Prediction of morphological changes of catalyst materials under reaction conditions by combined

Ab initio thermodynamics and microkinetic modelling

Raffaele Cheula, Aloysius Soon, Matteo Maestri

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

In this article, we couple microkinetic modelling, ab initio thermodynamics and Wulff-Kaishew construction to describe the structural variation of catalyst materials as a function of the chemical potential in the reactor. We focus specifically on experiments of catalytic partial oxidation (CPO) of methane on Rh/α-Al2O3. We employ a detailed structureless microkinetic model to calculate the profiles of the gaseous species molar fractions along the reactor coordinate and to select the most abundant reaction intermediates (MARIs) populating the catalyst surfaces in different zones of the reactor. Then, we calculate the most stable bulk and surface structures of the catalyst under different conditions of the reaction environment with density functional theory (DFT) calculations and ab initio thermodynamics, considering the presence of the MARIs on the catalyst surface in thermodynamic equilibrium with the partial pressures of their reservoirs in the gas phase surrounding the catalyst. Finally, we exploit the Wulff-Kaishew construction method to estimate the three-dimensional shape of the catalyst nanoparticles and the distribution of the active sites along the reactor coordinate. We find that the catalyst drastically modifies its morphology during CPO reaction by undergoing phase transition, in agreement with spectroscopy studies reported in the literature. The framework is also successfully applied for the analysis and interpretation of chemisorption experiments for catalyst characterization. These results demonstrate the crucial importance of rigorously accounting for the structural effect in microkinetic modeling simulations and pave the way towards the development of structure-dependent microkinetic analysis of catalytic processes.

Original languageEnglish
Pages (from-to)3493-3503
Number of pages11
JournalCatalysis Science and Technology
Volume8
Issue number14
DOIs
Publication statusPublished - 2018 Jan 1

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Thermodynamics
Catalysts
Reaction intermediates
Oxidation
Chemical potential
Methane
Chemisorption
Surface structure
Partial pressure
Density functional theory
Gases
Phase transitions
Experiments
Spectroscopy
Nanoparticles
Computer simulation

All Science Journal Classification (ASJC) codes

  • Catalysis

Cite this

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abstract = "In this article, we couple microkinetic modelling, ab initio thermodynamics and Wulff-Kaishew construction to describe the structural variation of catalyst materials as a function of the chemical potential in the reactor. We focus specifically on experiments of catalytic partial oxidation (CPO) of methane on Rh/α-Al2O3. We employ a detailed structureless microkinetic model to calculate the profiles of the gaseous species molar fractions along the reactor coordinate and to select the most abundant reaction intermediates (MARIs) populating the catalyst surfaces in different zones of the reactor. Then, we calculate the most stable bulk and surface structures of the catalyst under different conditions of the reaction environment with density functional theory (DFT) calculations and ab initio thermodynamics, considering the presence of the MARIs on the catalyst surface in thermodynamic equilibrium with the partial pressures of their reservoirs in the gas phase surrounding the catalyst. Finally, we exploit the Wulff-Kaishew construction method to estimate the three-dimensional shape of the catalyst nanoparticles and the distribution of the active sites along the reactor coordinate. We find that the catalyst drastically modifies its morphology during CPO reaction by undergoing phase transition, in agreement with spectroscopy studies reported in the literature. The framework is also successfully applied for the analysis and interpretation of chemisorption experiments for catalyst characterization. These results demonstrate the crucial importance of rigorously accounting for the structural effect in microkinetic modeling simulations and pave the way towards the development of structure-dependent microkinetic analysis of catalytic processes.",
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Prediction of morphological changes of catalyst materials under reaction conditions by combined : Ab initio thermodynamics and microkinetic modelling. / Cheula, Raffaele; Soon, Aloysius; Maestri, Matteo.

In: Catalysis Science and Technology, Vol. 8, No. 14, 01.01.2018, p. 3493-3503.

Research output: Contribution to journalArticle

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