The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum

被引:179
作者
Osawa, Masatoshi [1 ]
Komatsu, Kei-ichi [1 ]
Samjeske, Gabor [1 ]
Uchida, Taro [1 ]
Ikeshoji, Tamio [2 ]
Cuesta, Angel [3 ]
Gutierrez, Claudio [3 ]
机构
[1] Hokkaido Univ, Catalysis Res Ctr, Sapporo, Hokkaido 0010021, Japan
[2] Tohoku Univ, New Ind Creat Hatchery Ctr, Sendai, Miyagi 9808579, Japan
[3] CSIC, Inst Quim Fis Rocasolano, E-28006 Madrid, Spain
关键词
electrochemistry; formic acid; heterogeneous catalysis; platinum; surface chemistry; GALVANOSTATIC ELECTROOXIDATION; POLYCRYSTALLINE PLATINUM; POTENTIAL OSCILLATIONS; ACTIVE INTERMEDIATE; HCOOH OXIDATION; SURFACE; ABSORPTION; MECHANISM; DECOMPOSITION; SPECTROSCOPY;
D O I
10.1002/anie.201004782
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A bridge too far: Time-resolved surface-enhanced infrared spectroscopy (SEIRAS) coupled with chronoamperometry shows that formic acid is oxidized via bridge-bonded adsorbed formate, and that formate decomposition is the rate-determining step in the electrooxidation of formic acid to CO2 on Pt. The contribution of direct oxidation of formic acid via weakly adsorbed HCOOH is negligible at best. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
引用
收藏
页码:1159 / 1163
页数:5
相关论文
共 37 条
[1]  
ANGERSTE.H, 1973, J ELECTROANAL CHEM, V43, P9, DOI 10.1016/0368-1874(73)80226-6
[2]   Potential-dependent reorientation of water molecules at an electrode/electrolyte interface studied by surface-enhanced infrared absorption spectroscopy [J].
Ataka, K ;
Yotsuyanagi, T ;
Osawa, M .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (25) :10664-10672
[3]   Short-lived reactive intermediate in the decomposition of formate on NiO(111) surface observed by picosecond temperature jump [J].
Bandara, A ;
Kubota, J ;
Onda, K ;
Wada, A ;
Kano, SS ;
Domen, K ;
Hirose, C .
JOURNAL OF PHYSICAL CHEMISTRY B, 1998, 102 (31) :5951-5954
[4]  
Beden B., 1992, MODERN ASPECTS ELECT, P97, DOI DOI 10.1007/978-1-4615-3376-4_2
[5]   Oxidation of formic acid and carbon monoxide on gold electrodes studied by surface enhanced Raman spectroscopy and DFT [J].
Beltramo, GL ;
Shubina, TE ;
Koper, MTM .
CHEMPHYSCHEM, 2005, 6 (12) :2597-2606
[6]   OXIDATION OF FORMIC-ACID AT NOBLE-METAL ELECTRODES .1. REVIEW OF PREVIOUS WORK [J].
CAPON, A ;
PARSONS, R .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1973, 44 (01) :1-7
[7]   Bridge-bonded formate: Active intermediate or spectator species in formic acid oxidation on a Pt film electrode? [J].
Chen, Y. -X. ;
Heinen, M. ;
Jusys, Z. ;
Behm, R. J. .
LANGMUIR, 2006, 22 (25) :10399-10408
[8]   Kinetics and mechanism of the electrooxidation of formic acid - Spectroelectrochemical studies in a flow cell [J].
Chen, YX ;
Heinen, M ;
Jusys, Z ;
Behm, RJ .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (06) :981-985
[9]   Formate, an active intermediate for direct oxidation of methanol on Pt electrode [J].
Chen, YX ;
Miki, A ;
Ye, S ;
Sakai, H ;
Osawa, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (13) :3680-3681
[10]  
CHEN YX, 2006, ANGEW CHEM, V118, P995