Research progress in hydrogen production from decomposition of ammonia borane and its regeneration

doi:10.16085/j.issn.1000-6613.2019-0482

Abstract

Abstract:

Ammonia borane is one of the most promising hydrogen storage materials because of its high hydrogen-storage density (152.9g/L), mild hydrogen release conditions, non-toxicity, and easy storage and transportation for stable solid state at room temperature. In this paper, the recent progresses of ammonia borane for hydrogen production by thermolysis, methanolysis and hydrolysis in the presence of different catalysts and regeneration of ammonia borane by recycling the by-products are reviewed. The research on thermolysis of ammonia borane mainly focuses on reducing temperature and inhibiting the formation of gaseous by-products. The research hotspots of hydrogen production by hydrolysis or alcoholysis of ammonia borane are binary or ternary non-precious metal nano core shell or supported catalysts. Compared with ammonia borane thermolysis, hydrolysis or methanolysis are more practical ways of hydrogen generation from ammonia borane due to mild conditions and rapid hydrogen generation rate. The biggest challenge of ammonia borane as a hydrogen storage material is its regeneration problem. The by-product from ammonia borane decomposition and dehydrogenation cannot be directly hydrogenated to regenerate ammonia borane, and it is necessary to carry out regeneration off-board through a series of reactions. It is suggested that the regeneration of ammonia borane will be the focus in the future research.

Key words: ammonia borane, hydrogen, catalyst, hydrogen storage material, regeneration

摘要：

氨硼烷具有储氢密度高（152.9g/L）、放氢条件温和、无毒以及常温下为稳定的固体而易于储运等特点而成为最有前景的储氢材料之一。本文综述了近年来氨硼烷在不同催化剂作用下，通过热解、醇解和水解这3种方式制氢以及分解后的副产物循环再生氨硼烷的研究进展。分析讨论了氨硼烷的热解制氢研究主要集中在降低温度和抑制气态副产物的生成这两方面，而水解或醇解制氢的研究热点是二元或三元非贵金属纳米核壳或负载型催化剂。与氨硼烷的热解相比，水解或醇解由于条件温和、制氢速度快而更具实用性。指出氨硼烷作为储氢材料最大的挑战是其再生问题，氨硼烷分解脱氢后的副产物不能直接氢化而再生氨硼烷，需要通过一系列反应来进行间接的离线再生，因此氨硼烷的再生将是今后的重点研究方向。

关键词: 氨硼烷, 氢, 催化剂, 储氢材料, 再生

CLC Number:

TQ426.8

Yan LI,Yuzhen DENG,Jingling YU,Sifang LI. Research progress in hydrogen production from decomposition of ammonia borane and its regeneration[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5330-5338.

李燕,邓雨真,俞晶铃,黎四芳. 氨硼烷分解制氢及其再生的研究进展[J]. 化工进展, 2019, 38(12): 5330-5338.

Figures/Tables 3

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催化剂	n(Catalyst)/n(AB)	T/K	氢气产生速率/mL·min^-1·g_catalyst ^-1	TOF/mol_H2·min^-1·mol_catalyst ^-1	E_a /kJ·mol^-1	参考文献
Ni₅P₄	0.02	298	—	22.0	39.00	[15]
CuO-1	0.06	318	294	—	49.20	[5]
Co/石墨烯	0.05	298	—	13.8	32.75	[16]
3% Ni/ZIF-8	0.03	298	—	85.7	42.70	[17]
Co/MIL-101-1-U	0.02	298	—	51.4	31.30	[18]

催化剂	n(Catalyst)/n(AB)	T/K	氢气产生速率/mL·min^-1·g_catalyst ^-1	TOF/mol_H2·min^-1·mol_catalyst ^-1	E_a /kJ·mol^-1	参考文献
Ni₅P₄	0.02	298	—	22.0	39.00	[15]
CuO-1	0.06	318	294	—	49.20	[5]
Co/石墨烯	0.05	298	—	13.8	32.75	[16]
3% Ni/ZIF-8	0.03	298	—	85.7	42.70	[17]
Co/MIL-101-1-U	0.02	298	—	51.4	31.30	[18]

催化剂	n(catalyst)/n(AB)	温度T/K	氢气产生速率/mL·min^-1·g_catalyst ^-1	TOF/mol_H2·min^-1·mol_catalyst ^-1	E _a/kJ·mol^-1	参考文献
Fe_0.3Co_0.7	0.120	293	8945.50	—	16.30	[20]
Co_0.50Cu_0.50/NPs	0.083	333	10000.56	—	38.12	[21]
Co_0.52Cu_0.48	—	298	2179.00	3.40	33.70	[24]
Cu_0.2@Co_0.8	—	298	1364.00	—	59.10	[26]
Co_0.9Mo_0.1	0.060	298	—	14.90min^-1	51.00	[23]
Co@SiO₂/Ag	0.020	298	—	10.10min^-1	25.60	[30]
Ni_0.19Cu_0.81	—	298	2066.00	2.70	33.30	[31]
AuCo@MIL-101	0.017	298	—	23.50	—	[22]
Pd@Co@MIL-101	0.011	303	—	51.00	22.00	[27]
CuCo/MIL-101-1-U	0.020	298	—	51.70	30.50	[18]
Cu@Co/rGO	0.100	298	—	8.36	51.30	[28]
Cu_0.49Co_0.51/C	0.033	298	—	45.00	51.90	[35]
Co_0.9Ni_0.1/石墨烯	0.050	298	—	16.40	13.49	[36]
Ru@Co/CCF	—	303	—	139.59mol_H2·min^-1·mol_Ru ^-1	57.02	[29]

催化剂	n(catalyst)/n(AB)	温度T/K	氢气产生速率/mL·min^-1·g_catalyst ^-1	TOF/mol_H2·min^-1·mol_catalyst ^-1	E _a/kJ·mol^-1	参考文献
Fe_0.3Co_0.7	0.120	293	8945.50	—	16.30	[20]
Co_0.50Cu_0.50/NPs	0.083	333	10000.56	—	38.12	[21]
Co_0.52Cu_0.48	—	298	2179.00	3.40	33.70	[24]
Cu_0.2@Co_0.8	—	298	1364.00	—	59.10	[26]
Co_0.9Mo_0.1	0.060	298	—	14.90min^-1	51.00	[23]
Co@SiO₂/Ag	0.020	298	—	10.10min^-1	25.60	[30]
Ni_0.19Cu_0.81	—	298	2066.00	2.70	33.30	[31]
AuCo@MIL-101	0.017	298	—	23.50	—	[22]
Pd@Co@MIL-101	0.011	303	—	51.00	22.00	[27]
CuCo/MIL-101-1-U	0.020	298	—	51.70	30.50	[18]
Cu@Co/rGO	0.100	298	—	8.36	51.30	[28]
Cu_0.49Co_0.51/C	0.033	298	—	45.00	51.90	[35]
Co_0.9Ni_0.1/石墨烯	0.050	298	—	16.40	13.49	[36]
Ru@Co/CCF	—	303	—	139.59mol_H2·min^-1·mol_Ru ^-1	57.02	[29]

催化剂	n(catalyst)/n(AB)	T/K	氢气产生速率/mL·min^-1·g_catalyst ^-1	TOF/ mol_H2·min^-1·mol_catalyst ^-1	E _a/kJ·mol^-1	参考文献
Cu_0.4@Co_0.5Ni_0.1	0.040	298	7340.8	—	36.08	[41]
Cu_0.3@Fe_0.1Co_0.6	—	298	6674.2	10.50	38.75	[40]
Cu_0.81@Mo_0.09Co_0.10	0.040	298	—	49.60	22.20	[42]
Cu@FeCoNi/石墨烯	0.040	298	---	20.93	31.82	[43]
Cu_0.8Ni_0.1Co_0.1@MIL-101	0.027	298	---	70.10	29.10	[44]