Microkinetic Analysis of Complex Chemical Processes at Surfaces

Maestri, Matteo

doi:10.1002/9783527645824.ch10

Cited by 6 publications

(2 citation statements)

References 51 publications

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“…The hierarchical refinement proposed by Vlachos and co-workers ,, is used to quantitatively introduce into the microkinetic model the information derived from first-principles calculations. For different experimental conditions, we identify the catalytic cycle through RPA based on the net consumption rate of the reacting intermediates.…”

Section: Methodsmentioning

confidence: 99%

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH₄ Partial Oxidation on Rh

Maestri

Livio

Beretta

et al. 2014

Ind. Eng. Chem. Res.

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In this article, we demonstrate how first-principles calculations can be effectively employed in the development of microkinetic models for practical catalysis, despite material gaps and calculation uncertainties. In particular, we develop a hierarchically refined microkinetic model for the conversion of CH 4 to syngas on Rh/alumina that incorporates peculiar insights from first-principles modeling. This model is able to correctly describe the behavior of the reacting system under significantly different conditions and also exhibits consistency between the predicted catalytic cycle and the observed reaction orders. We show that consistency between the kinetic parameters of all of the elementary steps included in the microkinetic model is of utmost importance in achieving full predictivity of the model. As a consequence, the information from various levels of theory needs to be integrated in an underlying framework that accounts for coverage effects and thermodynamic and kinetic consistencies. Within this scope, we performed a detailed microkinetic analysis of kinetic experiments in an annular reactor to hierarchically modify the reaction parameters guided by first-principles analysis. Then, to further assess the capabilities of the refined microkinetic model, we performed a microkinetic analysis of spatially resolved CH 4 partial oxidation experiments on foams at different conditions of H 2 O and CO 2 cofeed. The insights derived from first-principles calculations and included in the semiempirical microkinetic model were found to be pivotal for explaining the roles of the WGS and r-WGS in catalytic partial oxidation experiments. On the whole, this contribution provides a clear demonstration of the current possibilities and potentialities of first-principles machinery in developing microkinetic models for complex catalytic processes and represents the first practical example of the full application of the first-principles hierarchical refinement of a microkinetic model.

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Section: Methodsmentioning

confidence: 99%

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH₄ Partial Oxidation on Rh

Maestri

Livio

Beretta

et al. 2014

Ind. Eng. Chem. Res.

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“…In the specific context of unravelling the reaction mechanism of a catalytic process, the hierarchical approach encompasses the following steps. 19 , 39 First, an estimation of the kinetic parameters of all the potential elementary reactions at the micro-scale is performed, using accurate but computationally non-demanding methodologies. These typically comprise semi-empirical theories such as the modified UBI-QEP method presented in Section 2.1.1.…”

Section: Escaping the Trap Of Complexitymentioning

confidence: 99%

Escaping the trap of complication and complexity in multiscale microkinetic modelling of heterogeneous catalytic processes

Maestri

2017

Chem. Commun.

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Multiscale Approaches for Modeling Hydrocarbon Conversion Reactions in Zeolites

Hansen

Keil

2013

Chemie Ingenieur Technik

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Methodological advances in quantum chemistry and classical molecular simulation combined with the ever increasing speed of computers allow for approaching chemical accuracy in the prediction of thermodynamic and kinetic parameters of zeolite catalyzed hydrocarbon reactions. In this account, progress in the area of multiscale modeling is illustrated by two examples taken from the authors' recent work and needs for further developments are identified.

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Microkinetic Analysis of Complex Chemical Processes at Surfaces

Cited by 6 publications

References 51 publications

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH₄ Partial Oxidation on Rh

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH₄ Partial Oxidation on Rh

Escaping the trap of complication and complexity in multiscale microkinetic modelling of heterogeneous catalytic processes

Multiscale Approaches for Modeling Hydrocarbon Conversion Reactions in Zeolites

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Microkinetic Analysis of Complex Chemical Processes at Surfaces

Cited by 6 publications

References 51 publications

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH4 Partial Oxidation on Rh

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH4 Partial Oxidation on Rh

Escaping the trap of complication and complexity in multiscale microkinetic modelling of heterogeneous catalytic processes

Multiscale Approaches for Modeling Hydrocarbon Conversion Reactions in Zeolites

Contact Info

Product

Resources

About

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH₄ Partial Oxidation on Rh

Hierarchical Refinement of Microkinetic Models: Assessment of the Role of the WGS and r-WGS Pathways in CH₄ Partial Oxidation on Rh