S-scheme CeO_(2)/Cd_(7.23)Zn_(2.77)S_(10)-DETA heterojunctions for superior cocatalyst-free visible-light photocatalytic hydrogen evolution  

S-型异质结CeO_(2)/Cd_(7.23)Zn_(2.77)S_(10)-DETA的高效无助催化剂可见光催化析氢

作　　者：LI Wen MENG Ao-yun LI Zhen ZHANG Jin-feng FU Jun-wei 李雯;孟奥运;李真;张金锋;傅俊伟(College of Food Science and Engineering,Anhui Science and Technology University,Fengyang 233100,China;School of Physics and Electronic Information,Huaibei Normal University,Huaibei 235000,China;Hunan Joint International Research Center for Carbon Dioxide Resource Utilization,School of Physics,Central South University,Changsha 410083,China)

机构地区：[1]College of Food Science and Engineering,Anhui Science and Technology University,Fengyang 233100,China [2]School of Physics and Electronic Information,Huaibei Normal University,Huaibei 235000,China [3]Hunan Joint International Research Center for Carbon Dioxide Resource Utilization,School of Physics,Central South University,Changsha 410083,China

出　　处：《Journal of Central South University》2024年第12期4572-4585,共14页中南大学学报(英文版)

基　　金：Project(42407636)supported by the National Natural Science Foundation of China;Project(2022AH040068)supported by the Major Foundation of the Educational Commission of Anhui Province,China;Project(2023AH051861)supported by the Natural Science Research Project for Colleges and Universities in Anhui Province,China;Project(SPYJ202201)supported by the Talent Introduction Foundation of Anhui Science and Technology University,China;Project(202310879096)supported by the Innovation and Entrepreneurship Training Program for College Students,China。

摘　　要：The intensifying global energy crisis,coupled with environmental degradation from fossil fuels,highlights that photocatalytic hydrogen evolution technology offers a promising solution due to its efficiency and sustainability.In this study,we synthesized CeO_(2)/Cd_(7.23)Zn_(2.77)S_(10)-DETA(diethylenetriamine is abbreviated as DETA,and subsequently CeO_(2)is referred to as EO,Cd_(7.23)Zn_(2.77)S_(10)-DETA is abbreviated as ZCS,and the composite with EO comprising 30%is abbreviated as EO/ZCS)nanocomposites with S-scheme heterojunctions.Under conditions without external co-catalysts and utilizing only visible light as the excitation source,EO/ZCS nanocomposites exhibited outstanding photocatalytic hydrogen evolution activity and remarkable stability,presenting significant advantages over conventional methods that rely on co-catalysts and ultraviolet light.The photocatalytic hydrogen evolution rate of EO/ZCS nanocomposites reached 4.11 mmol/(g·h),significantly surpassing that of EO(trace)and ZCS(2.78 mmol/(g·h)).This substantial enhancement is attributed to the S-scheme charge transfer mechanism at the heterojunctions in EO/ZCS nanocomposites,which effectively facilitates the efficient separation and transfer of photogenerated electron-hole pairs,thereby substantially enhancing photocatalytic hydrogen evolution activity.Through techniques such as X-ray photoelectron spectroscopy(XPS)and theoretical calculations,we confirmed the formation of S-scheme heterojunctions and elucidated their photocatalytic hydrogen evolution mechanism.The results underscore the potential of EO/ZCS nanocomposites as highly efficient and stable photocatalysts for hydrogen production under environmentally benign conditions.为应对全球能源危机的加剧以及化石燃料引起的环境恶化,光催化氢生成技术因其高效性和可持续性而提供了一个有前景的解决方案。在本研究中,我们合成了具有S型异质结的CeO_(2)/Cd_(7.23)Zn_(2.77)S_(10)-DETA(其中二乙烯三胺简称为DETA,后续CeO_(2)简称为EO,Cd_(7.23)Zn_(2.77)S_(10)-DETA简称为ZCS,CeO_(2)含量为30%的复合材料简称为EO/ZCS)纳米复合材料。在无需外部共催化剂且仅利用可见光作为激发源的条件下,EO/ZCS纳米复合材料展示出卓越的光催化氢生成活性和显著的稳定性,相较于依赖共催化剂和紫外光的传统方法具有显著优势。EO/ZCS纳米复合材料的光催化氢生成速率达到4.11 mmol/(g·h),显著超过EO(可忽略不计)和ZCS(2.78 mmol/(g·h))。这一显著提升归因于EO/ZCS纳米复合材料中异质结处的S-型电荷转移机制,该机制有效促进了光生电子-空穴对的高效分离和转移,从而大幅提升了光催化氢生成活性。通过X射线光电子能谱(XPS)和理论计算等技术,我们证实了S-型异质结的形成并阐明了其光催化氢生成机制。研究结果强调了EO/ZCS纳米复合材料作为在环境友好条件下高效且稳定的光催化剂用于氢气生产的潜力。

关 键 词：photocatalytic hydrogen nanocomposites S-scheme HETEROJUNCTIONS 

分 类 号：TM4[电气工程—电器]