{"title":"Dual Active Sites with Charge-asymmetry in Organic Semiconductors Promoting C-C Coupling for Highly Efficient CO2 Photoreduction to Ethanol","authors":"Haotian Tan, Wenping Si, Rongao Zhang, Wei Peng, Xiaoqing Liu, Xusheng Zheng, Feng Hou, Lichang Yin, Ji Liang","doi":"10.1002/anie.202416684","DOIUrl":null,"url":null,"abstract":"Selective CO2 photoreduction into high-energy-density and high-value-added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C-C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon-based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon-based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as-formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97% for C2H5OH and C2H5OH yield of 0.80 mmol g-1 h-1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non-metal multi-site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202416684","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Selective CO2 photoreduction into high-energy-density and high-value-added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C-C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon-based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon-based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as-formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97% for C2H5OH and C2H5OH yield of 0.80 mmol g-1 h-1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non-metal multi-site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.