Mechanism of formic acid oxidation on Bi modified Pt(111): Implication from the concentration effect of formic acid and different coverages of Bi

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Title: Mechanism of formic acid oxidation on Bi modified Pt(111): Implication from the concentration effect of formic acid and different coverages of Bi
Authors: Wei, Zhen | Yu, Anni | Gisbert-González, José M. | Cai, Jun | Chen, Yan-Xia | Feliu, Juan M. | Herrero, Enrique
Research Group/s: Electroquímica de Superficies
Center, Department or Service: Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica
Keywords: Pt(111) | Bismuth adatoms | Formic acid oxidation | Concentration effect | pH
Issue Date: 7-Mar-2023
Publisher: Elsevier
Citation: Electrochimica Acta. 2023, 449: 142188.
Abstract: The concentration dependence of the activity for the formic acid oxidation at pH 1.2 and 4 has been studied on Pt(111) with different coverages of bismuth. The results clearly show: (1) The FAOR on bismuth-modified Pt(111) has no relation with HCOOb adsorbed on platinum but depends on the bismuth coverage. (2) The Tafel slope is ca. 90 - 110 mV in lower potential and increases to nearly the vertical asymptote when the potential increases. (3) Free Pt sites are required for FAOR on bismuth-modified Pt(111). (4) Solution formate, rather than formic acid, is the active species. Combined with previous reports, a kinetic model in which monodentate formate, adsorbed on a Pt-Bi ensemble, is the active intermediate and solution formate is the active species has been proposed. The model is able to reproduce the experimental behavior and agrees with the reaction order measured experimentally. For low potentials, the reaction order for formate is 1, whereas a reaction order of 0.5 is obtained for high potentials.
Sponsor: This work has been financially supported by National Natural Science Foundation of China (no. 22172151, 21972131), Ministerio de Ciencia e Innovación (Project PID2019-105653GB-I00) and Generalitat Valenciana (Project PROMETEO/2020/063). Zhen Wei acknowledges support from the China Scholarship Council (award number 202106340060).
ISSN: 0013-4686 (Print) | 1873-3859 (Online)
DOI: 10.1016/j.electacta.2023.142188
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (
Peer Review: si
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