Manganese Doped‐Nitrogenated Carbon as an Efficient Catalyst for Acidic Electrocatalytic Reduction of CO₂

Abstract Renewable electricity‐driven CO₂ electroreduction to value‐added chemicals is a feasible approach to alleviate both environmental and energy issues. However, CO₂ reduction reaction (CO₂RR) systems in alkaline electrolytes are constrained by intrinsic limitations such as salt accumulation that impede further industrialization. Herein, an atomically dispersed Mn doped‐nitrogen carbon (AD MnNC) catalyst is developed to electrochemically reduce CO₂ to CO in both neutral and acidic media. Benefiting from well‐dispersed MnN_x sites, the maximum CO Faradaic efficiency (FE_CO) reaches ≈100% at −0.73 V versus reversible hydrogen electrode (RHE) with CO current density (J_CO) of 20.4 mA cm⁻² in neutral 0.5 m KHCO₃. Due to diminished ^*H adsorption, AD MnNC achieves a FE_CO of 85.3% at pH 2.0, effectively suppressing the hydrogen evolution reaction (HER) in an acidic electrolyte. The mechanistic study reveals that AD MnNC accelerates the production of ^*COOH intermediates through a proton‐coupled electron transfer (PCET) pathway and thus promotes CO formation.