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At least 289 records · Page 16

Shape- and Orientation-Dependent Scattering of Isolated Gold Nanostructures Using Polarized Dark-Field Microscopy

In this work, we demonstrate a simple and robust method for measuring the shape- and orientation-dependent optical scattering of various plasmonic nanostructures adsorbed onto a solid surface using polarized dark-field microscopy. By analyzing the dark-field scattering images of gold nanostructures using grazing incidence polarized light with a bench-top microscope, we are able to correlate optical scattering from the individual nanostructures with their shape and orientation. Depending on the size, shape, and orientation of the plasmonic nanostructures, they exhibit characteristic angle- and polarization-dependent scattering signals. Extracting the red, green, and blue channels of the scattering signals from a color-imaging detector as a function of azimuthal angle provides a polar plot of color intensity values that is characteristic of the underlying nanostructure. Examples are presented for various nanostructures, including spherical nanoparticles, nanotriangles, and nanorods. Experimental results are complemented by numerical calculations of the scattering spectra of representative model nanostructures. We demonstrate that the polarization- and orientation-dependent scattering behavior is a consequence of various localized surface plasmon modes existing in the nanostructures and can be used to verify the shape of individual objects as well as quickly identify the orientation of numerous objects on a densely populated substrate. We anticipate that this method will provide a rapid and efficient complement to the typical structural analysis of nanoparticles that is achieved by electron microscopy as well as providing a simple method for generating detailed information of the optical scattering of various types of individual plasmonic nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy

Battery performance is critically dependent on the nanostructure and electrochemical properties of the solid-electrolyte interphase (SEI)—a passivation film that exists on most lithium-battery anodes. However, knowledge of how the SEI nanostructure forms and its impact on ionic transport remains limited due to its sensitivity to transmission electron microscopy and difficulty in accurately probing the SEI impedance. Here, we track the voltage-dependent, stepwise evolution of the nanostructure and impedance of the SEI on CuO nanowires using cryogenic-electron microscopy (cryo-EM) and electrochemical impedance spectroscopy (EIS). In carbonate electrolyte, the SEI forms at 1.0 V vs Li/Li + as a 3 nm thick amorphous SEI and grows to 4 nm at 0.5 V; as the potential approaches 0.0 V vs Li/Li + , the SEI on the CuO nanowires forms an 8 nm thick inverted multilayered nanostructure in ethylene carbonate/diethyl carbonate (EC/DEC) electrolyte with 10 vol % fluoroethylene carbonate (FEC) and a mosaic nanostructure in EC/DEC electrolyte. Upon Li deposition, the total SEI thickness grows to 16 nm, and significant growth of the inner amorphous layer takes place in the inverted multilayered nanostructure, indicating that electrolyte permeates the SEI. Using a refined EIS methodology, we isolate the SEI impedance on Cu and find that the SEI nanostructure directly correlates to macroscopic Li-ion transport through the SEI. The inverted layered nanostructure decreases the interfacial impedance upon formation, whereas the mosaic nanostructure continually increases the interfacial impedance during growth. Furthermore these structural and electrochemical findings illustrate a more complete portrait of SEI formation and guide further improvements in engineered SEI.

25 ENERGY STORAGE↗

SAXS-guided unbiased coarse-grained Monte Carlo simulation for identification of self-assembly nanostructures and dimensions

Recent studies have shown that solvated amphiphiles can form nanostructured self-assemblies called dynamic binary complexes (DBCs) in the presence of ions. Since the nanostructures of DBCs are directly related to their viscoelastic properties, it is important to understand how the nanostructures change under different solution conditions. However, it is challenging to obtain a three-dimensional molecular description of these nanostructures by utilizing conventional experimental characterization techniques or thermodynamic models. To this end, we combined the structural data from small angle X-ray scattering (SAXS) experiments and thermodynamic knowledge from coarse-grained Monte Carlo (CGMC) simulations to identify the detailed three-dimensional nanostructure of DBCs. Specifically, unbiased CGMC simulations are performed with SAXS-guided initial conditions, which aids us to sample accurate nanostructures in a computationally efficient fashion. As a result, an elliptical bilayer nanostructure is obtained as the most probable nanostructure of DBCs whose dimensions are validated by scanning electron microscope (SEM) images. Then, utilizing the obtained molecular model of DBCs, here we could also explain the pH tunability of the system. Overall, our results from SAXS-guided unbiased CGMC simulations highlight that using potential energy combined with SAXS data, we can distinguish otherwise degenerate nanostructures resulting from the inherent ambiguity of SAXS patterns.

36 MATERIALS SCIENCE↗

CRISPR–Cas9-mediated nuclear transport and genomic integration of nanostructured genes in human primary cells

DNA nanostructures are a promising tool to deliver molecular payloads to cells. DNA origami structures, where long single-stranded DNA is folded into a compact nanostructure, present an attractive approach to package genes; however, effective delivery of genetic material into cell nuclei has remained a critical challenge. Here, we describe the use of DNA nanostructures encoding an intact human gene and a fluorescent protein encoding gene as compact templates for gene integration by CRISPR-mediated homology-directed repair (HDR). Our design includes CRISPR–Cas9 ribonucleoprotein binding sites on DNA nanostructures to increase shuttling into the nucleus. We demonstrate efficient shuttling and genomic integration of DNA nanostructures using transfection and electroporation. These nanostructured templates display lower toxicity and higher insertion efficiency compared to unstructured double-stranded DNA templates in human primary cells. Furthermore, our study validates virus-like particles as an efficient method of DNA nanostructure delivery, opening the possibility of delivering nanostructures in vivo to specific cell types. Together, these results provide new approaches to gene delivery with DNA nanostructures and establish their use as HDR templates, exploiting both their design features and their ability to encode genetic information. This work also opens a door to translate other DNA nanodevice functions, such as biosensing, into cell nuclei.

59 BASIC BIOLOGICAL SCIENCES↗

Synthesis, characterization, and hydrophobic properties of Bi{sub 2}S{sub 3} hierarchical nanostructures

Research highlights: {yields} Novel Bi{sub 2}S{sub 3} hierarchical nanostructures self-assembled by nanorods are successfully synthesized in mild benzyl alcohol system under hydrothermal conditions. {yields} The hierarchical nanostructures exhibit a flower-like shape. {yields} PVP plays an important role for the formation of the hierarchical nanostructures. {yields} Bi{sub 2}S{sub 3} film prepared from the flower-like hierarchical nanostructures exhibits good hydrophobic properties. -- Abstract: Novel Bi{sub 2}S{sub 3} hierarchical nanostructures self-assembled by nanorods are successfully synthesized in mild benzyl alcohol system under hydrothermal conditions. The hierarchical nanostructures exhibit a flower-like shape. X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) were used to characterize the as-synthesized samples. Meanwhile, the effect of various experimental parameters including the concentration of reagents and reaction time on final product has been investigated. In our experiment, PVP plays an important role for the formation of the hierarchical nanostructures and the possible mechanism was proposed. In addition, Bi{sub 2}S{sub 3} film prepared from the flower-like hierarchical nanostructures exhibits good hydrophobic properties, which may bring nontrivial functionalities and may have some promising applications in the future.

36 MATERIALS SCIENCE↗

Synthesis, characterization of WS{sub 2} nanostructures by vapor phase deposition

Ultrathin two-dimensional WS{sub 2} nanostructures with various morphologies have been prepared on SiO{sub 2}/Si (300 nm) and sapphire substrates by vapor phase deposition method. Simultaneously, tungsten nanostructures have also been obtained during the growth process. The nanostructures and morphologies of as-prepared products were systematically characterized by employing atomic force microscopy, Raman spectroscopy as well as scanning electron spectroscopy. The electrostatic properties of WS{sub 2} nanostructures were investigated exhibiting uniform surface potential and charge distributions. We have also detected the photoluminescence properties of WS{sub 2} nanostructures, which are dependent on the thickness and nanostructures of synthesized WS{sub 2}. These results suggest that the optoelectronic properties of WS{sub 2} nanostructures can be effectively tuned by quantum confinement effect and nanostructures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electrostatic interactions for directed assembly of high performance nanostructured energetic materials of Al/Fe{sub 2}O{sub 3}/multi-walled carbon nanotube (MWCNT)

Electrostatic self-assembly in organic solvent without intensively oxidative or corrosive environments, was adopted to prepare Al/Fe{sub 2}O{sub 3}/MWCNT nanostructured energetic materials as an energy generating material. The negatively charged MWCNT was used as a glue-like agent to direct the self-assembly of the well dispersed positively charged Al (fuel) and Fe{sub 2}O{sub 3} (oxide) nanoparticles. This spontaneous assembly method without any surfactant chemistry or other chemical and biological moieties decreased the aggregation of the same nanoparticles largely, moreover, the poor interfacial contact between the Al (fuel) and Fe{sub 2}O{sub 3} (oxide) nanoparticles was improved significantly, which was the key characteristic of high performance nanostructured energetic materials. In addition, the assembly process was confirmed as Diffusion-Limited Aggregation. The assembled Al/Fe{sub 2}O{sub 3}/MWCNT nanostructured energetic materials showed excellent performance with heat release of 2400 J/g, peak pressure of 0.42 MPa and pressurization rate of 105.71 MPa/s, superior to that in the control group Al/Fe{sub 2}O{sub 3} nanostructured energetic materials prepared by sonication with heat release of 1326 J/g, peak pressure of 0.19 MPa and pressurization rate of 33.33 MPa/s. Therefore, the approach, which is facile, opens a promising route to the high performance nanostructured energetic materials. - Graphical abstract: The negatively charged MWCNT was used as a glue-like agent to direct the self-assembly of the well dispersed positively charged Al (fuel) and Fe{sub 2}O{sub 3} (oxide) nanoparticles. - Highlights: • A facile spontaneous electrostatic assembly strategy without surfactant was adopted. • The fuels and oxidizers assembled into densely packed nanostructured composites. • The assembled nanostructured energetic materials have excellent performance. • This high performance energetic material can be scaled up for practical application. • This strategy can be applied into other nanostructured energetic material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation of highly ordered growth of single-crystalline Gd{sub 2}O{sub 2}S:Eu{sup 3+} nanostructures

Graphical abstract: Fabrication of highly ordered single-crystalline Gd{sub 2}O{sub 2}S:Eu{sup 3+} nanostructures over a porous anodized aluminum oxide (AAO) template via hydrothermal method is described. Well aligned non-collapsed Gd{sub 2}O{sub 2}S:Eu{sup 3+} nanostructures are ideal functional components for next generation luminescent devices. Research highlights: {yields} Synthesis of highly ordered Gd{sub 2}O{sub 2}S:Eu{sup 3+} nanotubes, nanorods and nanoflowers. {yields} Using template-assisted (AAO) hydrothermal method. {yields} Well aligned nanostructures for next generation luminescent devices. {yields} Detailed structural, morphology and the phase composition were studied. -- Abstract: A simple and facile template-assisted hydrothermal route has been demonstrated for the shape-selective preparation of highly ordered single-crystalline Gd{sub 2}O{sub 2}S:Eu{sup 3+} nanostructures, such as nanotubes, nanorods and nanoflowers. These fabricated nanostructures possess desirable atomic structures, surfaces, morphologies and properties to meet the growing demands and specific requirements of new technologies. The concentration of precursor chemicals, the temperature, the reaction time, and the use of a capping agent are key factors in the morphological control of Gd{sub 2}O{sub 2}S:Eu{sup 3+} nanostructures. The morphology and the phase composition of the prepared nanostructures were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy disperse spectroscopy (EDS) and photoluminescence (PL). We believe this technique will be readily adopted in realizing other forms of various nanostructured materials.

36 MATERIALS SCIENCE↗

Biotemplate synthesis of carbon nanostructures using bamboo as both the template and the carbon source

Graphical abstract: - Highlights: • A new method for the in situ growth of carbon nanostructures was demonstrated. • The bamboo was selected as both the green carbon source and the biotemplate. • Four distinct structural types of carbon nanostructure have been identified. • The corresponding growth mechanism of each carbon nanostructure was proposed. - Abstract: A series of carbon nanostructures were prepared via a biotemplate method by catalytic decomposition of bamboo impregnated with ferric nitrate. The natural nanoporous bamboo was used as both the green carbon source and the template for the in situ growth of carbon nanostructures. Scanning electron microscope, field emission transmission electron microscope and energy dispersive X-ray spectroscope were used to characterize the product. Four distinct structural types of carbon nanostructures have been identified, namely nanofibers, hollow carbon nanospheres, herringbone and bamboo-shaped nanotubes. The effect of reaction temperature (from 600 to 900 °C) on the growth behavior of carbon nanostructures was investigated and the corresponding growth mechanism was proposed. At low temperature the production of nanofibers was favored, while higher temperature led to bamboo-shaped nanostructures.

36 MATERIALS SCIENCE↗

Power generation from nanostructured PbTe-based thermoelectrics: comprehensive development from materials to modules

In this work, we demonstrate the use of high performance nanostructured PbTe-based materials in high conversion efficiency thermoelectric modules. We fabricated the samples of PbTe-2% MgTe doped with 4% Na and PbTe doped with 0.2% PbI2 with high thermoelectric figure of merit (ZT) and sintered them with Co-Fe diffusion barriers for use as p- and n-type thermoelectric legs, respectively. Transmission electron microscopy of the PbTe legs reveals two shapes of nanostructures, disk-like and spherical. The reduction in lattice thermal conductivity through nanostructuring gives a ZT of similar to 1.8 at 810 K for p-type PbTe and similar to 1.4 at 750 K for n-type PbTe. Nanostructured PbTe-based module and segmented-leg module using Bi2Te3 and nanostructured PbTe were fabricated and tested with hot-side temperatures up to 873 K in a vacuum. The maximum conversion efficiency of similar to 8.8% for a temperature difference (Delta T) of 570 K and B11% for a Delta T of 590 K have been demonstrated in the nanostructured PbTe-based module and segmented Bi2Te3/nanostructured PbTe module, respectively. Three-dimensional finite-element simulations predict that the maximum conversion efficiency of the nanostructured PbTe-based module and segmented Bi2Te3/nanostructured PbTe module reaches 12.2% for a Delta T of 570 K and 15.6% for a Delta T of 590 K respectively, which could be achieved if the electrical and thermal contact between the nanostructured PbTe legs and Cu interconnecting electrodes is further improved.

Hu, Xiaokai↗

Metal ion dopant-induced famatinite to chalcostibite phase transformation of copper antimony sulphide colloidal nanostructures: effect on photophysical and pseudocapacitance properties

Here, the strategic doping of transition metal ions into copper antimony sulphide (CAS) semiconducting nanostructures can significantly influence their photophysical and pseudocapacitive properties, for which there are few reports and therefore is the focus of this study. Accordingly, highly crystalline metal ion (Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ and Zn 2+ ) doped off-stoichiometric copper rich/poor, antimony-rich/poor, and sulphur-poor CAS nanostructures (10–23 nm) were grown via colloidal (hot-injection) synthesis using metal diethyldithiocarbamate precursors. Importantly, metal ion doping significantly influences the structure and composition of the off-stoichiometric CAS nanostructures. Data from powder X-ray diffraction, Raman spectroscopy, high-resolution scanning/transmission electron microscopy, and energy dispersive X-ray spectroscopy confirm that the heavier metal ion dopants induce a novel phase transformation from famatinite (fCAS) to chalcostibite (cCAS) nanostructures. The influence of the metal ion dopants is also observed in the optical properties of as-synthesized nanostructures. This involves blue-shifted ultraviolet-visible absorption, reduced Urbach tailing, and tunable bandgaps between 2.17 and 2.38 eV. Also, the doped nanostructures display broad visible-near infrared photoluminescence via a triple radiative pathway with relatively short decay lifetimes between 0.2 and 6.1 ns. This is mediated by electronic transitions involving intrinsic (copper/antimony/sulphur interstitial) and extrinsic (metal ion interstitial) defect states. Additionally, electrodes prepared from Mn 2+ -doped fCAS nanostructures show enhanced pseudocapacitance via Na+ surface adsorption and intercalation relative to undoped fCAS electrodes, while Zn 2+ -doped cCAS electrodes exhibit pseudocapacitance via a combination of Na+ surface adsorption, intercalation, and redox reactions. These electrodes exhibit reduced charge transfer resistance, improved electronic conductivity and notably enhanced specific capacitance (∼222 F g −1 ), and charge transport, as measured in 1 M Na 2 SO 4 electrolyte via cyclic voltammetry and electrochemical impedance spectroscopy. To this end, the discovery of the metal ion-induced phase transformation presents a new avenue for optimizing the functional properties of fCAS and cCAS nanostructures, highlighting the critical role of metal ion-related defects in controlling the optical and electrochemical properties, towards potential solar absorption and energy storage applications.

25 ENERGY STORAGE↗

DNA nanostructures coordinate gene silencing in mature plants

Delivery of biomolecules to plants relies on Agrobacterium infection or biolistic particle delivery, the former of which is amenable only to DNA delivery. The difficulty in delivering functional biomolecules such as RNA to plant cells is due to the plant cell wall, which is absent in mammalian cells and poses the dominant physical barrier to biomolecule delivery in plants. DNA nanostructure-mediated biomolecule delivery is an effective strategy to deliver cargoes across the lipid bilayer of mammalian cells; however, nanoparticle-mediated delivery without external mechanical aid remains unexplored for biomolecule delivery across the cell wall in plants. Herein, we report a systematic assessment of different DNA nanostructures for their ability to internalize into cells of mature plants, deliver siRNAs, and effectively silence a constitutively expressed gene in Nicotiana benthamiana leaves. We show that nanostructure internalization into plant cells and corresponding gene silencing efficiency depends on the DNA nanostructure size, shape, compactness, stiffness, and location of the siRNA attachment locus on the nanostructure. We further confirm that the internalization efficiency of DNA nanostructures correlates with their respective gene silencing efficiencies but that the endogenous gene silencing pathway depends on the siRNA attachment locus. Our work establishes the feasibility of biomolecule delivery to plants with DNA nanostructures and both details the design parameters of importance for plant cell internalization and also assesses the impact of DNA nanostructure geometry for gene silencing mechanisms.

59 BASIC BIOLOGICAL SCIENCES↗

Nanostructures of Boron, Carbon and Magnesium Diboride for High Temperature Superconductivity

Direct fabrication of Mg x B y nanostructures is achieved by employing metal (Ni,Mg) incorporated MCM-41 in the Hybrid Physical-Chemical Vapor Deposition (HPCVD) reaction. Different reaction conditions are tested to optimize the fabrication process. TEM analysis shows the fabrication of Mg x B y nanostructures starting at the reaction temperature of 600°C, with the yield of the nanostructures increasing with increasing reaction temperature. The as-synthesized Mg x B y nanostructures have the diameters in the range of 3-5nm, which do not increase with the reaction temperature consistent with templated synthesis. EELS analysis of the template removed nanostructures confirms the existence of B and Mg with possible contamination of Si and O. NEXAFS and Raman spectroscopy analysis suggested a concentric layer-by-layer MgxBy nanowire/nanotube growth model for our as-synthesized nanostructures. Ni k-edge XAS indicates that the formation of MgNi alloy particles is important for the Vapor-Liquid-Solid (VLS) growth of Mg x B y nanostructures with fine diameters, and the presence of Mg vapor not just Mg in the catalyst is crucial for the formation of Ni-Mg clusters. Physical templating by the MCM-41 pores was shown to confine the diameter of the nanostructures. DC magnetization measurements indicate possible superconductive behaviors in the as-synthesized samples.

36 MATERIALS SCIENCE↗

Synthesis and Properties of Nanostructured Exotic Superconductors (Final Report)

Superconductors are materials that conduct electricity with no resistance, i.e. no energy dissipation. In future electrically activated nanodevices, the use of superconducting interconnects is highly desirable, since it circumvents the damaging heat produced by energy dissipation in normal nano-conductors whose high resistance is inversely proportional to its cross-section area. Furthermore, the wave functions of the charge carriers - Cooper pairs will be strongly modified in a superconductor when they are squeezed into a small volume comparable to the coherence length or penetration depth. Thus, superconducting nanostructures provide unique platforms to investigate and discover novel superconducting phenomena in confined geometries. The objective of this DOE funded project was the development of novel approaches to synthesizing a new class of superconducting nanostructures such as nanowires and nanoribbons that are stable in atmosphere, enabling the exploration of superconducting properties and potential applications of individual nanostructures. We also pursued the modification of properties of the fabricated nanostructures by introducing artificial defects through nanoengineering. We developed a conversion approach comprised of two-steps to synthesize NbSe 2 and NbN nanowires/ribbons that were not achievable using other routes: first, we synthesized one-dimensional (1D) nanostructures of NbSe 3 and second, we converted these into desired 1D superconducting nanostructures of NbSe 2 and NbN by adjusting the composition of NbSe 3 nanostructure precursors while maintaining their shapes. Novel phenomena such as resistance oscillations with increasing magnetic fields were observed in both NbSe 2 and NbN nanowires/ribbons. By replacing the catalytic microparticles used in conventional whisker growth with the same kind of nanoparticles that are available now commercially, we improved whisker technologies for nanofabrication of high-T c superconductor nanowires/ribbons: we succeeded in the growth of Bi 2 Sr 2 CaCu 2 O 8+x (BSCCO-2212) and YBa 2 Cu 3 O 7-x (YBCO) nanowires and nanoribbons by annealing glassy precursors with alumina nanoparticles as growth sites. The high-quality whiskers enabled us to observe the ‘matching effect’ that represents itself as dips in the field dependence of the magnetoresistance and the influence of the periodic defects on the melting behavior of vortex matter. We also observed N-shaped V-I characteristics similar to those observed in semiconductor and plasma devices for the first time. Each nanofabrication technique has its advantages and drawbacks. For example, electron-beam lithography (EBL), in combination thin film deposition, has been widely used to fabricate nanowires (nanobridge) with well-defined cross-sections. However, electron-beam resist usually contaminates the sample up to a few hundred nanometers and hence degrades the quality of the entire nanowires if their widths are only a few hundred nanometers. We found that e-beam resist can degrade the superconducting critical temperature of a Nb nanowire from 9 K down to below 4 K if its width is less than 200 nm. We investigated the suitability of the various nanofabrication methods for achieving high-quality samples with desired properties. For example, we developed a novel way to achieve high quality Nb nanostrips with transverse dimensions of 150 nm or smaller. In the new process a superconducting bridge a few micrometers wide is fabricated with EBL. Subsequently, focused-ion-beam (FIB) is used to mill nano- 2 grooves to isolate an uncontaminated area of the microbridge to form a nanostrip. The high-quality superconducting Nb nanostrips with well-defined rectangular cross-sections fabricated using this new technique have enabled experimental confirmation of the theoretically predicted confinement-induced anisotropy effect on the magnetoresistance and critical field. We also found that FIB milling is more suitable than EBL in producing a pinning potential array with desired barrier between them into a MoGe film, which enabled us to realize the predicted vortex ices for the first time. By utilizing a filtration membrane as the substrate, we developed a new method to achieve networks of superconducting MoGe nanowires with transverse dimensions smaller than 10 nm. We observed superconducting confinement effect such as thermally activated phase slips and Little-Parks effect in these new samples. This research significantly advanced our knowledge on confined superconductors, in both their synthesis and physical properties. Though the new fabrication methods developed in this project aimed to achieve samples for studying new phenomena in confined superconductors, they can be utilized to obtain nanostructures of other functional materials. For example, we utilized the method developed to produce superconducting nanowire networks for the fabrication of networks of ultrasmall palladium (Pd) nanowires, which take advantage of single Pd nanowires while eliminating their nanofabrication obstacles, resulting in high-performance hydrogen sensors that are much more cost effective than those based on single Pd nanowires fabricated with lithography methods.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanostructured layers of thermoelectric materials

This disclosure provides systems, methods, and apparatus related to thermoelectric materials. In one aspect, a method includes providing a plurality of nanostructures. The plurality of nanostructures comprise a thermoelectric material, with each nanostructure of the plurality of nanostructures having first ligands disposed on a surface of the nanostructure. The plurality of nanostructures is mixed with a solution containing second ligands and a ligand exchange process occurs in which the first ligands disposed on the plurality of nanostructures are replaced with the second ligands. The plurality of nanostructures is deposited on a substrate to form a layer. The layer is thermally annealed.

36 MATERIALS SCIENCE↗

Nonaqueous seeded growth of flower-like mixed-phase titania nanostructures for photocatalytic applications

A nonaqueous seeded-grown synthesis of three-dimensional TiO{sub 2} nanostructures in the benzyl alcohol reaction system was reported. The synthesis was simple, high-yield, and requires no structural directing or capping agents. It could be largely accelerated by applying microwave heating. The TiO{sub 2} nanostructures had a unique flower-like morphology and high surface area. Furthermore, the structural analyses suggested that the nanostructures had a non-uniform distribution of crystalline phases, with the inner part rich in anatase and the outer part rich in rutile. After heat treatments, the mixed-phase TiO{sub 2} nanostructures exhibited high photocatalytic activities for the photodegradation of methylene blue as compared to Degussa P25. The high photoactivities may be associated with the high surface area and the synergistic effect resulting from the anisotropic mixed-phase nanostructures. The results demonstrate the uniqueness of the nonaqueous seeded growth and the potential of the TiO{sub 2} nanostructures for practical applications. - Graphical abstract: Flower-like TiO{sub 2} nanostructures synthesized by a nonaqueous seeded growth without using any structural directing or capping agents.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

In situ fabricate Cu{sub 2}S thin film with hierarchical petal-like nanostructures

Graphical abstract: - Highlights: • Cu{sub 2}S thin films with hierarchical nanostructures have been synthesized by solvothermal method using DMSO as reactant. • The band gap is estimated to be 1.0 eV of the Cu{sub 2}S hierarchical nanostructures. • The form process of Cu{sub 2}S and the possible mechanism of hierarchical nanostructures were proposed. - Abstract: In this paper, Cu{sub 2}S thin film with hierarchical petal-like nanostructures has been successfully in situ synthesized via a solvothermal method using DMSO as reactant under appropriate reaction conditions. The crystalline phase, morphology and optical properties of the resulting products were characterized by X-ray diffraction, energy-dispersive X-ray spectrometry, scanning electron microscopy and UV–vis absorption spectroscopy, respectively. The band gap is estimated to be about 1.0 eV by the results of UV–vis absorption spectroscopy of the Cu{sub 2}S thin film with hierarchical nanostructures that consisted of nanoslices with the thickness of 15 nm. The formation process of Cu{sub 2}S and the possible mechanism of hierarchical nanostructures were also proposed. These findings are valuable since Cu{sub 2}S thin film with hierarchical petal-like nanostructures are promising candidate as lithium ion battery and solar cell materials.

36 MATERIALS SCIENCE↗

Growth, characterization and electrochemical properties of hierarchical CuO nanostructures for supercapacitor applications

Graphical abstract: - Highlights: • Hierarchical CuO nanostructures were grown on Cu foil. • Monoclinic phase of CuO was grown. • XPS analysis revealed the presence of Cu(2p{sub 3/2}) and Cu(2p{sub 1/2}) on the surfaces. • Specific capacitance of 94 F/g was achieved for the CuO using cyclic voltammetry. • Impedance spectra show their pseudo capacitor applications. - Abstract: In this paper, we have investigated the electrochemical properties of hierarchical CuO nanostructures for pseudo-supercapacitor device applications. Moreover, the CuO nanostructures were formed on Cu substrate by in situ crystallization process. The as-grown CuO nanostructures were characterized using X-ray diffraction (XRD), Fourier transform-infra red spectroscopy (FT-IR), X-ray photoelectron spectroscopy and field emission-scanning electron microscope (FE-SEM) analysis. The XRD and FT-IR analysis confirm the formation of monoclinic CuO nanostructures. FE-SEM analysis shows the formation of leave like hierarchical structures of CuO with high uniformity and controlled density. The electrochemical analysis such as cyclic voltammetry and electrochemical impedance spectroscopy studies confirms the pseudo-capacitive behavior of the CuO nanostructures. Our experimental results suggest that CuO nanostructures will create promising applications of CuO toward pseudo-supercapacitors.

36 MATERIALS SCIENCE↗