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Title: Domain Structures of Ni and NiFe (Oxy)Hydroxide Oxygen-Evolution Catalysts from X-ray Pair Distribution Function Analysis

Abstract

Ni-Fe (oxy)hydroxides, Ni( i-z)Fe zO xH y, are among the fastest-known water oxidation catalysts in alkaline media on a per-cation basis. At current densities relevant for electrolysis (e.g., >0.5 A/cm( -2)), mass and electron transport through catalyst films with high mass loading are critical and depend substantially on the extended and intermediate catalyst architecture. We use X-ray pair distribution function (PDF) analysis to determine the intermediate nanostructures of electrodeposited Ni( i-z)Fe zO xH y films. We report the effects of electrodeposition technique (pulsed versus continuous), electrochemical cycling, and Fe content on the structure of the catalyst film. The PDF patterns for Ni( i-z)Fe zO xH y films are best simulated by model structures consisting of brucite-like β-Ni(OH) 2 fragments 1 to 3 layers in thickness. Only the oxidation state of the film significantly affects the intralayer scattering behavior (i.e., metal-oxygen bond distance). The interlayer interactions, however, are affected by Fe content and deposition conditions. The domain size of many of the systems are similar, extending to similar to ~5 nm, which are best modeled by sheets containing upward of similar to ~250 metal cations. Smaller domains were found for films deposited through a larger number of electrochemical cathodic current pulses.more » Films can be cycled between as-deposited, oxidized, and reduced states, with minimal loss of intrasheet coherence, indicating a degree of structural stability. We estimate heterogeneity in the domain structures by modeling the PDF data to linear combinations of oxyhydroxide fragments with different sizes and numbers of layers.« less

Authors:
 [1];  [2];  [1];  [2]; ORCiD logo [1]
  1. Univ. of Oregon, Eugene, OR (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); US Air Force Academy, CO (United States); Sloan Foundation; Dreyfus Foundation; W. M. Keck Foundation; M. J. Murdock Charitable Trust; Oregon Nanoscience and Microtechnologies Inst. (ONAMI), Corvallis, OR (United States); Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
OSTI Identifier:
1461297
Grant/Contract Number:  
AC02-06CH11357; CHE-1566348; SC0001059
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 45; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Batchellor, Adam S., Kwon, Gihan, Laskowski, Forrest A. L., Tiede, David M., and Boettcher, Shannon W. Domain Structures of Ni and NiFe (Oxy)Hydroxide Oxygen-Evolution Catalysts from X-ray Pair Distribution Function Analysis. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b10306.
Batchellor, Adam S., Kwon, Gihan, Laskowski, Forrest A. L., Tiede, David M., & Boettcher, Shannon W. Domain Structures of Ni and NiFe (Oxy)Hydroxide Oxygen-Evolution Catalysts from X-ray Pair Distribution Function Analysis. United States. doi:10.1021/acs.jpcc.7b10306.
Batchellor, Adam S., Kwon, Gihan, Laskowski, Forrest A. L., Tiede, David M., and Boettcher, Shannon W. Fri . "Domain Structures of Ni and NiFe (Oxy)Hydroxide Oxygen-Evolution Catalysts from X-ray Pair Distribution Function Analysis". United States. doi:10.1021/acs.jpcc.7b10306. https://www.osti.gov/servlets/purl/1461297.
@article{osti_1461297,
title = {Domain Structures of Ni and NiFe (Oxy)Hydroxide Oxygen-Evolution Catalysts from X-ray Pair Distribution Function Analysis},
author = {Batchellor, Adam S. and Kwon, Gihan and Laskowski, Forrest A. L. and Tiede, David M. and Boettcher, Shannon W.},
abstractNote = {Ni-Fe (oxy)hydroxides, Ni(i-z)FezOxHy, are among the fastest-known water oxidation catalysts in alkaline media on a per-cation basis. At current densities relevant for electrolysis (e.g., >0.5 A/cm(-2)), mass and electron transport through catalyst films with high mass loading are critical and depend substantially on the extended and intermediate catalyst architecture. We use X-ray pair distribution function (PDF) analysis to determine the intermediate nanostructures of electrodeposited Ni(i-z)FezOxHy films. We report the effects of electrodeposition technique (pulsed versus continuous), electrochemical cycling, and Fe content on the structure of the catalyst film. The PDF patterns for Ni(i-z)FezOxHy films are best simulated by model structures consisting of brucite-like β-Ni(OH)2 fragments 1 to 3 layers in thickness. Only the oxidation state of the film significantly affects the intralayer scattering behavior (i.e., metal-oxygen bond distance). The interlayer interactions, however, are affected by Fe content and deposition conditions. The domain size of many of the systems are similar, extending to similar to ~5 nm, which are best modeled by sheets containing upward of similar to ~250 metal cations. Smaller domains were found for films deposited through a larger number of electrochemical cathodic current pulses. Films can be cycled between as-deposited, oxidized, and reduced states, with minimal loss of intrasheet coherence, indicating a degree of structural stability. We estimate heterogeneity in the domain structures by modeling the PDF data to linear combinations of oxyhydroxide fragments with different sizes and numbers of layers.},
doi = {10.1021/acs.jpcc.7b10306},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 45,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}

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