where 𝑗 '%( , 𝜆 and 𝐸 * * represent the maximum current density obtained at |𝑒(𝐸 -𝐸 * * )| ≥ 2𝜆, the reorganization energy, and the equivalent standard potential of PCET (accounting for vibronic coupling between reactant and product, defined in Supplementary Note 2), respectively. 𝑘 ) , 𝑇, 𝐹, ℏ and 𝑒 are the Boltzmann constant, temperature (298 K in this work), the Faraday constant, the reduced Planck constant and the elementary charge, respectively. 𝑥 is the energy relative to the Fermi level in the unit of 𝑘 ) 𝑇, while 𝜌 -is the density of electronic states at the Fermi level of the Au electrode. 𝛽 is the decay coefficient of the electronic coupling, which decreases exponentially with the distance between the electrode and electron acceptor . [𝐶𝑂 # ] and [𝐻 # 𝑂] represent the concentrations of CO2 and H2O, respectively. 𝑉 *.