Modeling the Complexity of Electrochemical Environment with Grand Canonical Density Functional Theory

The development of ab initio methods for atomistic simulations of the electrochemical environment is essential for obtaining a mechanistic understanding of fundamental reactions. In this talk, we will first present our newly developed hybrid solvent model, SOLHYBRID, that is capable of describing the liquid/solid interface, and the efficient target potential routine, TPOT, that allows the control of the electrode potential, thereby enabling simulations at constant electrode potential, mimicking the experimental electrochemical cells. We will then discuss the application of the methodology to the study of the effect of caution on CO₂ reduction on the Bi electrode and hydrogen evolution reaction on Pt electrode. We will show that non-metal cations, such as ammonium, methyl ammonium, could alter reaction pathways and enhance CO₂ reduction and hydrogen evolution reaction on the considered electrodes. We will also present relevant experimental data [1] that validates our findings.



[1] X. Feng’s group, Private Communications.