析氢反应中氮掺杂石墨烯负载金属单/双原子催化活性起源

doi:10.19799/j.cnki.2095-4239.2021.0393

储能科学与技术 ›› 2021, Vol. 10 ›› Issue (6): 2008-2012.doi: 10.19799/j.cnki.2095-4239.2021.0393

析氢反应中氮掺杂石墨烯负载金属单/双原子催化活性起源

张诗诗¹(), 秦棪阳¹, 苏亚琼^1,²()

^1.西安交通大学化学学院，陕西西安 710049
^2.埃因霍温理工大学化学工程与化学系，荷兰埃因霍温 5600MB

收稿日期:2021-07-31 修回日期:2021-08-31 出版日期:2021-11-05 发布日期:2021-11-03
作者简介:张诗诗（1997—），女，硕士研究生，主要研究方向为计算电化学催化，E-mail：zhangshishi97@163.com|苏亚琼，研究员，主要研究方向为计算能源催化/材料，E-mail：yqsu1989@xjtu.edu.cn。
基金资助:
西安交通大学“青年拔尖人才”支持计划

Activity origin of single/double-atom catalyst for hydrogen evolution reaction

Shishi ZHANG¹(), Yanyang QIN¹, Yaqiong SU^1,²()

^1.School of Chemistry, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China
^2.Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven 5600MB, Netherlands

Received:2021-07-31 Revised:2021-08-31 Online:2021-11-05 Published:2021-11-03

摘要/Abstract

摘要：

电催化析氢反应(HER)是极具潜力的氢能转化手段，发展高性能、低成本的析氢催化剂是制氢技术的关键。本文选取了以过渡金属(Fe、Ni、Co)为活性中心、以氮掺杂石墨烯(N-graphene)为基底的单、双原子催化剂(SAC、DAC)，首先通过理论计算对其结构稳定性做出了讨论，证明了所选催化材料的可行性。然后，采用H吸附能为描述符，对催化剂的HER活性进行了分析讨论。结果表明CoN₄表现出最优异的HER活性，FeN₃、FeN₄、Fe₂N₆三种结构的Fe原子活性中心次之。最后，系统讨论了催化剂的电子结构，揭示了HER催化活性的来源。本文从理论计算角度对SAC、DAC的HER活性进行了对比，结果表明DAC具有较差的HER活性，SAC中CoN₄、FeN₃、FeN₄在HER中展现出优异的催化性能，可作为取代常用的贵金属(Pt/C)HER催化剂的理想选择。

关键词: 析氢反应, 单原子催化剂, 电催化剂, 密度泛函理论

Abstract:

Electrocatalytic hydrogen evolution reaction (HER) is a promising hydrogen energy conversion method. To develop high-performance and low-cost hydrogen evolution electrocatalysts, single- and double-atom catalysts (SACs, DACs) with transition metals (e.g., Fe, Ni, and Co) as the active center and nitrogen-doped graphene (N-graphene) as the substrate are selected for HER utilizing density functional theory calculations. The selected catalytic materials exhibit exceptional stability against sintering. We then chose H adsorption energy as the descriptor for analyzing the HER activity, and the results demonstrate that the CoN₄ site exhibits excellent HER activity over other candidates. In contrast, NiN₄ and Ni₂N₆ sites display inferior HER activity. In addition, the electronic structures of the catalysts are systematically discussed to uncover the origin of catalytic activity. This work reveals that DACs have poor HER activity compared to SACs and DACs, while the SACs (e.g., CoN₄, FeN₃, and FeN₄) show low overpotential in HER. Therefore, the SACs can substitute commercial precious metals catalysts (Pt/C) for HER catalysts.

Key words: hydrogen evolution reaction, single-atom catalyst, electrocatalyst, density functional theory

中图分类号:

TM 911

张诗诗, 秦棪阳, 苏亚琼. 析氢反应中氮掺杂石墨烯负载金属单/双原子催化活性起源[J]. 储能科学与技术, 2021, 10(6): 2008-2012.

Shishi ZHANG, Yanyang QIN, Yaqiong SU. Activity origin of single/double-atom catalyst for hydrogen evolution reaction[J]. Energy Storage Science and Technology, 2021, 10(6): 2008-2012.

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参考文献 16

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Item	FeN₃	FeN₄	CoN₄	NiN₄	Fe₂N₆	Co₂N₆	Ni₂N₆
TM—N/?	1.92	1.89	1.87	1.87	1.79/1.95	1.78/1.94	1.83/1.87
E_b/eV	-4.91	-7.59	-7.42	-4.64	-14.41	-13.90	-12.89

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析氢反应中氮掺杂石墨烯负载金属单/双原子催化活性起源

Activity origin of single/double-atom catalyst for hydrogen evolution reaction

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