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...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.展开更多
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)。
文摘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.
