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Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts

Ting-Wei Liao, Anupam Yadav, Piero Ferrari, Yubiao Niu, Xian-Kui Wei, Jerome Vernieres, Kuo-Juei Hu, Marc Heggen, Rafal E. Dunin-Borkowski, Richard Palmer Orcid Logo, Kari Laasonen, Didier Grandjean, Ewald Janssens, Peter Lievens

Chemistry of Materials, Volume: 31, Issue: 24, Pages: 10040 - 10048

Swansea University Author: Richard Palmer Orcid Logo

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DOI (Published version): 10.1021/acs.chemmater.9b02824

Abstract

Platinum is the most active anode and cathode catalyst in next-generation fuel cells using methanol as liquid source of hydrogen. Its catalytic activity can be significantly improved by alloying with 3d metals, although a precise tuning of its surface architecture is still required. Herein, we repor...

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Published in: Chemistry of Materials
ISSN: 0897-4756 1520-5002
Published: American Chemical Society (ACS) 2019
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URI: https://cronfa.swan.ac.uk/Record/cronfa53118
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spelling 2021-09-09T17:28:26.0629177 v2 53118 2020-01-06 Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts 6ae369618efc7424d9774377536ea519 0000-0001-8728-8083 Richard Palmer Richard Palmer true false 2020-01-06 ACEM Platinum is the most active anode and cathode catalyst in next-generation fuel cells using methanol as liquid source of hydrogen. Its catalytic activity can be significantly improved by alloying with 3d metals, although a precise tuning of its surface architecture is still required. Herein, we report the design of a highly active low-temperature (below 0 °C) methanol dehydrogenation anode catalyst with reduced CO poisoning based on ultralow amount of precisely defined PtxNi1–x (x = 0 to 1) bimetallic clusters (BCs) deposited on inert flat oxides by cluster beam deposition. These BCs feature clear composition-dependent atomic arrangements and electronic structures stemming from their nucleation mechanism, which are responsible for a volcano-type activity trend peaking at the Pt0.7Ni0.3 composition. Our calculations reveal that at this composition, a cluster skin of Pt atoms with d-band centers downshifted by subsurface Ni atoms weakens the CO interaction that in turn triggers a significant increase in the methanol dehydrogenation activity. Journal Article Chemistry of Materials 31 24 10040 10048 American Chemical Society (ACS) 0897-4756 1520-5002 24 12 2019 2019-12-24 10.1021/acs.chemmater.9b02824 STEM images and histograms of diameter distributions of clusters; DFT calculations of the mixing energy of tetramers; atomic-scale HAADF–STEM image of Au0.7Ag0.3 BC; TPD traces for methanol-d4 desorption from a SiO2 surface; CD3 mass signal (after background subtraction) measured during methanol decomposition; CO2 signal collected during methanol decomposition; overview of the CO binding energy as a function of d-band population for various Pt surfaces in Pt353Ni106and Pt4174Ni144 clusters; CO–Pt binding energy (in eV) for various Pt adsorption sites in Pt353Ni106 and Pt417Ni144; d-electron population of the atoms in Pt353Ni106 and Pt417Ni144 calculated using the Löwdin and Mulliken charge analysis methods; average charges on the Pt and Ni atoms in the Pt353Ni106 and Pt417Ni144 BCs, analyzed using four different charge decomposition methods; and additional material including a comparison of the preparation and structures of Au–Ag BCs with Pt–Ni BCs, TPD experiment and analysis procedures, and details on the DFT calculations (PDF)pdfcm9b02824_si_001.pdf (730.78 kb) COLLEGE NANME Aerospace, Civil, Electrical, and Mechanical Engineering COLLEGE CODE ACEM Swansea University 2021-09-09T17:28:26.0629177 2020-01-06T16:05:49.2590328 Faculty of Science and Engineering School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering Ting-Wei Liao 1 Anupam Yadav 2 Piero Ferrari 3 Yubiao Niu 4 Xian-Kui Wei 5 Jerome Vernieres 6 Kuo-Juei Hu 7 Marc Heggen 8 Rafal E. Dunin-Borkowski 9 Richard Palmer 0000-0001-8728-8083 10 Kari Laasonen 11 Didier Grandjean 12 Ewald Janssens 13 Peter Lievens 14 53118__16448__22a03d7616d746039abe5e045d006d2b.pdf 53118.pdf 2020-01-27T11:23:28.0243425 Output 921278 application/pdf Accepted Manuscript true 2020-11-19T00:00:00.0000000 true eng 12 true 10.1021/acs.chemmater.9b02824 true
title Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts
spellingShingle Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts
Richard Palmer
title_short Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts
title_full Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts
title_fullStr Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts
title_full_unstemmed Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts
title_sort Composition-Tuned Pt-Skinned PtNi Bimetallic Clusters as Highly Efficient Methanol Dehydrogenation Catalysts
author_id_str_mv 6ae369618efc7424d9774377536ea519
author_id_fullname_str_mv 6ae369618efc7424d9774377536ea519_***_Richard Palmer
author Richard Palmer
author2 Ting-Wei Liao
Anupam Yadav
Piero Ferrari
Yubiao Niu
Xian-Kui Wei
Jerome Vernieres
Kuo-Juei Hu
Marc Heggen
Rafal E. Dunin-Borkowski
Richard Palmer
Kari Laasonen
Didier Grandjean
Ewald Janssens
Peter Lievens
format Journal article
container_title Chemistry of Materials
container_volume 31
container_issue 24
container_start_page 10040
publishDate 2019
institution Swansea University
issn 0897-4756
1520-5002
doi_str_mv 10.1021/acs.chemmater.9b02824
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
hierarchytype
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
active_str 0
description Platinum is the most active anode and cathode catalyst in next-generation fuel cells using methanol as liquid source of hydrogen. Its catalytic activity can be significantly improved by alloying with 3d metals, although a precise tuning of its surface architecture is still required. Herein, we report the design of a highly active low-temperature (below 0 °C) methanol dehydrogenation anode catalyst with reduced CO poisoning based on ultralow amount of precisely defined PtxNi1–x (x = 0 to 1) bimetallic clusters (BCs) deposited on inert flat oxides by cluster beam deposition. These BCs feature clear composition-dependent atomic arrangements and electronic structures stemming from their nucleation mechanism, which are responsible for a volcano-type activity trend peaking at the Pt0.7Ni0.3 composition. Our calculations reveal that at this composition, a cluster skin of Pt atoms with d-band centers downshifted by subsurface Ni atoms weakens the CO interaction that in turn triggers a significant increase in the methanol dehydrogenation activity.
published_date 2019-12-24T13:58:26Z
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score 11.247077

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