A constant potential reactor framework for electrochemical reaction simulations

Abstract

Understanding the evolution of electrified solid-liquid interfaces during electrochemical reactions is crucial. However, capturing the dynamic behavior of the interfaces with high temporal resolution and accuracy over long timescales remains a major challenge for both experimental and computational techniques. Here, we present a constant potential reactor framework that enables the simulation of electrochemical reactions with ab initio accuracy over extended timescales, allowing for real-time atomic scale observations for the electrified solid-liquid interface evolution. By implementing an enhanced sampling active learning protocol, we develop fast, accurate, and scalable neural network potentials that generalize across systems with varying electron counts, based on high-throughput density functional theory computations within an explicit-implicit hybrid solvent model. The simulation of reactions in realistic electrochemical environments uncovers the intrinsic mechanisms through which alkali metal cations promote CO2 adsorption and suppress the hydrogen evolution reaction. These findings align with previous experimental results and clarify previously elusive observations, offering valuable computational insights. Our framework lay the groundwork for future studies exploring the dynamic interplay between interfacial structure and reactivity in electrochemical environments.