Md Habibur Rahman, Yujie Sun and Arun Mannodi-Kanakkithodi
{"title":"高通量筛选 ZnIn2S4 中用于光催化的单原子辅助催化剂†。","authors":"Md Habibur Rahman, Yujie Sun and Arun Mannodi-Kanakkithodi","doi":"10.1039/D4MA00616J","DOIUrl":null,"url":null,"abstract":"<p >In recent years, ZnIn<small><sub>2</sub></small>S<small><sub>4</sub></small> (ZIS) has garnered attention as a promising photocatalyst due to its attractive properties. However, its performance is hindered by its restricted range of visible light absorption and the rapid recombination of photoinduced holes and electrons. Single-atom co-catalysts (SACs) can improve photocatalytic activity by providing highly active sites for reactions, enhancing charge separation efficiency, and reducing the recombination rate of photo-generated carriers. In this work, we perform high-throughput density functional theory (DFT) computations to search for SACs in ZIS encompassing 3d, 4d, and 5d transition metals as well as lanthanides, considering both substitutional and interstitial sites. For a total of 172 SACs, defect formation energy (DFE) is computed as a function of chemical potential, charge, and Fermi level (<em>E</em><small><sub>F</sub></small>), leading to the identification of low energy dopants and their corresponding shallow or deep defect levels. Statistical data analysis shows that DFE is highly correlated with the difference in electron affinity between the host (Zn/In/S) atom and the SAC, followed by the electronegativity and boiling point. Among the 60 lowest energy SACs, Co<small><sub>In</sub></small>, Yb<small><sub>i</sub></small>, Tc<small><sub>Zn</sub></small>, Au<small><sub>S</sub></small>, La<small><sub>i</sub></small>, Eu<small><sub>i</sub></small>, Au<small><sub>i</sub></small>, Ta<small><sub>In</sub></small>, Hf<small><sub>In</sub></small>, Zr<small><sub>In</sub></small>, and Ni<small><sub>Zn</sub></small> lead to a lowering of the Gibbs free energy for hydrogen evolution reaction, improving upon previous ZIS results. The computational dataset and insights from this work promise to accelerate the experimental design of novel dopants in ZIS with optimized properties for photocatalysis and environmental remediation.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 21","pages":" 8673-8683"},"PeriodicalIF":5.2000,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00616j?page=search","citationCount":"0","resultStr":"{\"title\":\"High-throughput screening of single atom co-catalysts in ZnIn2S4 for photocatalysis†\",\"authors\":\"Md Habibur Rahman, Yujie Sun and Arun Mannodi-Kanakkithodi\",\"doi\":\"10.1039/D4MA00616J\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In recent years, ZnIn<small><sub>2</sub></small>S<small><sub>4</sub></small> (ZIS) has garnered attention as a promising photocatalyst due to its attractive properties. However, its performance is hindered by its restricted range of visible light absorption and the rapid recombination of photoinduced holes and electrons. Single-atom co-catalysts (SACs) can improve photocatalytic activity by providing highly active sites for reactions, enhancing charge separation efficiency, and reducing the recombination rate of photo-generated carriers. In this work, we perform high-throughput density functional theory (DFT) computations to search for SACs in ZIS encompassing 3d, 4d, and 5d transition metals as well as lanthanides, considering both substitutional and interstitial sites. For a total of 172 SACs, defect formation energy (DFE) is computed as a function of chemical potential, charge, and Fermi level (<em>E</em><small><sub>F</sub></small>), leading to the identification of low energy dopants and their corresponding shallow or deep defect levels. Statistical data analysis shows that DFE is highly correlated with the difference in electron affinity between the host (Zn/In/S) atom and the SAC, followed by the electronegativity and boiling point. Among the 60 lowest energy SACs, Co<small><sub>In</sub></small>, Yb<small><sub>i</sub></small>, Tc<small><sub>Zn</sub></small>, Au<small><sub>S</sub></small>, La<small><sub>i</sub></small>, Eu<small><sub>i</sub></small>, Au<small><sub>i</sub></small>, Ta<small><sub>In</sub></small>, Hf<small><sub>In</sub></small>, Zr<small><sub>In</sub></small>, and Ni<small><sub>Zn</sub></small> lead to a lowering of the Gibbs free energy for hydrogen evolution reaction, improving upon previous ZIS results. The computational dataset and insights from this work promise to accelerate the experimental design of novel dopants in ZIS with optimized properties for photocatalysis and environmental remediation.</p>\",\"PeriodicalId\":18242,\"journal\":{\"name\":\"Materials Advances\",\"volume\":\" 21\",\"pages\":\" 8673-8683\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2024-10-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00616j?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Materials Advances\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/ma/d4ma00616j\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Materials Advances","FirstCategoryId":"1085","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/ma/d4ma00616j","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
High-throughput screening of single atom co-catalysts in ZnIn2S4 for photocatalysis†
In recent years, ZnIn2S4 (ZIS) has garnered attention as a promising photocatalyst due to its attractive properties. However, its performance is hindered by its restricted range of visible light absorption and the rapid recombination of photoinduced holes and electrons. Single-atom co-catalysts (SACs) can improve photocatalytic activity by providing highly active sites for reactions, enhancing charge separation efficiency, and reducing the recombination rate of photo-generated carriers. In this work, we perform high-throughput density functional theory (DFT) computations to search for SACs in ZIS encompassing 3d, 4d, and 5d transition metals as well as lanthanides, considering both substitutional and interstitial sites. For a total of 172 SACs, defect formation energy (DFE) is computed as a function of chemical potential, charge, and Fermi level (EF), leading to the identification of low energy dopants and their corresponding shallow or deep defect levels. Statistical data analysis shows that DFE is highly correlated with the difference in electron affinity between the host (Zn/In/S) atom and the SAC, followed by the electronegativity and boiling point. Among the 60 lowest energy SACs, CoIn, Ybi, TcZn, AuS, Lai, Eui, Aui, TaIn, HfIn, ZrIn, and NiZn lead to a lowering of the Gibbs free energy for hydrogen evolution reaction, improving upon previous ZIS results. The computational dataset and insights from this work promise to accelerate the experimental design of novel dopants in ZIS with optimized properties for photocatalysis and environmental remediation.