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

doi:10.1016/j.actphy.2025.100051

物理化学学报 >> 2025, Vol. 41 >> Issue (6): 100051.doi: 10.1016/j.actphy.2025.100051

所属专题：光催化中的S型异质结

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

苗鑫宇¹^,†, 杨浩¹^,³^,†, 何杰¹^,*(), 王晶²^,*(), 靳治良¹^,*()

¹ 北方民族大学化学与化学工程学院, 宁夏太阳能化学转化技术重点实验室, 国家民族事务委员会化工技术基础重点实验室, 银川 750021
² 天津理工大学材料科学与工程学院, 天津 300384
³ 福州大学化学工程学院, 福州 350116

收稿日期:2024-11-25 修回日期:2025-01-10 录用日期:2025-01-13 发布日期:2025-04-19
通讯作者: Email: 406793019@qq.com (何杰)wangjing@email.tjut.edu.cn (王晶)zl-jin@nun.edu.cn (靳治良)
作者简介:
^† Equal contribution.
基金资助:
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

Adjusting the electronic structure of Keggin-type polyoxometalates to construct S-scheme heterojunction for photocatalytic hydrogen evolution

Xinyu Miao¹, Hao Yang¹^,³, Jie He¹^,*(), Jing Wang²^,*(), Zhiliang Jin¹^,*()

¹ School of Chemistry and Chemical Engineering, Ningxia Key Laboratory of Solar Chemical Conversion Technology, Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan 750021, China
² School of Materials Science & Engineering, Tianjin University of Technology, Tianjin 300384, China
³ College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China

Received:2024-11-25 Revised:2025-01-10 Accepted:2025-01-13 Published:2025-04-19
Contact: Email: 406793019@qq.com (Jie He)wangjing@email.tjut.edu.cn (Jing Wang)zl-jin@nun.edu.cn (Zhiliang Jin)
Supported by:
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

1. 2025.100051-SI-5p.pdf(2229KB)

摘要/Abstract

摘要：

缓慢的电子迁移速率和显著的电子-空穴复合是实现高光催化效率的重大障碍。利用多种催化剂构建异质结可以有效增强电荷分离。通过水热合成制备了一系列Keggin型空心十二面体多金属氧酸盐，并通过添加金属元素对其分子轨道进行修饰。金属元素的引入调节了多金属氧酸盐的电子结构，有效增强了多金属氧酸盐的电子聚集能力。单一组分催化剂常常面临严重的空穴-电子复合问题。为了解决这一问题，提出了构建异质结的方案以提高电子传输效率。通过将ZnCdS纳米颗粒固定在多金属氧酸盐表面形成异质结结构，显著增强了界面电荷传输能力。密度泛函理论(DFT)计算和实验结果表明，金属组分的调控使多金属氧酸盐具有更有利的能级轨道。ZnCdS和KMoP S型异质结的催化机制也得到了验证。S型异质结的形成进一步提高了电子传输效率，与其他传统异质结相比，实现了光生电子和空穴的高效利用。此外，S型异质结使催化剂的d带中心更接近费米能级，从而提高了导电能力。本文为多金属氧酸盐的能级调控和S型异质结的设计提供了一种新方法。

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

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.

Key words: ZnCdS, Keggin-type polyoxometalates, Hollow structure, Charge density difference, d band center adjustment, S-scheme heterojunction

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), 100051. doi: 10.1016/j.actphy.2025.100051

Xinyu Miao, Hao Yang, Jie He, Jing Wang, Zhiliang Jin. Adjusting the electronic structure of Keggin-type polyoxometalates to construct S-scheme heterojunction for photocatalytic hydrogen evolution[J]. Acta Phys. -Chim. Sin. 2025, 41(6), 100051. doi: 10.1016/j.actphy.2025.100051

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100051

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I6/100051

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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

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