Synergistic Cu <sub>2</sub> and Polyoxometalate Clusters in Metal–Organic Layers Enable Oxidant‐Free CH <sub>4</sub> Photooxidation
Abstract
Abstract Methane (CH 4 ) photooxidation under mild conditions represents a transformative approach for sustainable production of fuel and chemicals, however, it remains challenging due to the persistent requirement for exogenous oxidants. Herein, this study reports a series of well‐defined bicluster photocatalysts Cu 2 POF Mn /PCN‐n (n = 1/5/8/10, denoting the mass ratio of PCN: Cu 2 POF Mn ), constructed by integrating [Cu(µ 2 ‐I)] 2 (denoted as Cu 2 ) clusters and MnMo 6 polyoxometalates (POMs) within ultrathin metal–organic layers (MOLs) anchored on PCN nanoflakes. The optimized Cu 2 POF Mn /PCN‐8 photocatalyst achieves efficient CH 4 conversion to HCOOH with 10.5 mmol g POF −1 yield and 95% selectivity without any exogenous oxidant. Comprehensive studies demonstrated that the engineered MOLs architecture enables uniform and ordered assembly of complementary catalytic bicluster, where MnMo 6 POMs act as electron reservoirs to promote charge separation for in situ H 2 O 2 generation, and Cu 2 clusters mimic CH 4 monooxygenase to selectively cleave C−H bonds via forming Cu 2 −O···H···CH 3 intermediate. This work highlights the vital role of MOL‐directed bicluster assembly for C–H functionalization that bypasses the need for sacrificial oxidants in selective CH 4 functionalization.
Article Details
Authors (10)
Jing Ren
Baifan Wang
State Key Laboratory of Elemento‐Organic Chemistry, College of Chemistry Nankai University Tianjin China
Hua‐Qing Yin
State Key Laboratory of Crystal Materials Institute For New Energy Materials and Low Carbon Technologies School of Materials Science & Engineering Tianjin University of Technology Tianjin P. R. China
Qiu‐Ping Zhao
Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 China
Shen‐Yin Hou
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science & Engineering School of Chemistry and Chemical Engineering Tianjin University of Technology Tianjin 300384 P. R. China
Xin‐Hui Wang
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science & Engineering School of Chemistry and Chemical Engineering Tianjin University of Technology Tianjin 300384 P. R. China
Shu‐Yan Wei
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science & Engineering School of Chemistry and Chemical Engineering Tianjin University of Technology Tianjin 300384 P. R. China
Shuang Yao
Department of Otolaryngology Head and Neck Surgery, Beijing Tongren Hospital
Tong‐Bu Lu
State Key Laboratory of Crystal Materials Tianjin Key Laboratory of Functional Crystal Materials Institute of Functional Crystals Tianjin University of Technology Tianjin China
Zhi‐Ming Zhang
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin China