Microenvironment Manipulation Strategies for Acidic CO₂ Electrolysis

Abstract The electrochemical reduction of CO 2 (CO 2 RR) has gained significant attention due to its potential to reduce carbon emissions and produce valuable fuels and chemicals. CO 2 RR is typically carried out in neutral or alkaline conditions, while challenges such as the carbon crossover and salt precipitate can hinder the practical application. Conducting CO 2 RR in acidic media presents a promising method to address these issues, although it faces the problem of low efficiency and poor catalysis stability. Regulating the interface/surface microenvironment near the catalysts is crucial to minimize the competitive hydrogen evolution reaction and enhance CO 2 RR activity and long‐term stability. This review outlines recent advancements in acidic CO 2 RR, emphasizing various microenvironment engineering strategies for optimizing the CO 2 RR kinetics including electrolyte composition manipulation, catalyst design, electrode modification and cell configuration optimization. Additionally, the review addresses challenges into developing practical and cost‐effective CO 2 RR systems.