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Spontaneous formation of core/shell bimetallic nanoparticles: A calorimetric study

TitleSpontaneous formation of core/shell bimetallic nanoparticles: A calorimetric study
Publication TypeJournal Article
Year of Publication2005
AuthorsToshima, N, Kanemaru, M, Shiraishi, Y, Koga, Y
JournalJournal of Physical Chemistry B
Volume109
Pagination16326-16331
Date PublishedSep
Type of ArticleArticle
ISBN Number1520-6106
KeywordsABSORPTION FINE-STRUCTURE, BINDING, CATALYTIC-ACTIVITY, CLUSTERS, CORE-SHELL, GOLD NANOPARTICLES, isothermal titration calorimetry, NANOPARTICLES, PD, REDUCTION, STRUCTURAL-ANALYSIS
Abstract

We showed recently that low entropy core/shell structured nanoparticles form spontaneously from the physical mixture of a dispersion of Ag nanoparticles and that of another noble metal (Rh. Pd, or Pt) at room, temperature. Here we use isothermal titration calorimetry (ITC) and show that the initial step of such a spontaneous process is strongly exothermic. When the alcohol dispersion of poly(N-vinyl-2-pyrrolidone) (PVP)-protected Rh nanoparticles (average diameter 2.3 nm) was titrated into the alcoholic dispersion of PVP-protected Ag nanoparticles, a strong exothermic enthalpy change, Delta H. was observed: Delta H = -908 kJ/mol for Ag(S) nanoparticle (average diameter 10.8 nm) and -963 kJ/mol for Ag(L) nanoparticles (average diameter 22.5 nm). The strength of interaction increases in the order of Rh/Ag > Pd/Ag > Pt/Ag. This strong exothermic interaction is considered as a driving force to from low entropy bimetallic nanoparticles by simple mixing of two kinds of monometallic nanoparticles. We show also that exothermic interactions occur between a pair of noble metal nanoparticles themselves by using ITC.

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