Phosphorus Regulates Coordination Number and Electronegativity of Cobalt Atomic Sites Triggering Efficient Photocatalytic Water Splitting

作者：Yuqi Zhao, Xi Wu, Hengliang Wang, Ming Ma, Jian Tian, Xin Wang · 发表于：Nano Letters · 年份：2024 · DOI：10.1021/acs.nanolett.4c05201 · 被引用次数：70 · 研究领域：Advanced Photocatalysis Techniques、Ammonia Synthesis and Nitrogen Reduction、Electrocatalysts for Energy Conversion

High Resolution Image Download MS PowerPoint Slide Optimizing the local electronic structure of a single-atom catalyst (SAC) is crucial for efficient photocatalytic hydrogen evolution reactions. This study synthesized a Co-P 4 /g-C 3 N 4 heterostructure by selective phosphidation of the Co metal–organic framework/graphitic carbon nitride (Co-MOF/g-C 3 N 4 ), converting the Co-O 6 configuration into a highly electronegative, coordinatively unsaturated Co-P 4 configuration anchored to a carbon matrix. P-doping induces strong charge redistribution, shifting the d -band center toward the Fermi level, transforming the Co sites from an electron-deficient state to an electron-rich state, and resulting in a significant reduction in the free energy barrier for HER to −0.08 eV. The Co-P 4 / g -C 3 N 4 heterostructure demonstrated a HER rate of 13.51 mmol g –1 h –1, approximately 4.82–8.35 times greater than those of photocatalysts loaded with noble metals. The apparent quantum efficiency (AQE) was 28.45% at 380 nm. The synergistic effect of the low coordination number and high electronegativity metal sites significantly enhances the photocatalytic HER performance.