水解制氢材料研究进展

doi:10.15541/jim20200215

摘要/Abstract

摘要：

水解制氢是一种常温常压下的现场制氢方式。由于水解制氢材料氢含量高, 储存容易, 运输方便, 安全可靠, 一直受到研究者们的关注。本文综述了近年来水解制氢材料的总体发展情况, 介绍了三类主要的水解制氢材料, 包括硼氢化物(NaBH₄, NH₃·BH₃)、金属(Mg, Al)以及金属氢化物(MgH₂), 对不同材料的制氢原理、主要问题、催化剂与材料设计进行了详细介绍, 比较了不同体系的特点与制氢成本, 并对水解制氢及水解制氢材料的现状和商业化面临的困难做了评价, 最后对未来的发展方向进行了展望。

关键词: 制氢, 水解, 金属, 金属氢化物, 硼氢化物, 制氢成本

Abstract:

Hydrolysis is a unique method for hydrogen generation at ambient condition. Widespread attentions have been paid to materials for hydrogen generation via hydrolysis due to several advantages: high theoretical hydrogen capacity, moderate storage and operation condition, safety, etc. In this paper, recent progress and development in this area were reviewed. Three types of materials including borohydride (NaBH₄, NH₃·BH₃), metal (Mg, Al), and metal hydride (MgH₂) were introduced. Several issues about them were discussed specifically: mechanism, main problems, designments of catalysts and materials, etc. Based on these discussions, we compared the different materials mentioned above, commented their current performances and practical difficulties. At last, prospects in this field were presented.

Key words: hydrogen generation, hydrolysis, metal, metal hydride, borohydride, cost of hydrogen

中图分类号:

TQ174

邓霁峰, 陈顺鹏, 武晓娟, 郑捷, 李星国. 水解制氢材料研究进展[J]. 无机材料学报, 2021, 36(1): 1-8.

DENG Jifeng, CHEN Shunpeng, WU Xiaojuan, ZHENG Jie, LI Xingguo. Recent Progress on Materials for Hydrogen Generation via Hydrolysis[J]. Journal of Inorganic Materials, 2021, 36(1): 1-8.

图/表 10

图1 NaBH4的均相催化(A)和异相催化(B)水解反应机理 [13]

Fig. 1 Schemes for the mechanisms of homogeneous (A) and heterogeneous (B) hydrolysis of NaBH4[13]

Table 1 Fundamental performances of materials for hydrogen generation via hydrolysis

Material	Molar mass/(g·mol^-1)	Density/(g·cm^-3)	∆H^[6]/(kJ·mol^-1_H2)	C_M(H2)*/wt%	C_M(H2)(H₂O)^#/wt%	C_V(H2)^†/(g_H2·L^-1)
NaBH₄	37.83	1.07	-47.15	21.32	7.34	228.09
NH₃·BH₃	30.86	0.78	-75.67	19.50	7.05	151.60
Mg	24.31	1.74	-352.90	8.29	3.34	144.16
Ca	40.08	1.55	-413.60	5.03	2.65	77.97
Al	26.98	2.70	-284.40	11.21	3.73	302.62
LiH	7.95	0.82	-111.20	25.36	7.06	207.97
NaH	24.00	1.40	-83.70	8.40	4.80	117.60
KH	40.02	1.43	-81.10	5.04	3.47	72.04
MgH₂	26.32	1.45	-138.80	15.32	6.47	222.12
CaH₂	42.09	1.70	-116.05	9.58	5.16	162.84
AlH₃	30.00	1.49	-126.87	20.16	7.20	300.34

图2 NaBH4水解催化剂常用载体[25-26,28-35]

Fig. 2 Supports for catalysts of NaBH4 hydrolysis[25-26,28-35]

图3 Rh/VO2催化NH3·BH3水解的Arrhenius曲线(A),不同催化剂和基底的态密度计算结果(B)[42]

Fig. 3 Arrhenius plot for NH3·BH3 hydrolysis catalyzed by Rh/VO2 (A), calculated PDOS of several catalysts/supports (B)[42]

图4 不同阳离子对于OH-的亲和力与其促进Mg水解转化率的关系[49]

Fig. 4 Relationship between promotion of Mg hydrolysis and affinity to OH- for different cations[49]

图5 Hg促进Al水解的构造和机理示意图[57]

Fig. 5 Scheme of Al hydrolysis mechanism promoted by Hg[57]

图6 MgH2在去离子水(A)和MgCl2 (B)中的反应机理[60]

Fig. 6 Schemes of MgH2 hydrolysis mechanisms in H2O (A) and MgCl2(aq.) (B)[60]

图7 吸氢过后Mg@Pt的透射电镜照片(A)与高分辨透射电镜照片(B)[63]

Fig. 7 TEM (A) and HRTEM (B) images of hydrogenated Mg@Pt composite[63]

表2 主要制氢材料性能对比

Table 2 Performances of main materials for hydrogen production via hydrolysis

Performance	Metal	Metal hydride	Borohydride
Hydrogen capacity of hydrolysis	Low	High	High (affected by dissolution)
Cost	Low	High	High
Complexities of system	Complex	Complex	Relatively simple
Degree of study on hydrolysis	Modest	Rare	Extensive
Storage condition	H₂O & O₂ free	H₂O & O₂ free	H₂O free

表3 常见水解制氢材料的价格及制氢成本估算

Table 3 Prices of materials for hydrogen generation via hydrolysis and their corresponding costs of H2

Prices	Mg	Al	MgH₂	LiH	NaBH₄	NH₃·BH₃
Price of material /(yuan∙kg^-1)	120	80	800	4300	700	60000
Price of H₂ /(yuan∙kg^-1)	1450	710	5200	16960	3280	307700

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