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An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne

Theodoros Pavloudis, Joseph Kioseoglou Orcid Logo, Richard Palmer Orcid Logo

Physical Chemistry Chemical Physics, Volume: 24, Issue: 5, Pages: 3231 - 3237

Swansea University Authors: Theodoros Pavloudis, Richard Palmer Orcid Logo

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DOI (Published version): 10.1039/d1cp05470h

Abstract

The hydrogenation of alkynes is an important reaction in the synthesis of both fine and bulk chemicals. Palladium-based catalysts are widely used and therefore size-selected Pd nanoclusters may provide enhanced performance. An investigation of the adsorption and desorption of the molecules involved...

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Published in: Physical Chemistry Chemical Physics
ISSN: 1463-9076 1463-9084
Published: Royal Society of Chemistry (RSC) 2022
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URI: https://cronfa.swan.ac.uk/Record/cronfa59203
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spelling 2023-02-03T15:39:30.1334064 v2 59203 2022-01-17 An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne dd06e768e93bf50482735456af6f5a04 Theodoros Pavloudis Theodoros Pavloudis true false 6ae369618efc7424d9774377536ea519 0000-0001-8728-8083 Richard Palmer Richard Palmer true false 2022-01-17 FGSEN The hydrogenation of alkynes is an important reaction in the synthesis of both fine and bulk chemicals. Palladium-based catalysts are widely used and therefore size-selected Pd nanoclusters may provide enhanced performance. An investigation of the adsorption and desorption of the molecules involved in the reaction can shed light on the activity and selectivity of the catalysts. We employ ab initio calculations to investigate the binding energies of all the molecules related to the hydrogenation of 1-pentyne (1-pentyne, 1-pentene, cis-2-pentene, trans-2-pentene and pentane) on a comprehensive set of possible binding sites of two Pd147 and Pd561 cuboctahedral nanoclusters. We extract the site and size dependence of these binding energies. We find that the adsorption of 1-pentyne occurs preferably on the (100) facets of the nanoclusters, followed by their (111) facets, their edges and their vertices. The molecule binds more strongly on the larger nanoclusters, which are therefore expected to display higher activity. The binding energies of the pentenes are found to be lower on the smaller nanoclusters. Therefore, these molecules are expected to desorb more easily and the small clusters should display better selectivity, i.e., partial hydrogenation to 1-pentene, compared with large clusters. Our results provide guidelines for the optimal design of Pd nanocatalysts. Journal Article Physical Chemistry Chemical Physics 24 5 3231 3237 Royal Society of Chemistry (RSC) 1463-9076 1463-9084 19 1 2022 2022-01-19 10.1039/d1cp05470h COLLEGE NANME Science and Engineering - Faculty COLLEGE CODE FGSEN Swansea University External research funder(s) paid the OA fee (includes OA grants disbursed by the Library) This work was financially supported by the Engineering and Physical Sciences Research Council, EP/K006061/2. 2023-02-03T15:39:30.1334064 2022-01-17T15:27:34.0496215 Faculty of Science and Engineering School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering Theodoros Pavloudis 1 Joseph Kioseoglou 0000-0002-6933-2674 2 Richard Palmer 0000-0001-8728-8083 3 59203__22301__4be1e5867bfa4e8b98c35060890ecc9a.pdf 59203.pdf 2022-02-04T14:08:52.6752749 Output 2174021 application/pdf Version of Record true This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. true eng http://creativecommons.org/licenses/by/3.0/
title An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne
spellingShingle An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne
Theodoros Pavloudis
Richard Palmer
title_short An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne
title_full An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne
title_fullStr An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne
title_full_unstemmed An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne
title_sort An ab initio study of size-selected Pd nanocluster catalysts for the hydrogenation of 1-pentyne
author_id_str_mv dd06e768e93bf50482735456af6f5a04
6ae369618efc7424d9774377536ea519
author_id_fullname_str_mv dd06e768e93bf50482735456af6f5a04_***_Theodoros Pavloudis
6ae369618efc7424d9774377536ea519_***_Richard Palmer
author Theodoros Pavloudis
Richard Palmer
author2 Theodoros Pavloudis
Joseph Kioseoglou
Richard Palmer
format Journal article
container_title Physical Chemistry Chemical Physics
container_volume 24
container_issue 5
container_start_page 3231
publishDate 2022
institution Swansea University
issn 1463-9076
1463-9084
doi_str_mv 10.1039/d1cp05470h
publisher Royal Society of Chemistry (RSC)
college_str Faculty of Science and Engineering
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hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering
document_store_str 1
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description The hydrogenation of alkynes is an important reaction in the synthesis of both fine and bulk chemicals. Palladium-based catalysts are widely used and therefore size-selected Pd nanoclusters may provide enhanced performance. An investigation of the adsorption and desorption of the molecules involved in the reaction can shed light on the activity and selectivity of the catalysts. We employ ab initio calculations to investigate the binding energies of all the molecules related to the hydrogenation of 1-pentyne (1-pentyne, 1-pentene, cis-2-pentene, trans-2-pentene and pentane) on a comprehensive set of possible binding sites of two Pd147 and Pd561 cuboctahedral nanoclusters. We extract the site and size dependence of these binding energies. We find that the adsorption of 1-pentyne occurs preferably on the (100) facets of the nanoclusters, followed by their (111) facets, their edges and their vertices. The molecule binds more strongly on the larger nanoclusters, which are therefore expected to display higher activity. The binding energies of the pentenes are found to be lower on the smaller nanoclusters. Therefore, these molecules are expected to desorb more easily and the small clusters should display better selectivity, i.e., partial hydrogenation to 1-pentene, compared with large clusters. Our results provide guidelines for the optimal design of Pd nanocatalysts.
published_date 2022-01-19T04:16:20Z
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score 11.017797

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