is the vibronic coupling term between the ground vibronic state of reactant and product vibronic state 𝜈 based on the treatment of PCET by Hammes-Schiffer and co-workers . Derivations leading to Eq. 2 are included in Supplementary Note 2. Three key variables, i.e., 𝐸 * * , 𝜆 and 𝑗 '%( , that could be impacted by the identity of cations, were obtained by fitting 𝑗 !" -𝐸 curves with Eq. 2A (Fig. and). While 𝐸 * * represents the impact of cations on the thermodynamics of the RDS in CO2RR, 𝜆 and 𝑗 '%( reflect the cation effect on its kinetics.