In:
Angewandte Chemie, Wiley, Vol. 135, No. 23 ( 2023-06-05)
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 C 2 ‐C 4 hydrocarbon production rate of 683 μmol g −1 h −1 (83 % C 2 ‐C 4 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 CH 4 activation to methyl intermediates (*CH 3 ) migrating onto adjacent metal nanoparticles. The nature of the *CH 3 ‐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.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.23
DOI:
10.1002/ange.202304301
Language:
English
Publisher:
Wiley
Publication Date:
2023
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