Glycerol electrooxidation is a promising alternative to the oxygen evolution reaction in carbon dioxide electroreduction processes. It has the potential to both reduce the overall cell voltage and enable the commercialization of anodic oxidation products. Gold is a material that exhibits a high performance for glycerol oxidation but has a high manufacturing cost. In this work, a gold indium alloy has been synthesized that exhibits enhanced electrocatalytically properties, as evidenced by a reduction in the glycerol oxidation onset potential by 210 mV while reducing the electrode cost by 28%. This electrocatalyst has been evaluated in a flow cell configuration coupled with the cathodic reduction of carbon dioxide, and high faradaic efficiencies of up to 90% have been achieved for both the anodic and cathodic products.

In recent years, there has been a growing interest in the photoelectrochemical oxidation of glycerol to produce high-value products. Most studies have focused solely on the photocatalytic properties of the electrodes, overlooking their electrocatalytic properties and the different products obtained under dark conditions. Our work aims to address this gap by comparing the electrocatalytic activity under dark and light conditions to determine whether light influences the reactivity of the electrodes or if it just reduces the overpotential of the reaction. To achieve this, we employed two model semiconductors, TiO₂ and BiVO₄. We have analyzed their polarization curves under both dark and light conditions and evaluated the competence of glycerol oxidation reaction with the oxygen evolution reaction. Furthermore, we conducted long-term (photo)electrolysis revealing the beneficial role of light on the electrolytic process, as it enables the obtention of C3 products on illuminated TiO₂ photoanodes at low electrode polarization, comparable to the performance of BiVO₄.

Ethylene glycol oxidation reaction (EGOR) is a promising anodic process to reduce the cell voltage compared with the oxygen evolution reaction (OER). Using ethylene glycol (EG) obtained from biomass-derived streams—such as cellulose, hemicellulose or lignocellulosic intermediates—and polyethylene terephthalate (PET) waste contributes to the development of circular-economy models. This study investigates EGOR on a non-noble NiCo bimetallic electrode, focusing on the effects of temperature and current density. The presence of EG reduces the initial potential by 240 mV at 25 °C, with a further 60 mV decrease at elevated temperatures, while the catalyst maintains high formate selectivity (>65%) across the tested conditions. Faradaic efficiency peaks at 100 mA cm⁻² due to the full oxidation of formate to CO₂ or the competing OER at higher current densities. There are no significant discrepancies between simulated and experimental faradaic efficiencies, although the presence of terephthalic acid (TPA) affects the shift in the electrode potential. Overall, these results highlight the relevance of EGOR for future applications in which EG derived from recycled plastics and renewable biomass can be electrochemically valorized within integrated biorefinery frameworks.

The electrooxidation of glycerol presents a promising route for upgrading a biodiesel byproduct into high‐value chemicals while lowering the energy cost of electrochemical hydrogen production, but its mechanistic understanding remains incomplete. This work investigates the influence of temperature and catalyst composition on glycerol electrooxidation using three distinct electrocatalysts: first‐row transition‐metal NiCo oxide, noble metal AuIn alloy, and hybrid PdNi alloy. Electrochemical, in situ UV–vis reflectance and in situ Raman measurements reveal catalyst‐specific oxidation mechanisms: an oxyhydroxide‐mediated path for NiCo, an adsorbed hydroxide‐mediated path for AuIn which suffers from inhibition, and a dual mechanism for PdNi. Oxyhydroxide mechanisms favor formic acid, whereas adsorbed hydroxide pathways selectively promote C ₃ products such as glyceric acid and dihydroxyacetone. Flow cell electrolysis across a range of temperatures and flow rates relevant to industrial application shows that elevated temperature enhances reaction rates and mitigates catalyst inhibition, a relevant effect for the hybrid catalyst. These findings provide key mechanistic insights and practical guidelines for optimizing continuous‐flow glycerol electrooxidation systems.