# From Heat to Electrons: Bridging Heterogeneous Liquid‐Phase Thermal and Electrocatalytic Oxidation of Ethylene Glycol over Co3O4

## TL;DR

This study shows that using Co3O4, both thermal and electrocatalytic oxidation of ethylene glycol produce the same products, revealing shared mechanisms.

## Contribution

The paper establishes a mechanistic link between thermal and electrocatalytic oxidation of ethylene glycol using Co3O4.

## Key findings

- Co3O4 enables identical product distributions in thermal and electrocatalytic oxidation of ethylene glycol.
- Ab initio simulations show similar surface intermediates and roles of Co3+ and OH− in both reaction types.
- The catalyst's spinel structure remains robust, allowing multiple recycling cycles.

## Abstract

The selective oxidation of alcohols under thermal and electrocatalytic conditions presents a promising route to value‐added chemicals using sustainable energy sources. We establish mechanistic convergence between heterogeneous liquid‐phase thermal oxidation of ethylene glycol (EG) and its electrocatalytic oxidation reaction (EGOR) using mesostructured Co3O4 synthesized via hard templating as a catalyst. Comprehensive catalytic performance assessments and ab initio molecular dynamics simulations reveal analogous surface intermediates and pathways in both regimes, resulting in the same product distribution. Co3+ centers and OH− species facilitate oxidation via proton‐coupled electron transfer (PCET), with molecular oxygen or the applied anodic potential regenerating active sites. Product selectivity to glycolate, formate, and oxalate is governed by temperature, EG concentration, pH, applied O2 pressure, or potential. Surface and bulk characterization confirm the robustness of the spinel structure, enabling multiple catalyst recycling. These insights provide a first mechanistic framework connecting heterogeneous thermal and electrocatalytic oxidation over non‐noble metal oxide catalysts, paving the way for designing multi‐functional materials for chemical synthesis under electrothermal conditions.

The aerobic liquid‐phase thermal oxidation of ethylene glycol and its electrocatalytic oxidation resulted in the same product distribution using mesostructured Co3O4. Ab initio molecular dynamics simulations reveal analogous surface intermediates requiring Co3+ centers and OH− species with O2 or the anodic potential regenerating the reduced active sites.