Platinization assisted by Keggin-type heteropolytungstates

被引:21
作者
Borzenko, MI [1 ]
Chojak, M
Kulesza, PJ
Tsirlina, GA
Petrii, OA
机构
[1] Moscow MV Lomonosov State Univ, Dept Electrochem, Moscow 119992, Russia
[2] Warsaw Univ, Dept Chem, PL-02093 Warsaw, Poland
关键词
platinum deposition; polyoxotungstates; adsorption; nucleation; scanning tunneling microscopy;
D O I
10.1016/S0013-4686(03)00513-9
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Chronoamperometry and cyclic voltammetry (CV) were used to address the platinum deposition kinetics on glassy carbon and polycrystalline Pt supports from H2PtCl6-containing solutions with and without additives of different Keggin-type heteropoly acids (HPAs) of tungsten. The effect of addition of these polyoxometallates manifested itself in the pronounced disturbance of instantaneous nucleation and it can be interpreted in terms of strong HPA adsorption on certain nucleation centers followed by the modification of their activity. HPA additives decreased the current efficiency for Pt deposition despite the fact that the reduction of HPA additives was thermodynamically forbidden at the potentials chosen for electrodeposition. The latter fact can be explained as selective inhibition of the intermediate Pt-II reduction by tungstates. CV of Pt deposits in sulfuric acid solutions indicated a noticeable increase in the deposit roughness if P- and Si-containing HPA were added in the course of platinization. More complex behavior was found for B-dodecatungstate that most likely originated from its tendency to undergo codeposition with Pt. Ex situ scanning tunneling microscopy (STM) images demonstrate more pronounced globular structure and smaller crystal sizes for HPA-affected deposits as compared with usual platinized platinum. These features can be explained by HPA effects on deposition kinetics assumed on the basis of electrochemical data and demonstrate that HPA can act in template-like manner. (C) 2003 Elsevier Ltd. All rights reserved.
引用
收藏
页码:3797 / 3804
页数:8
相关论文
共 42 条
[1]   MODIFICATION OF POLYANILINE FILMS WITH HETEROPOLYANIONS - ELECTROCATALYTIC REDUCTION OF OXYGEN AND PROTONS [J].
BIDAN, G ;
GENIES, EM ;
LAPKOWSKI, M .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (08) :533-535
[2]   Adsorption of tungstate, isopoly tungstate, and heteropoly tungstate anions at the solution/mercury interface [J].
Borzenko, MI ;
Tsirlina, GA ;
Petrii, OA .
RUSSIAN JOURNAL OF ELECTROCHEMISTRY, 2000, 36 (04) :452-455
[3]  
BORZENKO MI, 2002, MENDELEEV COMMUN, V12, P4
[4]  
BORZENKO MI, UNPUB
[5]   1-12 PHOSPHOMOLYBDIC ANION MODIFIED GLASSY-CARBON ELECTRODE [J].
DONG, SJ ;
JIN, Z .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (24) :1871-1872
[6]   PLATINIZED PLATINUM ELECTRODES [J].
FELTHAM, AM ;
SPIRO, M .
CHEMICAL REVIEWS, 1971, 71 (02) :177-&
[7]  
GAMBURG YD, 1979, ELEKTROKHIMIYA, V9, P751
[8]  
GAMBURG YD, 2002, RUSS ELECTROCHEM+, V38, P9
[9]   Self-assembly of silicotungstate anions on silver surfaces [J].
Ge, MH ;
Zhong, BX ;
Klemperer, WG ;
Gewirth, AA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (24) :5812-5813
[10]   Platinum electrodeposition on graphite:: electrochemical study and STM imaging [J].
Gloaguen, F ;
Léger, JM ;
Lamy, C ;
Marmann, A ;
Stimming, U ;
Vogel, R .
ELECTROCHIMICA ACTA, 1999, 44 (11) :1805-1816