Efficiently Light-Driven Nonoxidative Coupling of Methane on Ag/NaTaO3: A Case for Molecular-Level Understanding of the Coupling Mechanism

Abstract

Metal-decorated oxide semiconductors are overwhelming photocatalysts for nonoxidative coupling of methane (NOCM). However, the overall NOCM mechanism remains an unopened black box, which hinders the design of high-performance catalysts. Herein, we systematically studied a series of noble metal (Ag, Au, Pt, Pd, Cu, and Ni)-decorated oxides (NaTaO3, CaTiO3, LiNbO3, and TiO2) for NOCM. We proposed that the active sites for H abstraction and C–C coupling of CH4 are spatially separated. Specifically, NaTaO3 only completes the initial H abstraction of CH4 activation, while metal nanoparticles are responsible for the final C–C coupling. Noble metals dominate NOCM by significantly decreasing the energy barrier of CH4 dissociation and promoting C–C coupling. Among various metals, Ag is preferential for the weak adsorption of ·CH3 intermediates and subsequent metal-induced C–C coupling. This contributes to Ag/NaTaO3 the highest C2H6 yield of 194 μmol g–1 h–1 and stoichiometric H2 with 11.2% quantum efficiency. This work provides a molecular-level insight into the CH4 coupling mechanism on metal-decorated photocatalysts.