Theories for Electrolyte Effects in CO2 Electroreduction

Electrochemical CO₂ reduction (eCO₂R) enables the conversion of waste CO₂ to high-value fuels and commodity chemicals powered by renewable electricity, thereby offering a viable strategy for reaching the goal of net-zero carbon emissions. Research in the past few decades has focused both on the optimization of the catalyst (electrode) and the electrolyte environment. Surface-area normalized current densities show that the latter can affect the CO₂ reduction activity by up to a few orders of magnitude.In this Account, we review theories of the mechanisms behind the effects of the electrolyte (cations, anions, and the electrolyte pH) on eCO₂R. As summarized in the conspectus graphic, the electrolyte influences eCO₂R activity via a field (ε) effect on dipolar (μ) reaction intermediates, changing the proton donor for the multi-step proton-electron transfer reaction, specifically adsorbed anions on the catalyst surface to block active sites, and tuning the local environment by homogeneous reactions. To be specific, alkali metal cations (M⁺) can stabilize reaction intermediates via electrostatic interactions with dipolar intermediates or buffer the interfacial pH via hydrolysis reactions, thereby promoting the eCO₂R activity with the following trend in hydrated size (corresponding to the local field strength ε)/hydrolysis ability: Cs⁺ > K⁺ > Na⁺ > Li⁺. The effect of the electrolyte pH can give a change in eCO₂R activity of up to several orders of magnitude, arising from linearly shifting the absolute interfacial field via the relationship U_SHE = U_RHE - (2.3k_BT)pH, homogeneous reactions between OH^- and desorbed intermediates, or changing the proton donor from hydronium to water along with increasing pH. Anions have been suggested to affect the eCO₂R reaction process by solution-phase reactions (e.g., buffer reactions to tune local pH), acting as proton donors or as a surface poison.So far, the existing models of electrolyte effects have been used to rationalize various experimentally observed trends, having yet to demonstrate general predictive capabilities. The major challenges in our understanding of the electrolyte effect in eCO₂R are (i) the long time scale associated with a dynamic ab initio picture of the catalyst|electrolyte interface and (ii) the overall activity determined by the length-scale interplay of intrinsic microkinetics, homogeneous reactions, and mass transport limitations. New developments in ab initio dynamic models and coupling the effects of mass transport can provide a more accurate view of the structure and intrinsic functions of the electrode-electrolyte interface and the corresponding reaction energetics toward comprehensive and predictive models for electrolyte design.