OSCILLATORY INSTABILITIES DURING FORMIC ACID OXIDATION ON PT(100), PT(110)AND PT(111) UNDER POTENTIOSTATIC CONTROL. II. MODEL CALCULATIONS

A kinetic model is developed for the electrocatalytic oxidation of formic acid on Pt under potentiostatic control. The model development proceeds stepwise via a simple model of the electrocatalytic CO oxidation. The full model consists of four coupled, nonlinear ordinary differential equations. The scanned and stationary current/outer potential (I/U) behavior, stationary current oscillations, two-parameter bifurcation diagrams and stirring effects are simulated using realistic model parameters. The numerical findings are found to be consistent with the experimental results given by Strasser et al. The model reproduces period-1 as well as mixed-mode oscillations. Furthermore, a mechanistic analysis of the model was performed: two suboscillators are identified whose characteristics allow a plausible interpretation of the observed dynamics. After a classification of the suboscillators into previously described categories, an attempt is made to identify the minimal mechanistic requirements for electrochemical...

[1]  G. Ertl,et al.  Oscillatory instabilities during formic acid oxidation on Pt(100), Pt(110) and Pt(111) under potentiostatic control. I. Experimental , 1997 .

[2]  Michael T. Heath,et al.  Scientific Computing , 2018 .

[3]  M. Koper.  Stability study and categorization of electrochemical oscillators by impedance spectroscopy , 1996 .

[4]  N. Tanaka,et al.  Modelling temporal kinetic oscillations for electrochemical oxidation of formic acid on Pt , 1996 .

[5]  K. Krischer,et al.  Experimental and theoretical description of potentiostatic current oscillations during H2 oxidation , 1995 .

[6]  M. Eiswirth,et al.  Current Oscillations in the Electrochemical Oxidation of Formic Acid at Pt Single Crystal Surfaces , 1994 .

[7]  M. Koper,et al.  Instabilities and oscillations in simple models of electrocatalytic surface reactions , 1994 .

[8]  P. Ross,et al.  Oscillatory behavior in the electrochemical oxidation of formic acid on platinum (100) , 1993 .

[9]  M. Koper,et al.  On the mathematical unification of a class of electrochemical oscillators and their design procedures , 1993 .

[10]  M. Eiswirth,et al.  Modelling the Oscillating Electrochemical Reduction of Peroxodisulfate , 1992 .

[11]  P. Gaspard,et al.  A one-parameter bifurcation analysis of the indium/thiocyanate electrochemical oscillator , 1992 .

[12]  Pierre Gaspard,et al.  The modeling of mixed‐mode and chaotic oscillations in electrochemical systems , 1992 .

[13]  M. Schell,et al.  Observation of bistability in cyclic voltammetric experiments on ethanol, propanol, butanol and formic acid/formate , 1992 .

[14]  Markus Eiswirth,et al.  Mechanistic Classification of Chemical Oscillators and the Role of Species , 2007 .

[15]  F. Albahadily,et al.  Observation of several different temporal patterns in the oxidation of formic acid at a rotating platinum-disk electrode in an acidic medium , 1991 .

[16]  Pierre Gaspard,et al.  Mixed-mode and chaotic oscillations in a simple model of an electrochemical oscillator , 1991 .

[17]  M. Koper,et al.  Electrochemical oscillators: their description through a mathematical model , 1991 .

[18]  R. Adzic,et al.  Structural effects in electrocatalysis : oxidation of formic acid on single crystal platinum electrodes and evidence for oscillatory behaviour , 1991 .

[19]  T. Yamazaki,et al.  POTENTIAL OSCILLATION OF PT ELECTRODE IN H2SO4 SOLUTION DURING THE ANODIC OXIDATION OF H2 AND CO , 1991 .

[20]  M. Schell,et al.  Bistability and oscillations in the electrocatalyzed oxidation of formaldehyde , 1990 .

[21]  R. Nichols,et al.  Current oscillations during formic acid oxidation on Pt(100) , 1990 .

[22]  B. Beden,et al.  The electrooxidation of CO: a test reaction in electrocatalysis , 1990 .

[23]  R. Ohnishi,et al.  Potential oscillation during anodic oxidation of hydrogen at a platinum electrode—II. Kinetic analysis , 1990 .

[24]  F. Albahadily,et al.  Characterization of oscillatory states in the electrochemical oxidation of formaldehyde and formate/formic acid , 1989 .

[25]  R. Parsons,et al.  The oxidation of small organic molecules: A survey of recent fuel cell related research , 1988 .

[26]  R. Ohnishi,et al.  Limit cycle in electrochemical oscillation—potential oscillation during anodic oxidation of H2☆ , 1988 .

[27]  I. Schreiber,et al.  Strange attractors in coupled reaction-diffusion cells , 1982 .

[28]  J. Boissonade,et al.  Transitions from bistability to limit cycle oscillations. Theoretical analysis and experimental evidence in an open chemical system , 1980 .

[29]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[30]  Brian E. Conway,et al.  Modern Aspects of Electrochemistry , 1974 .

[31]  R. D. Levie,et al.  On the electrocemical oscillator , 1970 .

[32]  B. Conway,et al.  Oscillatory Kinetics in the Electrochemical Oxidation of Formate and Ethylene , 1968 .

[33]  H. Degn.  Theory of electrochemical oscillations , 1968 .