Electrocatalytic activity and stability of substituted iron phthalocyanines towards oxygen reduction evaluated at different temperatures

Abstract A significant amount of work has been done in the field of the transition metal (TM) macrocyclic-catalyzed oxygen reduction reaction (ORR), but not as a function of temperature and substitution in an acidic electrolyte to simulate the environment of an operating PEM fuel cell. The electrocatalytic activity of several iron-based phthalocyanine macrocycles for the ORR were evaluated using cyclic voltammetric (CV) and rotating disc electrode (RDE) techniques. The activities of these substituted iron phthalocyanines were compared to those of the unsubstituted species in the temperature range of 20–80 °C. The activity was also evaluated in the presence of hydrogen peroxide, both a possible by-product of the ORR and potential de-activator of iron phthalocyanines. The kinetics and corresponding parameters such as overall ORR electron transfer numbers, reaction rate constants, Tafel slopes, electron transfer numbers in the rate-determining step, and electron transfer coefficients were all measured in the temperature range of 20–80 °C. A mechanism for the different FePc-catalyzed ORR's was suggested based on the experimental results. The effect of substitution and temperature on ORR kinetics was also studied in this paper.

[1]  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 .

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

[3]  A. Lever,et al.  Erratum to “Tuning metalloporphyrin and metallophthalocyanine redox potentials using ligand electrochemical (EL) and Hammett (σp) parametrization” [Coord. Chem. Rev. 216–217 (2001) 45–54] , 2001 .

[4]  F. Beck.  The redox mechanism of the chelate-catalysed oxygen cathode , 1977 .

[5]  Jiujun Zhang,et al.  High-surface-area CoTMPP/C synthesized by ultrasonic spray pyrolysis for PEM fuel cell electrocatalysts , 2007 .

[6]  S. Scheiner,et al.  Effects of peripheral substituents and axial ligands on the electronic structure and properties of iron phthalocyanine. , 2004, Inorganic chemistry.

[7]  J. Keshavayya,et al.  Synthesis and spectroscopic investigations of iron(III) complexes with chlorides and dianionic, symmetrically halogen substituted phthalocyanines as ligands. , 2003, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[8]  Michel Trudeau,et al.  Influence of Loading on the Activity and Stability of Heat‐Treated Carbon‐Supported Cobalt Phthalocyanine Electrocatalysts in Solid Polymer Electrolyte Fuel Cells , 1995 .

[9]  S. Volkov,et al.  Synthesis and physicochemical properties of highly soluble tetra-tert-butyl-2,3-naphthalocyanine complexes of lanthanides , 1996 .

[10]  T. Kuwana,et al.  Rotating-ring-disk analysis of iron tetra(N-methylpyridyl)porphyrin in electrocatalysis of oxygen , 1979 .

[11]  A. Yamada,et al.  Hexadecafluoro- and octacyano phthalocyanines as electrocatalysts for the reduction of dioxygen , 1991 .

[12]  Hiroshi Ogata,et al.  Synthesis, spectroscopy, and electrochemistry of tetra-tert-butylated tetraazaporphyrins, phthalocyanines, naphthalocyanines, and anthracocyanines, together with molecular orbital calculations. , 2004, Chemistry.

[13]  J. Randin.  Interpretation of the relative electrochemical activity of various metal phthalocyanines for the oxygen reduction reaction , 1974 .

[14]  A. Appleby.  Electrocatalysis of aqueous dioxygen reduction , 1993 .

[15]  R. McCreery,et al.  Elucidation of the Mechanism of Dioxygen Reduction on Metal‐Free Carbon Electrodes , 2000 .

[16]  R. C. Weast.  CRC Handbook of Chemistry and Physics , 1973 .

[17]  G. Cárdenas-Jirón.  Substituent effect in the chemical reactivity and selectivity of substituted cobalt phthalocyanines , 2002 .

[18]  J. Manassen.  A Comparison between the chemical and electrochemical catalysis by tetraphenylporphyrin and phthalocyanine complexes , 1974 .

[19]  Jiujun Zhang,et al.  Electrocatalytic activity of N,N′,N″,N‴-tetramethyl-tetra-3,4-pyridoporphyrazinocobalt(II) adsorbed on a graphite electrode towards the oxidation of hydrazine and hydroxylamine , 1996 .

[20]  Lei Zhang,et al.  Temperature and pH Dependence of Oxygen Reduction Catalyzed by Iron Fluoroporphyrin Adsorbed on a Graphite Electrode , 2005 .

[21]  J. Hutchison,et al.  Molecular Catalysts for Multielectron Redox Reactions of Small Molecules: The “Cofacial Metallodiporphyrin” Approach , 1994 .

[22]  J. Bockris,et al.  Activation Parameters for Oxygen Reduction Kinetics in Trifluoromethane Sulfonic Acid Systems , 1989 .

[23]  J. Zagal.  Metallophthalocyanines as catalysts in electrochemical reactions , 1992 .

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

[25]  Lei Zhang,et al.  Reversible one-electron electro-reduction of O2 to produce a stable superoxide (O2-) catalyzed by adsorbed Co(II) hexadecafluoro-phthalocyanine in aqueous alkaline solution , 2006 .

[26]  W. Visscher,et al.  The selectivity of oxygen reduction by pyrolysed iron porphyrin supported on carbon , 1998 .

[27]  Jiujun Zhang,et al.  Density Functional Theory Study of Transitional Metal Macrocyclic Complexes' Dioxygen-Binding Abilities and Their Catalytic Activities toward Oxygen Reduction Reaction , 2007 .

[28]  W. Sugimoto,et al.  Temperature dependence of the oxidation of carbon monoxide on carbon supported Pt, Ru, and PtRu , 2004 .

[29]  E. Yeager,et al.  A Mechanistic Study of O 2 Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite Electrodes , 1980 .

[30]  A. Lever,et al.  The phthalocyanines—molecules of enduring value; a two-dimensional analysis of redox potentials , 1999 .

[31]  M. N. Golovin,et al.  Perchlorinated phthalocyanines: spectroscopic properties and surface electrochemistry , 1990 .

[32]  A. Hantzsch.  Widerlegung von E. Biilmanns Auffassung der Homochromisomerie als Polymorphie , 1911 .

[33]  Richard G Compton,et al.  Oxygenated edge plane sites slow the electron transfer of the ferro-/ferricyanide redox couple at graphite electrodes. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[34]  Daniel Guay,et al.  Effect of the Pre-Treatment of Carbon Black Supports on the Activity of Fe-Based Electrocatalysts for the Reduction of Oxygen , 1999 .

[35]  F. Coowar,et al.  Electrocatalysis of O2 reduction to water in different acid media by iron naphthalocyanines , 1988 .

[36]  J. Leger,et al.  How does α-FePc catalysts dispersed onto high specific surface carbon support work towards oxygen reduction reaction (orr)? , 2006 .

[37]  E. Yeager,et al.  Spectroscopic and Electrochemical Studies of the Transition Metal Tetrasulfonated Phthalocyanines. Part 5. Voltammetric Studies of Adsorbed Tetrasulfonated Phthalocyanines (MTsPc) in Aqueous Solutions. , 1985 .

[38]  Patrick Bertrand,et al.  Oxygen reduction catalysts for polymer electrolyte fuel cells from the pyrolysis of FeII acetate adsorbed on 3,4,9,10-perylenetetracarboxylic dianhydride , 1999 .

[39]  James Larminie,et al.  Fuel Cell Systems Explained , 2000 .

[40]  C. Wilke,et al.  Correlation of diffusion coefficients in dilute solutions , 1955 .

[41]  Jean-Pol Dodelet,et al.  Fe-Based Catalysts for Oxygen Reduction in PEM Fuel Cells Pretreatment of the Carbon Support , 2004 .

[42]  Maritza Páez,et al.  Electrocatalytic activity of metal phthalocyanines for oxygen reduction , 1992 .

[43]  A. Lever,et al.  Cathodic reduction of oxygen and hydrogen peroxide at cobalt and iron crowned phthalocyanines adsorbed on highly oriented pyrolytic graphite electrodes , 1992 .

[44]  F. Anson,et al.  Catalytic pathways for the electroreduction of oxygen by iron tetrakis(4-N-methylpyridyl)porphyrin or iron tetraphenylporphyrin adsorbed on edge plane pyrolytic graphite electrodes , 1990 .

[45]  R. Battino,et al.  The Solubility of Oxygen and Ozone in Liquids , 1983 .

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

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

[48]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[49]  V. S. Bagotzky,et al.  Electrocatalysis of the oxygen reduction process on metal chelates in acid electrolyte , 1978 .

[50]  Lei Zhang,et al.  Temperature Dependence of Oxygen Reduction Catalyzed by Cobalt Fluoro‐Phthalocyanine Adsorbed on a Graphite Electrode , 2007 .

[51]  Sebastian Fiechter,et al.  EXAFS, XPS and electrochemical studies on oxygen reduction catalysts obtained by heat treatment of iron phenanthroline complexes supported on high surface area carbon black , 2002 .

[52]  C. Amatore,et al.  Trends in Molecular Electrochemistry , 2004 .

[53]  Frédéric Jaouen,et al.  Fe-Based Catalysts for Oxygen Reduction in PEMFCs Importance of the Disordered Phase of the Carbon Support , 2006 .

[54]  A. Lever,et al.  Tuning metalloporphyrin and metallophthalocyanine redox potentials using ligand electrochemical (EL) and Hammett (σp) parametrization , 2001 .

[55]  K. Shigehara,et al.  Electrocatalytic Activity of Three Iron Porphyrins in the Reductions of Dioxygen and Hydrogen Peroxide at Graphite Electrodes , 1982 .

[56]  Gregor Hoogers,et al.  Fuel Cell Technology Handbook , 2002 .

[57]  J. Zagal,et al.  N4-Macrocyclic Metal Complexes , 2006 .

[58]  J. Zagal,et al.  Linear versus volcano correlations between electrocatalytic activity and redox and electronic properties of metallophthalocyanines , 1998 .

[59]  N. Guillet,et al.  Electroreduction of oxygen on Co-based catalysts: determination of the parameters affecting the two-electron transfer reaction in an acid medium , 2004 .