Iron porphyrin-based cathode catalysts for PEM fuel cells: Influence of pyrolysis gas on activity and stability

Abstract Fe-based catalysts for the O2 reduction in acidic medium were prepared by impregnating chloro-iron tetramethoxyphenylporphyrin (Cl-FeTMPP) on a non-microporous carbon black and heat-treating the resulting material at 950 °C either in NH3 (Mode 1) or in Ar (Mode 2). The most active catalyst using Mode 1 has a Fe bulk content of 0.4 wt% and an activity of 17 mA mg−1 at 0.8 V in fuel cell. This activity is controlled by the microporous surface area of the catalyst. The most active catalysts using Mode 2 has an Fe bulk content of 3.7 wt% and an activity of 1.9 mA mg−1 at 0.8 V in fuel cell. In Mode 2, the nitrogen and/or the iron surface concentrations control the activity. Concerning stability, Mode 1-catalysts are unstable while Mode 2-catalysts show stability for at least 15 h when at least 66 wt% Cl-FeTMPP is impregnated onto N330 and heat-treated at 950 °C in Ar. The catalyst made with 66 wt% Cl-FeTMPP has a bulk Fe content of 5.2 wt% and an activity of 1.3 mA mg−1 at 0.8 V in fuel cell. Thus, in the present study, pyrolysis in NH3 gives active but unstable catalysts while pyrolysis in argon gives less active but more stable catalysts at high Cl-FeTMPP loading. Graphitization of Cl-FeTMPP during pyrolysis in argon seems to impart stability. Mode 2-catalysts are stable in spite of a high peroxide yield of 26% while Mode 1-catalysts are unstable in spite of a low 5% peroxide yield.

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

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

[3]  D. Avnir,et al.  Recommendations for the characterization of porous solids (Technical Report) , 1994 .

[4]  Sanjeev Mukerjee,et al.  Direct Spectroscopic Observation of the Structural Origin of Peroxide Generation from Co-Based Pyrolyzed Porphyrins for ORR Applications , 2008 .

[5]  P. Bogdanoff,et al.  Electrocatalysts for oxygen reduction prepared by plasma treatment of carbon-supported cobalt tetramethoxyphenylporphyrin , 2005 .

[6]  J.A.R. van Veen,et al.  Oxygen Reduction on Transition-Metal Porphyrins in Acid Electrolyte II. Stability , 1981 .

[7]  P. Atanassov,et al.  Non-platinum cathode catalyst layer composition for single Membrane Electrode Assembly Proton Exchange Membrane Fuel Cell , 2008 .

[8]  P. Aldebert,et al.  A new method for electrochemical screening basedon the rotating ring disc electrode and its applicationto oxygen reduction catalysts , 1998 .

[9]  H. Tributsch,et al.  Experimental and theoretical modeling of Fe-, Co-, Cu-, Mn-based electrocatalysts for oxygen reduction , 2008 .

[10]  J. Maruyama,et al.  Two-Step Carbonization as a Method of Enhancing Catalytic Properties of Hemoglobin at the Fuel Cell Cathode , 2007 .

[11]  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 .

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

[13]  Sebastian Fiechter,et al.  Nature of the Catalytic Centers of Porphyrin-Based Electrocatalysts for the ORR: A Correlation of Kinetic Current Density with the Site Density of Fe−N4 Centers , 2008 .

[14]  Svitlana Pylypenko,et al.  Non-platinum oxygen reduction electrocatalysts based on pyrolyzed transition metal macrocycles , 2008 .

[15]  Jean-Pol Dodelet,et al.  Influence of Structural Properties of Pristine Carbon Blacks on Activity of Fe ∕ N ∕ C Cathode Catalysts for PEFCs , 2007 .

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

[17]  D. Stevens,et al.  Magnetron Sputtered Fe – C – N , Fe – C , and C – N Based Oxygen Reduction Electrocatalysts , 2008 .

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

[19]  Volkmar M. Schmidt,et al.  Electrochemical characteristics and performance of CoTMPP/BP oxygen reduction electrocatalysts for PEM fuel cell , 2006 .

[20]  V. Bogdanovskaya,et al.  Nanosize catalysts based on carbon materials promoted by cobalt tetra(para-methoxyphenyl) porphyrin pyropolymer for oxygen electroreduction , 2008 .

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

[22]  Reinhard Niessner,et al.  Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information , 2005 .

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

[24]  Y. Kiros.  Metal Porphyrins for Oxygen Reduction in PEMFC , 2007, International Journal of Electrochemical Science.

[25]  Robert F. Savinell,et al.  Heat-treated iron(III) tetramethoxyphenyl porphyrin chloride supported on high-area carbon as an electrocatalyst for oxygen reduction:: Part III. Detection of hydrogen-peroxide during oxygen reduction , 1999 .

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

[27]  F. Jaouen,et al.  Increasing the activity of Fe/N/C catalysts in PEM fuel cell cathodes using carbon blacks with a high-disordered carbon content , 2008 .

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

[29]  M. L. Kremer.  Mechanism of the Fenton reaction. Evidence for a new intermediate , 1999 .

[30]  Ikuo Abe,et al.  Hemoglobin Pyropolymer Used as a Precursor of a Noble-Metal-Free Fuel Cell Cathode Catalyst , 2008 .

[31]  Frédéric Jaouen,et al.  Non-Noble Electrocatalysts for O2 Reduction: How Does Heat Treatment Affect Their Activity and Structure? Part I. Model for Carbon Black Gasification by NH3: Parametric Calibration and Electrochemical Validation , 2007 .

[32]  Frédéric Jaouen,et al.  Fe/N/C non-precious catalysts for PEM fuel cells: Influence of the structural parameters of pristine commercial carbon blacks on their activity for oxygen reduction , 2008 .

[33]  Xin Wang,et al.  Influence of preparation process on non-noble metal-based composite electrocatalysts for oxygen reduction reaction , 2008 .

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

[35]  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 .

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

[37]  Patrick Bertrand,et al.  Non-noble electrocatalysts for O-2 reduction: How does heat treatment affect their activity and structure? Part II. Structural changes observed by electron microscopy, Raman, and mass spectroscopy , 2007 .

[38]  Sundara Ramaprabhu,et al.  Cobalt-polypyrrole-multiwalled carbon nanotube catalysts for hydrogen and alcohol fuel cells , 2008 .

[39]  T. R. Ralph,et al.  Catalysis for low temperature fuel cells. Part I: The cathode challenges , 2002 .

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

[41]  P. Bertrand,et al.  Iron catalysts prepared by high-temperature pyrolysis of tetraphenylporphyrins adsorbed on carbon black for oxygen reduction in polymer electrolyte fuel cells , 1998 .

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

[43]  Michel Lefèvre,et al.  Fe-based electrocatalysts made with microporous pristine carbon black supports for the reduction of oxygen in PEM fuel cells , 2008 .

[44]  Hubert A. Gasteiger,et al.  Oxygen reduction on a high-surface area Pt/Vulcan carbon catalyst: a thin-film rotating ring-disk electrode study , 2001 .

[45]  Leis J.M,et al.  Proceedings of the Symposium , 1997 .

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

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

[48]  J. H. Field,et al.  Hydrogen cyanide produced from coal and ammonia. [1250/sup 0/C; effects of coal volatility] , 1967 .

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

[50]  Hubert A. Gasteiger,et al.  Handbook of fuel cells : fundamentals technology and applications , 2003 .

[51]  Xing Wu,et al.  Preparation and electrochemical characteristics of CoTMPP-TiO2NT/BP composite electrocatalyst for oxygen reduction reaction , 2007 .

[52]  K. Artyushkova,et al.  XPS Structural Studies of Nano-composite Non-platinum Electrocatalysts for Polymer Electrolyte Fuel Cells , 2007 .

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

[54]  H. Dunford,et al.  Oxidations of iron(II)/(III) by hydrogen peroxide: from aquo to enzyme , 2002 .

[55]  Der-Tau Chin.  Proceedings of the Symposium on Load Leveling and Energy Conservation in Industrial Processes , 1986 .

[56]  Frédéric Jaouen,et al.  Average turn-over frequency of O2 electro-reduction for Fe/N/C and Co/N/C catalysts in PEFCs , 2007 .

[57]  Uwe Schröder,et al.  Application of pyrolysed iron(II) phthalocyanine and CoTMPP based oxygen reduction catalysts as cathode materials in microbial fuel cells , 2005 .

[58]  Frédéric Jaouen,et al.  Heat-treated Fe/N/C catalysts for O2 electroreduction: are active sites hosted in micropores? , 2006, The journal of physical chemistry. B.

[59]  Yuyan Shao,et al.  Nitrogen-doped carbon nanostructures and their composites as catalytic materials for proton exchange membrane fuel cell , 2008 .

[60]  Jong-Won Lee,et al.  Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM Proton Exchange Membrane fuel cells , 2008 .