Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures

Ammonia(NH_(3))synthesis at mild conditions is of great significance,while the significant bottleneck of this process is the activation of N_(2) to realize the desired NH_(3) synthesis performance,which requires deep insight and rational design of active sites at the atomic level.Here,were synthesized atomically dispersed Co-based catalysts with different Co-N coordination numbers(CNs)to explore the coordination-sensitive NH_(3) synthesis reaction for the first time.Our studies showed that Co-based catalysts increased the NH_(3) synthesis rate gradually with a decrease in CN.The Co-N_(2) catalyst exhibited the highest NH_(3) synthesis rate of 85.3 mmol gCo^(−1) h^(−1) at 300℃ and 1 MPa,which outperformed most of the previously reported Co-based catalysts.Various characterizations and theoretical calculations demonstrated that atomically dispersed Co catalyst with low CN could generate more unoccupied Co 3d charges and tetrahedral cobalt(Ⅱ)sites.The unoccupied Co 3d charge,in turn,promoted the electron donation from the Co active center to the antibonding π-orbital(π*)of N_(2) and expedites N_(2) hydrogenation.Furthermore,the Co-N_(2) catalyst with more tetrahedral cobalt(II)sites could effectively facilitate the desorption of N-containing intermediate species(such as*NH_(3) and*N_(2)H_(4))to obtain a high NH_(3) synthesis rate.