Efficient noble metal-free (electro)catalysis of water and alcohol oxidations by zinc-cobalt layered double hydroxide.

Replacing rare and expensive noble metal catalysts with inexpensive and earth-abundant ones for various renewable energy-related chemical processes as well as for production of high value chemicals is one of the major goals of sustainable chemistry. Herein we show that a bimetallic Zn-Co layered double hydroxide (Zn-Co-LDH) can serve as an efficient electrocatalyst and catalyst for water and alcohol oxidation, respectively. In the electrochemical water oxidation, the material exhibits a lower overpotential, by ~100 mV, than monometallic Co-based solid-state materials (e.g., Co(OH)2 and Co3O4)-catalytic systems that were recently reported to be effective for this reaction. Moreover, the material's turnover frequency (TOF) per Co atoms is >10 times as high as those of the latter at the same applied potentials. The Zn-Co-LDH also catalyzes oxidation of alcohols to the corresponding aldehydes or ketones at relatively low temperature, with moderate to high conversion and excellent selectivity.

[1]  S. Fukuzumi,et al.  Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer. , 2010, Nature chemistry.

[2]  R. Bullock Catalysis without precious metals , 2010 .

[3]  Philipp Kurz,et al.  Calcium manganese(III) oxides (CaMn2O4.xH2O) as biomimetic oxygen-evolving catalysts. , 2010, Angewandte Chemie.

[4]  J. Barber Photosynthetic energy conversion: natural and artificial. , 2009, Chemical Society reviews.

[5]  T. Mallouk,et al.  Kinetics of Electron Transfer and Oxygen Evolution in the Reaction of [Ru(bpy)3]3+ with Colloidal Iridium Oxide , 2004 .

[6]  H. García,et al.  Layered double hydroxides as highly efficient photocatalysts for visible light oxygen generation from water. , 2009, Journal of the American Chemical Society.

[7]  Thomas E Mallouk,et al.  Design and development of photoanodes for water-splitting dye-sensitized photoelectrochemical cells. , 2013, Chemical Society reviews.

[8]  T. Mallouk,et al.  Photocatalytic Water Oxidation in a Buffered Tris(2,2‘-bipyridyl)ruthenium Complex-Colloidal IrO2 System , 2000 .

[9]  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.

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

[11]  Kazuhito Hashimoto,et al.  Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO2 electrocatalysts. , 2012, Journal of the American Chemical Society.

[12]  Qiushi Yin,et al.  A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals , 2010, Science.

[13]  Hong Lin,et al.  Co-Ni layered double hydroxides for water oxidation in neutral electrolyte. , 2013, Physical chemistry chemical physics : PCCP.

[14]  E. Garrone,et al.  CoAPO5 as a water oxidation catalyst and a light sensitizer. , 2012, Chemical communications.

[15]  Zhen He,et al.  Electrodeposition of Crystalline Co3O4—A Catalyst for the Oxygen Evolution Reaction , 2012 .

[16]  David M. Robinson,et al.  Water oxidation by lambda-MnO2: catalysis by the cubical Mn4O4 subcluster obtained by delithiation of spinel LiMn2O4. , 2010, Journal of the American Chemical Society.

[17]  David M. Robinson,et al.  Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis. , 2013, Journal of the American Chemical Society.

[18]  M. Risch,et al.  Cobalt-oxo core of a water-oxidizing catalyst film. , 2009, Journal of the American Chemical Society.

[19]  Matthew W Kanan,et al.  Mechanistic studies of the oxygen evolution reaction by a cobalt-phosphate catalyst at neutral pH. , 2010, Journal of the American Chemical Society.

[20]  Thomas E. Mallouk,et al.  Photocatalytic water oxidation by Nafion-stabilized iridium oxide colloids , 2000 .

[21]  M. A. Woo,et al.  Mixed valence Zn–Co-layered double hydroxides and their exfoliated nanosheets with electrode functionality , 2011 .

[22]  H. Dau,et al.  Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion , 2012 .

[23]  A. Baiker,et al.  Oxidation of alcohols with molecular oxygen on solid catalysts. , 2004, Chemical reviews.

[24]  W. Casey,et al.  A (31) P NMR investigation of the CoPi water-oxidation catalyst. , 2012, Chemistry.

[25]  J. Kang,et al.  Titanium-embedded layered double hydroxides as highly efficient water oxidation photocatalysts under visible light , 2011 .

[26]  Emily Y. Tsui,et al.  A Synthetic Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II , 2011, Science.

[27]  F. Jiao,et al.  Nanostructured cobalt oxide clusters in mesoporous silica as efficient oxygen-evolving catalysts. , 2009, Angewandte Chemie.

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

[29]  A. Bell,et al.  Size-Dependent Activity of Co 3 O 4 Nanoparticle Anodes for Alkaline Water Electrolysis , 2009 .

[30]  D. Nocera,et al.  Bidirectional and unidirectional PCET in a molecular model of a cobalt-based oxygen-evolving catalyst. , 2011, Journal of the American Chemical Society.

[31]  A. Bell,et al.  Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen. , 2011, Journal of the American Chemical Society.

[32]  David M. Robinson,et al.  A Co4O4 "cubane" water oxidation catalyst inspired by photosynthesis. , 2011, Journal of the American Chemical Society.

[33]  P. Liu,et al.  Aerobic oxidation of alcohols over hydrotalcite-supported gold nanoparticles: the promotional effect of transition metal cations. , 2011, Chemical communications.

[34]  M. Bauer,et al.  New spinel oxide catalysts for visible-light-driven water oxidation , 2012 .

[35]  J. Goodenough,et al.  A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles , 2011, Science.

[36]  T. Mallouk,et al.  Soft Chemical Conversion of Layered Double Hydroxides to Superparamagnetic Spinel Platelets , 2008 .

[37]  David M. Robinson,et al.  Structural requirements in lithium cobalt oxides for the catalytic oxidation of water. , 2012, Angewandte Chemie.

[38]  Elizabeth C. Landis,et al.  Fluoride-modulated cobalt catalysts for electrochemical oxidation of water under non-alkaline conditions. , 2010, ChemSusChem.