The electro-oxidation of CO at the Ru(0001) single-crystal electrode surface

被引:69
作者
Lin, WF
Christensen, PA
Hamnett, A
Zei, MS
Ertl, G
机构
[1] Newcastle Univ, Dept Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England
[2] Fritz Haber Inst Max Planck Gesellsch, D-14195 Berlin, Germany
关键词
D O I
10.1021/jp000936u
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In situ FTIR spectroscopic and electrochemical data and ex situ (emersion) electron diffraction (LEED and RHEED) and Auger spectroscopic data are presented on the structure and reactivity, with respect to the electro-oxidation of CO, of the Ru(0001) single-crystal surface in perchloric acid solution. In both the absence and the presence of adsorbed CO, the Ru(0001) electrode shows the potential-dependent formation of well-defined and ordered oxygen-containing adlayers. At low potentials (e.g., from -80 to +200 mV vs Ag/ AgCl), a (2 x 2)-O phase, which is unreactive toward CO oxidation, is formed, in agreement with UHV studies. Increasing the potential results in the formation of (3 x 1) and (1 x 1) phases at 410 and 1100 mV, respectively, with a concomitant increase in the reactivity of the surface toward CO oxidation. Both linear (COL) and three-fold-hollow (COH) binding CO adsorbates (bands at 2000-2040 and 1770-1800 cm(-1) respectively) were observed on the Ru(0001) electrode. The in situ FTIR data show that the adsorbed CO species remain in compact islands as CO oxidation proceeds, suggesting that the oxidation occurs at the boundaries between the COads and O-ads domains. At low CO coverages, reversible relaxation (at lower potentials) and compression (at higher potentials) of the COL adlayer were observed and rationalized in terms of the reduction and formation of surface O adlayers. The data obtained from the Ru(0001) electrode are in marked contrast to those observed on polycrystalline Ru, where only linear CO is observed.
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页码:6642 / 6652
页数:11
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共 77 条
[1]   STRUCTURAL-CHANGES OF A PT(111) ELECTRODE INDUCED BY ELECTROSORPTION OF OXYGEN IN ACIDIC SOLUTIONS - A COUPLED VOLTAMMETRY, LEED AND AES STUDY [J].
ABERDAM, D ;
DURAND, R ;
FAURE, R ;
ELOMAR, F .
SURFACE SCIENCE, 1986, 171 (02) :303-330
[2]   THE ELECTROOXIDATION OF CO - A TEST REACTION IN ELECTROCATALYSIS [J].
BEDEN, B ;
LAMY, C ;
DETACCONI, NR ;
ARVIA, AJ .
ELECTROCHIMICA ACTA, 1990, 35 (04) :691-704
[3]   ELECTROCATALYTIC OXIDATION OF METHANOL ON PLATINUM-BASED BINARY ELECTRODES [J].
BEDEN, B ;
KADIRGAN, F ;
LAMY, C ;
LEGER, JM .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1981, 127 (1-3) :75-85
[4]   MOLECULAR ORBITAL VIEW OF CHEMISORBED CARBON MONOXIDE [J].
BLYHOLDER, G .
JOURNAL OF PHYSICAL CHEMISTRY, 1964, 68 (10) :2772-&
[5]   Phonon- versus electron-mediated desorption and oxidation of CO on Ru(0001) [J].
Bonn, M ;
Funk, S ;
Hess, C ;
Denzler, DN ;
Stampfl, C ;
Scheffler, M ;
Wolf, M ;
Ertl, G .
SCIENCE, 1999, 285 (5430) :1042-1045
[6]   CO oxidation reaction over oxygen-rich Ru(0001) surfaces [J].
Böttcher, A ;
Niehus, H ;
Schwegmann, S ;
Over, H ;
Ertl, G .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (51) :11185-11191
[7]   COVERAGE-DEPENDENT AND POTENTIAL-DEPENDENT BINDING GEOMETRIES OF CARBON-MONOXIDE AT ORDERED LOW-INDEX PLATINUM AQUEOUS AND RHODIUM AQUEOUS INTERFACES - COMPARISONS WITH ADSORPTION IN CORRESPONDING METAL VACUUM ENVIRONMENTS [J].
CHANG, SC ;
WEAVER, MJ .
SURFACE SCIENCE, 1990, 238 (1-3) :142-162
[8]   In situ FTIR studies of the photo-electrochemical behaviour of thermal TiO2 films as a function of temperature [J].
Christensen, PA ;
Eameaim, J ;
Hamnett, A .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1999, 1 (23) :5315-5321
[9]   Surface structure effects in platinum/ruthenium methanol oxidation electrocatalysis [J].
Chrzanowski, W ;
Wieckowski, A .
LANGMUIR, 1998, 14 (08) :1967-1970
[10]   Enhancement in methanol oxidation by spontaneously deposited ruthenium on low-index platinum electrodes [J].
Chrzanowski, W ;
Kim, H ;
Wieckowski, A .
CATALYSIS LETTERS, 1998, 50 (1-2) :69-75