“Capture-activation-recapture” mechanism-guided design of double-atom catalysts for electrocatalytic nitrogen reduction  

作　　者：Cheng He Shiqi Yan Wenxue Zhang 

机构地区：[1]State Key Laboratory for Mechanical Behavior of Materials,School of Materials Science and Engineering,Xi’an Jiaotong University,Xi’an 710049,Shaanxi,China [2]School of Materials Science and Engineering,Chang’an University,Xi’an 710064,Shaanxi,China

出　　处：《Journal of Energy Chemistry》2024年第9期437-447,共11页能源化学（英文版）

基　　金：supports by the National Natural Science Foundation of China(52271113);the Natural Science Foundation of Shaanxi Province,China(2020JM 218);the Fundamental Research Funds for the Central Universities(CHD300102311405);HPC platform,Xi’an Jiaotong University.

摘　　要：Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental protection. However, the existing “acceptance-donation” mechanism is only applicable to bimetallic catalysts and nonmetallic double-atom catalysts containing boron atoms. Herein, a novel “capture-activation-recapture” mechanism for metal-nonmetal double-atom catalyst is proposed to solve the problem by adjusting the coordination environments of nonmetallic atoms and utilizing the activation effect of metal atoms on nitrogen. Based on this mechanism, the nitrogen reduction reaction (NRR) activity of 48 structures is calculated by density functional theory calculation, and four candidates are selected as outstanding electrocatalytic nitrogen reduction catalysts: Si-Fe@NG (U_(L) = –0.14 V), Si-Co@NG (U_(L)= –0.15 V), Si-Mo@BP1 (U_(L) = 0 V), and Si-Re@BP1 (U_(L) = –0.02 V). The analyses of electronic properties further confirm “capture-activation-recapture” mechanism and suggest that the difference in valence electron distribution between metal and Si atoms triggers the activation of N≡N bonds. In addition, a machine learning approach is utilized to generate an expression and an intrinsic descriptor that considers the coordination environment to predict the limiting potential. This study offers profound insight into the synergistic mechanism of TM and Si for NRR and guidance in the design of novel double-atom nitrogen fixation catalysts.

关 键 词："Capture-activation-recapture"mechanism Double-atom catalyst Nitrogen reduction reaction Density functional theory 

分 类 号：TQ113[化学工程—无机化工] TQ426