Understanding the Temperature Effect on Carbon‐Carbon Coupling during CO2 and CO Electroreduction in Zero‐Gap Electrolyzers†.

Comprehensive Summary: Cu‐catalyzed electrochemical CO2 reduction reaction (CO2RR) and CO reduction reaction (CORR) are of great interest due to their potential to produce carbon‐neutral and value‐added multicarbon (C2+) chemicals. In practice, CO2RR and CORR are typically operated at industrially relevant current densities, making the process exothermal. Although the increased operation temperature is known to affect the performance of CO2RR and CORR, the relationship between temperatures and kinetic parameters was not clearly elaborated, particularly in zero‐gap reactors. In this study, we detail the effect of the temperature on Cu‐catalyzed CO2RR and CORR. Our electrochemical and operando spectroscopic studies show that high temperatures increase the activity of CO2RR to CO and CORR to C2H4 by enhancing the mass transfer of CO2 and CO. As the rates of these two processes are highly influenced by reactant diffusion, elevating the operating temperature results in high local CO2 and CO availability to accelerate product formation. Consequently, the *CO coverage in both cases increases at higher temperatures. However, under CO2RR conditions, *CO desorption is more favorable than carbon‐carbon (C—C) coupling thermodynamically at high temperatures, causing the reduction in the Faradaic efficiency (FE) of C2H4. In CORR, the high‐temperature‐augmented CO diffusion overcomes the unfavorable adsorption thermodynamics, increasing the probability of C—C coupling. [ABSTRACT FROM AUTHOR]