中性环境下电催化析氧反应研究进展

doi:10.12422/j.issn.1006-396X.2023.05.001

摘要/Abstract

摘要：

清洁和可再生能源技术的发展被视为解决能源和环境问题的关键。电催化分解水过程中的析氧反应（OER）在太阳能和风能等间歇式能源存储方面发挥着关键作用。环境友好的中性环境下的OER受到了很大的关注，然而其电解水析氧效率远低于在碱性或酸性条件下电解水析氧效率。基于此，首先概括了目前研究者对中性环境下OER机理的认识；介绍了几种重要的原位跟踪OER电催化过程的表征技术，并概述了包括Co基、Ni基和Mn基等中性环境下的OER催化材料；最后，对促进中性环境下电催化分解水OER面临的挑战进行了总结，并提出了可能的解决策略。

关键词: 电催化, 析氧反应, 原位表征, 中性电解水

Abstract:

The development of clean and renewable energy technologies is seen as the key to addressing energy and environmental issues.Oxygen evolution reaction (OER) plays key roles in storage intermittent energy,such as solar and wind,from water splitting.Recently, OER under neutral conditions receives considerable interests due to its environmental friendliness.However,the efficiency of OER under neutral environment is far below that under alkaline or acidic condition.In this review,the current researchers' understanding of the mechanism of OER under mild pH conditions is firstly outlined.Thereafter,several important characterisation techniques for in situ tracking of the electrocatalytic process of OER are presented,which is crucial to reveal the OER mechanism under neutral conditions.Moreover,an overview over catalytic materials towards neutral OER,including Co?,Ni?,and Mn?based catalysts,is provided.Finally,a brief outlook on the remaining challenges and possible strategies for promoting neutral OER is given.

Key words: Electrocatalysis, Oxygen evolution reaction（OER）, In situ characterization, Neutral water electrolysis

中图分类号:

TQ151.1

杜坤, 郭佳欣, 马紫昂, 毛晶, 凌涛, 赵巍. 中性环境下电催化析氧反应研究进展[J]. 石油化工高等学校学报, 2023, 36(5): 1-14.

Kun DU, Jiaxin GUO, Ziang MA, Jing MAO, Tao LING, Wei ZHAO. Progress in Electrocatalytic Oxygen Precipitation Reaction under Neutral Environment[J]. Journal of Petrochemical Universities, 2023, 36(5): 1-14.

图/表 14

图1 中性环境下OER机理

Fig.1 The OER mechanism under neutral conditions

图2 质子?电子的协同和分步转移路径示意图

Fig.2 Illustration of the concerted and sequential proton electron transfer paths

图3 Co?Pi催化剂的OER机理[50]

Fig.3 Investigation on OER mechanism of a Co?Pi catalyst[50]

图4 纳米MnO的OER机理[24]

Fig.4 Investigation on OER mechanism of MnO nanoparticles[24]

图5 MnO2的pH依赖性OER机制

Fig.5 pH?dependent OER mechanism of MnO2

图6 中性环境下OER过程中MnO纳米颗粒电极原位UV?Vis[24]

Fig.6 In situ UV?Vis spectra of MnO nanoparticles electrode during OER process at neutral pH[24]

图7 原位XAS光谱测试

Fig.7 In situ XAS spectra set up

图8 原位IR光谱测试

Fig.8 In situ IR spectra set up

图9 原位表面增强Raman测试

Fig.9 In situ surface enhanced Raman spectra set up

图10 中性环境中Co?Pi催化剂[55]

Fig.10 Co?Pi catalyst in neutral medium[55]

图11 Co基催化剂在中性环境中的电化学测试结果

Fig.11 Electrochemical tests of Co?based catalyst in neutral electrolytes

图12 Ni基催化剂在不同电解质和pH条件下的电化学测试结果

Fig.12 Electrochemical measurement of Ni-based catalyst in different electrolytes and pH

图13 电位循环法活化电沉积的MnO x 膜[52]

Fig.13 Activated the electrodeposited MnO x film by potential cycling protocols[52]

表1 中性环境中OER电催化剂的测试和性能

Table 1 Measurement and performance of OER electrocatalysts in neutral media

催化剂		形貌	pH	电解质	电流密度/(mA· cm^-2)	η /mV	Tafel 斜率/ (mV· dec^-1)	参考文献
Co基	Co⁃Pi	薄膜	7.0	KPi	1.0	410	60.0	[55]
	Co⁃Bi	纳米片	7.0	PBS	14.4	570	160.0	[17]
	Co⁃Bi	纳米片	9.2	KBi	10.0	469	138.0	[67]
	Mn⁃Co⁃Bi	纳米线	9.2	KBi	10.0	366	193.0	[69]
	Ni⁃Co⁃Bi	纳米线	9.2	KBi	10.0	388	142.0	[68]
	Co₃O₄	纳米链	7.0	KBi	1.0	385	70.0	[76]
	Co₃O₄	纳米颗粒	7.0	KPi	10.0	390	-	[69]
	CoO _x H _y	纳米片阵列	7.0	PBS	10.0	430	121.0	[72]
	IrO _x /CoO _x	纳米颗粒	7.0	PBS	1.0	220	29.0	[77]
	CoIr	纳米片	7.0	PBS	10.0	373	117.0	[65]
	Co₃S₄	纳米片	7.0	PBS	起始过电势	310	151.0	[78]
	CoS_4.6O_0.6	多孔纳米管	7.0	PBS	起始过电势	270	164.0	[81]
	Na₂CoP₂O₇	块体	7.0	PBS	1.0	560	80.0	[79]
	Co₂P	纳米颗粒	7.0	PBS	起始过电势	320	129.8	[16]
	Ni_0.1Co_0.9P	多孔纳米片	7.0	PBS	起始过电势	250	133.0	[82]
	Co_1⁃_x Fe _x P	纳米片	7.0	PBS	10.0	500	-	[80]
Ni基	NiCoFeP	-	7.2	KHCO₃	10.0	330	-	[33]
	Ni⁃Bi	纳米阵列	9.2	KBi	10.0	470	107.0	[88]
	Nickel	-	9.2	KBi	1.0	540	57.0	[12]
	NiFeO _x	-	7.0	PBS	10.0	400	-	[85]
	S⁃doped NiFe₂O₄	纳米片	7.4	PBS	10.0	494	118.0	[87]
	NiS _x P _y	纳米线	8.5	KHCO₃	10.0	315	-	[86]
Mn基	MnO _x	薄膜	7.0	PBS	0.1	470	68.0	[52]
Mn基	Mn₅O₈	纳米颗粒	7.8	PBS	5.0	580	78.7	[92]

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