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Issue 12, 2013
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On the mechanism of the direct pathway for formic acid oxidation at a Pt(111) electrode

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Abstract

In order determine whether formate is a reaction intermediate of the direct pathway for formic acid oxidation at a Pt electrode, formic acid (HCOOH) oxidation at a Pt(111) electrode has been studied by normal and fast scan voltammetry in 0.1 M HClO4 solutions with different HCOOH concentrations. The relationship between the HCOOH oxidation current density (jox) and formate coverage (θformate) is quantitatively analyzed. The kinetic simulation reveals that the previously proposed formate pathway, with decomposition of the bridge-bonded formate (HCOOB) as a rate determining step (rds), cannot be the main pathway responsible for the majority of the current for HCOOH oxidation. Instead, a kinetic model based on a mechanism with formic acid adsorption Image ID:c3cp44074e-t1.gif, along with simultaneous C–H bond activation as the rds for the direct pathway, explains the measured data well. It was found for the relatively slow rate of formic acid oxidation, that adsorption–desorption of the formate is faster, which competes for the surface sites for formic acid oxidation.

Graphical abstract: On the mechanism of the direct pathway for formic acid oxidation at a Pt(111) electrode

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Publication details

The article was received on 15 Nov 2012, accepted on 21 Jan 2013 and first published on 22 Jan 2013


Article type: Paper
DOI: 10.1039/C3CP44074E
Citation: Phys. Chem. Chem. Phys., 2013,15, 4367-4376
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    On the mechanism of the direct pathway for formic acid oxidation at a Pt(111) electrode

    J. Xu, D. Yuan, F. Yang, D. Mei, Z. Zhang and Y. Chen, Phys. Chem. Chem. Phys., 2013, 15, 4367
    DOI: 10.1039/C3CP44074E

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