电解海水催化剂的设计与改性

doi:10.16085/j.issn.1000-6613.2022-0029

摘要/Abstract

摘要：

电解海水是一种可再生、可持续、低成本且节约淡水资源的氢气生产方案。因此，针对天然海水或盐水电解质的析氢反应（HER）和析氧反应（OER），设计开发高效、稳定的电催化剂具有良好的应用前景。为了深入了解海水电解所面临的现状和挑战，本文对电催化分解海水催化剂的设计思路与改性方法进行了系统的回顾和总结。首先详细讨论了电解海水中析氢反应、析氧反应、析氯反应的基本原理。随后对最近报道的在海水中能够稳定运行的HER和OER电催化剂进行了汇总和分析。针对阴极催化剂，分别概述了高效贵金属基电催化剂和低成本过渡金属基电催化剂。针对阳极催化剂，主要讨论了取得较大进展的镍基催化剂，随后对镍基之外的其他电催化剂进行对比补充。文章最后对电解海水催化剂目前所面临的挑战和发展方向进行了总结和展望，基于现有分析认为，在未来的研究中需要进一步探索新型电解海水催化剂的种类和结构，开发更高效稳定的阴极和具有更高OER选择性的阳极电催化剂，以满足分解海水电催化剂工业化应用的要求。

关键词: 海水分解, 电解, 催化剂, 制氢, 制氧

Abstract:

Electrolysis of seawater is a renewable, sustainable, low-cost, and fresh-water-saving way for hydrogen production. The design and development of efficient and stable electrocatalysts has good application prospects for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in natural seawater or brine electrolyte. After exploring the current situation and challenges of seawater electrolysis, we have systematically summarized the design ideas and modification methods for seawater-splitting electrocatalysts. This review first introduces in detail the basic principles of hydrogen evolution, oxygen evolution, and chlorine evolution. The recently reported electrocatalysts for HER and OER that can work stably in seawater are subsequently discussed. For cathodic reaction, efficient noble-metal based catalysts and low-cost transition metal-based catalysts are analyzed. For anodic reaction, the nickel-based catalysts are focused and compared with other catalysts. Finally, challenges and development directions of seawater electrolysis are presented. In the future, different electrocatalysts with various structures for seawater splitting should be further developed. Highly efficient and stable cathode electrocatalysts and those with higher OER selectivity for anodic reaction should be designed to meet the requirements of industrial applications.

Key words: seawater splitting, electrolysis, catalyst, hydrogen production, oxygen production

中图分类号:

TQ151

郑学文, 赵蕊, 吴家哲, 王朦胧, 陈玉彬. 电解海水催化剂的设计与改性[J]. 化工进展, 2022, 41(11): 5800-5810.

ZHENG Xuewen, ZHAO Rui, WU Jiazhe, WANG Menglong, CHEN Yubin. Design and modification of electrocatalysts for seawater splitting: a review[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5800-5810.

图/表 7

图1 析氧反应在酸性和碱性条件下的作用机制[35]

表1 酸性和碱性电解质溶液中OER的反应机理

总方程	反应机理
$4 O H a q - → O 2 + 2 H 2 O + 4 e -$ （碱性电解质）	$M + O H a q - → M O H + e -$
	$M O H + O H a q - → M O + H 2 O + e -$
	$M O + O H a q - → M O O H + e -$
	$M O O H + O H a q - → M + O 2 + H 2 O + e -$
$2 H 2 O → O 2 + 4 H a q + + 4 e -$ （酸性电解质）	$M + H 2 O → M O H + H a q + + e -$
	$M O H → M O + H a q + + e -$
	$M O + H 2 O → M O O H + H a q + + e -$
	$M O O H → M + O 2 + H a q + + e -$

表1 酸性和碱性电解质溶液中OER的反应机理

总方程	反应机理
$4 O H a q - → O 2 + 2 H 2 O + 4 e -$ （碱性电解质）	$M + O H a q - → M O H + e -$
	$M O H + O H a q - → M O + H 2 O + e -$
	$M O + O H a q - → M O O H + e -$
	$M O O H + O H a q - → M + O 2 + H 2 O + e -$
$2 H 2 O → O 2 + 4 H a q + + 4 e -$ （酸性电解质）	$M + H 2 O → M O H + H a q + + e -$
	$M O H → M O + H a q + + e -$
	$M O + H 2 O → M O O H + H a q + + e -$
	$M O O H → M + O 2 + H a q + + e -$

图2 析氯析氧反应竞争关系随pH的变化图[41]

图3 NiRuIr-Graphene的稳定性测试结果及测试结束后的XRD图谱[48]

图4 CoMoC/MXene/NC的合成策略及多界面协同作用对HER促进作用示意图[56]

图5 NiFe LDH的OER反应机理[51]

图6 Mn0.88Mo0.12O2.13和MnO2在模拟海水环境中不同时间稳定性测试后的SEM图[73]

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