Carbon-Supported Manganese Oxide Nanoparticles as Electrocatalysts for the Oxygen Reduction Reaction (ORR) in Alkaline Medium: Physical Characterizations and ORR Mechanism

MnOx/C and Me-MnOx/C (Me = Ni, Mg) electrocatalysts prepared by chemical deposition of manganese oxide nanoparticles on carbon have been characterized by Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), and chemical analysis. Their Oxygen Reduction Reaction (ORR) kinetics and mechanism have been investigated in alkaline KOH solutions by using the Rotating Disk Electrode (RDE) and the Rotating Ring-Disk Electrode (RRDE) setups. Doping the MnOx/C nanoparticles with nickel or magnesium divalent cations can considerably improve their oxygen reduction activity. As a result, the Me-MnOx/C electrocatalysts exhibit ORR specific or mass activities close to the benchmark 10 wt % Pt/C from E-TEK. At low ORR current densities, the undoped MnOx/C electrocatalyst displays a reaction order with respect to PO2 and OH- of 1 and −0.5, respectively, while ∂E/∂log i is ca. −59 mV dec-1. The ORR reaction order toward OH- is unchanged with the magnesium doping, while it becomes −2 with the nickel doping. RRDE d...

[1]  J. Vondrak,et al.  Kinetics of sodium borohydride direct oxidation and oxygen reduction in sodium hydroxide electrolyte: Part II. O2 reduction , 2006 .

[2]  E. Ticianelli,et al.  Oxygen reduction reaction on nanosized manganese oxide particles dispersed on carbon in alkaline solutions , 2006 .

[3]  Y. Bultel,et al.  Impedance study of the oxygen reduction reaction on platinum nanoparticles in alkaline media , 2003 .

[4]  Yuliang Cao,et al.  The mechanism of oxygen reduction on MnO2-catalyzed air cathode in alkaline solution , 2003 .

[5]  J. Vondrak,et al.  International meetings on Advanced Batteries and Accumulators , 2003 .

[6]  Dun Zhang,et al.  Mechanistic study of the reduction of oxygen in air electrode with manganese oxides as electrocatalysts , 2003 .

[7]  M. Chatenet,et al.  Silver-Platinum Bimetallic Catalysts for Oxygen Cathodes in Chlor-alkali Electrolysis: Comparison with Pure Platinum , 2003 .

[8]  M. Chatenet,et al.  Oxygen reduction on silver catalysts in solutions containing various concentrations of sodium hydroxide – comparison with platinum , 2002 .

[9]  Jiří Vondrák,et al.  MnOx/C composites as electrode materials II. Reduction of oxygen on bifunctional catalysts based on manganese oxides , 2002 .

[10]  O. Antoine,et al.  RRDE study of oxygen reduction on Pt nanoparticles inside Nafion®: H2O2 production in PEMFC cathode conditions , 2000 .

[11]  J. Vondrak,et al.  MnOx/C composites as electrode materials. I. Synthesis, XRD and cyclic voltammetric investigation , 1999 .

[12]  M. A. Hasan,et al.  Promotion of the hydrogen peroxide decomposition activity of manganese oxide catalysts , 1999 .

[13]  Robert Durand,et al.  Electrochemical reduction of oxygen on platinum nanoparticles in alkaline media , 1998 .

[14]  S. Suib,et al.  A Review of Porous Manganese Oxide Materials , 1998 .

[15]  T. Wen,et al.  An investigation of thermally prepared electrodes for oxygen reduction in alkaline solution , 1997 .

[16]  J. Zoval,et al.  Implementation of Electrochemically Synthesized Silver Nanocrystallites for the Preferential SERS Enhancement of Defect Modes on Thermally Etched Graphite Surfaces. , 1996, Analytical chemistry.

[17]  J. Zoval,et al.  Electrochemical Deposition of Silver Nanocrystallites on the Atomically Smooth Graphite Basal Plane , 1996 .

[18]  Robert Durand,et al.  Kinetic study of electrochemical reactions at catalyst-recast ionomer interfaces from thin active layer modelling , 1994 .

[19]  A. Arvia,et al.  Kinetics and mechanism of the electrochemical reduction of molecular oxygen on platinum in KOH: influence of preferred crystallographic orientation , 1994 .

[20]  W. Sachtler,et al.  Electron-deficient palladium clusters and bifunctional sites in zeolites , 1992 .

[21]  R. D. Venter,et al.  Electrochemical Reduction of Oxygen at Platinum Electrodes in KOH Solutions ‐ Temperature and Concentration Effects , 1986 .

[22]  K. Parida,et al.  Studies on MnO2—III. The kinetics and the mechanism for the catalytic decomposition of H2O2 over different crystalline modifications of MnO2 , 1981 .

[23]  A. Damjanović,et al.  Reaction intermediates as a controlling factor in the kinetics and mechanism of oxygen reduction at platinum electrodes , 1981 .

[24]  J. Mcbreen,et al.  The electrochemistry of -MnO2 and ?-MnO2 in alkaline electrolyte1 , 1975 .

[25]  Brian E. Conway,et al.  Modern Aspects of Electrochemistry , 1974 .

[26]  J. Goldstein,et al.  The kinetics of hydrogen peroxide decomposition catalyzed by cobalt-iron oxides , 1974 .

[27]  P. Żółtowski,et al.  Carbon-air electrode with regenerative short time overload capacity: Part 1. Effect of manganese dioxide , 1973 .

[28]  J. Giner,et al.  The Mechanism of Operation of the Teflon‐Bonded Gas Diffusion Electrode: A Mathematical Model , 1969 .

[29]  A. Damjanović,et al.  Electrode kinetics of oxygen reduction on oxide-free platinum electrodes☆ , 1967 .

[30]  A. Kozawa,et al.  The Cathodic Reduction Mechanism of Electrolytic Manganese Dioxide in Alkaline Electrolyte , 1965 .

[31]  Ralph E. White,et al.  Comprehensive Treatise of Electrochemistry , 1981 .

[32]  J. Brenet.  Electrochemical behaviour of metallic oxides , 1979 .

[33]  B. Warren,et al.  X-Ray Diffraction , 2014 .