Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrodes.

Hybrid porous nanowire arrays composed of strongly interacting Co3O4 and carbon were prepared by a facile carbonization of the metal-organic framework grown on Cu foil. The resulting material, possessing a high surface area of 251 m(2) g(-1) and a large carbon content of 52.1 wt %, can be directly used as the working electrode for oxygen evolution reaction without employing extra substrates or binders. This novel oxygen evolution electrode can smoothly operate in alkaline solutions (e.g., 0.1 and 1.0 M KOH), affording a low onset potential of 1.47 V (vs reversible hydrogen electrode) and a stable current density of 10.0 mA cm(-2) at 1.52 V in 0.1 M KOH solution for at least 30 h, associated with a high Faradaic efficiency of 99.3%. The achieved ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the state-of-the-art noble-metal/transition-metal and nonmetal catalysts, originate from the unique nanowire array electrode configuration and in situ carbon incorporation, which lead to the large active surface area, enhanced mass/charge transport capability, easy release of oxygen gas bubbles, and strong structural stability. Furthermore, the hybrid Co3O4-carbon porous nanowire arrays can also efficiently catalyze oxygen reduction reaction, featuring a desirable four-electron pathway for reversible oxygen evolution and reduction, which is potentially useful for rechargeable metal-air batteries, regenerative fuel cells, and other important clean energy devices.

[1]  Yi Cui,et al.  CoSe2 nanoparticles grown on carbon fiber paper: an efficient and stable electrocatalyst for hydrogen evolution reaction. , 2014, Journal of the American Chemical Society.

[2]  W. Schuhmann,et al.  Eine Stickstoff‐dotierte Kohlenstoffmatrix mit eingeschlossenen MnxOy/NC‐ und CoxOy/NC‐Nanopartikeln für leistungsfähige bifunktionale Sauerstoffelektroden , 2014 .

[3]  Song Jin,et al.  High-performance electrocatalysis using metallic cobalt pyrite (CoS₂) micro- and nanostructures. , 2014, Journal of the American Chemical Society.

[4]  Akihiko Hirata,et al.  Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors. , 2011, Nature nanotechnology.

[5]  F. Du,et al.  Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction , 2009, Science.

[6]  L. Wan,et al.  ITO@Cu2S tunnel junction nanowire arrays as efficient counter electrode for quantum-dot-sensitized solar cells. , 2014, Nano letters.

[7]  T. Jaramillo,et al.  Meso-structured platinum thin films: active and stable electrocatalysts for the oxygen reduction reaction. , 2012, Journal of the American Chemical Society.

[8]  Mietek Jaroniec,et al.  Graphitic carbon nitride nanosheet-carbon nanotube three-dimensional porous composites as high-performance oxygen evolution electrocatalysts. , 2014, Angewandte Chemie.

[9]  M. Fontecave,et al.  Splitting water with cobalt. , 2011, Angewandte Chemie.

[10]  Zhixiang Wei,et al.  Conducting polymer nanowire arrays for high performance supercapacitors. , 2014, Small.

[11]  G. K. Pradhan,et al.  Hydrated manganese(II) phosphate (Mn₃(PO₄)₂·3H₂O) as a water oxidation catalyst. , 2014, Journal of the American Chemical Society.

[12]  Si Hyoung Oh,et al.  Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries. , 2012, Nature chemistry.

[13]  Li-Jun Wan,et al.  Nanocarbon networks for advanced rechargeable lithium batteries. , 2012, Accounts of chemical research.

[14]  Xin-bo Zhang,et al.  An efficient three-dimensional oxygen evolution electrode. , 2013, Angewandte Chemie.

[15]  Yong Zhao,et al.  Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation , 2013, Nature Communications.

[16]  Xingcheng Xiao,et al.  Multifunctional TiO2-C/MnO2 core-double-shell nanowire arrays as high-performance 3D electrodes for lithium ion batteries. , 2013, Nano letters.

[17]  Hong Lin,et al.  Core–Ring Structured NiCo2O4 Nanoplatelets: Synthesis, Characterization, and Electrocatalytic Applications , 2008 .

[18]  Ioannis Katsounaros,et al.  Oxygen electrochemistry as a cornerstone for sustainable energy conversion. , 2014, Angewandte Chemie.

[19]  Hongsen Li,et al.  Mesoporous NiCo2O4 Nanowire Arrays Grown on Carbon Textiles as Binder‐Free Flexible Electrodes for Energy Storage , 2014 .

[20]  Juan Herranz,et al.  Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells. , 2011, Nature communications.

[21]  Guangyuan Zheng,et al.  Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction , 2014, Nature Communications.

[22]  Jun Chen,et al.  Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts. , 2012, Chemical Society reviews.

[23]  Charles C. L. McCrory,et al.  Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. , 2013, Journal of the American Chemical Society.

[24]  X. Lou,et al.  Mixed transition-metal oxides: design, synthesis, and energy-related applications. , 2014, Angewandte Chemie.

[25]  Kyoung-Shin Choi,et al.  Nanoporous BiVO4 Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting , 2014, Science.

[26]  Yiying Wu,et al.  NixCo3−xO4 Nanowire Arrays for Electrocatalytic Oxygen Evolution , 2010, Advanced materials.

[27]  Tom Regier,et al.  Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. , 2011, Nature materials.

[28]  Y. Shao-horn,et al.  Synthesis and Activities of Rutile IrO2 and RuO2 Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions. , 2012, The journal of physical chemistry letters.

[29]  Jun Chen,et al.  Hydrogenated Uniform Pt Clusters Supported on Porous CaMnO3 as a Bifunctional Electrocatalyst for Enhanced Oxygen Reduction and Evolution , 2014, Advanced materials.

[30]  M. Beller,et al.  Convenient and mild epoxidation of alkenes using heterogeneous cobalt oxide catalysts. , 2014, Angewandte Chemie.

[31]  Vincent Artero,et al.  Wasserspaltung mit Cobalt , 2011 .

[32]  Moreno de Respinis,et al.  Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst. , 2014, Nature chemistry.

[33]  Jian Jiang,et al.  Recent Advances in Metal Oxide‐based Electrode Architecture Design for Electrochemical Energy Storage , 2012, Advanced materials.

[34]  Tewodros Asefa,et al.  Efficient noble metal-free (electro)catalysis of water and alcohol oxidations by zinc-cobalt layered double hydroxide. , 2013, Journal of the American Chemical Society.

[35]  Shun Mao,et al.  High-performance bi-functional electrocatalysts of 3D crumpled graphene–cobalt oxide nanohybrids for oxygen reduction and evolution reactions , 2014 .

[36]  Dingshan Yu,et al.  Nitrogen-doped graphene/carbon nanotube hybrids: in situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction. , 2014, Small.

[37]  Jun Jiang,et al.  Water oxidation electrocatalyzed by an efficient Mn3O4/CoSe2 nanocomposite. , 2012, Journal of the American Chemical Society.

[38]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[39]  J. Kaduk,et al.  Salts of aromatic carboxylates: the crystal structures of nickel(II) and cobalt(II) 2,6-naphthalenedicarboxylate tetrahydrate , 2001 .

[40]  Tom Regier,et al.  An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation. , 2013, Journal of the American Chemical Society.

[41]  H. Zeng,et al.  Preparation of nanocomposites of metals, metal oxides, and carbon nanotubes via self-assembly. , 2007, Journal of the American Chemical Society.

[42]  Abdullah M. Asiri,et al.  Self-supported nanoporous cobalt phosphide nanowire arrays: an efficient 3D hydrogen-evolving cathode over the wide range of pH 0-14. , 2014, Journal of the American Chemical Society.

[43]  Zheng Chang,et al.  Hierarchical ZnxCo3–xO4 Nanoarrays with High Activity for Electrocatalytic Oxygen Evolution , 2014 .

[44]  Yinyi Gao,et al.  Oxygen evolution reaction on Ni-substituted Co 3O 4 nanowire array electrodes , 2011 .

[45]  C. Berlinguette,et al.  Water oxidation catalysis: electrocatalytic response to metal stoichiometry in amorphous metal oxide films containing iron, cobalt, and nickel. , 2013, Journal of the American Chemical Society.

[46]  D. Gu,et al.  Synthesis of non-siliceous mesoporous oxides. , 2014, Chemical Society reviews.

[47]  Linda F. Nazar,et al.  Bi-Functional N-Doped CNT/Graphene Composite as Highly Active and Durable Electrocatalyst for Metal Air Battery Applications , 2013 .

[48]  Ja-Yeon Choi,et al.  Advanced Extremely Durable 3D Bifunctional Air Electrodes for Rechargeable Zinc‐Air Batteries , 2014 .

[49]  Changzhou Yuan,et al.  Gemischte Übergangsmetalloxide: Design, Synthese und energierelevante Anwendungen , 2014 .

[50]  Yi Xie,et al.  Co3O4 nanocrystals on single-walled carbon nanotubes as a highly efficient oxygen-evolving catalyst , 2012, Nano Research.

[51]  Maria Chan,et al.  Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. , 2012, Nature materials.

[52]  H. Over.  Surface chemistry of ruthenium dioxide in heterogeneous catalysis and electrocatalysis: from fundamental to applied research. , 2012, Chemical reviews.

[53]  X. Lou,et al.  Growth of ultrathin mesoporous Co3O4 nanosheet arrays on Ni foam for high-performance electrochemical capacitors , 2012 .

[54]  N. Guillet,et al.  Electrochemical activity of ruthenium and iridium based catalysts for oxygen evolution reaction , 2012 .

[55]  Qiang Xu,et al.  Functional materials derived from open framework templates/precursors: synthesis and applications , 2014 .

[56]  W. Schuhmann,et al.  Mn(x)O(y)/NC and Co(x)O(y)/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes. , 2014, Angewandte Chemie.