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Titolo:
Scanning electrochemical microscopy of hydrogen electro-oxidation. Rate constant measurements and carbon monoxide poisoning on platinum
Autore:
Jambunathan, K; Shah, BC; Hudson, JL; Hillier, AC;
Indirizzi:
Univ Virginia, Dept Chem Engn, Charlottesville, VA 22903 USA Univ Virginia Charlottesville VA USA 22903 Charlottesville, VA 22903 USA Univ Virginia, Ctr Electrochem Sci & Engn, Charlottesville, VA 22903 USA Univ Virginia Charlottesville VA USA 22903 Charlottesville, VA 22903 USA
Titolo Testata:
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
fascicolo: 1-2, volume: 500, anno: 2001,
pagine: 279 - 289
Fonte:
ISI
Lingua:
ENG
Soggetto:
ROTATING-DISK ELECTRODE; PT-RU ALLOYS; H-2/CO MIXTURES; CO ELECTROOXIDATION; ACID-SOLUTIONS; SULFURIC-ACID; ELECTROCATALYTIC ACTIVITY; INFRARED-SPECTROSCOPY; CYCLIC VOLTAMMETRY; SURFACE SCIENCE;
Keywords:
scanning electrochemical microscopy; microelectrode; electrocatalysis; carbon monoxide; hydrogen oxidation; platinum; fuel cell;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
53
Recensione:
Indirizzi per estratti:
Indirizzo: Hillier, AC Univ Virginia, Dept Chem Engn, Charlottesville, VA 22903 USA Univ Virginia Charlottesville VA USA 22903 ille, VA 22903 USA
Citazione:
K. Jambunathan et al., "Scanning electrochemical microscopy of hydrogen electro-oxidation. Rate constant measurements and carbon monoxide poisoning on platinum", J ELEC CHEM, 500(1-2), 2001, pp. 279-289

Abstract

We describe an application of the scanning electrochemical microscope thatuses tip-sample feedback to characterize the electro-oxidation of hydrogenon a polycrystalline platinum electrode in sulfuric acid solutions in the presence and absence of adsorbed carbon monoxide. The hydrogen oxidation reaction is probed by reducing protons at a diffusion-limited rate at the microscope's tip electrode while it is positioned near a platinum substrate. Aseries of approach curves measured as a function of the substrate potential provides hydrogen oxidation rate constant values over a wide range of substrate conditions. In the absence of CO, the rate of hydrogen oxidation exceeds 1 cm s(-1) at potentials within the hydrogen adsorption and double layer charging regions. A Tafel slope of similar to 30 mV per decade is determined near the reversible potential. At increasingly positive substrate potentials, the hydrogen oxidation rate decreases exponentially with increasingpotential as the surface is covered with an oxide layer. The adsorption ofsolution-phase carbon monoxide completely deactivates the platinum substrate towards steady-state hydrogen oxidation over a large range of substrate potentials. Approach curves indicate a near-zero rate constant for hydrogenoxidation on CO-covered platinum at potentials below oxide formation. An increase in the hydrogen oxidation rate is seen at potentials sufficiently positive that CO fails to adsorb and the platinum oxide forms. In comparison, dynamic tip-substrate voltammetry depicts a complex substrate response whereby the adsorbed carbon monoxide layer transforms from a weakly adsorbed state at low potentials to a strongly adsorbed state at high potentials. Although steady-state approach curve measurements depict the complete deactivation of catalytic activity at these potentials, a significant hydrogen oxidation current is observed during the potential-induced transformation between these weakly and strongly adsorbed CO states. The rate of hydrogen oxidation approaches that of a pristine platinum surface during this surface transformation before returning to the poisoned state. (C) 2001 Elsevier Science B.V. All rights reserved.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 23/09/20 alle ore 12:32:18