Nitrogen reduction reaction on small iron clusters supported by N-doped graphene:A theoretical study of the atomically precise active-site mechanism

作     者：Chaonan Cui Hongchao Zhang Zhixun Luo Chaonan Cui;Hongchao Zhang;Zhixun Luo

作者机构：Beijing National Laboratory for Molecular Sciences(BNLMS)State Key Laboratory for Structural Chemistry of Unstable and Stable SpeciesInstitute of ChemistryChinese Academy of SciencesBeijing100190China University of Chinese Academy of SciencesBeijing100049China 

出 版 物：《Nano Research》 (纳米研究（英文版）)

年 卷 期：2020年第13卷第8期

页      面：2280-2288页

核心收录：

学科分类：081702[工学-化学工艺] 0808[工学-电气工程] 07[理学] 0809[工学-电子科学与技术（可授工学、理学学位）] 08[工学] 0817[工学-化学工程与技术] 070304[理学-物理化学(含∶化学物理)] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 0702[理学-物理学] 

基　　金：This work was financially supported by the National Natural Science Foundation of China(Nos.21802146 and 21722308) CAS Key Research Project of Frontier Science(No.QYZDB-SSW-SLH024) Frontier Cross Project of National Laboratory for Molecular Sciences(No.051Z011BZ3). 

主　　题：N2 reduction reaction(NRR) iron clusters cluster catalysis active-site mechanism density functional theory(DFT) 

摘      要：Nonprecious metal catalysts are known of significance for electrochemical N2 reduction reaction(NRR)of which the mechanism has been illustrated by ongoing investigations of single atom catalysis.However,it remains challenging to fully understand the size-dependent synergistic effect of active sites inherited in substantial nanocatalysts.In this work,four types of small iron clusters Fen(n=1–4)supported on nitrogen-doped graphene sheets are constructed to figure out the size dependence and synergistic effect of active sites for NRR catalytic activities.It is revealed that Fe3 and Fe4 clusters on N4G supports exhibit higher NRR activity than single-iron atom and iron dimer clusters,showing lowered limiting potential and restricted hydrogen evolution reaction(HER)which is a competitive reaction channel.In particular,the Fe4-N4G displays outstanding NRR performance for“side-onadsorption of N2 with a small limiting potential(−0.45 V).Besides the specific structure and strong interface interaction within the Fe4-N4G itself,the high NRR activity is associated with the unique bonding/antibonding orbital interactions of N-N and N-Fe for the adsorptive N2 and NNH intermediates,as well as relatively large charge transfer between N2 and the cluster Fe4-N4G.