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Synergy of Pd Clusters and TiO2 {101} for Photocatalytic Nonoxidative Coupling of Methane
Jianlong Yang1,2, Annika S Tang3, Junwang Tang1
1Industrial Catalysis Center, Department of Chemical Engineering, Tsinghua University, Beijing, China.
Abstract:
Photocatalytic nonoxidative coupling of methane (NOCM) offers a sustainable route to valorize CH4 into C2 hydrocarbons, yet it is impeded by low activity, poor stability, and overoxidation. We demonstrate a {101} facet-exposed TiO2 photocatalyst decorated with coexisting Pd single atoms and clusters, which achieves a high C2H6 production rate of 600 µmol·h-1·g-1 at room temperature with near 100% selectivity and stoichiometric H2 co-production. The catalyst exhibits exceptional durability, maintaining stable performance over 30 h in a flow reactor. This enhanced performance stems from efficient interfacial charge transfer between the {101} facet and the coexisting Pd single atoms and clusters. Moreover, stable three-fold coordinated surface oxygen atoms suppress lattice oxygen involvement, preventing overoxidation and ensuring high selectivity. This work overcomes key thermodynamic and kinetic limitations, presenting a robust design strategy for efficient photocatalytic methane conversion.
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