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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 
,
Kari Laasonen,
Didier Grandjean,
Ewald Janssens,
Peter Lievens
,
Kari Laasonen,
Didier Grandjean,
Ewald Janssens,
Peter Lievens
Chemistry of Materials, Volume: 31, Issue: 24, Pages: 10040 - 10048
Swansea University Author:
Richard Palmer
-
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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...
| Published in: | Chemistry of Materials |
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| ISSN: | 0897-4756 1520-5002 |
| Published: |
American Chemical Society (ACS)
2019
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| Online Access: |
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| URI: | https://cronfa.swan.ac.uk/Record/cronfa53118 |
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| 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 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. |
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| Item Description: |
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: |
Faculty of Science and Engineering |
| Issue: |
24 |
| Start Page: |
10040 |
| End Page: |
10048 |