TY - JOUR

T1 - Self-sustained oscillations within the temperature hysteresis in CO oxidation over Pd

T2 - Mathematical model of a cascade of continuous stirred-tank reactors

AU - Lashina, Elena A.

AU - Slavinskaya, Elena M.

AU - Chumakova, Nataliya A.

AU - Chumakov, Gennadii A.

AU - Boronin, Andrei I.

N1 - Publisher Copyright: © 2019 Wiley Periodicals, Inc. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2019/12/1

Y1 - 2019/12/1

N2 - The results of temperature-programmed reaction experimental studies and mathematical modeling of self-sustained oscillations within an inverse temperature hysteresis in CO oxidation over Pd catalyst are presented. The experimental data demonstrate the influence of the reaction medium on the catalyst activity under reaction conditions. Under oxygen excess in the feeding gas mixture and high temperature, the defects appeared on the initially flat surface of metallic palladium due to deep oxidation of palladium (three-dimensional PdO nanoparticles were observed). The palladium oxide reduced under cooling of the catalytic system, and the catalyst surface became flat again. To take into account these variations of the palladium surface structure, we consider the piecewise-constant dependence of the rate constant of some reaction step on the concentrations of oxygen species, namely, the dissolved oxygen or oxide in the palladium bulk. The proposed model of the process in the cascade of continuous stirred-tank reactors that account for these dependences qualitatively describes the inverse temperature hysteresis as well as the oscillatory dynamics within the hysteresis loop which were obtained experimentally.

AB - The results of temperature-programmed reaction experimental studies and mathematical modeling of self-sustained oscillations within an inverse temperature hysteresis in CO oxidation over Pd catalyst are presented. The experimental data demonstrate the influence of the reaction medium on the catalyst activity under reaction conditions. Under oxygen excess in the feeding gas mixture and high temperature, the defects appeared on the initially flat surface of metallic palladium due to deep oxidation of palladium (three-dimensional PdO nanoparticles were observed). The palladium oxide reduced under cooling of the catalytic system, and the catalyst surface became flat again. To take into account these variations of the palladium surface structure, we consider the piecewise-constant dependence of the rate constant of some reaction step on the concentrations of oxygen species, namely, the dissolved oxygen or oxide in the palladium bulk. The proposed model of the process in the cascade of continuous stirred-tank reactors that account for these dependences qualitatively describes the inverse temperature hysteresis as well as the oscillatory dynamics within the hysteresis loop which were obtained experimentally.

KW - a cascade of continuous stirred-tank reactors

KW - CO oxidation reaction

KW - inverse temperature hysteresis

KW - palladium bulk oxide

KW - self-sustained oscillations

KW - transformation of the palladium structure

UR - http://www.scopus.com/inward/record.url?scp=85073435209&partnerID=8YFLogxK

U2 - 10.1002/kin.21320

DO - 10.1002/kin.21320

M3 - Article

AN - SCOPUS:85073435209

VL - 51

SP - 918

EP - 930

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

SN - 0538-8066

IS - 12

ER -