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Reversible Kirkwood-Alder transition observed in Pt3Cu2 nanoctahedron assemblies under controlled solvent
Jun Zhang1, Zhiping Luo, Benjamin Martens
1Department of Chemistry, State University of New York at Binghamton, Binghamton, New York 13902, USA.
Abstract:
We report a Kirkwood-Alder transition in a system of nonspherical Pt(3)Cu(2) nanoctahedra coated with oleic acid and oleylamine ligands. Using both transmission electron microscopy tomography with 3D reconstruction analysis and synchrotron-based in-situ grazing-incidence small-angle X-ray scattering (GISAXS) techniques, we specifically determined that these nanoctahedra can assemble into an open structure in which the nanoctahedra are arranged tip-to-tip to form a bcc superlattice with a low packing efficiency. Using in-situ and real-time GISAXS, we further observed a "nanoctahedron crystallization" as a soft Kirkwood-Alder transition, that is, the soft nanoactahedra crystallize at a critical concentration and possess continuous crystalline states during a period of solvent evaporation. Finally, we found a reversible change of the superlattice constant during the solvent annealing and evaporation/drying processes.
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