On the mechanism of Ag(111) sub-monolayer oxidation:: a combined electrochemical, in situ SERS and ex situ XPS study

被引:65
作者
Savinova, ER
Zemlyanov, D
Pettinger, B
Scheybal, A
Schlögl, R
Doblhofer, K
机构
[1] Russian Acad Sci, Boreskov Inst Catalysis, Novosibirsk 630090, Russia
[2] Max Planck Gesell, Fritz Haber Inst, D-14195 Berlin, Germany
[3] Worcester Polytech Inst, Dept Chem Engn, Worcester, MA 01609 USA
关键词
Ag(111); sub-monolayer oxidation; alkaline electrolyte; surface enhanced Raman spectroscopy (SERS); X-ray photoelectron spectroscopy (XPS); ultraviolet photoelectron spectroscopy (UPS);
D O I
10.1016/S0013-4686(00)00571-5
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
In the present work in situ surface enhanced Raman spectroscopy (SERS), ex situ X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) are used to study the interface between a Ag(111) electrode and an alkaline electrolyte. Formation of a number of potential-dependent adsorbates is observed above the point of zero charge (E-pze) of the Ag electrode. These are: OH groups (OHadsgamma-) and oxide-like species (O-ads(delta-)). Electrochemisorbed hydroxide species show by the appearance of Raman bands at 540-560 cm(-1) and at 803-819 cm(-1), attributed to Ag-OH stretching and AgO-H bending vibrations respectively. Strong isotope shift of the Raman bands towards lower frequencies is observed in D2O solutions, proving their assignment. The O-ads(delta-) and OHadsgamma- species are characterised by the O Is peaks at ca. 529.5 and 531.6, respectively. Formation of the above-mentioned species is verified also by the UP spectra of the emersed electrodes, showing the bands at 3.0 eV typical for the oxide-like adsorbates and 9.0 and 11.1 eV for hydroxo-groups. The OHadsgamma- and O-ads(delta-) species are negatively charged, as evidenced by the adsorption of Na+ on the Ag electrode positive to the E-pzc. A mechanism of the Ag(lll) sub-monolayer oxidation is suggested on the basis of combined evidence from cyclic voltammetry, in situ SERS, ex situ XPS and UPS. (C) 2000 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:175 / 183
页数:9
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