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双金属片
催化作用
异质结
吸附
金属
金属有机骨架
光催化
化学
材料科学
结晶学
物理化学
有机化学
光电子学
作者
Wensheng Zhang,Tianren Liu,Qingmei Tan,Jianshen Li,Yuangong Ma,Yan He,Dongxue Han,Dongdong Qin,Li Niu
标识
DOI:10.1021/acscatal.2c05129
摘要
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.
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