Tan Dong, Ding Tengfei, Shen Kaidong, Xu Chang, Jin Shan, Hu Daqiao, Sun Song, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University Hefei Anhui 230601 China
Institutes of Physical Science and Information Technology, Anhui University Hefei Anhui 230601 China.
Chem Sci. 2025 Apr 25;16(21):9326-9336. doi: 10.1039/d5sc01735a. eCollection 2025 May 28.
Developing high-efficiency photocatalysts for photocatalytic hydrogen production and understanding the structure-property relationships is much desired. In this study, a family of PtAg ( = 9, 11, 13 and 14) nanoclusters (NCs), including a new PtAg(SR)(P(Ph-OMe)) NC, were designed and synthesized ligand engineering (SR = 2,3,5,6-tetrafluorothiophenol, P(Ph-OMe) = tris(4-methylphenyl)phosphine). The positive effect of the kernel structural defect on photocatalytic activity was investigated using the photocatalytic water-splitting reaction as a model, and the mechanistic relationship between the defect structure and catalytic activity was clarified. In this series of PtAg bimetallic NCs, the PtAg NC, which exhibits a distinctive defect-containing icosahedral kernel structure, displayed excellent catalytic performance for photocatalytic hydrogen evolution, with the hydrogen production rate reaching 1780 μmol g h. The experimental results revealed that the superior catalytic activity of PtAg/g-CN may originate from the formation of Z-scheme heterojunction between PtAg and the g-CN, facilitating efficient electron-hole separation and charge transfer. Furthermore, density-functional theory (DFT) calculations reveal the critical role of the defect-containing icosahedron-kernel on photocatalytic activity, which is favourable for the formation of the most stable nanocomposites and the easy absorption of H* intermediates on the Ag sites in PtAg/g-CN. This paper provides insights into the effect that the defects have on the mechanism of the photocatalytic hydrogen evolution reaction at the atomic level and promotes the rational design of high-efficiency photocatalysts.
开发用于光催化产氢的高效光催化剂并理解其结构-性能关系是非常必要的。在本研究中，设计并合成了一系列PtAg（n = 9、11、13和14）纳米团簇（NCs），包括一种新型的PtAg(SR)(P(Ph-OMe)) NC，采用配体工程（SR = 2,3,5,6-四氟苯硫酚，P(Ph-OMe) = 三(4-甲基苯基)膦）。以光催化水分解反应为模型，研究了内核结构缺陷对光催化活性的积极影响，并阐明了缺陷结构与催化活性之间的机理关系。在这一系列的PtAg双金属NCs中，具有独特含缺陷二十面体内核结构的PtAg NC对光催化析氢表现出优异的催化性能，产氢速率达到1780 μmol g-1 h-1。实验结果表明，PtAg/g-CN的优异催化活性可能源于PtAg与g-CN之间形成的Z型异质结，促进了有效的电子-空穴分离和电荷转移。此外，密度泛函理论（DFT）计算揭示了含缺陷二十面体内核对光催化活性的关键作用，这有利于形成最稳定的纳米复合材料以及H*中间体在PtAg/g-CN的Ag位点上的容易吸附。本文在原子水平上深入了解了缺陷对光催化析氢反应机理的影响，并促进了高效光催化剂的合理设计。
