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

Title: Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

Abstract

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoretical calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15more » fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Authors:
 [1];  [1];  [2];  [2];  [3];  [1]; ORCiD logo [4]
  1. Univ. of Pittsburgh, PA (United States). Chemical and Petroleum Engineering, Swanson School of Engineering
  2. Univ. of Pittsburgh, PA (United States). Swanson School of Engineering, Dept. of Bioengineering; Univ. of Pittsburgh, PA (United States). Center for Complex Engineered Multifunctional Materials
  3. Univ. of Pittsburgh, PA (United States). Swanson School of Engineering, Dept. of Bioengineering
  4. Univ. of Pittsburgh, PA (United States). Chemical and Petroleum Engineering, Swanson School of Engineering; Univ. of Pittsburgh, PA (United States). Swanson School of Engineering, Dept. of Bioengineering; Univ. of Pittsburgh, PA (United States). Center for Complex Engineered Multifunctional Materials; Univ. of Pittsburgh, PA (United States). Mechanical Engineering and Materials Science; Univ. of Pittsburgh, PA (United States). School of Dental Medicine
Publication Date:
Research Org.:
Univ. of Pittsburgh, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1426497
Grant/Contract Number:  
SC0001531
Resource Type:
Accepted Manuscript
Journal Name:
RSC Advances
Additional Journal Information:
Journal Volume: 7; Journal Issue: 28; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN

Citation Formats

Ghadge, Shrinath Dattatray, Patel, Prasad Prakash, Datta, Moni Kanchan, Velikokhatnyi, Oleg I., Kuruba, Ramalinga, Shanthi, Pavithra M., and Kumta, Prashant N. Fluorine substituted (Mn,Ir)O2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis. United States: N. p., 2017. Web. doi:10.1039/c6ra27354h.
Ghadge, Shrinath Dattatray, Patel, Prasad Prakash, Datta, Moni Kanchan, Velikokhatnyi, Oleg I., Kuruba, Ramalinga, Shanthi, Pavithra M., & Kumta, Prashant N. Fluorine substituted (Mn,Ir)O2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis. United States. doi:10.1039/c6ra27354h.
Ghadge, Shrinath Dattatray, Patel, Prasad Prakash, Datta, Moni Kanchan, Velikokhatnyi, Oleg I., Kuruba, Ramalinga, Shanthi, Pavithra M., and Kumta, Prashant N. Mon . "Fluorine substituted (Mn,Ir)O2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis". United States. doi:10.1039/c6ra27354h. https://www.osti.gov/servlets/purl/1426497.
@article{osti_1426497,
title = {Fluorine substituted (Mn,Ir)O2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis},
author = {Ghadge, Shrinath Dattatray and Patel, Prasad Prakash and Datta, Moni Kanchan and Velikokhatnyi, Oleg I. and Kuruba, Ramalinga and Shanthi, Pavithra M. and Kumta, Prashant N.},
abstractNote = {Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO2, RuO2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoretical calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO2 and IrO2, denoted as (Mn1-xIrx)O2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn1-xIrx)O2:F system as an OER electro-catalyst for PEM water electrolysis.},
doi = {10.1039/c6ra27354h},
journal = {RSC Advances},
number = 28,
volume = 7,
place = {United States},
year = {2017},
month = {3}
}

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

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Nanostructured robust cobalt metal alloy based anode electro-catalysts exhibiting remarkably high performance and durability for proton exchange membrane fuel cells
journal, January 2015

  • Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.
  • Journal of Materials Chemistry A, Vol. 3, Issue 26
  • DOI: 10.1039/C5TA01362C

Oxygen evolution in Co-doped RuO2 and IrO2: Experimental and theoretical insights to diminish electrolysis overpotential
journal, December 2014


Nanostructured MnO2 for Li batteries
journal, June 2003


Refinement of Macromolecular Structures by the Maximum-Likelihood Method
journal, May 1997

  • Murshudov, G. N.; Vagin, A. A.; Dodson, E. J.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 53, Issue 3
  • DOI: 10.1107/S0907444996012255

Heterogeneous photocatalytic hydrogen production from water and biomass derivatives
journal, January 2011

  • Shimura, Katsuya; Yoshida, Hisao
  • Energy & Environmental Science, Vol. 4, Issue 7
  • DOI: 10.1039/c1ee01120k

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


The physical–chemical properties and electrocatalytic performance of iridium oxide in oxygen evolution
journal, November 2011


Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers
journal, March 2008


An overview of polymer electrolyte membrane electrolyzer for hydrogen production: Modeling and mass transport
journal, March 2016


Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation
journal, June 1986


Role of Cu-Ion Doping in Cu-α-MnO 2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction
journal, July 2014

  • Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 31
  • DOI: 10.1021/jp5039865

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Vertically aligned nitrogen doped (Sn,Nb)O2 nanotubes – Robust photoanodes for hydrogen generation by photoelectrochemical water splitting
journal, June 2016

  • Patel, Prasad Prakash; Hanumantha, Prashanth Jampani; Velikokhatnyi, Oleg I.
  • Materials Science and Engineering: B, Vol. 208
  • DOI: 10.1016/j.mseb.2016.02.001

MnO 2 by XPS
journal, January 1999

  • Stranick, Michael A.
  • Surface Science Spectra, Vol. 6, Issue 1
  • DOI: 10.1116/1.1247888

Batteries: Higher energy density than gasoline?
journal, July 2009


Data Reduction and Error Analysis for Accurate Single Crystal Diffraction Intensities
journal, January 1987


XSEDE: Accelerating Scientific Discovery
journal, September 2014

  • Towns, John; Cockerill, Timothy; Dahan, Maytal
  • Computing in Science & Engineering, Vol. 16, Issue 5
  • DOI: 10.1109/MCSE.2014.80

Nitrogen and cobalt co-doped zinc oxide nanowires – Viable photoanodes for hydrogen generation via photoelectrochemical water splitting
journal, December 2015


MnO 2 -Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media
journal, February 2010

  • Cheng, Fangyi; Su, Yi; Liang, Jing
  • Chemistry of Materials, Vol. 22, Issue 3
  • DOI: 10.1021/cm901698s

A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011


Ligand effects in heterogeneous catalysis and electrochemistry
journal, May 2007


Fluorine-Doped IrO 2 : A Potential Electrocatalyst for Water Electrolysis
journal, September 2013

  • Velikokhatnyi, Oleg I.; Kadakia, Karan; Datta, Moni K.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 40
  • DOI: 10.1021/jp308947h

Green process for hydrogen production from cellulose derivative using visible light-harvesting function of Mg chlorophyll-a
journal, January 2005

  • Himeshima, Noriko; Amao, Yutaka
  • Green Chemistry, Vol. 7, Issue 10
  • DOI: 10.1039/b504377h

The anodic characteristics of manganese dioxide electrodes prepared by thermal decomposition of manganese nitrate
journal, April 1977


Oxygen Electrochemistry as a Cornerstone for Sustainable Energy Conversion
journal, December 2013

  • Katsounaros, Ioannis; Cherevko, Serhiy; Zeradjanin, Aleksandar R.
  • Angewandte Chemie International Edition, Vol. 53, Issue 1
  • DOI: 10.1002/anie.201306588

Flexible graphene/MnO2 composite papers for supercapacitor electrodes
journal, January 2011

  • Li, Zhangpeng; Mi, Yongjuan; Liu, Xiaohong
  • Journal of Materials Chemistry, Vol. 21, Issue 38
  • DOI: 10.1039/c1jm11941a

Novel F-doped IrO2 oxygen evolution electrocatalyst for PEM based water electrolysis
journal, January 2013


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


Proton exchange membrane water electrolysis with short-side-chain Aquivion® membrane and IrO2 anode catalyst
journal, April 2014


Electrolysis of water on oxide surfaces
journal, September 2007


Nanostructured (Ir,Sn)O 2 :F – Oxygen Evolution Reaction Anode Electro-Catalyst Powders for PEM Based Water Electrolysis
journal, January 2014

  • Kadakia, Karan Sandeep; Jampani, Prashanth; Velikokhatnyi, Oleg I.
  • Journal of The Electrochemical Society, Vol. 161, Issue 9
  • DOI: 10.1149/2.0381409jes

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


Interpretation of XPS Mn(2p) spectra of Mn oxyhydroxides and constraints on the mechanism of MnO 2 precipitation
journal, April 1998


High performance and durable nanostructured TiN supported Pt50–Ru50 anode catalyst for direct methanol fuel cell (DMFC)
journal, October 2015


Dynamic potential–pH diagrams application to electrocatalysts for wateroxidation
journal, January 2012

  • Minguzzi, Alessandro; Fan, Fu-Ren F.; Vertova, Alberto
  • Chem. Sci., Vol. 3, Issue 1
  • DOI: 10.1039/C1SC00516B

Hydrothermal Synthesis and Pseudocapacitance Properties of MnO 2 Nanostructures
journal, November 2005

  • Subramanian, V.; Zhu, Hongwei; Vajtai, Robert
  • The Journal of Physical Chemistry B, Vol. 109, Issue 43
  • DOI: 10.1021/jp0543330

A highly efficient polysulfide mediator for lithium–sulfur batteries
journal, January 2015

  • Liang, Xiao; Hart, Connor; Pang, Quan
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6682

Molecular Insight in Structure and Activity of Highly Efficient, Low-Ir Ir–Ni Oxide Catalysts for Electrochemical Water Splitting (OER)
journal, September 2015

  • Reier, Tobias; Pawolek, Zarina; Cherevko, Serhiy
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b07788

Nanostructured F doped IrO2 electro-catalyst powders for PEM based water electrolysis
journal, December 2014


The future of hydrogen – opportunities and challenges☆
journal, January 2009


WO 3 based solid solution oxide – promising proton exchange membrane fuel cell anode electro-catalyst
journal, January 2015

  • Patel, Prasad Prakash; Jampani, Prashanth H.; Datta, Moni Kanchan
  • Journal of Materials Chemistry A, Vol. 3, Issue 35
  • DOI: 10.1039/C5TA03792A

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

Electrochemical performances of PEM water electrolysis cells and perspectives
journal, March 2011


Conversion of inert cryptomelane-type manganese oxide into a highly efficient oxygen evolution catalyst via limited Ir doping
journal, January 2016

  • Sun, Wei; Cao, Li-mei; Yang, Ji
  • Journal of Materials Chemistry A, Vol. 4, Issue 32
  • DOI: 10.1039/C6TA03011D

Structural and electrochemical studies of α-manganese dioxide (α-MnO2)
journal, October 1997


Electrochemical surface characterization of IrO2 + SnO2 mixed oxide electrocatalysts
journal, October 1995


Pure hydrogen production by PEM electrolysis for hydrogen energy
journal, February 2006


Performance of a PEM water electrolysis cell using IrxRuyTazO2IrxRuyTazO2 electrocatalysts for the oxygen evolution electrode
journal, September 2007


Degradation mechanism of long service life Ti/IrO2–Ta2O5 oxide anodes in sulphuric acid
journal, August 2002


Hydrogen production in single-chamber tubular microbial electrolysis cells using non-precious-metal catalysts
journal, October 2009


Fluorine doped (Ir,Sn,Nb)O2 anode electro-catalyst for oxygen evolution via PEM based water electrolysis
journal, January 2014

  • Kadakia, Karan; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.
  • International Journal of Hydrogen Energy, Vol. 39, Issue 2
  • DOI: 10.1016/j.ijhydene.2013.10.123

High performance fluorine doped (Sn,Ru)O2 oxygen evolution reaction electro-catalysts for proton exchange membrane based water electrolysis
journal, January 2014


Synthesis and characterization of electrocatalysts for the oxygen evolution in PEM water electrolysis
journal, August 2011


Electrocatalytic properties of transition metal oxides for oxygen evolution reaction
journal, May 1986


Synthesis, Characterization, Electronic Structure, and Photocatalytic Activity of Nitrogen-Doped TiO 2 Nanocatalyst
journal, December 2005

  • Sathish, M.; Viswanathan, B.; Viswanath, R. P.
  • Chemistry of Materials, Vol. 17, Issue 25
  • DOI: 10.1021/cm052047v

Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts
journal, July 2016

  • Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep28367

    Works referencing / citing this record:

    Mesoporous Co x Sn (1– x ) O 2 as an efficient oxygen evolution catalyst support for SPE water electrolyzer
    journal, April 2019

    • Chen, Gang; Li, Jiakun; Lv, Hong
    • Royal Society Open Science, Vol. 6, Issue 4
    • DOI: 10.1098/rsos.182223

    Mesoporous Co x Sn (1– x ) O 2 as an efficient oxygen evolution catalyst support for SPE water electrolyzer
    journal, April 2019

    • Chen, Gang; Li, Jiakun; Lv, Hong
    • Royal Society Open Science, Vol. 6, Issue 4
    • DOI: 10.1098/rsos.182223