(560bl) Understanding Mechanisms of CO2 Electroreduction on Cu(100) with Kinetic Monte Carlo Simulations

Converting carbon dioxide (CO₂) to value-added chemicals or fuels through electrocatalysis is an appealing approach to tackle both CO₂ emission and energy storage challenges. Cu catalyzes direct electrochemical reduction of CO₂ to hydrocarbons in an aqueous bicarbonate solution with a high current density. However, the underlying mechanism remains elusive due to multistep kinetic pathways and complexities of surface reactions1. Traditionally, the microkinetic model is used with energetics from quantum chemical simulations within a mean-field approximation. Going beyond this approximation and ideally taking into account adsorbate-adsorbate interactions in surface reactions is important for unraveling kinetics of surface reactions. In this poster, we employed kinetic Monte Carlo simulations with DFT-derived neural network potentials to understand the effect of pH and operating potentials on CO₂ reduction on Cu(100) surface2. Particularly, we show that with proper consideration of CO-CO interactions the kinetic Monte Carlo method can better capture observed trends of kinetic current than the traditional microkinetic method.

1. Peterson, A. A., Abild-Pedersen, F., Studt, F., Rossmeisl, J. & Nørskov, J. K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 3, 1311–1315 (2010).
2. Goodpaster, J. D., Bell, A. T. & Head-Gordon, M. Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO2: New Theoretical Insights from an Improved Electrochemical Model. J. Phys. Chem. Lett. 7, 1471–1477 (2016).