Here we only consider the reduction reaction. 𝑘 ( , 𝑇, ℏ and 𝑒 are the Boltzmann constant, temperature (298 K in this work), 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 . 𝑃 * is the equilibrium Boltzmann population of the reactant vibronic state 𝜅. 𝑉 *+ is the vibronic coupling coefficient of the vibronic state of reactant 𝜅 and product vibronic state 𝜈. 𝜆 is the reorganization energy. ∆𝐺 is the free energy of the reaction from the vibronic state 𝜅 of the reactant to the vibronic state 𝜈 of the product with the electron at the Fermi level of the electrode. A Born cycle could be constructed to decompose Eq. S2 into an ET followed by a PT, with the free energies of ∆𝐺 ,-and ∆𝐺 .-, respectively: