摘要
缺陷工程被认为是提高光催化剂分解水制氢性能的关键策略之一,然而有关缺陷诱导半导体材料电子结构演变并增强光生载流子传输机制尚不明确.我们通过简单的一步水热合成法成功构建了富含S缺陷的In_(2)S_(3)半导体光催化剂(V_(S)-In_(2)S_(3)),在模拟太阳光辐照下其光催化分解水产氢性能相比传统的In_(2)S_(3)(P-In_(2)S_(3))提升了近一个数量级(达到221.18μmol∙g^(−1)∙h^(−1)).此外,利用自主研发的原位X射线光电子能谱(SI-XPS)结合相关密度泛函理论计算证实:S缺陷可诱导强还原性的低价态In(In^((3−x)+))暴露,进而增强In位点对H_(2)O的吸附和活化能力,因此,S缺陷型In_(2)S_(3)表现出显著增强的光催化析氢活性.此外,可视化观测到H_(2)分子在原位光照下脱质子转化为OH的分解水制氢过程.该研究为缺陷型光催化剂设计及光催化分解水反应机制和过程研究提供了一定的见解.
Defect engineering is considered as one of the key strategies to enhance the photocatalyst performance for water splitting hydrogen production.However,it is still unclear how defects induce changes in the electronic structure of semiconductor materials and enhance the photogenerated carrier transfer.In this study,we successfully synthesized In_(2)S_(3)photocatalyst with abundant sulfur defects(V_(S)-In_(2)S_(3))by a simple one-step hydrothermal method.It exhibits a photocatalytic hydrogen production performance of 221.18μmol∙g^(−1)∙h^(−1),and nearly one order magnitude higher than that of In_(2)S_(3)(P-In_(2)S_(3)).Furthermore,employing self-developed in situ X-ray photoelectron spectroscopy(SI-XPS)combined with density functional theory(DFT)calculations confirmed that sulfur defects induce the exposure of highly reducible low-valence state In(In^((3−x)+)),thereby enhancing the adsorption and activation capability of In sites towards H_(2).Consequently,sulfur-defective In_(2)S_(3)exhibits significantly enhanced photocatalytic hydrogen evolution activity.Additionally,the proton reduction of H_(2)molecules to OH has been visualized during the water splitting hydrogen production process under illumination conditions.This work provides new insights into defect-engineered photocatalyst design and the mechanism of photocatalytic water splitting reaction processes.
作者
王凤娇
闫良霖
耿来红
刘建华
毕迎普
董国俊
WANG Feng-jiao;YAN Liang-lin;GENG Lai-hong;LIU Jian-hua;BI Ying-pu;DONG Guo-jun(State Key Laboratory of Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China;University of Chinese Academy of Sciences,Beijing 100049,China;College of Earth and Environmental Sciences,Lanzhou University,Lanzhou 730000,China;Gansu Research Institute of Chemical Industry Co.,Ltd.,Lanzhou 730000,China)
出处
《分子催化（中英文）》
CAS
CSCD
北大核心
2024年第3期215-223,I0001,I0002,共11页
Journal of Molecular Catalysis(China)
基金
国家自然科学基金资助项目(No.22372181)
中国科学院兰州化学物理研究所自主部署项目(No.2022000126)。
关键词
光催化
S缺陷
硫化铟
电子结构
析氢反应
photocatalysis
sulfur defects
In_(2)S_(3)
electronic structure
H_(2) evolution
作者简介
王凤娇(1998−),女,硕士研究生,主要从事半导体光催化材料制备及电荷转移机理研究.E-mail:wangfengjiao21@mails.ucas.ac.cn;通信联系人:刘建华,E-mail:jhliu@licp.cas.cn;通信联系人:董国俊,E-mail:dongguojun@licp.cas.cn.
