skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on August 24, 2021

Title: Phase segregation reversibility in mixed-metal hydroxide water oxidation catalysts

Abstract

Achieving stable, low-cost electrocatalysts represents a daunting challenge towards practical water oxidation reactions. Here, we report that a degraded electrocatalyst can be revivified under catalytic operating conditions by manipulating reversible phase segregation. Under the oxygen evolution reaction conditions, Fe segregation develops in the Ni–Fe hydroxide host lat- tice, with the formation of FeOOH, resulting in an interface between the FeOOH and the host lattice. A dynamic metal dissolu- tion–redeposition process accelerates the Fe segregation and formation of the FeOOH secondary phase, resulting in catalyst deactivation. Operando synchrotron spectroscopic and microscopic analyses suggest that the phase segregation is revers- ible between the water oxidation potential and the catalyst reduction potential. Therefore, we have developed an intermittent reduction methodology to revivify the catalytic activity under the operating conditions, enhancing catalyst durability. The pres- ent study highlights that tailoring phase segregation at the catalyst/electrolyte interface constitutes an important strategy for revivifying and stabilizing catalytic activity.

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [2];  [4];  [5]; ORCiD logo [5];  [6];  [3]; ORCiD logo [7]; ORCiD logo [3]; ORCiD logo [2]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Tianjin Univ. (China)
  2. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  3. Tianjin Univ. (China)
  4. Tianjin Univ. (China); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  7. Univ. of Adelaide, SA (Australia)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); USDOE
OSTI Identifier:
1671340
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 3; Journal Issue: 9; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English

Citation Formats

Kuai, Chunguang, Xu, Zhengrui, Xi, Cong, Hu, Anyang, Yang, Zhijie, Zhang, Yan, Sun, Cheng-Jun, Li, Luxi, Sokaras, Dimosthenis, Dong, Cunku, Qiao, Shi-Zhang, Du, Xi-Wen, and Lin, Feng. Phase segregation reversibility in mixed-metal hydroxide water oxidation catalysts. United States: N. p., 2020. Web. doi:10.1038/s41929-020-0496-z.
Kuai, Chunguang, Xu, Zhengrui, Xi, Cong, Hu, Anyang, Yang, Zhijie, Zhang, Yan, Sun, Cheng-Jun, Li, Luxi, Sokaras, Dimosthenis, Dong, Cunku, Qiao, Shi-Zhang, Du, Xi-Wen, & Lin, Feng. Phase segregation reversibility in mixed-metal hydroxide water oxidation catalysts. United States. doi:10.1038/s41929-020-0496-z.
Kuai, Chunguang, Xu, Zhengrui, Xi, Cong, Hu, Anyang, Yang, Zhijie, Zhang, Yan, Sun, Cheng-Jun, Li, Luxi, Sokaras, Dimosthenis, Dong, Cunku, Qiao, Shi-Zhang, Du, Xi-Wen, and Lin, Feng. Mon . "Phase segregation reversibility in mixed-metal hydroxide water oxidation catalysts". United States. doi:10.1038/s41929-020-0496-z.
@article{osti_1671340,
title = {Phase segregation reversibility in mixed-metal hydroxide water oxidation catalysts},
author = {Kuai, Chunguang and Xu, Zhengrui and Xi, Cong and Hu, Anyang and Yang, Zhijie and Zhang, Yan and Sun, Cheng-Jun and Li, Luxi and Sokaras, Dimosthenis and Dong, Cunku and Qiao, Shi-Zhang and Du, Xi-Wen and Lin, Feng},
abstractNote = {Achieving stable, low-cost electrocatalysts represents a daunting challenge towards practical water oxidation reactions. Here, we report that a degraded electrocatalyst can be revivified under catalytic operating conditions by manipulating reversible phase segregation. Under the oxygen evolution reaction conditions, Fe segregation develops in the Ni–Fe hydroxide host lat- tice, with the formation of FeOOH, resulting in an interface between the FeOOH and the host lattice. A dynamic metal dissolu- tion–redeposition process accelerates the Fe segregation and formation of the FeOOH secondary phase, resulting in catalyst deactivation. Operando synchrotron spectroscopic and microscopic analyses suggest that the phase segregation is revers- ible between the water oxidation potential and the catalyst reduction potential. Therefore, we have developed an intermittent reduction methodology to revivify the catalytic activity under the operating conditions, enhancing catalyst durability. The pres- ent study highlights that tailoring phase segregation at the catalyst/electrolyte interface constitutes an important strategy for revivifying and stabilizing catalytic activity.},
doi = {10.1038/s41929-020-0496-z},
journal = {Nature Catalysis},
number = 9,
volume = 3,
place = {United States},
year = {2020},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on August 24, 2021
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Formation of stacking faults and enhanced diffusion in the oxidation of silicon
journal, April 1974


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Surface Reconstructions of Metal Oxides and the Consequences on Catalytic Chemistry
journal, May 2019


Hard X-ray fluorescence tomography—an emerging tool for structural visualization
journal, October 2010


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

Projector augmented-wave method
journal, December 1994


In Silico Discovery of New Dopants for Fe-Doped Ni Oxyhydroxide (Ni 1– x Fe x OOH) Catalysts for Oxygen Evolution Reaction
journal, April 2018

  • Shin, Hyeyoung; Xiao, Hai; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 140, Issue 22
  • DOI: 10.1021/jacs.8b02225

Using Surface Segregation To Design Stable Ru-Ir Oxides for the Oxygen Evolution Reaction in Acidic Environments
journal, October 2014

  • Danilovic, Nemanja; Subbaraman, Ramachandran; Chang, Kee Chul
  • Angewandte Chemie International Edition, Vol. 53, Issue 51
  • DOI: 10.1002/anie.201406455

Tracking Catalyst Redox States and Reaction Dynamics in Ni–Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH
journal, January 2017

  • Görlin, Mikaela; Ferreira de Araújo, Jorge; Schmies, Henrike
  • Journal of the American Chemical Society, Vol. 139, Issue 5
  • DOI: 10.1021/jacs.6b12250

Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries
journal, January 2016


In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution
journal, May 2020


Layered Structure Causes Bulk NiFe Layered Double Hydroxide Unstable in Alkaline Oxygen Evolution Reaction
journal, August 2019


Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery
journal, April 2019


Fe (Oxy)hydroxide Oxygen Evolution Reaction Electrocatalysis: Intrinsic Activity and the Roles of Electrical Conductivity, Substrate, and Dissolution
journal, November 2015


Vitreous silica bulk and surface self-diffusion analysis by molecular dynamics
journal, September 1997


A highly active and stable IrO x /SrIrO 3 catalyst for the oxygen evolution reaction
journal, September 2016


MAPS : A set of software tools for analysis and visualization of 3D X-ray fluorescence data sets
journal, March 2003


Electrochemical and Spectroscopic Evidence on the Participation of Quadrivalent Nickel in the Nickel Hydroxide Redox Reaction
journal, January 1989

  • Corrigan, Dennis A.; Knight, Sandra L.
  • Journal of The Electrochemical Society, Vol. 136, Issue 3, p. 613-619
  • DOI: 10.1149/1.2096697

Advanced Evaluation of the Long-Term Stability of Oxygen Evolution Electrocatalysts
journal, July 2016


Unified structural motifs of the catalytically active state of Co(oxyhydr)oxides during the electrochemical oxygen evolution reaction
journal, September 2018


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

In situ study of electrochemical activation and surface segregation of the SOFC electrode material La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3±δ
journal, January 2012

  • Huber, Anne-Katrin; Falk, Mareike; Rohnke, Marcus
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 2
  • DOI: 10.1039/C1CP21743G

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion
journal, May 2017


Activity–stability relationship in the surface electrochemistry of the oxygen evolution reaction
journal, January 2014

  • Chang, Seo Hyoung; Connell, Justin G.; Danilovic, Nemanja
  • Faraday Discuss., Vol. 176
  • DOI: 10.1039/C4FD00134F

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014

  • Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4865107

Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts
journal, March 2019


Wavelet analysis of extended x-ray absorption fine structure data
journal, March 2005


Scaled‐Up Synthesis of Amorphous NiFeMo Oxides and Their Rapid Surface Reconstruction for Superior Oxygen Evolution Catalysis
journal, October 2019

  • Duan, Yu; Yu, Zi‐You; Hu, Shao‐Jin
  • Angewandte Chemie International Edition, Vol. 58, Issue 44
  • DOI: 10.1002/anie.201909939

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles
journal, January 2018


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers
journal, January 2016

  • Irvine, John T. S.; Neagu, Dragos; Verbraeken, Maarten C.
  • Nature Energy, Vol. 1, Issue 1
  • DOI: 10.1038/nenergy.2015.14

Direct observation of active catalyst surface phases and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting
journal, January 2019

  • Qiu, Zhen; Tai, Cheuk-Wai; Niklasson, Gunnar A.
  • Energy & Environmental Science, Vol. 12, Issue 2
  • DOI: 10.1039/C8EE03282C

Geometric distortions in nickel (oxy)hydroxide electrocatalysts by redox inactive iron ions
journal, January 2018

  • Smith, Rodney D. L.; Pasquini, Chiara; Loos, Stefan
  • Energy & Environmental Science, Vol. 11, Issue 9
  • DOI: 10.1039/C8EE01063C

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments
journal, March 2016


Chemical potential dependence of defect formation energies in GaAs: Application to Ga self-diffusion
journal, October 1991


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


Sr Segregation in Perovskite Oxides: Why It Happens and How It Exists
journal, August 2018


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

Empowering multicomponent cathode materials for sodium ion batteries by exploring three-dimensional compositional heterogeneities
journal, January 2018

  • Rahman, Muhammad Mominur; Xu, Yahong; Cheng, Hao
  • Energy & Environmental Science, Vol. 11, Issue 9
  • DOI: 10.1039/C8EE00309B

Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis
journal, June 2013

  • Cui, Chunhua; Gan, Lin; Heggen, Marc
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3668

An Amorphous Nickel–Iron‐Based Electrocatalyst with Unusual Local Structures for Ultrafast Oxygen Evolution Reaction
journal, May 2019


A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes
journal, July 1997

  • Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G.
  • Journal of the American Chemical Society, Vol. 119, Issue 27
  • DOI: 10.1021/ja964352a

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

Ir–O–V Catalytic Group in Ir-Doped NiV(OH) 2 for Overall Water Splitting
journal, July 2019


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

A new FEFF -based wavelet for EXAFS data analysis
journal, August 2007

  • Funke, Harald; Chukalina, Marina; Scheinost, Andreas C.
  • Journal of Synchrotron Radiation, Vol. 14, Issue 5
  • DOI: 10.1107/S0909049507031901

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

Cation Size Mismatch and Charge Interactions Drive Dopant Segregation at the Surfaces of Manganite Perovskites
journal, May 2013

  • Lee, Wonyoung; Han, Jeong Woo; Chen, Yan
  • Journal of the American Chemical Society, Vol. 135, Issue 21
  • DOI: 10.1021/ja3125349

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

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Fully Oxidized Ni–Fe Layered Double Hydroxide with 100% Exposed Active Sites for Catalyzing Oxygen Evolution Reaction
journal, May 2019


Eliminating degradation in solid oxide electrochemical cells by reversible operation
journal, December 2014

  • Graves, Christopher; Ebbesen, Sune Dalgaard; Jensen, Søren Højgaard
  • Nature Materials, Vol. 14, Issue 2
  • DOI: 10.1038/nmat4165

Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films
journal, January 2017

  • Li, Nancy; Bediako, D. Kwabena; Hadt, Ryan G.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 7
  • DOI: 10.1073/pnas.1620787114

Carbon oxidation reactions could misguide the evaluation of carbon black-based oxygen-evolution electrocatalysts
journal, January 2017

  • Wang, Wang; Luo, Jin; Chen, Shengli
  • Chem. Commun., Vol. 53, Issue 84
  • DOI: 10.1039/C7CC04611A