Title: Crystallographic facet selective HER catalysis: exemplified in FeP and NiP ₂ single crystals

Abstract

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-NiP₂). 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-NiP₂ 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_dlmore » = 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.« less

Authors:

Owens-Baird, Bryan  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-3128-5363"

Sousa, Juliana P. S. ^[2]; Ziouani, Yasmine ^[2]; Petrovykh, Dmitri Y.  ^[2];

• Search DOE PAGES for author "Petrovykh, Dmitri Y."
• Search DOE PAGES for ORCID "0000-0001-9089-4076"

Zarkevich, Nikolai A.  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-1919-0177"

Johnson, Duane D.  ^[4];

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• Search DOE PAGES for ORCID "0000-0003-0794-7283"

Kolen'ko, Yury V.  ^[2];

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• Search DOE PAGES for ORCID "0000-0001-7493-1762"

Kovnir, Kirill  ^[1]

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• Search DOE PAGES for ORCID "0000-0003-1152-1912"

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+ Show Author Affiliations

1. Department of Chemistry, Iowa State University, Ames, USA, Ames Laboratory
2. Nanochemistry Research Group, International Iberian Nanotechnology Laboratory, Braga 4715-330, Portugal
3. Ames Laboratory, U.S. Department of Energy, Ames, USA
4. Ames Laboratory, U.S. Department of Energy, Ames, USA, Department of Materials Science & Engineering

Publication Date:

Wed May 20 00:00:00 EDT 2020

Research Org.:

Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; European Union (EU)

OSTI Identifier:

1616773

Alternate Identifier(s):

OSTI ID: 1617024

Report Number(s):

IS-J-10,197
Journal ID: ISSN 2041-6520; CSHCBM

Grant/Contract Number:  

AC02-07CH11358; 686053

Resource Type:

Published Article

Journal Name:

Chemical Science

Additional Journal Information:

Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 19; Journal ID: ISSN 2041-6520

Publisher:

Royal Society of Chemistry

Country of Publication:

United Kingdom

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY