Aqueous room-temperature synthesis of Au-Rh, Au-Pt, Pt-Rh, and Pd-Rh alloy nanoparticles

Fully tunable compositions within the miscibility gaps

Elizabeth R. Essinger-Hileman, Danielle Decicco, James F. Bondi, Raymond Edward Schaak

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Many binary late transition metal systems have large bulk miscibility gaps, and a variety of synthetic strategies have been developed to generate these non-equilibrium alloys as nanoparticles. While many of these methods strive to co-nucleate both elements by exploiting fast reduction kinetics or co-sequestration within a confined space, we show here that simple room-temperature borohydride co-reduction of appropriate aqueous metal salt solutions yields alloy nanoparticles in the bulk-immiscible Au-Rh, Au-Pt, Pt-Rh, and Pd-Rh systems. The compositions can be tuned across the entire Au 1-xRhx, Au1-xPtx, Pt 1-xRhx, and Pd1-xRhx solid solutions by varying the ratio of metal salt reagents, and they form in the presence of a variety of molecular and polymeric surface stabilizers. Reaction pathway studies on the model Au-Rh system suggest that the alloy nanoparticles form via a "conversion chemistry" mechanism: Au nanoparticle templates nucleate first, followed by diffusion of Rh to form homogeneous Au-Rh alloy nanoparticles. The alloy nanoparticles tend to be agglomerated, but this can be minimized by forming the nanoparticles directly on catalytically relevant high surface area carbon and biological supports, e.g. Vulcan carbon and wild-type M13 bacteriophage.

Original languageEnglish (US)
Pages (from-to)11599-11604
Number of pages6
JournalJournal of Materials Chemistry
Volume21
Issue number31
DOIs
StatePublished - Aug 21 2011

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Solubility
Nanoparticles
Chemical analysis
Temperature
Carbon
Salts
Metals
Borohydrides
Bacteriophages
Transition metals
Solid solutions
Kinetics

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Chemistry

Cite this

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abstract = "Many binary late transition metal systems have large bulk miscibility gaps, and a variety of synthetic strategies have been developed to generate these non-equilibrium alloys as nanoparticles. While many of these methods strive to co-nucleate both elements by exploiting fast reduction kinetics or co-sequestration within a confined space, we show here that simple room-temperature borohydride co-reduction of appropriate aqueous metal salt solutions yields alloy nanoparticles in the bulk-immiscible Au-Rh, Au-Pt, Pt-Rh, and Pd-Rh systems. The compositions can be tuned across the entire Au 1-xRhx, Au1-xPtx, Pt 1-xRhx, and Pd1-xRhx solid solutions by varying the ratio of metal salt reagents, and they form in the presence of a variety of molecular and polymeric surface stabilizers. Reaction pathway studies on the model Au-Rh system suggest that the alloy nanoparticles form via a {"}conversion chemistry{"} mechanism: Au nanoparticle templates nucleate first, followed by diffusion of Rh to form homogeneous Au-Rh alloy nanoparticles. The alloy nanoparticles tend to be agglomerated, but this can be minimized by forming the nanoparticles directly on catalytically relevant high surface area carbon and biological supports, e.g. Vulcan carbon and wild-type M13 bacteriophage.",
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Aqueous room-temperature synthesis of Au-Rh, Au-Pt, Pt-Rh, and Pd-Rh alloy nanoparticles : Fully tunable compositions within the miscibility gaps. / Essinger-Hileman, Elizabeth R.; Decicco, Danielle; Bondi, James F.; Schaak, Raymond Edward.

In: Journal of Materials Chemistry, Vol. 21, No. 31, 21.08.2011, p. 11599-11604.

Research output: Contribution to journalArticle

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