Atomic‐Level Insight into Optimizing the Hydrogen Evolution Pathway over a Co 1 ‐N 4 Single‐Site Photocatalyst

作者：Yuanjie Cao, Si Chen, Qiquan Luo, Huan Yan, Yue Lin, Wei Liu, Linlin Cao, Junling Lu, Jinlong Yang, Tao Yao, Shiqiang Wei · 发表于：Angewandte Chemie International Edition · 年份：2017 · DOI：10.1002/anie.201706467 · 被引用次数：358 · 研究领域：Advanced Photocatalysis Techniques、Copper-based nanomaterials and applications、Catalytic Processes in Materials Science

Abstract Knowledge of the photocatalytic H 2 evolution mechanism is of great importance for designing active catalysts toward a sustainable energy supply. An atomic‐level insight, design, and fabrication of single‐site Co 1 ‐N 4 composite as a prototypical photocatalyst for efficient H 2 production is reported. Correlated atomic characterizations verify that atomically dispersed Co atoms are successfully grafted by covalently forming a Co 1 ‐N 4 structure on g‐C 3 N 4 nanosheets by atomic layer deposition. Different from the conventional homolytic or heterolytic pathway, theoretical investigations reveal that the coordinated donor nitrogen increases the electron density and lowers the formation barrier of key Co hydride intermediate, thereby accelerating H–H coupling to facilitate H 2 generation. As a result, the composite photocatalyst exhibits a robust H 2 production activity up to 10.8 μmol h −1 , 11 times higher than that of pristine counterpart.