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Selectivity and microkinetic insights on ethylene oligomerization over Ni encapsulated in a Brønsted-less hollow ZSM-5 zeolite

Selectivity and microkinetic insights on ethylene oligomerization over Ni encapsulated in a Brønsted-less hollow ZSM-5 zeolite
Selectivity and microkinetic insights on ethylene oligomerization over Ni encapsulated in a Brønsted-less hollow ZSM-5 zeolite

We encapsulated Ni nanoparticles in a hollow ZSM-5 zeolite catalyst using the dissolution-recrystallization method to catalyze ethylene oligomerization. Our aim is to engineer an idealized catalyst free of Brønsted acid contributions to kinetics or deactivation, having isolated and encapsulated Ni2⁺–zeolite species, to study the intrinsic oligomerization kinetics on Ni2⁺–zeolite through an experimental and microkinetic standpoint. We proved how the hollow architecture encapsulates both Ni2⁺ and NiO species, being the former significantly more active and selective toward dimerization. A comprehensive microkinetic model, grounded in the Cossee-Arlman mechanism and parameterized using experimental data, provides a detailed understanding of the reaction network on isolated Ni2⁺ sites. The model reveals that while linear butene formation dominates, its selectivity decreases with increasing ethylene conversion, temperature, and pressure, highlighting the contribution of isomerization pathways at elevated temperatures. This study focuses on the method to develop isolated oligomerization sites and then studies the intrinsic microkinetic pathways and rates.

Ethylene dimerization, Isolated Ni⁺, Kinetic modeling, Lewis acidity, Linear butene
1867-3880
Abed, Omar
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Mohammed, Hend Omar
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Khairova, Rushana
4ff6ca2d-4004-4f5c-abfa-e2533919242d
Hita, Idoia
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Velisoju, Vijay
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Morlanés, Natalia
0cef3342-a3db-4a73-bf22-acdcbafcb47f
Meijerink, Mark
3c478e42-abdc-48ef-bdd1-0a0f531d1a9f
Emwas, Abdul Hamid
cd674aa3-9f3d-43ad-badf-f0ca96ce3089
Vernuccio, Sergio
4bafd7f3-0943-4f6c-bc78-b4026516ccdb
Castaño, Pedro
26b3d9b0-ca55-460b-9756-985ddb81bffa
Abed, Omar
8f24cf17-dad8-4b17-9b6b-b63e98251444
Mohammed, Hend Omar
c672d438-df41-43d6-a909-57259803da58
Khairova, Rushana
4ff6ca2d-4004-4f5c-abfa-e2533919242d
Hita, Idoia
9a52d991-fdde-4942-8536-50159e31bae9
Velisoju, Vijay
94638663-5c5f-4487-b702-611fcf3692cb
Morlanés, Natalia
0cef3342-a3db-4a73-bf22-acdcbafcb47f
Meijerink, Mark
3c478e42-abdc-48ef-bdd1-0a0f531d1a9f
Emwas, Abdul Hamid
cd674aa3-9f3d-43ad-badf-f0ca96ce3089
Vernuccio, Sergio
4bafd7f3-0943-4f6c-bc78-b4026516ccdb
Castaño, Pedro
26b3d9b0-ca55-460b-9756-985ddb81bffa

Abed, Omar, Mohammed, Hend Omar, Khairova, Rushana, Hita, Idoia, Velisoju, Vijay, Morlanés, Natalia, Meijerink, Mark, Emwas, Abdul Hamid, Vernuccio, Sergio and Castaño, Pedro (2025) Selectivity and microkinetic insights on ethylene oligomerization over Ni encapsulated in a Brønsted-less hollow ZSM-5 zeolite. ChemCatChem, 17 (18), [e00957]. (doi:10.1002/cctc.202500957).

Record type: Article

Abstract

We encapsulated Ni nanoparticles in a hollow ZSM-5 zeolite catalyst using the dissolution-recrystallization method to catalyze ethylene oligomerization. Our aim is to engineer an idealized catalyst free of Brønsted acid contributions to kinetics or deactivation, having isolated and encapsulated Ni2⁺–zeolite species, to study the intrinsic oligomerization kinetics on Ni2⁺–zeolite through an experimental and microkinetic standpoint. We proved how the hollow architecture encapsulates both Ni2⁺ and NiO species, being the former significantly more active and selective toward dimerization. A comprehensive microkinetic model, grounded in the Cossee-Arlman mechanism and parameterized using experimental data, provides a detailed understanding of the reaction network on isolated Ni2⁺ sites. The model reveals that while linear butene formation dominates, its selectivity decreases with increasing ethylene conversion, temperature, and pressure, highlighting the contribution of isomerization pathways at elevated temperatures. This study focuses on the method to develop isolated oligomerization sites and then studies the intrinsic microkinetic pathways and rates.

Text
CCTC-S-25-01166 - Accepted Manuscript
Restricted to Repository staff only until 15 August 2026.
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More information

Accepted/In Press date: 10 July 2025
Published date: 15 August 2025
Keywords: Ethylene dimerization, Isolated Ni⁺, Kinetic modeling, Lewis acidity, Linear butene

Identifiers

Local EPrints ID: 505849
URI: http://eprints.soton.ac.uk/id/eprint/505849
ISSN: 1867-3880
PURE UUID: 9562bd2a-9b1a-4546-bfae-ea1f450a0d8b
ORCID for Sergio Vernuccio: ORCID iD orcid.org/0000-0003-1254-0293

Catalogue record

Date deposited: 21 Oct 2025 16:51
Last modified: 22 Oct 2025 02:12

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Contributors

Author: Omar Abed
Author: Hend Omar Mohammed
Author: Rushana Khairova
Author: Idoia Hita
Author: Vijay Velisoju
Author: Natalia Morlanés
Author: Mark Meijerink
Author: Abdul Hamid Emwas
Author: Sergio Vernuccio ORCID iD
Author: Pedro Castaño

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