Mesoporous titanium nitride supported Pt nanoparticles as high performance catalysts for methanol electrooxidation.

Mesoporous titanium nitride (TiN) with high surface area and good electrical conductivity was prepared by a novel solid-solid phase separation method from a Zn containing titanium oxide, Zn(2)TiO(4). The PXRD shows single phase rocksalt structure of TiN with a domain size of 25 nm. The conductivity of mesoporous TiN at 35 bar is 395 S cm(-1). The Pt/TiN catalyst exhibits more negative onset potential for methanol electrooxidation (0.15 V) than Pt/C (0.22 V), showing a higher intrinsic electrocatalytic activity, while its peak current density (228 mA mg(-1) Pt) is ∼1.5 times higher than that of Pt/C (148 mA mg(-1) Pt). The Pt/TiN catalyst also demonstrates excellent long-term stability. This work provides an efficient method to prepare mesoporous nitrides as a promising support towards oxidation of small organic molecules in fuel cells.

[1]  A. Fuertes Chemistry and applications of oxynitride perovskites , 2012 .

[2]  P. Bruce,et al.  Nanostructured materials for advanced energy conversion and storage devices , 2005, Nature materials.

[3]  Christoph Strunk,et al.  Superinsulator and quantum synchronization , 2008, Nature.

[4]  W. Sugimoto,et al.  Temperature dependence of the oxidation of carbon monoxide on carbon supported Pt, Ru, and PtRu , 2004 .

[5]  C. Yeh,et al.  Poly(vinylpyrrolidone)-modified graphite carbon nanofibers as promising supports for PtRu catalysts in direct methanol fuel cells. , 2007, Journal of the American Chemical Society.

[6]  L. Toth Transition Metal Carbides and Nitrides , 1971 .

[7]  S. Kaskel,et al.  Synthesis and characterisation of titanium nitride based nanoparticles , 2003 .

[8]  Lei Zhang,et al.  A review of anode catalysis in the direct methanol fuel cell , 2006 .

[9]  Francis J. DiSalvo,et al.  Recent developments in nitride chemistry , 1998 .

[10]  Changpeng Liu,et al.  Pt nanoparticles supported on WO3/C hybrid materials and their electrocatalytic activity for methanol electro-oxidation , 2011 .

[11]  Mark K. Debe,et al.  Electrocatalyst approaches and challenges for automotive fuel cells , 2012, Nature.

[12]  S. Kurtz,et al.  Chemical vapor deposition of titanium nitride at low temperatures , 1986 .

[13]  S. Kaskel,et al.  Catalytic properties of high surface area titanium nitride materials , 2004 .

[14]  H. Cesiulis,et al.  Electrocrystallization and electrodeposition of silver on titanium nitride , 2000 .

[15]  C. Bock,et al.  Size-selected synthesis of PtRu nano-catalysts: reaction and size control mechanism. , 2004, Journal of the American Chemical Society.

[16]  Chang Ming Li,et al.  PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells. , 2011, Physical chemistry chemical physics : PCCP.

[17]  Jong‐Sung Yu,et al.  Fabrication of ordered uniform porous carbon networks and their application to a catalyst supporter. , 2002, Journal of the American Chemical Society.

[18]  Changpeng Liu,et al.  Enhanced activity of Pt nano-crystals supported on a novel TiO2@N-doped C nano-composite for methanol oxidation reaction , 2012 .

[19]  Wenzheng Li,et al.  Titanium nitride nanoparticles based electrocatalysts for proton exchange membrane fuel cells , 2009 .

[20]  E. Kierzek-Pecold,et al.  Vapour-phase crystallization and some physical properties of titanium nitride , 1971 .

[21]  R. Pecenka,et al.  Structural, compositional, optical and colorimetric characterization of TiN-nanoparticles , 2004 .

[22]  K. Pfaffinger,et al.  Structure and Strength Effects in CVD Titanium Carbide and Titanium Nitride Coatings , 1976 .

[23]  A. Karma,et al.  Evolution of nanoporosity in dealloying , 2001, Nature.

[24]  M. Antonietti,et al.  High-surface-area TiO2 and TiN as catalysts for the C-C coupling of alcohols and ketones. , 2008, ChemSusChem.

[25]  M. Yin,et al.  Recent advances in catalysts for direct methanol fuel cells , 2011 .

[26]  Chang Ming Li,et al.  Highly dispersed MoO(x) on carbon nanotube as support for high performance Pt catalyst towards methanol oxidation. , 2011, Chemical communications.

[27]  R. Gordon,et al.  Synthesis of thin films by atmospheric pressure chemical vapor deposition using amido and imido titanium(IV) compounds as precursors , 1990 .

[28]  Richard G Compton,et al.  Metal nanoparticles and related materials supported on carbon nanotubes: methods and applications. , 2006, Small.

[29]  W. Sugimoto,et al.  Effect of Structure of Carbon‐Supported PtRu Electrocatalysts on the Electrochemical Oxidation of Methanol , 2000 .

[30]  R. Gordon,et al.  Chemical vapor deposition of titanium, zirconium, and hafnium nitride thin films , 1991 .

[31]  T. Su,et al.  Electrodeposition of platinum metal on TiN thin films , 2005 .

[32]  M. Roldan,et al.  Carbothermal synthesis of titanium nitride (TiN) : Kinetics and mechanism , 2005 .

[33]  Minghui Yang,et al.  Mesoporous vanadium nitride as a high performance catalyst support for formic acid electrooxidation. , 2012, Chemical communications.

[34]  Yan-Jie Wang,et al.  Noncarbon support materials for polymer electrolyte membrane fuel cell electrocatalysts. , 2011, Chemical reviews.

[35]  Alejandro A. Franco,et al.  Impact of carbon monoxide on PEFC catalyst carbon support degradation under current-cycled operating conditions , 2009 .

[36]  M. Winter,et al.  What are batteries, fuel cells, and supercapacitors? , 2004, Chemical reviews.

[37]  D. Pantea,et al.  Electrical conductivity of thermal carbon blacks: Influence of surface chemistry , 2001 .

[38]  F. Hahn,et al.  In situ FTIRS study of the electrocatalytic oxidation of carbon monoxide and methanol at platinum–ruthenium bulk alloy electrodes , 1998 .