Publication date: 26th March 2026
The electrooxidation of glycerol presents a dual opportunity for sustainable chemistry: upgrading a biodiesel byproduct and reducing the energetic cost of some electrolytic processes by replacing the oxygen evolution reaction. Despite this dual benefit, the reaction remains highly complex, with multiple competing pathways and a strong dependence on catalyst composition and operating conditions. In this contribution, we present the recent advances from our group aimed at developing anodic materials suitable for coupling glycerol oxidation with CO2 electroreduction, following two complementary research lines.
The first line focuses on understanding how electrocatalyst composition and reaction environment influence activity and product distribution. We have examined three representative materials supported on nickel foams: NiCo oxide, AuIn alloy, and PdNi alloy. Electrochemical characterization, combined with in situ UV–vis reflectance spectroscopy, reveals clear differences in the oxidation pathways. Operating conditions also play a significant role. Continuous‑flow experiments show that temperature enhances reaction kinetics, reduces cell potential, and accelerates surface reactivation, helping to mitigate catalyst passivation. Flow rate provides an additional lever to tune residence time, thereby modifying the balance between intermediate and deeper oxidation products.
The second research line explores photoassisted glycerol oxidation using semiconductor electrodes. We have evaluated the electrocatalytic and photoelectrochemical behavior of TiO2, BiVO4, and a Bi‑rich graded BiVO4. Illumination not only decreases the energetic requirements of the process but also alters product selectivity by suppressing the oxygen evolution reaction to a lesser extent than glycerol oxidation. Operating near the OER onset photopotential maximizes faradaic efficiency toward C3 products, particularly in TiO2, while the Bi‑rich graded BiVO4 improves charge separation and photocurrent without affecting selectivity.
Overall, these results highlight the importance of integrating catalytic and engineering considerations when designing practical electrochemical systems.
This work has been funded by Ministerio de Ciencia e Innovación and FEDER-UE through project PID2022–138491OBC33 (MICIU/AEI/10.13039/501100011033) and from AGAUR Generalitat de Catalunya (2024 FI-1 0042).
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