Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Fluorine substituted (Mn,Ir)O2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

Journal Article · · RSC Advances
DOI:https://doi.org/10.1039/c6ra27354h· OSTI ID:1426497
 [1];  [2];  [3];  [3];  [4];  [2];  [5]
  1. Univ. of Pittsburgh, PA (United States). Chemical and Petroleum Engineering, Swanson School of Engineering; None
  2. Univ. of Pittsburgh, PA (United States). Chemical and Petroleum Engineering, Swanson School of Engineering
  3. 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
  4. Univ. of Pittsburgh, PA (United States). Swanson School of Engineering, Dept. of Bioengineering
  5. 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

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.

Research Organization:
Univ. of Pittsburgh, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
SC0001531
OSTI ID:
1426497
Journal Information:
RSC Advances, Journal Name: RSC Advances Journal Issue: 28 Vol. 7; ISSN 2046-2069; ISSN RSCACL
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (61)

Oxygen Electrochemistry as a Cornerstone for Sustainable Energy Conversion journal December 2013
The anodic characteristics of manganese dioxide electrodes prepared by thermal decomposition of manganese nitrate journal April 1977
Electrochemical surface characterization of IrO2 + SnO2 mixed oxide electrocatalysts journal October 1995
Electrocatalytic properties of transition metal oxides for oxygen evolution reaction journal May 1986
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Degradation mechanism of long service life Ti/IrO2–Ta2O5 oxide anodes in sulphuric acid journal August 2002
Nanostructured MnO2 for Li batteries journal June 2003
Structural and electrochemical studies of α-manganese dioxide (α-MnO2) journal October 1997
Ligand effects in heterogeneous catalysis and electrochemistry journal May 2007
Electrocatalysis by nanoparticles: Optimization of the loading level and operating pH for the oxygen evolution at crystallographically oriented manganese oxide nanorods modified electrodes journal May 2008
The physical–chemical properties and electrocatalytic performance of iridium oxide in oxygen evolution journal November 2011
The electrocatalytic properties of an IrO2/SnO2 catalyst using SnO2 as a support and an assisting reagent for the oxygen evolution reaction journal January 2012
Batteries: Higher energy density than gasoline? journal July 2009
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
The future of hydrogen – opportunities and challenges☆ journal January 2009
Hydrogen production in single-chamber tubular microbial electrolysis cells using non-precious-metal catalysts journal October 2009
Electrochemical performances of PEM water electrolysis cells and perspectives journal March 2011
Synthesis and characterization of electrocatalysts for the oxygen evolution in PEM water electrolysis journal August 2011
Fluorine doped (Ir,Sn,Nb)O2 anode electro-catalyst for oxygen evolution via PEM based water electrolysis journal January 2014
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
Electrochemical controlled synthesis and characterization of well-aligned IrO2 nanotube arrays with enhanced electrocatalytic activity toward oxygen evolution reaction journal January 2013
Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers journal March 2008
Novel F-doped IrO2 oxygen evolution electrocatalyst for PEM based water electrolysis journal January 2013
High performance fluorine doped (Sn,Ru)O2 oxygen evolution reaction electro-catalysts for proton exchange membrane based water electrolysis journal January 2014
Oxygen evolution in Co-doped RuO2 and IrO2: Experimental and theoretical insights to diminish electrolysis overpotential journal December 2014
Nanostructured F doped IrO2 electro-catalyst powders for PEM based water electrolysis journal December 2014
High performance and durable nanostructured TiN supported Pt50–Ru50 anode catalyst for direct methanol fuel cell (DMFC) journal October 2015
Nitrogen and cobalt co-doped zinc oxide nanowires – Viable photoanodes for hydrogen generation via photoelectrochemical water splitting journal December 2015
An overview of polymer electrolyte membrane electrolyzer for hydrogen production: Modeling and mass transport journal March 2016
Vertically aligned nitrogen doped (Sn,Nb)O2 nanotubes – Robust photoanodes for hydrogen generation by photoelectrochemical water splitting journal June 2016
Recent progress in alkaline water electrolysis for hydrogen production and applications journal June 2010
Synthesis, Characterization, Electronic Structure, and Photocatalytic Activity of Nitrogen-Doped TiO 2 Nanocatalyst journal December 2005
MnO 2 -Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media journal February 2010
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction journal October 2013
Molecular Insight in Structure and Activity of Highly Efficient, Low-Ir Ir–Ni Oxide Catalysts for Electrochemical Water Splitting (OER) journal September 2015
Hydrothermal Synthesis and Pseudocapacitance Properties of MnO 2 Nanostructures journal November 2005
Fluorine-Doped IrO 2 : A Potential Electrocatalyst for Water Electrolysis journal September 2013
Role of Cu-Ion Doping in Cu-α-MnO 2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction journal July 2014
A highly efficient polysulfide mediator for lithium–sulfur batteries journal January 2015
Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities journal March 2015
Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts journal July 2016
Dynamic potential–pH diagrams application to electrocatalysts for wateroxidation journal January 2012
Nanostructured robust cobalt metal alloy based anode electro-catalysts exhibiting remarkably high performance and durability for proton exchange membrane fuel cells journal January 2015
WO 3 based solid solution oxide – promising proton exchange membrane fuel cell anode electro-catalyst journal January 2015
Conversion of inert cryptomelane-type manganese oxide into a highly efficient oxygen evolution catalyst via limited Ir doping journal January 2016
Green process for hydrogen production from cellulose derivative using visible light-harvesting function of Mg chlorophyll-a journal January 2005
Heterogeneous photocatalytic hydrogen production from water and biomass derivatives journal January 2011
Flexible graphene/MnO2 composite papers for supercapacitor electrodes journal January 2011
High performance robust F-doped tin oxide based oxygen evolution electro-catalysts for PEM based water electrolysis journal January 2013
Data Reduction and Error Analysis for Accurate Single Crystal Diffraction Intensities journal January 1987
Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation journal June 1986
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Refinement of Macromolecular Structures by the Maximum-Likelihood Method journal May 1997
XSEDE: Accelerating Scientific Discovery journal September 2014
MnO 2 by XPS journal January 1999
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles journal October 2011
Nanostructured (Ir,Sn)O 2 :F – Oxygen Evolution Reaction Anode Electro-Catalyst Powders for PEM Based Water Electrolysis journal January 2014
Interpretation of XPS Mn(2p) spectra of Mn oxyhydroxides and constraints on the mechanism of MnO 2 precipitation journal April 1998

Cited By (5)


Similar Records

Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts
Journal Article · Wed Jul 06 00:00:00 EDT 2016 · Scientific Reports · OSTI ID:1312963

SISGR-Fundamental Experimental and Theoretical Studies on a Novel Family of Oxide Catalyst Supports for Water Electrolysis
Technical Report · Fri Oct 03 00:00:00 EDT 2014 · OSTI ID:1159120

High performance robust F-doped tin oxide based oxygen evolution electro-catalysts for PEM based water electrolysis
Journal Article · Mon Dec 31 23:00:00 EST 2012 · Journal of Materials Chemistry A · OSTI ID:1115421

Related Subjects