Huiliang Li , Qiuhong Wei , Kuan Lu , Lining Zhao , Ruihan Tang , Zhichang Xiao , Xue Liu , Xiang Cheng , Peng Han , Zheng Wang
{"title":"掺K氮化碳中的缺陷定制:实现光反应和暗反应的高效解耦,从而实现及时和延迟的按需太阳能制氢","authors":"Huiliang Li , Qiuhong Wei , Kuan Lu , Lining Zhao , Ruihan Tang , Zhichang Xiao , Xue Liu , Xiang Cheng , Peng Han , Zheng Wang","doi":"10.1016/j.jcat.2024.115628","DOIUrl":null,"url":null,"abstract":"<div><p>Decoupling hydrogen production from diurnal cycles is challenging in solar energy conversion. Recently, defect-modified K-doped carbon nitride has demonstrated the potential to realize this unique property. However, the concomitant undesirable defects during eutectic treatment, such as triazine ring insertion, impose substantial limitations on the decoupling performance. In this study, a one-step eutectic method assisted by CCl<sub>4</sub> was developed, which removed the detrimental triazine-based defects while introducing beneficial nitrogen vacancies. The engineered structure efficiently enhances visible light absorption, and spatially separates the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The localized LUMO on N-K sites serves as an electron reservoir, facilitating carrier separation and inhibiting the recombination. Consequently, one of the highest timely light-driven activities among polymeric photocatalysts was achieved, reaching 2557 times the H<sub>2</sub> production rate compared to the un-engineered counterpart. More significantly, the electron reservoir could store active electrons for several weeks, successfully enabling delayed on-demand solar H<sub>2</sub> production and decoupling H<sub>2</sub> evolution from diurnal cycles. This study effectively achieves both spatial and temporal separation of light absorption, solar storage, and release through defect tailoring, which is expected to advance the development of decoupled catalytic studies.</p></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":6.5000,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Defect tailoring in K-doped carbon nitride: Enabling efficient decoupling of light and dark reactions for timely and delayed on-demand solar hydrogen production\",\"authors\":\"Huiliang Li , Qiuhong Wei , Kuan Lu , Lining Zhao , Ruihan Tang , Zhichang Xiao , Xue Liu , Xiang Cheng , Peng Han , Zheng Wang\",\"doi\":\"10.1016/j.jcat.2024.115628\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Decoupling hydrogen production from diurnal cycles is challenging in solar energy conversion. Recently, defect-modified K-doped carbon nitride has demonstrated the potential to realize this unique property. However, the concomitant undesirable defects during eutectic treatment, such as triazine ring insertion, impose substantial limitations on the decoupling performance. In this study, a one-step eutectic method assisted by CCl<sub>4</sub> was developed, which removed the detrimental triazine-based defects while introducing beneficial nitrogen vacancies. The engineered structure efficiently enhances visible light absorption, and spatially separates the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The localized LUMO on N-K sites serves as an electron reservoir, facilitating carrier separation and inhibiting the recombination. Consequently, one of the highest timely light-driven activities among polymeric photocatalysts was achieved, reaching 2557 times the H<sub>2</sub> production rate compared to the un-engineered counterpart. More significantly, the electron reservoir could store active electrons for several weeks, successfully enabling delayed on-demand solar H<sub>2</sub> production and decoupling H<sub>2</sub> evolution from diurnal cycles. This study effectively achieves both spatial and temporal separation of light absorption, solar storage, and release through defect tailoring, which is expected to advance the development of decoupled catalytic studies.</p></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-06-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951724003415\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951724003415","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Defect tailoring in K-doped carbon nitride: Enabling efficient decoupling of light and dark reactions for timely and delayed on-demand solar hydrogen production
Decoupling hydrogen production from diurnal cycles is challenging in solar energy conversion. Recently, defect-modified K-doped carbon nitride has demonstrated the potential to realize this unique property. However, the concomitant undesirable defects during eutectic treatment, such as triazine ring insertion, impose substantial limitations on the decoupling performance. In this study, a one-step eutectic method assisted by CCl4 was developed, which removed the detrimental triazine-based defects while introducing beneficial nitrogen vacancies. The engineered structure efficiently enhances visible light absorption, and spatially separates the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The localized LUMO on N-K sites serves as an electron reservoir, facilitating carrier separation and inhibiting the recombination. Consequently, one of the highest timely light-driven activities among polymeric photocatalysts was achieved, reaching 2557 times the H2 production rate compared to the un-engineered counterpart. More significantly, the electron reservoir could store active electrons for several weeks, successfully enabling delayed on-demand solar H2 production and decoupling H2 evolution from diurnal cycles. This study effectively achieves both spatial and temporal separation of light absorption, solar storage, and release through defect tailoring, which is expected to advance the development of decoupled catalytic studies.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.