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Colloidal nanocrystal synthesis and the organic-inorganicinterface

Description: Colloidal nanocrystals are nanometer-sized, solution-grown inorganic particles stabilized by a layer of surfactants attached to their surface. The inorganic cores exhibit useful properties controlled by composition as well as size and shape, while the surfactant coating ensures that these structures are easy to fabricate and process. It is this combination of features that makes colloidal nanocrystals attractive and promising building blocks for advanced materials and devices. But their full potential can only be exploited if we achieve exquisite control over their composition, size, shape, crystal structure and surface properties. Here we review what is known about nanocrystal growth and outline strategies for controlling it.
Date: May 12, 2005
Creator: Yin, Yadong & Alivisatos, A. Paul
Partner: UNT Libraries Government Documents Department

Faceting of Nanocrystals during Chemical Transformation: FromSolid Silver Spheres to Hollow Gold Octahedra

Description: Sustained progress in nanocrystal synthesis has enabled recent use of these materials as inorganic, macromolecular precursors that can be chemically transformed into new nanostructures. The literature now contains several cases with chemical transformations being accompanied by varying degrees of modification of properties, including crystal structure and particle shape. As a recent example, we demonstrated that as-synthesized metallic nanocrystals yield, upon oxidation, nanostructures with modified morphologies such as hollow particles. This morphological change derives from directional material flows due to differing diffusivities for the reacting atomic species, in a nanoscale version of the well-known Kirkendall Effect. This general methodology has since been extended by other groups to produce nanostructures with various compositions and shapes. We demonstrate that performing a replacement reaction on single crystalline Ag nanospheres of {approx}10 nm in diameter in an organic solvent produces hollow Au nanocrystals with an octahedral shape. Different from those Au shells made by starting with Ag particles about one order of magnitude larger, which largely reproduce that of the sacrificial Ag counterparts, the hollow nanocrystals obtained in this work show significant changes in the external morphology from the spherical Ag precursors. This evolution of a faceted external morphology during chemical transformation is made possible by the enhanced role of surface effects in our smaller nanocrystals. The competition between the Au atom deposition and Ag atom dissolution on various nanocrystal surfaces is believed to determine the final octahedral shape of the hollow Au nanocrystals. Simultaneous achievement of surface-mediated shape control and a hollow morphology in a one-pot, single-step synthetic procedure in this study promises an avenue to finer tuning of particle morphology, and thus physical properties such as surface plasmon resonance.
Date: June 23, 2006
Creator: Yin, Yadong; Erdonmez, Can & Alivisatos, A. Paul
Partner: UNT Libraries Government Documents Department

Soft X-ray Spectroscopy Study of the Electronic Structure of Oxidized and Partially Oxidized Magnetite Nanoparticles

Description: The crystal structure of magnetite nanoparticles may be transformed to maghemite by complete oxidation, but under many relevant conditions the oxidation is partial, creating a mixed-valence material with structural and electronic properties that are poorly characterized. We used X-ray diffraction, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, and soft X-ray absorption and emission spectroscopy to characterize the products of oxidizing uncoated and oleic acid-coated magnetite nanoparticles in air. The oxidization of uncoated magnetite nanoparticles creates a material that is structurally and electronically indistinguishable from maghemite. By contrast, while oxidized oleic acid-coated nanoparticles are also structurally indistinguishable from maghemite, Fe L-edge spectroscopy revealed the presence of interior reduced iron sites even after a 2-year period. We used X-ray emission spectroscopy at the O K-edge to study the valence bands (VB) of the iron oxide nanoparticles, using resonant excitation to remove the contributions from oxygen atoms in the ligands and from low-energy excitations that obscured the VB edge. The bonding in all nanoparticles was typical of maghemite, with no detectable VB states introduced by the long-lived, reduced-iron sites in the oleic acid-coated sample. However, O K-edge absorption spectroscopy observed a 0.2 eV shift in the position of the lowest unoccupied states in the coated sample, indicating an increase in the semiconductor band gap relative to bulk stoichiometric maghemite that was also observed by optical absorption spectroscopy. The results show that the ferrous iron sites within ferric iron oxide nanoparticles coated by an organic ligand can persist under ambient conditions with no evidence of a distinct interior phase and can exert an effect on the global electronic and optical properties of the material. This phenomenon resembles the band gap enlargement caused by electron accumulation in the conduction band of TiO2.
Date: October 24, 2010
Creator: Gilbert, Benjamin; Katz, Jordan E.; Denlinger, Jonathan D.; Yin, Yadong; Falcone, Roger & Waychunas, Glenn A.
Partner: UNT Libraries Government Documents Department

Sulfidation of Cadmium at the Nanoscale

Description: We investigate the evolution of structures that result when spherical Cd nanoparticles of a few hundred nanometers in diameter react with dissolved molecular sulfur species in solution to form hollow CdS. Over a wide range of temperatures and concentrations, we find that rapid Cd diffusion through the growing CdS shell localizes the reaction front at the outermost CdS/S interface, leading to hollow particles when all the Cd is consumed. When we examine partially reacted particles, we find that this system differs significantly from others in which the nanoscale Kirkendall effect has been used to create hollow particles. In previously reported systems, partial reaction creates a hollow particle with a spherically symmetric metal core connected to the outer shell by filaments. In contrast, here we obtain a lower symmetry structure, in which the unreacted metal core and the coalesced vacancies separate into two distinct spherical caps, minimizing the metal/void interface. This pattern of void coalescence is likely to occur in situations where the metal/vacancy self-diffusivities in the core are greater than the diffusivity of the cations through the shell.
Date: May 22, 2008
Creator: Cabot, Andreu; Smith, Rachel; Yin, Yadong; Zheng, Haimei; Reinhard, Bjorn; Liu, Haitao et al.
Partner: UNT Libraries Government Documents Department

Formation of hollow nanocrystals through the nanoscale kirkendall effect

Description: We demonstrate that hollow nanocrystals can be synthesized through a mechanism analogous to the Kirkendall Effect, in which pores form due to the difference in diffusion rates between two components in a diffusion couple. Cobalt nanocrystals are chosen as a primary example to show that their reaction in solution with oxygen, sulfur or selenium leads to the formation of hollow nanocrystals of the resulting oxide and chalcogenides. This process provides a general route to the synthesis of hollow nanostructures of large numbers of compounds. A simple extension of this process yields platinum-cobalt oxide yolk-shell nanostructures which may serve as nanoscale reactors in catalytic applications.
Date: March 11, 2004
Creator: Yin, Yadong; Rioux, Robert M.; Erdonmez, Can K.; Hughes, Steven; Somorjai, Gabor A. & Alivisatos, A. Paul
Partner: UNT Libraries Government Documents Department

TiO2 Nanoparticles as a Soft X-ray Molecular Probe

Description: With the emergence of soft x-ray techniques for imaging cells, there is a pressing need to develop protein localization probes that can be unambiguously identified within the region of x-ray spectrum used for imaging. TiO2 nanocrystal colloids, which have a strong absorption cross-section within the "water-window" region of x-rays, areideally suited as soft x-ray microscopy probes. To demonstrate their efficacy, TiO2-streptavidin nanoconjugates were prepared and subsequently labeled microtubules polymerized from biotinylated tubulin. The microtubules were imaged using scanning transmission x-ray microscopy (STXM), and the TiO2 nanoparticle tags were specifically identified using x-ray absorption near edge spectroscopy (XANES). These experiments demonstrate that TiO2 nanoparticles are potential probes for protein localization analyses using soft x-ray microscopy.
Date: June 30, 2007
Creator: Larabell, Carolyn; Ashcroft, Jared M.; Gu, Weiwei; Zhang, Tierui; Hughes, Steven M.; Hartman, Keith B. et al.
Partner: UNT Libraries Government Documents Department

Nanoplasmonic molecular ruler for nuclease activity and DNAfootprinting

Description: We have constructed a nanoplasmonic molecular ruler, which can perform label-free and real-time monitoring of DNA length changes and perform DNA footprinting. The ruler was created by tethering double-stranded DNA to single Au nanoparticles. The scattering spectra of Au-DNA nanoconjugates showed red-shifted peak plasmon resonance wavelength dependent on DNA length, which can be measured with sub-nanometer axial resolution, averaging {approx}1.24 nm peak wavelength shift per DNA base pair. The spectra of individual Au-DNA nanoconjugates in the presence of nuclease showed a time-resolved dependence on the reaction dynamics, allowing quantitative, kinetic and real-time measurement of nuclease activity. The ruler was further developed into a new DNA footprinting platform. We showed the specific binding of a protein to DNA and the accurate mapping of its footprint. This work promises a very fast and convenient platform for mapping DNA-protein interactions, for nuclease activity monitoring, and for other DNA size-based methods.
Date: August 15, 2006
Creator: Chen, Fanqing Frank; Liu, Gang L.; Yin, Yadong; Gerion, Daniele; Kunchakarra, Siri; Mukherjee, Bipasha et al.
Partner: UNT Libraries Government Documents Department

Electronic structure of cobalt nanocrystals suspended inliquid

Description: The electronic structure of cobalt nanocrystals suspended in liquid as a function of size has been investigated using in-situ x-ray absorption and emission spectroscopy. A sharp absorption peak associated with the ligand molecules is found that increases in intensity upon reducing the nanocrystal size. X-ray Raman features due to d-d and to charge-transfer excitations of ligand molecules are identified. The study reveals the local symmetry of the surface of {var_epsilon}-Co phase nanocrystals, which originates from a dynamic interaction between Co nanocrystals and surfactant + solvent molecules.
Date: July 16, 2007
Creator: Liu, Hongjian; Guo, Jinghua; Yin, Yadong; Augustsson, Andreas; Dong, Chungli; Nordgren, Joseph et al.
Partner: UNT Libraries Government Documents Department

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Description: Formation of cobalt sulfide hollow nanocrystals through amechanism similar to the Kirkendall Effect has been investigated indetail. It was found that performing the reaction at>120oC leads tofast formation of a single void ins ide each shell, whereas at roomtemperature multiple voids are formed within each shell, which can beattributed to strongly temperature-dependent diffusivities for vacancies.The void formation process is dominated by outward diffusion of cobaltcations; still, significant inward transport of sulfur anions can beinferred to occur as the final voids are smaller in diameter than theoriginal cobalt nanocrystals. Comparison of volume distributions forinitial and final nanostructures indicates excess apparent volume inshells implying significant porosity and/or a defective structure.Indirect evidence for shells to fracture during growth at lowertemperatures was observed in shell size statisticsand TEM of as-grownshells. An idealized model of the diffusional process imposes two minimalrequirements on material parameters for shell growth to be obtainablewithin a specific synthetic system.
Date: March 16, 2006
Creator: Yin, Yadong; Erdonmez, Can K.; Cabot, Andreu; Hughes, Steven & Alivisatos, A. Paul
Partner: UNT Libraries Government Documents Department