Advanced electron microscopy characterization of multimetallic nanoparticles

Research in noble metal nanoparticles has led to exciting progress in a versatile array of applications. For the purpose of better tailoring of nanoparticles activities and understanding the correlation between their structures and properties, control over the composition, shape, size and architecture of bimetallic and multimetallic nanomaterials plays an important role on revealing their new or enhanced functions for potentials application. Advance electron microscopy techniques were used to provide atomic scale insights into the structure-properties of different materials: PtPd, Au-Au 3 Cu, Cu-Pt, AgPd/Pt and AuCu/Pt nanoparticles. The objective of this work is to understand the physical and chemical properties of nanomaterials and describe synthesis, characterization, surface properties and growth mechanism of various bimetallic and multimetallic nanoparticles. The findings have provided us with novel and significant insights into the physical and chemical properties of noble metal nanoparticles. Different synthesis routes allowed us to synthesize bimetallic: Pt-Pd, Au-Au 3 Cu, Cu-Pt and trimetallic: AgPd/Pt, AuCu/Pt, core-shell and alloyed nanoparticles with monodispersed sizes, controlled shapes and tunable surface properties. For example, we have synthesized the polyhedral PtPd core-shell nanoparticles with octahedral, decahedral, and triangular plates. Decahedral PtPd core-shell structures are novel morphologies for this system. For the first time we fabricated that the Au core and Au 3 Cu alloyed shell nanoparticles passivated with CuS2 surface layers and characterized by Cs-corrected scanning transmission electron microscopy. The analysis of the high-resolution micrographs reveals that these nanoparticles have decahedral structure with shell periodicity, and that each of the particles is composed by Au core and Au 3 Cu ordered superlattice alloyed shell surrounded by CuS 2 surface layer. Additionally, we have described both experimental and theoretical methods of synthesis and growth mechanism of highly monodispersed Cu-Pt nanoclusters. The advance electron microscopy of microanalysis allowed us to study the distribution of Cu and Pt with atomistic resolution. The microanalysis revealed that Pt is embedded randomly in the Cu lattice. A novel grand canonical - Langevin dynamics simulation showed the formation of alloy structures in good agreement with the experimental evidence. Finally, we demonstrated the synthesis of AgPd-Pt trimetallic nanoparticles with two different morphologies: multiply twinned core-shell, and hollow particles. We also investigated the growth mechanism of the nanoparticles using grand canonical-Monte Carlo simulations. We found that the Pt regions grow at overpotentials on the AgPd nanoalloys, forming 3D islands at the early stages of the deposition process and presenting very good agreement between the simulated structures and those observed experimentally. Similarly, we also investigated AuCu/Pt core-shell trimetallic nanoparticles, presenting new way to control the nanoparticles morphologies due to the presence of third metal (Pt). Where, we observed the Pt layers are overgrowth on the as prepared AuCu core by Frank-van der Merwe (FM) and Stranski-Krastanov (SK) growth modes. In addition, these nanostructure presents high index facet surfaces with {lcub}211{rcub} and (321{rcub} families, that are highly open structure surfaces and interesting for the catalytic applications. The results of these studies will be useful for the future applications and the design of advanced functional nanomaterials.