Heteroepitaxial growth of high-index-faceted palladium nanoshells and their catalytic performance.

The development of high-performance nanocatalysts relies essentially on the generation of stable and active surface sites at the atomic scale through synthetic control of the size, shape, and chemical composition of nanoscale metals and metal oxides. One promising route is to induce the exposure of catalytically active high-index facets of nanostructures through shape-controlled syntheses. We have designed and prepared two types of Pd nanoshells that are enclosed by high-index {730} and {221} facets through heteroepitaxial growth on high-index-faceted Au nanocrystals. The turnover numbers per surface atom of the high-index-faceted Pd nanoshells have been found to be 3-7 times those of Pd and Au-Pd core-shell nanocubes that possess only {100} facets in catalyzing the Suzuki coupling reaction. These results open up a potential for the development of inexpensive and highly active metal nanocatalysts.

[1]  G. Somorjai,et al.  Mechanism of catalysis of hydrocarbon reactions by platinum surfaces , 1975, Nature.

[2]  Zhaoxiong Xie,et al.  Synthesis of trisoctahedral gold nanocrystals with exposed high-index facets by a facile chemical method. , 2008, Angewandte Chemie.

[3]  Jin Zou,et al.  Anatase TiO2 single crystals with a large percentage of reactive facets , 2008, Nature.

[4]  G. Somorjai,et al.  Molecular surface chemistry by metal single crystals and nanoparticles from vacuum to high pressure. , 2008, Chemical Society reviews.

[5]  A. Baiker,et al.  Shape-selective enantioselective hydrogenation on Pt nanoparticles. , 2009, Journal of the American Chemical Society.

[6]  G. Somorjai,et al.  Molecular factors of catalytic selectivity. , 2008, Angewandte Chemie.

[7]  G. Somorjai,et al.  Nanoscale advances in catalysis and energy applications. , 2010, Nano letters.

[8]  Zhong-Qun Tian,et al.  Epitaxial growth of heterogeneous metal nanocrystals: from gold nano-octahedra to palladium and silver nanocubes. , 2008, Journal of the American Chemical Society.

[9]  G. Ertl,et al.  Identification of the "Active Sites" of a Surface-Catalyzed Reaction , 1996, Science.

[10]  J. Nørskov,et al.  Role of Steps in N 2 Activation on Ru(0001) , 1999 .

[11]  Michael H. Huang,et al.  Au nanocube-directed fabrication of Au-Pd core-shell nanocrystals with tetrahexahedral, concave octahedral, and octahedral structures and their electrocatalytic activity. , 2010, Journal of the American Chemical Society.

[12]  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.

[13]  Xingyu Jiang,et al.  Formation of rectangularly shaped Pd/Au bimetallic nanorods: evidence for competing growth of the Pd shell between the 110 and 100 side facets of Au nanorods. , 2006, Nano letters.

[14]  Feibelman,et al.  O Binding Sites on Stepped Pt(111) Surfaces. , 1996, Physical review letters.

[15]  Thomas Bligaard,et al.  Identification of Non-Precious Metal Alloy Catalysts for Selective Hydrogenation of Acetylene , 2008, Science.

[16]  Guobao Xu,et al.  Seed-Mediated Growth of Nearly Monodisperse Palladium Nanocubes with Controllable Sizes , 2008 .

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

[18]  Thomas Bligaard,et al.  The nature of the active site in heterogeneous metal catalysis. , 2008, Chemical Society reviews.

[19]  Rutger A. van Santen.  Complementary structure sensitive and insensitive catalytic relationships. , 2009 .

[20]  Peidong Yang,et al.  Sub-10 nm platinum nanocrystals with size and shape control: catalytic study for ethylene and pyrrole hydrogenation. , 2009, Journal of the American Chemical Society.

[21]  Michael H. Huang,et al.  Seed-mediated synthesis of palladium nanorods and branched nanocrystals and their use as recyclable Suzuki coupling reaction catalysts. , 2009, Journal of the American Chemical Society.

[22]  Michael H. Huang,et al.  Seed-mediated synthesis of gold nanocrystals with systematic shape evolution from cubic to trisoctahedral and rhombic dodecahedral structures. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[23]  T. Hyeon,et al.  Fabrication of hollow palladium spheres and their successful application to the recyclable heterogeneous catalyst for suzuki coupling reactions. , 2002, Journal of the American Chemical Society.

[24]  M. H. Yeung,et al.  Heteroepitaxial growth of core-shell and core-multishell nanocrystals composed of palladium and gold. , 2010, Small.

[25]  Younan Xia,et al.  A comparison study of the catalytic properties of Au-based nanocages, nanoboxes, and nanoparticles. , 2010, Nano letters.

[26]  Daniel L. Feldheim.  The New Face of Catalysis , 2007, Science.

[27]  H. Zeng,et al.  Controllable polyol synthesis of uniform palladium icosahedra: effect of twinned structure on deformation of crystalline lattices. , 2009, Angewandte Chemie.

[28]  D. King,et al.  Dynamic interplay between diffusion and reaction: nitrogen recombination on Rh{211} in car exhaust catalysis. , 2008, Journal of the American Chemical Society.

[29]  Y. Shao-horn,et al.  Roles of surface steps on Pt nanoparticles in electro-oxidation of carbon monoxide and methanol. , 2009, Journal of the American Chemical Society.

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

[31]  A. Bell.  The Impact of Nanoscience on Heterogeneous Catalysis , 2003, Science.

[32]  G. Somorjai.  Modern Surface Science and Surface Technologies: An Introduction. , 1996, Chemical reviews.