Reduction of dinitrogen to ammonia on doped three‐atom clusters Nb <sub>2</sub> M (M = Sc to Cu & Y to Ag)
Ran Cheng, Chaonan Cui, Zhixun Luo
Abstract
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 geometric/electronic structures and cooperative active sites. Here a study of N 2 activation and reduction on seventeen bimetallic Nb 2 M (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 2 Ni, Nb 2 Rh and Nb 2 Pd) 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.