Selective Plasmonic C─H Bond Editing for Low‐Temperature Light‐Driven Greenhouse Gas Upgrading

Abstract Light‐driven greenhouse gases upgrading (GGU) into syngas is a promising approach to reduce CO 2 emissions and supply green fuels simultaneously. However, this reaction usually suffers from high operation temperature and low conversion rate due to stringent thermodynamic constraints. Herein, a selective plasmonic CH bond editing strategy is presented via incorporating ultralow amounts of Cu into Ni‐based catalysts by electrostatic adsorption. A remarkable CO 2 conversion rate 2.69 times as high as the thermodynamic limit and extraordinary light‐to‐fuel efficiency of 24.95% at low temperature of 500 °C are achieved, outperforming the state‐of‐the‐art literature reports. The extremely low fraction of Cu (0.06 wt%) assists the injection of localized surface plasmon resonance induced hot electrons into the antibonding orbital of reactants, accelerating cleavage of the first CH bond of * CH 4 , which is usually the rate‐determining step for GGU. Simultaneously, * CH intermediates are induced to proceed along * CH+ * O = * CHO rather than * CH = * C+ * H, thus avoid complete cleavage of CH 4 and subsequent coke deposition, leading to stable on‐stream operation over 20 h. Such a selective CH bond editing approach enables ordered conversion of CH 4 and CO 2 with high conversion rate and high efficiency synergistically beyond thermodynamic limits.