Issue 31, 2010

Intrinsic activity and poisoning rate for HCOOHoxidation on platinum stepped surfaces

Abstract

Pulsed voltammetry has been used to study formic acid oxidation on platinum stepped surfaces to determine the kinetics of the reaction and the role of the surface structure in the reactivity. From the current transients at different potentials, the intrinsic activity of the electrode through the active intermediate reaction path (jθ = 0), as well as the rate constant for the CO formation (kads) have been calculated. The kinetics for formic acid oxidation through the active intermediate reaction path is strongly dependent on the surface structure of the electrode, with the highest activity found for the Pt(100) surface. The presence of steps, both on (100) and (111) terraces, does not increase the activity of these surfaces. CO formation only takes place in a narrow potential window very close to the local potential of zero total charge. The extrapolation of the results obtained with stepped surfaces with (111) terraces to zero step density indicates that CO formation should not occur on an ideal Pt(111) electrode. Additionally, the analysis of the Tafel slopes obtained for the different electrodes suggests that the oxidation of formic acid is strongly affected by the presence of adsorbed anions, hydrogen and water.

Graphical abstract: Intrinsic activity and poisoning rate for HCOOH oxidation on platinum stepped surfaces

Article information

Article type
Paper
Submitted
12 Dec 2009
Accepted
09 Apr 2010
First published
10 Jun 2010

Phys. Chem. Chem. Phys., 2010,12, 8822-8831

Intrinsic activity and poisoning rate for HCOOH oxidation on platinum stepped surfaces

V. Grozovski, V. Climent, E. Herrero and J. M. Feliu, Phys. Chem. Chem. Phys., 2010, 12, 8822 DOI: 10.1039/B925472B

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