Utilizing electrochemical conversion of CO(2) into hydrocarbons and oxygenates is envisioned as a promising path towards closing the carbon cycle in modern technology. To this day, however, the exact reaction mechanisms towards the plethora of single and multi-carbon products on Cu electrodes are still disputed. This uncertainty even extends to the rate-limiting step of the respective reactions. Since multi-carbon products do not show a dependence on the electrolyte pH in neutral and alkaline media, CO dimerization on the Cu surface has been proposed as the rate-limiting step. However, other elementary steps would lead to the same pH dependence, namely the proton-electron transfer to *CO followed by subsequent coupling or the protonation of the *OCCO dimer. The pH dependence of methane production on the other hand suggests that the rate limiting step is located beyond the first proton-electron transfer to *CO. In order to conclusively identify the rate limiting steps in CO reduction, we analyzed the mechanisms on the basis of constant potential DFT calculations, CO reduction experiments on Cu at varying pH values (3 - 13) and fundamental rate theory. We find that, even in acidic media, the reaction rate towards multi-carbon products is nearly unchanged on an SHE potential scale, which indicates that its rate limiting step does not involve a proton donor. Hence, we deduce that the rate limiting step can indeed only consist of the coupling of two CO molecules on the surface, both in acidic and alkaline conditions. For methane, on the other hand, the rate-limiting step changes with the electrolyte pH from the first protonation step in acidic/neutral conditions to a later step in alkaline conditions. Finally, based on an in-depth kinetic analysis, we conclude that the pathway towards CH4 involving a surface combination of *CO and *H is unlikely, since it is unable to reproduce the measured current densities and Tafel slopes.
Adrenodoxin reductase.adrenodoxin complex. Flavin to iron-sulfur electron transfer as the rate-limiting step in the NADPH-cytochrome c reductase reaction.
