Hydroxyl-functionalized SiO₂-supported CuO Composite Catalysts Enabling Highly Selective CO₂ Electroreduction to CH₄ at Industrial Current Densities

Abstract

Selective producing CH₄ by CO₂ electroreduction remains challenging, primarily hindered by the complexity of reduction products, sluggish protonation kinetics, and competitive hydrogen evolution reaction. Herein, we developed a silica-copper composite catalyst (CuO/SiO₂), where CuO nanoparticles are dispersed on the hydroxyl-functionalized SiO₂ nanosheet. The hydroxyl-functionalized SiO₂ support promotes the formation and transfer of interfacial reactive hydrogen species, lowers the energy barrier for the reduction of CO₂ to CH₄ by stabilizing *COOH, *CO, and *H intermediates. Meanwhile, it favors the hydrogenation of *CHO over C—C coupling between C1 intermediates, thereby shifting product selectivity from multi-carbon products towards CH₄. As a result, CuO/SiO₂ catalyst delivers high CH₄ selectivity over a broad current density range of 0.2–0.9 A/cm², with a peak Faradaic efficiency of 66.2% at 0.6 A/cm². This work demonstrates an effective interfacial engineering strategy for enhancing the selectivity of CO₂-to-CH₄ conversion.

Keywords

CO₂ electroreduction / CO₂ methanation / Interfacial engineering / Silica

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Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH