The electrocatalytic CO2 reduction reaction (CO2RR) is a sustainable route for converting CO2 into value-added fuels and feedstocks, advancing a carbon-neutral economy. The electrolyte critically influences CO2 utilization, reaction rate and product selectivity. While typically conducted in neutral/alkaline aqueous electrolytes, the CO2RR faces challenges due to (bi)carbonate formation and its crossover to the anolyte, reducing efficiency and stability. Acidic media offer promise by suppressing these processes, but the low Faradaic efficiency, especially for multicarbon (C2+) products, and poor electrocatalyst stability persist. The effective regulation of the reaction environment at the cathode is essential to favor the CO2RR over the competitive hydrogen evolution reaction (HER) and improve long-term stability. This review examines progress in the acidic CO2RR, focusing on reaction environment regulation strategies such as electrocatalyst design, electrode modification and electrolyte engineering to promote the CO2RR. Insights into the reaction mechanisms via in situ/operando techniques and theoretical calculations are discussed, along with critical challenges and future directions in acidic CO2RR technology, offering guidance for developing practical systems for the carbon-neutral community.
Keywords: Acidic media; Electrocatalyst; Electrocatalytic CO2 reduction; Microenvironment; stability.
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