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 CO₂ 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 CO₂ 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 ^*CH₄, 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 CH₄ 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 CH₄ and CO₂ with high conversion rate and high efficiency synergistically beyond thermodynamic limits.