碱性电解水析氢催化剂的研究进展及展望

doi:10.16085/j.issn.1000-6613.2024-1750

摘要/Abstract

摘要：

氢能是推动能源结构转型的理想能源载体，电解水制氢是实现制氢规模化的重要依托手段，碱性电解水因技术成熟、成本低、污染小而具备商业推广可行性。催化剂的催化活性、稳定性及成本是制约碱性电解水析氢技术发展的关键因素。基于此，本文综述了贵金属、过渡金属和碳基材料等碱性析氢催化剂的研究进展。分析了当前主要应用的优化策略对其本征活性的影响，结果表明，催化剂性能的提升得益于对形貌、电子轨道、晶格结构以及载体支撑等多方面因素的综合调控。结合当前实际存在的问题，本文从制备工艺、形貌结构以及优化本征特性等多个方面，对析氢催化剂未来的研究方向和发展前景提出了展望。

关键词: 电解, 析氢, 催化剂, 碱性, 过渡金属, 反应动力学

Abstract:

Hydrogen energy is an ideal energy carrier to promote the transformation of energy structure, and water electrolysis is an important means to achieve large scale hydrogen production. Alkaline water electrolysis has commercial feasibility because of its mature technology, low cost and small pollution. The catalytic activity, stability and cost of catalysts are the key factors in the development of alkaline water electrolysis technology. Herein, the research progress of catalysts for alkaline hydrogen evolution, including noble metals, transition metals, and carbon-based materials, is summarized. This paper analyzes the influence of the currently applied major optimization strategies on catalyst intrinsic activity, and the results show that the improvement of catalyst performance benefits from the comprehensive regulation and control of various factors, such as morphology, electronic orbit, lattice structure and support. According to the existing issues, the future research direction and development prospect of hydrogen evolution catalyst are proposed from the aspects of preparation technology, catalyst morphology and structure, and optimization of intrinsic properties.

Key words: electrolysis, hydrogen evolution, catalyst, alkaline, transition metal, reaction kinetics

中图分类号:

TQO643.36

陈心悦, 陈彬剑, 毛煜东, 闫敏, 薛璐. 碱性电解水析氢催化剂的研究进展及展望[J]. 化工进展, 2025, 44(11): 6334-6349.

CHEN Xinyue, CHEN Binjian, MAO Yudong, YAN Min, XUE Lu. Research progress and prospect of hydrogen evolution catalysts for alkaline water electrolysis[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6334-6349.

图/表 15

表1 电解水析氢技术类型及优缺点

项目	碱性电解水	质子交换膜电解水	固体氧化物电解水
电解质	30% KOH或25% NaOH	纯水	水蒸气
工作温度/℃	60~80	50~80	500~1000
工作效率/％	70~80	74~87	100
产氢纯度/％	99.95	>99.99	>99.90
成本/CNY·kW^-1	2600~4000	6500~9800	10000~13000
优点	成本低、使用寿命长、技术成熟	氢气纯度高、电流密度高	环境污染小、制氢效率高
缺点	电极腐蚀易失活、电流密度低	成本高、使用寿命短	高温稳定性差、成本高

图1 碱性水电解析氢示意图

图2 HER交换电流密度与M—H键强度间的火山关系

图3 部分贵金属析氢催化剂的反应机理、表征及电化学测试谱图

表2 部分贵金属电催化剂的电化学性质

催化剂	过电位（10mA·cm^-2）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
Pt@NGCs	27	30	<16	—	8.78	[22]
Pt-Ni/rGO	78	53	—	352	—	[23]
RuIr@NrC	28	35	—	1602	64.7	[24]

表2 部分贵金属电催化剂的电化学性质

催化剂	过电位（10mA·cm^-2）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
Pt@NGCs	27	30	<16	—	8.78	[22]
Pt-Ni/rGO	78	53	—	352	—	[23]
RuIr@NrC	28	35	—	1602	64.7	[24]

图4 部分过渡金属硫化物析氢催化剂的反应机理和表征

图5 部分过渡金属硒化物析氢催化剂的反应机理、表征及电化学测试谱图

图6 部分过渡金属氮化物析氢催化剂的反应机理、表征及电化学测试谱图

图7 部分过渡金属磷化物析氢催化剂的反应机理和表征

表3 部分过渡金属化合物催化剂的电化学性质

过渡金属化合物	催化剂	过电位（10mA/cm²）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
过渡金属硫化物（TMSs）	1T@2H-MoS₂	—	—	—	—	—	[36]
	MoS₂/rGO	100	41	250	—	—	[37]
	HCSN	—	—	0.45	566	—	[38]
过渡金属硒化物（TMSes）	MoSe₂NWs	259	59.8	—	—	—	[39]
	WSe₂NWs	306	77.4	—	—	—	[39]
	NiSe₂@NC-PZ	162	88	—	—	5.88	[49]
	MoSe₂ /NiSe₂NWs	249 （100mA/cm²）	46.9	2.17	—	8.8	[53]
过渡金属氮化物（TMNs）	NiMoN	89	79	18.6	—	—	[59]
	Ni₃N_1-_x /NF	55	54	18.1	—	—	[60]
	V-Co₄N/NF	37	44	6.2	—	152	[61]
过渡金属磷化物（TMPs）	FeP@C	115	56	29.2	—	65.3	[73]
	Co₂P@NPG	61 （1mA/cm²）	96	28	—	66.8	[74]
	Ni₂P-NW	139	92	6.8	—	65.1	[75]

表3 部分过渡金属化合物催化剂的电化学性质

过渡金属化合物	催化剂	过电位（10mA/cm²）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
过渡金属硫化物（TMSs）	1T@2H-MoS₂	—	—	—	—	—	[36]
	MoS₂/rGO	100	41	250	—	—	[37]
	HCSN	—	—	0.45	566	—	[38]
过渡金属硒化物（TMSes）	MoSe₂NWs	259	59.8	—	—	—	[39]
	WSe₂NWs	306	77.4	—	—	—	[39]
	NiSe₂@NC-PZ	162	88	—	—	5.88	[49]
	MoSe₂ /NiSe₂NWs	249 （100mA/cm²）	46.9	2.17	—	8.8	[53]
过渡金属氮化物（TMNs）	NiMoN	89	79	18.6	—	—	[59]
	Ni₃N_1-_x /NF	55	54	18.1	—	—	[60]
	V-Co₄N/NF	37	44	6.2	—	152	[61]
过渡金属磷化物（TMPs）	FeP@C	115	56	29.2	—	65.3	[73]
	Co₂P@NPG	61 （1mA/cm²）	96	28	—	66.8	[74]
	Ni₂P-NW	139	92	6.8	—	65.1	[75]

图8 部分掺杂稀土元素析氢催化剂的反应机理和电化学测试谱图

表4 部分掺杂稀土元素催化剂的电化学性能

催化剂	过电位（10mA/cm²）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
Er-CoP NMs	66	61	—	1234	—	[86]
Er-CoP NMs	66	61	—	—	143.1	[86]
Co₄N-CeO₂/GP	24	61	27	—	—	[87]

表4 部分掺杂稀土元素催化剂的电化学性能

催化剂	过电位（10mA/cm²）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
Er-CoP NMs	66	61	—	1234	—	[86]
Er-CoP NMs	66	61	—	—	143.1	[86]
Co₄N-CeO₂/GP	24	61	27	—	—	[87]

图9 部分无金属析氢催化剂的的反应机理和表征

表5 非金属材料催化剂的电化学性能

催化剂	过电位（10mA/cm²）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
g-C₃N₄-G	207	54	—	—	13	[96]
MPSA/GO-1000	210（30mA/cm²）	89	—	—	—	[97]

表5 非金属材料催化剂的电化学性能

催化剂	过电位（10mA/cm²）/mV	Tafel斜率/mV·dec^-1	R_ct/ $Ω$	ECSA/cm²·mg^-1	C_dl/mF·cm^-2	参考文献
g-C₃N₄-G	207	54	—	—	13	[96]
MPSA/GO-1000	210（30mA/cm²）	89	—	—	—	[97]

表6 碱性电解水析氢催化剂的优化方法和反应机理

优化方式	反应机理	制备策略
改变形貌	改变催化剂本身结构，增大反应面积；改变催化剂晶格相提升性能；缺陷工程增加成核位点	并非使用单一优化方法，采用多种优化方式结合以制备高效稳定的析氢催化剂
掺杂元素	元素协同作用优化催化剂电子结构；优化表面电子-质子耦合机制；杂原子提升催化剂稳定性和活性；掺杂具有独特电子结构的稀土元素，调节催化剂电子态密度
使用载体	均匀分散催化剂；载体与催化剂耦合界面提升传质和电子转移；提供成核位点；非金属材料互相耦合掺杂调整碳晶格，提升稳定性

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