A waveguide kinetics framework for electrochemical polarization

TL;DR

This paper introduces a universal waveguide kinetics framework for hydrogen electrocatalysis that accurately models polarization curves without assuming specific mechanisms, aiding catalyst design and mechanistic understanding.

Contribution

It presents a theory-neutral, modal-based model that fits diverse polarization data and provides transferable diagnostics for interfacial efficiency and mechanism analysis.

Findings

Successfully fits four experimental polarization datasets

Provides interpretable diagnostics like reflection amplitude

Establishes a platform for catalyst design and mechanistic insights

Abstract

Hydrogen electrocatalysis (HER/HOR) exhibits an anomalous, non-Nernstian pH dependence that has motivated competing mechanistic narratives yet still lacks a unified, transferable, and quantitatively predictive description across conditions. Here, we introduce a theory-neutral waveguide kinetics framework that reinterprets the polarization curve as a power-flow-like response, enabling a compact modal representation of interfacial kinetics. Without presuming any specific mechanism, the model quantitatively fits four representative polarization datasets historically explained by divergent theories. From each fit, we extract interpretable diagnostics, including a reflection amplitude and a useful-output density, that provide transferable metrics for interfacial efficiency. The framework thus establishes a computational experiment platform for mechanistic triangulation, operating-regime diagnosis, and the rational design of hydrogen electrocatalysts across the pH spectrum.