Mechanistic aspects of the linear stabilization of non-stationary electrochemical oscillations

被引:35
作者
Cabral, Murilo F. [1 ]
Nagao, Raphael [1 ]
Sitta, Elton [1 ]
Eiswirth, Markus [2 ,3 ]
Varela, Hamilton [1 ,3 ]
机构
[1] Univ Sao Paulo, Inst Chem Sao Carlos, BR-13560970 Sao Carlos, SP, Brazil
[2] Fritz Haber Inst, D-14195 Berlin, Germany
[3] GIST, Ertl Ctr Electrochem & Catalysis, Kwangju 500712, South Korea
基金
巴西圣保罗研究基金会;
关键词
FORMIC-ACID; FORMALDEHYDE OXIDATION; POTENTIAL OSCILLATIONS; METHANOL OXIDATION; GALVANOSTATIC ELECTROOXIDATION; ELECTROCATALYTIC OXIDATION; PLATINUM-ELECTRODE; TEMPERATURE; PATTERNS; PATHWAY;
D O I
10.1039/c2cp42890c
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 problem of non-stationarity in experimentally recorded time-series is common in many (electro)chemical systems. Underlying this non-stationarity is the slow drift in some uncontrollable parameter, and it occurs in spite of the fact that all controllable parameters are kept constant. Particularly for electrochemical systems, some of us have recently suggested [J. Phys. Chem. C, 144, (2010), 22262-22268] an empirical method to stabilize experimental time-series. The method was exemplified for the electro-oxidation of methanol and different patterns were satisfactorily stabilized. In this paper we further elaborate some mechanistic aspects of this method and test it for the electro-oxidation of formaldehyde, a system that has some resemblance with the electro-oxidation of methanol, but produces a richer dynamics. In terms of the reaction mechanism, we were able to describe the coupling and to separate the surface processes of the two sub-systems: the fast one (or the core-oscillator) and the slow one, responsible for the drift.
引用
收藏
页码:1437 / 1442
页数:6
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