摘要
近年来,光催化产氢与有机物氧化的偶联反应备受关注,如何设计高效双功能光催化剂实现偶联反应成为研究重点.在众多光催化剂中,ZnIn_(2)S_(4)以其优异的可见光吸收能力、本征的极化电场以及较强的氧化还原能力成为双功能催化剂的热点备选材料.然而,电子空穴分离效率低以及光生电子空穴复合率高的问题限制了ZnIn_(2)S_(4)光电转化效率的进一步提高.针对这一问题,我们采用了具有较高导电性和独特结构的金属相1T-MoS_(2)作为助催化剂与花状ZnIn_(2)S_(4)复合形成“海胆状”的1T-MoS_(2)/ZnIn_(2)S_(4)欧姆结复合材料.理论计算结合XPS数据揭示了欧姆结与内建电场的形成,一系列光谱表征表明由欧姆结所形成的强内建电场促进了ZnIn_(2)S_(4)体内光生电子快速向1T-MoS_(2)转移,同时活性测试与EPR表征证明了苯甲醇的氧化反应可以作为光生空穴的有效捕获剂.最终,1T-MoS_(2)/ZnIn_(2)S_(4)复合光催化剂实现了4.6倍光催化性能的提高,420 nm波长下表光量子效率达6.75%.本项工作通过精确调节电荷转移机制,实现了ZnIn_(2)S_(4)双功能催化剂光电效率的进一步提高,为光催化剂载流子调控设计提供了新思路.
The synergistic coupling of photocatalytic hydrogen evolution andα-C±H bond activation reactions enables the comprehensive harnessing of the redox potential of semiconductor catalysts,yielding exceptionally high utilization of photocatalytic technology.Guiding and optimizing the charge migration within photocatalysts constitute a pivotal strategy for achieving remarkable overall solar energy conversion efficiency.Here,we engineer metallic 1T-MoS2/ZnIn_(2)S_(4)heterojunction photocatalysts by incorporating the distinctive 1T-MoS2 structure into the intricate flower-like ZnIn_(2)S_(4)framework.The modulation of charge migration within the 1T-MoS2/ZnIn_(2)S_(4)heterojunction photocatalysts is induced by an engineered interfacial electric field and an efficient hole transfer agent(benzyl alcohol).Steering charge migration results in an impressive 4.6-fold enhancement in photocatalytic performance compared with the pristine ZnIn_(2)S_(4).Moreover,comprehensive spectroscopy and theoretical analyses prove that the interfacial electric field facilitates the rapid electron transfer along the direction from the[S±Mo]to[In−S]layers.Simultaneously,swift hole capture is achieved by dehydrogenating theα-C±H bond in benzyl alcohol.
作者
张洪文
姚雪
山巍
刘玥
唐华
Hongwen Zhang;Xue Yao;Wei Shan;Yue Liu;Hua Tang(School of Environmental Science and Engineering,Qingdao University,Qingdao 266071,China;School of Materials Science and Engineering,Jiangsu University,Zhenjiang 212013,China)
基金
supported by the National Natural Science Foundation of China(21975110,22378219,22302106)
the Technology Support Program for the Youth Innovation Team of Shandong Higher Education Institutions(2023KJ225)
the support from Taishan Youth Scholar Program of Shandong Province。
作者简介
Hongwen Zhang received his PhD degree from Fuzhou University in 2019.After postdoctoral training at cMACS Institute of KU Leven University,he joined the School of Environmental Science and Engineering,Qingdao University as an associate professor.His research interests focus on the photoelectrochemical water splitting and plastic degradation;Corresponding author:Wei Shan received his PhD degree from Shanghai Institute of Ceramics,Chinese Academy of Sciences in 2020.After postdoctoral training at the Ocean University of China,he joined the School of Environmental Science and Engineering,Qingdao University.His research interests focus on the piezoelectric catalysis,email:shanwei@qdu.edu.cn;Corresponding author:Hua Tang received his PhD degree from Wuhan University of Technology in 2008.Then he joined the School of Materials Science and Engineering,Jiangsu University.In 2021,he joined the School of Environmental Science and Engineering,Qingdao University as a professor.His research interests focus on the photocatalytic water splitting and plastic high-value conversion.email:huatang79@163.com。
