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.

Alkaline-earth metal elements in s-block of periodic table have rarely been studied as active sites for nitrogen (N2) photofixation. Here, we reported a single-atom calcium (Ca) modified mesoporous g-C3N4 (Ca/m-g-C3N4)...

The conversion of N2 and CO2 into urea through photocatalytic C–N coupling reaction under ambient condition serves as a novel green avenue for urea synthesis. However, the poor adsorption and...

Owing to the advantages of easy separation and recovery, the development of magnetic photocatalysts is essential to create a viable photocatalytic technology for the degradation of antibiotic contaminants in water....

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