Plasmonic Photocatalysis Enables Selective Oxidative Coupling of Methane with Nitrous Oxide under Ambient Conditions

Abstract

Methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases that represent substantial chemical energy. Conversion of these abundant waste gases to high-value chemicals typically requires high temperatures up to 1000 C, producing substantial CO2 emissions and limited selectivity toward desirable multi-carbon products. Here we demonstrate a plasmonic photocatalyst that enables CH4 and N2O conversion under ambient conditions to form C2 and C3 hydrocarbons. By systematically tuning AuPd alloys on TiO2, we identify an optimal composition (AuPd0.05) where Au enhances light harvesting and Pd enables selective C-H activation and C-C coupling. Under visible-light illumination, this catalyst produces C2H4, C2H6, C3H6, and C3H8 with ~80% selectivity while suppressing CO2 formation. In-situ spectroscopy and hot-carrier calculations show that plasmon-generated carriers redistribute interfacial hydroxyl intermediates, shifting the hydrophilic center to suppress overoxidation. Ab-initio calculations further reveal the reduction in C-C coupling barriers from 2.7 eV to 0.7 eV under illumination. Our work illustrates how engineering interfacial electronic and adsorbate dynamics enables selective multicarbon formation.