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Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals
How the crystal structures of ordered transition-metal phosphide catalysts affect the hydrogen-evolution reaction (HER) is investigated by measuring the anisotropic catalytic activities of selected crystallographic facets on large (mm-sized) single crystals of iron-phosphide (FeP) and monoclinic nic...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159208/ https://www.ncbi.nlm.nih.gov/pubmed/34122957 http://dx.doi.org/10.1039/d0sc00676a |
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author | Owens-Baird, Bryan Sousa, Juliana P. S. Ziouani, Yasmine Petrovykh, Dmitri Y. Zarkevich, Nikolai A. Johnson, Duane D. Kolen'ko, Yury V. Kovnir, Kirill |
author_facet | Owens-Baird, Bryan Sousa, Juliana P. S. Ziouani, Yasmine Petrovykh, Dmitri Y. Zarkevich, Nikolai A. Johnson, Duane D. Kolen'ko, Yury V. Kovnir, Kirill |
author_sort | Owens-Baird, Bryan |
collection | PubMed |
description | How the crystal structures of ordered transition-metal phosphide catalysts affect the hydrogen-evolution reaction (HER) is investigated by measuring the anisotropic catalytic activities of selected crystallographic facets on large (mm-sized) single crystals of iron-phosphide (FeP) and monoclinic nickel-diphosphide (m-NiP(2)). We find that different crystallographic facets exhibit distinct HER activities, in contrast to a commonly held assumption of severe surface restructuring during catalytic activity. Moreover, density-functional-theory-based computational studies show that the observed facet activity correlates well with the H-binding energy to P atoms on specific surface terminations. Direction dependent catalytic properties of two different phosphides with different transition metals, crystal structures, and electronic properties (FeP is a metal, while m-NiP(2) is a semiconductor) suggests that the anisotropy of catalytic properties is a common trend for HER phosphide catalysts. This realization opens an additional rational design for highly efficient HER phosphide catalysts, through the growth of nanocrystals with specific exposed facets. Furthermore, the agreement between theory and experimental trends indicates that screening using DFT methods can accelerate the identification of desirable facets, especially for ternary or multinary compounds. The large single-crystal nature of the phosphide electrodes with well-defined surfaces allows for determination of the catalytically important double-layer capacitance of a flat surface, C(dl) = 39(2) μF cm(−2) for FeP, useful for an accurate calculation of the turnover frequency (TOF). X-ray photoelectron spectroscopy (XPS) studies of the catalytic crystals that were used show the formation of a thin oxide/phosphate overlayer, presumably ex situ due to air-exposure. This layer is easily removed for FeP, revealing a surface of pristine metal phosphide. |
format | Online Article Text |
id | pubmed-8159208 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81592082021-06-11 Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals Owens-Baird, Bryan Sousa, Juliana P. S. Ziouani, Yasmine Petrovykh, Dmitri Y. Zarkevich, Nikolai A. Johnson, Duane D. Kolen'ko, Yury V. Kovnir, Kirill Chem Sci Chemistry How the crystal structures of ordered transition-metal phosphide catalysts affect the hydrogen-evolution reaction (HER) is investigated by measuring the anisotropic catalytic activities of selected crystallographic facets on large (mm-sized) single crystals of iron-phosphide (FeP) and monoclinic nickel-diphosphide (m-NiP(2)). We find that different crystallographic facets exhibit distinct HER activities, in contrast to a commonly held assumption of severe surface restructuring during catalytic activity. Moreover, density-functional-theory-based computational studies show that the observed facet activity correlates well with the H-binding energy to P atoms on specific surface terminations. Direction dependent catalytic properties of two different phosphides with different transition metals, crystal structures, and electronic properties (FeP is a metal, while m-NiP(2) is a semiconductor) suggests that the anisotropy of catalytic properties is a common trend for HER phosphide catalysts. This realization opens an additional rational design for highly efficient HER phosphide catalysts, through the growth of nanocrystals with specific exposed facets. Furthermore, the agreement between theory and experimental trends indicates that screening using DFT methods can accelerate the identification of desirable facets, especially for ternary or multinary compounds. The large single-crystal nature of the phosphide electrodes with well-defined surfaces allows for determination of the catalytically important double-layer capacitance of a flat surface, C(dl) = 39(2) μF cm(−2) for FeP, useful for an accurate calculation of the turnover frequency (TOF). X-ray photoelectron spectroscopy (XPS) studies of the catalytic crystals that were used show the formation of a thin oxide/phosphate overlayer, presumably ex situ due to air-exposure. This layer is easily removed for FeP, revealing a surface of pristine metal phosphide. The Royal Society of Chemistry 2020-04-20 /pmc/articles/PMC8159208/ /pubmed/34122957 http://dx.doi.org/10.1039/d0sc00676a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Owens-Baird, Bryan Sousa, Juliana P. S. Ziouani, Yasmine Petrovykh, Dmitri Y. Zarkevich, Nikolai A. Johnson, Duane D. Kolen'ko, Yury V. Kovnir, Kirill Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals |
title | Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals |
title_full | Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals |
title_fullStr | Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals |
title_full_unstemmed | Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals |
title_short | Crystallographic facet selective HER catalysis: exemplified in FeP and NiP(2) single crystals |
title_sort | crystallographic facet selective her catalysis: exemplified in fep and nip(2) single crystals |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159208/ https://www.ncbi.nlm.nih.gov/pubmed/34122957 http://dx.doi.org/10.1039/d0sc00676a |
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