Grand canonical DFT based constant charge method for electrochemical deuterium/hydrogen evolution reaction micro-kinetics on Pt (1 1 1)

Abstract

Applied external potential is considered to have significant impact on the reaction mechanisms and kinetic behaviors for electrochemical reactions. The electrochemical isotope deuterium/hydrogen (D/H) evolution shows significant different kinetic behavior under applied potential conditions, but the intrinsic mechanisms from the electrochemical isotope effect remains unclear. In this work, the grand canonical density functional theory (GC-DFT) based constant charge method was used to systematically investigate the electrochemical D/H evolution reactions (DER/HER) on the Pt (111) surface. By using this method, the linear and quadratic relationship between charge distribution (q), electronic energy (Eelect) and applied potential (U) were observed respectively, which are resulted from solving of linear Poisson-Boltzmann equation and Kohn-Sham-Mermin equations in combination of solvent modification. Equilibrium Pourbaix diagrams of D/H adsorbing on Pt (111) surface was subsequently investigated to revealed the electrode structure in real reaction condition, with θD/H coverages on the cathode surface calculated to be 0.0 monolayer (ML) and 1/6 ML for alkaline and acidic solvent at −1.23 V to 0.0 V vs. SHE. Mechanistic studies of HER/DER on the Pt (111) surface revealed that Volmer-Tafel reaction pathway is more favorable than the Volmer-Heyrovsky pathway. Analysis of the applied potential effect on the reaction energy barriers show that the acidic Volmer step is very sensitive toward the applied potential condition, with the structure of transition state likely to shift. Comparisons of the calculated current–potential polarization curves between HER and DER revealed that in the acidic condition, the calculated current density of HER is close to DER, revealing that the H*/D* migration and coupling on the electrode is comparable to each other when the solution is saturated with H3O+/D3O+. In the alkaline reaction condition, discrepancies of j value between DER and HER becomes slightly larger, revealing that jointly control effect from Volmer and Tafel step was enhanced. This work provides the new insight for investigating the microkinetic properties of electrochemical isotope reaction.