Electroactivity of cobalt and nickel glyoximes with regard to the electro-reduction of protons into molecular hydrogen in acidic media

Water electrolysis is a key technological process for the production of hydrogen and the storage of intermittent and renewable energy sources. For domestic applications, the proton exchange membrane (PEM) process provides a safe and efficient way to split water into molecular hydrogen and oxygen but this technology, which requires platinum family electro-catalysts, remains too expensive. Molecular chemistry offers new opportunities for synthesizing alternative low-cost compounds, sufficiently stable in strong acidic media. In this paper, results obtained with different nickel and cobalt glyoximes are presented. They have been chemically (using UV–visible spectroscopy) and electrochemically (using cyclic voltammetry and spectro-electrochemistry) characterized. Their ability to electroreduce protons into molecular hydrogen from aqueous acidic solutions is discussed, the compounds being either dissolved in solution or immobilized at the surface of a solid electrode using recast Nafion® films in view of PEM applications.

[1]  D. Lexa,et al.  Low temperature spectroelectrochemistry for the characterization of highly reduced σ-alkyl iron halogenated porphyrins , 1996 .

[2]  M. Kaneko,et al.  pH-dependent electrocatalysis for proton reduction by bis(2,2' :6', 2-terpyridine) cobalt(II) complex embedded in Nafion® membrane , 2001 .

[3]  J. Sauvage,et al.  Electrocatalytic properties of (tetraazacyclotetradecane)nickel(2+) and Ni2(biscyclam)4+ with respect to carbon dioxide and water reduction , 1988 .

[4]  U. Koelle.  TRANSITION METAL CATALYZED PROTON REDUCTION , 1992 .

[5]  A. Bakac,et al.  Unimolecular and bimolecular homolytic reactions of organochromium and organocobalt complexes. Kinetics and equilibria , 1984 .

[6]  J. Espenson,et al.  Cobalt-catalyzed evolution of molecular hydrogen , 1986 .

[7]  D. Busch,et al.  Oxidation and reduction behavior of macrocyclic complexes of nickel. Electrochemical and electron spin resonance studies , 1974 .

[8]  R. Gagne,et al.  One-electron-reduced nickel(II)-macrocyclic ligand complexes. Four-coordinate nickel(I) species and nickel(II)-ligand radical species which form paramagnetic, five-coordinate nickel(I) adducts , 1981 .

[9]  G. Grynkewich,et al.  Rational synthesis of unidimensional mixed valence solids. Structural, spectral, and electrical studies of charge distribution and transport in partially oxidized nickel and palladium bisdiphenylglyoximates , 1979 .

[10]  T. Alleau,et al.  Characterization of membrane-electrode assemblies for solid polymer electrolyte water electrolysis , 1993 .

[11]  Y. Nonaka,et al.  The electrochemical behavior of BR2-linked bis(glyoximato)nickel(II) complexes in a nonaqueous solvent. , 1985 .

[12]  T. Spiro,et al.  Cobalt(I) porphyrin catalysis of hydrogen production from water , 1985 .

[13]  R. Gagne,et al.  Intramolecular electron transfer and valence isomerization in mononuclear nickel-macrocyclic ligand complexes: formation of paramagnetic nickel(I)-carbonyl complexes , 1980 .

[14]  G. Schrauzer.  Chemie der Metall-Koordinationsverbindungen, I. Reaktion von Bis-dimethylglyoxim-nickel mit Borverbindungen , 1962 .

[15]  J. Fauvarque,et al.  Comparative study of protonic conducting polymers incorporated in the oxygen electrode of the PEMFC , 2005 .

[16]  J. Savéant,et al.  Homogeneous redox catalysis of electrochemical reactions: Part V. Cyclic voltammetry , 1980 .

[17]  J. Savéant,et al.  Homogeneous Catalysis of Electrochemical Hydrogen Evolution by Iron(0) Porphyrins , 1996 .

[18]  W. T. Grubb.  Batteries with Solid Ion Exchange Electrolytes I . Secondary Cells Employing Metal Electrodes , 1959 .

[19]  Pierre Millet,et al.  Design and performance of a solid polymer electrolyte water electrolyzer , 1996 .

[20]  A. Bard,et al.  Heterogeneous Photocatalytic Preparation of Supported Catalysts. Photodeposition of Platinum on TiO2 Powder and Other Substrates , 1978 .

[21]  A. Bakac,et al.  Characterization of the structure, properties, and reactivity of a cobalt(II) macrocyclic complex , 1986 .

[22]  M. Fontecave,et al.  Proton electroreduction catalyzed by cobaloximes: functional models for hydrogenases. , 2005, Inorganic chemistry.