MgCl2-Supported Ziegler-Natta Catalysts: a DFT-D "Flexible-Cluster" Approach to Internal Donor Adducts

Emanuele Breuza; Giuseppe Antinucci; Peter H. M. Budzelaar; Vincenzo Busico; Andrea Correa; Christian Ehm

doi:10.1021/acs.jpcc.8b01500

MgCl2-Supported Ziegler-Natta Catalysts: a DFT-D "Flexible-Cluster" Approach to Internal Donor Adducts

Emanuele Breuza, Giuseppe Antinucci, Peter H. M. Budzelaar, Vincenzo Busico, Andrea Correa, Christian Ehm

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

A "flexible cluster" model approach to Ziegler-Natta catalysts for the production of isotactic polypropylene, allowing the use of realistically sized MgCl2 monolayer clusters (up to 38 MgCl2 units) without any constraints, was employed to investigate the formation of adducts between the MgCl2 support and three industrially relevant internal donor classes, namely phthalates, succinates, and 1,3-dimethoxypropanes. The calculated adsorption modes and thermochemical data for adducts of single-donor molecules confirmed earlier literature trends only in part. Results for adducts with multiple donor molecules, in turn, did not confirm the indications of periodic models about steric repulsion between neighboring adsorbates hampering high degrees of surface coverage; as a matter of fact, such repulsions seem to be largely traceable to unnecessary constraints inherent in periodic calculations.

Original language	English (US)
Pages (from-to)	9046-9053
Number of pages	8
Journal	JOURNAL OF PHYSICAL CHEMISTRY C
Volume	122
Issue number	16
DOIs	https://doi.org/10.1021/acs.jpcc.8b01500
State	Published - Apr 4 2018
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2022-06-03
Acknowledgements: This work is part of the Research Programme of the Dutch Polymer Institute, Eindhoven, The Netherlands, Projects #754 and #793. E.B. and A.C. thank CINECA (ISCRA grant) for the availability of high-performance computing resources and support. Preliminary work was carried out at KAUST (King Abdullah University of Science and Technology) by E.B. E.B. thanks Prof. Luigi Cavallo for useful discussions.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

Surfaces, Coatings and Films
General Energy
Physical and Theoretical Chemistry
Electronic, Optical and Magnetic Materials

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abstract = "A {"}flexible cluster{"} model approach to Ziegler-Natta catalysts for the production of isotactic polypropylene, allowing the use of realistically sized MgCl2 monolayer clusters (up to 38 MgCl2 units) without any constraints, was employed to investigate the formation of adducts between the MgCl2 support and three industrially relevant internal donor classes, namely phthalates, succinates, and 1,3-dimethoxypropanes. The calculated adsorption modes and thermochemical data for adducts of single-donor molecules confirmed earlier literature trends only in part. Results for adducts with multiple donor molecules, in turn, did not confirm the indications of periodic models about steric repulsion between neighboring adsorbates hampering high degrees of surface coverage; as a matter of fact, such repulsions seem to be largely traceable to unnecessary constraints inherent in periodic calculations.",

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AU - Busico, Vincenzo

AU - Correa, Andrea

AU - Ehm, Christian

N1 - KAUST Repository Item: Exported on 2022-06-03 Acknowledgements: This work is part of the Research Programme of the Dutch Polymer Institute, Eindhoven, The Netherlands, Projects #754 and #793. E.B. and A.C. thank CINECA (ISCRA grant) for the availability of high-performance computing resources and support. Preliminary work was carried out at KAUST (King Abdullah University of Science and Technology) by E.B. E.B. thanks Prof. Luigi Cavallo for useful discussions. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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MgCl2-Supported Ziegler-Natta Catalysts: a DFT-D "Flexible-Cluster" Approach to Internal Donor Adducts

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