物理化学学报2025，Vol.41Issue(6)：23-35,13.DOI:10.1016/j.actphy.2025.100051
调整Keggin型多金属氧酸盐电子结构构建S型异质结用于光催化析氢
Adjusting the electronic structure of Keggin-type polyoxometalates to construct S-scheme heterojunction for photocatalytic hydrogen evolution
摘要
Abstract
The sluggish electron migration rate and pronounced electron-hole recombination,pose significant obstacles to achieving high photocatalytic efficiency.The utilization of multiple catalysts for the construction of heterojunctions can effectively enhance charge separation.A series of Keggin-type hollow dodecahedral polyoxometalates were prepared via hydrothermal synthesis,and their molecular orbitals were modified through the addition of metal elements.The incorporation of metal elements modulated the electronic structure of polyoxometalates,effectively enhancing the electron aggregation capability of polyoxometalates.Single-component catalysts often face serious hole-electron recombination.In order to solve this problem,the scheme of constructing heterojunction is proposed to improve the electron transport efficiency.By immobilizing ZnCdS nanoparticles onto the polyoxometalate surface,the heterojunction architecture was engineered to significantly enhance the interfacial charge transfer capability.Density Functional Theory(DFT)calculations and the experimental results indicate that the modulation of metallic components renders the polyoxometalate a more favorable energy-level orbital.The catalytic mechanism of ZnCdS and KMoP S-scheme heterojunction was also verified.The formation of S-scheme heterojunctions further improves the electron transfer efficiency compared to other traditional heterojunctions,achieving efficient utilization of photo generated electrons and holes.Additionally,the S-scheme heterojunction shifts the catalystʼs d-band center closer to the Fermi level,thereby improving electrical conductivity.This article provides a new approach for energy level regulation of polyoxometalates and the design of S-scheme heterojunctions.关键词
ZnCdS/Keggin型多金属氧酸盐/空心结构/电荷密度差分/d带中心调节/S型异质结Key words
ZnCdS/Keggin-type polyoxometalates/Hollow structure/Charge density difference/d band center adjustment/S-scheme heterojunction分类
化学化工引用本文复制引用
苗鑫宇,杨浩,何杰,王晶,靳治良..调整Keggin型多金属氧酸盐电子结构构建S型异质结用于光催化析氢[J].物理化学学报,2025,41(6):23-35,13.基金项目
The project was supported by the Innovative Team for Transforming Waste Cooking Oil into Clean Energy and High Value-Added Chemicals of China and Ningxia Low-Grade Resource High Value Utilization And Environmental Chemical Integration Technology Innovation Team Project of Ningxia.该项目由中国餐厨废油转化清洁能源与高附加值化学品创新团队和宁夏低品位资源高价值利用与环境化工一体化技术创新团队项目支持 （）
