Prediction of morphological changes of catalyst materials under reaction conditions by combined: Ab initio thermodynamics and microkinetic modelling

Raffaele Cheula, Aloysius Soon, Matteo Maestri

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19 Citations (Scopus)


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
Issue number14
Publication statusPublished - 2018

Bibliographical note

Funding Information:
The project leading to this work has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Project SHAPE – grant agreement No. 677423). Computational time at CINECA, Bologna (Italy) is gratefully acknowledged.

Publisher Copyright:
© 2018 The Royal Society of Chemistry.

All Science Journal Classification (ASJC) codes

  • Catalysis


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