Relevance of heterometallic binding energy for metal underpotential deposition

被引:26
作者
Sanchez, CG
Leiva, EPM [1 ]
Kohanoff, J
机构
[1] Univ Nacl Cordoba, INFIQC, Fac Ciencias Quim, Unidad Matemat & Fis, RA-5000 Cordoba, Argentina
[2] Queens Univ Belfast, Sch Math & Phys, Atomist Simulat Grp, Belfast BT7 1NN, Antrim, North Ireland
关键词
D O I
10.1021/la001639j
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We present first-principles calculations for a number of metals adsorbed on several different metallic substrates. Some of these systems are very relevant in electrochemistry, especially in the field of underpotential deposition phenomena. The present studies reveal the existence of a relationship between the excess binding energy and the surface energy difference between substrate and adsorbate. Comparisons with experimental underpotential shifts show that excess binding energies are systematically underestimated. By analyzing experimental information on different systems, we conclude that this discrepancy between our vacuum calculations and experiments carried out in an electrolytic solution is likely to be due to anion adsorption and/or solvent effects.
引用
收藏
页码:2219 / 2227
页数:9
相关论文
共 49 条
[21]   Recent developments in the theory of metal upd [J].
Leiva, E .
ELECTROCHIMICA ACTA, 1996, 41 (14) :2185-2206
[22]  
Leiva E. P. M., 1993, CURRENT TOPICS ELECT, V2, P269
[23]   Changes in surface stress caused by the adsorption of an epitaxial metal monolayer [J].
Leiva, EPM ;
Del Pópolo, MG ;
Schmickler, W .
CHEMICAL PHYSICS LETTERS, 2000, 320 (5-6) :393-397
[24]  
LOPEZ MB, 1990, J MOL STRUC-THEOCHEM, V210, P353
[25]  
LOPEZ MB, 1990, J MOL STRUC-THEOCHEM, V210, P365
[26]   EFFECT OF ANIONS ON THE UNDERPOTENTIAL DEPOSITION OF CU ON PT(111) AND PT(100) SURFACES [J].
MARKOVIC, N ;
ROSS, PN .
LANGMUIR, 1993, 9 (02) :580-590
[27]   ELECTRODEPOSITION OF COPPER ON PT(111) AND PT(100) SINGLE-CRYSTAL SURFACES [J].
MARKOVIC, NM ;
ROSS, PN .
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A-VACUUM SURFACES AND FILMS, 1993, 11 (04) :2225-2231
[28]   COPPER ELECTRODEPOSITION ON PT(111) IN THE PRESENCE OF CHLORIDE AND (BI)SULFATE - ROTATING-RING PT(111) DISK ELECTRODE STUDIES [J].
MARKOVIC, NM ;
GASTEIGER, HA ;
ROSS, PN .
LANGMUIR, 1995, 11 (10) :4098-4108
[29]   THE EFFECT OF HALIDES ON THE STRUCTURE OF COPPER UNDERPOTENTIAL-DEPOSITED ONTO PT(111) - A LOW-ENERGY ELECTRON-DIFFRACTION AND X-RAY PHOTOELECTRON-SPECTROSCOPY STUDY [J].
MICHAELIS, R ;
ZEI, MS ;
ZHAI, RS ;
KOLB, DM .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1992, 339 (1-2) :299-310
[30]   SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS [J].
CHADI, DJ .
PHYSICAL REVIEW B, 1977, 16 (04) :1746-1747