Pu Wang, Dr. Run Shi, Dr. Yunxuan Zhao, Dr. Zhenhua Li, Jiaqing Zhao, Jiaqi Zhao, Prof. Geoffrey I. N. Waterhouse, Prof.?Dr. Li-Zhu Wu, Prof.?Dr. Tierui Zhang
{"title":"Selective Photocatalytic Oxidative Coupling of Methane via Regulating Methyl Intermediates over Metal/ZnO Nanoparticles","authors":"Pu Wang, Dr. Run Shi, Dr. Yunxuan Zhao, Dr. Zhenhua Li, Jiaqing Zhao, Jiaqi Zhao, Prof. Geoffrey I. N. Waterhouse, Prof.?Dr. Li-Zhu Wu, Prof.?Dr. Tierui Zhang","doi":"10.1002/anie.202304301","DOIUrl":null,"url":null,"abstract":"<p>Methane conversion to higher hydrocarbons requires harsh reaction conditions due to high energy barriers associated with C−H bond activation. Herein, we report a systematic investigation of photocatalytic oxidative coupling of methane (OCM) over transition-metal-loaded ZnO photocatalysts. A 1 wt % Au/ZnO delivered a remarkable C<sub>2</sub>-C<sub>4</sub> hydrocarbon production rate of 683 μmol g<sup>−1</sup> h<sup>−1</sup> (83 % C<sub>2</sub>-C<sub>4</sub> selectivity) under light irradiation with excellent photostability over two days. The metal type and its interaction with ZnO strongly influence the selectivity toward C−C coupling products. Photogenerated Zn<sup>+</sup>-O<sup>−</sup> sites enable CH<sub>4</sub> activation to methyl intermediates (*CH<sub>3</sub>) migrating onto adjacent metal nanoparticles. The nature of the *CH<sub>3</sub>-metal interaction controls the OCM products. In the case of Au, strong d-σ orbital hybridization reduces metal-C−H bond angles and steric hindrance, thereby enabling efficient methyl coupling. Findings indicate the d-σ center may be a suitable descriptor for predicting product selectivity during OCM over metal/ZnO photocatalysts.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2023-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"10","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/anie.202304301","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: 10
Abstract
Methane conversion to higher hydrocarbons requires harsh reaction conditions due to high energy barriers associated with C−H bond activation. Herein, we report a systematic investigation of photocatalytic oxidative coupling of methane (OCM) over transition-metal-loaded ZnO photocatalysts. A 1 wt % Au/ZnO delivered a remarkable C2-C4 hydrocarbon production rate of 683 μmol g−1 h−1 (83 % C2-C4 selectivity) under light irradiation with excellent photostability over two days. The metal type and its interaction with ZnO strongly influence the selectivity toward C−C coupling products. Photogenerated Zn+-O− sites enable CH4 activation to methyl intermediates (*CH3) migrating onto adjacent metal nanoparticles. The nature of the *CH3-metal interaction controls the OCM products. In the case of Au, strong d-σ orbital hybridization reduces metal-C−H bond angles and steric hindrance, thereby enabling efficient methyl coupling. Findings indicate the d-σ center may be a suitable descriptor for predicting product selectivity during OCM over metal/ZnO photocatalysts.
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.