Tunable Concave Surface Features of Mesoporous Palladium Nanocrystals Prepared from Supramolecular Micellar Templates.

Concave metallic nanocrystals with a high density of low-coordinated atoms on the surface are essential for the realization of unique catalytic properties. Herein, mesoporous palladium nanocrystals (MPNs) that possess various degrees of curvature are successfully synthesized following an approach that relies on a facile polymeric micelle assembly approach. The as-prepared MPNs exhibit larger surface areas compared to conventional Pd nanocrystals and their nonporous counterparts. The MPNs display enhanced electrocatalytic activity for ethanol oxidation when compared to state-of-the-art commercial palladium black and conventional palladium nanocubes used as catalysts. Interestingly, as the degree of curvature increases, the surface-area-normalized activity also increases, demonstrating that the curvature of MPNs and the presence of high-index facets are crucial considerations for the design of electrocatalysts.

[1]  C. Mirkin,et al.  Shape regulation of high-index facet nanoparticles by dealloying , 2019, Science.

[2]  W. El-said,et al.  Improving the electrocatalytic performance of Pd nanoparticles supported on indium/tin oxide substrates towards glucose oxidation , 2019, Applied Catalysis A: General.

[3]  Yong‐Mook Kang,et al.  Chemical Design of Palladium-Based Nanoarchitectures for Catalytic Applications. , 2019, Small.

[4]  Y. Bando,et al.  Electrochemical Synthesis of Mesoporous Au-Cu Alloy Films with Vertically Oriented Mesochannels Using Block Copolymer Micelles. , 2018, ACS applied materials & interfaces.

[5]  Younan Xia,et al.  Facile synthesis of Pd concave nanocubes: From kinetics to mechanistic understanding and rationally designed protocol , 2018, Nano Research.

[6]  Y. Yamauchi,et al.  Mesoporous Bimetallic RhCu Alloy Nanospheres Using a Sophisticated Soft-Templating Strategy , 2018 .

[7]  F. Calle‐Vallejo,et al.  Nature of Highly Active Electrocatalytic Sites for the Hydrogen Evolution Reaction at Pt Electrodes in Acidic Media , 2017, ACS omega.

[8]  Cuiling Li,et al.  Mesoporous metallic rhodium nanoparticles , 2017, Nature Communications.

[9]  Michelle L. Personick,et al.  Bimetallic Nanoparticles with Exotic Facet Structures via Iodide‐Assisted Reduction of Palladium , 2017 .

[10]  P. Sautet,et al.  Ethanol Electro-oxidation on Palladium Revisited Using Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) and Density Functional Theory (DFT): Why Is It Difficult To Break the C–C Bond? , 2016 .

[11]  Shouzhong Zou,et al.  Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials , 2015 .

[12]  M. Shao,et al.  Mechanisms of Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction on High-Index Platinum n(111)-(111) Surfaces. , 2015, The journal of physical chemistry letters.

[13]  Hyejin Chang,et al.  Concave Rhombic Dodecahedral Au Nanocatalyst with Multiple High-Index Facets for CO2 Reduction. , 2015, ACS nano.

[14]  Cuiling Li,et al.  Multimetallic Mesoporous Spheres Through Surfactant‐Directed Synthesis , 2015, Advanced science.

[15]  Y. Yoon,et al.  Anode catalysts for direct methanol fuel cells in acidic media: do we have any alternative for Pt or Pt-Ru? , 2014, Chemical reviews.

[16]  Zhong Lin Wang,et al.  Enhanced electrocatalytic activity on gold nanocrystals enclosed by high-index facets for oxygen reduction , 2014 .

[17]  C. P. Vinod,et al.  Structure sensitive chemical reactivity by palladium concave nanocubes and nanoflowers synthesised by a seed mediated procedure in aqueous medium. , 2014, Nanoscale.

[18]  Jie Ren,et al.  Electrocatalysis of Ethanol on a Pd Electrode in Alkaline Media: An in Situ Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy Study , 2014 .

[19]  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.

[20]  Aya Hitotsuyanagi,et al.  Active sites for the oxygen reduction reaction on the high index planes of Pt , 2013 .

[21]  Xun Wang,et al.  Growth of concave polyhedral Pd nanocrystals with 32 facets through in situ facet-selective etching. , 2013, ChemSusChem.

[22]  Jinlin Li,et al.  Controlled synthesis of concave tetrahedral palladium nanocrystals by reducing Pd(acac)2 with carbon monoxide , 2012 .

[23]  Song Gao,et al.  FePt concave nanocubes with enhanced methanol oxidation activity , 2012 .

[24]  C. Mirkin,et al.  Defining rules for the shape evolution of gold nanoparticles. , 2012, Journal of the American Chemical Society.

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

[26]  Xiaoping Song,et al.  A green chemical approach for preparation of PtxCuy nanoparticles with a concave surface in molten salt for methanol and formic acid oxidation reactions , 2012 .

[27]  S. Skrabalak,et al.  Octopods versus concave nanocrystals: control of morphology by manipulating the kinetics of seeded growth via co-reduction. , 2011, Nano letters.

[28]  Moon J. Kim,et al.  Synthesis of Pd-Pt bimetallic nanocrystals with a concave structure through a bromide-induced galvanic replacement reaction. , 2011, Journal of the American Chemical Society.

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

[30]  Jian Zhang,et al.  Concave cubic gold nanocrystals with high-index facets. , 2010, Journal of the American Chemical Society.

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

[32]  T. Zhao,et al.  Density Functional Theory Studies of the Structure Sensitivity of Ethanol Oxidation on Palladium Surfaces , 2010 .

[33]  Tian Ming,et al.  Growth of tetrahexahedral gold nanocrystals with high-index facets. , 2009, Journal of the American Chemical Society.

[34]  N. Zheng,et al.  Controlled formation of concave tetrahedral/trigonal bipyramidal palladium nanocrystals. , 2009, Journal of the American Chemical Society.

[35]  Y. Yamauchi,et al.  Block copolymer mediated synthesis of dendritic platinum nanoparticles. , 2009, Journal of the American Chemical Society.

[36]  Stefano de Gironcoli,et al.  QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[37]  T. Zhao,et al.  Mechanism study of the ethanol oxidation reaction on palladium in alkaline media , 2009 .

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

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

[40]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[41]  Daeha Seo,et al.  Polyhedral gold nanocrystals with O h symmetry: from octahedra to cubes. , 2006, Journal of the American Chemical Society.

[42]  T. Yokoshima,et al.  Highly ordered mesostructured Ni particles prepared from lyotropic liquid crystals by electroless deposition: the effect of reducing agents on the ordering of mesostructure , 2005 .

[43]  P. Bartlett,et al.  Electrochemical deposition of nanostructured (H1-e) layers of two metals in which pores within the two layers interconnect , 2003 .

[44]  L. Olsson,et al.  Electronic Absorption Spectra of Square-Planar Chloro-Aqua and Bromo-Aqua Complexes of Palladium(II) and Platinum(II) , 1978 .

[45]  U. Schubert,et al.  From Cubic Palladium to Concave Core-Shell Platinum Palladium Nanoparticles: Evolution of the Structure and Their Electrochemical Properties , 2018 .