Why do RuO electrodes catalyze electrochemical CO reduction to methanol rather than methane or perhaps neither of those?

The electrochemical CO 2 reduction reaction (CO 2 RR) on RuO 2 and RuO 2 -based electrodes has been shown experimentally to produce high yields of methanol, formic acid and/or hydrogen while methane formation is not detected. This CO 2 RR selectivity on RuO 2 is in stark contrast to copper metal electrodes that produce methane and hydrogen in the highest yields whereas methanol is only formed in trace amounts. Density functional theory calculations on RuO 2 (110) where only adsorption free energies of intermediate species are considered, i.e. solvent effects and energy barriers are not included, predict however, that the overpotential and the potential limiting step for both methanol and methane are the same. In this work, we use both ab initio molecular dynamics simulations at room temperature and total energy calculations to improve the model system and methodology by including both explicit solvation effects and calculations of proton-electron transfer energy barriers to elucidate the reaction mechanism towards several CO 2 RR products: methanol, methane, formic acid, CO and methanediol, as well as for the competing H 2 evolution. We observe a significant difference in energy barriers towards methane and methanol, where a substantially larger energy barrier is calculated towards methane formation than towards methanol formation, explaining why methanol has been detected experimentally but not methane. Furthermore, the calculations show why RuO 2 also catalyzes the CO 2 RR towards formic acid and not CO(g) and methanediol, in agreement with experimental results. However, our calculations predict RuO 2 to be much more selective towards H 2 formation than for the CO 2 RR at any applied potential. Only when a large overpotential of around −1 V is applied, can both formic acid and methanol be evolved, but low faradaic efficiency is predicted because of the more facile H 2 formation. Energy barriers are calculated for the electrochemical CO 2 reduction reaction on the RuO 2 (110) surface towards methanol, methane, formic acid, methanediol, CO and the competing H 2 formation and compared with experimental literature.