electrocatalysis on surfaces modified... - Brookhaven National ...

or species with a carbonyl bond. By using subtractively normalized Fourier transform
infrared spectroscopy (SNFTIRS), Iwasita et al. [86] have determined absolute absortion
bands for linear-, bridge-, multi-bonded CO and COH adsorbates. Nichols and Bewick
[87], by using a flow IR-electrochemical cell, identified COH and CH x OH species as
reactive intermediates. Recent results with DEMS indicate predominantly a mixture of
CO and COH, or only CO as adsorbed intermediates [84,88, 89]. Model calculations of
methanol oxidation on Pt(111) that provide a good fit to the experimental data without
adjustable parameters involve a reactive intermediate with the stoichiometry H:C:O [90].
Negligible catalytic [2,91,92], and predominantly inhibition effects [93] are
observed for methanol oxidation on Pt in acid solutions. The exceptions are the effects of
Sn [50, 94,95], and Ge [95]. Significant catalytic effects have been observed for Pb, and
Bi on Pt in alkaline solutions [96,97]. However, carbonization of the alkaline electrolyte
with CO 2 makes these systems unsuitable for practical applications. For single crystal
Pt(100) and Pt(111) surfaces, the reaction has been found to be inhibited by the Bi
adlayer [47,98].
Some agreement exists on the effects of Sn, although the results are not
reproducible. The UPD of tin differs from the majority of the UPD systems [99]. Its
oxidation state is extremly potential dependent. The effects of Sn on the oxidation of
CH 3 OH on Pt are attractive because they occur at very low potentials. The system Pt-Sn
has been investigated in three forms: Sn irreversibly adsorbed, Sn adsorbed by UPD, and
ordered single crystal Pt 3 Sn alloy [100]. Vassiliev et al. [94] found a Temkin adsorption
behavior of neutral Sn at Pt in the potential region from 0 V to 0.2. Above 0.2 V tin
undergoes a partial oxidation to Sn + , or SnOH at ~0.5V. A ten-fold increase of the rate in
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