Electrodeposition of Crystalline Co3O4—A Catalyst for the Oxygen Evolution Reaction

Crystalline films of Co3O4 are deposited by electrochemically oxidizing a tartrate complex of Co2+ in an aqueous, alkaline solution at elevated temperatures. The crystallinity and stability of the films are a strong function of the deposition temperature. Films deposited at temperatures from 50 to 90 °C are amorphous, but films deposited from refluxing solution at 103 °C are crystalline. The crystalline films adhere strongly to the substrate, whereas the amorphous films peel off of the substrate when dried due to drying stresses. The crystalline films deposit with the normal spinel structure, with a lattice parameter of 0.8097 nm and crystallite size of 26 nm. The catalytic activity of Co3O4 for the oxygen evolution reaction (OER) of the crystalline and amorphous films is compared by Tafel analysis in alkaline solution at pH 14. The crystalline Co3O4 film has a Tafel slope of 49 mV/decade and an exchange current density of 2.0 × 10–10 A cm–2, whereas an amorphous film deposited at 50 °C has a Tafel slope ...

[1]  J. Switzer.  The n‐Silicon/Thallium(III) Oxide Heterojunction Photoelectrochemical Solar Cell , 1986 .

[2]  M. Langell,et al.  Surface composition and structure of Co3O4(110) and the effect of impurity segregation , 2004 .

[3]  Ravindra Singh,et al.  Electrochemical Studies on Protective Thin Co3 O 4 and NiCo2 O 4 Films Prepared on Titanium by Spray Pyrolysis for Oxygen Evolution , 1990 .

[4]  Yohan Park,et al.  Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation. , 2011, Nature materials.

[5]  A. Bard,et al.  Dynamic potential–pH diagrams application to electrocatalysts for water oxidation , 2012 .

[6]  O. Petrii,et al.  Real surface area measurements in electrochemistry , 1991 .

[7]  Kyoo-Seung Han,et al.  Effect of 20°–200oC Fabrication Temperature on Microstructure of Hydrothermally Prepared LiCoO2 Films , 2004 .

[8]  M. Yoshimura,et al.  Preparation of BaTiO3 Thin Film by Hydrothermal Electrochemical Method , 1989 .

[9]  Jay A. Switzer,et al.  Epitaxial Electrodeposition of Zinc Oxide Nanopillars on Single-Crystal Gold , 2001 .

[10]  M. Yoshimura,et al.  In situ fabrication of morphology-controlled advanced ceramic materials by Soft Solution Processing , 1997 .

[11]  James R. McKone,et al.  Solar water splitting cells. , 2010, Chemical reviews.

[12]  J. L. Gautier,et al.  Thin films of Co3O4 and NiCo2O4 obtained by the method of chemical spray pyrolysis for electrocatalysis III. The electrocatalysis of oxygen evolution , 1990 .

[13]  Daniel G. Nocera,et al.  In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+ , 2008, Science.

[14]  Efficient photocatalytic degradation of phenol over Co3O4/BiVO4 composite under visible light irradiation. , 2006, The journal of physical chemistry. B.

[15]  Saurabh Singh,et al.  Preparation of thin Co3O4 films on Ni and their electrocatalytic surface properties towards oxygen evolution , 1996 .

[16]  D. Gamelin,et al.  Photoelectrochemical water oxidation by cobalt catalyst ("Co-Pi")/alpha-Fe(2)O(3) composite photoanodes: oxygen evolution and resolution of a kinetic bottleneck. , 2010, Journal of the American Chemical Society.

[17]  J. R. Vilche,et al.  Oxygen evolution on electrodeposited cobalt oxides , 1998 .

[18]  J. Switzer,et al.  Epitaxial Electrodeposition of Tin(II) Sulfide Nanodisks on Single-Crystal Au(100) , 2008 .

[19]  S. Trasatti.  Electrocatalysis in the anodic evolution of oxygen and chlorine , 1984 .

[20]  M. Yoshimura,et al.  Direct preparation of BaTiO3 powders from titanium metal by anodic oxidation under hydrothermal conditions , 1989 .

[21]  A. Fujishima,et al.  Electrochemical behavior of cobalt oxide films deposited at conductive diamond electrodes , 2003 .

[22]  J. Yang,et al.  Hierarchically porous Co3O4 film with mesoporous walls prepared via liquid crystalline template for supercapacitor application , 2011 .

[23]  I. Casella.  Electrodeposition of cobalt oxide films from carbonate solutions containing Co(II)–tartrate complexes , 2002 .

[24]  Xianglan Xu,et al.  Bulk and surface properties of spinel Co3O4 by density functional calculations , 2009 .

[25]  J. Switzer,et al.  Epitaxial electrodeposition of Fe(3)O(4) thin films on the low-index planes of gold. , 2002, Journal of the American Chemical Society.

[26]  Shumsky,et al.  Electrodeposited ceramic single crystals , 1999, Science.

[27]  K. Ogura,et al.  Electrochemical Deposition of Spinel-Type Cobalt Oxide from Alkaline Solution of Co2 + with Glycine , 2002 .

[28]  S. G. Kandalkar,et al.  Synthesis of cobalt oxide interconnected flacks and nano-worms structures using low temperature chemical bath deposition , 2009 .

[29]  S. Trasatti,et al.  Electrochemical surface properties of Co3O4 electrodes , 1987 .

[30]  X. Xia,et al.  Pseudocapacitive properties of electrodeposited porous nanowall Co3O4 film , 2011 .

[31]  Qing Peng,et al.  Selective synthesis of Co3O4 nanocrystal with different shape and crystal plane effect on catalytic property for methane combustion. , 2008, Journal of the American Chemical Society.

[32]  Wenjie Shen,et al.  Low-temperature oxidation of CO catalysed by Co3O4 nanorods , 2009, Nature.

[33]  Hartmut Wendt,et al.  Materials research and development of electrocatalysts for alkaline water electrolysis , 1989 .

[34]  I. Casella,et al.  Anodic electrodeposition of cobalt oxides from an alkaline bath containing Co-gluconate complexes on glassy carbon. An electroanalytical investigation , 2011 .

[35]  M. Yoshimura,et al.  A solution flow system for hydrothermal–electrochemical growth of multilayered thin films , 1999 .

[36]  Jun Zhang,et al.  Cobalt Oxide Ordered Bowl-Like Array Films Prepared by Electrodeposition through Monolayer Polystyrene Sphere Template and Electrochromic Properties , 2010 .

[37]  W. Casey,et al.  Electrochemical water oxidation with cobalt-based electrocatalysts from pH 0-14: the thermodynamic basis for catalyst structure, stability, and activity. , 2011, Journal of the American Chemical Society.

[38]  E. B. Castro,et al.  Electrodeposited Ni–Co-oxide electrodes:characterization and kinetics of the oxygen evolution reaction , 2000 .