Amine Structure Governs Corrosion Rates of Copper Catalysts in Electrochemical Reactive Capture of CO₂

Reactive capture of CO₂(RCC) offers an integrated approach that combines CO₂capture with its direct electrochemical conversion, eliminating the need for CO₂release from the capture agent. By avoiding the pH, pressure, and temperature swings required for the release step, RCC has the potential to reduce both energy consumption and capital costs compared to the conventional sequential process of CO₂capture, release, concentration, and conversion. Amines, widely used in industrial CO₂capture, face challenges in RCC systems due to their incompatibility with transition metal catalysts as well as their tendency to promote electrode corrosion and parasitic hydrogen evolution. Identifying suitable combinations of amines and catalysts is therefore critical to enabling integrated CO₂capture and conversion. This work systematically investigates the performance of four primary and four secondary amines for RCC on polycrystalline Cu catalysts. Among the eight tested amines, only dimethylamine showed no measurable Cu corrosion near the open circuit potential. In contrast, ammonia, methylamine, ethylamine, monoethanolamine, diethylamine, diethanolamine, and piperazine all induced Cu corrosion. Corrosion rates correlate with the pK_aand steric hindrance of the amines, highlighting key parameters for catalyst–amine codesign. Grand canonical DFT calculations indicate a correlation between the adsorption strength of protonated amines, their pK_a, and the extent of Cu corrosion, suggesting that both the surface binding of protonated amines and the lability of their protons play critical roles in corrosion acceleration near open circuit potentials. These finding suggest that amines with high pK_avalues and weak binding of their protonated forms to Cu surfaces are preferred, as they offer better corrosion resistance.