Zhao Yuqi, Wu Xi, Wang Hengliang, Ma Ming, Tian Jian, Wang Xin
School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China.
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China.
Nano Lett. 2024 Dec 18;24(50):16175-16183. doi: 10.1021/acs.nanolett.4c05201. Epub 2024 Dec 9.
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/g-CN heterostructure by selective phosphidation of the Co metal-organic framework/graphitic carbon nitride (Co-MOF/g-CN), converting the Co-O configuration into a highly electronegative, coordinatively unsaturated Co-P configuration anchored to a carbon matrix. P-doping induces strong charge redistribution, shifting the -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/-CN heterostructure demonstrated a HER rate of 13.51 mmol g h, 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.
优化单原子催化剂（SAC）的局部电子结构对于高效光催化析氢反应至关重要。本研究通过对钴金属有机框架/石墨相氮化碳（Co-MOF/g-CN）进行选择性磷化合成了Co-P/g-CN异质结构，将Co-O构型转变为锚定在碳基质上的高电负性、配位不饱和的Co-P构型。P掺杂引起强烈的电荷重新分布，使价带中心向费米能级移动，将Co位点从缺电子状态转变为富电子状态，并导致析氢反应的自由能垒显著降低至-0.08 eV。Co-P/g-CN异质结构的析氢速率为13.51 mmol g⁻¹ h⁻¹，约为负载贵金属的光催化剂的4.82 - 8.35倍。在380 nm处的表观量子效率（AQE）为28.45%。低配位数和高电负性金属位点的协同效应显著提高了光催化析氢性能。
