Enhanced methane selectivity by electrochemical CO2 reduction at a choline-alaninate/Au(111) interface: DFT and microkinetic insights.

Using explicit interfacial models with extensive AIMD simulations, we reveal that a choline-alaninate ([Cho]+[Ala]-) functionalized Au(111) interface selectively enriches CO2 while suppressing H2O accumulation through interfacial ion-pair interactions. Our DFT and microkinetic analyses show that kinetically preferred proton-coupled C-O bond cleavage of the *OCH3 intermediate (k ∼ 1011 M-1 S-1) drives selective CH4 formation during the CO2 reduction reaction.