单原子位点催化剂及其电催化应用研究进展

doi:10.16085/j.issn.1000-6613.2021-0658

摘要/Abstract

摘要：

单原子位点催化剂作为新兴类别，由于具有接近100%的高效原子利用率，出色的活性、选择性和稳定性等优异特性，受到广泛的关注和研究。本文综述了单原子位点催化剂的最新研究成果及在电催化领域的应用。详细介绍了单原子位点催化剂的制备方法，包括“自下而上”合成策略中的共沉淀法、电化学沉淀法、原子层沉积法、光化学法和原子约束法等，“自上而下”合成策略中的高温原子迁移捕获法、高温热解法和悬挂键捕获法。分析了用于表征单原子位点催化剂的高角环形暗场透射扫描显微镜和X射线吸收光谱表征技术，进行单原子位点催化剂理论计算的密度泛函理论（DFT）和第一性原理。在电催化领域的应用主要包括氧还原反应（ORR）、氮还原反应（NRR）、CO₂还原反应（CO₂RR）、氢析出反应（HER）和氧析出反应（OER）。最后指出目前单原子位点催化剂存在无法大规模生产和催化机制不清晰等问题并给出相关建议，展望了单原子位点催化剂的发展前景，指出创新制备方法以实现稳定型单原子位点催化剂的大规模制备及工业应用，利用先进表征技术进一步明确单原子位点催化剂催化机制是未来发展的方向。

关键词: 单原子位点催化剂, 制备, 表征技术, 计算机模拟, 电化学, 应用

Abstract:

Single-atom site catalysts have received extensive attention due to their close to 100% atom utilization efficiency, and excellent activity, selectivity and stability. This review describes the latest research results of single-atom site catalysts and their applications in electrocatalysis. The preparation methods of single-atom site catalysts are introduced in detail, including the co-precipitation, electrochemical precipitation, atomic layer deposition, photochemical and atomic confinement using the “bottom-up” synthesis strategy, as well as the high-temperature atom migration trapping, high-temperature pyrolysis and hanging key trapping using the "top-down" synthesis strategy. Characterization techniques of high-angle annular dark field transmission scanning microscope and X-ray absorption spectroscopy are analyzed. Theoretical calculations by density functional theory and first principle are also analyzed. Applications in electrocatalysis, mainly including oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), CO₂ reduction reaction (CO₂RR), hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are introduced. Finally, the current problems of single-atom catalysts such as the inability to large scale production and the unclear catalytic mechanism are pointed out and relevant suggestions are given. The prospect of single-atom site catalysts is proposed. Innovative preparation of stable single-atom site catalysts to achieve their large-scale preparation and industrial application, and the use of advanced characterization techniques to further clarify the catalytic mechanism should be the directions of future development.

Key words: single-atom site catalyst, preparation, characterization technique, computer simulation, electrochemistry, application

中图分类号:

O643.3

竹涛, 韩一伟, 刘帅, 谢蔚, 苑博, 宋慧平, 程芳琴. 单原子位点催化剂及其电催化应用研究进展[J]. 化工进展, 2022, 41(2): 666-681.

ZHU Tao, HAN Yiwei, LIU Shuai, XIE Wei, YUAN Bo, SONG Huiping, CHEGN Fangqin. Progress in electrocatalysis by single-atom site catalysts[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 666-681.

图/表 7

图1 不同金属物种的化学势和电子结构随粒径变化关系

表1 单原子位点催化剂常见制备方法汇总

制备方法	催化剂	金属负载量（质量分数）	应用	文献
共沉淀法	Ni₁/HAP-Ce	0.5%～8.5％（ICP-AES）	DRM	［27］
电化学沉淀法	Ir₁/Co（OH）₂	2.0％（ICP-AES）	氢析出反应	［28］
电化学沉淀法	Ni₁/GD和Fe₁/GD	0.278%和0.680%（ICP-MS）	氢析出反应	［29］
原子层沉积法	Pt-Ru/NCNT	0.9％ Pt/0.31％ Ru（ICP-OES）	氢析出反应	［30］
原子层沉积法	Pt_1/GNS	10.5％（ICP-OES）	甲醇氧化反应（MOR）	［31］
光化学法	Pd₁/TiO₂	1.5％（ICP-MS）	C $? ???$ C键加氢	［32］
	Pt₁/CoSe_2-_x	2.25%（ICP-AES）	氧析出反应	［33］
	Pt₁/NPC	3.8%（ICP-OES）	燃料电池和制氢	［34］
原子约束法	Er₁/CN-NT	2.5%（ICP-AES）	光催化CO₂还原反应	［35］
原子约束法	M/meso_S-C（M=Ru，Rh，Pd，Ir，Pt）	10%（ICP-AES）	甲酸氧化和喹啉加氢	［36］
配体法	M-SASCs（M=Ni，Mn，Fe，Co，Cr，Cu，Zn，Ru，Pt及其组合）	2.5%（ICP-OES）	CO₂电化学还原为CO	［37］
	Fe₁/N-C	1.5%（ICP-OES）	氧还原反应	［38］
	Pt₁/MNSs	12%（ICP-OES）	光催化水制氢	［39］
模板辅助法	Fe₁/NSC	0.87%（ICP-MS）	氧还原反应	［40］
模板辅助法	Co₁/HNCS	2.2%（ICP-OES）	氧还原反应	［41］
高温原子迁移捕集法	Cu₁/NC	0.45%（ICP-AES）	氧还原反应	［42］
高温原子迁移捕集法	Pt₁/Fe₂O₃	1.9%（ICP-AES）	甲烷催化燃烧	［43］
高温热解	Ru₁/MAFO	2.09%（ICP-OES）	N₂O分解	［44］
悬挂键捕获法	Fe₁/GO	6.7%（ICP-AES）	氧还原反应	［45］

表1 单原子位点催化剂常见制备方法汇总

制备方法	催化剂	金属负载量（质量分数）	应用	文献
共沉淀法	Ni₁/HAP-Ce	0.5%～8.5％（ICP-AES）	DRM	［27］
电化学沉淀法	Ir₁/Co（OH）₂	2.0％（ICP-AES）	氢析出反应	［28］
电化学沉淀法	Ni₁/GD和Fe₁/GD	0.278%和0.680%（ICP-MS）	氢析出反应	［29］
原子层沉积法	Pt-Ru/NCNT	0.9％ Pt/0.31％ Ru（ICP-OES）	氢析出反应	［30］
原子层沉积法	Pt_1/GNS	10.5％（ICP-OES）	甲醇氧化反应（MOR）	［31］
光化学法	Pd₁/TiO₂	1.5％（ICP-MS）	C $? ???$ C键加氢	［32］
	Pt₁/CoSe_2-_x	2.25%（ICP-AES）	氧析出反应	［33］
	Pt₁/NPC	3.8%（ICP-OES）	燃料电池和制氢	［34］
原子约束法	Er₁/CN-NT	2.5%（ICP-AES）	光催化CO₂还原反应	［35］
原子约束法	M/meso_S-C（M=Ru，Rh，Pd，Ir，Pt）	10%（ICP-AES）	甲酸氧化和喹啉加氢	［36］
配体法	M-SASCs（M=Ni，Mn，Fe，Co，Cr，Cu，Zn，Ru，Pt及其组合）	2.5%（ICP-OES）	CO₂电化学还原为CO	［37］
	Fe₁/N-C	1.5%（ICP-OES）	氧还原反应	［38］
	Pt₁/MNSs	12%（ICP-OES）	光催化水制氢	［39］
模板辅助法	Fe₁/NSC	0.87%（ICP-MS）	氧还原反应	［40］
模板辅助法	Co₁/HNCS	2.2%（ICP-OES）	氧还原反应	［41］
高温原子迁移捕集法	Cu₁/NC	0.45%（ICP-AES）	氧还原反应	［42］
高温原子迁移捕集法	Pt₁/Fe₂O₃	1.9%（ICP-AES）	甲烷催化燃烧	［43］
高温热解	Ru₁/MAFO	2.09%（ICP-OES）	N₂O分解	［44］
悬挂键捕获法	Fe₁/GO	6.7%（ICP-AES）	氧还原反应	［45］

图2 电化学还原法合成Ni/GD和Fe/GD示意图[29]

图3 氮掺杂碳纳米管上Pt–Ru二聚体的ALD合成示意图[30]

图4 气体传输策略制备Cu1/NC示意图和表征[42]

图5 HAADF-STEM图像和结构模型[58]（a）Pt4Au96核壳结构的STEM及EDX图谱；（b）Pt7Au93核壳结构的STEM及EDX图谱；（c）Pt78Au22核壳结构的STEM及EDX图谱；（d）单原子覆盖的纳米颗粒模型；（e）PtAu表面的单原子Pt位点；（f）PtAu表面的少量Pt团簇；（g）PtAu表面的Pt壳层

图6 CO氧化循环的势能图和配置[72]

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