Sp/sp^(2)carbon ratio-driven high-throughput screening of electrocatalytic nitrogen reduction performance on transition metal single-atom catalysts  

作　　者：Ze-Xiang Yin Yu-Dan Li Yu-Huan Ye Yuan Liu Mian-Feng Li Zi-Jun Yang Xue-Rong Zheng Hao-Zhi Wang Yang Wang Yi-Da Deng 

机构地区：[1]State Key Laboratory of Marine Resource Utilization in South China Sea,School of Materials Science and Engineering,Hainan University,Haikou 570100,China [2]School of Materials Science and Engineering,Tianjin Key Laboratory of Composite and Functional Materials,Key Laboratory of Advanced Ceramics and Machining Technology(Ministry of Education),Tianjin University,Tianjin 300072,China

出　　处：《Rare Metals》2024年第11期5781-5791,共11页稀有金属（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(Nos.52301011,52231008,52142304,52177220,52101182 and U23A200767);Hainan Provincial Natural Science Foundation of China(No.524QN226);the Key research and development program of Hainan province(No.ZDYF2022GXJS006);the Starting Research Fund from the Hainan University(No.KYQD(ZR)23026);the International Science&Technology Cooperation Program of Hainan Province(No.GHYF2023007)。

摘　　要：Single-atom catalysts(SACs)have been widely utilized in electrochemical nitrogen reduction reactions(NRR)due to their high atomic utilization and selectivity.Owing to the unique sp/sp^(2)co-hybridization,graphyne materials can offer stable adsorption sites for single metal atoms.To investigate the influence of the sp/sp^(2)hybrid carbon ratio on the electrocatalytic NRR performance of graphyne,a high-throughput screening of 81 catalysts,with27 transition metals loaded on graphyne(GY1),graphdiyne(GY2),and graphtriyne(GY3),was conducted using firstprinciples calculations.The results of the screening revealed that Ti@GY3 exhibits the lowest energy barrier for the rate-determining step(0.32 eV)in NRR.Further,to explore the impact of different sp/sp^(2)-hybridized carbon ratios on the catalytic activity of SACs,the mechanism of nitrogen(N_(2))adsorption,activation,and the comprehensive pathway of NRR on Ti@GY1,Ti@GY2,and Ti@GY3 was systematically investigated.It was found that the ratio of sp/sp^(2)-hybridized carbon can significantly modulate the d-band center of the metal,thus affecting the energy barrier of the rate-determining step in NRR,decreasing from Ti@GY1(0.59 eV)to Ti@GY2(0.49 eV);and further to Ti@GY3(0.32 eV).Additionally,the Hall conductance was found to increase with the bias voltage in the range of 0.4-1 V,as calculated by Nanodcal software,demonstrating an improvement in the conductivity of the SAC.In summary,this work provides theoretical guidance for modulating the electrocatalytic nitrogen reduction activity of SACs by varying the ratio of sp/sp^(2)hybrid carbon,with Ti@GY3 showing potential as an excellent NRR catalyst.

关 键 词：Nitrogen reduction reactions Single-atom catalysts Graphyne Ratio of sp/sp^(2)hybrid carbon High-throughput screening 

分 类 号：TQ113.2[化学工程—无机化工] O643.36[理学—物理化学]