Tailoring Electrocatalytic Pathways: A Comparative Review of the Electrolyte’s Effects on Five Key Energy Conversion Reactions

The advancement of efficient energy conversion and storage technologies is fundamentally linked to the development of electrochemical systems, including fuel cells, batteries, and electrolyzers, whose performance depends on key electrocatalytic reactions: hydrogen evolution (HER), oxygen evolution (OER), oxygen reduction (ORR), carbon dioxide reduction (CO2RR), and nitrogen reduction (NRR). Beyond catalyst design, the electrolyte microenvironment significantly influences these reactions by modulating charge transfer, intermediate stabilization, and mass transport, making electrolyte engineering a powerful tool for enhancing performance. This review provides a comprehensive analysis of how fundamental electrolyte properties, including pH, ionic strength, ion identity, and solvent structure, affect the mechanisms and kinetics of these five reactions. We examine in detail how the electrolyte composition and individual ion contributions impact reaction pathways, catalytic activity, and product selectivity. For HER and OER, we discuss the interplay between acidic and alkaline environments, the effects of specific ions, interfacial electric fields, and catalyst stability. In ORR, we highlight pH-dependent activity, selectivity, and the roles of cations and anions in steering 2e− versus 4e− pathways. The CO2RR and NRR sections explore how the electrolyte composition, local pH, buffering capacity, and proton sources influence activity and the product distribution. We also address challenges in electrolyte optimization, such as managing competing reactions and maximizing Faradaic efficiency. By comparing the electrolyte’s effects across these reactions, this review identifies general trends and design guidelines for enhancing electrocatalytic performance and outlines key open questions and future research directions relevant to practical energy technologies.