Atomically Precise Dinuclear Ni2 Active Site-Modified MOF-Derived ZnO@NC Heterojunction toward High-Performance N2 Photofixation

The development of heterogeneous catalysts with atom-dispersed active sites is essential to facilitate nitrogen (N2) activation for the N2 reduction reaction (NRR). However, it remains a major challenge to tune the coordination configuration of the metal centers to further accelerate the activation kinetics. Herein, an atomically precise dinuclear Ni2 site-modified metal–organic framework (MOF)-derived ZnO@NC heterojunction (ZnO@NC-Ni2) was developed for effective N2 photofixation under mild conditions. Moreover, advanced structural characterization indicates that the most active N-coordinated bimetallic site configurations are Ni2–N6, where two Ni1–N4 moieties are shared with two N atoms. Theoretical calculations further demonstrate that the binuclear Ni2 active sites of ZnO@NC-Ni2 could adjust the N2 adsorption configuration as the side-on bridging adsorption mode (denoted as "*N≡N*"), while the single metal Ni1 sites of ZnO@NC-Ni1 tend to form a terminal adsorption configuration with N2 ("*N≡N" type). As a result, the unique electronic structure of binuclear Ni2 active sites in ZnO@NC-Ni2 tends to proceed as an associative alternating pathway, thereby decreasing the activation energy barrier of the reaction procedure and favoring the photocatalytic NRR. The present study provides a perspective to probe the relationship between the coordination architecture of earth-abundant metal active centers and NRR activities.