Synergy of Pd Clusters and TiO ₂ {101} for Photocatalytic Nonoxidative Coupling of Methane

ABSTRACT Photocatalytic nonoxidative coupling of methane (NOCM) offers a sustainable route to valorize CH ₄ into C ₂ hydrocarbons, yet it is impeded by low activity, poor stability, and overoxidation. We demonstrate a {101} facet‐exposed TiO ₂ photocatalyst decorated with coexisting Pd single atoms and clusters, which achieves a high C ₂ H ₆ production rate of 600 µmol·h ⁻¹ ·g ⁻¹ at room temperature with near 100% selectivity and stoichiometric H ₂ 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.