Computational and experimental study of the cyclic voltammetry response of partially blocked electrodes. Part 1. Nonoverlapping, uniformly distributed blocking systems

被引:108
作者
Brookes, BA
Davies, TJ
Fisher, AC
Evans, RG
Wilkins, SJ
Yunus, K
Wadhawan, JD
Compton, RG
机构
[1] Univ Oxford, Phys & Theoret Chem Lab, Oxford OX1 3QZ, England
[2] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
关键词
D O I
10.1021/jp021810v
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 cyclic voltammetry response of partially blocked electrodes is modeled using finite difference simulations and a method presented for determining currents at electrode surfaces which have a well-defined geometric blocking pattern. Peak current and peak separation data are presented for six decades of scan rates, blocking coverage values between 0.1 and 0.9 and between the limits of reversible and irreversible electrochemistry. The validity of the simulation approach employed is verified by data obtained experimentally from purpose-built partially blocked gold film electrodes, with either a cubic or hexagonal geometric array of electroinactive disks uniformly distributed on the electrode surface. Comparison of theory with experiment suggests that the modeling of hexagonally distributed blocking systems is superior to that of the cubically arranged ones.
引用
收藏
页码:1616 / 1627
页数:12
相关论文
共 40 条
[1]   A general method for electrochemical simulations .1. Formulation of the strategy for two-dimensional simulations [J].
Alden, JA ;
Compton, RG .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (44) :8941-8954
[2]   A general method for electrochemical simulations .2. Application to the simulation of steady-state currents at microdisk electrodes: Homogeneous and heterogeneous kinetics [J].
Alden, JA ;
Compton, RG .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (46) :9606-9616
[3]   CHARGE-TRANSFER AT PARTIALLY BLOCKED SURFACES - A MODEL FOR THE CASE OF MICROSCOPIC ACTIVE AND INACTIVE SITES [J].
AMATORE, C ;
SAVEANT, JM ;
TESSIER, D .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1983, 147 (1-2) :39-51
[4]   Microring electrodes: A computational study of transport-limited processes [J].
Brookes, BA ;
Gavaghan, DJ ;
Compton, RG .
JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (18) :4886-4896
[5]  
BROOKES BA, UNPUB
[6]   CHARACTERIZATION AND IDENTIFICATION OF PARTIALLY BLOCKED ELECTRODES [J].
CONTAMIN, O ;
LEVART, E .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1982, 136 (02) :259-270
[7]  
COOKE J, 1970, Q J APPL MATH, V10, P366
[8]   ROTATING-DISK ELECTRODE FOR VOLTAMMETRY AND ELECTROCHEMICAL IMPEDANCE MEASUREMENTS - APPLICATION TO THE STUDY OF PARTIALLY BLOCKED ELECTRODES [J].
ETMAN, M ;
LEVART, E ;
SCARBECK, G ;
SCHUHMANN, D .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1979, 101 (02) :153-170
[9]   CONVECTIVE-DIFFUSION IMPEDANCE FOR A PARTIALLY BLOCKED ROTATING-DISK ELECTRODE [J].
ETMAN, M ;
LEVART, E ;
SCHUHMANN, D .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1979, 101 (02) :141-152
[10]  
ETMAN M, 1985, J ELECTROANAL CHEM, V187, P247