Co-adsorption of fluoride and hydroxide ions on Ag(111) in alkaline electrolytes: Electrochemical and SHG studies

被引：6

作者：

Danckwerts, M

Savinova, ER

Horswell, SL

Pettinger, B

Doblhofer, K

机构：

[1] Max Planck Gesell, Fritz Haber Inst, D-14195 Berlin, Germany

[2] Russian Acad Sci, Boreskov Inst Catalysis, Novosibirsk 630090, Russia

来源：

ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS | 2003年 / 217卷 / 05期

关键词：

Ag(111); second harmonic generation (SHG); fluoride; hydroxide; co-adsorption; surface oxide; alkaline electrolyte;

D O I：

10.1524/zpch.217.5.557.20458

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：

Hydroxide (OH-) adsorption at Ag(111)/alkaline electrolyte interfaces is the initial step leading to the formation of surface oxide. We investigate how OH- anion adsorption is influenced by co-adsorption of supporting electrolyte anions (F-). Pure NaF and NaOH as well as mixed electrolytes ranging from pH = 5.8 to 14 are investigated. The rotational anisotropy of the second harmonic generation (SHG) signal is measured to distinguish adsorptive processes from structural changes on the Ag surface. Our results clearly show a cross-over from F-dominated to OH--dominated adsorption, while both species remain charged upon adsorption. At more positive potentials, but below the reversible potential of bulk oxide growth, OH is discharged leading to sub-monolayer oxide build-up, whereas in acidic electrolyte, Ag is dissolved. At intermediate pH, the formation of a structured OH-/F- co-adsorbed layer is proposed.

引用

页码：557 / 572

页数：16

共 16 条

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