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Understanding the reaction mechanism of Kolbe electrolysis on Pt anodes

Liu, Sihang; Govindarajan, Nitish; Prats, Hector; Chan, Karen; (2022) Understanding the reaction mechanism of Kolbe electrolysis on Pt anodes. Chem Catalysis , 2 (5) pp. 1100-1113. 10.1016/j.checat.2022.02.014. Green open access

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Abstract

Kolbe electrolysis has been proposed as an efficient electro-oxidation process to synthesize (un)symmetrical dimers from biomass-based carboxylic acids, but its mechanism remains controversial. In this work, we develop a microkinetic model based on density functional theory to study the reaction mechanism of Kolbe electrolysis of acetic acid (CH3COOH) on both pristine and partially oxidized Pt anodes. We show that the shift in the rate-determining step of the oxygen evolution reaction (OER) on a Pt(111)@α-PtO2 surface from OH∗ formation to H2O adsorption gives rise to large Tafel slopes, i.e., the inflection zones observed experimentally at high anodic potentials on Pt. Our simulations find that the CH3COO∗ decarboxylation and CH3∗ dimerization steps determine the activity of the Kolbe reaction. This work resolves major controversies in the mechanism of Kolbe electrolysis on Pt anodes: the origin of the inflection zone and the identity of the rate-limiting step.

Type: Article
Title: Understanding the reaction mechanism of Kolbe electrolysis on Pt anodes
Open access status: An open access version is available from UCL Discovery
DOI: 10.1016/j.checat.2022.02.014
Publisher version: https://doi.org/10.1016/j.checat.2022.02.014
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
Keywords: Kolbe electrolysis, oxygen evolution reaction, density functional theory, microkinetic modeling, electrocatalysis, biomass
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL
URI: https://discovery.ucl.ac.uk/id/eprint/10155759
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