文献类型：期刊文献

英文题名：Density functional theory study of transition metal single-atoms anchored on graphyne as efficient electrocatalysts for the nitrogen reduction reaction

作者：Song, Wei[1];Xie, Kun[2];Wang, Jinlong[3];Guo, Yongliang[1];He, Chaozheng[4,5];Fu, Ling[6]

第一作者：Song, Wei

通讯作者：Fu, L[1]

机构：[1]Henan Inst Technol, Sch Sci, Xinxiang 453003, Henan, Peoples R China;[2]Henan Polytech Univ, Henan Key Lab Mat Deep Earth Engn, Sch Mat Sci & Engn, Jiaozuo 454000, Henan, Peoples R China;[3]Xinxiang Univ, Dept Elect Commun Engn, Xinxiang 453003, Henan, Peoples R China;[4]Xian Technol Univ, Sch Mat Sci & Chem Engn, Xian 710021, Shaanxi, Peoples R China;[5]Xian Technol Univ, Inst Environm & Energy Catalysis, Sch Mat Sci & Chem Engn, Xian 710021, Peoples R China;[6]Tianshui Normal Univ, Coll Resources & Environm Engn, Tianshui 741001, Peoples R China

第一机构：Henan Inst Technol, Sch Sci, Xinxiang 453003, Henan, Peoples R China

通讯机构：[1]corresponding author), Tianshui Normal Univ, Coll Resources & Environm Engn, Tianshui 741001, Peoples R China.

年份：2021

卷号：23

期号：17

起止页码：10418-10428

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20212010354133);Scopus(收录号：2-s2.0-85105669237);WOS:【SCI-EXPANDED(收录号:WOS:000642434700001)】；

基金：The authors thank the National Natural Science Foundation of China for financial support (Grant No. 11904081 and 21603109). This research was also supported by the Henan Joint Funds of the National Natural Science Foundation of China (U1404216). The scientific research program funded by Shaanxi Provincial Education Department (Program No. 20JK0676).

语种：英文

外文关键词：Ammonia - Chemical industry - Electrocatalysts - Electrolysis - Electronic properties - Free energy - Nitrogen - Organic chemicals - Transition metals

摘要：Ammonia (NH3) is the main raw material for the organic chemical industry and a critical feedstock for the fertilizer industry with great significance for the global economy. The NH3 demand has gradually increased with modern society development. Moreover, the electrocatalytic nitrogen reduction reaction (NRR) is a promising NH3 synthesis technology. However, the design of efficient electrocatalysts for the NRR is still challenging. In this study, we systematically analyzed transition metal (TM) single-atoms (Ti, V, Cr, Mn, Zr, Nb, and Mo) anchored on graphyne (GY) as NRR catalysts using density functional theory calculations. The calculation results for the first and last hydrogenation steps (*NNH formation and *NH3 desorption, respectively) revealed that Mn@GY (with an end-on configuration) and V@GY (with a side-on configuration) were the most suitable catalytic substrates for the NRR. The free-energy profiles of the TM@GY catalysts indicated that Mn@GY was the best NRR electrocatalyst owing to its distal pathway with a minimum free-energy barrier of 0.36 eV. In addition, the electronic properties, namely the Bader charge, charge density difference, partial density of states, and crystal orbital Hamilton population, of the TM@GY catalysts were analyzed in detail, and the results further confirmed that Mn@GY was an efficient electrocatalyst. The insights obtained from this comprehensive study can provide useful guidelines for designing new and efficient electrocatalysts.