Lecture
Van Marum Colloquium: NiOOH-Catalyzed Glucose and Other Organic Molecule Electrooxidations
- Date
- Friday 7 February 2025
- Time
- Location
-
Gorlaeus Building
Einsteinweg 55
2333 CC Leiden - Room
- CM.3.23
Abstract
Ni and NiFe oxyhydroxides are among the most widely studied catalytic materials for the oxygen evolution reaction (OER) in alkaline media. It is however well known that along with water oxidation, NiOOH catalyzes oxidation of various organic molecules. Fleischmann et al [1] have rationalized electrocatalysis on NiOOH electrodes through an EC’ mechanism whereby Ni(OH)2, in an electrochemical step, is converted in NiOOH, the latter reacting with a dissolved organic molecule in a chemical step recovering the Ni(OH)2 species.
The electrochemical glucose oxidation reaction has attracted much attention as a part of the global effort to produce hydrogen and high-value-added chemicals from biomass. In this work we combine electrochemistry, operando spectroscopies, microkinetic modeling and analytical methods to investigate the mechanism of the glucose and other organic molecule oxidation on Ni in alkaline media [2, 3]. Electrochemical measurements along with the X-ray absorption spectroscopy investigation allowed us to confirm the EC’ mechanism of the glucose oxidation. However, our microkinetic modeling study suggests that along with the NiOOH sites required for the glucose oxidation, Ni(OH)2 sites are needed for the glucose adsorption on the electrode surface. We then compare electrooxidation of various organic molecules and discuss how the nature of their functional groups affects the reaction ‘onset’ and the oxidation mechanism. Finally, we will show that contrary to the OER on NiOOH, which is significantly accelerated in the presence of Fe, the latter has detrimental effect on glucose and other organic molecules oxidation.
Acknowledgements
This study was funded by the French National Research Agency (ANR): grant ANR-20-CE43-0005. The author gratefully acknowledges A. Medrano-Banda, A. Bonnefont, A. Oshchepkov, T. Faverge, M. Chatenet, C. Coutanceau, T. Asset, G. Kéranguéven, J. Guehl, C. Bouillet, V. Papaefthimiou, E. Ginoux, E. Fonda, A. Brige and P. Cognet.
References
- M Fleischmann, K Korinek, and D Pletcher, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 1971, 31, 39–49.
- A. Medrano-Banda, Medrano-Banda, J. Guehl, G. Kéranguéven, A. Oshchepkov, E. Savinova, A. Bonnefont, Electrochimica Acta, 2024, 476, 143692.
- A. Medrano-Banda, E. Ginoux, T. Faverge, A. Oshchepkov, A. Bonnefont, M. Chatenet, C. Coutanceau, G. Kéranguéven, P. Cognet, E. Savinova, Electrochimica Acta, 2024, 487, 144159.