Harnessing Cation-Dependent Non-Nernstian Effects for Selective Proton-Coupled Electron Transfer

Inspired by Zhang et al. (2025), who revealed how specific cations (Li, Cs) and anions (sulfate) produce non-Nernstian pH shifts in the ORR by mediating new proton transfer pathways, this idea pushes the envelope by designing electrocatalytic systems—across a range of energy reactions (HER, CO2RR, NO3RR)—where the electrolyte composition is intentionally engineered to modulate PCET selectivity and kinetics. We’d use multi-ion electrolytes, coupled with advanced theoretical modeling (LRE model, microkinetics), to identify combinations that yield unique or even “switched” selectivity profiles. This could lead to “electrolyte-tuned” catalyst platforms, where selectivity is achieved not just through catalyst design but by exploiting the complex interplay between ions, adsorbates, and the electrical double layer—a dimension often underexplored experimentally.

References:

1. Proton-Relaying Adsorbates Induce Non-Nernstian Behavior in Oxygen Reduction. Lulu Zhang, Dongchen Zhao, Weiqiang Tang, Yanxia Chen, Jun Huang (2025). ACS Catalysis.