{"title":"Unlocking Copper-Free Interfacial Asymmetric C–C Coupling for Ethylene Photosynthesis from CO2 and H2O","authors":"Wentao Song, Cheng Wang, Yong Liu, Kok Chan Chong, Xinyue Zhang, Tie Wang, Yuanming Zhang, Bowen Li, Jianwu Tian, Xianhe Zhang, Xinyun Wang, Bingqing Yao, Xi Wang, Yukun Xiao, Yingfang Yao, Xianwen Mao, Qian He, Zhiqun Lin, Zhigang Zou, Bin Liu","doi":"10.1021/jacs.4c10023","DOIUrl":null,"url":null,"abstract":"Solar-driven carbon dioxide (CO<sub>2</sub>) reduction into C<sub>2+</sub> products such as ethylene represents an enticing route toward achieving carbon neutrality. However, due to sluggish electron transfer and intricate C–C coupling, it remains challenging to achieve highly efficient and selective ethylene production from CO<sub>2</sub> and H<sub>2</sub>O beyond capitalizing on Cu-based catalysts. Herein, we report a judicious design to attain asymmetric C–C coupling through interfacial defect-rendered tandem catalytic centers within a sulfur-vacancy-rich MoS<sub><i>x</i></sub>/Fe<sub>2</sub>O<sub>3</sub> photocatalyst sheet, enabling a robust CO<sub>2</sub> photoreduction to ethylene without the need for copper, noble metals, and sacrificial agents. Specifically, interfacial S vacancies induce adjacent under-coordinated S atoms to form Fe–S bonds as a rapid electron-transfer pathway for yielding a Z-scheme band alignment. Moreover, these S vacancies further modulate the strong coupling interaction to generate a nitrogenase-analogous Mo–Fe heteronuclear unit and induce the upward shift of the d-band center. This bioinspired interface structure effectively suppresses electrostatic repulsion between neighboring *CO and *COH intermediates via d-p hybridization, ultimately facilitating an asymmetric C–C coupling to achieve a remarkable solar-to-chemical efficiency of 0.565% with a superior selectivity of 84.9% for ethylene production. Further strengthened by MoS<sub><i>x</i></sub>/WO<sub>3</sub>, our design unveils a promising platform for optimizing interfacial electron transfer and offers a new option for C<sub>2+</sub> synthesis from CO<sub>2</sub> and H<sub>2</sub>O using copper-free and noble metal-free catalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c10023","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
Solar-driven carbon dioxide (CO2) reduction into C2+ products such as ethylene represents an enticing route toward achieving carbon neutrality. However, due to sluggish electron transfer and intricate C–C coupling, it remains challenging to achieve highly efficient and selective ethylene production from CO2 and H2O beyond capitalizing on Cu-based catalysts. Herein, we report a judicious design to attain asymmetric C–C coupling through interfacial defect-rendered tandem catalytic centers within a sulfur-vacancy-rich MoSx/Fe2O3 photocatalyst sheet, enabling a robust CO2 photoreduction to ethylene without the need for copper, noble metals, and sacrificial agents. Specifically, interfacial S vacancies induce adjacent under-coordinated S atoms to form Fe–S bonds as a rapid electron-transfer pathway for yielding a Z-scheme band alignment. Moreover, these S vacancies further modulate the strong coupling interaction to generate a nitrogenase-analogous Mo–Fe heteronuclear unit and induce the upward shift of the d-band center. This bioinspired interface structure effectively suppresses electrostatic repulsion between neighboring *CO and *COH intermediates via d-p hybridization, ultimately facilitating an asymmetric C–C coupling to achieve a remarkable solar-to-chemical efficiency of 0.565% with a superior selectivity of 84.9% for ethylene production. Further strengthened by MoSx/WO3, our design unveils a promising platform for optimizing interfacial electron transfer and offers a new option for C2+ synthesis from CO2 and H2O using copper-free and noble metal-free catalysts.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.