Room temperature CO(ad) desorption/exchange kinetics on Pt electrodes-A combined in situ IR and mass spectrometry study.
The room temperature desorption and exchange of CO in a saturated CO adlayer on a Pt electrode, at potentials far below the onset of oxidation, was investigated by isotope labeling experiments, using a novel spectroelectrochemical setup, which allows the simultaneous detection of adsorbed species by in situ IR spectroscopy and of volatile (side) products and reactants by online mass spectrometry under controlled electrolyte flow conditions. Time-resolved IR spectra show a rapid, statistical exchange of pre-adsorbed (13)CO(ad) by (12)CO(ad) in (12)CO containing electrolyte; mass spectrometric data reveal first-order exchange kinetics, with the rate increasing with CO partial pressure. The increasing CO(ad) desorption rate in equilibrium with a CO containing electrolyte is explained by a combination of an increasing CO(ad) coverage upon increasing the CO pressure, and a decrease of the CO adsorption energy with coverage, due to repulsive CO(ad)-CO(ad) interactions.
Heinen
Martin
M
Institute of Surface Chemistry and Catalysis, Ulm University, 89069 Ulm, Germany.
Chen
Yan-Xia
YX
Jusys
Zenonas
Z
Behm
Rolf Jürgen
RJ
D000327:Adsorption; D002248:Carbon Monoxide / Q000737:chemistry*; D004566:Electrodes; D007700:Kinetics; D013058:Mass Spectrometry; D010984:Platinum / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013696:Temperature
D010984:Platinum; D002248:Carbon Monoxide