Advances in CO2 reduction on bulk and two-dimensional electrocatalysts: From first principles to experimental outcomes

Designing catalyst materials for the electrochemical carbon dioxide reduction reaction (CO₂RR) requires an understanding of the underlying thermodynamics and kinetics. In this review, we discuss the characteristics of two-dimensional (2D) and bulk materials, which distinguish their catalytic properties. We map catalyst performance in the faradaic efficiency–applied potential space for various hydrocarbons and oxygenates on these catalyst classes. We explain different approaches for modeling catalytic CO₂RR, such as the computational hydrogen electrode, grand canonical (GC) potential kinetics, and GC density functional theory, with the lattermost accurately capturing potential-dependent kinetics. We review recent attempts made to break scaling relationships between intermediate adsorption energies and describe unique features found in 2D materials. Finally, we compare kinetics on both material classes using microkinetic modeling. We conclude that future studies should focus on realistic simulations of the electrode–electrolyte interface and combining the favorable properties of 2D and bulk materials to engineer high-performance CO₂RR catalysts.