Adsorbed formate: the key intermediate in the oxidation of formic acid on platinum electrodes

被引：102

作者：

Cuesta, Angel ^{[1
]}

Cabello, Gema ^{[1
]}

Gutierrez, Claudio ^{[1
]}

Osawa, Masatoshi ^{[2
]}

机构：

[1] CSIC, Inst Quim Fis Rocasolano, E-28006 Madrid, Spain

[2] Hokkaido Univ, Catalysis Res Ctr, Sapporo, Hokkaido 0010021, Japan

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2011年 / 13卷 / 45期

关键词：

SINGLE-CRYSTAL ELECTRODES; ZERO TOTAL CHARGE; GALVANOSTATIC ELECTROOXIDATION; POLYCRYSTALLINE PLATINUM; POTENTIAL OSCILLATIONS; MODIFIED PT(111); IR SPECTROSCOPY; GOLD ELECTRODES; CARBON-MONOXIDE; ADSORPTION;

D O I：

10.1039/c1cp22498k

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：

The electrooxidation of formic acid on Pt and other noble metal electrodes proceeds through a dual-path mechanism, composed of a direct path and an indirect path through adsorbed carbon monoxide, a poisoning intermediate. Adsorbed formate had been identified as the reactive intermediate in the direct path. Here we show that actually it is also the intermediate in the indirect path and is, hence, the key reaction intermediate, common to both the direct and indirect paths. Furthermore, it is confirmed that the dehydration of formic acid on Pt electrodes requires adjacent empty sites, and it is demonstrated that the reaction follows an apparently paradoxical electrochemical mechanism, in which an oxidation is immediately followed by a reduction.

引用

页码：20091 / 20095

页数：5

共 37 条

[21] A study of immersion processes of activating polished crystalline silicon for autocatalytic electroless deposition of palladium and other metals [J].

Karmalkar, S ;

Banerjee, J .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (02) :580-584

[22] Formic acid decomposition on polycrystalline platinum and palladized platinum electrodes [J].

Lu, GQ ;

Crown, A ;

Wieckowski, A .

JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (44) :9700-9711

[23] Adsorbate-adsorbate interactions and chemisorption at different coverages studied by accurate ab initio calculations: CO on transition metal surfaces [J].

Mason, SE ;

Grinberg, I ;

Rappe, AM .

JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (08) :3816-3822

[24] STABILIZATION EFFECTS IN THE DECOMPOSITION OF FORMATE ON RU(001) [J].

MENG, B ;

JACHIMOWSKI, TA ;

SUN, Y ;

WEINBERG, WH .

SURFACE SCIENCE, 1994, 315 (1-2) :L959-L963

[25] Surface-enhanced IR absorption on platinum nanoparticles: an application to real-time monitoring of electrocatalytic reactions [J].

Miki, A ;

Ye, S ;

Osawa, M .

CHEMICAL COMMUNICATIONS, 2002, (14) :1500-1501

[26] Electrochemical behaviour of benzoic acid on platinum and gold electrodes [J].

Montilla, F ;

Morallón, E ;

Vázquez, JL .

LANGMUIR, 2003, 19 (24) :10241-10246

[27] Potential oscillations in galvanostatic electrooxidation of formic acid on platinum:: A mathematical modeling and simulation [J].

Mukouyama, Yoshiharu ;

Kikuchi, Mitsunobu ;

Samjeske, Gabor ;

Osawa, Masatoshi ;

Okamoto, Hiroshi .

JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (24) :11912-11917

[28] The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum [J].

Osawa, Masatoshi ;

Komatsu, Kei-ichi ;

Samjeske, Gabor ;

Uchida, Taro ;

Ikeshoji, Tamio ;

Cuesta, Angel ;

Gutierrez, Claudio .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (05) :1159-1163

[29] AN FTIR STUDY ON THE ADSORPTION OF ACETATE AT THE BASAL PLANES OF PLATINUM SINGLE-CRYSTAL ELECTRODES [J].

RODES, A ;

PASTOR, E ;

IWASITA, T .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1994, 376 (1-2) :109-118

[30] Hydroxylamine electrochemistry at low-index single-crystal platinum electrodes in acidic media [J].

Rosca, V ;

Beltramo, GL ;

Koper, MTM .

JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (24) :8294-8304

← 1 2 3 4 →