Abstract
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 geo-metric/electronic structures and cooperative active sites.Here a study of N2 activation and reduction on seventeen bimetallic Nb2M(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(Nb2Ni,Nb2Rh and Nb2Pd)are highlighted with out-standing catalytic performance.The d-σ and d-π*orbital hybridizations between these metal clusters and N2 were demonstrated and the internal association with the N ≡ N bond activation was unveiled.By examining the ammonia synthesis on four chosen Nb2M 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 N2 reduction on the bimetallic Nb2M clusters,but also guides efficient bimetallic catalyst design.
基金项目
CAS Project for Young Scientists in Basic Research(YSBR-050)
National Natural Science Foundation of China(92261113)
National Natural Science Foundation of China(222721809)
Beijing Natural Science Foundation(2232035)
万方数据