Defect-dominated shape recovery of nanocrystals: a new strategy for trimetallic catalysts.

Here we present a shape recovery phenomenon of Pt-Ni bimetallic nanocrystals that is unequivocally attributed to the defect effects. High-resolution electron microscopy revealed the overall process of conversion from concave octahedral Pt3Ni to regular octahedral Pt3Ni@Ni upon Ni deposition. Further experiments and theoretical investigations indicated that the intrinsic defect-dominated growth mechanism allows the site-selective nucleation of a third metal around the defects to achieve the sophisticated design of trimetallic Pt3Ni@M core-shell structures (M = Au, Ag, Cu, Rh). Consideration of geometrical and electronic effects indicated that trimetallic atomic steps in Pt3Ni@M could serve as reactive sites to significantly improve the catalytic performance, and this was corroborated by several model reactions. The synthesis strategy based on our work paves the way for the atomic-level design of trimetallic catalysts.

[1]  Shouheng Sun,et al.  Monodisperse AgPd alloy nanoparticles and their superior catalysis for the dehydrogenation of formic acid. , 2013, Angewandte Chemie.

[2]  Zhi-You Zhou,et al.  Nanomaterials of high surface energy with exceptional properties in catalysis and energy storage. , 2011, Chemical Society reviews.

[3]  Jens K Nørskov,et al.  Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. , 2006, Angewandte Chemie.

[4]  J. Hrbek,et al.  Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction , 2007, Science.

[5]  M. Engelhard,et al.  Correlation between atomic coordination structure and enhanced electrocatalytic activity for trimetallic alloy catalysts. , 2011, Journal of the American Chemical Society.

[6]  Miaofang Chi,et al.  Highly stable silver nanoplates for surface plasmon resonance biosensing. , 2012, Angewandte Chemie.

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

[8]  H. Wegner,et al.  Gold for C-C coupling reactions: a Swiss-Army-knife catalyst? , 2011, Angewandte Chemie.

[9]  D. M. Newns.  Self-Consistent Model of Hydrogen Chemisorption , 1969 .

[10]  F. D. Boer.  Cohesion in Metals: Transition Metal Alloys , 1989 .

[11]  Zhipan Liu,et al.  General rules for predicting where a catalytic reaction should occur on metal surfaces: a density functional theory study of C-H and C-O bond breaking/making on flat, stepped, and kinked metal surfaces. , 2003, Journal of the American Chemical Society.

[12]  Guobao Xu,et al.  Synthesis and applications of noble metal nanocrystals with high-energy facets , 2012 .

[13]  C. Rey,et al.  Glass formation in the Cu–Ti–Zr system and its associated binary systems , 1992 .

[14]  Yadong Li,et al.  Catalysis based on nanocrystals with well-defined facets. , 2012, Angewandte Chemie.

[15]  B. Hwang,et al.  Simple replacement reaction for the preparation of ternary Fe(1-x)PtRu(x) nanocrystals with superior catalytic activity in methanol oxidation reaction. , 2012, Journal of the American Chemical Society.

[16]  Yadong Li,et al.  A strategy for designing a concave Pt-Ni alloy through controllable chemical etching. , 2012, Angewandte Chemie.

[17]  Wenjie Shen,et al.  Stabilized gold nanoparticles on ceria nanorods by strong interfacial anchoring. , 2012, Journal of the American Chemical Society.

[18]  菊池 潮美.  Cohesion in Metals, Transition Metal alloys, F.R.de Boer,R.Boom,W.C.M.Mattens,A.R.Miedema,A.K.Niessen(共著), F.R de boer,D.G.pettifor編Cohesion and Structure Vol.1, 1989年, North-Holland発行, 23×15.5cm, 758ページ, Dfl.250 , 1990 .

[19]  E. Wang,et al.  Noble metal nanomaterials: Controllable synthesis and application in fuel cells and analytical sensors , 2011 .

[20]  J. Hong,et al.  Controlled synthesis of Pd-Pt alloy hollow nanostructures with enhanced catalytic activities for oxygen reduction. , 2012, ACS nano.

[21]  Jackie Y Ying,et al.  Nanocomposites of Ag2S and noble metals. , 2011, Angewandte Chemie.

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

[23]  Jiye Fang,et al.  High-index faceted noble metal nanocrystals. , 2013, Accounts of chemical research.

[24]  Yadong Li,et al.  A seed-based diffusion route to monodisperse intermetallic CuAu nanocrystals. , 2010, Angewandte Chemie.

[25]  Z. Wang,et al.  Transmission Electron Microscopy of Shape-Controlled Nanocrystals and Their Assemblies , 2000 .

[26]  Younan Xia,et al.  Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics? , 2009, Angewandte Chemie.