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  • Title: Electrochemical solid-state phase transformations of silver nanoparticles.
    Author: Singh P, Parent KL, Buttry DA.
    Journal: J Am Chem Soc; 2012 Mar 28; 134(12):5610-7. PubMed ID: 22385520.
    Abstract:
    Adenosine triphosphate (ATP)-capped silver nanoparticles (ATP-Ag NPs) were synthesized by reduction of AgNO(3) with borohydride in water with ATP as a capping ligand. The NPs obtained were characterized using transmission electron microscopy (TEM), UV-vis absorption spectroscopy, X-ray diffraction, and energy-dispersive X-ray analysis. A typical preparation produced ATP-Ag NPs with diameters of 4.5 ± 1.1 nm containing ~2800 Ag atoms and capped with 250 ATP capping ligands. The negatively charged ATP caps allow NP incorporation into layer-by-layer (LbL) films with poly(diallyldimethylammonium) chloride at thiol-modified Au electrode surfaces. Cyclic voltammetry in a single-layer LbL film of NPs showed a chemically reversible oxidation of Ag NPs to silver halide NPs in aqueous halide solutions and to Ag(2)O NPs in aqueous hydroxide solutions. TEM confirmed that this takes place via a redox-driven solid-state phase transformation. The charge for these nontopotactic phase transformations corresponded to a one-electron redox process per Ag atom in the NP, indicating complete oxidation and reduction of all Ag atoms in each NP during the electrochemical phase transformation.
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