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

Title: In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen

Abstract

An in situ Raman spectroscopic investigation has been carried out to identify the composition of the active phase present on the surface of nickel electrodes used for the electrochemical evolution of oxygen. The electrolyte in all cases was 0.1 M KOH. A freshly polished Ni electrode oxidized upon immersion in the electrolyte and at potentials approaching the evolution of oxygen developed a layer of γ-NiOOH. Electrochemical cycling of this film transformed it into β-NiOOH, which was observed to be three times more active than γ-NiOOH. The higher activity of β-NiOOH is attributed to an unidentified Ni oxide formed at a potential above 0.52 V (vs Hg/HgO reference). We have also observed that a submonolayer of Ni oxide deposited on Au exhibits a turnover frequency (TOF) for oxygen evolution that is an order of magnitude higher than that for a freshly prepared γ-NiOOH surface and more than 2-fold higher than that for a β-NiOOH surface. By contrast, a similar film deposited on Pd exhibits a TOF that is similar to that of bulk γ-NiOOH. Furthermore it is proposed that the high activity of submonolayer deposits of Ni oxide on Au is due to charge transfer from the oxide to the highlymore » electronegative Au, leading to the possible formation of a mixed Ni/Au surface oxide.« less

Authors:
 [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1511336
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 116; Journal Issue: 15; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yeo, Boon Siang, and Bell, Alexis T. In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen. United States: N. p., 2012. Web. doi:10.1021/jp3007415.
Yeo, Boon Siang, & Bell, Alexis T. In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen. United States. doi:10.1021/jp3007415.
Yeo, Boon Siang, and Bell, Alexis T. Wed . "In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen". United States. doi:10.1021/jp3007415. https://www.osti.gov/servlets/purl/1511336.
@article{osti_1511336,
title = {In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen},
author = {Yeo, Boon Siang and Bell, Alexis T.},
abstractNote = {An in situ Raman spectroscopic investigation has been carried out to identify the composition of the active phase present on the surface of nickel electrodes used for the electrochemical evolution of oxygen. The electrolyte in all cases was 0.1 M KOH. A freshly polished Ni electrode oxidized upon immersion in the electrolyte and at potentials approaching the evolution of oxygen developed a layer of γ-NiOOH. Electrochemical cycling of this film transformed it into β-NiOOH, which was observed to be three times more active than γ-NiOOH. The higher activity of β-NiOOH is attributed to an unidentified Ni oxide formed at a potential above 0.52 V (vs Hg/HgO reference). We have also observed that a submonolayer of Ni oxide deposited on Au exhibits a turnover frequency (TOF) for oxygen evolution that is an order of magnitude higher than that for a freshly prepared γ-NiOOH surface and more than 2-fold higher than that for a β-NiOOH surface. By contrast, a similar film deposited on Pd exhibits a TOF that is similar to that of bulk γ-NiOOH. Furthermore it is proposed that the high activity of submonolayer deposits of Ni oxide on Au is due to charge transfer from the oxide to the highly electronegative Au, leading to the possible formation of a mixed Ni/Au surface oxide.},
doi = {10.1021/jp3007415},
journal = {Journal of Physical Chemistry. C},
number = 15,
volume = 116,
place = {United States},
year = {2012},
month = {4}
}

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

Citation Metrics:
Cited by: 303 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: (a) Cyclic voltammograms and (b) linear sweep voltammograms of Ni $α$/$γ$ (red trace) and Ni $β$/$β$ (black trace) electrodes. In situ Raman spectra collected during linear sweep voltammetry from (c) Ni $α$/$γ$ and (d) Ni $β$/$β$ electrodes. The 735 cm−1 peak in panel c originates from the Teflonmore » film used in covering the water immersion objective.« less

Save / Share:

Works referencing / citing this record:

Expansion of the urea electrocatalytic oxidation window by adsorbed nickel ions
journal, July 2019


Paired Electrocatalytic Oxygenation and Hydrogenation of Organic Substrates with Water as the Oxygen and Hydrogen Source
journal, May 2019

  • Zhang, Peili; Sheng, Xia; Chen, Xiaoyu
  • Angewandte Chemie International Edition, Vol. 58, Issue 27
  • DOI: 10.1002/anie.201903936

Reliable electrochemical phase diagrams of magnetic transition metals and related compounds from high-throughput ab initio calculations
journal, June 2019


Metal organic frameworks for electrochemical applications
journal, January 2012

  • Morozan, Adina; Jaouen, Frédéric
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee22989g

A nanostructured nickel/carbon matrix as an efficient oxygen evolution reaction electrocatalyst for rechargeable zinc–air batteries
journal, January 2019

  • Cui, Chengqiang; Ge, Xiaoming; An, Tao
  • Inorganic Chemistry Frontiers, Vol. 6, Issue 7
  • DOI: 10.1039/c9qi00402e

Hierarchically Structured 3D Integrated Electrodes by Galvanic Replacement Reaction for Highly Efficient Water Splitting
journal, March 2017

  • Wang, Jianying; Ji, Lvlv; Zuo, Shangshang
  • Advanced Energy Materials, Vol. 7, Issue 14
  • DOI: 10.1002/aenm.201700107

Paired Electrocatalytic Oxygenation and Hydrogenation of Organic Substrates with Water as the Oxygen and Hydrogen Source
journal, May 2019

  • Zhang, Peili; Sheng, Xia; Chen, Xiaoyu
  • Angewandte Chemie International Edition, Vol. 58, Issue 27
  • DOI: 10.1002/anie.201903936

Expansion of the urea electrocatalytic oxidation window by adsorbed nickel ions
journal, July 2019


Reliable electrochemical phase diagrams of magnetic transition metals and related compounds from high-throughput ab initio calculations
journal, June 2019


Metal organic frameworks for electrochemical applications
journal, January 2012

  • Morozan, Adina; Jaouen, Frédéric
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee22989g

Oxygen evolution on Fe-doped NiO electrocatalysts deposited via microplasma
journal, January 2017

  • Pebley, Andrew C.; Decolvenaere, Elizabeth; Pollock, Tresa M.
  • Nanoscale, Vol. 9, Issue 39
  • DOI: 10.1039/c7nr04302c

A nanostructured nickel/carbon matrix as an efficient oxygen evolution reaction electrocatalyst for rechargeable zinc–air batteries
journal, January 2019

  • Cui, Chengqiang; Ge, Xiaoming; An, Tao
  • Inorganic Chemistry Frontiers, Vol. 6, Issue 7
  • DOI: 10.1039/c9qi00402e

Ultrasmall Dispersible Crystalline Nickel Oxide Nanoparticles as High-Performance Catalysts for Electrochemical Water Splitting
journal, March 2014

  • Fominykh, Ksenia; Feckl, Johann M.; Sicklinger, Johannes
  • Advanced Functional Materials, Vol. 24, Issue 21
  • DOI: 10.1002/adfm.201303600

Transition-Metal (Co, Ni, and Fe)-Based Electrocatalysts for the Water Oxidation Reaction
journal, August 2016


Efficient Water Splitting Using a Simple Ni/N/C Paper Electrocatalyst
journal, December 2014

  • Ren, Jiawen; Antonietti, Markus; Fellinger, Tim-Patrick
  • Advanced Energy Materials, Vol. 5, Issue 6
  • DOI: 10.1002/aenm.201401660

Creating Highly Active Atomic Layer Deposited NiO Electrocatalysts for the Oxygen Evolution Reaction
journal, June 2015

  • Nardi, Katie L.; Yang, Nuoya; Dickens, Colin F.
  • Advanced Energy Materials, Vol. 5, Issue 17
  • DOI: 10.1002/aenm.201500412

NiFe-Based (Oxy)hydroxide Catalysts for Oxygen Evolution Reaction in Non-Acidic Electrolytes
journal, July 2016


Electrocatalytic Oxygen Evolution Reaction in Acidic Environments - Reaction Mechanisms and Catalysts
journal, October 2016

  • Reier, Tobias; Nong, Hong Nhan; Teschner, Detre
  • Advanced Energy Materials, Vol. 7, Issue 1
  • DOI: 10.1002/aenm.201601275

Recent Progress on Multimetal Oxide Catalysts for the Oxygen Evolution Reaction
journal, January 2018

  • Kim, Ju Seong; Kim, Byunghoon; Kim, Hyunah
  • Advanced Energy Materials, Vol. 8, Issue 11
  • DOI: 10.1002/aenm.201702774

Understanding the Role of Gold Nanoparticles in Enhancing the Catalytic Activity of Manganese Oxides in Water Oxidation Reactions
journal, October 2014

  • Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha
  • Angewandte Chemie, Vol. 127, Issue 8
  • DOI: 10.1002/ange.201407783

Paired Electrocatalytic Oxygenation and Hydrogenation of Organic Substrates with Water as the Oxygen and Hydrogen Source
journal, May 2019


Enhancement of Oxygen Evolution Activity of Nickel Oxyhydroxide by Electrolyte Alkali Cations
journal, July 2019

  • Garcia, Amanda C.; Touzalin, Thomas; Nieuwland, Celine
  • Angewandte Chemie, Vol. 131, Issue 37
  • DOI: 10.1002/ange.201905501

Identification of Key Reversible Intermediates in Self‐Reconstructed Nickel‐Based Hybrid Electrocatalysts for Oxygen Evolution
journal, November 2019


An Efficient Three-Dimensional Oxygen Evolution Electrode
journal, April 2013

  • Wang, Jun; Zhong, Hai-xia; Qin, Yu-ling
  • Angewandte Chemie International Edition, Vol. 52, Issue 20
  • DOI: 10.1002/anie.201301066

Synergistic Effect between Metal-Nitrogen-Carbon Sheets and NiO Nanoparticles for Enhanced Electrochemical Water-Oxidation Performance
journal, July 2015

  • Wang, Jun; Li, Kai; Zhong, Hai-xia
  • Angewandte Chemie International Edition, Vol. 54, Issue 36
  • DOI: 10.1002/anie.201504358

Enhancement of Oxygen Evolution Activity of Nickel Oxyhydroxide by Electrolyte Alkali Cations
journal, July 2019

  • Garcia, Amanda C.; Touzalin, Thomas; Nieuwland, Celine
  • Angewandte Chemie International Edition, Vol. 58, Issue 37
  • DOI: 10.1002/anie.201905501

Identification of Key Reversible Intermediates in Self‐Reconstructed Nickel‐Based Hybrid Electrocatalysts for Oxygen Evolution
journal, November 2019

  • Huang, Jianwen; Li, Yaoyao; Zhang, Yadong
  • Angewandte Chemie International Edition, Vol. 58, Issue 48
  • DOI: 10.1002/anie.201910716

Enhancing Activity for the Oxygen Evolution Reaction: The Beneficial Interaction of Gold with Manganese and Cobalt Oxides
journal, November 2014


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


Effects of Metal Electrode Support on the Catalytic Activity of Fe(oxy)hydroxide for the Oxygen Evolution Reaction in Alkaline Media
journal, August 2019

  • Enman, Lisa J.; Vise, Ashlee E.; Burke Stevens, Michaela
  • ChemPhysChem, Vol. 20, Issue 22
  • DOI: 10.1002/cphc.201900511

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering
journal, March 2017


NiFe Oxalate Nanomesh Array with Homogenous Doping of Fe for Electrocatalytic Water Oxidation
journal, October 2019


Ternary NiCoP nanosheet arrays: An excellent bifunctional catalyst for alkaline overall water splitting
journal, June 2016


Ni(OH)2 nanoflakes supported on 3D hierarchically nanoporous gold/Ni foam as superior electrodes for supercapacitors
journal, December 2017


Gold-supported cerium-doped NiOx catalysts for water oxidation
journal, April 2016

  • Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal
  • Nature Energy, Vol. 1, Issue 5
  • DOI: 10.1038/nenergy.2016.53

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation
journal, January 2018


Value added transformation of ubiquitous substrates into highly efficient and flexible electrodes for water splitting
journal, May 2018


Atomic-level insight into super-efficient electrocatalytic oxygen evolution on iron and vanadium co-doped nickel (oxy)hydroxide
journal, July 2018


Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes
journal, January 2013

  • Doyle, Richard L.; Godwin, Ian J.; Brandon, Michael P.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 33
  • DOI: 10.1039/c3cp51213d

Anodic deposition of NiOx water oxidation catalysts from macrocyclic nickel(ii) complexes
journal, January 2013

  • Singh, Archana; Chang, Shery L. Y.; Hocking, Rosalie K.
  • Catalysis Science & Technology, Vol. 3, Issue 7
  • DOI: 10.1039/c3cy00017f

Engineering of ZnCo-layered double hydroxide nanowalls toward high-efficiency electrochemical water oxidation
journal, January 2014

  • Li, Ying; Zhang, Lu; Xiang, Xu
  • Journal of Materials Chemistry A, Vol. 2, Issue 33
  • DOI: 10.1039/c4ta01275e

Photoelectrochemical water splitting at low applied potential using a NiOOH coated codoped (Sn, Zr) α-Fe 2 O 3 photoanode
journal, January 2015

  • Tamirat, Andebet Gedamu; Su, Wei-Nien; Dubale, Amare Aregahegn
  • Journal of Materials Chemistry A, Vol. 3, Issue 11
  • DOI: 10.1039/c4ta06915c

Characterisation of gold catalysts
journal, January 2016

  • Villa, Alberto; Dimitratos, Nikolaos; Chan-Thaw, Carine E.
  • Chemical Society Reviews, Vol. 45, Issue 18
  • DOI: 10.1039/c5cs00350d

Amorphous NiO electrocatalyst overcoated ZnO nanorod photoanodes for enhanced photoelectrochemical performance
journal, January 2016

  • Mao, Yanchao; Cheng, Yongguang; Wang, Junqiao
  • New Journal of Chemistry, Vol. 40, Issue 1
  • DOI: 10.1039/c5nj01815c

The importance of nickel oxyhydroxide deprotonation on its activity towards electrochemical water oxidation
journal, January 2016

  • Diaz-Morales, Oscar; Ferrus-Suspedra, David; Koper, Marc T. M.
  • Chemical Science, Vol. 7, Issue 4
  • DOI: 10.1039/c5sc04486c

Self-standing non-noble metal (Ni–Fe) oxide nanotube array anode catalysts with synergistic reactivity for high-performance water oxidation
journal, January 2015

  • Zhao, Zhenlu; Wu, Haoxi; He, Haili
  • Journal of Materials Chemistry A, Vol. 3, Issue 13
  • DOI: 10.1039/c5ta00160a

Single-crystalline Ni(OH) 2 nanosheets vertically aligned on a three-dimensional nanoporous metal for high-performance asymmetric supercapacitors
journal, January 2015

  • Hou, Chao; Lang, Xing-You; Wen, Zi
  • Journal of Materials Chemistry A, Vol. 3, Issue 46
  • DOI: 10.1039/c5ta05335h

Junction behavior of n-Si photoanodes protected by thin Ni elucidated from dual working electrode photoelectrochemistry
journal, January 2017

  • Laskowski, Forrest A. L.; Nellist, Michael R.; Venkatkarthick, Radhakrishnan
  • Energy & Environmental Science, Vol. 10, Issue 2
  • DOI: 10.1039/c6ee03505a

Nanostructured catalysts for electrochemical water splitting: current state and prospects
journal, January 2016

  • Li, Xiumin; Hao, Xiaogang; Abudula, Abuliti
  • Journal of Materials Chemistry A, Vol. 4, Issue 31
  • DOI: 10.1039/c6ta02334g

Facile synthesis of sponge-like Ni 3 N/NC for electrocatalytic water oxidation
journal, January 2017

  • Chen, Mingxing; Qi, Jing; Guo, Dingyi
  • Chemical Communications, Vol. 53, Issue 69
  • DOI: 10.1039/c7cc05172g

Nickel oxide–polypyrrole nanocomposite electrode materials for electrocatalytic water oxidation
journal, January 2018

  • Morales, Daniela V.; Astudillo, Catalina N.; Lattach, Youssef
  • Catalysis Science & Technology, Vol. 8, Issue 16
  • DOI: 10.1039/c7cy01949a

Roles of soluble species in the alkaline oxygen evolution reaction on a nickel anode
journal, January 2018

  • Ye, Jia-Ming; He, Ding-Hong; Li, Fang
  • Chemical Communications, Vol. 54, Issue 72
  • DOI: 10.1039/c8cc05896b

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

Facile efficient earth abundant NiO/C composite electrocatalyst for the oxygen evolution reaction
journal, January 2019

  • Mugheri, Abdul Qayoom; Tahira, Aneela; Aftab, Umair
  • RSC Advances, Vol. 9, Issue 10
  • DOI: 10.1039/c8ra10472g

Accelerated active phase transformation of NiO powered by Pt single atoms for enhanced oxygen evolution reaction
journal, January 2018

  • Lin, Chao; Zhao, Yonghui; Zhang, Haojie
  • Chemical Science, Vol. 9, Issue 33
  • DOI: 10.1039/c8sc02015a

Intensification of anodic charge transfer by contaminant degradation for efficient H 2 production
journal, January 2018

  • Zhang, Kai; Zhang, Gong; Qu, Jiuhui
  • Journal of Materials Chemistry A, Vol. 6, Issue 22
  • DOI: 10.1039/c8ta01849a

Direct storage of holes in ultrathin Ni(OH) 2 on Fe 2 O 3 photoelectrodes for integrated solar charging battery-type supercapacitors
journal, January 2018

  • Zhu, Kaijian; Zhu, Guoxiang; Wang, Jun
  • Journal of Materials Chemistry A, Vol. 6, Issue 43
  • DOI: 10.1039/c8ta08384c

An advanced and efficient Co 3 O 4 /C nanocomposite for the oxygen evolution reaction in alkaline media
journal, January 2019

  • Mugheri, Abdul Qayoom; Tahira, Aneela; Aftab, Umair
  • RSC Advances, Vol. 9, Issue 59
  • DOI: 10.1039/c9ra07224a

Investigation of mixed-metal (oxy)fluorides as a new class of water oxidation electrocatalysts
journal, January 2019

  • Lemoine, Kévin; Lhoste, Jérôme; Hémon-Ribaud, Annie
  • Chemical Science, Vol. 10, Issue 40
  • DOI: 10.1039/c9sc04027g

Magnetic bipolar transistor based on ZnO/NiO/Si heterostructure using pulsed laser deposition
journal, January 2020

  • Kaur, Harsimrat; Sharma, Monika; Ghosh, RamKrishna
  • AIP Advances, Vol. 10, Issue 1
  • DOI: 10.1063/1.5130046

Laser processed Ni-Fe alloys as electrocatalyst toward oxygen evolution reaction
journal, June 2018

  • Cui, Xiaodan; Zhang, Boliang; Zeng, Congyuan
  • Materials Research Express, Vol. 5, Issue 6
  • DOI: 10.1088/2053-1591/aaca72

In Situ Raman Study of Amorphous and Crystalline Ni-Co Alloys for the Alkaline Oxygen Evolution Reaction
journal, January 2018

  • Cole, K. M.; Kirk, D. W.; Thorpe, S. J.
  • Journal of The Electrochemical Society, Vol. 165, Issue 15
  • DOI: 10.1149/2.0131815jes

Nickel Cysteine Complexes as Anodic Electrocatalysts for Fuel Cells
journal, January 2014

  • Chen, Dayi; Giroud, Fabien; Minteer, Shelley D.
  • Journal of The Electrochemical Society, Vol. 161, Issue 9
  • DOI: 10.1149/2.0811409jes

A Comparative Study on Gold and Platinum Dissolution in Acidic and Alkaline Media
journal, January 2014

  • Cherevko, Serhiy; Zeradjanin, Aleksandar R.; Keeley, Gareth P.
  • Journal of The Electrochemical Society, Vol. 161, Issue 12
  • DOI: 10.1149/2.0881412jes

Glycerol Electro-Oxidation in Alkaline Media and Alkaline Direct Glycerol Fuel Cells
journal, November 2019


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.