DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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)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 ofmore » 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). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); US Air Force Academy; Sloan Foundation; Dreyfus Foundation; W. M. Keck Foundation; M. J. Murdock Charitable Trust; Air Force Research Laboratory (AFRL)
OSTI Identifier:
1461297
Grant/Contract Number:  
AC02-06CH11357; CHE-1566348; SC0001059
Resource Type:
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. https://doi.org/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. https://doi.org/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},
number = 45,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Operando Analysis of NiFe and Fe Oxyhydroxide Electrocatalysts for Water Oxidation: Detection of Fe 4+ by Mössbauer Spectroscopy
journal, November 2015

  • Chen, Jamie Y. C.; Dang, Lianna; Liang, Hanfeng
  • Journal of the American Chemical Society, Vol. 137, Issue 48
  • DOI: 10.1021/jacs.5b10699

Revised Oxygen Evolution Reaction Activity Trends for First-Row Transition-Metal (Oxy)hydroxides in Alkaline Media
journal, August 2015

  • Burke, Michaela S.; Zou, Shihui; Enman, Lisa J.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
  • DOI: 10.1021/acs.jpclett.5b01650

Oxyanion induced variations in domain structure for amorphous cobalt oxide oxygen evolving catalysts, resolved by X-ray pair distribution function analysis
journal, December 2015

  • Kwon, Gihan; Kokhan, Oleksandr; Han, Ali
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 71, Issue 6
  • DOI: 10.1107/S2052520615022180

Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution
journal, October 2015

  • Bergmann, Arno; Martinez-Moreno, Elias; Teschner, Detre
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9625

High Specific Surface Area Nickel Mixed Oxide Powders LaNiO3 (Perovskite) and NiCo2O4 (Spinel) via Sol-Gel Type Routes for Oxygen Electrocatalysis in Alkaline Media
journal, April 1995

  • El Baydi, Mustapha; Tiwari, Shashi Kant; Singh, Ravindra Nath
  • Journal of Solid State Chemistry, Vol. 116, Issue 1
  • DOI: 10.1006/jssc.1995.1197

X-ray diffraction "fingerprinting" of DNA structure in solution for quantitative evaluation of molecular dynamics simulation
journal, February 2006

  • Zuo, X.; Cui, G.; Merz, K. M.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 10
  • DOI: 10.1073/pnas.0600022103

Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts
journal, July 2015

  • Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep12167

Recent progress in alkaline water electrolysis for hydrogen production and applications
journal, June 2010


Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Effects of Fe Electrolyte Impurities on Ni(OH) 2 /NiOOH Structure and Oxygen Evolution Activity
journal, March 2015

  • Klaus, Shannon; Cai, Yun; Louie, Mary W.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 13
  • DOI: 10.1021/acs.jpcc.5b00105

Advanced alkaline water electrolysis
journal, November 2012


Multiphase Nanostructure of a Quinary Metal Oxide Electrocatalyst Reveals a New Direction for OER Electrocatalyst Design
journal, February 2015

  • Haber, Joel A.; Anzenburg, Eitan; Yano, Junko
  • Advanced Energy Materials, Vol. 5, Issue 10
  • DOI: 10.1002/aenm.201402307

Anodically electrodeposited Co+Ni mixed oxide electrode: preparation and electrocatalytic activity for oxygen evolution in alkaline media
journal, October 2004

  • Wu, Gang; Li, Ning; Zhou, De-Rui
  • Journal of Solid State Chemistry, Vol. 177, Issue 10, p. 3682-3692
  • DOI: 10.1016/j.jssc.2004.06.027

PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions
journal, March 2013


Contributions to activity enhancement via Fe incorporation in Ni-(oxy)hydroxide/borate catalysts for near-neutral pH oxygen evolution
journal, January 2015

  • Smith, Adam M.; Trotochaud, Lena; Burke, Michaela S.
  • Chemical Communications, Vol. 51, Issue 25
  • DOI: 10.1039/C4CC08670H

Iron-Doped Nickel Oxide Nanocrystals as Highly Efficient Electrocatalysts for Alkaline Water Splitting
journal, April 2015


Hydrothermal Continuous Flow Synthesis and Exfoliation of NiCo Layered Double Hydroxide Nanosheets for Enhanced Oxygen Evolution Catalysis
journal, January 2015

  • Liang, Hanfeng; Meng, Fei; Cabán-Acevedo, Miguel
  • Nano Letters, Vol. 15, Issue 2
  • DOI: 10.1021/nl504872s

Ni3S2 nanorods/Ni foam composite electrode with low overpotential for electrocatalytic oxygen evolution
journal, January 2013

  • Zhou, Weijia; Wu, Xue-Jun; Cao, Xiehong
  • Energy & Environmental Science, Vol. 6, Issue 10
  • DOI: 10.1039/c3ee41572d

An Advanced Ni–Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation
journal, May 2013

  • Gong, Ming; Li, Yanguang; Wang, Hailiang
  • Journal of the American Chemical Society, Vol. 135, Issue 23
  • DOI: 10.1021/ja4027715

Highly Active Mixed-Metal Nanosheet Water Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids
journal, September 2014

  • Hunter, Bryan M.; Blakemore, James D.; Deimund, Mark
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja506087h

Nature of Activated Manganese Oxide for Oxygen Evolution
journal, November 2015

  • Huynh, Michael; Shi, Chenyang; Billinge, Simon J. L.
  • Journal of the American Chemical Society, Vol. 137, Issue 47
  • DOI: 10.1021/jacs.5b06382

Ab initio calculation of electronic coupling in the photosynthetic reaction center
journal, November 1998

  • Zhang, L. Y.; Friesner, R. A.
  • Proceedings of the National Academy of Sciences, Vol. 95, Issue 23
  • DOI: 10.1073/pnas.95.23.13603

Clean energy new deal for a sustainable world: from non-CO2 generating energy sources to greener electrochemical storage devices
journal, January 2011

  • Poizot, Philippe; Dolhem, Franck
  • Energy & Environmental Science, Vol. 4, Issue 6
  • DOI: 10.1039/c0ee00731e

Solar Water Splitting Cells
journal, November 2010

  • Walter, Michael G.; Warren, Emily L.; McKone, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
  • DOI: 10.1021/cr1002326

Ni 2 P as a Janus catalyst for water splitting: the oxygen evolution activity of Ni 2 P nanoparticles
journal, January 2015

  • Stern, Lucas-Alexandre; Feng, Ligang; Song, Fang
  • Energy & Environmental Science, Vol. 8, Issue 8
  • DOI: 10.1039/C5EE01155H

Charge-Transfer Effects in Ni–Fe and Ni–Fe–Co Mixed-Metal Oxides for the Alkaline Oxygen Evolution Reaction
journal, December 2015


PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data
journal, July 2004

  • Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L.
  • Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678
  • DOI: 10.1107/S0021889804011744

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010

  • Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y.
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr100246c

Ni/Fe electrodes prepared by electrodeposition method over different substrates for oxygen evolution reaction in alkaline medium
journal, March 2014


Solution-Cast Metal Oxide Thin Film Electrocatalysts for Oxygen Evolution
journal, October 2012

  • Trotochaud, Lena; Ranney, James K.; Williams, Kerisha N.
  • Journal of the American Chemical Society, Vol. 134, Issue 41
  • DOI: 10.1021/ja307507a

Nickel-oxido structure of a water-oxidizing catalyst film
journal, January 2011

  • Risch, Marcel; Klingan, Katharina; Heidkamp, Jonathan
  • Chemical Communications, Vol. 47, Issue 43
  • DOI: 10.1039/c1cc15072c

Basic study of alkaline water electrolysis
journal, June 2013


First implementation of alkaline polymer electrolyte water electrolysis working only with pure water
journal, January 2012

  • Xiao, Li; Zhang, Shuai; Pan, Jing
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee22146b

Domain structure for an amorphous iridium-oxide water-oxidation catalyst characterized by X-ray pair distribution function analysis
journal, January 2014

  • Huang, Jier; Blakemore, James D.; Fazi, Diego
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 5
  • DOI: 10.1039/C3CP54878C

NiSe Nanowire Film Supported on Nickel Foam: An Efficient and Stable 3D Bifunctional Electrode for Full Water Splitting
journal, July 2015

  • Tang, Chun; Cheng, Ningyan; Pu, Zonghua
  • Angewandte Chemie International Edition, Vol. 54, Issue 32
  • DOI: 10.1002/anie.201503407

Effect of interlayer anions on [NiFe]-LDH nanosheet water oxidation activity
journal, January 2016

  • Hunter, B. M.; Hieringer, W.; Winkler, J. R.
  • Energy & Environmental Science, Vol. 9, Issue 5
  • DOI: 10.1039/C6EE00377J

Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water
journal, August 2013

  • Bajdich, Michal; García-Mota, Mónica; Vojvodic, Aleksandra
  • Journal of the American Chemical Society, Vol. 135, Issue 36
  • DOI: 10.1021/ja405997s

Tunable composition of NiII–AlIII and NiII–FeIII layered hydroxides within a wide range of layer charge
journal, January 2011


Measurement Techniques for the Study of Thin Film Heterogeneous Water Oxidation Electrocatalysts
journal, October 2016


Intermediate-Range Structure of Self-Assembled Cobalt-Based Oxygen-Evolving Catalyst
journal, April 2013

  • Farrow, Christopher L.; Bediako, D. Kwabena; Surendranath, Yogesh
  • Journal of the American Chemical Society, Vol. 135, Issue 17
  • DOI: 10.1021/ja401276f

Zur kenntnis der nickelhydroxidelektrode—I.Über das nickel (II)-hydroxidhydrat
journal, August 1966


Progress in electrical energy storage system: A critical review
journal, March 2009


The Catalysis of the Oxygen Evolution Reaction by Iron Impurities in Thin Film Nickel Oxide Electrodes
journal, January 1987

  • Corrigan, Dennis A.
  • Journal of The Electrochemical Society, Vol. 134, Issue 2
  • DOI: 10.1149/1.2100463

Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction
journal, October 2013

  • McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C.
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja407115p

X-ray diffraction patterns of graphite and turbostratic carbon
journal, July 2007


Effect of Coprecipitated Metal Ions on the Electrochemistry of Nickel Hydroxide Thin Films: Cyclic Voltammetry in 1M KOH
journal, January 1989

  • Corrigan, Dennis A.
  • Journal of The Electrochemical Society, Vol. 136, Issue 3
  • DOI: 10.1149/1.2096717

Oxygen Evolution Reaction Electrocatalysis on Transition Metal Oxides and (Oxy)hydroxides: Activity Trends and Design Principles
journal, October 2015


Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni–Fe Oxide Water Splitting Electrocatalysts
journal, April 2016

  • Görlin, Mikaela; Chernev, Petko; Ferreira de Araújo, Jorge
  • Journal of the American Chemical Society, Vol. 138, Issue 17
  • DOI: 10.1021/jacs.6b00332

Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting
journal, January 2015

  • Friebel, Daniel; Louie, Mary W.; Bajdich, Michal
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja511559d

Alkaline Water Electrolysis Anode Materials
journal, January 1985

  • Hall, D. E.
  • Journal of The Electrochemical Society, Vol. 132, Issue 2
  • DOI: 10.1149/1.2113856

Reactive Fe-Sites in Ni/Fe (Oxy)hydroxide Are Responsible for Exceptional Oxygen Electrocatalysis Activity
journal, August 2017

  • Stevens, Michaela Burke; Trang, Christina D. M.; Enman, Lisa J.
  • Journal of the American Chemical Society, Vol. 139, Issue 33
  • DOI: 10.1021/jacs.7b07117

Mapping the performance of amorphous ternary metal oxide water oxidation catalysts containing aluminium
journal, January 2015

  • Zhang, Cuijuan; Fagan, Randal D.; Smith, Rodney D. L.
  • Journal of Materials Chemistry A, Vol. 3, Issue 2
  • DOI: 10.1039/C4TA04495A

Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation
journal, April 2014

  • Trotochaud, Lena; Young, Samantha L.; Ranney, James K.
  • Journal of the American Chemical Society, Vol. 136, Issue 18
  • DOI: 10.1021/ja502379c

Comprehensive Structural, Surface-Chemical and Electrochemical Characterization of Nickel-Based Metallic Foams
journal, June 2013

  • van Drunen, Julia; Kinkead, Brandy; Wang, Michael C. P.
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 14
  • DOI: 10.1021/am401606n

Elucidating the Domain Structure of the Cobalt Oxide Water Splitting Catalyst by X-ray Pair Distribution Function Analysis
journal, June 2012

  • Du, Pingwu; Kokhan, Oleksandr; Chapman, Karena W.
  • Journal of the American Chemical Society, Vol. 134, Issue 27
  • DOI: 10.1021/ja303826a

Structure–Activity Correlations in a Nickel–Borate Oxygen Evolution Catalyst
journal, April 2012

  • Bediako, D. Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh
  • Journal of the American Chemical Society, Vol. 134, Issue 15
  • DOI: 10.1021/ja301018q

Role of Catalyst Preparation on the Electrocatalytic Activity of Ni 1– x Fe x OOH for the Oxygen Evolution Reaction
journal, August 2015

  • Klaus, Shannon; Louie, Mary W.; Trotochaud, Lena
  • The Journal of Physical Chemistry C, Vol. 119, Issue 32
  • DOI: 10.1021/acs.jpcc.5b04776

Benchmarking the Stability of Oxygen Evolution Reaction Catalysts: The Importance of Monitoring Mass Losses
journal, October 2014

  • Frydendal, Rasmus; Paoli, Elisa A.; Knudsen, Brian P.
  • ChemElectroChem, Vol. 1, Issue 12
  • DOI: 10.1002/celc.201402262

Water Oxidation at Electrodes Modified with Earth-Abundant Transition-Metal Catalysts
journal, October 2014


Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis
journal, March 2013

  • Smith, Rodney D. L.; Prévot, Mathieu S.; Fagan, Randal D.
  • Science, Vol. 340, Issue 6128
  • DOI: 10.1126/science.1233638

Efficient Water Oxidation Using Nanostructured α-Nickel-Hydroxide as an Electrocatalyst
journal, May 2014

  • Gao, Minrui; Sheng, Wenchao; Zhuang, Zhongbin
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja502128j

Enhanced electrochemical performance of nickel hydroxide electrode with monolayer hollow spheres composed of nanoflakes
journal, October 2011


The intensification technologies to water electrolysis for hydrogen production – A review
journal, January 2014


Accuracy of pair distribution function analysis applied to crystalline and non-crystalline materials
journal, May 1992

  • Toby, B. H.; Egami, T.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 48, Issue 3
  • DOI: 10.1107/S0108767391011327

Structural Characteristics and Eutaxy in the Photo-Deposited Amorphous Iron Oxide Oxygen Evolution Catalyst
journal, April 2015


Works referencing / citing this record:

Ternary Ni-Co-Fe oxyhydroxide oxygen evolution catalysts: Intrinsic activity trends, electrical conductivity, and electronic band structure
journal, April 2019

  • Stevens, Michaela Burke; Enman, Lisa J.; Korkus, Ester Hamal
  • Nano Research, Vol. 12, Issue 9
  • DOI: 10.1007/s12274-019-2391-y

Identifying high-efficiency oxygen evolution electrocatalysts from Co–Ni–Cu based selenides through combinatorial electrodeposition
journal, January 2019

  • Cao, Xi; Johnson, Emily; Nath, Manashi
  • Journal of Materials Chemistry A, Vol. 7, Issue 16
  • DOI: 10.1039/c9ta00863b