The nature of chemisorbed hydroxyl radicals

Patrito, E.M.; Olivera, P.Paredes; Sellers, Harrell

doi:10.1016/0039-6028(94)90085-x

Cited by 41 publications

(20 citation statements)

References 44 publications

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“…This allowed us to find a simple parameter set that produces both the cyclic voltammetry data as well as the potential-step transients for rhodium. We believe that this assumption is justified as ab initio quantum-chemical calculations as well as experimental results show that OH binds more strongly on rhodium than on platinum [1,[38][39][40] and Koper et al [9] showed that the most suitable model for the CO stripping voltammetry on Rh(100) is obtained when the CO + OH reaction rate is slower than the OH adsorption rate. Moreover, in contrast to stepped platinum electrodes, the potential at which the CO electrooxidation reaction on Rh[n(1 1 1) · (1 1 1)] type electrodes occurs overlaps with the surface oxidation potential, which, in model terms, translates as the CO-OH reaction being slower than the OH adsorption.…”

Section: Resultsmentioning

confidence: 94%

“…[2]). The fact that, after a small current plateau [5,[40][41][42][43][44], the experimentally obtained voltammograms also display a rapidly increasing current, followed by a slower decrease, suggests that the one-dimensional oxidation mechanism proposed for the steps may be applicable. As surface oxidation starts playing an increasingly more important role for higher step densities, this characteristic shape is not as well defined on Rh(5 5 3) as it is on Rh(5 5 4).…”

Section: Modeling the Co Electrooxidation At Step Sitesmentioning

confidence: 89%

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CO oxidation on stepped single crystal electrodes: A dynamic Monte Carlo study

Housmans

Hermse

Koper

2007

Journal of Electroanalytical Chemistry

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Section: Resultsmentioning

confidence: 94%

Section: Modeling the Co Electrooxidation At Step Sitesmentioning

confidence: 89%

CO oxidation on stepped single crystal electrodes: A dynamic Monte Carlo study

Housmans

Hermse

Koper

2007

Journal of Electroanalytical Chemistry

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“…For instance, the formation of hydrogen bonds is thought to be responsible for stabilization of hydroxylated metal surfaces. 34 However, one needs to examine the thermodynamic stability of surface intermediates and kinetics of chemisorption and surface migration to assess fully the phenomena for diamond CVD.…”

Section: Discussionmentioning

confidence: 99%

Theoretical study of oxygenated (100) diamond surfaces in the presence of hydrogen

1997

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Quantum ab initio calculations and quantum semiempirical molecular-dynamics simulations were employed to study reconstructions of ͑100͒ diamond surfaces in the presence of hydrogen and oxygen. The results indicate that the energetically most favorable structures of oxygenated surfaces are those with chemisorbed hydroxyl groups. It was found that hydrogen bonds are formed among chemisorbed oxygenated species. The formation of these hydrogen bonds lowers the adlayer energy. A number of important vibrational modes characteristic of oxygenated diamond surfaces were identified. The analysis of surface vibrational spectra demonstrates the influence of the local environment on the position of vibrational modes and can be useful for interpretation of experimental data.

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“…It is known that for high CO coverages the most dominant binding site for CO is the on-top site. 8 The adsorption site for OH on transition-metal surfaces is controversial and presumably depends on the lateral adsorbate interactions; 22 in ab initio quantum-chemical calculations, the preferred adsorption site on small Pt clusters is found to be the one-fold on-top site. 23 From in-situ IR and STM measurements, at high CO coverages some CO is known to be adsorbed on the bridge-bonded and multicoordinated sites.…”

Section: ͑22͒mentioning

confidence: 99%

Monte Carlo simulations of a simple model for the electrocatalytic CO oxidation on platinum

Koper

Jansen

Santen

et al. 1998

The Journal of Chemical Physics

195

253

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A simple lattice-gas model for the electrocatalytic carbon monoxide oxidation on a platinum electrode is studied by dynamic Monte Carlo simulations. The CO oxidation takes place through a Langmuir-Hinshelwood reaction between adsorbed CO and an adsorbed OH radical resulting from the dissociative adsorption of water. The model enables the investigation of the role of CO surface mobility on the macroscopic electrochemical response such as linear sweep voltammetry and potential step chronoamperometry. Our results show that the mean-field approximation, the traditional but often tacitly made assumption in electrochemistry, breaks down severely in the limit of vanishing CO surface mobility. Comparison of the simulated and experimental voltammetry suggests that on platinum CO oxidation is the intrinsically fastest reaction on the surface and that CO has a high surface mobility. However, under the same conditions, the model predicts some interesting deviations from the potential step current transients derived from the classical nucleation and growth theories. Such deviations have not been reported experimentally. Furthermore, it is shown that our simple model predicts different Tafel slopes at low and high potential, the qualitative features of which are not strongly influenced by the CO mobility. The comparison of our simulation results to the experimental literature is discussed in some detail.

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The nature of chemisorbed hydroxyl radicals

Cited by 41 publications

References 44 publications

CO oxidation on stepped single crystal electrodes: A dynamic Monte Carlo study

CO oxidation on stepped single crystal electrodes: A dynamic Monte Carlo study

Theoretical study of oxygenated (100) diamond surfaces in the presence of hydrogen

Monte Carlo simulations of a simple model for the electrocatalytic CO oxidation on platinum

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