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Atomic‐Level Insight into Optimizing the Hydrogen Evolution Pathway over a Co 1 ‐N 4 Single‐Site Photocatalyst
Author(s) -
Cao Yuanjie,
Chen Si,
Luo Qiquan,
Yan Huan,
Lin Yue,
Liu Wei,
Cao Linlin,
Lu Junling,
Yang Jinlong,
Yao Tao,
Wei Shiqiang
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201706467
Subject(s) - heterolysis , photocatalysis , homolysis , atomic layer deposition , catalysis , materials science , water splitting , hydride , covalent bond , nanotechnology , density functional theory , photochemistry , chemistry , metal , layer (electronics) , computational chemistry , radical , biochemistry , organic chemistry , metallurgy
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.