustainable Chemical Transformations for financial support.

Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions

Yilun Dong^1,2,3, Kang Xue^1,2,3,4, Zexing He^1,2,3, Chongjun Li^1,2,3, Ruijie Gao^1,2,3,4, Zhenfeng Huang^1,2,3,4, Chengxiang Shi^1,2,3,4, Xiangwen Zhang^1,2,3,4, Lun Pan^1,2,3,4, Jijun Zou^1,2,3,4

1 Key Laboratory for Green Chemical Technology of the Ministry of Education, Institute of Molecular Plus, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
2 National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300072, China;
3 Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China;
4 Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China

通讯作者: Kang Xue,E-mail:xuekang@tju.edu.cn;Jijun Zou,E-mail:jj_zou@tju.edu.cn
基金资助:
The authors appreciate the support from the National Natural Science Foundation of China (22222808, 21978200, 22208330), the Postdoctoral Fellowship Program of CPSF (GZC20241204), the China Postdoctoral Science Foundation-Tianjin Joint Support Program (2023T022TJ) and the Haihe Laboratory of Sustainable Chemical Transformations for financial support.

Abstract

Abstract: The efficient and cost-effective implementation of ammonia borane (AB) hydrolysis dehydrogenation for hydrogen storage is crucial. This study investigated the role of solid acid Amberlyst-15 (A-15) for hydrogen evolution from AB hydrolysis. Notably, AB hydrogen evolution rate can reach 194.15 ml·min^-1 at 30℃, with a low apparent activation energy of 8.20 kJ·mol^-1. After five cycles of reuse, the reaction involving A-15 could keep a conversion rate of about 93%. The AB hydrolysis follows quasi first-order kinetics with respect to the AB concentration and quasi zero-order kinetics with respect to the A-15 mass. According to the characterization results of XRD, ATR-FTIR, and in-situ MS, the boric acid was the dominant hydrolyzate, while water as a hydrogen donor in this reaction. Furthermore, based on the reasoning that hydrogen bonds between A-15 and AB (aq) promotes the diffusion of AB, release of H₂ and the cleavage of OdH bond of H₂O, a possible mechanism was proposed.

Key words: Ammonia borane, Hydrolysis, Hydrogen production, Amberlyst-15, Kinetics

摘要： The efficient and cost-effective implementation of ammonia borane (AB) hydrolysis dehydrogenation for hydrogen storage is crucial. This study investigated the role of solid acid Amberlyst-15 (A-15) for hydrogen evolution from AB hydrolysis. Notably, AB hydrogen evolution rate can reach 194.15 ml·min^-1 at 30℃, with a low apparent activation energy of 8.20 kJ·mol^-1. After five cycles of reuse, the reaction involving A-15 could keep a conversion rate of about 93%. The AB hydrolysis follows quasi first-order kinetics with respect to the AB concentration and quasi zero-order kinetics with respect to the A-15 mass. According to the characterization results of XRD, ATR-FTIR, and in-situ MS, the boric acid was the dominant hydrolyzate, while water as a hydrogen donor in this reaction. Furthermore, based on the reasoning that hydrogen bonds between A-15 and AB (aq) promotes the diffusion of AB, release of H₂ and the cleavage of OdH bond of H₂O, a possible mechanism was proposed.

关键词: Ammonia borane, Hydrolysis, Hydrogen production, Amberlyst-15, Kinetics

Yilun Dong, Kang Xue, Zexing He, Chongjun Li, Ruijie Gao, Zhenfeng Huang, Chengxiang Shi, Xiangwen Zhang, Lun Pan, Jijun Zou. Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions[J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 217-228.

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Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions

Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions

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