Reduction of dinitrogen to ammonia on doped three-atom clusters Nb_(2)M(M=Sc to Cu & Y to Ag)  

作　　者：Ran Cheng Chao-Nan Cui Zhi-Xun Luo 

机构地区：[1]Beijing National Laboratory for Molecular Science(BNLMS),State Key Laboratory for Structural Chemistry of Unstable and Stable Species,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China [2]School of Chemical Science,University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Rare Metals》2024年第8期3810-3818,共9页稀有金属（英文版）

基　　金：financially supported by CAS Project for Young Scientists in Basic Research (No.YSBR-050);the National Natural Science Foundation of China (Nos.92261113 and 222721809);Beijing Natural Science Foundation (No.2232035)。

摘　　要：Catalytic reduction of dinitrogen to ammonia under mild conditions remains an attractive topic for the purpose of lowering energy consumption.Three-atom metal clusters have been proved an ideal model to explore highly efficient catalysts taking advantage of unique geometric/electronic structures and cooperative active sites.Here a study of N2 activation and reduction on seventeen bimetallic Nb_2M(M=Sc to Cu,and Y to Ag) clusters was reported.Three key processes for ammonia fixation(namely nitrogen activation,hydrogenation,and ammonia desorption) are fully studied,and three preferred systems(Nb_2Ni,Nb_2Rh and Nb_2Pd) are highlighted with outstanding catalytic performance.The d-σ and d-π~* orbital hybridizations between these metal clusters and N_(2) were demonstrated and the internal association with the N≡N bond activation was unveiled.By examining the ammonia synthesis on four chosen Nb_(2)M clusters(M=Fe,Ni,Rh and Pd),it can be elucidated that the distal pathway is more favorable than the alternative pathway in these systems.This work not only clarifies the N_(2) reduction on the bimetallic Nb_(2)M clusters,but also guides efficient bimetallic catalyst design.

关 键 词：Three-atom cluster catalysis Three-criteria strategy Nitrogen fixation Ammonia synthesis Theoretical calculations 

分 类 号：TQ113.2[化学工程—无机化工] TQ426