Showing papers by "Christopher B. Murray published in 2015"

Prospects of Nanoscience with Nanocrystals

Abstract: Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today’s strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. The performance of inorganic NC-based photovoltaic and light-emitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenom...

Charge transport in strongly coupled quantum dot solids

Abstract: The emergence of high-mobility, colloidal semiconductor quantum dot (QD) solids has triggered fundamental studies that map the evolution from carrier hopping through localized quantum-confined states to band-like charge transport in delocalized and hybridized states of strongly coupled QD solids, in analogy with the construction of solids from atoms. Increased coupling in QD solids has led to record-breaking performance in QD devices, such as electronic transistors and circuitry, optoelectronic light-emitting diodes, photovoltaic devices and photodetectors, and thermoelectric devices. Here, we review the advances in synthesis, assembly, ligand treatments and doping that have enabled high-mobility QD solids, as well as the experiments and theory that depict band-like transport in the QD solid state. We also present recent QD devices and discuss future prospects for QD materials and device design.

Efficient Removal of Organic Ligands from Supported Nanocrystals by Fast Thermal Annealing Enables Catalytic Studies on Well-Defined Active Phases

Abstract: A simple yet efficient method to remove organic ligands from supported nanocrystals is reported for activating uniform catalysts prepared by colloidal synthesis procedures. The method relies on a fast thermal treatment in which ligands are quickly removed in air, before sintering can cause changes in the size and shape of the supported nanocrystals. A short treatment at high temperatures is found to be sufficient for activating the systems for catalytic reactions. We show that this method is widely applicable to nanostructures of different sizes, shapes, and compositions. Being rapid and effective, this procedure allows the production of monodisperse heterogeneous catalysts for studying a variety of structure-activity relationships. We show here results on methane steam reforming, where the particle size controls the CO/CO2 ratio on alumina-supported Pd, demonstrating the potential applications of the method in catalysis.

Substitutional doping in nanocrystal superlattices

Abstract: Doping is a process in which atomic impurities are intentionally added to a host material to modify its properties. It has had a revolutionary impact in altering or introducing electronic, magnetic, luminescent, and catalytic properties for several applications, for example in semiconductors. Here we explore and demonstrate the extension of the concept of substitutional atomic doping to nanometre-scale crystal doping, in which one nanocrystal is used to replace another to form doped self-assembled superlattices. Towards this goal, we show that gold nanocrystals act as substitutional dopants in superlattices of cadmium selenide or lead selenide nanocrystals when the size of the gold nanocrystal is very close to that of the host. The gold nanocrystals occupy random positions in the superlattice and their density is readily and widely controllable, analogous to the case of atomic doping, but here through nanocrystal self-assembly. We also show that the electronic properties of the superlattices are highly tunable and strongly affected by the presence and density of the gold nanocrystal dopants. The conductivity of lead selenide films, for example, can be manipulated over at least six orders of magnitude by the addition of gold nanocrystals and is explained by a percolation model. As this process relies on the self-assembly of uniform nanocrystals, it can be generally applied to assemble a wide variety of nanocrystal-doped structures for electronic, optical, magnetic, and catalytic materials.

Synthesis and X-ray Characterization of Cobalt Phosphide (Co2P) Nanorods for the Oxygen Reduction Reaction.

Abstract: Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co2P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable than conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.

Binary and ternary superlattices self-assembled from colloidal nanodisks and nanorods.

Abstract: Self-assembly of multicomponent anisotropic nanocrystals with controlled orientation and spatial distribution allows the design of novel metamaterials with unique shape- and orientation-dependent collective properties. Although many phases of binary structures are theoretically proposed, the examples of multicomponent assemblies, which are experimentally realized with colloidal anisotropic nanocrystals, are still limited. In this report, we demonstrate the formation of binary and ternary superlattices from colloidal two-dimensional LaF3 nanodisks and one-dimensional CdSe/CdS nanorods via liquid interfacial assembly. The colloidal nanodisks and nanorods are coassembled into AB-, AB2-, and AB6-type binary arrays determined by their relative size ratio and concentration to maximize their packing density. The position and orientation of anisotropic nanocrystal building blocks are tightly controlled in the self-assembled binary and ternary lattices. The macroscopic orientation of the superlattices is further t...

Large-Area Nanoimprinted Colloidal Au Nanocrystal-Based Nanoantennas for Ultrathin Polarizing Plasmonic Metasurfaces.

Abstract: We report a low-cost, large-area fabrication process using solution-based nanoimprinting and compact ligand exchange of colloidal Au nanocrystals to define anisotropic, subwavelength, plasmonic nanoinclusions for optical metasurfaces. Rod-shaped, Au nanocrystal-based nanoantennas possess strong, localized, plasmonic resonances able to control polarization. We fabricate metasurfaces from rod-shaped nanoantennas tailored in size and spacing to demonstrate Au nanocrystal-based quarter-wave plates that operate with extreme bandwidths and provide high polarization conversion efficiencies in the near-to-mid infrared.

Lifetime, Mobility, and Diffusion of Photoexcited Carriers in Ligand-Exchanged Lead Selenide Nanocrystal Films Measured by Time-Resolved Terahertz Spectroscopy

Abstract: Colloidal semiconductor nanocrystals have been used as building blocks for electronic and optoelectronic devices ranging from field-effect transistors to solar cells. Properties of the nanocrystal films depend sensitively on the choice of capping ligand to replace the insulating synthesis ligands. Thus far, ligands leading to the best performance in transistors result in poor solar cell performance, and vice versa. To gain insight into the nature of this dichotomy, we used time-resolved terahertz spectroscopy measurements to study the mobility and lifetime of PbSe nanocrystal films prepared with five common ligand-exchange reagents. Noncontact terahertz spectroscopy measurements of conductivity were corroborated by contacted van der Pauw measurements of the same samples. The films treated with different displacing ligands show more than an order of magnitude difference in the peak conductivities and a bifurcation of time dynamics. Inorganic chalcogenide ligand exchanges with sodium sulfide (Na2S) or ammon...

Comparison of HMF hydrodeoxygenation over different metal catalysts in a continuous flow reactor

Abstract: The three-phase hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) and hydrogenation of 2,5-dimethylfuran (DMF) were studied over six carbon-supported metal catalysts (Pt, Pd, Ir, Ru, Ni, and Co) using a tubular flow reactor with 1-propanol solvent, at 180 °C and 33 bar. By varying the space time in the reactor, the reaction of HMF is shown to be sequential, with HMF reacting first to furfuryl ethers and other partially hydrogenated products, which then form 2,5-dimethylfuran (DMF). Ring-opened products and 2,5-dimethyltetrahydrofuran (DMTHF) were produced only from reaction of DMF. Rate constants for the pseudo-first-order sequential reactions were obtained for each of the metals. The selectivities for the reaction of DMF varied with the metal catalyst, with Pd forming primarily DMTHF, Ir forming a mixture of DMTHF and open-ring products, and the other metals forming primarily open-ring products. Catalyst stabilities followed the order Pt ∼ Ir > Pd > Ni > Co > Ru. Since the stability order correlated with carbon balances in the product (>93% for Pt;

Synergistic Oxygen Evolving Activity of a TiO2-Rich Reconstructed SrTiO3(001) Surface

Abstract: In addition to composition, the structure of a catalyst is another fundamental determinant of its catalytic reactivity. Recently, anomalous Ti oxide-rich surface phases of ternary oxides have been stabilized as nonstoichiometric epitaxial overlayers. These structures give rise to different modes of oxygen binding, which may lead to different oxidative chemistry. Through density functional theory investigations and electrochemical measurements, we predict and subsequently show that such a TiO2 double-layer surface reconstruction enhances the oxygen evolving activity of the perovskite-type oxide SrTiO3. Our theoretical work suggests that the improved activity of the restructured TiO2(001) surface toward oxygen formation stems from (i) having two Ti sites with distinct oxidation activity and (ii) being able to form a strong O–O moiety (which reduces overbonding at Ti sites), which is a direct consequence of (iii) having a labile lattice O that is able to directly participate in the reaction. Here, we demonst...

Smectic Nanorod Superlattices Assembled on Liquid Subphases: Structure, Orientation, Defects, and Optical Polarization

Abstract: Directing the orientation of anisotropic nanocrystal assemblies is important for harnessing the shape-dependent properties of nanocrystal solids in devices. We control the orientation of smectic B superlattices of CdSe/CdS dot-in-rod nanocrystals through assembly on different polar interfaces and quantify the superlattice orientation through correlated small- and wide-angle grazing-incidence diffraction. Small-angle scattering is used to determine the phase of the nanorod superlattices and their preferential growth directions from the subphase. Wide-angle diffraction is used to quantify the orientations of nanorods within the superlattices and with respect to the substrate. Not only are the nanorod long axes aligned within the structures, but truncation of the short axes also coaligns the crystal axes of the nanorods with the zone axes in assembled smectic B crystals. Three dimensional orientational alignment of nanocrystals in superlattices is highly desirable in device applications. Depending on the sub...

Dendron-Mediated Engineering of Interparticle Separation and Self-Assembly in Dendronized Gold Nanoparticles Superlattices

Abstract: Self-assembly of nanoparticles into designed structures with controlled interparticle separations is of crucial importance for the engineering of new materials with tunable functions and for the subsequent bottom-up fabrication of functional devices. In this study, a series of lipophilic, highly flexible, disulfide dendritic wedges (generations 0–4), based on 2,2-bis(hydroxymethyl)propionic acid, was designed to bind Au nanoparticles with a thiolate bond. By controlling the solvent evaporation rate, the corresponding dendron-capped Au hybrids were found to self-organize into hexagonal close-packed (hcp) superlattices. The interparticular spacing was progressively varied from 2.2 to 6.3 nm with increasing dendritic generation, covering a range that is intermediate between commercial ligands and DNA-based ligand shells. Dual mixtures made from some of these dendronized hybrids (i.e., same inner core size but different dendritic covering) yielded binary superlattice structures of unprecedented single inorgan...

Flexible, High-Speed CdSe Nanocrystal Integrated Circuits.

Abstract: We report large-area, flexible, high-speed analog and digital colloidal CdSe nanocrystal integrated circuits operating at low voltages. Using photolithography and a newly developed process to fabricate vertical interconnect access holes, we scale down device dimensions, reducing parasitic capacitances and increasing the frequency of circuit operation, and scale up device fabrication over 4 in. flexible substrates. We demonstrate amplifiers with ∼7 kHz bandwidth, ring oscillators with <10 μs stage delays, and NAND and NOR logic gates.

Deposition of Wafer-Scale Single-Component and Binary Nanocrystal Superlattice Thin Films Via Dip-Coating

Abstract: E. A. Gaulding, Z. J. Vrtis, Prof. C. R. Kagan, Prof. C. B. Murray Department of Materials Science and Engineering University of Pennsylvania Philadelphia , PA 19104 , USA E-mail: cbmurray@sas.upenn.edu B. T. Diroll, E. D. Goodwin, Prof. C. R. Kagan, Prof. C. B. Murray Department of Chemistry University of Pennsylvania Philadelphia , PA 19104 , USA Prof. C. R. Kagan Department of Electrical and Systems Engineering University of Pennsylvania Philadelphia , PA 19104 , USA

Quantifying “Softness” of Organic Coatings on Gold Nanoparticles Using Correlated Small-Angle X-ray and Neutron Scattering

Abstract: Small-angle X-ray and neutron scattering provide powerful tools to selectively characterize the inorganic and organic components of hybrid nanomaterials. Using hydrophobic gold nanoparticles coated with several commercial and dendritic thiols, the size of the organic layer on the gold particles is shown to increase from 1.2 to 4.1 nm. A comparison between solid-state diffraction from self-assembled lattices of nanoparticles and the solution data from neutron scattering suggests that engineering softness/deformability in nanoparticle coatings is less straightforward than simply increasing the organic size. The “dendritic effect” in which higher generations yield increasingly compact molecules explains changes in the deformability of organic ligand shells.

Increased carrier mobility and lifetime in CdSe quantum dot thin films through surface trap passivation and doping.

Abstract: Passivating surface defects and controlling the carrier concentration and mobility in quantum dot (QD) thin films is prerequisite to designing electronic and optoelectronic devices. We investigate the effect of introducing indium in CdSe QD thin films on the dark mobility and the photogenerated carrier mobility and lifetime using field-effect transistor (FET) and time-resolved microwave conductivity (TRMC) measurements. We evaporate indium films ranging from 1 to 11 nm in thickness on top of approximately 40 nm thick thiocyanate-capped CdSe QD thin films and anneal the QD films at 300 °C to densify and drive diffusion of indium through the films. As the amount of indium increases, the FET and TRMC mobilities and the TRMC lifetime increase. The increase in mobility and lifetime is consistent with increased indium passivating midgap and band-tail trap states and doping the films, shifting the Fermi energy closer to and into the conduction band.

Probing the Structure, Composition, and Spatial Distribution of Ligands on Gold Nanorods.

Abstract: The structure and size of ligands attached to the surfaces of gold nanorods, such as adsorbed surfactants or grafted polymers, are important considerations that facilitate the use of such nanoparticles in the human body, in advanced materials for energy harvesting, or in devices for single molecule detection. Here, we report small-angle neutron scattering (SANS) measurements from surfactant or poly(ethylene glycol) (PEG) coated gold nanorods in solution, which quantitatively determine the location, structure, and composition of these surface layers. In addition, by synthesizing gold nanorods using seed crystals which are coated with deuterated cetyltrimethylammonium bromide (dCTAB), we are able to exploit the isotopic sensitivity of SANS to study, for the first time, the retention of surfactant from the seed crystals to the final gold nanorod product, finding that very little exchange of the deuterated with hydrogenated surfactant occurs. Finally, we demonstrate that, when Au NRs are PEGylated using stand...

Shape-Controlled Synthesis of Isotopic Yttrium-90-Labeled Rare Earth Fluoride Nanocrystals for Multimodal Imaging.

Abstract: Isotopically labeled nanomaterials have recently attracted much attention in biomedical research, environmental health studies, and clinical medicine because radioactive probes allow the elucidation of in vitro and in vivo cellular transport mechanisms, as well as the unambiguous distribution and localization of nanomaterials in vivo. In addition, nanocrystal-based inorganic materials have a unique capability of customizing size, shape, and composition; with the potential to be designed as multimodal imaging probes. Size and shape of nanocrystals can directly influence interactions with biological systems, hence it is important to develop synthetic methods to design radiolabeled nanocrystals with precise control of size and shape. Here, we report size- and shape-controlled synthesis of rare earth fluoride nanocrystals doped with the β-emitting radioisotope yttrium-90 ((90)Y). Size and shape of nanocrystals are tailored via tight control of reaction parameters and the type of rare earth hosts (e.g., Gd or Y) employed. Radiolabeled nanocrystals are synthesized in high radiochemical yield and purity as well as excellent radiolabel stability in the face of surface modification with different polymeric ligands. We demonstrate the Cerenkov radioluminescence imaging and magnetic resonance imaging capabilities of (90)Y-doped GdF3 nanoplates, which offer unique opportunities as a promising platform for multimodal imaging and targeted therapy.

Fast Nanorod Diffusion through Entangled Polymer Melts

Abstract: Nanorod diffusion in polymer melts is faster than predicted by the continuum model (CM). Rutherford backscattering spectrometry is used to measure the concentration profile of titanium dioxide (TiO2) nanorods (L = 43 nm, d = 5 nm) in a polystyrene (PS) matrix having molecular weights (M) from 9 to 2000 kDa. In the entangled regime, the tracer diffusion coefficients (D) of TiO2 decrease as the M–1.4, whereas the CM predicts DCM ∼ M–3.0 using the measured zero-shear viscosity of TiO2(1 vol %): PS(M) blends. By plotting D/DCM versus M/Me, where Me is the entanglement molecular weight, diffusion is enhanced by a factor of 10–103 as M/Me increases. The faster diffusion is attributed to decoupling of nanorod diffusion from polymer relaxations in the surrounding matrix, which is facilitated by the nanorod dimensions (i.e., L greater than and d less than the entanglement mesh size, 8 nm).

Spectrally-Resolved Dielectric Functions of Solution-Cast Quantum Dot Thin Films

Abstract: Quantum confinement is the divergence, at small crystallite size, of the electronic structure of semiconductor nanocrystals, or quantum dots, from the properties of larger crystals of the same materials. Although the extinction properties of quantum dots in the dispersed state have been extensively studied, many applications for quantum dots require the formation of a solid material which nonetheless retains a size-dependent electronic structure. The complex index of refraction (or complex dielectric function), including the extinction coefficient, is critical information for interpretation of optoelectronic measurements and use of quantum dot solids in optoelectronic devices. Here, spectroscopic ellipsometry is used to provide an all-optical method to determine the thickness, complex index, and extinction coefficient of thin films made of quantum-confined materials through the visible and near-infrared spectral ranges. The characteristic, size-dependent spectral features in the absorption of monodisperse...

Selective p- and n-Doping of Colloidal PbSe Nanowires To Construct Electronic and Optoelectronic Devices.

Abstract: We report the controlled and selective doping of colloidal PbSe nanowire arrays to define pn junctions for electronic and optoelectronic applications. The nanowires are remotely doped through their surface, p-type by exposure to oxygen and n-type by introducing a stoichiometric imbalance in favor of excess lead. By employing a patternable poly(methyl)methacrylate blocking layer, we define pn junctions in the nanowires along their length. We demonstrate integrated complementary metal-oxide semiconductor inverters in axially doped nanowires that have gains of 15 and a near full signal swing. We also show that these pn junction PbSe nanowire arrays form fast switching photodiodes with photocurrents that can be optimized in a gated-diode structure. Doping of the colloidal nanowires is compatible with device fabrication on flexible plastic substrates, promising a low-cost, solution-based route to high-performance nanowire devices.

Uniform Bimetallic Nanocrystals by High-Temperature Seed-Mediated Colloidal Synthesis and Their Catalytic Properties for Semiconducting Nanowire Growth

Abstract: A general procedure to prepare uniform gold-based bimetallic nanocrystals (NCs) is reported. The method relies on a seed-mediated approach in which deposition and in-situ alloying of a second metal (Ag, Pt, Hg, Sn, Cd) onto monodisperse Au seeds are performed at relatively high temperatures, giving access to bimetallic NCs of tunable compositions and properties. The position of the plasmon resonance in the original Au NCs is tunable over a wide range (∼300–520 nm) of the electromagnetic spectrum. We demonstrate the catalytic properties of these monodisperse NCs for growing single-crystalline semiconductor nanowires of uniform, small diameter (∼15–30 nm) via a vapor–liquid–solid (VLS) mechanism at low temperatures. This seeded-mediated approach is not restricted to Au but can be extended to several other combinations, making this procedure a straightforward method to prepare highly monodisperse and controllable multimetallic nanocrystals for optical and catalytic applications.

Characterization of Shape and Monodispersity of Anisotropic Nanocrystals through Atomistic X-ray Scattering Simulation

Abstract: Nanocrystals with anisotropic shape and high uniformity are now commonly produced as a result of significant advances in synthetic control. In most cases, the morphology of such materials is characterized only by electron microscopy, which makes the extraction of statistical information laborious and subject to bias. In this work, we describe how X-ray scattering patterns in conjunction with Debye formula simulations can be used to provide accurate atomisitic models for ensembles of anisotropic nanocrystals to complement and extend microscopic studies. Methods of sample preparation and measurement conditions are also discussed to provide appropriate experimental data. The scripts written to implement the Debye function are provided as a tool to allow researchers to obtain atomisitic models of nanocrystals.

Thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2 thin films

Abstract: The catalytic and photo-catalytic activity of well-defined anatase TiO2 nanocrystals for the partial oxidation of methanol was investigated using temperature-programmed desorption (TPD) in ultra-high vacuum in order to determine how crystallite size and shape affect reactivity. The TiO2 films used in this study were prepared from well-defined TiO2 nanocrystals synthesized by colloidal methods. These nanocrystals had a truncated bi-pyramidal shape which exposes primarily (101) and to a lesser extent (001) surfaces and ranged in size from 10 to 25 nm. Two distinct regimes of reactivity were investigated, namely in the dark and under UV light illumination. In the dark, methanol adsorbed dissociatively on the (001) planes and only molecularly on the (101) surfaces. Dissociated methoxy groups on the (001) surfaces coupled to produce dimethyl ether, suggesting the presence of fourfold coordinate Ti cations. Under UV light illumination, the nanocrystals were additionally found to be active for the photo-catalytic oxidation of methanol to methyl formate. On the (101) surfaces, this reaction proceeded in a stepwise photocatalytic pathway involving dehydrogenation of methanol to form methoxy groups and then formaldehyde, followed by coupling of these latter two species to form methyl formate. The (001) surfaces were also found to be photo-catalytically active but surface methoxy groups could be produced thermally and the reaction proceeds only to formaldehyde in the absence of molecularly adsorbed methanol. The overall photocatalytic activity of the nanocrystals was also was found to increase with increasing crystallite size. The results of this study show that thin films of well-defined nanocrystals are excellent model systems that can be used to help bridge the materials gap between studies of single crystal surfaces and high surface area polycrystalline catalysts.

Ultrafast electron trapping in ligand-exchanged quantum dot assemblies.

Abstract: We use time-integrated and time-resolved photoluminescence and absorption to characterize the low-temperature optical properties of CdSe quantum dot solids after exchanging native aliphatic ligands for thiocyanate and subsequent thermal annealing. In contrast to trends established at room temperature, our data show that at low temperature the band-edge absorptive bleach is dominated by 1S3/2h hole occupation in the quantum dot interior. We find that our ligand treatments, which bring enhanced interparticle coupling, lead to faster surface state electron trapping, a greater proportion of surface-related photoluminescence, and decreased band-edge photoluminescence lifetimes.

Characterization of rare-earth-doped nanophosphors for photodynamic therapy excited by clinical ionizing radiation beams

Abstract: We investigated the optical properties of novel terbium (Tb 3+ )-doped nanophosphors with various host compounds irradiated by clinical electron, photon, and proton beams for their potential as optical probes. The emission spectra of nanophosphors embedded in tissue-mimicking phantoms were collected by an optical fiber connected to a CCD-coupled spectrograph while the samples were irradiated with electron and photon beams generated by a medical linear accelerator and proton beams generated by a clinical cyclotron. We characterized the luminescence of such nanophosphors as a function of the beam energy and observed a dose dependency of the luminescence signal. We demonstrated x-ray luminescence, cathodoluminescence, and ionoluminescence of the nanophosphors in clinical ionizing radiation fields, which indicates their potential as downconverters of high-energy radiation into visible light.

Phosphor-based fiber optic microprobes for ionizing beam radiation dosimetry

Abstract: We have designed, fabricated, and characterized a fiberoptic probe composed of terbium-based phosphors for ionizing radiation dosimetry. Fiber optic probes consisting of ~1 mm layer of TbF3 covering the tip embedded in tissue-mimicking phantoms were irradiated with electron beams produced by a medical linear accelerator. Optical spectra of irradiated tips were taken using a fiber spectrometer. The luminescence signal from the phosphors was spectrally separated from the Cerenkov radiation generated in the fiber. In order to obtain the percent depth dose curve, the resultant decomposed spectra corresponding to the emission from the phosphors were considered as a measure of the absorbed dose. The measured depth dose curves using our fiber probes are in agreement with measurements performed by an electron diode, indicating the feasibility of using such fiber probes for ionizing radiation dosimetry.

Structure determination and modeling of monoclinic trioctylphosphine oxide.

Abstract: Trioctylphosphine oxide (TOPO), C24H51OP, was recrystallized from ambient evaporation in acetone. TOPO single crystals form with a monoclinic P21/c structure. Fourier transform IR (FT–IR) spectroscopy captures the characteristic stretching modes from the seven methyl­ene groups, the phosphoryl P=O bond, and the phosphor­yl–carbon bond.

Structure, morphology and catalytic properties of pure and alloyed Au–ZnO hierarchical nanostructures

Abstract: A novel preparation of Au@ZnO and Au/Cd–ZnO structures is reported. The different morphologies of the two nanostructures are the result of either multiple or single nucleation events depending on the crystalline nature of the Au or Au/Cd seeds. Both samples are surprisingly active for CO oxidation and the water–gas shift-reaction (WGSR) despite the large size (6–8 nm) of the Au cores, and show interesting support effects when deposited on different oxides.