Enhancement of the electrochemical oxidation of formic acid. Effects of anion adsorption and variation of rotation rate

被引:27
作者
Chen, SL [1 ]
Lee, D [1 ]
Schell, M [1 ]
机构
[1] So Methodist Univ, Dept Chem, Dallas, TX 75275 USA
关键词
formic acid; anion adsorption; fuel cells; oscillations; rotating electrode;
D O I
10.1016/S0013-4686(01)00635-1
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Results are presented from a study on the electrochemical oxidation of formic acid. Perturbing a HCOOH + HClO4 solution by causing a small amount of any one of several different anions to be present dramatically changes observed nonlinear behavior in an apparently unique manner. Quantitative changes are also observed. In current-control experiments, the presence of fluoroborate ions causes a substantial increase in the value of the applied current density for which low valued stationary potentials remain stable. In potential-control experiments, the current density substantially increases at relevant potential values. Although most properties possessed by the fluoroborate anion exist among the other anions studied, the presence of any one of these other ions in solution yields inferior current-potential characteristics. Results from current-control experiments show that changes in rotation rates have no effect on the observed behavior regardless of anion composition or whether the limiting state is stationary or oscillating. (C) 2001 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:3481 / 3492
页数:12
相关论文
共 48 条
[1]   ELEMENTARY STEPS OF ELECTROCHEMICAL OXIDATION OF SINGLE-CRYSTAL PLANES OF AU .1. CHEMICAL BASIS OF PROCESSES INVOLVING GEOMETRY OF ANIONS AND THE ELECTRODE SURFACES [J].
ANGERSTEINKOZLOWSKA, H ;
CONWAY, BE ;
HAMELIN, A ;
STOICOVICIU, L .
ELECTROCHIMICA ACTA, 1986, 31 (08) :1051-1061
[2]   ELEMENTARY STEPS OF ELECTROCHEMICAL OXIDATION OF SINGLE-CRYSTAL PLANES OF AU .2. A CHEMICAL AND STRUCTURAL BASIS OF OXIDATION OF THE (111) PLANE [J].
ANGERSTEINKOZLOWSKA, H ;
CONWAY, BE ;
HAMELIN, A ;
STOICOVICIU, L .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1987, 228 (1-2) :429-453
[3]   ELECTROCATALYTIC OXIDATION OF METHANOL ON PLATINUM-BASED BINARY ELECTRODES [J].
BEDEN, B ;
KADIRGAN, F ;
LAMY, C ;
LEGER, JM .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1981, 127 (1-3) :75-85
[4]   A COMPARATIVE-STUDY OF FORMIC-ACID ADSORPTION ON A PLATINUM-ELECTRODE BY BOTH ELECTROCHEMICAL AND EMIRS TECHNIQUES [J].
BEDEN, B ;
BEWICK, A ;
LAMY, C .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1983, 150 (1-2) :505-511
[5]   A STUDY BY ELECTROCHEMICALLY MODULATED INFRARED REFLECTANCE SPECTROSCOPY OF THE ELECTROSORPTION OF FORMIC-ACID AT A PLATINUM-ELECTRODE [J].
BEDEN, B ;
BEWICK, A ;
LAMY, C .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1983, 148 (01) :147-160
[6]   ELECTROCHEMICALLY MODULATED INFRARED-SPECTROSCOPY (EMIRS) - EXPERIMENTAL DETAILS [J].
BEWICK, A ;
KUNIMATSU, K ;
PONS, BS ;
RUSSELL, JW .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1984, 160 (1-2) :47-61
[7]   VOLTAMMETRIC AND CHRONOPOTENTIOMETRIC STUDY OF THE ANODIC OXIDATION OF METHANOL, FORMALDEHYDE, AND FORMIC ACID [J].
BUCK, RP ;
GRIFFITH, LR .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1962, 109 (11) :1005-1013
[8]   EFFECT OF BI AND SN ADATOMS ON FORMIC-ACID AND METHANOL OXIDATION AT WELL DEFINED PLATINUM SURFACES [J].
CAMPBELL, SA ;
PARSONS, R .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1992, 88 (06) :833-841
[9]   Differences in oscillations and sequences of dynamical states caused by anion adsorption in the electrochemical oxidation of formic acid [J].
Chen, SL ;
Noles, T ;
Schell, M .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (29) :6791-6798
[10]   Effects of anion adsorption different from blocking surface sites deduced from instabilities in the oxidation of formic acid [J].
Chen, SL ;
Schell, M .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 2001, 504 (01) :78-88