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Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation

Olumide Bolarinwa Ayodele, Rongsheng Cai, Jianguang Wang, Yasmine Ziouani, Zhifu Liang, Maria Chiara Spadaro, Kirill Kovnir, Jordi Arbiol, Jaakko Akola, Richard Palmer Orcid Logo, Yury V. Kolen’ko

ACS Catalysis, Volume: 10, Issue: 1, Pages: 451 - 457

Swansea University Author: Richard Palmer Orcid Logo

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DOI (Published version): 10.1021/acscatal.9b03539

Abstract

Semihydrogenation of acetylene (SHA) in an ethylene-rich stream is an important process for polymer industries. Presently, Pd-based catalysts have demonstrated good acetylene conversion (XC2H2), however, at the expense of ethylene selectivity (SC2H4). In this study, we have employed a systematic app...

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Published in: ACS Catalysis
ISSN: 2155-5435 2155-5435
Published: American Chemical Society (ACS) 2020
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URI: https://cronfa.swan.ac.uk/Record/cronfa53132
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spelling 2020-05-22T13:27:47.4691696 v2 53132 2020-01-07 Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation 6ae369618efc7424d9774377536ea519 0000-0001-8728-8083 Richard Palmer Richard Palmer true false 2020-01-07 MECH Semihydrogenation of acetylene (SHA) in an ethylene-rich stream is an important process for polymer industries. Presently, Pd-based catalysts have demonstrated good acetylene conversion (XC2H2), however, at the expense of ethylene selectivity (SC2H4). In this study, we have employed a systematic approach using density functional theory (DFT) to identify the best catalyst in a Cu–Pt system. The DFT results showed that with a 55 atom system at ∼1.1 Pt/Cu ratio for Pt28Cu27/Al2O3, the d-band center shifted −2.2 eV relative to the Fermi level leading to electron-saturated Pt, which allows only adsorption of ethylene via a π-bond, resulting in theoretical 99.7% SC2H4 at nearly complete XC2H2. Based on the DFT results, Pt–Cu/Al2O3 (PtCu) and Pt/Al2O3 (Pt) nanocatalysts were synthesized via cluster beam deposition (CBD), and their properties and activities were correlated with the computational predictions. For bimetallic PtCu, the electron microscopy results show the formation of alloys. The bimetallic PtCu catalyst closely mimics the DFT predictions in terms of both electronic structure, as confirmed by X-ray photoelectron spectroscopy, and catalytic activity. The alloying of Pt with Cu was responsible for the high C2H4 specific yield resulting from electron transfer between Cu and Pt, thus making PtCu a promising catalyst for SHA. Journal Article ACS Catalysis 10 1 451 457 American Chemical Society (ACS) 2155-5435 2155-5435 microkinetic model, hydrogenation, nanoclusters, alloys, cluster beam deposition 3 1 2020 2020-01-03 10.1021/acscatal.9b03539 COLLEGE NANME Mechanical Engineering COLLEGE CODE MECH Swansea University 2020-05-22T13:27:47.4691696 2020-01-07T11:27:29.8119601 Olumide Bolarinwa Ayodele 1 Rongsheng Cai 2 Jianguang Wang 3 Yasmine Ziouani 4 Zhifu Liang 5 Maria Chiara Spadaro 6 Kirill Kovnir 7 Jordi Arbiol 8 Jaakko Akola 9 Richard Palmer 0000-0001-8728-8083 10 Yury V. Kolen’ko 11 53132__16217__c20967243136416d99d5ca28176c379f.pdf ayodele2019.pdf 2020-01-07T11:30:31.3201203 Output 1254272 application/pdf Accepted Manuscript true 2020-12-09T00:00:00.0000000 true eng
title Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation
spellingShingle Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation
Richard Palmer
title_short Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation
title_full Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation
title_fullStr Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation
title_full_unstemmed Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation
title_sort Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation
author_id_str_mv 6ae369618efc7424d9774377536ea519
author_id_fullname_str_mv 6ae369618efc7424d9774377536ea519_***_Richard Palmer
author Richard Palmer
author2 Olumide Bolarinwa Ayodele
Rongsheng Cai
Jianguang Wang
Yasmine Ziouani
Zhifu Liang
Maria Chiara Spadaro
Kirill Kovnir
Jordi Arbiol
Jaakko Akola
Richard Palmer
Yury V. Kolen’ko
format Journal article
container_title ACS Catalysis
container_volume 10
container_issue 1
container_start_page 451
publishDate 2020
institution Swansea University
issn 2155-5435
2155-5435
doi_str_mv 10.1021/acscatal.9b03539
publisher American Chemical Society (ACS)
document_store_str 1
active_str 0
description Semihydrogenation of acetylene (SHA) in an ethylene-rich stream is an important process for polymer industries. Presently, Pd-based catalysts have demonstrated good acetylene conversion (XC2H2), however, at the expense of ethylene selectivity (SC2H4). In this study, we have employed a systematic approach using density functional theory (DFT) to identify the best catalyst in a Cu–Pt system. The DFT results showed that with a 55 atom system at ∼1.1 Pt/Cu ratio for Pt28Cu27/Al2O3, the d-band center shifted −2.2 eV relative to the Fermi level leading to electron-saturated Pt, which allows only adsorption of ethylene via a π-bond, resulting in theoretical 99.7% SC2H4 at nearly complete XC2H2. Based on the DFT results, Pt–Cu/Al2O3 (PtCu) and Pt/Al2O3 (Pt) nanocatalysts were synthesized via cluster beam deposition (CBD), and their properties and activities were correlated with the computational predictions. For bimetallic PtCu, the electron microscopy results show the formation of alloys. The bimetallic PtCu catalyst closely mimics the DFT predictions in terms of both electronic structure, as confirmed by X-ray photoelectron spectroscopy, and catalytic activity. The alloying of Pt with Cu was responsible for the high C2H4 specific yield resulting from electron transfer between Cu and Pt, thus making PtCu a promising catalyst for SHA.
published_date 2020-01-03T04:05:58Z
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score 10.997979

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