A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

Abstract A major hurdle to the widespread commercialization of proton exchange membrane fuel cells (PEMFCs) is the high loading of noble metal (Pt/Pt-alloy) catalyst at the cathode, which is necessary to facilitate the inherently sluggish oxygen reduction reaction (ORR). To eliminate the use of Pt/Pt-alloy catalysts at the cathode of PEMFCs and thus significantly reduce the cost, extensive research on non-precious metal catalysts (NPMCs) has been carried out over the past decade. Major advances in improving the ORR activity of NPMCs, particularly Fe- and Co-based NPMCs, have elevated these materials to a level at which they can start to be considered as potential alternatives to Pt/Pt-alloy catalysts. Unfortunately, the stability (performance loss following galvanostatic experiments) of these materials is currently unacceptably low and the durability (performance loss following voltage cycling) remains uncertain. The three primary mechanisms of instability are: (a) Leaching of the metal site, (b) Oxidative attack by H2O2, and (c) Protonation followed by possible anion adsorption of the active site. While (a) has largely been solved, further work is required to understand and prevent losses from (b) and/or (c). Thus, this review is focused on historical progress in (and possible future strategies for) improving the stability/durability of NPMCs.

[1]  Hui Meng,et al.  Iron porphyrin-based cathode catalysts for polymer electrolyte membrane fuel cells: Effect of NH3 and Ar mixtures as pyrolysis gases on catalytic activity and stability , 2010 .

[2]  J. Dodelet,et al.  Fe-Based Electrocatalysts for Oxygen Reduction in PEMFCs Using Ballmilled Graphite Powder as a Carbon Support , 2008 .

[3]  J. Dodelet,et al.  Activity and stability in proton exchange membrane fuel cells of iron-based cathode catalysts synthesized with addition of carbon fibers , 2014 .

[4]  Frano Barbir,et al.  PEM Fuel Cells: Theory and Practice , 2012 .

[5]  S. Marcotte,et al.  Oxygen Reduction Catalysts for Polymer Electrolyte Fuel Cells from the Pyrolysis of Iron Acetate Adsorbed on Various Carbon Supports , 2003 .

[6]  B. Yi,et al.  Fe-N-carbon black for the oxygen reduction reaction in sulfuric acid , 2013 .

[7]  Branko N. Popov,et al.  Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells , 2010 .

[8]  Kateryna Artyushkova,et al.  Performance Durability of Polyaniline-derived Non-precious Cathode Catalysts , 2009 .

[9]  Andrew Dicks,et al.  Non precious metal catalysts for the PEM fuel cell cathode , 2012 .

[10]  J. Ozaki,et al.  Formation of uniformly and finely dispersed nanoshells by carbonization of cobalt-coordinated oxine–formaldehyde resin and their electrochemical oxygen reduction activity , 2012 .

[11]  Dustin Banham,et al.  Pt/Carbon Catalyst Layer Microstructural Effects on Measured and Predicted Tafel Slopes for the Oxygen Reduction Reaction , 2009 .

[12]  Gang Wu,et al.  High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt , 2011, Science.

[13]  P. Bertrand,et al.  Unveiling N-protonation and anion-binding effects on Fe/N/C-catalysts for O2 reduction in PEM fuel cells. , 2011, The journal of physical chemistry. C, Nanomaterials and interfaces.

[14]  K. Ota,et al.  Stability and electrocatalytic activity for oxygen reduction in WC + Ta catalyst , 2004 .

[15]  Drew C. Higgins,et al.  Recent progress in non‐precious metal catalysts for PEM fuel cell applications , 2013 .

[16]  Y. Shao-horn,et al.  Fe-N-modified multi-walled carbon nanotubes for oxygen reduction reaction in acid. , 2011, Physical chemistry chemical physics : PCCP.

[17]  K. Artyushkova,et al.  Cyanamide-derived non-precious metal catalyst for oxygen reduction , 2010 .

[18]  I. Abe,et al.  Formation of Platinum-Free Fuel Cell Cathode Catalyst with Highly Developed Nanospace by Carbonizing Catalase , 2005 .

[19]  S. Campbell,et al.  Effect of Preparation Conditions of Sol–Gel-Derived Co–N–C-Based Catalysts on ORR Activity in Acidic Solutions , 2008 .

[20]  N. Alonso‐Vante,et al.  In situ Free-Surfactant Synthesis and ORR- Electrochemistry of Carbon-Supported Co3S4 and CoSe2 Nanoparticles , 2008 .

[21]  Frédéric Jaouen,et al.  Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells , 2009, Science.

[22]  Lei Zhang,et al.  Ultrasonic spray pyrolyzed iron-polypyrrole mesoporous spheres for fuel celloxygen reduction electrocatalysts , 2009 .

[23]  Patrick Bertrand,et al.  Heat-treated iron and cobalt tetraphenylporphyrins adsorbed on carbon black: Physical characterization and catalytic properties of these materials for the reduction of oxygen in polymer electrolyte fuel cells , 1996 .

[24]  Minoru Inaba,et al.  Durability of perfluorinated ionomer membrane against hydrogen peroxide , 2006 .

[25]  Umit S. Ozkan,et al.  The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction , 2006 .

[26]  B. Popov,et al.  Power source research at USC: Development of advanced electrocatalysts for polymer electrolyte membrane fuel cells , 2011 .

[27]  G. Tamizhmani,et al.  Physical, Chemical and Electrochemical Characterization of Heat-treated Tetracarboxylic Cobalt Phthalocyanine Adsorbed On Carbon-black As Electrocatalyst for Oxygen Reduction in Polymer Electrolyte Fuel-cells , 1995 .

[28]  Piotr Zelenay,et al.  A class of non-precious metal composite catalysts for fuel cells , 2006, Nature.

[29]  P. Bertrand,et al.  Is nitrogen important in the formulation of Fe-based catalysts for oxygen reduction in solid polymer fuel cells? , 1997 .

[30]  M. Chi,et al.  Core/shell Pd/FePt nanoparticles as an active and durable catalyst for the oxygen reduction reaction. , 2010, Journal of the American Chemical Society.

[31]  Piotr Zelenay,et al.  Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells , 2011 .

[32]  Michael H. Robson,et al.  Highly active and durable templated non-PGM cathode catalysts derived from iron and aminoantipyrine , 2012 .

[33]  O. Terasaki,et al.  Transition Metal Ion-Chelating Ordered Mesoporous Carbons as Noble Metal-Free Fuel Cell Catalysts , 2013 .

[34]  Drew C. Higgins,et al.  Nitrogen doped carbon nanotubes synthesized from aliphatic diamines for oxygen reduction reaction , 2011 .

[35]  S. Woo,et al.  Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity. , 2012, ACS nano.

[36]  H. Binder,et al.  Mechanism of the electrocatalytic reduction of oxygen on metal chelates , 1973 .

[37]  S. C. Tang,et al.  On Active-Site Heterogeneity in Pyrolyzed Carbon-Supported Iron Porphyrin Catalysts for the Electrochemical Reduction of Oxygen: An In Situ Mössbauer Study , 2002 .

[38]  Dan Bizzotto,et al.  Characterization of FeS2-Based Thin Films as Model Catalysts for the Oxygen Reduction Reaction , 2007 .

[39]  Lei Zhang,et al.  Ternary non-noble metal chalcogenide (W-Co-Se) as electrocatalyst for oxygen reduction reaction , 2007 .

[40]  Patrick Bertrand,et al.  O-2 reduction in PEM fuel cells: Activity and active site structural information for catalysts obtained by the pyrolysis at high temperature of Fe precursors , 2000 .

[41]  R. Li,et al.  High oxygen-reduction activity and durability of nitrogen-doped graphene , 2011 .

[42]  B. Popov,et al.  Experimental and Theoretical Study of Cobalt Selenide as a Catalyst for O2 Electroreduction , 2007 .

[43]  Jeff Tollefson,et al.  Hydrogen vehicles: Fuel of the future? , 2010, Nature.

[44]  Michel Lefèvre,et al.  Fe-based catalysts for the reduction of oxygen in polymer electrolyte membrane fuel cell conditions: determination of the amount of peroxide released during electroreduction and its influence on the stability of the catalysts , 2003 .

[45]  A. Ōya,et al.  Preparation and oxygen reduction activity of BN-doped carbons , 2007 .

[46]  H Jahnke,et al.  Organic dyestuffs as catalysts for fuel cells. , 1976, Topics in current chemistry.

[47]  D. Stevens,et al.  Fuel Cell Studies on a Non-Noble Metal Catalyst Prepared by a Template-Assisted Synthesis Route , 2008 .

[48]  T. Jarvi,et al.  Electrocatalytic corrosion of carbon support in PEMFC cathodes , 2004 .

[49]  H. Tributsch,et al.  Catalysts for the Oxygen Reduction from Heat-Treated Iron(III) Tetramethoxyphenylporphyrin Chloride: Structure and Stability of Active Sites , 2003 .

[50]  Jeanette E. Owejan,et al.  Mitigation of Perfluorosulfonic Acid Membrane Chemical Degradation Using Cerium and Manganese Ions , 2008 .

[51]  W. Koppenol,et al.  Kinetic Simulation of the Chemical Stabilization Mechanism in Fuel Cell Membranes Using Cerium and Manganese Redox Couples , 2011 .

[52]  Jong-Won Lee,et al.  A review of the development of nitrogen-modified carbon-based catalysts for oxygen reduction at USC , 2011 .

[53]  Ernest Yeager,et al.  Heat-treated polyacrylonitrile-based catalysts for oxygen electroreduction , 1989 .

[54]  B. Yi,et al.  A novel non-noble electrocatalyst for PEM fuel cell based on molybdenum nitride , 2006 .

[55]  F. Coms The Chemistry of Fuel Cell Membrane Chemical Degradation , 2008, ECS Transactions.

[56]  J. Ozaki,et al.  Enhancement of oxygen reduction activity of nanoshell carbons by introducing nitrogen atoms from metal phthalocyanines , 2010 .

[57]  Li Jin,et al.  Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. , 2013, Angewandte Chemie.

[58]  S. Joo,et al.  Preparation of high loading Pt nanoparticles on ordered mesoporous carbon with a controlled Pt size and its effects on oxygen reduction and methanol oxidation reactions , 2009 .

[59]  M. Dignam,et al.  Sputtered Cobalt‐Carbon‐Nitrogen Thin Films as Oxygen Reduction Electrocatalysts II. Electrochemical Stability and Proposed Mechanism , 1998 .

[60]  V. Stamenkovic,et al.  Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide. , 2010, Nature chemistry.

[61]  Edmar P. Marques,et al.  A review of Fe-N/C and Co-N/C catalysts for the oxygen reduction reaction , 2008 .

[62]  Jiujun Zhang,et al.  A review of accelerated stress tests of MEA durability in PEM fuel cells , 2009 .

[63]  H. Meier,et al.  Application of radioisotope techniques for the study of phthalocyanine catalyzed electrochemical processes in fuel cells , 1977 .

[64]  J. Dodelet,et al.  Recent Advances in Non-Precious Metal Electrocatalysts for Oxygen Reduction in PEM Fuel Cells , 2012 .

[65]  Robert M. Darling,et al.  Model of Carbon Corrosion in PEM Fuel Cells , 2006 .

[66]  Mark K. Debe,et al.  Electrocatalyst approaches and challenges for automotive fuel cells , 2012, Nature.

[67]  Jiujun Zhang,et al.  PEM Fuel Cell Electrocatalysts and Catalyst Layers , 2008 .

[68]  B. Popov,et al.  Activity and stability of non-precious metal catalysts for oxygen reduction in acid and alkaline electrolytes , 2010 .

[69]  R. Li,et al.  Non-noble metal oxygen reduction electrocatalysts based on carbon nanotubes with controlled nitrogen contents , 2011 .

[70]  Bruno Jousselme,et al.  Low-platinum and platinum-free catalysts for the oxygen reduction reaction at fuel cell cathodes , 2011 .

[71]  Matthew Thorum,et al.  Electroreduction of dioxygen for fuel-cell applications: materials and challenges. , 2010, Inorganic chemistry.

[72]  J. Riga,et al.  Oxygen electrocatalysis under fuel cell conditions: behaviour of cobalt porphyrins and tetraazaannulene analogues , 1996 .

[73]  S. Woo,et al.  Electrochemical oxygen reduction on nitrogen doped graphene sheets in acid media , 2010 .

[74]  H. Tang,et al.  PEM fuel cell cathode carbon corrosion due to the formation of air/fuel boundary at the anode , 2006 .

[75]  K. Ota,et al.  Progress in non-precious metal oxide-based cathode for polymer electrolyte fuel cells , 2010 .

[76]  K. Ota,et al.  Catalytic activity of titanium oxide for oxygen reduction reaction as a non-platinum catalyst for PEFC , 2007 .

[77]  Lorenz Gubler,et al.  Radical (HO•, H• and HOO•) Formation and Ionomer Degradation in Polymer Electrolyte Fuel Cells , 2011 .

[78]  B. Popov,et al.  Stability Study of Nitrogen-Modified Carbon Composite Catalysts for Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells , 2009 .

[79]  H. Gasteiger,et al.  Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs , 2005 .

[80]  Zhongwei Chen,et al.  A review on non-precious metal electrocatalysts for PEM fuel cells , 2011 .

[81]  S. Moriya,et al.  Carbon Nitride as a Nonprecious Catalyst for Electrochemical Oxygen Reduction , 2009 .

[82]  Branko N. Popov,et al.  Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon , 2009 .

[83]  M. Manzoli,et al.  Characterisation of Co-based electrocatalytic materials for O2 reduction in fuel cells , 2005 .

[84]  S. Miyata,et al.  Indirect contribution of transition metal towards oxygen reduction reaction activity in iron phthalocyanine-based carbon catalysts for polymer electrolyte fuel cells , 2012 .

[85]  K. S. Weil,et al.  A Novel Non-Platinum Group Electrocatalyst for PEM Fuel Cell Application , 2011 .

[86]  A. Ōya,et al.  Simultaneous doping of boron and nitrogen into a carbon to enhance its oxygen reduction activity in proton exchange membrane fuel cells , 2006 .

[87]  Michael S. Crocker,et al.  Pourbaix (E-pH-M) Diagrams in Three Dimensions , 2012 .

[88]  H. Tributsch,et al.  Thermogravimetry/Mass Spectrometry Investigations on the Formation of Oxygen Reduction Catalysts for PEM Fuel Cells on the Basis of Heat‐Treated Iron Phenanthroline Complexes , 2002 .

[89]  A. Ōya,et al.  Enhancement of oxygen reduction activity by carbonization of furan resin in the presence of phthalocyanines , 2006 .

[90]  F. Wei,et al.  An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. , 2012, Nature nanotechnology.

[91]  J. Newman,et al.  Mass Transport in Gas‐Diffusion Electrodes: A Diagnostic Tool for Fuel‐Cell Cathodes , 1998 .

[92]  M. Dignam,et al.  Sputtered Cobalt‐Carbon‐Nitrogen Thin Films as Oxygen Reduction Electrocatalysts I. Physical and Electrochemical Characterization , 1998 .

[93]  A. Ōya,et al.  Structures, physicochemical properties and oxygen reduction activities of carbons derived from ferrocene-poly(furfuryl alcohol) mixtures , 2006 .

[94]  Michael H. Robson,et al.  Templated non-PGM cathode catalysts derived from iron and poly(ethyleneimine) precursors , 2012 .

[95]  R. Jasinski,et al.  A New Fuel Cell Cathode Catalyst , 1964, Nature.

[96]  Lei Zhang,et al.  Progress in preparation of non-noble electrocatalysts for PEM fuel cell reactions , 2006 .

[97]  F. Du,et al.  Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction , 2009, Science.

[98]  S. Moriya,et al.  Preparation of carbon alloy catalysts for polymer electrolyte fuel cells from nitrogen-containing rigid-rod polymers , 2010 .

[99]  Bin Wang,et al.  Recent development of non-platinum catalysts for oxygen reduction reaction , 2005 .

[100]  A. Ōya,et al.  Preparation of BN-doped carbon blacks by mechanochemical alloying of carbon and h-BN and its use as a catalyst for the oxygen reduction (小特集 炭素材料科学の進展と物性・機能評価) , 2007 .

[101]  P. Crouigneau,et al.  Conducting polymer electrodes modified by metal tetrasulfonated phthalocyanines: Preparation and electrocatalytic behaviour towards dioxygen reduction in acid medium , 1995 .

[102]  Thomas E. Wood,et al.  Non-precious metal oxygen reduction catalyst for PEM fuel cells based on nitroaniline precursor ☆ , 2008 .

[103]  W. Visscher,et al.  Oxygen reduction on pyrolysed carbon-supported transition metal chelates , 1986 .

[104]  Yan Liu,et al.  Transition Metal Oxides as DMFC Cathodes Without Platinum , 2007 .

[105]  Stève Baranton,et al.  Oxygen reduction reaction in acid medium at iron phthalocyanine dispersed on high surface area carbon substrate: tolerance to methanol, stability and kinetics , 2005 .

[106]  Ruizhi Yang,et al.  Impact of Loading in RRDE Experiments on Fe-N-C Catalysts: Two- or Four-Electron Oxygen Reduction? , 2008 .