Urea hydrogen bond donor-mediated synthesis of high-index faceted platinum concave nanocubes grown on multi-walled carbon nanotubes and their enhanced electrocatalytic activity.

We have reported, for the first time, in situ growth of high-index {hk0} faceted concave Pt nanocubes on multi-walled carbon nanotubes (CNTs) via an electrochemical method in choline chloride-urea (ChCl-U) based deep eutectic solvents (DESs). Mechanistic studies indicate that a urea hydrogen bond donor (HBD) plays a key role in the formation of concave Pt nanocubes, in which the urea HBD preferentially adsorbs onto the {100} faces and blocks the growth of nanocrystals along the 〈100〉 axis. The as-prepared concave Pt nanocubes are characterized to be enclosed mainly with high-index {710}, {610} and {510} facets. It has been determined that the concave cubic Pt/CNT exhibits higher catalytic activity and stability than the flower-like Pt/CNT and commercial Pt/C catalysts, and this is ascribed to its high density of surface atomic steps and the synergistic effect between the CNT and Pt nanocubes.

[1]  Shigang Sun,et al.  Hydrogen adsorption-mediated synthesis of concave Pt nanocubes and their enhanced electrocatalytic activity. , 2016, Nanoscale.

[2]  Shigang Sun,et al.  Electrochemically Seed-Mediated Synthesis of Sub-10 nm Tetrahexahedral Pt Nanocrystals Supported on Graphene with Improved Catalytic Performance. , 2016, Journal of the American Chemical Society.

[3]  Ling Huang,et al.  Structure Design and Performance Tuning of Nanomaterials for Electrochemical Energy Conversion and Storage. , 2016, Accounts of Chemical Research.

[4]  P. Serp,et al.  Carbon nanotubes and nanofibers in catalysis , 2003 .

[5]  E. Antolini.  Catalysts for direct ethanol fuel cells , 2007 .

[6]  Jing Zhuang,et al.  Glycine-mediated syntheses of Pt concave nanocubes with high-index {hk0} facets and their enhanced electrocatalytic activities. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[7]  A. Abbott,et al.  Application of hole theory to define ionic liquids by their transport properties. , 2007, The journal of physical chemistry. B.

[8]  David L Davies,et al.  Novel solvent properties of choline chloride/urea mixtures. , 2003, Chemical communications.

[9]  Chang Liu,et al.  A review of carbon nanotube- and graphene-based flexible thin-film transistors. , 2013, Small.

[10]  A. Abbott,et al.  Double layer effects on metal nucleation in deep eutectic solvents. , 2011, Physical chemistry chemical physics : PCCP.

[11]  Zhong Lin Wang,et al.  Synthesis of Tetrahexahedral Platinum Nanocrystals with High-Index Facets and High Electro-Oxidation Activity , 2007, Science.

[12]  T. White,et al.  Electrocatalytic Activity and Interconnectivity of Pt Nanoparticles on Multiwalled Carbon Nanotubes for Fuel Cells , 2009 .

[13]  Zhi-You Zhou,et al.  Electrochemically shape-controlled synthesis in deep eutectic solvents-A new route to prepare Pt nanocrystals enclosed by high-index facets with high catalytic activity , 2012 .

[14]  Z. Tian,et al.  Selective heterogeneous nucleation and growth of size-controlled metal nanoparticles on carbon nanotubes in solution. , 2006, Chemistry.

[15]  Zhi-You Zhou,et al.  Synthesis of convex hexoctahedral Pt micro/nanocrystals with high-index facets and electrochemistry-mediated shape evolution. , 2013, Journal of the American Chemical Society.

[16]  M. J. Weaver,et al.  Real-time FTIR spectroscopy as an electrochemical mechanistic probe: Electrooxidation of ethanol and related species on well-defined Pt (111) surfaces , 1989 .

[17]  Lan-sun Zheng,et al.  Facile syntheses and enhanced electrocatalytic activities of Pt nanocrystals with {hkk} high-index surfaces , 2012, Nano Research.

[18]  B. Pollet,et al.  Support materials for PEMFC and DMFC electrocatalysts—A review , 2012 .

[19]  Qiang Wang,et al.  High-index faceted platinum nanocrystals supported on carbon black as highly efficient catalysts for ethanol electrooxidation. , 2010, Angewandte Chemie.

[20]  San Ping Jiang,et al.  Prospects of Fuel Cell Technologies , 2017 .

[21]  L. Liz‐Marzán,et al.  Highly Catalytic Single-Crystal Dendritic Pt Nanostructures Supported on Carbon Nanotubes , 2009 .

[22]  David A. Leigh,et al.  Cover Picture: Light‐Driven Transport of a Molecular Walker in Either Direction along a Molecular Track (Angew. Chem. Int. Ed. 1/2011) , 2011 .

[23]  Shigang Sun,et al.  Seeds and Potentials Mediated Synthesis of High-Index Faceted Gold Nanocrystals with Enhanced Electrocatalytic Activities. , 2017, Langmuir : the ACS journal of surfaces and colloids.

[24]  Hui Zhang,et al.  Palladium concave nanocubes with high-index facets and their enhanced catalytic properties. , 2011, Angewandte Chemie.

[25]  Shigang Sun,et al.  Shape Evolution of Platinum Nanocrystals by Electrochemistry , 2014 .

[26]  N. Zheng,et al.  Amine-assisted synthesis of concave polyhedral platinum nanocrystals having {411} high-index facets. , 2011, Journal of the American Chemical Society.

[27]  Ermete Antolini,et al.  Alkaline direct alcohol fuel cells , 2010 .

[28]  Lu Wei,et al.  Electrochemically shape-controlled synthesis in deep eutectic solvents: triambic icosahedral platinum nanocrystals with high-index facets and their enhanced catalytic activity. , 2013, Chemical communications.

[29]  Hui Zhang,et al.  Noble-metal nanocrystals with concave surfaces: synthesis and applications. , 2012, Angewandte Chemie.

[30]  N. Rösch,et al.  Theoretical study of the adsorption of urea related species on Pt(100) electrodes. , 2001 .

[31]  Jin Wang,et al.  Multi-walled carbon nanotube supported Pd nanocubes with enhanced electrocatalytic activity , 2016 .

[32]  S. Karthikeyan,et al.  Pt–WO3 supported on carbon nanotubes as possible anodes for direct methanol fuel cells , 2002 .

[33]  F. Mjalli,et al.  Phosphonium-Based Ionic Liquids Analogues and Their Physical Properties , 2010 .

[34]  A. Aldaz,et al.  On the Electrochemical and in-Situ Fourier Transform Infrared Spectroscopy Characterization of Urea Adlayers at Pt(100) Electrodes , 1997 .

[35]  V. Del Colle,et al.  Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: electrochemical and spectroscopic studies. , 2008, Physical chemistry chemical physics : PCCP.

[36]  D. Tang,et al.  High-index {hk0} faceted platinum concave nanocubes with enhanced peroxidase-like activity for an ultrasensitive colorimetric immunoassay of the human prostate-specific antigen. , 2017, The Analyst.

[37]  C. R. Raj,et al.  Facile In Situ Synthesis of Multiwall Carbon Nanotube Supported Flowerlike Pt Nanostructures: An Efficient Electrocatalyst for Fuel Cell Application , 2010 .

[38]  Youjun Fan,et al.  Highly dispersed Pt nanoparticles supported on manganese oxide–poly(3,4-ethylenedioxythiophene)–carbon nanotubes composite for enhanced methanol electrooxidation , 2013 .

[39]  Na Tian,et al.  Electrochemically shape-controlled synthesis of trapezohedral platinum nanocrystals with high electrocatalytic activity. , 2012, Chemical communications.

[40]  Shigang Sun,et al.  Electrochemically Shape-Controlled Synthesis of Pd Concave-Disdyakis Triacontahedra in Deep Eutectic Solvent , 2016 .

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

[42]  Shigang Sun,et al.  Direct electrodeposition of tetrahexahedral Pd nanocrystals with high-index facets and high catalytic activity for ethanol electrooxidation. , 2010, Journal of the American Chemical Society.

[43]  Raymond K. Rasheed,et al.  Deep eutectic solvents formed between choline chloride and carboxylic acids: versatile alternatives to ionic liquids. , 2004, Journal of the American Chemical Society.

[44]  Zhi-You Zhou,et al.  Nanoparticle catalysts with high energy surfaces and enhanced activity synthesized by electrochemical method. , 2008, Faraday discussions.

[45]  Shigang Sun,et al.  Overpotential-dependent shape evolution of gold nanocrystals grown in a deep eutectic solvent , 2016, Nano Research.