Theoretical Screening of Transition Metal Single Atoms Anchored onγ-Graphyne as Electrocatalysts for Nitrogen Reduction Reaction  

γ-石墨单炔锚定的过渡金属单原子作为氮还原反应电催化剂的理论筛选

作　　者：Hang Li Qiang Fu Zhenyu Li 李航;付强;李震宇(中国科学技术大学化学物理系,肥230026;中国科学技术大学未来技术学院,合肥230026;国科学技术大学合肥微尺度物质科学国家研究中心,合肥230026;中国科学技术大学精准智能化学重点实验室,合肥230026)

机构地区：[1]Department of Chemical Physics,University of Science and Technology of China,Hefei 230026,China [2]School of Future Technology,University of Science and Technology of China,Hefei 230026,China [3]Hefei National Research Center for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei 230026,China [4]Key Laboratory of Precision and Intelligent Chemistry,University of Science and Technology of China,Hefei 230026,China

出　　处：《Chinese Journal of Chemical Physics》2025年第1期63-72,I0023-I0031,I0056,共20页化学物理学报(英文)

基　　金：supported by the National Natural Science Foundation of China(No.21825302);the Strate-gic Priority Research Program of the Chinese Academy of Sciences(XDB0450101);USTC-SCC,SCCAS,Tianjin,and Shanghai Supercomputer Centers.

摘　　要：Ammonia(NH_(3))plays an important role in the world economy and its demand is steadily rising alongside the progress of modern society.The electrocatalytic nitrogen reduction reaction(NRR)is presently regarded as a high-po-tential method for the synthesis of NH_(3).Nev-ertheless,the development of efficient NRR electrocatalysts remains a challenging task.In this study,various transition metal(TM)sin-gle atoms(TM=Sc-Zn,Y-Cd except Tc,and Ta-Pt)anchored onγ-graphyne(γ-GY)are sys-tematically investigated as NRR electrocatalysts using density functional theory(DFT)cal-culations.According to several criteria regarding the adsorption stability of isolated TM sin-gle atoms onγ-graphyne,the adsorption properties of N_(2) on these TM single atoms,the ad-sorption competition between N_(2) and H,and the free energy change in the initial protonation process for N_(2),we find that Os@γ-GY and Re@γ-GY may be suitable electrocatalysts for NRR,and analyze the reasons why the two types of single atoms can well adsorb and activate N_(2) molecules.From the reaction pathways of NRR catalyzed by the two single-atom systems,we further find that NRR is hindered by the step of*NH_(2) hydrogenation to*NH_(3) on Re@γ-GY but can proceed well on Os@γ-GY.Thus,Os@γ-GY behaves best in catalyzing NRR among theγ-GY anchored single atom systems studied.This work has the potential to offer valuable recommendations for the development of novel and highly effective NRR electrocat-alysts.氨在世界经济中发挥着重要作用,其需求量随着现代社会的进步稳步上升.目前,电催化氮还原反应被认为是一种具有很大潜力的合成氨方法。然而,开发高效的氮还原反应电催化剂仍是一项具有挑战性的任务.本工作基于密度泛函理论计算,系统研究了锚定在石墨单炔的各种过渡金属单原子(Sc~Zn、Y~Cd(Tc除外)和Ta~Pt)作为氮还原反应电催化剂的表现.根据孤立过渡金属单原子在r石墨.单炔的稳定性、在单原子上的吸附特性、与H的吸附竞争性以及初始质子化过程的自由能变化等几个指标,本文发现Os@γ-石墨单炔.和Re@r-石墨单炔可能是合适的氮还原反应电催化剂,并分析了这两种单原子能够很好地吸附与活化N_(2)分子的原因.从两种单原子体系催化氮还原反应的路径中进一步发现,在Re@γ-石墨单炔上,氮还原反应受阻于*NH_(2)加氢为*NH_(3)的步骤,而反应过程在Os@γ-石墨单炔上可以很好地进行.因此,本文研究的γ-石墨单炔单原子锚定体系中,Os@y-石墨单炔在电催化氮还原反应方面表现最佳.本工作有望为开发新型高效的氮还原反应电催化剂提供有价值的信息.

关 键 词：Electrocatalytic synthesis of ammonia Transition metal Single-atom catalyst γ-Graphyne First principle 

分 类 号：O64[理学—物理化学]