Surface-interface Control of CO₂ Electroreduction on Gold-based Catalysts

Abstract

Electrochemical CO₂ reduction (CO₂RR) offers a compelling route for converting CO₂ into value-added chemicals using renewable electricity, yet its practical deployment is fundamentally constrained by sluggish kinetics, complex electrified interfaces, and limited control over product selectivity. Gold-based catalysts have long been regarded as benchmarks for CO-selective CO₂RR; however, growing evidence indicates that their catalytic behavior is not dictated by intrinsic adsorption energetics alone, but instead emerges from a tightly coupled interplay between surface structure, dynamic interface evolution, and the local reaction microenvironment. In this review, we critically examine recent advances in Au-based CO₂RR catalysts through the unifying lens of surface-interface control, encompassing morphology and defect engineering, alloy and cluster design, molecular surface modification, electrolyte cation regulation, and tandem or cascade catalytic architectures. Particular emphasis is placed on mechanistic insights derived from operando spectroscopy and kinetic analysis, which reveal dynamic phenomena, such as water-mediated proton transfer, CO-induced site blocking, surface reconstruction, and the breakdown of single-parameter activity descriptors. By integrating catalyst design with interfacial chemistry, mass transport, and solvation effects, this review establishes a unified mechanistic framework for understanding CO₂ electroreduction on gold-based catalysts and distills general principles for the rational design of efficient and selective electrochemical CO₂ conversion systems.

Keywords

Gold-based catalyst / CO₂ electroreduction / Surface and interface control / Reaction microenvironment

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