A new generation of alloyed/multimetal chalcogenide nanowires by chemical transformation

PubMed Central

Yang, Yuan; Wang, Kai; Liang, Hai-Wei; Liu, Guo-Qiang; Feng, Mei; Xu, Liang; Liu, Jian-Wei; Wang, Jin-Long; Yu, Shu-Hong

2015-01-01

One-dimensional metal chalcogenide nanostructures are important candidates for many technological applications such as photovoltaic and thermoelectric devices. However, the design and synthesis of one-dimensional metal chalcogenide nanostructured materials with controllable components and properties remain a challenge. We report a general chemical transformation process for the synthesis of more than 45 kinds of one-dimensional alloyed/hybrid metal chalcogenide nanostructures inherited from mother template TexSey@Se core-shell nanowires with tunable compositions. As many as nine types of monometal chalcogenide alloy nanowires (including AgSeTe, HgSeTe, CuSeTe, BiSeTe, PbSeTe, CdSeTe, SbSeTe, NiSeTe, and CoSeTe) can be synthesized. Alloyed and hybrid nanowires integrated with two or more alloyed metal chalcogenide phases can also be prepared. The compositions of all of these metal chalcogenide nanowires are tunable within a wide range. This protocol provides a new general route for the controllable synthesis of a new generation of one-dimensional metal chalcogenide nanostructures. PMID:26601137

A new generation of alloyed/multimetal chalcogenide nanowires by chemical transformation.

PubMed

Yang, Yuan; Wang, Kai; Liang, Hai-Wei; Liu, Guo-Qiang; Feng, Mei; Xu, Liang; Liu, Jian-Wei; Wang, Jin-Long; Yu, Shu-Hong

2015-11-01

One-dimensional metal chalcogenide nanostructures are important candidates for many technological applications such as photovoltaic and thermoelectric devices. However, the design and synthesis of one-dimensional metal chalcogenide nanostructured materials with controllable components and properties remain a challenge. We report a general chemical transformation process for the synthesis of more than 45 kinds of one-dimensional alloyed/hybrid metal chalcogenide nanostructures inherited from mother template Te x Se y @Se core-shell nanowires with tunable compositions. As many as nine types of monometal chalcogenide alloy nanowires (including AgSeTe, HgSeTe, CuSeTe, BiSeTe, PbSeTe, CdSeTe, SbSeTe, NiSeTe, and CoSeTe) can be synthesized. Alloyed and hybrid nanowires integrated with two or more alloyed metal chalcogenide phases can also be prepared. The compositions of all of these metal chalcogenide nanowires are tunable within a wide range. This protocol provides a new general route for the controllable synthesis of a new generation of one-dimensional metal chalcogenide nanostructures.

Nano-scaled top-down of bismuth chalcogenides based on electrochemical lithium intercalation

NASA Astrophysics Data System (ADS)

Chen, Jikun; Zhu, Yingjie; Chen, Nuofu; Liu, Xinling; Sun, Zhengliang; Huang, Zhenghong; Kang, Feiyu; Gao, Qiuming; Jiang, Jun; Chen, Lidong

2011-12-01

A two-step method has been used to fabricate nano-particles of layer-structured bismuth chalcogenide compounds, including Bi2Te3, Bi2Se3, and Bi2Se0.3Te2.7, through a nano-scaled top-down route. In the first step, lithium (Li) atoms are intercalated between the van der Waals bonded quintuple layers of bismuth chalcogenide compounds by controllable electrochemical process inside self-designed lithium ion batteries. And in the second step, the Li intercalated bismuth chalcogenides are subsequently exposed to ethanol, in which process the intercalated Li atoms would explode like atom-scaled bombs to exfoliate original microscaled powder into nano-scaled particles with size around 10 nm. The influence of lithium intercalation speed and amount to three types of bismuth chalcogenide compounds are compared and the optimized intercalation conditions are explored. As to maintain the phase purity of the final nano-particle product, the intercalation lithium amount should be well controlled in Se contained bismuth chalcogenide compounds. Besides, compared with binary bismuth chalcogenide compound, lower lithium intercalation speed should be applied in ternary bismuth chalcogenide compound.

Synthesis of 2D Metal Chalcogenide Thin Films through the Process Involving Solution-Phase Deposition.

PubMed

Giri, Anupam; Park, Gyeongbae; Yang, Heeseung; Pal, Monalisa; Kwak, Junghyeok; Jeong, Unyong

2018-04-24

2D metal chalcogenide thin films have recently attracted considerable attention owing to their unique physicochemical properties and great potential in a variety of applications. Synthesis of large-area 2D metal chalcogenide thin films in controllable ways remains a key challenge in this research field. Recently, the solution-based synthesis of 2D metal chalcogenide thin films has emerged as an alternative approach to vacuum-based synthesis because it is relatively simple and easy to scale up for high-throughput production. In addition, solution-based thin films open new opportunities that cannot be achieved from vacuum-based thin films. Here, a comprehensive summary regarding the basic structures and properties of different types of 2D metal chalcogenides, the mechanistic details of the chemical reactions in the synthesis of the metal chalcogenide thin films, recent successes in the synthesis by different reaction approaches, and the applications and potential uses is provided. In the last perspective section, the technical challenges to be overcome and the future research directions in the solution-based synthesis of 2D metal chalcogenides are discussed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High surface area graphene-supported metal chalcogenide assembly

DOEpatents

Worsley, Marcus A.; Kuntz, Joshua D.; Orme, Christine A.

2017-04-25

Disclosed here is a method for hydrocarbon conversion, comprising contacting at least one graphene-supported assembly with at least one hydrocarbon feedstock, wherein the graphene-supported assembly comprises (i) a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds and (ii) at least one metal chalcogenide compound disposed on the graphene sheets, wherein the chalcogen of the metal chalcogenide compound is selected from S, Se and Te, and wherein the metal chalcogenide compound accounts for at least 20 wt. % of the graphene-supported assembly.

Hydrogen treatment as a detergent of electronic trap states in lead chalcogenide nanoparticles

DOE PAGES

Vörös, Márton; Brawand, Nicholas P.; Galli, Giulia

2016-11-15

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial formore » charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Lastly, our findings suggest that postsynthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films.« less

Surface Chemistry in Cobalt Phosphide-Stabilized Lithium-Sulfur Batteries.

PubMed

Zhong, Yiren; Yin, Lichang; He, Peng; Liu, Wen; Wu, Zishan; Wang, Hailiang

2018-01-31

Chemistry at the cathode/electrolyte interface plays an important role for lithium-sulfur batteries in which stable cycling of the sulfur cathode requires confinement of the lithium polysulfide intermediates and their fast electrochemical conversion on the electrode surface. While many materials have been found to be effective for confining polysulfides, the underlying chemical interactions remain poorly understood. We report a new and general lithium polysulfide-binding mechanism enabled by surface oxidation layers of transition-metal phosphide and chalcogenide materials. We for the first time find that CoP nanoparticles strongly adsorb polysulfides because their natural oxidation (forming Co-O-P-like species) activates the surface Co sites for binding polysulfides via strong Co-S bonding. With a surface oxidation layer capable of confining polysulfides and an inner core suitable for conducting electrons, the CoP nanoparticles are thus a desirable candidate for stabilizing and improving the performance of sulfur cathodes in lithium-sulfur batteries. We demonstrate that sulfur electrodes that hold a high mass loading of 7 mg cm -2 and a high areal capacity of 5.6 mAh cm -2 can be stably cycled for 200 cycles. We further reveal that this new surface oxidation-induced polysulfide-binding scheme applies to a series of transition-metal phosphide and chalcogenide materials and can explain their stabilizing effects for lithium-sulfur batteries.

Sulfur in oleylamine as a powerful and versatile etchant for oxide, sulfide, and metal colloidal nanoparticles: Sulfur in oleylamine as a powerful and versatile etchant

DOE PAGES

Yuan, Bin; Tian, Xinchun; Shaw, Santosh; ...

2016-11-02

Understanding of crystal growth is essential to the design of materials with improved properties. Unfortunately, still very little is understood about the basic growth mechanisms of nanostructures, even in the most established colloidal synthetic routes. Etching is one of the most important mechanisms to consider during particle growth, but it is rarely considered in the syntheses of oxide or chalcogenide nanostructures. Here in this paper, we report that the most common precursor for the synthesis of sulfide nanostructures – the mixture of sulfur and oleylamine – acts as a very powerful etchant for oxide, chalcogenide, and metal nanostructures. Specifically, wemore » discuss its effect on several nanoparticle compositions (PbS, Cu 2S, Fe 3O 4, and Au) and compare it to control conditions in which only oleylamine is present. Our experiments suggest that the etching results from the evolution of H 2S from the sulfur–oleylamine precursor. We predict that the simultaneous role of this precursor as both etchant and ligand stabilizer will make it a useful tool for the chemical post-processing (e.g., size reduction, focusing of size distributions, faceting) of nanocrystal dispersions.« less

Optimization of Phase Change Memory with Thin Metal Inserted Layer on Material Properties

NASA Astrophysics Data System (ADS)

Harnsoongnoen, Sanchai; Sa-Ngiamsak, Chiranut; Siritaratiwat, Apirat

This works reports, for the first time, the thorough study and optimisation of Phase Change Memory (PCM) structure with thin metal inserted chalcogenide via electrical resistivity (ρ) using finite element modeling. PCM is one of the best candidates for next generation non-volatile memory. It has received much attention recently due to its fast write speed, non-destructive readout, superb scalability, and great compatibility with current silicon-based mass fabrication. The setback of PCM is a high reset current typically higher than 1mA based on 180nm lithography. To reduce the reset current and to solve the over-programming failure, PCM with thin metal inserted chalcogenide (bottom chalcogenide/metal inserted/top chalcogenide) structure has been proposed. Nevertheless, reports on optimisation of the electrical resistivity using the finite element method for this new PCM structure have never been published. This work aims to minimize the reset current of this PCM structure by optimizing the level of the electrical resistivity of the PCM profile using the finite element approach. This work clearly shows that PCM characteristics are strongly affected by the electrical resistivity. The 2-D simulation results reveal clearly that the best thermal transfer of and self-joule-heating at the bottom chalcogenide layer can be achieved under conditions; ρ_bottom chalcogenide > ρ_metal inserted > ρ_top chalcogenide More specifically, the optimized electrical resistivity of PCMTMI is attained with ρ_top chalcogenide: ρ_metal inserted: ρ_bottom chalcogenide ratio of 1:6:16 when ρ_top chalcogenide is 10-3 Ωm. In conclusion, high energy efficiency can be obtained with the reset current as low as 0.3mA and with high speed operation of less than 30ns.

Growth Mechanism of Transition Metal Dichalcogenide Monolayers: The Role of Self-Seeding Fullerene Nuclei.

PubMed

Cain, Jeffrey D; Shi, Fengyuan; Wu, Jinsong; Dravid, Vinayak P

2016-05-24

Due to their unique optoelectronic properties and potential for next generation devices, monolayer transition metal dichalcogenides (TMDs) have attracted a great deal of interest since the first observation of monolayer MoS2 a few years ago. While initially isolated in monolayer form by mechanical exfoliation, the field has evolved to more sophisticated methods capable of direct growth of large-area monolayer TMDs. Chemical vapor deposition (CVD) is the technique used most prominently throughout the literature and is based on the sulfurization of transition metal oxide precursors. CVD-grown monolayers exhibit excellent quality, and this process is widely used in studies ranging from the fundamental to the applied. However, little is known about the specifics of the nucleation and growth mechanisms occurring during the CVD process. In this study, we have investigated the nucleation centers or "seeds" from which monolayer TMDs typically grow. This was accomplished using aberration-corrected scanning transmission electron microscopy to analyze the structure and composition of the nuclei present in CVD-grown MoS2-MoSe2 alloys. We find that monolayer growth proceeds from nominally oxi-chalcogenide nanoparticles which act as heterogeneous nucleation sites for monolayer growth. The oxi-chalcogenide nanoparticles are typically encased in a fullerene-like shell made of the TMD. Using this information, we propose a step-by-step nucleation and growth mechanism for monolayer TMDs. Understanding this mechanism may pave the way for precise control over the synthesis of 2D materials, heterostructures, and related complexes.

Method to synthesize metal chalcogenide monolayer nanomaterials

DOEpatents

Hernandez-Sanchez, Bernadette A.; Boyle, Timothy J.

2016-12-13

Metal chalcogenide monolayer nanomaterials can be synthesized from metal alkoxide precursors by solution precipitation or solvothermal processing. The synthesis routes are more scalable, less complex and easier to implement than other synthesis routes.

Hydrogen treatment as a detergent of electronic trap states in lead chalcogenide nanoparticles

NASA Astrophysics Data System (ADS)

Voros, Marton; Brawand, Nicholas; Galli, Giulia

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations, irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial for charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Our findings suggest that post-synthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films. Work supported by the Center for Advanced Solar Photophysics, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (NB) and U.S. DOE under Contract No. DE-AC02-06CH11357 (MV).

Precision synthesis of colloidal inorganic nanocrystals using metal and metalloid amides

NASA Astrophysics Data System (ADS)

Yarema, Maksym; Caputo, Riccarda; Kovalenko, Maksym V.

2013-08-01

Rational selection of molecular precursors is the key consideration in the synthesis of inorganic nanocrystals and nanoparticles. This review highlights the state-of-the-art and future potential of metal amides as precursors in the solution-phase synthesis of monodisperse colloidal nanocrystals of metals and metal alloys, as well as metal oxides and chalcogenides. We exclusively focus on homoleptic metal and metalloid alkylamides M(NR2)n and silylamides M[N(SiMe3)2]n as predominant choice of element-nitrogen bonded precursors, which are often advantageous to commonly used metal-oxygen and metal-carbon bonded counterparts. In particular, these amides are highly reactive in oxidation, reduction and metathesis reactions; they are oxygen-free, easy-to-make and/or commercially available. A comprehensive literature review is complemented by our theoretical studies on the thermal stability of metal silylamides using molecular dynamics simulations.

Metal–metal chalcogenide molecular precursors to binary, ternary, and quaternary metal chalcogenide thin films for electronic devices

DOE PAGES

Zhang, Ruihong; Cho, Seonghyuk; Lim, Daw Gen; ...

2016-03-15

We found that bulk metals and metal chalcogenides dissolve in primary amine–dithiol solvent mixtures at ambient conditions. Thin-films of CuS, SnS, ZnS, Cu 2Sn(Sx,Se 1-x) 3, and Cu 2ZnSn(SxSe 1-x) 4 (0 ≤ x ≤ 1) were deposited using the as-dissolved solutions. Furthermore, Cu 2ZnSn(SxSe 1-x) 4 solar cells with efficiencies of 6.84% and 7.02% under AM1.5 illumination were fabricated from two example solution precursors, respectively.

Electroactive Nanoporous Metal Oxides and Chalcogenides by Chemical Design

PubMed Central

2017-01-01

The archetypal silica- and aluminosilicate-based zeolite-type materials are renowned for wide-ranging applications in heterogeneous catalysis, gas-separation and ion-exchange. Their compositional space can be expanded to include nanoporous metal chalcogenides, exemplified by germanium and tin sulfides and selenides. By comparison with the properties of bulk metal dichalcogenides and their 2D derivatives, these open-framework analogues may be viewed as three-dimensional semiconductors filled with nanometer voids. Applications exist in a range of molecule size and shape discriminating devices. However, what is the electronic structure of nanoporous metal chalcogenides? Herein, materials modeling is used to describe the properties of a homologous series of nanoporous metal chalcogenides denoted np-MX2, where M = Si, Ge, Sn, Pb, and X = O, S, Se, Te, with Sodalite, LTA and aluminum chromium phosphate-1 structure types. Depending on the choice of metal and anion their properties can be tuned from insulators to semiconductors to metals with additional modification achieved through doping, solid solutions, and inclusion (with fullerene, quantum dots, and hole transport materials). These systems form the basis of a new branch of semiconductor nanochemistry in three dimensions. PMID:28572706

High surface area graphene-supported metal chalcogenide assembly

DOEpatents

Worsley, Marcus A.; Kuntz, Joshua; Orme, Christine A.

2016-04-19

A composition comprising at least one graphene-supported assembly, which comprises a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds, and at least one metal chalcogenide compound disposed on said graphene sheets, wherein the chalcogen of said metal chalcogenide compound is selected from S, Se and Te. Also disclosed are methods for making and using the graphene-supported assembly, including graphene-supported MoS.sub.2. Monoliths with high surface area and conductivity can be achieved. Lower operating temperatures in some applications can be achieved. Pore size and volume can be tuned.

Tunable Room-Temperature Synthesis of Coinage Metal Chalcogenide Nanocrystals from N -Heterocyclic Carbene Synthons

DOE PAGES

Lu, Haipeng; Brutchey, Richard L.

2017-01-23

Here we present a new toolset of precursors for semiconductor nanocrystal synthesis, N-heterocyclic carbene (NHC)-metal halide complexes, which enables a tunable molecular platform for the preparation of coinage metal chalcogenide quantum dots (QDs). Phase-pure and highly monodisperse coinage metal chalcogenide (Ag 2E, Cu 2-xE; E = S, Se) QDs are readily synthesized from the direct reaction of an NHC-MBr synthon (where M = Ag, Cu) with alkylsilyl chalcogenide reagents at room temperature. We demonstrate that the size of the resulting QDs is well tailored by the electron-donating ability of the L-type NHC ligands, which are further confirmed to be themore » only organic capping ligands on the QD surface, imparting excellent colloidal stability. Local superstructures of the NHC-capped Ag 2S QDs are observed by TEM, further demonstrating their potential for synthesizing monodisperse ensembles and mediating self-assembly.« less

Tunable Room-Temperature Synthesis of Coinage Metal Chalcogenide Nanocrystals from N -Heterocyclic Carbene Synthons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Haipeng; Brutchey, Richard L.

Here we present a new toolset of precursors for semiconductor nanocrystal synthesis, N-heterocyclic carbene (NHC)-metal halide complexes, which enables a tunable molecular platform for the preparation of coinage metal chalcogenide quantum dots (QDs). Phase-pure and highly monodisperse coinage metal chalcogenide (Ag 2E, Cu 2-xE; E = S, Se) QDs are readily synthesized from the direct reaction of an NHC-MBr synthon (where M = Ag, Cu) with alkylsilyl chalcogenide reagents at room temperature. We demonstrate that the size of the resulting QDs is well tailored by the electron-donating ability of the L-type NHC ligands, which are further confirmed to be themore » only organic capping ligands on the QD surface, imparting excellent colloidal stability. Local superstructures of the NHC-capped Ag 2S QDs are observed by TEM, further demonstrating their potential for synthesizing monodisperse ensembles and mediating self-assembly.« less

Open framework metal chalcogenides as efficient photocatalysts for reduction of CO2 into renewable hydrocarbon fuel.

PubMed

Sasan, Koroush; Lin, Qipu; Mao, Chengyu; Feng, Pingyun

2016-06-07

Open framework metal chalcogenides are a family of porous semiconducting materials with diverse chemical compositions. Here we show that these materials containing covalent three-dimensional superlattices of nanosized supertetrahedral clusters can function as efficient photocatalysts for the reduction of CO2 to CH4. Unlike dense semiconductors, metal cations are successfully incorporated into the channels of the porous semiconducting materials to further tune the physical properties of the materials such as electrical conductivity and band gaps. In terms of the photocatalytic properties, the metal-incorporated porous chalcogenides demonstrated enhanced solar energy absorption and higher electrical conductivity and improved photocatalytic activity.

Solution-based synthesis and design of late transition metal chalcogenide materials for oxygen reduction reaction (ORR).

PubMed

Gao, Min-Rui; Jiang, Jun; Yu, Shu-Hong

2012-01-09

Late transition metal chalcogenide (LTMC) nanomaterials have been introduced as a promising Pt-free oxygen reduction reaction (ORR) electrocatalysts because of their low cost, good ORR activity, high methanol tolerance, and facile synthesis. Herein, an overview on the design and synthesis of LTMC nanomaterials by solution-based strategies is presented along with their ORR performances. Current solution-based synthetic approaches towards LTMC nanomaterials include a hydrothermal/solvothermal approach, single-source precursor approach, hot-injection approach, template-directed soft synthesis, and Kirkendall-effect-induced soft synthesis. Although the ORR activity and stability of LTMC nanomaterials are still far from what is needed for practical fuel-cell applications, much enhanced electrocatalytic performance can be expected. Recent advances have emphasized that decorating the surface of the LTMC nanostructures with other functional nanoparticles can lead to much better ORR catalytic activity. It is believed that new synthesis approaches to LTMCs, modification techniques of LTMCs, and LTMCs with desirable morphology, size, composition, and structures are expected to be developed in the future to satisfy the requirements of commercial fuel cells. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vörös, Márton; Brawand, Nicholas P.; Galli, Giulia

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial formore » charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Lastly, our findings suggest that postsynthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films.« less

Colloidal chemical synthesis and formation kinetics of uniformly sized nanocrystals of metals, oxides, and chalcogenides.

PubMed

Kwon, Soon Gu; Hyeon, Taeghwan

2008-12-01

Nanocrystals exhibit interesting electrical, optical, magnetic, and chemical properties not achieved by their bulk counterparts. Consequently, to fully exploit the potential of nanocrystals, the synthesis of nanocrystals must focus on producing materials with uniform size and shape. Top-down physical processes can produce large quantities of nanocrystals, but controlling the size is difficult with these methods. On the other hand, colloidal chemical synthetic methods can produce uniform nanocrystals with a controlled particle size. In this Account, we present our synthesis of uniform nanocrystals of various shapes and materials, and we discuss the kinetics of nanocrystal formation. We employed four different synthetic approaches including thermal decomposition, nonhydrolytic sol-gel reactions, thermal reduction, and use of reactive chalcogen reagents. We synthesized uniform oxide nanocrystals via heat-up methods. This method involved slowly heat-up reaction mixtures composed of metal precursors, surfactants, and solvents from room temperature to high temperature. We then held reaction mixtures at an aging temperature for a few minutes to a few hours. Kinetics studies revealed a three-step mechanism for the synthesis of nanocrystals through the heat-up method with size distribution control. First, as metal precursors thermally decompose, monomers accumulate. At the aging temperature, burst nucleation occurs rapidly; at the end of this second phase, nucleation stops, but continued diffusion-controlled growth leads to size focusing to produce uniform nanocrystals. We used nonhydrolytic sol-gel reactions to synthesize various transition metal oxide nanocrystals. We employed ester elimination reactions for the synthesis of ZnO and TiO(2) nanocrystals. Uniform Pd nanoparticles were synthesized via a thermal reduction reaction induced by heating up a mixture of Pd(acac)(2), tri-n-octylphosphine, and oleylamine to the aging temperature. Similarly, we synthesized nanoparticles of copper and nickel using metal(II) acetylacetonates. Ni/Pd core/shell nanoparticles were synthesized by simply heating the reaction mixture composed of acetylacetonates of nickel and palladium. Using alternative chalcogen reagents, we synthesized uniform nanocrystals of various metal chalcogenides. Uniform nanocrystals of PbS, ZnS, CdS, and MnS were obtained by heating reaction mixtures composed of metal chlorides and sulfur dissolved in oleylamine. In the future, a detailed understanding of nanocrystal formation kinetics and synthetic chemistry will lead to the synthesis of uniform nanocrystals with controlled size, shape, and composition. In particular, the synthesis of uniform nanocrystals of doped materials, core/shell materials, and multicomponent materials is still a challenge. We expect that these uniformly sized nanocrystals will find important applications in areas including information technology, biomedicine, and energy/environmental technology.

2D Metal Chalcogenides Incorporated into Carbon and their Assembly for Energy Storage Applications.

PubMed

Deng, Zongnan; Jiang, Hao; Li, Chunzhong

2018-05-01

2D metal chalcogenides have become a popular focus in the energy storage field because of their unique properties caused by their single-atom thicknesses. However, their high surface energy and van der Waals attraction easily cause serious stacking and restacking, leading to the generation of more inaccessible active sites with rapid capacity fading. The hybridization of 2D metal chalcogenides with highly conductive materials, particularly, incorporating ultrasmall and few-layered metal chalcogenides into carbon frameworks, can not only maximize the exposure of active sites but also effectively avoid their stacking and aggregation during the electrochemical reaction process. Therefore, a satisfactory specific capacity will be achieved with a long cycle life. In this Concept, the representative progress on such intriguing nanohybrids and their applications in energy storage devices are mainly summarized. Finally, an outlook of the future development and challenges of such nanohybrids for achieving an excellent energy storage capability is also provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multitopic ligand directed assembly of low-dimensional metal-chalcogenide organic frameworks.

PubMed

Liu, Yi; Ye, Kaiqi; Wang, Yue; Zhang, Qichun; Bu, Xianhui; Feng, Pingyun

2017-01-31

Despite tremendous progress in metal-organic frameworks, only limited success has been achieved with metal-chalcogenide organic frameworks. Metal-chalcogenide organic frameworks are desirable because they offer a promising route towards tunable semiconducting porous frameworks. Here, four novel semiconducting chalcogenide-organic hybrid compounds have been synthesized through a solvothermal method. Multitopic organic molecules, i.e., 1,2-di-(4-pyridyl)ethylene (L 1 ), 1,3,5-tris(4-pyridyl-trans-ethenyl)benzene (L 2 ) and tetrakis(4-pyridyloxymethylene)methane (L 3 ), have been used as linkers to assemble Zn(SAr) 2 or Zn 2 (SAr) 4 units to generate different patterns of spatial organizations. Single-crystal structural analyses indicate that compounds NTU-2, NTU-3 and NTU-4 possess two-dimensional layer structures, while compound NTU-1 adopts a one-dimensional coordination framework (NTU-n, where n is the number related to a specific structure). The diffuse-reflectance spectra demonstrate that these four compounds possess indirect bandgaps and their tunable bandgaps are correlated with their compositions and crystal structures.

Repairing Nanoparticle Surface Defects.

PubMed

Marino, Emanuele; Kodger, Thomas E; Crisp, Ryan W; Timmerman, Dolf; MacArthur, Katherine E; Heggen, Marc; Schall, Peter

2017-10-23

Solar devices based on semiconductor nanoparticles require the use of conductive ligands; however, replacing the native, insulating ligands with conductive metal chalcogenide complexes introduces structural defects within the crystalline nanostructure that act as traps for charge carriers. We utilized atomically thin semiconductor nanoplatelets as a convenient platform for studying, both microscopically and spectroscopically, the development of defects during ligand exchange with the conductive ligands Na 4 SnS 4 and (NH 4 ) 4 Sn 2 S 6 . These defects can be repaired via mild chemical or thermal routes, through the addition of L-type ligands or wet annealing, respectively. This results in a higher-quality, conductive, colloidally stable nanomaterial that may be used as the active film in optoelectronic devices. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Chalcogenide Nanoionic-based Radio Frequency Switch

NASA Technical Reports Server (NTRS)

Nessel, James (Inventor); Lee, Richard (Inventor)

2013-01-01

A nonvolatile nanoionic switch is disclosed. A thin layer of chalcogenide glass engages a substrate and a metal selected from the group of silver and copper photo-dissolved in the chalcogenide glass. A first oxidizable electrode and a second inert electrode engage the chalcogenide glass and are spaced apart from each other forming a gap therebetween. A direct current voltage source is applied with positive polarity applied to the oxidizable electrode and negative polarity applied to the inert electrode which electrodeposits silver or copper across the gap closing the switch. Reversing the polarity of the switch dissolves the electrodeposited metal and returns it to the oxidizable electrode. A capacitor arrangement may be formed with the same structure and process.

Chalcogenide Nanoionic-Based Radio Frequency Switch

NASA Technical Reports Server (NTRS)

Nessel, James (Inventor); Lee, Richard (Inventor)

2011-01-01

A nonvolatile nanoionic switch is disclosed. A thin layer of chalcogenide glass engages a substrate and a metal selected from the group of silver and copper photo-dissolved in the chalcogenide glass. A first oxidizable electrode and a second inert electrode engage the chalcogenide glass and are spaced apart from each other forming a gap there between. A direct current voltage source is applied with positive polarity applied to the oxidizable electrode and negative polarity applied to the inert electrode which electrodeposits silver or copper across the gap closing the switch. Reversing the polarity of the switch dissolves the electrodeposited metal and returns it to the oxidizable electrode. A capacitor arrangement may be formed with the same structure and process.

Low-Temperature Growth of Two-Dimensional Layered Chalcogenide Crystals on Liquid.

PubMed

Zhou, Yubing; Deng, Bing; Zhou, Yu; Ren, Xibiao; Yin, Jianbo; Jin, Chuanhong; Liu, Zhongfan; Peng, Hailin

2016-03-09

The growth of high-quality two-dimensional (2D) layered chalcogenide crystals is highly important for practical applications in future electronics, optoelectronics, and photonics. Current route for the synthesis of 2D chalcogenide crystals by vapor deposition method mainly involves an energy intensive high-temperature growth process on solid substrates, often suffering from inhomogeneous nucleation density and grain size distribution. Here, we first demonstrate a facile vapor-phase synthesis of large-area high-quality 2D layered chalcogenide crystals on liquid metal surface with relatively low surface energy at a growth temperature as low as ∼100 °C. Uniform and large-domain-sized 2D crystals of GaSe and GaxIn1-xSe were grown on liquid metal surface even supported on a polyimide film. As-grown 2D GaSe crystals have been fabricated to flexible photodetectors, showing high photoresponse and excellent flexibility. Our strategy of energy-sustainable low-temperature growth on liquid metal surface may open a route to the synthesis of high-quality 2D crystals of Ga-, In-, Bi-, Hg-, Pb-, or Sn-based chalcogenides and halides.

Atomic layer deposition of quaternary chalcogenides

DOEpatents

Thimsen, Elijah J; Riha, Shannon C; Martinson, Alex B.F.; Elam, Jeffrey W; Pellin, Michael J

2014-06-03

Methods and systems are provided for synthesis and deposition of chalcogenides (including Cu.sub.2ZnSnS.sub.4). Binary compounds, such as metal sulfides, can be deposited by alternating exposures of the substrate to a metal cation precursor and a chalcogen anion precursor with purge steps between.

Half-Metallic Ferromagnetism and Stability of Transition Metal Pnictides and Chalcogenides

NASA Astrophysics Data System (ADS)

Liu, Bang-Gui

It is highly desirable to explore robust half-metallic ferromagnetic materials compatible with important semiconductors for spintronic applications. A state-of-the-art full potential augmented plane wave method within the densityfunctional theory is reliable enough for this purpose. In this chapter we review theoretical research on half-metallic ferromagnetism and structural stability of transition metal pnictides and chalcogenides. We show that some zincblende transition metal pnictides are half-metallic and the half-metallic gap can be fairly wide, which is consistent with experiment. Systematic calculations reveal that zincblende phases of CrTe, CrSe, and VTe are excellent half-metallic ferromagnets. These three materials have wide half-metallic gaps, are low in total energy with respect to the corresponding ground-state phases, and, importantly, are structurally stable. Halfmetallic ferromagnetism is also found in wurtzite transition metal pnictides and chalcogenides and in transition-metal doped semiconductors as well as deformed structures. Some of these half-metallic materials could be grown epitaxially in the form of ultrathin .lms or layers suitable for real spintronic applications.

Low-Temperature Synthesis of New Ternary Chalcogenide Compounds of Copper, Gold, and Mercury Using Alkali Metal Polychalcogenide Fluxes

NASA Astrophysics Data System (ADS)

Park, Younbong

In last two decades great efforts have been exerted to find new materials with interesting optical, electrical, and catalytic properties. Metal chalcogenides have been studied extensively because of their interesting physical properties and rich structural chemistry, among the potential materials. Prior to this work, most known metal chalcogenides had been synthesized at high temperature (T > 500^circC). Intermediate temperature synthesis in solid state chemistry was seldom pursued because of the extremely slow diffusion rates between reactants. This intermediate temperature regime could be a new synthesis condition if one looks for new materials with unusual structural features and properties. Metastable or kinetically stable compounds can be stabilized in this intermediate temperature regime, in contrast to the thermodynamically stable high temperature compounds. Molten salts, especially alkali metal polychalcogenide fluxes, can provide a route for exploring new chalcogenide materials at intermediate temperatures. These fluxes are very reactive and melt as low as 145^circC (mp of K_2S_4). Using these fluxes as reaction media, we have encountered many novel chalcogenide compounds with unusual structures and interesting electrical properties (semiconductors to metallic conductors). Low-dimensional polychalcogenide compounds of alpha-ACuQ_4 (A = K, Cs; Q = S, Se), beta -KCuS_4, KAuQ_5 (Q = S, Se), K_3AuSe_ {13}, Na_3AuSe _8, and CsAuSe_3 exhibit the beautiful structural diversity and bonding flexibility of the polychalcogenide ligands. In addition, many novel chalcogenide compounds of Cu, Hg, and Au with low-dimensional structures. The preparation of novel mixed -valence Cu compounds, K_2Cu _5Te_5, Cs _3Cu_8Te_ {10}, Na_3Cu _4Se_4, K _3Cu_8S_4 Te_2, and KCu_4 S_2Te, which show interesting metallic properties, especially underscores the enormous potential of the molten salt method for the synthesis of new chalcogenide materials with interesting physical properties. The materials prepared in this study can be classified as a new class of chalcogenide compounds due to their unique structures. In this dissertation the synthesis, characterization with emphasis on structures, charge transport properties, and magnetic susceptibilities of the materials will be illustrated.

Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes.

PubMed

Abdelhamid, Hani Nasser

2018-03-01

Nanoparticle assisted laser desorption/ionization mass spectrometry (NPs-ALDI-MS) shows remarkable characteristics and has a promising future in terms of real sample analysis. The incorporation of NPs can advance several methods including surface assisted LDI-MS, and surface enhanced LDI-MS. These methods have advanced the detection of many thermally labile and nonvolatile biomolecules. Nanoparticles circumvent the drawbacks of conventional organic matrices for the analysis of small molecules. In most cases, NPs offer a clear background without interfering peaks, absence of fragmentation of thermally labile molecules, and allow the ionization of species with weak noncovalent interactions. Furthermore, an enhancement in sensitivity and selectivity can be achieved. NPs enable straightforward analysis of target species in a complex sample. This review (with 239 refs.) covers the progress made in laser-based mass spectrometry in combination with the use of metallic NPs (such as AuNPs, AgNPs, PtNPs, and PdNPs), NPs consisting of oxides and chalcogenides, silicon-based NPs, carbon-based nanomaterials, quantum dots, and metal-organic frameworks. Graphical abstract An overview is given on nanomaterials for use in surface-assisted laser desorption/ionization mass spectrometry of small molecules.

High-performance and scalable metal-chalcogenide semiconductors and devices via chalco-gel routes

PubMed Central

Jo, Jeong-Wan; Kim, Hee-Joong; Kwon, Hyuck-In; Kim, Jaekyun; Ahn, Sangdoo; Kim, Yong-Hoon; Lee, Hyung-ik

2018-01-01

We report a general strategy for obtaining high-quality, large-area metal-chalcogenide semiconductor films from precursors combining chelated metal salts with chalcoureas or chalcoamides. Using conventional organic solvents, such precursors enable the expeditious formation of chalco-gels, which are easily transformed into the corresponding high-performance metal-chalcogenide thin films with large, uniform areas. Diverse metal chalcogenides and their alloys (MQx: M = Zn, Cd, In, Sb, Pb; Q = S, Se, Te) are successfully synthesized at relatively low processing temperatures (<400°C). The versatility of this scalable route is demonstrated by the fabrication of large-area thin-film transistors (TFTs), optoelectronic devices, and integrated circuits on a 4-inch Si wafer and 2.5-inch borosilicate glass substrates in ambient air using CdS, CdSe, and In2Se3 active layers. The CdSe TFTs exhibit a maximum field-effect mobility greater than 300 cm2 V−1 s−1 with an on/off current ratio of >107 and good operational stability (threshold voltage shift < 0.5 V at a positive gate bias stress of 10 ks). In addition, metal chalcogenide–based phototransistors with a photodetectivity of >1013 Jones and seven-stage ring oscillators operating at a speed of ~2.6 MHz (propagation delay of < 27 ns per stage) are demonstrated. PMID:29662951

The Optoelectronic Properties of Nanoparticles from First Principles Calculations

NASA Astrophysics Data System (ADS)

Brawand, Nicholas Peter

The tunable optoelectronic properties of nanoparticles through the modification of their size, shape, and surface chemistry, make them promising platforms for numerous applications, including electronic and solar conversion devices. However, the rational design and optimization of nanostructured materials remain open challenges, e.g. due to difficulties in controlling and reproducing synthetic processes and in precise atomic-scale characterization. Hence, the need for accurate theoretical predictions, which can complement and help interpret experiments and provide insight into the underlying physical properties of nanostructured materials. This dissertation focuses on the development and application of first principles calculations to predict the optoelectronic properties of nanoparticles. Novel methods based on density functional theory are developed, implemented, and applied to predict both optical and charge transport properties. In particular, the generalization of dielectric dependent hybrid functionals to finite systems is introduced and shown to yield highly accurate electronic structure properties of molecules and nanoparticles, including photoemission and absorption properties. In addition, an implementation of constrained density functional theory is discussed, for the calculation of hopping transport in nanoparticle systems. The implementation was verified against literature results and compared against other methods used to compute transport properties, showing that some methods used in the literature give unphysical results for thermally disordered systems. Furthermore, the constrained density functional theory implementation was coupled to the self-consistent image charge method, making it possible to include image charge effects self-consistently when predicting charge transport properties of nanoparticles near interfaces. The methods developed in this dissertation were then applied to study the optoelectronic and transport properties of specific systems, in particular, silicon and lead chalcogenide nanoparticles. In the case of Si, blinking in oxidized Si nanoparticles was addressed. Si dangling bonds at the surface were found to introduce defect states which, depending on their charge and local stress conditions, may give rise to ON and OFF states responsible for exponential blinking statistics. We also investigated, engineering of band edge positions of nanoparticles through post-synthetic surface chemistry modification, with a focus on lead chalcogenides. In collaboration with experiment, we demonstrated how band edge positions of lead sulfide nanoparticles can be tuned by over 2.0 eV. We established a clear relationship between ligand dipole moments and nanoparticle band edge shifts which can be used to engineer nanoparticles for optoelectronic applications. Calculations of transport properties focused on charge transfer in silicon and lead chalcogenide nanoparticles. Si nanoparticles with deep defects and shallow impurities were investigated, showing that shallow defects may be more detrimental to charge transport than previously assumed. In the case of lead chalcogenide nanoparticles, hydrogen was found to form complexes with defects which can be used to remove potentially detrimental charge traps in nanoparticle solids. The methods and results presented in this dissertation are expected to help guide engineering of nanoparticles for future device applications.

Emergent Electronic and Dielectric Properties of Interacting Nanoparticles at Finite Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenwood, Arin R.; Voros, Marton; Giberti, Federico

Lead chalcogenide nanoparticle solids have been successfully integrated into certified solar cells and represent promising platforms for the design of novel photoabsorbers for photoelectrochemical cells. While much attention has been drawn to improving efficiency and device performance through altering the character of the individual nanoparticles, the role of interactions between nanoparticles is not yet well-understood. Using first-principles molecular dynamics and electronic structure calculations, we investigated the combined effect of temperature and interaction on functionalized lead chalcogenide nanoparticles (NPs). Here, we show that at finite temperature, interacting NPs are dynamical dipolar systems, with the average values of dipole moments and polarizabilitiesmore » substantially increased with respect to those of the isolated building blocks. In addition, we show that the interacting NPs exhibit slightly smaller fundamental gaps that decrease as a function of temperature and that the radiative lifetimes of both the isolated NPs and the solids are greatly reduced at finite temperature compared to T = 0. Lastly, we present a critical discussion of various results reported in the literature for the values of dipole moments of nanoparticles.« less

Emergent Electronic and Dielectric Properties of Interacting Nanoparticles at Finite Temperature

DOE PAGES

Greenwood, Arin R.; Voros, Marton; Giberti, Federico; ...

2017-12-11

Lead chalcogenide nanoparticle solids have been successfully integrated into certified solar cells and represent promising platforms for the design of novel photoabsorbers for photoelectrochemical cells. While much attention has been drawn to improving efficiency and device performance through altering the character of the individual nanoparticles, the role of interactions between nanoparticles is not yet well-understood. Using first-principles molecular dynamics and electronic structure calculations, we investigated the combined effect of temperature and interaction on functionalized lead chalcogenide nanoparticles (NPs). Here, we show that at finite temperature, interacting NPs are dynamical dipolar systems, with the average values of dipole moments and polarizabilitiesmore » substantially increased with respect to those of the isolated building blocks. In addition, we show that the interacting NPs exhibit slightly smaller fundamental gaps that decrease as a function of temperature and that the radiative lifetimes of both the isolated NPs and the solids are greatly reduced at finite temperature compared to T = 0. Lastly, we present a critical discussion of various results reported in the literature for the values of dipole moments of nanoparticles.« less

Recent Advances in Metal Chalcogenides (MX; X = S, Se) Nanostructures for Electrochemical Supercapacitor Applications: A Brief Review

PubMed Central

Theerthagiri, Jayaraman; Durai, Govindarajan; Rana, Abu ul Hassan Sarwar; Sangeetha, Kirubanandam; Kuppusami, Parasuraman; Kim, Hyun-Seok

2018-01-01

Supercapacitors (SCs) have received a great deal of attention and play an important role for future self-powered devices, mainly owing to their higher power density. Among all types of electrical energy storage devices, electrochemical supercapacitors are considered to be the most promising because of their superior performance characteristics, including short charging time, high power density, safety, easy fabrication procedures, and long operational life. An SC consists of two foremost components, namely electrode materials, and electrolyte. The selection of appropriate electrode materials with rational nanostructured designs has resulted in improved electrochemical properties for high performance and has reduced the cost of SCs. In this review, we mainly spotlight the non-metallic oxide, especially metal chalcogenides (MX; X = S, Se) based nanostructured electrode materials for electrochemical SCs. Different non-metallic oxide materials are highlighted in various categories, such as transition metal sulfides and selenides materials. Finally, the designing strategy and future improvements on metal chalcogenide materials for the application of electrochemical SCs are also discussed. PMID:29671823

Magnetic chalcogenides in 3 and lower dimensions

NASA Astrophysics Data System (ADS)

Furdyna, J. K.; Dong, S.-N.; Lee, S.; Liu, X.; Dobrowolska, M.

2018-06-01

In this article we review magnetic phenomena that occur in the chalcogenide family involving transition metals. Magnetic properties displayed by bulk 3D chalcogenides compounds and alloys produced by equilibrium growth methods are discussed. 2D magnetic chalcogenide systems such as epitaxial films and more complex multilayers, whose formation is made possible by epitaxial methods and/or by van der Waals epitaxy, are presented in detail. We present a brief overview of magnetic effects emerging as the dimensionality of chalcogenide materialss is reduced to 1D (nanowires and related structures) and to zero-D (quantum dots formed by both top-down and bottom-up methods).

Method of producing stable metal oxides and chalcogenides and power source

DOEpatents

Doddapaneni, N.; Ingersoll, D.

1996-10-22

A method is described for making chemically and electrochemically stable oxides or other chalcogenides for use as cathodes for power source applications, and of making batteries comprising such materials. 6 figs.

Synthesis and structures of metal chalcogenide precursors

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.

1990-01-01

The reactivity of early transition metal sandwich complexes with sulfur-rich molecules such as dithiocarboxylic acids was studied. Researchers recently initiated work on precursors to CuInSe2 and related chalcopyrite semiconductors. Th every high radiation tolerance and the high absorption coefficient of CuInSe2 makes this material extremely attractive for lightweight space solar cells. Their general approach in early transition metal chemistry, the reaction of low-valent metal complexes or metal powders with sulfur and selenium rich compounds, was extended to the synthesis of chalcopyrite precursors. Here, the researchers describe synthesis, structures, and and routes to single molecule precursors to metal chalcogenides.

Evolution of the Valley Position in Bulk Transition-Metal Chalcogenides and Their Monolayer Limit.

PubMed

Yuan, Hongtao; Liu, Zhongkai; Xu, Gang; Zhou, Bo; Wu, Sanfeng; Dumcenco, Dumitru; Yan, Kai; Zhang, Yi; Mo, Sung-Kwan; Dudin, Pavel; Kandyba, Victor; Yablonskikh, Mikhail; Barinov, Alexei; Shen, Zhixun; Zhang, Shoucheng; Huang, Yingsheng; Xu, Xiaodong; Hussain, Zahid; Hwang, Harold Y; Cui, Yi; Chen, Yulin

2016-08-10

Layered transition metal chalcogenides with large spin orbit coupling have recently sparked much interest due to their potential applications for electronic, optoelectronic, spintronics, and valleytronics. However, most current understanding of the electronic structure near band valleys in momentum space is based on either theoretical investigations or optical measurements, leaving the detailed band structure elusive. For example, the exact position of the conduction band valley of bulk MoS2 remains controversial. Here, using angle-resolved photoemission spectroscopy with submicron spatial resolution (micro-ARPES), we systematically imaged the conduction/valence band structure evolution across representative chalcogenides MoS2, WS2, and WSe2, as well as the thickness dependent electronic structure from bulk to the monolayer limit. These results establish a solid basis to understand the underlying valley physics of these materials, and also provide a link between chalcogenide electronic band structure and their physical properties for potential valleytronics applications.

Evolution of the Valley Position in Bulk Transition-Metal Chalcogenides and Their Monolayer Limit

DOE PAGES

Yuan, Hongtao; Liu, Zhongkai; Xu, Gang; ...

2016-07-12

Valley physics based on layered transition metal chalcogenides have recently sparked much interest due to their potential spintronics and valleytronics applications. However, most current understanding of the electronic structure near band valleys in momentum space is based on either theoretical investigations or optical measurements, leaving the detailed band structure elusive. For example, the exact position of the conduction band valley of bulk MoS 2 remains controversial. Here, using angle-resolved photoemission spectroscopy with sub-micron spatial resolution (micro- ARPES), we systematically imaged the conduction/valence band structure evolution across representative chalcogenides MoS 2, WS 2 and WSe 2, as well as the thicknessmore » dependent electronic structure from bulk to the monolayer limit. These results establish a solid basis to understand the underlying valley physics of these materials, and also provide a link between chalcogenide electronic band structure and their physical properties for potential valleytronics applications.« less

Infrared emitting and photoconducting colloidal silver chalcogenide nanocrystal quantum dots from a silylamide-promoted synthesis.

PubMed

Yarema, Maksym; Pichler, Stefan; Sytnyk, Mykhailo; Seyrkammer, Robert; Lechner, Rainer T; Fritz-Popovski, Gerhard; Jarzab, Dorota; Szendrei, Krisztina; Resel, Roland; Korovyanko, Oleksandra; Loi, Maria Antonietta; Paris, Oskar; Hesser, Günter; Heiss, Wolfgang

2011-05-24

Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag(2)Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag(2)Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.

Chalcogenide and pnictide nanocrystals from the silylative deoxygenation of metal oxides

DOE PAGES

Lin, Chia-Cheng; Tan, Shannon J.; Vela, Javier

2017-09-11

Transition metal chalcogenide and pnictide nanocrystals are of interest for optoelectronic and catalytic applications. In this paper, we present a generalized route to the synthesis of these materials from the silylative deoxygenation of metal oxides with trimethylsilyl reagents. Specific nanophases produced in this way include Ni 3S 2, Ni 5Se 5, Ni 2P, Co 9S 8, Co 3Se 4, CoP, Co 2P, and heterobimetallic (Ni/Co) 9S 8. The resulting chalcogenide nanocrystals are hollow, likely due to differential rates of ion diffusion during the interfacial phase transformation reaction (Kirkendall-type effect). In contrast, the phosphide nanocrystals are solid, likely because they formmore » at higher reaction temperatures. Finally, in all cases, simultaneous partial decomposition of the deoxygenating silyl reagent produces a coating of amorphous silica around the newly formed nanocrystals, which could impact their stability and recyclability.« less

N4H9Cu7S4: a hydrazinium-based salt with a layered Cu7S4- framework.

PubMed

Mitzi, David B

2007-02-05

Crystals of a hydrazinium-based copper(I) sulfide salt, N4H9Cu7S4 (1), have been isolated by an ambient temperature solution-based process. In contrast to previously reported hydrazinium salts of main-group metal chalcogenides, which consist of isolated metal chalcogenide anions, and ACu7S4 (A = NH4+, Rb+, Tl+, K+), which contains a more three-dimensional Cu7S4- framework with partial Cu-site occupancy, the structure of 1 [P21, a = 6.8621(4) A, b = 7.9851(4) A, c = 10.0983(5) A, beta = 99.360(1) degrees , Z = 2] is composed of extended two-dimensional Cu7S4- slabs with full Cu-site occupancy. The Cu7S4- slabs are separated by a mixture of hydrazinium and hydrazine moieties. Thermal decomposition of 1 into copper(I) sulfide proceeds at a significantly lower temperature than that observed for analogous hydrazinium salts of previously considered metal chalcogenides, completing the transition at temperatures as low as 120 degrees C. Solutions of 1 may be used in the solution deposition of a range of Cu-containing chalcogenide films.

Carbon-armored Co9S8 nanoparticles as all-pH efficient and durable H2-evolving electrocatalysts.

PubMed

Feng, Liang-Liang; Li, Guo-Dong; Liu, Yipu; Wu, Yuanyuan; Chen, Hui; Wang, Yun; Zou, Yong-Cun; Wang, Dejun; Zou, Xiaoxin

2015-01-14

Splitting water to produce hydrogen requires the development of non-noble-metal catalysts that are able to make this reaction feasible and energy efficient. Herein, we show that cobalt pentlandite (Co9S8) nanoparticles can serve as an electrochemically active, noble-metal-free material toward hydrogen evolution reaction, and they work stably in neutral solution (pH 7) but not in acidic (pH 0) and basic (pH 14) media. We, therefore, further present a carbon-armoring strategy to increase the durability and activity of Co9S8 over a wider pH range. In particular, carbon-armored Co9S8 nanoparticles (Co9S8@C) are prepared by direct thermal treatment of a mixture of cobalt nitrate and trithiocyanuric acid at 700 °C in N2 atmosphere. Trithiocyanuric acid functions as both sulfur and carbon sources in the reaction system. The resulting Co9S8@C material operates well with high activity over a broad pH range, from pH 0 to 14, and gives nearly 100% Faradaic yield during hydrogen evolution reaction under acidic (pH 0), neutral (pH 7), and basic (pH 14) media. To the best of our knowledge, this is the first time that a transition-metal chalcogenide material is shown to have all-pH efficient and durable electrocatalytic activity. Identifying Co9S8 as the catalytically active phase and developing carbon-armoring as the improvement strategy are anticipated to give a fresh impetus to rational design of high-performance noble-metal-free water splitting catalysts.

Molecular level control of nanoscale composition and morphology: Toward photocatalytic nanocomposites for solar-to-chemical energy conversion of biomass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruberu, Thanthrige P.

2013-01-01

Understanding the factors influencing nanocrystal formation is a challenge yet to be realized. In comparison to the large number of studies on nanocrystal synthesis and their applications, the number of studies on the effect of the precursor chemistry on nanocrystal composition and shape remains low. Although photochemical fabrication of metalsemiconductor nano-heterostructures is reported in literature, control over the free particle formation and the site of metal deposition have not been achieved. Moreover, utilization of metal- semiconductor nano-heterostructures in photocatalytic reactions other than water splitting is hardly explored. In this thesis, we studied the effect of chalcogenide precursor reactivity on themore » composition, morphology and the axial anisotropy of cadmiumchalcogenide nanocrystals. We also investigated the influence of the irradiation wavelength in synthesizing metal-semiconductor nano-heterostructures. Finally, we showed that metal semiconductor nano-heterostructures can be used as a photocatalyst for alcohol dehydrogenation reactions. We explored the pathways for the formation of Pt and Pd nanoparticles on CdS and CdS{sub 0.4}Se{sub 0.6} nanorods. This study revealed that the wavelength of irradiation is critical to control free-standing vs. bound metal (Pt and Pd) nanoparticles to semiconductor. Additionally, we observed that metal photodeposition occurs on specific segments of axially anisotropic, compositionally graded CdS0.4Se0.6 nanorods due to the band-gap differential between their nano-domains. We used semiconductor-metal heterostructures for sunlightdriven dehydrogenation and hydrogenolysis of benzyl alcohol. Heterostructure composition dictates activity (turnovers) and product distribution. A few metal (Pt, Pd) islands on the semiconductor surface significantly enhance activity and selectivity and also greatly stabilize the semiconductor against photoinduced etching and degradation.« less

Interfacial scanning tunneling spectroscopy (STS) of chalcogenide/metal hybrid nanostructure

NASA Astrophysics Data System (ADS)

Saad, Mahmoud M.; Abdallah, Tamer; Easawi, Khalid; Negm, Sohair; Talaat, Hassan

2015-05-01

The electronic structure at the interface of chalcogenide/metal hybrid nanostructure (CdSe-Au tipped) had been studied by UHV scanning tunneling spectroscopy (STS) technique at room temperature. This nanostructure was synthesized by a phase transfer chemical method. The optical absorption of this hybrid nanostructure was recorded, and the application of the effective mass approximation (EMA) model gave dimensions that were confirmed by the direct measurements using the scanning tunneling microscopy (STM) as well as the high-resolution transmission electron microscope (HRTEM). The energy band gap obtained by STS agrees with the values obtained from the optical absorption. Moreover, the STS at the interface of CdSe-Au tipped hybrid nanostructure between CdSe of size about 4.1 ± 0.19 nm and Au tip of size about 3.5 ± 0.29 nm shows a band bending about 0.18 ± 0.03 eV in CdSe down in the direction of the interface. Such a result gives a direct observation of the electron accumulation at the interface of CdSe-Au tipped hybrid nanostructure, consistent with its energy band diagram. The presence of the electron accumulation at the interface of chalcogenides with metals has an important implication for hybrid nanoelectronic devices and the newly developed plasmon/chalcogenide photovoltaic solar energy conversion.

Electrochemistry of 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene ligands: free phosphines, metal complexes, and chalcogenides.

PubMed

Mandell, Chelsea L; Kleinbach, Shannon S; Dougherty, William G; Kassel, W Scott; Nataro, Chip

2010-10-18

The oxidative electrochemistries of a series of chiral bisphosphinoferrocene ligands, 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene (FerroTANE) and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene (FerroLANE), were examined. The reversibility of the oxidation is sensitive to the steric bulk of the alkyl groups. New transition metal compounds and phosphine chalcogenides of these ligands were prepared and characterized. X-ray crystal structures of 10 of these compounds are reported. The percent buried volume (%V(bur)) is a recently developed measurement based on crystallographic data that examines the steric bulk of N-heterocyclic carbene and phosphine ligands. The %V(bur) for the FerroTANE and FerroLANE structures with methyl or ethyl substituents suggests these ligands are similar in steric properties to 1,1'-bis(diphenylphosphino)ferrocene (dppf). In addition the %V(bur) has been found to correlate well with the Tolman cone angle for phosphine chalcogenides. The oxidative electrochemistries of the transition metal complexes occur at more positive potentials than the free ligands. While a similar positive shift is seen for the oxidative electrochemistries of the phosphine chalcogenides, the oxidation of the phosphine selenides does not occur at the iron center, but rather oxidation occurs at the selenium atoms.

Synthesis of quaternary chalcogenide CZTS nanoparticles by a hydrothermal route

NASA Astrophysics Data System (ADS)

Das, S.; Sa, K.; Mahakul, P. C.; Raiguru, J.; Alam, I.; Subramanyam, BVRS; Mahanandia, P.

2018-03-01

Cu2ZnSnS4 (CZTS) has emerged as a potential absorber towards inorganic photovoltaic device application for its outstanding properties like non toxicity, earth abundancy nature, optimal band gap matched with solar spectrum (1.45- 1.65eV), high absorption coefficient (104cm‑1). Here, a low cost, environment friendly facile hydrothermal route to synthesize phase pure CZTS nanoparticles using Cu (II), Zn (II), Sn (II) inorganic metal salts and thiourea as Sulphur source in distilled water solution as precursor is reported. The as synthesized samples characterized by X-Ray diffraction (XRD) and RAMAN confirmed structure and phase of CZTS nanocrystals. The morphology of the prepared CZTS have been characterized by scanning electron microscopy (SEM). The particle size is found in the range 4-5 nm with crystalline nature have been characterized by transmission electron microscope (TEM). The optical band gap of the as prepared samples is calculated to be 1.65eV from UV-Visible analysis which proves it can be used towards photovoltaic applications.

Structural Flexibility and Alloying in Ultrathin Transition-Metal Chalcogenide Nanowires

DOE PAGES

Lin, Junhao; Zhang, Yuyang; Zhou, Wu; ...

2016-01-18

Metallic transition-metal chalcogenide (TMC) nanowires are an important building block for 2D electronics that may be fabricated within semiconducting transition-metal dichalcogenide (TMDC) monolayers. Tuning the geometric structure and electronic properties of such nanowires is a promising way to pattern diverse functional channels for wiring multiple units inside a 2D electronic circuit. Nevertheless, few experimental investigations have been reported exploring the structural and compositional tunability of these nanowires, due to difficulties in manipulating the structure and chemical composition of an individual nanowire. Here, using a combination of scanning transmission electron microscopy (STEM) and density functional theory (DFT), we report that TMCmore » nanowires have substantial intrinsic structural flexibility and their chemical composition can be manipulated.« less

Electron transport in some transition metal di-chalcogenides: MoS2 and WS2

NASA Astrophysics Data System (ADS)

Ferry, D. K.

2017-08-01

The transition metal di-chalcogenides are promising single monolayer materials that hold promise for applications in several fields, including nanoelectronics. Here, I study the transport of electrons in two of these materials, MoS2 and WS2. While the low-field behavior shows very low mobility, due mostly to impurity scattering, the high-field behavior shows a relatively high saturated velocity and a high breakdown field. Complications arise due to the relative narrowness of the conduction band, and the effect of this on the transport is discussed.

The third-order optical nonlinearities of Ge-Ga-Sb(In)-S chalcogenide glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Haitao, E-mail: guoht_001@opt.ac.cn; Chen, Hongyan; Hou, Chaoqi

2011-05-15

Research highlights: {yields} It is firstly demonstrated that the nonlinear refractive index n{sub 2} is dependent on the covalency of bonds in chalcogenide glass. {yields} Homopolar metallic bonds in chalcogenide glass have positive contribution to large nonlinear refractive index n{sub 2} also. {yields} The 80GeS{sub 2}.20Sb{sub 2}S{sub 3} glass would be expected to be used in the all-optical switches working at 1330 nm and 1550 nm telecommunication wavelengths. -- Abstract: The third-order optical nonlinearities of 80GeS{sub 2}.(20 - x)Ga{sub 2}S{sub 3}.xY{sub 2}S{sub 3} (x = 0, 5, 10, 15, 20 and Y = Sb or In) chalcogenide glasses were investigatedmore » utilizing the Z-scan method at the wavelength of 800 nm and their linear optical properties and structure were also studied. By analyzing the compositional dependences and possible influencing factors including the linear refractive index, the concentration of lone electron pairs, the optical bandgap and the amount of weak covalent/homopolar bonds, it indicates that the electronic contribution in weak heteropolar covalent and homopolar metallic bonds is responsible for large nonlinear refractive index n{sub 2} in the chalcogenide glasses. These chalcogenide glasses have characteristics of environmentally friendship, wide transparency in the visible region, high nonlinear refractive index n{sub 2} and low nonlinear absorption coefficient {beta}, and would be expected to be used in the all-optical switches working at 1330 nm and 1550 nm telecommunication wavelengths.« less

[Ag115S34(SCH2C6H4 t Bu)47(dpph)6]: synthesis, crystal structure and NMR investigations of a soluble silver chalcogenide nanocluster.

PubMed

Bestgen, Sebastian; Fuhr, Olaf; Breitung, Ben; Kiran Chakravadhanula, Venkata Sei; Guthausen, Gisela; Hennrich, Frank; Yu, Wen; Kappes, Manfred M; Roesky, Peter W; Fenske, Dieter

2017-03-01

With the aim to synthesize soluble cluster molecules, the silver salt of (4-( tert -butyl)phenyl)methanethiol [AgSCH 2 C 6 H 4 t Bu] was applied as a suitable precursor for the formation of a nanoscale silver sulfide cluster. In the presence of 1,6-(diphenylphosphino)hexane (dpph), the 115 nuclear silver cluster [Ag 115 S 34 (SCH 2 C 6 H 4 t Bu) 47 (dpph) 6 ] was obtained. The molecular structure of this compound was elucidated by single crystal X-ray analysis and fully characterized by spectroscopic techniques. In contrast to most of the previously published cluster compounds with more than a hundred heavy atoms, this nanoscale inorganic molecule is soluble in organic solvents, which allowed a comprehensive investigation in solution by UV-Vis spectroscopy and one- and two-dimensional NMR spectroscopy including 31 P/ 109 Ag-HSQC and DOSY experiments. These are the first heteronuclear NMR investigations on coinage metal chalcogenides. They give some first insight into the behavior of nanoscale silver sulfide clusters in solution. Additionally, molecular weight determinations were performed by 2D analytical ultracentrifugation and HR-TEM investigations confirm the presence of size-homogeneous nanoparticles present in solution.

A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

PubMed

Jothi, Palani R; Yubuta, Kunio; Fokwa, Boniface P T

2018-04-01

Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pressure tuning the lattice and optical response of silver sulfide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Zhao, E-mail: zhaozhao@stanford.edu; Wei, Hua; Mao, Wendy L.

2016-06-27

Binary transition metal chalcogenides have attracted increasing attention for their unique structural and electronic properties. High pressure is a powerful tool for tuning the lattice and electronic structure of transition metal chalcogenides away from their pristine states. In this work, we systematically studied the in situ structural and optical behavior of silver sulfide (Ag{sub 2}S) under pressure by synchrotron X-ray diffraction and infrared spectroscopy measurements in a diamond anvil cell. Upon compression, Ag{sub 2}S undergoes structural symmetrization accompanied by a series of structural transitions while the crystallographic inequivalence of the two Ag sites is maintained. Electronically, pressure effectively tunes themore » ambient semiconducting Ag{sub 2}S into a metal at ∼22 GPa. Drude model analysis shows that the optical conductivity evolves significantly, reaching the highest value of 100 Ω{sup −1} cm{sup −1} at ∼40 GPa. Our results highlight the structural and electronic tunability of silver chalcogenides as a function of pressure and suggest the potential of Ag{sub 2}S as a platform for developing optical and opto-electronic applications.« less

The Surface Chemistry of Metal Chalcogenide Nanocrystals

NASA Astrophysics Data System (ADS)

Anderson, Nicholas Charles

The surface chemistry of metal chalcogenide nanocrystals is explored through several interrelated analytical investigations. After a brief discussion of the nanocrystal history and applications, molecular orbital theory is used to describe the electronic properties of semiconductors, and how these materials behave on the nanoscale. Quantum confinement plays a major role in dictating the optical properties of metal chalcogenide nanocrystals, however surface states also have an equally significant contribution to the electronic properties of nanocrystals due to the high surface area to volume ratio of nanoscale semiconductors. Controlling surface chemistry is essential to functionalizing these materials for biological imaging and photovoltaic device applications. To better understand the surface chemistry of semiconducting nanocrystals, three competing surface chemistry models are presented: 1.) The TOPO model, 2.) the Non-stoichiometric model, and 3.) the Neutral Fragment model. Both the non-stoichiometric and neutral fragment models accurately describe the behavior of metal chalcogenide nanocrystals. These models rely on the covalent bond classification system, which divides ligands into three classes: 1.) X-type, 1-electron donating ligands that balance charge with excess metal at the nanocrystal surface, 2.) L-type, 2-electron donors that bind metal sites, and 3.) Z-type, 2-electron acceptors that bind chalcogenide sites. Each of these ligand classes is explored in detail to better understand the surface chemistry of metal chalcogenide nanocrystals. First, chloride-terminated, tri-n-butylphosphine (Bu 3P) bound CdSe nanocrystals were prepared by cleaving carboxylate ligands from CdSe nanocrystals with chlorotrimethylsilane in Bu3P solution. 1H and 31P{1H} nuclear magnetic resonance spectra of the isolated nanocrystals allowed assignment of distinct signals from several free and bound species, including surface-bound Bu3P and [Bu3P-H]+[Cl]- ligands as well as a Bu3P complex of cadmium chloride. Nuclear magnetic resonance spectroscopy supports complete cleavage of the X-type carboxylate ligands. Combined with measurements of the Se:Cd:Cl ratio using Rutherford backscattering spectrometry, these studies support a structural model of nanocrystals where chloride ligands terminate the crystal lattice by balancing the charges of excess Cd2+ ions. The adsorption of dative phosphine ligands leads to nanocrystals who's solubility is afforded by reversibly bound and readily exchanged L-type ligands, e.g. primary amines and phosphines. The other halides (Br and I) can also be used to prepare Bu 3P-bound, halide-terminated CdSe nanocrystals, however these nanocrystals are not soluble after exchange. The change in binding affinity of Bu 3P over the halide series is briefly discussed. Next, we report a series of L-type ligand exchanges using Bu3P-bound, chloride-terminated CdSe nanocrystals with several Lewis bases, including aromatic, cyclic, and non-cyclic sulfides, and ethers; primary, secondary, and tertiary amines and phosphines; tertiary phosphine chalcogenides; primary alcohols, isocyanides, and isothiocyanides. Using 31P nuclear magnetic resonance spectroscopy, we establish a relative binding affinity for these ligands that reflects electronic considerations but is dominated primarily by steric interactions, as determined by comparing binding affinity to Tolmann cone angles. We also used chloride-terminated CdSe nanocrystals to explore the reactivity of ionic salts at nanocrystal surfaces. These salts, particularly [Bu3P-H]+[Cl]-, bind nanocrystals surfaces as L-type ligands, making them soluble in polar solvents such as acetonitrile. This information should provide insight for rational ligand design for future applications involving metal chalcogenide nanocrystals. The strongest ligand, primary n-alkylamine, rapidly displace the Bu3P from halide-terminated CdSe nanocrystals, leading to amine-bound nanocrystals with higher dative ligand coverages and greatly increased photoluminescence quantum yields. The importance of ligand coverage to both the UV-visible absorption and photoluminescence spectra are discussed. (Abstract shortened by UMI.).

Recent Advances in Layered Metal Chalcogenides as Superconductors and Thermoelectric Materials: Fe-Based and Bi-Based Chalcogenides.

PubMed

Mizuguchi, Yoshikazu

2016-04-01

Recent advances in layered (Fe-based and Bi-based) chalcogenides as superconductors or functional materials are reviewed. The Fe-chalcogenide (FeCh) family are the simplest Fe-based high-Tc superconductors. The superconductivity in the FeCh family is sensitive to external or chemical pressure, and high Tc is attained when the local structure (anion height) is optimized. The Bi-chalcogenide (BiCh2) family are a new group of layered superconductors with a wide variety of stacking structures. Their physical properties are also sensitive to external or chemical pressure. Recently, we revealed that the emergence of superconductivity and the Tc in this family correlate with the in-plane chemical pressure. Since the flexibility of crystal structure and electronic states are an advantage of the BiCh2 family for designing functionalities, I briefly review recent developments in this family as not only superconductors but also other functional materials. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasmonic doped semiconductor nanocrystals: Properties, fabrication, applications and perspectives

NASA Astrophysics Data System (ADS)

Kriegel, Ilka; Scotognella, Francesco; Manna, Liberato

2017-02-01

Degenerately doped semiconductor nanocrystals (NCs) are of recent interest to the NC community due to their tunable localized surface plasmon resonances (LSPRs) in the near infrared (NIR). The high level of doping in such materials with carrier densities in the range of 1021cm-3 leads to degeneracy of the doping levels and intense plasmonic absorption in the NIR. The lower carrier density in degenerately doped semiconductor NCs compared to noble metals enables LSPR tuning over a wide spectral range, since even a minor change of the carrier density strongly affects the spectral position of the LSPR. Two classes of degenerate semiconductors are most relevant in this respect: impurity doped semiconductors, such as metal oxides, and vacancy doped semiconductors, such as copper chalcogenides. In the latter it is the density of copper vacancies that controls the carrier concentration, while in the former the introduction of impurity atoms adds carriers to the system. LSPR tuning in vacancy doped semiconductor NCs such as copper chalcogenides occurs by chemically controlling the copper vacancy density. This goes in hand with complex structural modifications of the copper chalcogenide crystal lattice. In contrast the LSPR of degenerately doped metal oxide NCs is modified by varying the doping concentration or by the choice of host and dopant atoms, but also through the addition of capacitive charge carriers to the conduction band of the metal oxide upon post-synthetic treatments, such as by electrochemical- or photodoping. The NIR LSPRs and the option of their spectral fine-tuning make accessible important new features, such as the controlled coupling of the LSPR to other physical signatures or the enhancement of optical signals in the NIR, sensing application by LSPR tracking, energy production from the NIR plasmon resonance or bio-medical applications in the biological window. In this review we highlight the recent advances in the synthesis of various different plasmonic semiconductor NCs with LSPRs covering the entire spectral range, from the mid- to the NIR. We focus on copper chalcogenide NCs and impurity doped metal oxide NCs as the most investigated alternatives to noble metals. We shed light on the structural changes upon LSPR tuning in vacancy doped copper chalcogenide NCs and deliver a picture for the fundamentally different mechanism of LSPR modification of impurity doped metal oxide NCs. We review on the peculiar optical properties of plasmonic degenerately doped NCs by highlighting the variety of different optical measurements and optical modeling approaches. These findings are merged in an exhaustive section on new and exciting applications based on the special characteristics that plasmonic semiconductor NCs bring along.

Te Monolayer-Driven Spontaneous van der Waals Epitaxy of Two-dimensional Pnictogen Chalcogenide Film on Sapphire.

PubMed

Hwang, Jae-Yeol; Kim, Young-Min; Lee, Kyu Hyoung; Ohta, Hiromichi; Kim, Sung Wng

2017-10-11

Demands on high-quality layer structured two-dimensional (2D) thin films such as pnictogen chalcogenides and transition metal dichalcogenides are growing due to the findings of exotic physical properties and potentials for device applications. However, the difficulties in controlling epitaxial growth and the unclear understanding of van der Waals epitaxy (vdWE) for a 2D chalcogenide film on a three-dimensional (3D) substrate have been major obstacles for the further advances of 2D materials. Here, we exploit the spontaneous vdWE of a high-quality 2D chalcogenide (Bi 0.5 Sb 1.5 Te 3 ) film by the chalcogen-driven surface reconstruction of a conventional 3D sapphire substrate. It is verified that the in situ formation of a pseudomorphic Te atomic monolayer on the surface of sapphire, which results in a dangling bond-free surface, allows the spontaneous vdWE of 2D chalcogenide film. Since this route uses the natural surface reconstruction of sapphire with chalcogen under vacuum condition, it can be scalable and easily utilized for the developments of various 2D chalcogenide vdWE films through conventional thin-film fabrication technologies.

Switching Plasmons: Gold Nanorod-Copper Chalcogenide Core-Shell Nanoparticle Clusters with Selectable Metal/Semiconductor NIR Plasmon Resonances.

PubMed

Muhammed, Madathumpady Abubaker Habeeb; Döblinger, Markus; Rodríguez-Fernández, Jessica

2015-09-16

Exerting control over the near-infrared (NIR) plasmonic response of nanosized metals and semiconductors can facilitate access to unexplored phenomena and applications. Here we combine electrostatic self-assembly and Cd(2+)/Cu(+) cation exchange to obtain an anisotropic core-shell nanoparticle cluster (NPC) whose optical properties stem from two dissimilar plasmonic materials: a gold nanorod (AuNR) core and a copper selenide (Cu(2-x)Se, x ≥ 0) supraparticle shell. The spectral response of the AuNR@Cu2Se NPCs is governed by the transverse and longitudinal plasmon bands (LPB) of the anisotropic metallic core, since the Cu2Se shell is nonplasmonic. Under aerobic conditions the shell undergoes vacancy doping (x > 0), leading to the plasmon-rich NIR spectrum of the AuNR@Cu(2-x)Se NPCs. For low vacancy doping levels the NIR optical properties of the dually plasmonic NPCs are determined by the LPBs of the semiconductor shell (along its major longitudinal axis) and of the metal core. Conversely, for high vacancy doping levels their NIR optical response is dominated by the two most intense plasmon modes from the shell: the transverse (along the shortest transversal axis) and longitudinal (along the major longitudinal axis) modes. The optical properties of the NPCs can be reversibly switched back to a purely metallic plasmonic character upon reversible conversion of AuNR@Cu(2-x)Se into AuNR@Cu2Se. Such well-defined nanosized colloidal assemblies feature the unique ability of holding an all-metallic, a metallic/semiconductor, or an all-semiconductor plasmonic response in the NIR. Therefore, they can serve as an ideal platform to evaluate the crosstalk between plasmonic metals and plasmonic semiconductors at the nanoscale. Furthermore, their versatility to display plasmon modes in the first, second, or both NIR windows is particularly advantageous for bioapplications, especially considering their strong absorbing and near-field enhancing properties.

Phosphorene for energy and catalytic application—filling the gap between graphene and 2D metal chalcogenides

NASA Astrophysics Data System (ADS)

Jain, Rishabh; Narayan, Rekha; Padmajan Sasikala, Suchithra; Lee, Kyung Eun; Jung, Hong Ju; Ouk Kim, Sang

2017-12-01

Phosphorene, a newly emerging graphene analogous 2D elemental material of phosphorous atoms, is unique on the grounds of its natural direct band gap opening, highly anisotropic and extraordinary physical properties. This review highlights the current status of phosphorene research in energy and catalytic applications. The initial part illustrates the typical physical properties of phosphorene, which successfully bridge the prolonged gap between graphene and 2D metal chalcogenides. Various synthetic methods available for black phosphorus (BP) and the exfoliation/growth techniques for single to few-layer phosphorene are also overviewed. The latter part of this review details the working mechanisms and performances of phosphorene/BP in batteries, supercapacitors, photocatalysis, and electrocatalysis. Special attention has been paid to the research efforts to overcome the inherent shortcomings faced by phosphorene based devices. The relevant device performances are compared with graphene and 2D metal chalcogenides based counterparts. Furthermore, the underlying mechanism behind the unstable nature of phosphorene under ambient condition is discussed along with the various approaches to avoid ambient degradation. Finally, comments are offered for the future prospective explorations and outlook as well as challenges lying in the road ahead for phosphorene research.

Cu2ZnSnS4/MoS2-Reduced Graphene Oxide Heterostructure: Nanoscale Interfacial Contact and Enhanced Photocatalytic Hydrogen Generation.

PubMed

Ha, Enna; Liu, Wei; Wang, Luyang; Man, Ho-Wing; Hu, Liangsheng; Tsang, Shik Chi Edman; Chan, Chris Tsz-Leung; Kwok, Wai-Ming; Lee, Lawrence Yoon Suk; Wong, Kwok-Yin

2017-01-03

Hydrogen generation from water using noble metal-free photocatalysts presents a promising platform for renewable and sustainable energy. Copper-based chalcogenides of earth-abundant elements, especially Cu 2 ZnSnS 4 (CZTS), have recently arisen as a low-cost and environment-friendly material for photovoltaics and photocatalysis. Herein, we report a new heterostructure consisting of CZTS nanoparticles anchored onto a MoS 2 -reduced graphene oxide (rGO) hybrid. Using a facile two-step method, CZTS nanoparticles were in situ grown on the surface of MoS 2 -rGO hybrid, which generated high density of nanoscale interfacial contact between CZTS and MoS 2 -rGO hybrid. The photoexcited electrons of CZTS can be readily transported to MoS 2 through rGO backbone, reducing the electron-hole pair recombination. In photocatalytic hydrogen generation under visible light irradiation, the presence of MoS 2 -rGO hybrids enhanced the hydrogen production rate of CZTS by 320%, which can be attributed to the synergetic effect of increased charge separation by rGO and more catalytically active sites from MoS 2 . Furthermore, this CZTS/MoS 2 -rGO heterostructure showed much higher photocatalytic activity than both Au and Pt nanoparticle-decorated CZTS (Au/CZTS and Pt/CZTS) photocatalysts, indicating the MoS 2 -rGO hybrid is a better co-catalyst for photocatalytic hydrogen generation than the precious metal. The CZTS/MoS 2 -rGO system also demonstrated stable photocatalytic activity for a continuous 20 h reaction.

Cu2ZnSnS4/MoS2-Reduced Graphene Oxide Heterostructure: Nanoscale Interfacial Contact and Enhanced Photocatalytic Hydrogen Generation

NASA Astrophysics Data System (ADS)

Ha, Enna; Liu, Wei; Wang, Luyang; Man, Ho-Wing; Hu, Liangsheng; Tsang, Shik Chi Edman; Chan, Chris Tsz-Leung; Kwok, Wai-Ming; Lee, Lawrence Yoon Suk; Wong, Kwok-Yin

2017-01-01

Hydrogen generation from water using noble metal-free photocatalysts presents a promising platform for renewable and sustainable energy. Copper-based chalcogenides of earth-abundant elements, especially Cu2ZnSnS4 (CZTS), have recently arisen as a low-cost and environment-friendly material for photovoltaics and photocatalysis. Herein, we report a new heterostructure consisting of CZTS nanoparticles anchored onto a MoS2-reduced graphene oxide (rGO) hybrid. Using a facile two-step method, CZTS nanoparticles were in situ grown on the surface of MoS2-rGO hybrid, which generated high density of nanoscale interfacial contact between CZTS and MoS2-rGO hybrid. The photoexcited electrons of CZTS can be readily transported to MoS2 through rGO backbone, reducing the electron-hole pair recombination. In photocatalytic hydrogen generation under visible light irradiation, the presence of MoS2-rGO hybrids enhanced the hydrogen production rate of CZTS by 320%, which can be attributed to the synergetic effect of increased charge separation by rGO and more catalytically active sites from MoS2. Furthermore, this CZTS/MoS2-rGO heterostructure showed much higher photocatalytic activity than both Au and Pt nanoparticle-decorated CZTS (Au/CZTS and Pt/CZTS) photocatalysts, indicating the MoS2-rGO hybrid is a better co-catalyst for photocatalytic hydrogen generation than the precious metal. The CZTS/MoS2-rGO system also demonstrated stable photocatalytic activity for a continuous 20 h reaction.

Cu2ZnSnS4/MoS2-Reduced Graphene Oxide Heterostructure: Nanoscale Interfacial Contact and Enhanced Photocatalytic Hydrogen Generation

PubMed Central

Ha, Enna; Liu, Wei; Wang, Luyang; Man, Ho-Wing; Hu, Liangsheng; Tsang, Shik Chi Edman; Chan, Chris Tsz-Leung; Kwok, Wai-Ming; Lee, Lawrence Yoon Suk; Wong, Kwok-Yin

2017-01-01

Hydrogen generation from water using noble metal-free photocatalysts presents a promising platform for renewable and sustainable energy. Copper-based chalcogenides of earth-abundant elements, especially Cu2ZnSnS4 (CZTS), have recently arisen as a low-cost and environment-friendly material for photovoltaics and photocatalysis. Herein, we report a new heterostructure consisting of CZTS nanoparticles anchored onto a MoS2-reduced graphene oxide (rGO) hybrid. Using a facile two-step method, CZTS nanoparticles were in situ grown on the surface of MoS2-rGO hybrid, which generated high density of nanoscale interfacial contact between CZTS and MoS2-rGO hybrid. The photoexcited electrons of CZTS can be readily transported to MoS2 through rGO backbone, reducing the electron-hole pair recombination. In photocatalytic hydrogen generation under visible light irradiation, the presence of MoS2-rGO hybrids enhanced the hydrogen production rate of CZTS by 320%, which can be attributed to the synergetic effect of increased charge separation by rGO and more catalytically active sites from MoS2. Furthermore, this CZTS/MoS2-rGO heterostructure showed much higher photocatalytic activity than both Au and Pt nanoparticle-decorated CZTS (Au/CZTS and Pt/CZTS) photocatalysts, indicating the MoS2-rGO hybrid is a better co-catalyst for photocatalytic hydrogen generation than the precious metal. The CZTS/MoS2-rGO system also demonstrated stable photocatalytic activity for a continuous 20 h reaction. PMID:28045066

Thermal, electronic and ductile properties of lead-chalcogenides under pressure.

PubMed

Gupta, Dinesh C; Bhat, Idris Hamid

2013-09-01

Fully relativistic pseudo-potential ab-initio calculations have been performed to investigate the high pressure phase transition, elastic and electronic properties of lead-chalcogenides including the less known lead polonium. The calculated ground state parameters, for the rock-salt structure show good agreement with the experimental data. PbS, PbSe, PbTe and PbPo undergo a first-order phase transition from rock-salt to CsCl structure at 19.4, 15.5, 11.5 and 7.3 GPa, respectively. The elastic properties have also been calculated. The calculations successfully predicted the location of the band gap at L-point of Brillouin zone and the band gap for each material at ambient pressure. It is observed that unlike other lead-chalcogenides, PbPo is semi-metal at ambient pressure. The pressure variation of the energy gap indicates that these materials metalize under pressure. The electronic structures of these materials have been computed in parent as well as in high pressure B2 phase.

Dielectric and structural characterisation of chalcogenide glasses via terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Ravagli, A.; Naftaly, M.; Craig, C.; Weatherby, E.; Hewak, D. W.

2017-07-01

Terahertz time-domain spectroscopy (THz TDS) was used to investigate a series of chalcogenide glasses. In particular, the dielectric properties at terahertz frequencies were determined and correlated with the glass composition. The experimental results showed a strong relationship between the dielectric properties and the polarizability of the glasses studied. A new explanation based on the coordination number of the metallic cations was proposed to understand these observations.

Pressure-induced metal-insulator transitions in chalcogenide NiS2-xSex

NASA Astrophysics Data System (ADS)

Hussain, Tayyaba; Oh, Myeong-jun; Nauman, Muhammad; Jo, Younjung; Han, Garam; Kim, Changyoung; Kang, Woun

2018-05-01

We report the temperature-dependent resistivity ρ(T) of chalcogenide NiS2-xSex (x = 0.1) using hydrostatic pressure as a control parameter in the temperature range of 4-300 K. The insulating behavior of ρ(T) survives at low temperatures in the pressure regime below 7.5 kbar, whereas a clear insulator-to-metallic transition is observed above 7.5 kbar. Two types of magnetic transitions, from the paramagnetic (PM) to the antiferromagnetic (AFM) state and from the AFM state to the weak ferromagnetic (WF) state, were evaluated and confirmed by magnetization measurement. According to the temperature-pressure phase diagram, the WF phase survives up to 7.5 kbar, and the transition temperature of the WF transition decreases as the pressure increases, whereas the metal-insulator transition temperature increases up to 9.4 kbar. We analyzed the metallic behavior and proposed Fermi-liquid behavior of NiS1.9Se0.1.

Solution-processing of chalcogenide materials for device applications

NASA Astrophysics Data System (ADS)

Zha, Yunlai

Chalcogenide glasses are well-known for their desirable optical properties, which have enabled many infrared applications in the fields of photonics, medicine, environmental sensing and security. Conventional deposition methods such as thermal evaporation, chemical vapor deposition, sputtering or pulse laser deposition are efficient for fabricating structures on flat surfaces. However, they have limitations in deposition on curved surfaces, deposition of thick layers and component integration. In these cases, solution-based methods, which involve the dissolution of chalcogenide glasses and processing as a liquid, become a better choice for their flexibility. After proper treatment, the associated structures can have similar optical, chemical and physical properties to the bulk. This thesis presents an in-depth study of solution-processing chalcogenide glasses, starting from the "solution state" to the "film state" and the "structure state". Firstly, chalcogenide dissolution is studied to reveal the mechanisms at molecular level and build a foundation for material processing. Dissolution processes for various chalcogenide solvent pairs are reviewed and compared. Secondly, thermal processing, in the context of high temperature annealing, is explained along with the chemical and physical properties of the annealed films. Another focus is on nanopore formation in propylamine-processed arsenic sulfide films. Pore density changes with respect to annealing temperatures and durations are characterized. Base on a proposed vacancy coalescence theory, we have identified new dissolution strategies and achieved the breakthrough of pore-free film deposition. Thirdly, several solution methods developed along with the associated photonic structures are demonstrated. The first example is "spin-coating and lamination", which produces thick (over 10 mum) chalcogenide structures. Both homogeneous thick chalcogenide structures and heterogeneous layers of different chalcogenide glasses or metals can be fabricated. Second, "micro-molding in capillaries" (MIMIC) and "micro-transfer molding" (muTM) methods are introduced for fabricating waveguides on flat and curved surfaces. The flexibility of the solution process allows waveguides to be patterned, for the first time, on a curved surface. Third, "micro channel filling" is demonstrated to produce the lowest loss among solution-processed chalcogenide waveguides. These results contribute to the advancement of chalcogenide processing technologies and help move closer towards the ultimate goal of fabricating reliable IR sensors.

An in-situ phosphorus source for the synthesis of Cu 3P and the subsequent conversion to Cu 3PS 4 nanoparticle clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheets, Erik J.; Stach, Eric A.; Yang, Wei -Chang

2015-09-20

The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I-V-VI chalcogenides including copper phosphide (Cu 3P) and copper thiophosphate (Cu 3PS 4). Herein, we report a one-pot, solution-based synthesis of Cu 3P nanocrystals utilizing an in-situ phosphorus source: phosphorus pentasulfide (P 2S 5) in trioctylphosphine (TOP). By injecting this phosphorus source into a copper solution in oleylamine (OLA), uniform and size controlled Cu 3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cumore » 3P nanocrystals with decomposing thiourea forms nanoscale Cu 3PS 4 particles having p-type conductivity and an effective optical band gap of 2.36 eV.« less

Hexagonal VS2 Anchored MWCNTs: First Approach to Design Flexible Solid-State Symmetric Supercapacitor Device.

PubMed

Pandit, Bidhan; Karade, Swapnil S; Sankapal, Babasaheb R

2017-12-27

Transition metal chalcogenides (TMCs) embedded with a carbon network are gaining much attention because of their high power capability, which can be easily integrated to portable electronic devices. Facile chemical route has been explored to synthesize hexagonal structured VS 2 nanoparticles onto multiwalled carbon nanotubes (MWCNTs) matrix. Such surface-modified VS 2 /MWCNTs electrode has boosted the electrochemical performance to reach high capacitance to 830 F/g and excellent stability to 95.9% over 10 000 cycles. Designed flexible solid-state symmetric supercapacitor device (FSSD) with a wide voltage window of 1.6 V exhibited maximum gain in specific capacitance value of 182 F/g at scan rate of 2 mV/s along with specific energy of 42 Wh/kg and a superb stability of 93.2% over 5000 cycles. As a practical approach, FSSD has lightened up "VNIT" panel consisting of 21 red LEDs.

High-Performance Quantum Dot Thin-Film Transistors with Environmentally Benign Surface Functionalization and Robust Defect Passivation.

PubMed

Jung, Su Min; Kang, Han Lim; Won, Jong Kook; Kim, JaeHyun; Hwang, ChaHwan; Ahn, KyungHan; Chung, In; Ju, Byeong-Kwon; Kim, Myung-Gil; Park, Sung Kyu

2018-01-31

The recent development of high-performance colloidal quantum dot (QD) thin-film transistors (TFTs) has been achieved with removal of surface ligand, defect passivation, and facile electronic doping. Here, we report on high-performance solution-processed CdSe QD-TFTs with an optimized surface functionalization and robust defect passivation via hydrazine-free metal chalcogenide (MCC) ligands. The underlying mechanism of the ligand effects on CdSe QDs has been studied with hydrazine-free ex situ reaction derived MCC ligands, such as Sn 2 S 6 4- , Sn 2 Se 6 4- , and In 2 Se 4 2- , to allow benign solution-process available. Furthermore, the defect passivation and remote n-type doping effects have been investigated by incorporating indium nanoparticles over the QD layer. Strong electronic coupling and solid defect passivation of QDs could be achieved by introducing electronically active MCC capping and thermal diffusion of the indium nanoparticles, respectively. It is also noteworthy that the diffused indium nanoparticles facilitate charge injection not only inter-QDs but also between source/drain electrodes and the QD semiconductors, significantly reducing contact resistance. With benign organic solvents, the Sn 2 S 6 4- , Sn 2 Se 6 4- , and In 2 Se 4 2- ligand based QD-TFTs exhibited field-effect mobilities exceeding 4.8, 12.0, and 44.2 cm 2 /(V s), respectively. The results reported here imply that the incorporation of MCC ligands and appropriate dopants provide a general route to high-performance, extremely stable solution-processed QD-based electronic devices with marginal toxicity, offering compatibility with standard complementary metal oxide semiconductor processing and large-scale on-chip device applications.

Laser-induced growth of nanocrystals embedded in porous materials

PubMed Central

2013-01-01

Space localization of the linear and nonlinear optical properties in a transparent medium at the submicron scale is still a challenge to yield the future generation of photonic devices. Laser irradiation techniques have always been thought to structure the matter at the nanometer scale, but combining them with doping methods made it possible to generate local growth of several types of nanocrystals in different kinds of silicate matrices. This paper summarizes the most recent works developed in our group, where the investigated nanoparticles are either made of metal (gold) or chalcogenide semiconductors (CdS, PbS), grown in precursor-impregnated porous xerogels under different laser irradiations. This review is associated to new results on silver nanocrystals in the same kind of matrices. It is shown that, depending on the employed laser, the particles can be formed near the sample surface or deep inside the silica matrix. Photothermal and/or photochemical mechanisms may be invoked to explain the nanoparticle growth, depending on the laser, precursor, and matrix. One striking result is that metal salt reduction, necessary to the production of the corresponding nanoparticles, can efficiently occur due to the thermal wrenching of electrons from the matrix itself or due to multiphoton absorption of the laser light by a reducer additive in femtosecond regime. Very localized semiconductor quantum dots could also be generated using ultrashort pulses, but while PbS nanoparticles grow faster than CdS particles due to one-photon absorption, this better efficiency is counterbalanced by a sensitivity to oxidation. In most cases where the reaction efficiency is high, particles larger than the pores have been obtained, showing that a fast diffusion of the species through the interconnected porosity can modify the matrix itself. Based on our experience in these techniques, we compare several examples of laser-induced nanocrystal growth in porous silica xerogels, which allows extracting the best experimental conditions to obtain an efficient particle production and to avoid stability or oxidation problems. PMID:23742134

Direct imprinting on chalcogenide glass and fabrication of infrared wire-grid polarizer

NASA Astrophysics Data System (ADS)

Yamada, Itsunari; Yamashita, Naoto; Einishi, Toshihiko; Saito, Mitsunori; Fukumi, Kouhei; Nishii, Junji

2013-05-01

Infrared wire-grid polarizers were fabricated consisting of a 500-nm pitch Al grating on a low toxic chalcogenide glass (Sb-Ge-Sn-S system) using the direct imprinting of subwavelength grating followed by a deposition of Al metal by thermal evaporation. To fabricate the subwavelength grating on a chalcogenide glass more easily, the sharp grating was formed on the mold surface. The fabricated polarizer with Al thickness of 130 nm exhibited a polarization function with a transverse magnetic transmittance greater than 60% in the 5-9-μm wavelength range, and an extinction ratio greater than 20 dB in the 4-11-μm wavelength range. The polarizer can be fabricated at lower costs and simpler fabrication processes compared to conventional infrared polarizers.

Thermally tolerant multilayer metal membrane

DOEpatents

Dye, Robert C.; Snow, Ronny C.

2001-01-01

A composite metal membrane including a first metal layer of a Group IVB or Group VB metal sandwiched between two layers of a Group VIIIB metal selected from the group consisting of palladium, platinum, nickel, rhodium, iridium, cobalt, and alloys thereof, and a non-continuous layer of a metal chalcogenide upon one layer of the Group VIIIB metal is disclosed together with a process for the recovery of hydrogen from a gaseous mixture using such a composite membrane and a process for forming such a composite metal membrane.

Enhanced interfacial thermal transport in pnictogen tellurides metallized with a lead-free solder alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devender,; Ramanath, Ganpati, E-mail: Ramanath@rpi.edu; Lofgreen, Kelly

2015-11-15

Controlling thermal transport across metal–thermoelectric interfaces is essential for realizing high efficiency solid-state refrigeration and waste-heat harvesting power generation devices. Here, the authors report that pnictogen chalcogenides metallized with bilayers of Sn{sub 96.5}Ag{sub 3}Cu{sub 0.5} solder and Ni barrier exhibit tenfold higher interfacial thermal conductance Γ{sub c} than that obtained with In/Ni bilayer metallization. X-ray diffraction and x-ray spectroscopy indicate that reduced interdiffusion and diminution of interfacial SnTe formation due to Ni layer correlates with the higher Γ{sub c}. Finite element modeling of thermoelectric coolers metallized with Sn{sub 96.5}Ag{sub 3}Cu{sub 0.5}/Ni bilayers presages a temperature drop ΔT ∼ 22 K that is 40%more » higher than that obtained with In/Ni metallization. Our results underscore the importance of controlling chemical intermixing at solder–metal–thermoelectric interfaces to increase the effective figure of merit, and hence, the thermoelectric cooling efficiency. These findings should facilitate the design and development of lead-free metallization for pnictogen chalcogenide-based thermoelectrics.« less

Two-Dimensional Transition Metal Oxide and Chalcogenide-Based Photocatalysts

NASA Astrophysics Data System (ADS)

Haque, Farjana; Daeneke, Torben; Kalantar-zadeh, Kourosh; Ou, Jian Zhen

2018-06-01

Two-dimensional (2D) transition metal oxide and chalcogenide (TMO&C)-based photocatalysts have recently attracted significant attention for addressing the current worldwide challenges of energy shortage and environmental pollution. The ultrahigh surface area and unconventional physiochemical, electronic and optical properties of 2D TMO&Cs have been demonstrated to facilitate photocatalytic applications. This review provides a concise overview of properties, synthesis methods and applications of 2D TMO&C-based photocatalysts. Particular attention is paid on the emerging strategies to improve the abilities of light harvesting and photoinduced charge separation for enhancing photocatalytic performances, which include elemental doping, surface functionalization as well as heterojunctions with semiconducting and conductive materials. The future opportunities regarding the research pathways of 2D TMO&C-based photocatalysts are also presented. [Figure not available: see fulltext.

Observation of universal strong orbital-dependent correlation effects in iron chalcogenides

DOE PAGES

Yi, M.; Liu, Z. -K.; Zhang, Y.; ...

2015-07-23

Establishing the appropriate theoretical framework for unconventional superconductivity in the iron-based materials requires correct understanding of both the electron correlation strength and the role of Fermi surfaces. This fundamental issue becomes especially relevant with the discovery of the iron chalcogenide superconductors. Here, we use angle-resolved photoemission spectroscopy to measure three representative iron chalcogenides, FeTe 0.56Se 0.44, monolayer FeSe grown on SrTiO 3 and K 0.76Fe 1.72Se 2. We show that these superconductors are all strongly correlated, with an orbital-selective strong renormalization in the dxy bands despite having drastically different Fermi surface topologies. Furthermore, raising temperature brings all three compounds frommore » a metallic state to a phase where the dxy orbital loses all spectral weight while other orbitals remain itinerant. As a result, these observations establish that iron chalcogenides display universal orbital-selective strong correlations that are insensitive to the Fermi surface topology, and are close to an orbital-selective Mott phase, hence placing strong constraints for theoretical understanding of iron-based superconductors.« less

Observation of universal strong orbital-dependent correlation effects in iron chalcogenides

PubMed Central

Yi, M.; Liu, Z-K; Zhang, Y.; Yu, R.; Zhu, J.-X.; Lee, J.J.; Moore, R.G.; Schmitt, F.T.; Li, W.; Riggs, S.C.; Chu, J.-H.; Lv, B.; Hu, J.; Hashimoto, M.; Mo, S.-K.; Hussain, Z.; Mao, Z.Q.; Chu, C.W.; Fisher, I.R.; Si, Q.; Shen, Z.-X.; Lu, D.H.

2015-01-01

Establishing the appropriate theoretical framework for unconventional superconductivity in the iron-based materials requires correct understanding of both the electron correlation strength and the role of Fermi surfaces. This fundamental issue becomes especially relevant with the discovery of the iron chalcogenide superconductors. Here, we use angle-resolved photoemission spectroscopy to measure three representative iron chalcogenides, FeTe0.56Se0.44, monolayer FeSe grown on SrTiO3 and K0.76Fe1.72Se2. We show that these superconductors are all strongly correlated, with an orbital-selective strong renormalization in the dxy bands despite having drastically different Fermi surface topologies. Furthermore, raising temperature brings all three compounds from a metallic state to a phase where the dxy orbital loses all spectral weight while other orbitals remain itinerant. These observations establish that iron chalcogenides display universal orbital-selective strong correlations that are insensitive to the Fermi surface topology, and are close to an orbital-selective Mott phase, hence placing strong constraints for theoretical understanding of iron-based superconductors. PMID:26204461

Synthesis of SnS nanoparticles by SILAR method for quantum dot-sensitized solar cells.

PubMed

Tsukigase, Hiroki; Suzuki, Yoshikazu; Berger, Marie-Hélène; Sagawa, Takashi; Yoshikawa, Susumu

2011-03-01

SnS-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs) which are environmentally more favorable than conventional Cd or Pb-chalcogenide-sensitized electrodes. SnS nanoparticles were well-distributed over the surface of TiO2 nanoparticles by the successive ionic layer adsorption and reaction (SILAR) method. Deposited SnS nanoparticles had diameter about 3 nm. Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the energy conversion efficiency of obtained cells reached a value of 0.21% (0.25 cm2) at SILAR coating cycles of 5. In addition, the photovoltaic performance was improved by additional ZnS coating on the surface of SnS-sensitized TiO2 electrodes.

Microbial synthesis of chalcogenide semiconductor nanoparticles: a review.

PubMed

Jacob, Jaya Mary; Lens, Piet N L; Balakrishnan, Raj Mohan

2016-01-01

Chalcogenide semiconductor quantum dots are emerging as promising nanomaterials due to their size tunable optoelectronic properties. The commercial synthesis and their subsequent integration for practical uses have, however, been contorted largely due to the toxicity and cost issues associated with the present chemical synthesis protocols. Accordingly, there is an immediate need to develop alternative environment-friendly synthesis procedures. Microbial factories hold immense potential to achieve this objective. Over the past few years, bacteria, fungi and yeasts have been experimented with as eco-friendly and cost-effective tools for the biosynthesis of semiconductor quantum dots. This review provides a detailed overview about the production of chalcogen-based semiconductor quantum particles using the inherent microbial machinery. © 2015 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Volatile transport on Venus and implications for surface geochemistry and geology

NASA Technical Reports Server (NTRS)

Brackett, Robert A.; Fegley, Bruce; Arvidson, Raymond E.

1995-01-01

The high vapor pressure of volatile metal halides and chalcogenides (e.g., of Cu, Zn, Sn, Pb, As, Sb, Bi) at typical Venus surface temperatures, coupled with the altitude-dependent temperature gradient of approximately 8.5 K/km, is calculated to transport volatile metal vapors to the highlands of Venus, where condensation and accumulation will occur. The predicted geochemistry of volatile metals on Venus is supported by observations of CuCl in volcanic gases at Kilauea and Nyiragongo, and large enrichments of these and other volatile elements in terrestrial volcanic aerosols. A one-dimensional finite difference vapor transport model shows the diffusive migration of a thickness of 0.01 to greater than 10 microns/yr of moderately to highly volatile phases (e.g., metal halides and chalcogenides) from the hot lowlands (740 K) to the cold highlands (660 K) on Venus. The diffusive transport of volatile phases on Venus may explain the observed low emissivity of the Venusian highlands, hazes at 6-km altitude observed by two Pioneer Venus entry probes, and the Pioneer Venus entry probe anomalies at 12.5 km.

The intercalation chemistry of layered iron chalcogenide superconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vivanco, Hector K.; Rodriguez, Efrain E., E-mail: efrain@umd.edu

The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichalcogenides, fullerenes, and layered cobalt oxides. From past studies of these intercalated superconductors, we discuss the rolemore » of the intercalates in terms of charge doping, structural distortions, and Fermi surface reconstruction. We also briefly review the physical and chemical properties of the host materials—mackinawite-type FeS and β-FeSe. The three types of intercalates for the iron chalcogenides can be placed in three categories: 1.) alkali and alkaline earth cations intercalated through the liquid ammonia technique; 2.) cations intercalated with organic amines such as ethylenediamine; and 3.) layered hydroxides intercalated during hydrothermal conditions. A recurring theme in these studies is the role of the intercalated guest in electron doping the chalcogenide host and in enhancing the two-dimensionality of the electronic structure by spacing the FeSe layers apart. We end this review discussing possible new avenues in the intercalation chemistry of transition metal monochalcogenides, and the promise of these materials as a unique set of new inorganic two-dimensional systems.« less

Synchronous γ (Co60) photons and thermal processing induced insulator metal transition in amorphous chalcogenide As4Se3Te3 composition

NASA Astrophysics Data System (ADS)

El-Sayed, S. A.; Morsy, M. A.

2018-05-01

Amorphous chalcogenide composition AS4Se3Te3 is prepared by conventional quenching technique. The separate annealing or γ quanta irradiation not effect on the dc conductivity properties of the prepared composition. When the prepared samples are subjected to simultaneous annealing at temperature 413 K and γ quanta irradiation the dc conductivity increases. The dark dc conductivity increases by increasing the time of exposure to γ irradiation. At irradiation dose 1.47 × 104 Gy the dc conductivity starts to have metallic like conductivity character. These samples could be used as high temperature γ quanta dosimeter. By applying scaling theory on the samples irradiated with different dose of γ irradiation the critical exponents are determined and found to be < 2. The dark dc conductivity continuously decreases to 0 as temperature tends to zero. The steric value is low in the insulator side of conductivity, but high and almost saturated in the metallic side of conductivity.

Study of linear optical parameters of sodium sulphide nano-particles added ADP crystals

NASA Astrophysics Data System (ADS)

Kochuparampil, A. P.; Joshi, J. H.; Dixit, K. P.; Jethva, H. O.; Joshi, M. J.

2017-05-01

Ammonium Dihydrogen Phosphate (ADP) is one of the nonlinear optical crystals. It is having various applications like optical mixing, electro-optical modulator, harmonic generators, etc. Chalcogenide compounds are poorly soluble in water and difficult to add in the water soluble ADP crystals. The solubility of Chalcogenide compounds can be increased by synthesizing the nano-structured samples with suitable capping agent. In the present study sodium sulphide was added in to ADP to modify its linear optical parameters. Sodium sulphide nano particles were synthesized by co-precipitation technique using Ethylene diamine as capping agent followed by microwave irradiation. The powder XRD confirmed the nano-structured nature of sodium sulphide nano particles. The solubility of nanoparticles of sodium sulphide increased significantly in water compared to the bulk. Pure and Na2S added ADP crystals were grown by slow solvent evaporation method at room temperature. The presence of sodium in ADP was confirmed by AAS. The UV-Vis spectra were recorded for all crystals. Various optical parameters like, transmittance, energy band gap, extinction coefficient, refractive index, optical conductivity, etc. were evaluated. The electronic polarizibility of pure and doped crystals calculated from energy band gap. The effect of doping concentration was found on various parameters.

Electron spin resonance in Cu1-xFexCr2Se4 nanoparticles synthesized with the thermal decomposition method

NASA Astrophysics Data System (ADS)

Edelman, I. S.; Zharkov, S. M.; Pankrats, A. I.; Vorotynov, A. M.; Tugarinov, V. I.; Ivantsov, R. D.; Petrov, D. A.; Velikanov, D. A.; Lin, Chun-Rong; Chen, Chin-Chang; Tseng, Yaw-Teng; Hsu, Hua-Shu

2017-08-01

In this paper, we present a study of the electron spin resonance (ESR) of nanoparticles (NPs) of Cu1-xFexCr2Se4 chalcogenides with x = 0, 0.2, and 0.4. NPs were synthesized via the thermal decomposition of metal chloride salts and selenium powder in a high-temperature organic solvent. According to the XRD and HRTEM data, the NPs were single crystalline nearly hexagonal plates with the structure close to CuCr2Se4 (Fd-3m, a = 10.337 Å). For x = 0 and 0.2, the NPs tend to form long stacks consisting of the plates ;face to face; attached to each other due to the magnetostatic interparticle interaction. Only separate NPs were observed in the case of x = 0.4. Peculiarities were revealed in the ESR temperature behavior for the NPs with x = 0 and 0.2 consistent with the features in the temperature dependences of the NPs magnetization. The non-monotonous dependence of the resonance field Hres on the temperature with a kink near 130 K and the energy gap in the resonance spectrum depending on the type of nanoparticle compacting are the distinct peculiarities. One of the main factors is discussed in order to explain the peculiarities: the coexistence of two types of anisotropy in the Cu1-xFexCr2Se4 NPs, in-plain shape anisotropy and magnetocrystalline anisotropy with four easy axes, which increases strongly with the temperature decrease.

Infrared Polarizer Fabrication by Imprinting on Sb-Ge-Sn-S Chalcogenide Glass

NASA Astrophysics Data System (ADS)

Yamada, Itsunari; Yamashita, Naoto; Tani, Kunihiko; Einishi, Toshihiko; Saito, Mitsunori; Fukumi, Kouhei; Nishii, Junji

2012-01-01

We fabricated infrared wire-grid polarizers consisting of a 500-nm pitch Al grating on a low toxic chalcogenide glass (Sb-Ge-Sn-S system) using the direct imprinting of subwavelength grating followed by a deposition of Al metal by thermal evaporation. To fabricate the subwavelength grating on a chalcogenide glass more easily, the sharp grating was formed on the mold surface. The fabricated polarizer with Al thickness of 130 nm exhibited a polarization function with a transverse magnetic transmittance greater than 60% in the 5-9 µm wavelength range, and an extinction ratio greater than 20 dB in 3.5-11 µm wavelength range. The extinction ratio of the element with Al wires of 180-nm thickness reached 27 dB at 5.4-µm wavelength. The polarizer can be fabricated at lower costs and simpler fabrication processes compared to conventional infrared polarizers.

Topological Aspects of Infinite Metal Clusters and Superconductors.

DTIC Science & Technology

1987-08-11

tetrahedra. T chemical bonding topologies qf discrete octahedral metal clusters can be either edge- localized (e.g., MoX8L 6 4 derivatives), face- localized ...constructed from edge- localized metal polyhedra such as the Mo 6 octahedra in the ternary molybdenum chalcogenides (Chevrel phases) and Rh4 tetrahedra in the...chemical bonding topologies of discrete octahedral metal clusters can be either e4ge- localized (e.g., No X L 4+ derivatives), face- localized (e.g

Local structural order and relaxation effects in metal-chalcogenide glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saleh, Z.M.

1990-01-01

Nuclear quadrupole resonance (NQR) and nuclear magnetic resonance (NMR) have been employed to study the local structural order and the relaxation mechanisms in metal-arsenic-chalcogenide glasses for metal concentrations within the glass forming region. The glass forming region in the Cu-As-S and Cu-As-se glassy systems extends approximately to 6 and 25 at. % copper, respectively. In the composition Cu[sub x](As[sub 2/5]Ch[sub 3/5])[sub 1[minus]x], where Ch = S or Se, there is evidence of dramatic changes in the local structure as copper is added to the system. One important change is the formation of As-As bonds which are absent in As[sub 2]Ch[submore » 3]. The [sup 75]As NQR measurements indicate that the density of these bonds increases with copper concentration x. These results are consistent with the predictions of a model proposed recently to explain the local structural order in glassy metal chalcogenides. While NQR data show that arsenic atoms are threefold coordinated, EXAFs measurements have shown that copper is fourfold coordinated within the glass forming ranges in both systems. The NMR measurements confirm this result and quantitatively determine the local environment around the copper nuclei. For the naturally occurring mineral luzonite (Cu[sub 3]AsS[sub 4]) copper is fourfold coordinated. The known structure of this mineral has been used as a guide to understanding the local structure in the glasses. Copper and arsenic nuclear relaxation measurements were used to study the dynamics of these systems. The temperature and frequency dependence of the spin-lattice and spin-spin relaxation times have been carefully measured to determine the relaxation mechanisms.« less

Recent Progress in Light-Triggered Nanotheranostics for Cancer Treatment

PubMed Central

Zhang, Pengcheng; Hu, Chunhua; Ran, Wei; Meng, Jia; Yin, Qi; Li, Yaping

2016-01-01

Treatments of high specificity are desirable for cancer therapy. Light-triggered nanotheranostics (LTN) mediated cancer therapy could be one such treatment, as they make it possible to visualize and treat the tumor specifically in a light-controlled manner with a single injection. Because of their great potential in cancer therapy, many novel and powerful LTNs have been developed, and are mainly prepared from photosensitizers (PSs) ranging from small organic dyes such as porphyrin- and cyanine-based dyes, semiconducting polymers, to inorganic nanomaterials such as gold nanoparticles, transition metal chalcogenides, carbon nanotubes and graphene. Using LTNs and localized irradiation in combination, complete tumor ablation could be achieved in tumor-bearing animal models without causing significant toxicity. Given their great advances and promising future, we herein review LTNs that have been tested in vivo with a highlight on progress that has been made in the past a couple of years. The current challenges faced by these LTNs are also briefly discussed. PMID:27217830

Study of the self-organization processes in lead sulfide quantum dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tarasov, S. A., E-mail: SATarasov@mail.ru; Aleksandrova, O. A.; Maksimov, A. I.

A procedure is described for the synthesis of nanoparticles based on lead chalcogenides. The procedure combines the synthesis of colloidal quantum dots (QDs) in aqueous solutions with simultaneous organization of the QDs into ordered arrays. The processes of the self-organization of QDs are analyzed at the nano- and microscopic levels by the photoluminescence method, atomic-force microscopy, and optical microscopy.

Synthesis of chalcogenide and pnictide crystals in salt melts using a steady-state temperature gradient

NASA Astrophysics Data System (ADS)

Chareev, D. A.; Volkova, O. S.; Geringer, N. V.; Koshelev, A. V.; Nekrasov, A. N.; Osadchii, V. O.; Osadchii, E. G.; Filimonova, O. N.

2016-07-01

Some examples of growing crystals of metals, alloys, chalcogenides, and pnictides in melts of halides of alkali metals and aluminum at a steady-state temperature gradient are described. Transport media are chosen to be salt melts of eutectic composition with the participation of LiCl, NaCl, KCl, RbCl, CsCl, AlCl3, AlBr3, KBr, and KI in a temperature range of 850-150°C. Some crystals have been synthesized only using a conducting contour. This technique of crystal growth is similar to the electrochemical method. In some cases, to exclude mutual influence, some elements have been isolated and forced to migrate to the crystal growth region through independent channels. As a result, crystals of desired quality have been obtained using no special equipment and with sizes sufficient for study under laboratory conditions.

Stabilized CdSe-CoPi composite photoanode for light-assisted water oxidation by transformation of a CdSe/cobalt metal thin film.

PubMed

Costi, Ronny; Young, Elizabeth R; Bulović, Vladimir; Nocera, Daniel G

2013-04-10

Integration of water splitting catalysts with visible-light-absorbing semiconductors would enable direct solar-energy-to-fuel conversion schemes such as those based on water splitting. A disadvantage of some common semiconductors that possess desirable optical bandgaps is their chemical instability under the conditions needed for oxygen evolution reaction (OER). In this study, we demonstrate the dual benefits gained from using a cobalt metal thin-film as the precursor for the preparation of cobalt-phosphate (CoPi) OER catalyst on cadmium chalcogenide photoanodes. The cobalt layer protects the underlying semiconductor from oxidation and degradation while forming the catalyst and simultaneously facilitates the advantageous incorporation of the cadmium chalcogenide layer into the CoPi layer during continued processing of the electrode. The resulting hybrid material forms a stable photoactive anode for light-assisted water splitting.

Self-surface charge exfoliation and electrostatically coordinated 2D hetero-layered hybrids

PubMed Central

Yang, Min-Quan; Xu, Yi-Jun; Lu, Wanheng; Zeng, Kaiyang; Zhu, Hai; Xu, Qing-Hua; Ho, Ghim Wei

2017-01-01

At present, the technological groundwork of atomically thin two-dimensional (2D) hetero-layered structures realized by successive thin film epitaxial growth is in principle constrained by lattice matching prerequisite as well as low yield and expensive production. Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically, bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a dissimilar transition metal dichalcogenide, MoSe2, into scalable hetero-layered hybrids. Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal high visible-light photoreactivity, efficient charge transfer and intimate contact interface for stable cycling and storage purposes. Such a synthetic approach renders independent thickness and composition control anticipated to advance the development of ‘design-and-build' 2D layered heterojunctions for large-scale exploration and applications. PMID:28146147

Preparation of uniform nanoparticles of ultra-high purity metal oxides, mixed metal oxides, metals, and metal alloys

DOEpatents

Woodfield, Brian F.; Liu, Shengfeng; Boerio-Goates, Juliana; Liu, Qingyuan; Smith, Stacey Janel

2012-07-03

In preferred embodiments, metal nanoparticles, mixed-metal (alloy) nanoparticles, metal oxide nanoparticles and mixed-metal oxide nanoparticles are provided. According to embodiments, the nanoparticles may possess narrow size distributions and high purities. In certain preferred embodiments, methods of preparing metal nanoparticles, mixed-metal nanoparticles, metal oxide nanoparticles and mixed-metal nanoparticles are provided. These methods may provide tight control of particle size, size distribution, and oxidation state. Other preferred embodiments relate to a precursor material that may be used to form nanoparticles. In addition, products prepared from such nanoparticles are disclosed.

How Does a SILAR CdSe Film Grow? Tuning the Deposition Steps to Suppress Interfacial Charge Recombination in Solar Cells.

PubMed

Becker, Matthew A; Radich, James G; Bunker, Bruce A; Kamat, Prashant V

2014-05-01

Successive ionic layer adsorption and reaction (SILAR) is a popular method of depositing the metal chalcogenide semiconductor layer on the mesoscopic metal oxide films for designing quantum-dot-sensitized solar cells (QDSSCs) or extremely thin absorber (ETA) solar cells. While this deposition method exhibits higher loading of the light-absorbing semiconductor layer than direct adsorption of presynthesized colloidal quantum dots, the chemical identity of these nanostructures and the evolution of interfacial structure are poorly understood. We have now analyzed step-by-step SILAR deposition of CdSe films on mesoscopic TiO2 nanoparticle films using X-ray absorption near-edge structure analysis and probed the interfacial structure of these films. The film characteristics interestingly show dependence on the order in which the Cd and Se are deposited, and the CdSe-TiO2 interface is affected only during the first few cycles of deposition. Development of a SeO2 passivation layer in the SILAR-prepared films to form a TiO2/SeO2/CdSe junction facilitates an increase in photocurrents and power conversion efficiencies of quantum dot solar cells when these films are integrated as photoanodes in a photoelectrochemical solar cell.

[Ag115S34(SCH2C6H4 tBu)47(dpph)6]: synthesis, crystal structure and NMR investigations of a soluble silver chalcogenide nanocluster† †Dedicated to Evamarie Hey-Hawkins on the occasion of her 60th birthday. ‡ ‡Electronic supplementary information (ESI) available: CCDC 1507868. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc04578b Click here for additional data file. Click here for additional data file.

PubMed Central

Fuhr, Olaf; Breitung, Ben; Kiran Chakravadhanula, Venkata Sei; Guthausen, Gisela; Hennrich, Frank; Yu, Wen; Kappes, Manfred M.; Roesky, Peter W.

2017-01-01

With the aim to synthesize soluble cluster molecules, the silver salt of (4-(tert-butyl)phenyl)methanethiol [AgSCH2C6H4 tBu] was applied as a suitable precursor for the formation of a nanoscale silver sulfide cluster. In the presence of 1,6-(diphenylphosphino)hexane (dpph), the 115 nuclear silver cluster [Ag115S34(SCH2C6H4 tBu)47(dpph)6] was obtained. The molecular structure of this compound was elucidated by single crystal X-ray analysis and fully characterized by spectroscopic techniques. In contrast to most of the previously published cluster compounds with more than a hundred heavy atoms, this nanoscale inorganic molecule is soluble in organic solvents, which allowed a comprehensive investigation in solution by UV-Vis spectroscopy and one- and two-dimensional NMR spectroscopy including 31P/109Ag-HSQC and DOSY experiments. These are the first heteronuclear NMR investigations on coinage metal chalcogenides. They give some first insight into the behavior of nanoscale silver sulfide clusters in solution. Additionally, molecular weight determinations were performed by 2D analytical ultracentrifugation and HR-TEM investigations confirm the presence of size-homogeneous nanoparticles present in solution. PMID:28507679

Inorganic Nanotubes and Fullerene-like Nanoparticles at the Crossroads between Solid-State Chemistry and Nanotechnology.

PubMed

Višić, Bojana; Panchakarla, Leela Srinivas; Tenne, Reshef

2017-09-20

Inorganic nanotubes (NTs) and fullerene-like nanoparticles (NPs) of WS 2 were discovered some 25 years ago and are produced now on a commercial scale for various applications. This Perspective provides a brief description of recent progress in this scientific discipline. The conceptual evolution leading to the discovery of these NTs and NPs is briefly discussed. Subsequently, recent progress in the synthesis of such NPs from a variety of inorganic compounds with layered (2D) structure is described. In particular, we discuss the synthesis of NTs from chalcogenide- and oxide-based ternary misfit layered compounds, as well as their structure and different growth mechanisms. Next we deliberate on the mechanical, optical, electrical, and electromechanical properties, which delineate them from their bulk counterparts and also from their graphene-like analogues. Here, different experiments with individual NTs coupled with first-principles and molecular dynamics calculations demonstrate the unique physical nature of these quasi-1D nanostructures. Finally, the various applications of the fullerene-like NPs of WS 2 and NTs formed therefrom are deliberated. Foremost among the possibilities are their extensive uses as superior solid lubricants. Combined with their nontoxicity and their facile dispersion, these NTs, with an ultimate strength of about 20 GPa, are likely to find numerous applications in reinforcing polymers, adhesives, textiles, medical devices, metallic alloys, and even concrete. Other potential applications in energy-harvesting and catalysis are discussed in brief.

Electrochromic devices based on lithium insertion

DOEpatents

Richardson, Thomas J.

2006-05-09

Electrochromic devices having as an active electrode materials comprising Sb, Bi, Si, Ge, Sn, Te, N, P, As, Ga, In, Al, C, Pb, I and chalcogenides are disclosed. The addition of other metals, i.e. Ag and Cu to the active electrode further enhances performance.

Validity of the local approximation in iron pnictides and chalcogenides

DOE PAGES

Sémon, Patrick; Haule, Kristjan; Kotliar, Gabriel

2017-05-08

We introduce a methodology to treat different degrees of freedom at different levels of approximation. We use cluster DMFT (dynamical mean field theory) for the t 2g electrons and single site DMFT for the e g electrons to study the normal state of the iron pnictides and chalcogenides. Furthermore, in the regime of moderate mass renormalizations, the self-energy is very local, justifying the success of single site DMFT for these materials and for other Hunds metals. Here we solve the corresponding impurity model with CTQMC (continuous time quantum Monte Carlo) and find that the minus sign problem is not severemore » in regimes of moderate mass renormalization.« less

Transition-Metal Chalcogenide/Graphene Ensembles for Light-Induced Energy Applications.

PubMed

Kagkoura, Antonia; Skaltsas, Theodosis; Tagmatarchis, Nikos

2017-09-21

Recently, nanomaterials that harvest solar energy and convert it to other forms of energy are of great interest. In this context, transition metal chalcogenides (TMCs) have recently been in the spotlight due to their optoelectronic properties that render them potential candidates mainly in energy conversion applications. Integration of TMCs onto a strong electron-accepting material, such as graphene, yielding novel TMC/graphene ensembles is of high significance, since photoinduced charge-transfer phenomena, leading to intra-ensemble charge separation, may occur. In this review, we highlight the utility of TMC/graphene ensembles, with a specific focus on latest trends in applications, while their synthetic routes are also discussed. In fact, TMC/graphene ensembles are photocatalytically active and superior as compared to intact TMCs analogues, when examined toward photocatalytic H 2 evolution, dye degradation and redox transformations of organic compounds. Moreover, TMC/graphene ensembles have shown excellent prospect when employed in photovoltaics and biosensing applications. Finally, the future prospects of such materials are outlined. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Final Project Report for ER15351 “A Study of New Actinide Zintl Ion Materials”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peter K. Dorhout

2007-11-12

The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorous-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metalmore » salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples.« less

High-mobility ultrathin semiconducting films prepared by spin coating.

PubMed

Mitzi, David B; Kosbar, Laura L; Murray, Conal E; Copel, Matthew; Afzali, Ali

2004-03-18

The ability to deposit and tailor reliable semiconducting films (with a particular recent emphasis on ultrathin systems) is indispensable for contemporary solid-state electronics. The search for thin-film semiconductors that provide simultaneously high carrier mobility and convenient solution-based deposition is also an important research direction, with the resulting expectations of new technologies (such as flexible or wearable computers, large-area high-resolution displays and electronic paper) and lower-cost device fabrication. Here we demonstrate a technique for spin coating ultrathin (approximately 50 A), crystalline and continuous metal chalcogenide films, based on the low-temperature decomposition of highly soluble hydrazinium precursors. We fabricate thin-film field-effect transistors (TFTs) based on semiconducting SnS(2-x)Se(x) films, which exhibit n-type transport, large current densities (>10(5) A cm(-2)) and mobilities greater than 10 cm2 V(-1) s(-1)--an order of magnitude higher than previously reported values for spin-coated semiconductors. The spin-coating technique is expected to be applicable to a range of metal chalcogenides, particularly those based on main group metals, as well as for the fabrication of a variety of thin-film-based devices (for example, solar cells, thermoelectrics and memory devices).

High-mobility ultrathin semiconducting films prepared by spin coating

NASA Astrophysics Data System (ADS)

Mitzi, David B.; Kosbar, Laura L.; Murray, Conal E.; Copel, Matthew; Afzali, Ali

2004-03-01

The ability to deposit and tailor reliable semiconducting films (with a particular recent emphasis on ultrathin systems) is indispensable for contemporary solid-state electronics. The search for thin-film semiconductors that provide simultaneously high carrier mobility and convenient solution-based deposition is also an important research direction, with the resulting expectations of new technologies (such as flexible or wearable computers, large-area high-resolution displays and electronic paper) and lower-cost device fabrication. Here we demonstrate a technique for spin coating ultrathin (~50Å), crystalline and continuous metal chalcogenide films, based on the low-temperature decomposition of highly soluble hydrazinium precursors. We fabricate thin-film field-effect transistors (TFTs) based on semiconducting SnS2-xSex films, which exhibit n-type transport, large current densities (>105Acm-2) and mobilities greater than 10cm2V-1s-1-an order of magnitude higher than previously reported values for spin-coated semiconductors. The spin-coating technique is expected to be applicable to a range of metal chalcogenides, particularly those based on main group metals, as well as for the fabrication of a variety of thin-film-based devices (for example, solar cells, thermoelectrics and memory devices).

Temperature, Crystalline Phase and Influence of Substrate Properties in Intense Pulsed Light Sintering of Copper Sulfide Nanoparticle Thin Films.

PubMed

Dexter, Michael; Gao, Zhongwei; Bansal, Shalu; Chang, Chih-Hung; Malhotra, Rajiv

2018-02-02

Intense Pulsed Light sintering (IPL) uses pulsed, visible light to sinter nanoparticles (NPs) into films used in functional devices. While IPL of chalcogenide NPs is demonstrated, there is limited work on prediction of crystalline phase of the film and the impact of optical properties of the substrate. Here we characterize and model the evolution of film temperature and crystalline phase during IPL of chalcogenide copper sulfide NP films on glass. Recrystallization of the film to crystalline covellite and digenite phases occurs at 126 °C and 155 °C respectively within 2-7 seconds. Post-IPL films exhibit p-type behavior, lower resistivity (~10 -3 -10 -4  Ω-cm), similar visible transmission and lower near-infrared transmission as compared to the as-deposited film. A thermal model is experimentally validated, and extended by combining it with a thermodynamic approach for crystal phase prediction and via incorporating the influence of film transmittivity and optical properties of the substrate on heating during IPL. The model is used to show the need to a-priori control IPL parameters to concurrently account for both the thermal and optical properties of the film and substrate in order to obtain a desired crystalline phase during IPL of such thin films on paper and polycarbonate substrates.

Transition metal-doped zinc chalcogenides: Spectroscopy and laser demonstration of a new class of gain media

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeLoach, L.D.; Page, R.H.; Wilke, G.D.

The absorption and emission properties of transition metal (TM)-doped Zinc chalcogenides have been investigated to understand their potential application as room-temperature, mid-infrared tunable laser media. Crystals of ZnS, ZnSe, and ZnTe, individually doped with Cr{sup 2+}, Co{sup 2+}, Ni{sup 2+}, or Fe{sup 2+}, have been evaluated. The absorption and emission properties are presented and discussed in terms of the energy levels from which they arise. The absorption spectra of the crystals studied exhibit strong bands between 1.4 and 2.0 {micro}m which overlap with the output of strained-layer InGaAs diodes. The room-temperature emission spectra reveal wide-band emissions from 2--3 {micro}m formore » Cr and from 2.8--1.0 {micro}m for Co. Laser demonstrations of Cr:ZnS and Cr:ZnSe have been performed in a laser-pumped laser cavity with a Co:MgF{sub 2} pump laser. The output of both lasers were determined to peak at wavelengths near 2.35 {micro}m, and both lasers demonstrated a maximum slope efficiency of approximately 20%. Based on these initial results, the Cr{sup 2+} ion is predicted to be a highly favorable laser ion for the mid-IR when doped into the zinc chalcogenides; Co{sup 2+} may also serve usefully, but laser demonstrations yet remain to be performed.« less

Assembly of metals and nanoparticles into novel nanocomposite superstructures

PubMed Central

Xu, Jiaquan; Chen, Lianyi; Choi, Hongseok; Konish, Hiromi; Li, Xiaochun

2013-01-01

Controlled assembly of nanoscale objects into superstructures is of tremendous interests. Many approaches have been developed to fabricate organic-nanoparticle superstructures. However, effective fabrication of inorganic-nanoparticle superstructures (such as nanoparticles linked by metals) remains a difficult challenge. Here we show a novel, general method to assemble metals and nanoparticles rationally into nanocomposite superstructures. Novel metal-nanoparticle superstructures are achieved by self-assembly of liquid metals and nanoparticles in immiscible liquids driven by reduction of free energy. Superstructures with various architectures, such as metal-core/nanoparticle-shell, nanocomposite-core/nanoparticle-shell, network of metal-linked core/shell nanostructures, and network of metal-linked nanoparticles, were successfully fabricated by simply tuning the volume ratio between nanoparticles and liquid metals. Our approach provides a simple, general way for fabrication of numerous metal-nanoparticle superstructures and enables a rational design of these novel superstructures with desired architectures for exciting applications.

Controlling the Photophysical Properties of Semiconductor Quantum Dot Arrays by Strategically Altering Their Surface Chemistry

NASA Astrophysics Data System (ADS)

Marshall, Ashley R.

Semiconductor quantum dots (QDs) are interesting materials that, after less than 40 years of research, are used in commercial products. QDs are now found in displays, such as Samsung televisions and the Kindle Fire, and have applications in lighting, bio-imaging, quantum computing, and photovoltaics. They offer a large range of desirable properties: a controllable band gap, solution processability, controlled energy levels, and are currently the best materials for multiple exciton generation. The tunable optoelectronic properties of QDs can be controlled using size, shape, composition, and surface treatments--as shown here. Due to the quasi-spherical shape of QDs the surface to volume ratio is high, i.e. many of the constituent atoms are found on the QD surface. This makes QDs highly sensitive to surface chemistry modifications. This thesis encompasses the effects of surface treatments for QDs of two semiconducting materials: lead chalcogenides and CsPbI3. Our group developed a new synthetic technique for lead chalcogenide QDs via the cation exchange of cadmium chalcogenides. An in-depth chemical analysis is paired with optical and electrical studies and we find that metal halide residue contributes to the oxidative stability and decreased trap state density in cation-exchanged PbS QDs. We exploit these properties to make air-stable QD photovoltaic devices from both PbS and PbSe QD materials. Beyond the effects of residual atoms left from the synthetic technique, I investigated how to controllably add atoms onto the surface of QDs. I found that by introducing metal halides as a post-treatment in an electronically coupled array I am able to control the performance parameters in QD photovoltaic devices. These treatments fully infiltrate the assembled film, even under short exposure times and allow me to add controlled quantities of surface atoms to study their effects on film properties and photovoltaic device performance. Finally, I sought to apply the knowledge of the lead chalcogenide QD surfaces to produce QD photovoltaics from a new material: CsPbI3. I fabricated the first perovskite QD photovoltaic devices and using similar treatment methods as the lead chalcogenide QD arrays, I am able to influence the photophysical properties of CsPbI3 QD arrays.

77 FR 39682 - Application(s) for Duty-Free Entry of Scientific Instruments

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-05

... oxides, metal chalcogenides, DNA, quantum dots, and carbon nanomaterials to determine their size, shape... Number: 12-031. Applicant: Penn State College of Medicine, 500 University Dr., Hershey, PA 17033... to further advance the body of research of the College of Medicine and the greater scientific...

Substituent-Modulated Assembly Formation: An Approach to Enhancing the Photostability of Photoelectric-Sensitive Chalcogenide-Based Ion-Pair Hybrids.

PubMed

Lin, Jian; Fu, Zhixing; Zhang, Jiaxu; Zhu, Yujia; Hu, Dandan; Li, Dongsheng; Wu, Tao

2017-03-20

A series of electronically active viologen dications (RV) with tunable substituent groups were utilized to hybridize with [Ge 4 S 10 ] 4- (T2 cluster) to form the hybrids of T2@RV. These hybrids exhibited variable supermolecular assembly formation, tunable optical absorption properties, and different photoelectric response under the influence of different RV dications. Raman testing and time-dependent photocurrent response indicated that the photosensitivity and photostability of T2@RV could be integrated while choosing suitable RV dications. Current research provides a general method to build a tunable hybrid system based on crystalline metal chalcogenide compounds through the replacement of photoinactive cationic organic templates with photoactive ones with different substituent groups.

Synthesis of sub-micro-flakes CrSe2 on glass and (110) Si substrates by solvothermal method

NASA Astrophysics Data System (ADS)

Tang, Qingkai; Liu, Changyou; Zhang, Binbin; Jie, Wanqi

2018-06-01

Layered structure MX2 (M = transition metal, X = S, Se and Te) chalcogenides have rich physic properties and potential applications. While it is still a challenge to prepare the chalcogenides by solvothermal method. In this work, we reported a new solution method to prepare CrSe2 sub-micro-flakes on different substrates. The surface morphologies, structures and compositions of the precursor CrSe2(en)1/2 and CrSe2 were investigated by SEM, XRD, thermogravimetric, IR and Raman spectra. The CrSe2 flakes with the sizes of 5-15 μm were obtained on both glass and (110) Si crystalline substrates. The formation mechanism of CrSe2 sub-micro-flakes is suggested.

Superconductivity in films of Pb/PbSe core/shell nanocrystals.

PubMed

Zolotavin, Pavlo; Guyot-Sionnest, Philippe

2012-09-25

Superconductivity in films of electronically coupled colloidal lead nanocrystals is reported. The coupling between particles is in situ controlled through the conversion of the oxides present on the surface of the nanoparticles to chalcogenides. This transformation allows for a 10(9)-fold increase in the conductivity. The temperature of the onset of the superconductivity was found to depend upon the degree of coupling of the nanoparticles in the vicinity of the insulator-superconductor transition. The critical current density of the best sample of Pb/PbSe nanocrystals at zero magnetic field was determined to be 4 × 10(3) A/cm(2). In turn, the critical field of the sample shows 50-fold enhancement compared to bulk Pb.

A library of atomically thin metal chalcogenides.

PubMed

Zhou, Jiadong; Lin, Junhao; Huang, Xiangwei; Zhou, Yao; Chen, Yu; Xia, Juan; Wang, Hong; Xie, Yu; Yu, Huimei; Lei, Jincheng; Wu, Di; Liu, Fucai; Fu, Qundong; Zeng, Qingsheng; Hsu, Chuang-Han; Yang, Changli; Lu, Li; Yu, Ting; Shen, Zexiang; Lin, Hsin; Yakobson, Boris I; Liu, Qian; Suenaga, Kazu; Liu, Guangtong; Liu, Zheng

2018-04-01

Investigations of two-dimensional transition-metal chalcogenides (TMCs) have recently revealed interesting physical phenomena, including the quantum spin Hall effect 1,2 , valley polarization 3,4 and two-dimensional superconductivity 5 , suggesting potential applications for functional devices 6-10 . However, of the numerous compounds available, only a handful, such as Mo- and W-based TMCs, have been synthesized, typically via sulfurization 11-15 , selenization 16,17 and tellurization 18 of metals and metal compounds. Many TMCs are difficult to produce because of the high melting points of their metal and metal oxide precursors. Molten-salt-assisted methods have been used to produce ceramic powders at relatively low temperature 19 and this approach 20 was recently employed to facilitate the growth of monolayer WS 2 and WSe 2 . Here we demonstrate that molten-salt-assisted chemical vapour deposition can be broadly applied for the synthesis of a wide variety of two-dimensional (atomically thin) TMCs. We synthesized 47 compounds, including 32 binary compounds (based on the transition metals Ti, Zr, Hf, V, Nb, Ta, Mo, W, Re, Pt, Pd and Fe), 13 alloys (including 11 ternary, one quaternary and one quinary), and two heterostructured compounds. We elaborate how the salt decreases the melting point of the reactants and facilitates the formation of intermediate products, increasing the overall reaction rate. Most of the synthesized materials in our library are useful, as supported by evidence of superconductivity in our monolayer NbSe 2 and MoTe 2 samples 21,22 and of high mobilities in MoS 2 and ReS 2 . Although the quality of some of the materials still requires development, our work opens up opportunities for studying the properties and potential application of a wide variety of two-dimensional TMCs.

Discovery of New Mineral Butianite, Ni6SnS2, an Alteration Phase from Allende

NASA Astrophysics Data System (ADS)

Ma, C.

2017-07-01

Butianite (Ni6SnS2) is a new chalcogenide mineral from an Allende CAI, along with nuwaite (Ni6GeS2), formed from a late-stage sulfidation process, where Ni-Fe metals reacted with a low-temperature fluid enriched in S, Ge, Sn and Te.

Quantum soldering of individual quantum dots.

PubMed

Roy, Xavier; Schenck, Christine L; Ahn, Seokhoon; Lalancette, Roger A; Venkataraman, Latha; Nuckolls, Colin; Steigerwald, Michael L

2012-12-07

Making contact to a quantum dot: Single quantum-dot electronic circuits are fabricated by wiring atomically precise metal chalcogenide clusters with conjugated molecular connectors. These wired clusters can couple electronically to nanoscale electrodes and be tuned to control the charge-transfer characteristics (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid microwave-assisted preparation of binary and ternary transition metal sulfide compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butala, Megan M.; Perez, Minue A.; Arnon, Shiri

Transition metal chalcogenides are of interest for energy applications, including energy generation in photoelectrochemical cells and as electrodes for next-generation electrochemical energy storage. Synthetic routes for such chalcogenides typically involve extended heating at elevated temperatures for multiple weeks. We demonstrate here the feasibility of rapidly preparing select sulfide compounds in a matter of minutes, rather than weeks, using microwave-assisted heating in domestic microwaves. We report the preparations of phase pure FeS2, CoS2, and solid solutions thereof from the elements with only 40 min of heating. Conventional furnace and rapid microwave preparations of CuTi2S4 both result in a majority of themore » targeted phase, even with the significantly shorter heating time of 40 min for microwave methods relative to 12 days using a conventional furnace. The preparations we describe for these compounds can be extended to related structures and chemistries and thus enable rapid screening of the properties and performance of various compositions of interest for electronic, optical, and electrochemical applications.« less

High speed chalcogenide glass electrochemical metallization cells with various active metals.

PubMed

Hughes, Mark A; Burgess, Alexander; Hinder, Steven; Gholizadeh, A Baset; Craig, Christopher; Hewak, Daniel W

2018-08-03

We fabricated electrochemical metallization cells using a GaLaSO solid electrolyte, an InSnO inactive electrode and active electrodes consisting of various metals (Cu, Ag, Fe, Cu, Mo, Al). Devices with Ag and Cu active metals showed consistent and repeatable resistive switching behaviour, and had a retention of 3 and >43 days, respectively; both had switching speeds of <5 ns. Devices with Cr and Fe active metals displayed incomplete or intermittent resistive switching, and devices with Mo and Al active electrodes displayed no resistive switching ability. Deeper penetration of the active metal into the GaLaSO layer resulted in greater resistive switching ability of the cell. The off-state resistivity was greater for more reactive active metals which may be due to a thicker intermediate layer.

Wet-chemical synthesis and applications of non-layer structured two-dimensional nanomaterials

PubMed Central

Tan, Chaoliang; Zhang, Hua

2015-01-01

Non-layer structured nanomaterials with single- or few-layer thickness have two-dimensional sheet-like structures and possess intriguing properties. Recent years have seen major advances in development of a host of non-layer structured ultrathin two-dimensional nanomaterials such as noble metals, metal oxides and metal chalcogenides. The wet-chemical synthesis has emerged as the most promising route towards high-yield and mass production of such nanomaterials. These nanomaterials are now finding increasing applications in a wide range of areas including catalysis, energy production and storage, sensor and nanotherapy, to name but a few. PMID:26303763

Pressure-driven phase transition from antiferromagnetic semiconductor to nonmagnetic metal in the two-leg ladders A Fe 2 X 3 ( A = Ba , K ; X = S , Se )

DOE PAGES

Zhang, Yang; Lin, Lingfang; Zhang, Jun -Jie; ...

2017-03-15

The recent discovery of superconductivity in BaFe 2S 3 has stimulated considerable interest in 123-type iron chalcogenides. This material is the first reported iron-based two-leg ladder superconductor, as opposed to the prevailing two-dimensional layered structures of the iron superconductor family. Once the hydrostatic pressure exceeds 11 GPa, BaFe 2S 3 changes from a semiconductor to a superconductor below 24 K. Although previous calculations correctly explained its ground-state magnetic state and electronic structure, the pressure-induced phase transition was not successfully reproduced. In this work, our first-principles calculations show that with increasing pressure the lattice constants as well as local magnetic momentsmore » are gradually suppressed, followed by a first-order magnetic transition at a critical pressure, with local magnetic moments dropping to zero suddenly. Our calculations suggest that the self-doping caused by electrons transferred from S to Fe may play a key role in this transition. The development of a nonmagnetic metallic phase at high pressure may pave the way to superconductivity. As extensions of this effort, two other 123-type iron chalcogenides, KFe 2S 3 and KFe 2Se 3, have also been investigated. KFe 2S 3 also displays a first-order transition with increasing pressure, but KFe 2Se 3 shows instead a second-order or weakly first-order transition. Here, the required pressures for KFe 2S 3 and KFe 2Se 3 to quench the magnetism are higher than for BaFe 2S 3. Further experiments could confirm the predicted first-order nature of the transition in BaFe 2S 3 and KFe 2S 3, as well as the possible metallic/superconductivity state in other 123-type iron chalcogenides under high pressure.« less

Structural and electronic properties of copper-doped chalcogenide glasses

NASA Astrophysics Data System (ADS)

Guzman, David M.; Strachan, Alejandro

2017-10-01

Using ab initio molecular dynamics based on density functional theory, we study the atomic and electronic structure, and transport properties of copper-doped germanium-based chalcogenide glasses. These mixed ionic-electronic conductor materials exhibit resistance or threshold switching under external electric field depending on slight variations of chemical composition. Understanding the origin of the transport character is essential for the functionalization of glassy chalcogenides for nanoelectronics applications. To this end, we generated atomic structures for GeX3 and GeX6 (X = S, Se, Te) at different copper concentrations and characterized the atomic origin of electronic states responsible for transport and the tendency of copper clustering as a function of metal concentration. Our results show that copper dissolution energies explain the tendency of copper to agglomerate in telluride glasses, consistent with filamentary conduction. In contrast, copper is less prone to cluster in sulfides and selenides leading to hysteresisless threshold switching where the nature of transport is dominated by electronic midgap defects derived from polar chalcogen bonds and copper atoms. Simulated I -V curves show that at least 35% by weight of copper is required to achieve the current demands of threshold-based devices for memory applications.

Volume-labeled nanoparticles and methods of preparation

DOEpatents

Wang, Wei; Gu, Baohua; Retterer, Scott T; Doktycz, Mitchel J

2015-04-21

Compositions comprising nanosized objects (i.e., nanoparticles) in which at least one observable marker, such as a radioisotope or fluorophore, is incorporated within the nanosized object. The nanosized objects include, for example, metal or semi-metal oxide (e.g., silica), quantum dot, noble metal, magnetic metal oxide, organic polymer, metal salt, and core-shell nanoparticles, wherein the label is incorporated within the nanoparticle or selectively in a metal oxide shell of a core-shell nanoparticle. Methods of preparing the volume-labeled nanoparticles are also described.

How metallic is the binding state of indium hosted by excess-metal chalcogenides in ore deposits?

NASA Astrophysics Data System (ADS)

Ondina Figueiredo, Maria; Pena Silva, Teresa; Oliveira, Daniel; Rosa, Diogo

2010-05-01

Discovered in 1863, indium is nowadays a strategic scarce metal used both in classical technologic fields (like low melting-temperature alloys and solders) and in innovative nano-technologies to produce "high-tech devices" by means of new materials, namely liquid crystal displays (LCDs), organic light emitting diodes (OLEDs) and the recently introduced transparent flexible thin-films manufactured with ionic amorphous oxide semiconductors (IAOS). Indium is a typical chalcophile element, seldom forming specific minerals and occurring mainly dispersed within polymetallic sulphides, particularly with excess metal ions [1]. The average content of indium in the Earth's crust is very low but a further increase in its demand is still expected in the next years, thus focusing a special interest in uncovering new exploitation sites through promising polymetallic sulphide ores - e.g., the Iberian Pyrite Belt (IPB) [2] - and in improving recycling technologies. Indium recovery stands mostly on zinc extraction from sphalerite, the natural cubic sulphide which is the prototype of so-called "tetrahedral sulphides" where metal ions fill half of the available tetrahedral sites within the cubic closest packing of sulphur anions where the double of unfilled interstices are available for further in-filling. It is worth remarking that such packing array is particularly suitable for accommodating polymetallic cations by filling closely located interstitial sites [3] as happens in excess-metal tetrahedral sulphides - e.g. bornite, ideally Cu5FeS4, recognized as an In-carrying mineral [4]. Studying the tendency towards In-In interactions able of leading to the formation of polycations would efficiently contribute to understand indium crystal chemistry and the metal binding state in natural chalcogenides. Accordingly, an X-ray absorption near-edge spectroscopy (XANES) study at In L3-edge was undertaken using the instrumental set-up of ID21 beamline at the ESRF (European Synchrotron Radiation Facility, in Grenoble/France). Polymetallic chalcogenide minerals and various model compounds displaying distinct bonding situations of indium to other ligands (oxygen and halides) were studied. Encouraging results from a first experiment [5] showed the presence of a "white line" in the XANES spectra collected from InF3 and from In-hosting bornite; however, the impossibility of clearly identifying the nanoscale phase hosting indium in sulphide ore samples has hindered a full interpretation of X-ray absorption data. The crystal chemistry of indium in natural chalcogenides is now reanalysed and XANES results obtained so far for polymetallic sulphides are accordingly re-evaluated, disclosing a challenging clue for indium binding state in these host minerals within sulphide ores. [1] M.O. Figueiredo et al. (2007) Procd. 9th Biennial SGA Mtg., Dublin/Ireland, edt. C. Andrew et al., 1355-1357. [2] O.C. Gaspar (2002) Canad. Miner. 40, 611-636. [3] M.O. Figueiredo & T.P. Silva (2009) ICANS 23, 23rd Int. Conf. Amorphous & Nano-crystalline Semiconductors, Netherlands, August 23-28. Poster ID 229 (abstract). [4] T. Seifert & D. Sandmann (2002) Ore Geol. Reviews 28, 1-31. [5] M.O. Figueiredo & T.P. Silva (2009) XVIII Int. Mater. Res. Congr., Mexico, August 16-20. Symp. 20, Poster nr. 1 (abstract). * Work developed within the research project PTDC/CTE-GIN/67027/2006 financed by the Portuguese Foundation for Science & Technology (FCT/MCTES). The financial support from EU to perform the experiments at the ESRF is also acknowledged.

Layered transition metal dichalcogenide electrochemistry: journey across the periodic table.

PubMed

Chia, Xinyi; Pumera, Martin

2018-06-08

Studies on layered transition metal dichalcogenides (TMDs), in particular for Group VIB TMDs like MoS2 and WS2, have long reached a crescendo in the realms of electrochemical applications initiated by their remarkable catalytic and electronic properties. One area that garnered considerable attention is the fervent pursuit of layered TMDs as electrocatalysts for hydrogen evolution reaction (HER), driven by global efforts towards reducing carbon footprint and attaining hydrogen economy. This Tutorial Review captures the essence of electrochemistry of different classes of layered TMDs and metal chalcogenides across the period table and showcases their tuneable electrochemical and HER catalytic attributes that are governed by the elemental composition, structure and anisotropy. Of interest to the assiduously studied Group VIB TMDs, we describe the role of elemental constituents and material purity in aspects of surface composition and structure, on their electrochemistry. Across families of layered TMDs in the periodic table, we highlight the apparent trends in their electrochemical and electrocatalytic properties through diligent comparison. Inevitably, these trends vary according to the type of chalcogen or transition metal that constitutes the eventual TMD. Beyond layered TMDs, we discuss the electrochemistry and recent progress in HER electrocatalysis of other layered metal chalcogenides that are overshadowed by the success of Group VIB TMDs. At the pinnacle of the emergent applications of layered TMDs, it is prudent to demystify the intrinsic electrochemical behaviour that originates from the participation of the elemental constitution of transition metal or chalcogen. Moreover, knowledge of the catalytic and electronic properties of the various TMD families and emerging trends across the period or down the group is of paramount importance when introducing or refining their prospective uses. The annotations in this Tutorial Review are envisioned to promote discourse into the catalytic and electrochemical trends of TMDs that is currently absent.

Synthesis, structure, and thermal properties of soluble hydrazinium germanium(IV) and tin(IV) selenide salts.

PubMed

Mitzi, David B

2005-05-16

The crystal structures of two hydrazinium-based germanium(IV) and tin(IV) selenide salts are determined. (N(2)H(5))(4)Ge(2)Se(6) (1) [I4(1)cd, a = 12.708(1) Angstroms, c = 21.955(2) Angstroms, Z = 8] and (N(2)H(4))(3)(N(2)H(5))(4)Sn(2)Se(6) (2) [P, a = 6.6475(6) Angstroms, b = 9.5474(9) Angstroms, c = 9.8830(10) Angstroms, alpha = 94.110(2) degrees, beta = 99.429(2) degrees, gamma = 104.141(2) degrees, Z = 1] each consist of anionic dimers of edge-sharing metal selenide tetrahedra, M(2)Se(6)(4-) (M = Ge or Sn), separated by hydrazinium cations and, for 2, additional neutral hydrazine molecules. Substantial hydrogen bonding exists among the hydrazine/hydrazinium molecules as well as between the hydrazinium cations and the selenide anions. Whereas the previously reported tin(IV) sulfide system, (N(2)H(5))(4)Sn(2)S(6), decomposes cleanly to microcrystalline SnS(2) when heated to 200 degrees C in an inert atmosphere, higher temperatures (>300 degrees C) are required to dissociate selenium from 1 and 2 for the analogous preparations of single-phase metal selenides. The metal chalcogenide salts are highly soluble in hydrazine, as well as in a variety of amines and DMSO, highlighting the potential usefulness of these compounds as precursors for the solution deposition of the corresponding metal chalcogenide films.

General Synthetic Strategy for Libraries of Supported Multicomponent Metal Nanoparticles.

PubMed

Yang, Hui; Bradley, Siobhan J; Wu, Xin; Chan, Andrew; Waterhouse, Geoffrey I N; Nann, Thomas; Zhang, Jian; Kruger, Paul E; Ma, Shengqian; Telfer, Shane G

2018-04-18

Nanoparticles comprising three or more different metals are challenging to prepare. General methods that tackle this challenge are highly sought after as multicomponent metal nanoparticles display favorable properties in applications such as catalysis, biomedicine, and imaging. Herein, we report a practical and versatile approach for the synthesis of nanoparticles composed of up to four different metals. This method relies on the thermal decomposition of nanostructured composite materials assembled from platinum nanoparticles, a metal-organic framework (ZIF-8), and a tannic acid coordination polymer. The controlled integration of multiple metal cations (Ni, Co, Cu, Mn, Fe, and/or Tb) into the tannic acid shell of the precursor material dictates the composition of the final multicomponent metal nanoparticles. Upon thermolysis, the platinum nanoparticles seed the growth of the multicomponent metal nanoparticles via coalescence with the metallic constituents of the tannic acid coordination polymer. The nanoparticles are supported in the walls of hollow nitrogen-doped porous carbon capsules created by the decomposition of the organic components of the precursor. The capsules prevent sintering and detachment of the nanoparticles, and their porosity allows for efficient mass transport. To demonstrate the utility of producing a broad library of supported multicomponent metal nanoparticles, we tested their electrocatalytic performance toward the hydrogen evolution reaction and oxygen evolution reaction. We discovered functional relationships between the composition of the nanoparticles and their electrochemical activity and identified the PtNiCu and PtNiCuFe nanoparticles as particularly efficient catalysts. This highlights how to generate diverse libraries of multicomponent metal nanoparticles that can be synthesized and subsequently screened to identify high-performance materials for target applications.

Porous carbonaceous electrode structure and method for secondary electrochemical cell

DOEpatents

Kaun, Thomas D.

1977-03-08

Positive and negative electrodes are provided as rigid, porous carbonaceous matrices with particulate active material fixedly embedded. Active material such as metal chalcogenides, solid alloys of alkali metal or alkaline earth metals along with other metals and their oxides in particulate form are blended with a thermosetting resin and a solid volatile to form a paste mixture. Various electrically conductive powders or current collector structures can be blended or embedded into the paste mixture which can be molded to the desired electrode shape. The molded paste is heated to a temperature at which the volatile transforms into vapor to impart porosity as the resin begins to cure into a rigid solid structure.

Bacteriostatic and anti-collagenolytic dental materials through the incorporation of polyacrylic acid modified CuI nanoparticles

DOEpatents

Renne, Walter George; Mennito, Anthony Samuel; Schmidt, Michael Gerard; Vuthiganon, Jompobe; Chumanov, George

2015-05-19

Provided are antibacterial and antimicrobial surface coatings and dental materials by utilizing the antimicrobial properties of copper chalcogenide and/or copper halide (CuQ, where Q=chalcogens including oxygen, or halogens, or nothing). An antimicrobial barrier is created by incorporation of CuQ nanoparticles of an appropriate size and at a concentration necessary and sufficient to create a unique bioelectrical environment. The unique bioelectrical environment results in biocidal effectiveness through a multi-factorial mechanism comprising a combination of the intrinsic quantum flux of copper (Cu.sup.0, Cu.sup.1+, Cu.sup.2+) ions and the high surface-to-volume electron sink facilitated by the nanoparticle. The result is the constant quantum flux of copper which manifests and establishes the antimicrobial environment preventing or inhibiting the growth of bacteria. The presence of CuQ results in inhibiting or delaying bacterial destruction and endogenous enzymatic breakdown of the zone of resin inter-diffusion, the integrity of which is essential for dental restoration longevity.

Antibacterial studies of novel Cu2WS4 ternary chalcogenide synthesized by hydrothermal process

NASA Astrophysics Data System (ADS)

Kannan, Selvaraj; Vinitha, Perumal; Mohanraj, Kannusamy; Sivakumar, Ganesan

2018-02-01

This is the first report for the synthesis of L-cysteine mediated Cu2WS4 nanoparticles for different temperatures by an inexpensive and less pollutive hydrothermal method. The as-synthesized particles were characterized by XRD, FTIR, FESEM, UV-vis diffuse reflectance and PL spectra technique respectively. The phase purity and structural confirmation were studied by X-ray powder diffraction technique. It is observed that the synthesis temperature affecting the crystalline size. The optical analysis of the Cu2WS4 nanoparticles showed direct band gap in the range of 2.1-2.3 eV. The intensity of the PL emission spectra decreases with increase of reaction temperature. The antibacterial performance of Cu2WS4 nanoparticles were investigated by agar well diffusion method and the results confirm that the antibacterial activity of Cu2WS4 against Gram-positive (B. subtilis, M. luteus) and Gram-negative (E. coli, P. aeruginosa and K. pneumoniae) bacteria.

Morphology-Controlled Synthesis of Au/Cu₂FeSnS₄ Core-Shell Nanostructures for Plasmon-Enhanced Photocatalytic Hydrogen Generation.

PubMed

Ha, Enna; Lee, Lawrence Yoon Suk; Man, Ho-Wing; Tsang, Shik Chi Edman; Wong, Kwok-Yin

2015-05-06

Copper-based chalcogenides of earth-abundant elements have recently arisen as an alternate material for solar energy conversion. Cu2FeSnS4 (CITS), a quaternary chalcogenide that has received relatively little attention, has the potential to be developed into a low-cost and environmentlly friendly material for photovoltaics and photocatalysis. Herein, we report, for the first time, the synthesis, characterization, and growth mechanism of novel Au/CITS core-shell nanostructures with controllable morphology. Precise manipulations in the core-shell dimensions are demonstrated to yield two distinct heterostructures with spherical and multipod gold nanoparticle (NP) cores (Au(sp)/CITS and Au(mp)/CITS). In photocatalytic hydrogen generation with as-synthesized Au/CITS NPs, the presence of Au cores inside the CITS shell resulted in higher hydrogen generation rates, which can be attributed to the surface plasmon resonance (SPR) effect. The Au(sp)/CITS and Au(mp)/CITS core-shell NPs enhanced the photocatalytic hydrogen generation by about 125% and 240%, respectively, compared to bare CITS NPs.

Noncentrosymmetric rare-earth copper gallium chalcogenides RE3CuGaCh7 (RE=La-Nd; Ch=S, Se): An unexpected combination

NASA Astrophysics Data System (ADS)

Iyer, Abishek K.; Rudyk, Brent W.; Lin, Xinsong; Singh, Harpreet; Sharma, Arzoo Z.; Wiebe, Christopher R.; Mar, Arthur

2015-09-01

The quaternary rare-earth chalcogenides RE3CuGaS7 and RE3CuGaSe7 (RE=La-Nd) have been prepared by reactions of the elements at 1050 °C and 900 °C, respectively. They crystallize in the noncentrosymmetric La3CuSiS7-type structure (hexagonal, space group P63, Z=2) in which the a-parameter is largely controlled by the RE component (a=10.0-10.3 Å for the sulfides and 10.3-10.6 Å for the selenides) whereas the c-parameter is essentially fixed by the choice of Ga and chalcogen atoms within tetrahedral units (c=6.1 Å for the sulfides and 6.4 Å for the selenides). They extend the series RE3MGaCh7, previously known for divalent metal atoms (M=Mn-Ni), differing in that the Cu atoms in RE3CuGaCh7 occupy trigonal planar sites instead of octahedral sites. Among quaternary chalcogenides RE3MM‧Ch7, the combination of monovalent (M=Cu) and trivalent (M‧=Ga) metals is unusual because it appears to violate the condition of charge balance satisfied by most La3CuSiS7-type compounds. The possibility of divalent Cu atoms was ruled out by bond valence sum analysis, magnetic measurements, and X-ray photoelectron spectroscopy. The electron deficiency in RE3CuGaCh7 is accommodated through S-based holes at the top of the valence band, as shown by band structure calculations on La3CuGaS7. An optical band gap of about 2.0 eV was found for La3CuGaSe7.

Lithium-aluminum-magnesium electrode composition

DOEpatents

Melendres, Carlos A.; Siegel, Stanley

1978-01-01

A negative electrode composition is presented for use in a secondary, high-temperature electrochemical cell. The cell also includes a molten salt electrolyte of alkali metal halides or alkaline earth metal halides and a positive electrode including a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent and a magnesium-aluminum alloy as a structural matrix. Various binary and ternary intermetallic phases of lithium, magnesium, and aluminum are formed but the electrode composition in both its charged and discharged state remains substantially free of the alpha lithium-aluminum phase and exhibits good structural integrity.

Method for producing metallic microparticles

DOEpatents

Phillips, Jonathan; Perry, William L.; Kroenke, William J.

2004-06-29

Method for producing metallic particles. The method converts metallic nanoparticles into larger, spherical metallic particles. An aerosol of solid metallic nanoparticles and a non-oxidizing plasma having a portion sufficiently hot to melt the nanoparticles are generated. The aerosol is directed into the plasma where the metallic nanoparticles melt, collide, join, and spheroidize. The molten spherical metallic particles are directed away from the plasma and enter the afterglow where they cool and solidify.

Ordered porous mesostructured materials from nanoparticle-block copolymer self-assembly

DOEpatents

Warren, Scott; Wiesner, Ulrich; DiSalvo, Jr., Francis J

2013-10-29

The invention provides mesostructured materials and methods of preparing mesostructured materials including metal-rich mesostructured nanoparticle-block copolymer hybrids, porous metal-nonmetal nanocomposite mesostructures, and ordered metal mesostructures with uniform pores. The nanoparticles can be metal, metal alloy, metal mixture, intermetallic, metal-carbon, metal-ceramic, semiconductor-carbon, semiconductor-ceramic, insulator-carbon or insulator-ceramic nanoparticles, or combinations thereof. A block copolymer/ligand-stabilized nanoparticle solution is cast, resulting in the formation of a metal-rich (or semiconductor-rich or insulator-rich) mesostructured nanoparticle-block copolymer hybrid. The hybrid is heated to an elevated temperature, resulting in the formation of an ordered porous nanocomposite mesostructure. A nonmetal component (e.g., carbon or ceramic) is then removed to produce an ordered mesostructure with ordered and large uniform pores.

Intermetallic nanoparticles

DOEpatents

Singh, Dileep; Yusufoglu, Yusuf; Timofeeva, Elena; Routbort, Jules

2015-07-14

A process for preparing intermetallic nanoparticles of two or more metals is provided. In particular, the process includes the steps: a) dispersing nanoparticles of a first metal in a solvent to prepare a first metal solution, b) forming a reaction mixture with the first metal solution and a reducing agent, c) heating the reaction mixture to a reaction temperature; and d) adding a second metal solution containing a salt of a second metal to the reaction mixture. During this process, intermetallic nanoparticles, which contain a compound with the first and second metals are formed. The intermetallic nanoparticles with uniform size and a narrow size distribution is also provided. An electrochemical device such as a battery with the intermetallic nanoparticles is also provided.

Intermetallic nanoparticles

DOEpatents

Singh, Dileep; Yusufoglu, Yusuf; Timofeeva, Elena; Routbort, Jules L.

2015-11-20

A process for preparing intermetallic nanoparticles of two or more metals is provided. In particular, the process includes the steps: a) dispersing nanoparticles of a first metal in a solvent to prepare a first metal solution, b) forming a reaction mixture with the first metal solution and a reducing agent, c) heating the reaction mixture to a reaction temperature; and d) adding a second metal solution containing a salt of a second metal to the reaction mixture. During this process, intermetallic nanoparticles, which contain a compound with the first and second metals are formed. The intermetallic nanoparticles with uniform size and a narrow size distribution is also provided. An electrochemical device such as a battery with the intermetallic nanoparticles is also provided.

Intermetallic nanoparticles

DOEpatents

Singh, Dileep; Yusufoglu, Yusuf; Timofeeva, Elena; Routbort, Jules L.

2017-01-03

A process for preparing intermetallic nanoparticles of two or more metals is provided. In particular, the process includes the steps: a) dispersing nanoparticles of a first metal in a solvent to prepare a first metal solution, b) forming a reaction mixture with the first metal solution and a reducing agent, c) heating the reaction mixture to a reaction temperature; and d) adding a second metal solution containing a salt of a second metal to the reaction mixture. During this process, intermetallic nanoparticles, which contain a compound with the first and second metals are formed. The intermetallic nanoparticles with uniform size and a narrow size distribution is also provided. An electrochemical device such as a battery with the intermetallic nanoparticles is also provided.

Bi-metallic nanoparticles as cathode electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Jun; Amine, Khalil; Wang, Xiaoping

A lithium-air battery cathode catalyst includes core-shell nanoparticles on a carbon support, wherein: a core of the core-shell nanoparticles is platinum metal; and a shell of the core-shell nanoparticles is copper metal; wherein: the core-shell nanoparticles have a weight ratio of the copper metal to the platinum metal from about 4% to about 6% copper to from about 2% to about 12% platinum, with a remaining percentage being the carbon support.

Thermoelectric properties and thermal stability of layered chalcogenides, TlScQ2, Q = Se, Te.

PubMed

Aswathy, Vijayakumar Sajitha; Sankar, Cheriyedath Raj; Varma, Manoj Raama; Assoud, Abdeljalil; Bieringer, Mario; Kleinke, Holger

2017-12-12

A few thallium based layered chalcogenides of α-NaFeO 2 structure-type are known for their excellent thermoelectric properties and interesting topological insulator nature. TlScQ 2 belongs to this structural category. In the present work, we have studied the electronic structure, electrical and thermal transport properties and thermal stability of the title compounds within the temperature range 2-600 K. Density functional theory (DFT) predicts a metallic nature for TlScTe 2 and a semiconducting nature for TlScSe 2 . DFT calculations also show significant lowering of energies of frontier bands upon inclusion of spin-orbit coupling contribution in the calculation. The electronic structure also shows the simultaneous occurrence of holes and electron pockets for the telluride. Experiments reveal that the telluride shows a semi-metallic behaviour whereas the selenide is a semiconductor. The thermoelectric properties for both the materials were also investigated. Both these materials possess very low thermal conductivity which is an attractive feature for thermoelectrics. However, they lack thermal stability and decompose upon warming above room temperature, as evidenced from high temperature powder X-ray diffraction and thermal analysis.

A monotopic aluminum telluride with an Al=Te double bond stabilized by N-heterocyclic carbenes

PubMed Central

Franz, Daniel; Szilvási, Tibor; Irran, Elisabeth; Inoue, Shigeyoshi

2015-01-01

Aluminum chalcogenides are mostly encountered in the form of bulk aluminum oxides that are structurally diverse but typically consist of networks with high lattice energy in which the chalcogen atoms bridge the metal centres. This makes their molecular congeners difficult to synthesize because of a pronounced tendency for oligomerization. Here we describe the isolation of the monotopic aluminum chalcogenide (LDipN)AlTe(LEt)2 (LDip=1,3-(2,6-diisopropylphenyl)-imidazolin-2-imine, LEt=1,3-diethyl-4,5-dimethyl-imidazolin-2-ylidene). Unique features of (LDipN)AlTe(LEt)2 are the terminal position of the tellurium atom, the shortest aluminum–tellurium distance hitherto reported for a molecular complex and the highest bond order reported for an interaction between these elements, to the best of our knowledge. At elevated temperature (LDipN)AlTe(LEt)2 equilibrates with dimeric {(LDipN)AlTe(LEt)}2 in which the chalcogen atoms assume their common role as bridges between the metal centres. These findings demonstrate that (LDipN)AlTe(LEt)2 comprises the elusive Al=Te double bond in the form of an N-heterocyclic carbene-stabilized species. PMID:26612781

Structural and Thermal Diffusivity Studies of Polycrystalline (CuSe)1-XSeX Metal Chalcogenide Compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Josephine, L. Y. C.; Talib, Z. A.; Yunus, W. M. M.

2007-05-09

This paper reports the preparation and the characterization of the (CuSe)1-xSex metal chalcogenide semiconductor compounds with different stoichiometric compositions of Se (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) in bulk form. The (CuSe)1-xSex compounds were prepared using the solid state reaction by varying the ratio of CuSe:Se in the reaction mixture. X-ray powder diffraction analysis is used to identify and measure the mass absorption coefficient of the (CuSe)1-xSex compounds to support the thermal diffusivity behaviour. The thermal diffusivity of the polycrystalline (CuSe)1-xSex compounds were measured and analyzed for the first time, using the photoflash technique. The thermal diffusivitymore » values were determined to be in the range of 2.524 x 10-3 cm2/s to 1.125 x 10-2 cm2/s. It was found that the thermal diffusivity value tends to decrease as the parameter x increases. The relationship between the thermal diffusivity, mass absorption coefficient and density of the (CuSe)1-xSex are discussed in detail.« less

Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

NASA Astrophysics Data System (ADS)

Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

2018-05-01

A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

Microbial-mediated method for metal oxide nanoparticle formation

DOEpatents

Rondinone, Adam J.; Moon, Ji Won; Love, Lonnie J.; Yeary, Lucas W.; Phelps, Tommy J.

2015-09-08

The invention is directed to a method for producing metal oxide nanoparticles, the method comprising: (i) subjecting a combination of reaction components to conditions conducive to microbial-mediated formation of metal oxide nanoparticles, wherein said combination of reaction components comprise: metal-reducing microbes, a culture medium suitable for sustaining said metal-reducing microbes, an effective concentration of one or more surfactants, a reducible metal oxide component containing one or more reducible metal species, and one or more electron donors that provide donatable electrons to said metal-reducing microbes during consumption of the electron donor by said metal-reducing microbes; and (ii) isolating said metal oxide nanoparticles, which contain a reduced form of said reducible metal oxide component. The invention is also directed to metal oxide nanoparticle compositions produced by the inventive method.

Conducting metal oxide and metal nitride nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

DiSalvo, Jr., Francis J.; Subban, Chinmayee V.

Conducting metal oxide and nitride nanoparticles that can be used in fuel cell applications. The metal oxide nanoparticles are comprised of for example, titanium, niobium, tantalum, tungsten and combinations thereof. The metal nitride nanoparticles are comprised of, for example, titanium, niobium, tantalum, tungsten, zirconium, and combinations thereof. The nanoparticles can be sintered to provide conducting porous agglomerates of the nanoparticles which can be used as a catalyst support in fuel cell applications. Further, platinum nanoparticles, for example, can be deposited on the agglomerates to provide a material that can be used as both an anode and a cathode catalyst supportmore » in a fuel cell.« less

Semiconductor assisted metal deposition for nanolithography applications

DOEpatents

Rajh, Tijana; Meshkov, Natalia; Nedelijkovic, Jovan M.; Skubal, Laura R.; Tiede, David M.; Thurnauer, Marion

2001-01-01

An article of manufacture and method of forming nanoparticle sized material components. A semiconductor oxide substrate includes nanoparticles of semiconductor oxide. A modifier is deposited onto the nanoparticles, and a source of metal ions are deposited in association with the semiconductor and the modifier, the modifier enabling electronic hole scavenging and chelation of the metal ions. The metal ions and modifier are illuminated to cause reduction of the metal ions to metal onto the semiconductor nanoparticles.

Semiconductor assisted metal deposition for nanolithography applications

DOEpatents

Rajh, Tijana; Meshkov, Natalia; Nedelijkovic, Jovan M.; Skubal, Laura R.; Tiede, David M.; Thurnauer, Marion

2002-01-01

An article of manufacture and method of forming nanoparticle sized material components. A semiconductor oxide substrate includes nanoparticles of semiconductor oxide. A modifier is deposited onto the nanoparticles, and a source of metal ions are deposited in association with the semiconductor and the modifier, the modifier enabling electronic hole scavenging and chelation of the metal ions. The metal ions and modifier are illuminated to cause reduction of the metal ions to metal onto the semiconductor nanoparticles.

Synthesis of Metal Nanoparticles in Metal-Phenolic Networks: Catalytic and Antimicrobial Applications of Coated Textiles.

PubMed

Yun, Gyeongwon; Pan, Shuaijun; Wang, Ting-Yi; Guo, Junling; Richardson, Joseph J; Caruso, Frank

2018-03-01

The synthesis of metal nanoparticle (NP)-coated textiles (nanotextiles) is achieved by a dipping process in water without toxic chemicals or complicated synthetic procedures. By taking advantage of the unique nature of tannic acid, metal-phenolic network-coated textiles serve as reducing and stabilizing sites for the generation of metal nanoparticles of controllable size. The textiles can be decorated with various metal nanoparticles, including palladium, silver, or gold, and exhibit properties derived from the presence of the metal nanoparticles, for example, catalytic activity in water (>96% over five cycles using palladium nanoparticles) and antibacterial activity against Gram-negative bacteria (inhibition of Escherichia coli using silver nanoparticles) that outperforms a commercial bandage. The reported strategy offers opportunities for the development of hybrid nanomaterials that may have application in fields outside of catalysis and antimicrobials, such as sensing and smart clothing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal Nanoparticles for the Treatment and Diagnosis of Neurodegenerative Brain Diseases.

PubMed

Vio, Valentina; Marchant, Maria Jose; Araya, Eyleen; Kogan, Marcelo J

2017-01-01

This review focuses on the application of metal nanoparticles in the diagnosis and treatment of Alzheimer's and Parkinson's diseases. Metal nanoparticles present interesting physicochemical properties that can be applied to increase biomarker detection sensitivities in vitro and in vivo. Furthermore, these nanoparticles could be used in different strategies for the treatment of central nervous system diseases, particularly in regards to drug delivery. Herein, specific potential applications of metal nanoparticles are separately discussed for the contexts of in vitro diagnoses and treatments. Briefly, research using surface plasmon resonance methodologies has mainly used these nanoparticles for the in vitro detection of Aβ and, to a lesser extent, of α-synuclein. Regarding treatment approaches, in vitro studies have focused on using metal nanoparticles to manipulate the Aβ aggregation, thus reducing toxicity. Furthermore, in vivo applications of metal nanoparticles are also discussed, with many of the existing studies focusing on a magnetic nanoparticle-detection of Aβ through magnetic resonance imaging and, to a lesser degree, extension fluorescence techniques. Finally, conclusions and perspectives are provided regarding the real potential for using metal nanoparticles in the treatment and diagnosis of central nervous system diseases. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

2D materials: Graphene and others

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bansal, Suneev Anil, E-mail: suneev@gmail.com; Singh, Amrinder Pal; Kumar, Suresh

Present report reviews the recent advancements in new atomically thick 2D materials. Materials covered in this review are Graphene, Silicene, Germanene, Boron Nitride (BN) and Transition metal chalcogenides (TMC). These materials show extraordinary mechanical, electronic and optical properties which make them suitable candidates for future applications. Apart from unique properties, tune-ability of highly desirable properties of these materials is also an important area to be emphasized on.

Recent developments in the fabrication of infrared fiber Bragg gratings

NASA Astrophysics Data System (ADS)

Busse, Lynda; Florea, Catalin; Shaw, Brandon; Sanghera, Jas; Nguyen, Vinh; Chin, Geoff; Aggarwal, Ishwar

2012-02-01

We report on the study of adding metal dopants in chalcogenide glasses to enhance the photosensitivity of the fiber core versus cladding compositions, with goal to enable high reflectivity gratings in infrared-transmitting fibers. Results for the optical and thermal properties of these glasses will be presented, as well as for gratings formation in the glasses using various writing wavelengths for the different doped compositions.

Microbial exopolysaccharide-mediated synthesis and stabilization of metal nanoparticles.

PubMed

Sathiyanarayanan, Ganesan; Dineshkumar, Krishnamoorthy; Yang, Yung-Hun

2017-11-01

Exopolysaccharides (EPSs) are structurally and functionally valuable biopolymer secreted by different prokaryotic and eukaryotic microorganisms in response to biotic/abiotic stresses and to survive in extreme environments. Microbial EPSs are fascinating in various industrial sectors due to their excellent material properties and less toxic, highly biodegradable, and biocompatible nature. Recently, microbial EPSs have been used as a potential template for the rapid synthesis of metallic nanoparticles and EPS-mediated metal reduction processes are emerging as simple, harmless, and environmentally benign green chemistry approaches. EPS-mediated synthesis of metal nanoparticles is a distinctive metabolism-independent bio-reduction process due to the formation of interfaces between metal cations and the polyanionic functional groups (i.e. hydroxyl, carboxyl and amino groups) of the EPS. In addition, the range of physicochemical features which facilitates the EPS as an efficient stabilizing or capping agents to protect the primary structure of the metal nanoparticles with an encapsulation film in order to separate the nanoparticle core from the mixture of composites. The EPS-capping also enables the further modification of metal nanoparticles with expected material properties for multifarious applications. The present review discusses the microbial EPS-mediated green synthesis/stabilization of metal nanoparticles, possible mechanisms involved in EPS-mediated metal reduction, and application prospects of EPS-based metal nanoparticles.

Fabrication of transparent ceramics using nanoparticles

DOEpatents

Cherepy, Nerine J; Tillotson, Thomas M; Kuntz, Joshua D; Payne, Stephen A

2012-09-18

A method of fabrication of a transparent ceramic using nanoparticles synthesized via organic acid complexation-combustion includes providing metal salts, dissolving said metal salts to produce an aqueous salt solution, adding an organic chelating agent to produce a complexed-metal sol, heating said complexed-metal sol to produce a gel, drying said gel to produce a powder, combusting said powder to produce nano-particles, calcining said nano-particles to produce oxide nano-particles, forming said oxide nano-particles into a green body, and sintering said green body to produce the transparent ceramic.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iyer, Abishek K.; Rudyk, Brent W.; Lin, Xinsong

The quaternary rare-earth chalcogenides RE{sub 3}CuGaS{sub 7} and RE{sub 3}CuGaSe{sub 7} (RE=La–Nd) have been prepared by reactions of the elements at 1050 °C and 900 °C, respectively. They crystallize in the noncentrosymmetric La{sub 3}CuSiS{sub 7}-type structure (hexagonal, space group P6{sub 3}, Z=2) in which the a-parameter is largely controlled by the RE component (a=10.0–10.3 Å for the sulfides and 10.3–10.6 Å for the selenides) whereas the c-parameter is essentially fixed by the choice of Ga and chalcogen atoms within tetrahedral units (c=6.1 Å for the sulfides and 6.4 Å for the selenides). They extend the series RE{sub 3}MGaCh{sub 7}, previouslymore » known for divalent metal atoms (M=Mn–Ni), differing in that the Cu atoms in RE{sub 3}CuGaCh{sub 7} occupy trigonal planar sites instead of octahedral sites. Among quaternary chalcogenides RE{sub 3}MM′Ch{sub 7}, the combination of monovalent (M=Cu) and trivalent (M′=Ga) metals is unusual because it appears to violate the condition of charge balance satisfied by most La{sub 3}CuSiS{sub 7}-type compounds. The possibility of divalent Cu atoms was ruled out by bond valence sum analysis, magnetic measurements, and X-ray photoelectron spectroscopy. The electron deficiency in RE{sub 3}CuGaCh{sub 7} is accommodated through S-based holes at the top of the valence band, as shown by band structure calculations on La{sub 3}CuGaS{sub 7}. An optical band gap of about 2.0 eV was found for La{sub 3}CuGaSe{sub 7}. - Graphical abstract: The chalcogenides RE{sub 3}CuGaCh{sub 7} contain monovalent Cu in trigonal planes and trivalent Ga in tetrahedra; they are electron-deficient representatives of La{sub 3}CuSiS{sub 7}-type compounds, which normally satisfy charge balance. - Highlights: • Quaternary chalcogenides RE{sub 3}CuGaCh{sub 7} (RE=La–Nd; Ch=S, Se) were prepared. • Bond valence sums, magnetism, and XPS data give evidence for monovalent Cu. • Crystal structures reveal high anisotropy of Cu displacement. • Electron deficiency is accommodated by S-based holes in valence band.« less

Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate.

PubMed

Huang, Caijin; Liu, Qiuwen; Fan, Wenjie; Qiu, Xiaoqing

2015-11-16

Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material--hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application.

Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate

PubMed Central

Huang, Caijin; liu, Qiuwen; Fan, Wenjie; Qiu, Xiaoqing

2015-01-01

Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material—hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application. PMID:26567862

Poisson's ratio and the densification of glass under high pressure.

PubMed

Rouxel, T; Ji, H; Hammouda, T; Moréac, A

2008-06-06

Because of a relatively low atomic packing density, (Cg) glasses experience significant densification under high hydrostatic pressure. Poisson's ratio (nu) is correlated to Cg and typically varies from 0.15 for glasses with low Cg such as amorphous silica to 0.38 for close-packed atomic networks such as in bulk metallic glasses. Pressure experiments were conducted up to 25 GPa at 293 K on silica, soda-lime-silica, chalcogenide, and bulk metallic glasses. We show from these high-pressure data that there is a direct correlation between nu and the maximum post-decompression density change.

Metal nanoparticles in the presence of lipopolysaccharides trigger the onset of metal allergy in mice

NASA Astrophysics Data System (ADS)

Hirai, Toshiro; Yoshioka, Yasuo; Izumi, Natsumi; Ichihashi, Ko-Ichi; Handa, Takayuki; Nishijima, Nobuo; Uemura, Eiichiro; Sagami, Ko-Ichi; Takahashi, Hideki; Yamaguchi, Manami; Nagano, Kazuya; Mukai, Yohei; Kamada, Haruhiko; Tsunoda, Shin-Ichi; Ishii, Ken J.; Higashisaka, Kazuma; Tsutsumi, Yasuo

2016-09-01

Many people suffer from metal allergy, and the recently demonstrated presence of naturally occurring metal nanoparticles in our environment could present a new candidate for inducing metal allergy. Here, we show that mice pretreated with silver nanoparticles (nAg) and lipopolysaccharides, but not with the silver ions that are thought to cause allergies, developed allergic inflammation in response to the silver. nAg-induced acquired immune responses depended on CD4+ T cells and elicited IL-17A-mediated inflammation, similar to that observed in human metal allergy. Nickel nanoparticles also caused sensitization in the mice, whereas gold and silica nanoparticles, which are minimally ionizable, did not. Quantitative analysis of the silver distribution suggested that small nAg (≤10 nm) transferred to the draining lymph node and released ions more readily than large nAg (>10 nm). These results suggest that metal nanoparticles served as ion carriers to enable metal sensitization. Our data demonstrate a potentially new trigger for metal allergy.

General and programmable synthesis of hybrid liposome/metal nanoparticles

PubMed Central

Lee, Jin-Ho; Shin, Yonghee; Lee, Wooju; Whang, Keumrai; Kim, Dongchoul; Lee, Luke P.; Choi, Jeong-Woo; Kang, Taewook

2016-01-01

Hybrid liposome/metal nanoparticles are promising candidate materials for biomedical applications. However, the poor selectivity and low yield of the desired hybrid during synthesis pose a challenge. We designed a programmable liposome by selective encoding of a reducing agent, which allows self-crystallization of metal nanoparticles within the liposome to produce stable liposome/metal nanoparticles alone. We synthesized seven types of liposome/monometallic and more complex liposome/bimetallic hybrids. The resulting nanoparticles are tunable in size and metal composition, and their surface plasmon resonance bands are controllable in visible and near infrared. Owing to outer lipid bilayer, our liposome/Au nanoparticle shows better colloidal stability in biologically relevant solutions as well as higher endocytosis efficiency than gold nanoparticles without the liposome. We used this hybrid in intracellular imaging of living cells via surface-enhanced Raman spectroscopy, taking advantage of its improved physicochemical properties. We believe that our method greatly increases the utility of metal nanoparticles in in vivo applications. PMID:28028544

General and programmable synthesis of hybrid liposome/metal nanoparticles.

PubMed

Lee, Jin-Ho; Shin, Yonghee; Lee, Wooju; Whang, Keumrai; Kim, Dongchoul; Lee, Luke P; Choi, Jeong-Woo; Kang, Taewook

2016-12-01

Hybrid liposome/metal nanoparticles are promising candidate materials for biomedical applications. However, the poor selectivity and low yield of the desired hybrid during synthesis pose a challenge. We designed a programmable liposome by selective encoding of a reducing agent, which allows self-crystallization of metal nanoparticles within the liposome to produce stable liposome/metal nanoparticles alone. We synthesized seven types of liposome/monometallic and more complex liposome/bimetallic hybrids. The resulting nanoparticles are tunable in size and metal composition, and their surface plasmon resonance bands are controllable in visible and near infrared. Owing to outer lipid bilayer, our liposome/Au nanoparticle shows better colloidal stability in biologically relevant solutions as well as higher endocytosis efficiency than gold nanoparticles without the liposome. We used this hybrid in intracellular imaging of living cells via surface-enhanced Raman spectroscopy, taking advantage of its improved physicochemical properties. We believe that our method greatly increases the utility of metal nanoparticles in in vivo applications.

Screening Methods for Metal-Containing Nanoparticles in Water

EPA Science Inventory

Screening-level analysis of water for metal-containing nanoparticles is achieved with single particle-inductively coupled plasma mass spectrometry (SP-ICPMS). This method measures both the concentration of nanoparticles containing an analyte metal and the mass of the metal in eac...

Gate-Induced Interfacial Superconductivity in 1T-SnSe2.

PubMed

Zeng, Junwen; Liu, Erfu; Fu, Yajun; Chen, Zhuoyu; Pan, Chen; Wang, Chenyu; Wang, Miao; Wang, Yaojia; Xu, Kang; Cai, Songhua; Yan, Xingxu; Wang, Yu; Liu, Xiaowei; Wang, Peng; Liang, Shi-Jun; Cui, Yi; Hwang, Harold Y; Yuan, Hongtao; Miao, Feng

2018-02-14

Layered metal chalcogenide materials provide a versatile platform to investigate emergent phenomena and two-dimensional (2D) superconductivity at/near the atomically thin limit. In particular, gate-induced interfacial superconductivity realized by the use of an electric-double-layer transistor (EDLT) has greatly extended the capability to electrically induce superconductivity in oxides, nitrides, and transition metal chalcogenides and enable one to explore new physics, such as the Ising pairing mechanism. Exploiting gate-induced superconductivity in various materials can provide us with additional platforms to understand emergent interfacial superconductivity. Here, we report the discovery of gate-induced 2D superconductivity in layered 1T-SnSe 2 , a typical member of the main-group metal dichalcogenide (MDC) family, using an EDLT gating geometry. A superconducting transition temperature T c ≈ 3.9 K was demonstrated at the EDL interface. The 2D nature of the superconductivity therein was further confirmed based on (1) a 2D Tinkham description of the angle-dependent upper critical field B c2 , (2) the existence of a quantum creep state as well as a large ratio of the coherence length to the thickness of superconductivity. Interestingly, the in-plane B c2 approaching zero temperature was found to be 2-3 times higher than the Pauli limit, which might be related to an electric field-modulated spin-orbit interaction. Such results provide a new perspective to expand the material matrix available for gate-induced 2D superconductivity and the fundamental understanding of interfacial superconductivity.

Synthesis of Lithium Metal Oxide Nanoparticles by Induction Thermal Plasmas.

PubMed

Tanaka, Manabu; Kageyama, Takuya; Sone, Hirotaka; Yoshida, Shuhei; Okamoto, Daisuke; Watanabe, Takayuki

2016-04-06

Lithium metal oxide nanoparticles were synthesized by induction thermal plasma. Four different systems-Li-Mn, Li-Cr, Li-Co, and Li-Ni-were compared to understand formation mechanism of Li-Me oxide nanoparticles in thermal plasma process. Analyses of X-ray diffractometry and electron microscopy showed that Li-Me oxide nanoparticles were successfully synthesized in Li-Mn, Li-Cr, and Li-Co systems. Spinel structured LiMn₂O₄ with truncated octahedral shape was formed. Layer structured LiCrO₂ or LiCoO₂ nanoparticles with polyhedral shapes were also synthesized in Li-Cr or Li-Co systems. By contrast, Li-Ni oxide nanoparticles were not synthesized in the Li-Ni system. Nucleation temperatures of each metal in the considered system were evaluated. The relationship between the nucleation temperature and melting and boiling points suggests that the melting points of metal oxides have a strong influence on the formation of lithium metal oxide nanoparticles. A lower melting temperature leads to a longer reaction time, resulting in a higher fraction of the lithium metal oxide nanoparticles in the prepared nanoparticles.

Dependence of reflection and transmission of soliton on angle of incidence at an interface between chalcogenide fibre and gallium nanoparticle film by phase plane trajectories

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naruka, Preeti, E-mail: preety-naruka@Yyahoo.co.in; Bissa, Shivangi; Nagar, A. K.

In the present paper, we study propagation of a soliton at an interface formed between special type of chalcogenide fibre and gallium in three different phases with the help of equivalent particle theory. Critical angle of incidence and critical power required for transmission and reflection of soliton beam have investigated. Here it is found that if the incident angle of the beam or initial velocity of the equivalent particle is insufficient to overcome the maximum increase in potential energy then the particle (light beam) is reflected by the interface and if this incident angle is greater than a critical anglemore » then light beam will be transmitted by the interface. From an equation these critical angles for α-gallium, one of a metastable phase and liquid gallium are calculated and concluded that at large incident angles, the soliton is transmitted through the boundary, whereas at small incidence angles the soliton get reflected on keeping the power of incident beam constant. These results are explained by phase plane trajectories of the effective potential which are experimentally as well as theoretically proved.« less

Coaxial Lithography

NASA Astrophysics Data System (ADS)

Ozel, Tuncay

The optical and electrical properties of heterogeneous nanowires are profoundly related to their composition and nanoscale architecture. However, the intrinsic constraints of conventional synthetic and lithographic techniques have limited the types of multi-compositional nanowires that can be realized and studied in the laboratory. This thesis focuses on bridging templated electrochemical synthesis and lithography for expanding current synthetic capabilities with respect to materials generality and the ability to tailor two-dimensional growth in the formation of core-shell structures for the rational design and preparation of nanowires with very complex architectures that cannot be made by any other techniques. Chapter 1 introduces plasmonics, templated electrochemical synthesis, and on-wire lithography concepts and their significances within chemistry and materials science. Chapter 2 details a powerful technique for the deposition of metals and semiconductors with nanometer resolution in segment and gap lengths using on-wire lithography, which serves as a new platform to explore plasmon-exciton interactions in the form of long-range optical nanoscale rulers. Chapter 3 highlights an approach for the electrochemical synthesis of solution dispersible core-shell polymeric and inorganic semiconductor nanowires with metallic leads. A photodetector based on a single core-shell semiconductor nanowire is presented to demonstrate the functionality of the nanowires produced using this approach. Chapter 4 describes a new materials general technique, termed coaxial lithography (COAL), bridging templated electrochemical synthesis and lithography for generating coaxial nanowires in a parallel fashion with sub-10 nanometer resolution in both axial and radial dimensions. Combinations of coaxial nanowires composed of metals, metal oxides, metal chalcogenides, conjugated polymers, and a core/shell semiconductor nanowire with an embedded plasmonic nanoring are presented to demonstrate the possibilities afforded by COAL. Chapter 5 addresses the use of COAL for the synthesis of solution dispersible metal nanorings and nanotubes with exceptional architectural tailorability of inner diameter, outer diameter, and length leading to precise spectral control over the resulting plasmonic fields ranging from visible to the near-IR. Chapter 6 is an outlook on templated electrochemical synthesis using coaxial lithography and highlights a few promising applications from nanoparticle assembly to light-matter interactions.

Chemoelectronic circuits based on metal nanoparticles

NASA Astrophysics Data System (ADS)

Yan, Yong; Warren, Scott C.; Fuller, Patrick; Grzybowski, Bartosz A.

2016-07-01

To develop electronic devices with novel functionalities and applications, various non-silicon-based materials are currently being explored. Nanoparticles have unique characteristics due to their small size, which can impart functions that are distinct from those of their bulk counterparts. The use of semiconductor nanoparticles has already led to improvements in the efficiency of solar cells, the processability of transistors and the sensitivity of photodetectors, and the optical and catalytic properties of metal nanoparticles have led to similar advances in plasmonics and energy conversion. However, metals screen electric fields and this has, so far, prevented their use in the design of all-metal nanoparticle circuitry. Here, we show that simple electronic circuits can be made exclusively from metal nanoparticles functionalized with charged organic ligands. In these materials, electronic currents are controlled by the ionic gradients of mobile counterions surrounding the ‘jammed’ nanoparticles. The nanoparticle-based electronic elements of the circuitry can be interfaced with metal nanoparticles capable of sensing various environmental changes (humidity, gas, the presence of various cations), creating electronic devices in which metal nanoparticles sense, process and ultimately report chemical signals. Because the constituent nanoparticles combine electronic and chemical sensing functions, we term these systems ‘chemoelectronic’. The circuits have switching times comparable to those of polymer electronics, selectively transduce parts-per-trillion chemical changes into electrical signals, perform logic operations, consume little power (on the scale of microwatts), and are mechanically flexible. They are also ‘green’, in the sense that they comprise non-toxic nanoparticles cast at room temperature from alcohol solutions.

Chemoelectronic circuits based on metal nanoparticles.

PubMed

Yan, Yong; Warren, Scott C; Fuller, Patrick; Grzybowski, Bartosz A

2016-07-01

To develop electronic devices with novel functionalities and applications, various non-silicon-based materials are currently being explored. Nanoparticles have unique characteristics due to their small size, which can impart functions that are distinct from those of their bulk counterparts. The use of semiconductor nanoparticles has already led to improvements in the efficiency of solar cells, the processability of transistors and the sensitivity of photodetectors, and the optical and catalytic properties of metal nanoparticles have led to similar advances in plasmonics and energy conversion. However, metals screen electric fields and this has, so far, prevented their use in the design of all-metal nanoparticle circuitry. Here, we show that simple electronic circuits can be made exclusively from metal nanoparticles functionalized with charged organic ligands. In these materials, electronic currents are controlled by the ionic gradients of mobile counterions surrounding the 'jammed' nanoparticles. The nanoparticle-based electronic elements of the circuitry can be interfaced with metal nanoparticles capable of sensing various environmental changes (humidity, gas, the presence of various cations), creating electronic devices in which metal nanoparticles sense, process and ultimately report chemical signals. Because the constituent nanoparticles combine electronic and chemical sensing functions, we term these systems 'chemoelectronic'. The circuits have switching times comparable to those of polymer electronics, selectively transduce parts-per-trillion chemical changes into electrical signals, perform logic operations, consume little power (on the scale of microwatts), and are mechanically flexible. They are also 'green', in the sense that they comprise non-toxic nanoparticles cast at room temperature from alcohol solutions.

Ultrasmall water-soluble metal-iron oxide nanoparticles as T1-weighted contrast agents for magnetic resonance imaging.

PubMed

Zeng, Leyong; Ren, Wenzhi; Zheng, Jianjun; Cui, Ping; Wu, Aiguo

2012-02-28

Using an improved hydrolysis method of inorganic salts assisted with water-bath incubation, ultrasmall water-soluble metal-iron oxide nanoparticles (including Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles) were synthesized in aqueous solutions, which were used as T(1)-weighted contrast agents for magnetic resonance imaging (MRI). The morphology, structure, MRI relaxation properties and cytotoxicity of the as-prepared metal-iron oxide nanoparticles were characterized, respectively. The results showed that the average sizes of nanoparticles were about 4 nm, 4 nm and 5 nm for Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles, respectively. Moreover, the nanoparticles have good water dispersibility and low cytotoxicity. The MRI test showed the strong T(1)-weighted, but the weak T(2)-weighted MRI performance of metal-iron oxide nanoparticles. The high T(1)-weighted MRI performance can be attributed to the ultrasmall size of metal-iron oxide nanoparticles. Therefore, the as-prepared metal-iron oxide nanoparticles with good water dispersibility and ultrasmall size can have potential applications as T(1)-weighted contrast agent materials for MRI.

Large patternable metal nanoparticle sheets by photo/e-beam lithography

NASA Astrophysics Data System (ADS)

Saito, Noboru; Wang, Pangpang; Okamoto, Koichi; Ryuzaki, Sou; Tamada, Kaoru

2017-10-01

Techniques for micro/nano-scale patterning of large metal nanoparticle sheets can potentially be used to realize high-performance photoelectronic devices because the sheets provide greatly enhanced electrical fields around the nanoparticles due to localized surface plasmon resonances. However, no single metal nanoparticle sheet currently exists with sufficient durability for conventional lithographical processes. Here, we report large photo and/or e-beam lithographic patternable metal nanoparticle sheets with improved durability by incorporating molecular cross-linked structures between nanoparticles. The cross-linked structures were easily formed by a one-step chemical reaction; immersing a single nanoparticle sheet consisting of core metals, to which capping molecules ionically bond, in a dithiol ethanol solution. The ligand exchange reaction processes were discussed in detail, and we demonstrated 20 μm wide line and space patterns, and a 170 nm wide line of the silver nanoparticle sheets.

Biomedical applications of green synthesized Nobel metal nanoparticles.

PubMed

Khan, Zia Ul Haq; Khan, Amjad; Chen, Yongmei; Shah, Noor S; Muhammad, Nawshad; Khan, Arif Ullah; Tahir, Kamran; Khan, Faheem Ullah; Murtaza, Behzad; Hassan, Sadaf Ul; Qaisrani, Saeed Ahmad; Wan, Pingyu

2017-08-01

Synthesis of Nobel metal nanoparticles, play a key role in the field of medicine. Plants contain a substantial number of organic constituents, like phenolic compounds and various types of glycosides that help in synthesis of metal nanoparticles. Synthesis of metal nanoparticles by green method is one of the best and environment friendly methods. The major significance of the green synthesis is lack of toxic by-products produced during metal nanoparticle synthesis. The nanoparticles, synthesized by green method show various significant biological activities. Most of the research articles report the synthesized nanoparticles to be active against gram positive and gram negative bacteria. Some of these bacteria include Escherichia coli, Bacillus subtilis, Klebsiella pneumonia and Pseudomonas fluorescens. The synthesized nanoparticles also show significant antifungal activity against Trichophyton simii, Trichophyton mentagrophytes and Trichophyton rubrum as well as different types of cancer cells such as breast cancer cell line. They also exhibit significant antioxidant activity. The activities of these Nobel metal nano-particles mainly depend on the size and shape. The particles of small size with large surface area show good activity in the field of medicine. The synthesized nanoparticles are also active against leishmanial diseases. This research article explores in detail the green synthesis of the nanoparticles and their uses thereof. Copyright © 2017 Elsevier B.V. All rights reserved.

Fabrication of Metallic Hollow Nanoparticles

NASA Technical Reports Server (NTRS)

Lillehei, Peter T. (Inventor); Chu, Sang-Hyon (Inventor); Park, Yeonjoon (Inventor); Kim, Jae-Woo (Inventor); Choi, Sr., Sang H. (Inventor); King, Glen C. (Inventor); Elliott, James R. (Inventor)

2016-01-01

Metal and semiconductor nanoshells, particularly transition metal nanoshells, are fabricated using dendrimer molecules. Metallic colloids, metallic ions or semiconductors are attached to amine groups on the dendrimer surface in stabilized solution for the surface seeding method and the surface seedless method, respectively. Subsequently, the process is repeated with additional metallic ions or semiconductor, a stabilizer, and NaBH.sub.4 to increase the wall thickness of the metallic or semiconductor lining on the dendrimer surface. Metallic or semiconductor ions are automatically reduced on the metallic or semiconductor nanoparticles causing the formation of hollow metallic or semiconductor nanoparticles. The void size of the formed hollow nanoparticles depends on the dendrimer generation. The thickness of the metallic or semiconductor thin film around the dendrimer depends on the repetition times and the size of initial metallic or semiconductor seeds.

Platinum-coated non-noble metal-noble metal core-shell electrocatalysts

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir

2015-04-14

Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.

Electrochemical synthesis of elongated noble metal nanoparticles, such as nanowires and nanorods, on high-surface area carbon supports

DOEpatents

Adzic, Radoslav; Blyznakov, Stoyan; Vukmirovic, Miomir

2015-08-04

Elongated noble-metal nanoparticles and methods for their manufacture are disclosed. The method involves the formation of a plurality of elongated noble-metal nanoparticles by electrochemical deposition of the noble metal on a high surface area carbon support, such as carbon nanoparticles. Prior to electrochemical deposition, the carbon support may be functionalized by oxidation, thus making the manufacturing process simple and cost-effective. The generated elongated nanoparticles are covalently bound to the carbon support and can be used directly in electrocatalysis. The process provides elongated noble-metal nanoparticles with high catalytic activities and improved durability in combination with high catalyst utilization since the nanoparticles are deposited and covalently bound to the carbon support in their final position and will not change in forming an electrode assembly.

Alloy nanoparticle synthesis using ionizing radiation

DOEpatents

Nenoff, Tina M [Sandia Park, NM; Powers, Dana A [Albuquerque, NM; Zhang, Zhenyuan [Durham, NC

2011-08-16

A method of forming stable nanoparticles comprising substantially uniform alloys of metals. A high dose of ionizing radiation is used to generate high concentrations of solvated electrons and optionally radical reducing species that rapidly reduce a mixture of metal ion source species to form alloy nanoparticles. The method can make uniform alloy nanoparticles from normally immiscible metals by overcoming the thermodynamic limitations that would preferentially produce core-shell nanoparticles.

Shuttling single metal atom into and out of a metal nanoparticle.

PubMed

Wang, Shuxin; Abroshan, Hadi; Liu, Chong; Luo, Tian-Yi; Zhu, Manzhou; Kim, Hyung J; Rosi, Nathaniel L; Jin, Rongchao

2017-10-10

It has long been a challenge to dope metal nanoparticles with a specific number of heterometal atoms at specific positions. This becomes even more challenging if the heterometal belongs to the same group as the host metal because of the high tendency of forming a distribution of alloy nanoparticles with different numbers of dopants due to the similarities of metals in outmost electron configuration. Herein we report a new strategy for shuttling a single Ag or Cu atom into a centrally hollow, rod-shaped Au 24 nanoparticle, forming AgAu 24 and CuAu 24 nanoparticles in a highly controllable manner. Through a combined approach of experiment and theory, we explain the shuttling pathways of single dopants into and out of the nanoparticles. This study shows that the single dopant is shuttled into the hollow Au 24 nanoparticle either through the apex or side entry, while shuttling a metal atom out of the Au 25 to form the Au 24 nanoparticle occurs mainly through the side entry.Doping a metal nanocluster with heteroatoms dramatically changes its properties, but it remains difficult to dope with single-atom control. Here, the authors devise a strategy to dope single atoms of Ag or Cu into hollow Au nanoclusters, creating precise alloy nanoparticles atom-by-atom.

Shape Evolution of Metal Nanoparticles in Water Vapor Environment.

PubMed

Zhu, Beien; Xu, Zhen; Wang, Chunlei; Gao, Yi

2016-04-13

The structures of the metal nanoparticles are crucial for their catalytic activities. How to understand and even control the shape evolution of nanoparticles under reaction condition is a big challenge in heterogeneous catalysis. It has been proved that many reactive gases hold the capability of changing the structures and properties of metal nanoparticles. One interesting question is whether water vapor, such a ubiquitous environment, could induce the shape evolution of metal nanoparticles. So far this question has not received enough attention yet. In this work, we developed a model based on the density functional theory, the Wulff construction, and the Langmuir adsorption isotherm to explore the shape of metal nanoparticle at given temperature and water vapor pressure. By this model, we show clearly that water vapor could notably increase the fraction of (110) facets and decrease that of (111) facets for 3-8 nm Cu nanoparticles, which is perfectly consistent with the experimental observations. Further investigations indicate the water vapor has different effects on the different metal species (Cu, Au, Pt, and Pd). This work not only helps to understand the water vapor effect on the structures of metal nanoparticles but also proposes a simple but effective model to predict the shape of nanoparticles in certain environment.

Synthesis of Au-induced structurally ordered AuPdCo intermetallic core-shell nanoparticles and their use as oxygen reduction catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.

Embodiments of the disclosure relate to intermetallic nanoparticles. Embodiments include nanoparticles having an intermetallic core including a first metal and a second metal. The first metal may be palladium and the second metal may be at least one of cobalt, iron, nickel, or a combination thereof. The nanoparticles may further have a shell that includes palladium and gold.

Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

PubMed

Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

2012-01-09

Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cation/Anion Substitution in Cu2ZnSnS4 for Improved Photovoltaic Performance

PubMed Central

Ananthoju, Balakrishna; Mohapatra, Jeotikanta; Jangid, Manoj K.; Bahadur, D.; Medhekar, N. V.; Aslam, M.

2016-01-01

Cations and anions are replaced with Fe, Mn, and Se in CZTS in order to control the formations of the secondary phase, the band gap, and the micro structure of Cu2ZnSnS4. We demonstrate a simplified synthesis strategy for a range of quaternary chalcogenide nanoparticles such as Cu2ZnSnS4 (CZTS), Cu2FeSnS4 (CFTS), Cu2MnSnS4 (CMTS), Cu2ZnSnSe4 (CZTSe), and Cu2ZnSn(S0.5Se0.5)4 (CZTSSe) by thermolysis of metal chloride precursors using long chain amine molecules. It is observed that the crystal structure, band gap and micro structure of the CZTS thin films are affected by the substitution of anion/cations. Moreover, secondary phases are not observed and grain sizes are enhanced significantly with selenium doping (grain size ~1 μm). The earth-abundant Cu2MSnS4/Se4 (M = Zn, Mn and Fe) nanoparticles have band gaps in the range of 1.04–1.51 eV with high optical-absorption coefficients (~104 cm−1) in the visible region. The power conversion efficiency of a CZTS solar cell is enhanced significantly, from 0.4% to 7.4% with selenium doping, within an active area of 1.1 ± 0.1 cm2. The observed changes in the device performance parameters might be ascribed to the variation of optical band gap and microstructure of the thin films. The performance of the device is at par with sputtered fabricated films, at similar scales. PMID:27748406

Synthesis of carbon-encapsulated metal nanoparticles from wood char

Treesearch

Yicheng Du; Chuji Wang; Hossein Toghiani; Zhiyong Cai; Xiaojian Liu; Jilei Zhang; Qiangu Yan

2010-01-01

Carbon-encapsulated metal nanoparticles were synthesized by thermal treatment of wood char, with or without transition metal ions pre-impregnated, at 900ºC to 1,100ºC. Nanoparticles with concentric multilayer shells were observed. The nanoparticles were analyzed by scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction...

Fluorescence quenching near small metal nanoparticles.

PubMed

Pustovit, V N; Shahbazyan, T V

2012-05-28

We develop a microscopic model for fluorescence of a molecule (or semiconductor quantum dot) near a small metal nanoparticle. When a molecule is situated close to metal surface, its fluorescence is quenched due to energy transfer to the metal. We perform quantum-mechanical calculations of energy transfer rates for nanometer-sized Au nanoparticles and find that nonlocal and quantum-size effects significantly enhance dissipation in metal as compared to those predicted by semiclassical electromagnetic models. However, the dependence of transfer rates on molecule's distance to metal nanoparticle surface, d, is significantly weaker than the d(-4) behavior for flat metal surface with a sharp boundary predicted by previous calculations within random phase approximation.

Nitride stabilized core/shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuttiyiel, Kurian Abraham; Sasaki, Kotaro; Adzic, Radoslav R.

Nitride stabilized metal nanoparticles and methods for their manufacture are disclosed. In one embodiment the metal nanoparticles have a continuous and nonporous noble metal shell with a nitride-stabilized non-noble metal core. The nitride-stabilized core provides a stabilizing effect under high oxidizing conditions suppressing the noble metal dissolution during potential cycling. The nitride stabilized nanoparticles may be fabricated by a process in which a core is coated with a shell layer that encapsulates the entire core. Introduction of nitrogen into the core by annealing produces metal nitride(s) that are less susceptible to dissolution during potential cycling under high oxidizing conditions.

Electrode including porous particles with embedded active material for use in a secondary electrochemical cell

DOEpatents

Vissers, Donald R.; Nelson, Paul A.; Kaun, Thomas D.; Tomczuk, Zygmunt

1978-04-25

Particles of carbonaceous matrices containing embedded electrode active material are prepared for vibratory loading within a porous electrically conductive substrate. In preparing the particles, active materials such as metal chalcogenides, solid alloys of alkali or alkaline earth metals along with other metals and their oxides in powdered or particulate form are blended with a thermosetting resin and particles of a volatile to form a paste mixture. The paste is heated to a temperature at which the volatile transforms into vapor to impart porosity at about the same time as the resin begins to cure into a rigid, solid structure. The solid structure is then comminuted into porous, carbonaceous particles with the embedded active material.

Method of preparing porous, active material for use in electrodes of secondary electrochemical cells

DOEpatents

Vissers, Donald R.; Nelson, Paul A.; Kaun, Thomas D.; Tomczuk, Zygmunt

1977-01-01

Particles of carbonaceous matrices containing embedded electrode active material are prepared for vibratory loading within a porous electrically conductive substrate. In preparing the particles, active materials such as metal chalcogenides, solid alloys of alkali or alkaline earth metals along with other metals and their oxides in powdered or particulate form are blended with a thermosetting resin and particles of a volatile to form a paste mixture. The paste is heated to a temperature at which the volatile transforms into vapor to impart porosity at about the same time as the resin begins to cure into a rigid, solid structure.The solid structure is then comminuted into porous, carbonaceous particles with the embedded active material.

Composite materials with metal oxide attached to lead chalcogenide nanocrystal quantum dots with linkers

DOEpatents

Fuke, Nobuhiro; Koposov, Alexey Y; Sykora, Milan; Hoch, Laura

2014-12-16

Composite materials useful for devices such as photoelectrochemical solar cells include a substrate, a metal oxide film on the substrate, nanocrystalline quantum dots (NQDs) of lead sulfide, lead selenide, and lead telluride, and linkers that attach the NQDs to the metal oxide film. Suitable linkers preserve the 1s absorption peak of the NQDs. A suitable linker has a general structure A-B-C where A is a chemical group adapted for binding to a MO.sub.x and C is a chemical group adapted for binding to a NQD and B is a divalent, rigid, or semi-rigid organic spacer moiety. Other linkers that preserve the 1s absorption peak may also be used.

In situ generation of highly dispersed metal nanoparticles on two-dimensional layered SiO2 by topotactic structure conversion and their superior catalytic activity

NASA Astrophysics Data System (ADS)

Chen, Zhe; Jia, Da-Shuang; Zhou, Yue; Hao, Jiang; Liang, Yu; Cui, Zhi-Min; Song, Wei-Guo

2018-03-01

Metal nanoparticles such as Ag, Cu and Fe are effective catalysts for many reactions, whereas a facile method to prepare metal nanoparticles with high uniformed dispersion is still desirable. Herein, the topotactic structure conversion of layered silicate, RUB-15, was utilized to support metal nanoparticles. Through simple ion-exchange and following calcination step, metal nanoparticles were generated in situ inside the interlayer space of layered silica, and the topotactic structure conversion process assured nano-sized and highly uniformed dispersion of metal nanoparticles. The obtained Ag/SiO2 composite showed superior catalytic activity for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB), with a rate constant as high as 0.0607 s-1 and 0.0778 s-1. The simple and universal synthesis method as well as high activity of the product composite endow the strategy good application prospect.

Cryochemistry of Metal Nanoparticles

NASA Astrophysics Data System (ADS)

Sergeev, Gleb B.

2003-12-01

The interaction of metal atoms, clusters and nanoparticles with different organic and inorganic substances were studied at low temperature (10-40K). Combination of matrix isolation technique and preparative cryochemistry was applied for the investigation of activity and selectivity of metal particles of different size. Encapsulation of metal nanoparticles in polymers was studied. The metal-polymer films thus obtained exhibited satisfactory sensitivity to ammonia.

Metal ion displacements in noncentrosymmetric chalcogenides La3Ga1.67S7, La3Ag0.6GaCh7 (Ch=S, Se), and La3MGaSe7 (M=Zn, Cd)

NASA Astrophysics Data System (ADS)

Iyer, Abishek K.; Yin, Wenlong; Rudyk, Brent W.; Lin, Xinsong; Nilges, Tom; Mar, Arthur

2016-11-01

The quaternary Ga-containing chalcogenides La3Ag0.6GaS7, La3Ag0.6GaSe7, La3ZnGaSe7, and La3CdGaSe7, as well as the related ternary chalcogenide La3Ga1.67S7, were prepared by reactions of the elements at 950 °C. They adopt noncentrosymmetric hexagonal structures (space group P63, Z=2) with cell parameters (a=10.2 Å, c=6.1 Å for the sulfides; a=10.6 Å, c=6.4 Å for the selenides) that are largely controlled by the geometrical requirements of one-dimensional stacks of Ga-centered tetrahedra separated by the La atoms. Among these compounds, which share the common formulation La3M1-xGaCh7 (M=Ga, Ag, Zn, Cd; Ch=S, Se), the M atoms occupy sites within a stacking of trigonal antiprisms formed by Ch atoms. The location of the M site varies between extremes with trigonal antiprismatic (CN6) and trigonal planar (CN3) geometry. Partial occupation of these sites and intermediate ones accounts for the considerable versatility of these structures and the occurrence of large metal displacement parameters. The site occupations can be understood in a simple way as being driven by the need to satisfy appropriate bond valence sums for both the M and Ch atoms. Band structure calculations rationalize the substoichiometry observed in the Ag-containing compounds (La3Ag0.6GaS7, La3Ag0.6GaSe7) as a response to overbonding. X-ray photoelectron spectroscopy supports the presence of monovalent Ag atoms in these compounds, which are not charge-balanced.

Polarized Optical Scattering Measurements of Metallic Nanoparticles on a Thin Film Silicon Wafer

NASA Astrophysics Data System (ADS)

Liu, Cheng-Yang; Liu, Tze-An; Fu, Wei-En

2009-09-01

Light scattering has shown its powerful diagnostic capability to characterize optical quality surfaces. In this study, the theory of bidirectional reflectance distribution function (BRDF) was used to analyze the metallic nanoparticles' sizes on wafer surfaces. The BRDF of a surface is defined as the angular distribution of radiance scattered by the surface normalized by the irradiance incident on the surface. A goniometric optical scatter instrument has been developed to perform the BRDF measurements on polarized light scattering on wafer surfaces for the diameter and distribution measurements of metallic nanoparticles. The designed optical scatter instrument is capable of distinguishing various types of optical scattering characteristics, which are corresponding to the diameters of the metallic nanoparticles, near surfaces by using the Mueller matrix calculation. The metallic nanoparticle diameter of measurement is 60 nm on 2 inch thin film wafers. These measurement results demonstrate that the polarization of light scattered by metallic particles can be used to determine the size of metallic nanoparticles on silicon wafers.

Method for producing metallic nanoparticles

DOEpatents

Phillips, Jonathan; Perry, William L.; Kroenke, William J.

2004-02-10

Method for producing metallic nanoparticles. The method includes generating an aerosol of solid metallic microparticles, generating non-oxidizing plasma with a plasma hot zone at a temperature sufficiently high to vaporize the microparticles into metal vapor, and directing the aerosol into the hot zone of the plasma. The microparticles vaporize in the hot zone to metal vapor. The metal vapor is directed away from the hot zone and to the plasma afterglow where it cools and condenses to form solid metallic nanoparticles.

Bioavailability, Intracellular Mobilization of Nickel, and HIF-1α Activation in Human Lung Epithelial Cells Exposed to Metallic Nickel and Nickel Oxide Nanoparticles

PubMed Central

Liu, Xinyuan; Smith, Ashley; McNeil, Kevin; Weston, Paula; Zhitkovich, Anatoly; Hurt, Robert; Kane, Agnes B.

2011-01-01

Micron-sized particles of poorly soluble nickel compounds, but not metallic nickel, are established human and rodent carcinogens. In contrast, little is known about the toxic effects of a growing number of Ni-containing materials in the nano-sized range. Here, we performed physicochemical characterization of NiO and metallic Ni nanoparticles and examined their metal ion bioavailability and toxicological properties in human lung epithelial cells. Cellular uptake of metallic Ni and NiO nanoparticles, but not metallic Ni microparticles, was associated with the release of Ni(II) ions after 24–48 h as determined by Newport Green fluorescence. Similar to soluble NiCl2, NiO nanoparticles induced stabilization and nuclear translocation of hypoxia-inducible factor 1α (HIF-1α) transcription factor followed by upregulation of its target NRDG1 (Cap43). In contrast to no response to metallic Ni microparticles, nickel nanoparticles caused a rapid and prolonged activation of the HIF-1α pathway that was stronger than that induced by soluble Ni (II). Soluble NiCl2 and NiO nanoparticles were equally toxic to H460 human lung epithelial cells and primary human bronchial epithelial cells; metallic Ni nanoparticles showed lower toxicity and Ni microparticles were nontoxic. Cytotoxicity induced by all forms of Ni occurred concomitant with activation of an apoptotic response, as determined by dose- and time-dependent cleavage of caspases and poly (ADP-ribose) polymerase. Our results show that metallic Ni nanoparticles, in contrast to micron-sized Ni particles, activate a toxicity pathway characteristic of carcinogenic Ni compounds. Moderate cytotoxicity and sustained activation of the HIF-1α pathway by metallic Ni nanoparticles could promote cell transformation and tumor progression. PMID:21828359

Impact of metal and metal oxide nanoparticles on plant: A critical review

NASA Astrophysics Data System (ADS)

Rastogi, Anshu; Zivcak, Marek; Sytar, Oksana; Kalaji, Hazem M.; He, Xiaolan; Mbarki, Sonia; Brestic, Marian

2017-10-01

An increasing need of nanotechnology in various industries may cause a huge environment dispersion of nanoparticles in coming years. A concern about nanoparticles interaction with flora and fauna is raised due to a growing load of it in the environment. In recent years, several investigators have shown impact of nanoparticles on plant growth and its accumulation in food source. This review examines the research performed in the last decade to show how metal and metal oxide nanoparticles are influencing the plant metabolisms. We addressed here, the impact of nanoparticle on plant in relation to its size, concentration, and exposure methodology. Based on the available reports, we proposed oxidative burst as a general mechanism through which the toxic effects of nanoparticles are spread in plants. This review summarises the current understanding and the future possibilities of plant-nanoparticle research.

Kinetics of Spontaneous Bimetallization between Silver and Noble Metal Nanoparticles.

PubMed

Hirakawa, Kazutaka; Kaneko, Tetsuya; Toshima, Naoki

2018-06-05

A physical mixture of polymer-protected Ag nanoparticles and Rh, Pd, or Pt nanoparticles spontaneously forms Ag-core bimetallic nanoparticles. The formed nanoparticles were smaller than the parent Ag nanoparticles. In the initial process of this reaction, the surface plasmon absorption of Ag nanoparticles diminished and then almost ceased within one hour. Within several minutes, the decrease in Ag surface plasmon absorption could be analyzed by second-order reaction. This reaction was accelerated with an increase of temperature and the energy gap in the Fermi level between Ag and the other metals. The activation energy (E a ) of this reaction could be determined. An electron transfer reaction from Ag to other metal nanoparticles was proposed as the initial interaction between these metal nanoparticles because the Fermi level of Ag is relatively high, and the electron transfer is possible in terms of energy. The Marcus plot between the rate constant and the driving force, roughly estimated from the work function of metals, and the observed E a values reasonably explained the proposed electron transfer mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile synthesis of CuSe nanoparticles and high-quality single-crystal two-dimensional hexagonal nanoplatelets with tunable near-infrared optical absorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yimin; Korolkov, Ilia; Qiao, Xvsheng

2016-06-15

A rapid injection approach is used to synthesize the copper selenide nanoparticles and two-dimensional single crystal nanoplates. This technique excludes the use of toxic or expensive materials, increasing the availability of two-dimensional binary chalcogenide semiconductors. The structure of the nanocrystals has been studied and the possible formation mechanism of the nanoplates has been proposed. The optical absorption showed that the nanoplates demonstrated wide and tuneable absorption band in the visible and near infrared region. These nanoplates could be interesting for converting solar energy and for nanophotonic devices operating in the near infrared. - Graphical abstract: TEM images of the coppermore » selenides nanoparticles and nanoplates synthesized at 180 °C for 0 min, 10 min, 60 min. And the growth mechanism of the copper selenide nanoplates via the “oriented attachment”. Display Omitted - Highlights: • CuSe nanoparticles and nanoplates are synthesized by a rapid injection approach. • CuSe band gap can be widely tuned simply by modifying the synthesized time. • Al{sup 3+} ions have a significant impact on the growth rate of the nanoplates. • Growth mechanism of the CuSe nanoplates is based on the “oriented attachment”.« less

Synthesis of Metal Nanoparticle-decorated Carbon Nanotubes under Ambient Conditions

NASA Technical Reports Server (NTRS)

Lin, Yi; Watson, Kent A.; Ghose, Sayata; Smith, Joseph G.; Connell, John W.

2008-01-01

This viewgraph presentation reviews the production of Metal Nanoparticle-decorated carbon Nanotubes. Multi-walled carbon nanotubes (MWCNTs) were efficiently decorated with metal nanoparticles (e.g. Ag, Pt, etc.) using the corresponding metal acetate in a simple mixing process without the need of chemical reagents or further processing. The conversion of acetate compounds to the corresponding metal reached over 90%, forming nanoparticles with average diameters less than 10 nm under certain conditions. The process was readily scalable allowing for the convenient preparation of multi-gram quantities of metal nanoparticle-decorated MWCNTs in a matter of a few minutes. These materials are under evaluation for a variety of electrical and catalytic applications. The preparation and characterization of these materials will be presented. The microscopic views of the processed MWCNTs are shown

Metallic Nickel Nanoparticles May Exhibit Higher Carcinogenic Potential than Fine Particles in JB6 Cells

PubMed Central

Bowman, Linda; Zou, Baobo; Mao, Guochuan; Xu, Jin; Castranova, Vincent; Zhao, Jinshun; Ding, Min

2014-01-01

While numerous studies have described the pathogenic and carcinogenic effects of nickel compounds, little has been done on the biological effects of metallic nickel. Moreover, the carcinogenetic potential of metallic nickel nanoparticles is unknown. Activator protein-1 (AP-1) and nuclear factor-κB (NF-κB) have been shown to play pivotal roles in tumor initiation, promotion, and progression. Mutation of the p53 tumor suppressor gene is considered to be one of the steps leading to the neoplastic state. The present study examines effects of metallic nickel fine and nanoparticles on tumor promoter or suppressor gene expressions as well as on cell transformation in JB6 cells. Our results demonstrate that metallic nickel nanoparticles caused higher activation of AP-1 and NF-κB, and a greater decrease of p53 transcription activity than fine particles. Western blot indicates that metallic nickel nanoparticles induced a higher level of protein expressions for R-Ras, c-myc, C-Jun, p65, and p50 in a time-dependent manner. In addition, both metallic nickel nano- and fine particles increased anchorage-independent colony formation in JB6 P+ cells in the soft agar assay. These results imply that metallic nickel fine and nanoparticles are both carcinogenetic in vitro in JB6 cells. Moreover, metallic nickel nanoparticles may exhibit higher carcinogenic potential, which suggests that precautionary measures should be taken in the use of nickel nanoparticles or its compounds in nanomedicine. PMID:24691273

In Situ Synthesis of Metal Nanoparticle Embedded Hybrid Soft Nanomaterials.

PubMed

Divya, Kizhmuri P; Miroshnikov, Mikhail; Dutta, Debjit; Vemula, Praveen Kumar; Ajayan, Pulickel M; John, George

2016-09-20

The allure of integrating the tunable properties of soft nanomaterials with the unique optical and electronic properties of metal nanoparticles has led to the development of organic-inorganic hybrid nanomaterials. A promising method for the synthesis of such organic-inorganic hybrid nanomaterials is afforded by the in situ generation of metal nanoparticles within a host organic template. Due to their tunable surface morphology and porosity, soft organic materials such as gels, liquid crystals, and polymers that are derived from various synthetic or natural compounds can act as templates for the synthesis of metal nanoparticles of different shapes and sizes. This method provides stabilization to the metal nanoparticles by the organic soft material and advantageously precludes the use of external reducing or capping agents in many instances. In this Account, we exemplify the green chemistry approach for synthesizing these materials, both in the choice of gelators as soft material frameworks and in the reduction mechanisms that generate the metal nanoparticles. Established herein is the core design principle centered on conceiving multifaceted amphiphilic soft materials that possess the ability to self-assemble and reduce metal ions into nanoparticles. Furthermore, these soft materials stabilize the in situ generated metal nanoparticles and retain their self-assembly ability to generate metal nanoparticle embedded homogeneous organic-inorganic hybrid materials. We discuss a remarkable example of vegetable-based drying oils as host templates for metal ions, resulting in the synthesis of novel hybrid nanomaterials. The synthesis of metal nanoparticles via polymers and self-assembled materials fabricated via cardanol (a bioorganic monomer derived from cashew nut shell liquid) are also explored in this Account. The organic-inorganic hybrid structures were characterized by several techniques such as UV-visible spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Utilization of silver nanoparticle-based hybrid nanomaterials as an antimicrobial material is another illustration of the advantage of hybrid nanomaterials. We envision that the results summarized in this Account will help the scientific community to design and develop diverse organic-inorganic hybrid materials using environmentally benign methods and that these materials will yield advanced properties that have multifaceted applications in various research fields.

Static impedance behavior of programmable metallization cells

NASA Astrophysics Data System (ADS)

Rajabi, S.; Saremi, M.; Barnaby, H. J.; Edwards, A.; Kozicki, M. N.; Mitkova, M.; Mahalanabis, D.; Gonzalez-Velo, Y.; Mahmud, A.

2015-04-01

Programmable metallization cell (PMC) devices work by growing and dissolving a conducting metallic bridge across a chalcogenide glass (ChG) solid electrolyte, which changes the resistance of the cell. PMC operation relies on the incorporation of metal ions in the ChG films via photo-doping to lower the off-state resistance and stabilize resistive switching, and subsequent transport of these ions by electric fields induced from an externally applied bias. In this paper, the static on- and off-state resistance of a PMC device composed of a layered (Ag-rich/Ag-poor) Ge30Se70 ChG film with active Ag and inert Ni electrodes is characterized and modeled using three dimensional simulation code. Calibrating the model to experimental data enables the extraction of device parameters such as material bandgaps, workfunctions, density of states, carrier mobilities, dielectric constants, and affinities.

Metal-based nanoparticle interactions with the nervous system: the challenge of brain entry and the risk of retention in the organism.

PubMed

Yokel, Robert; Grulke, Eric; MacPhail, Robert

2013-01-01

This review of metal-based nanoparticles focuses on factors influencing their distribution into the nervous system, evidence they enter brain parenchyma, and nervous system responses. Gold is emphasized as a model metal-based nanoparticle and for risk assessment in the companion review. The anatomy and physiology of the nervous system, basics of colloid chemistry, and environmental factors that influence what cells see are reviewed to provide background on the biological, physical-chemical, and internal milieu factors that influence nervous system nanoparticle uptake. The results of literature searches reveal little nanoparticle research included the nervous system, which about equally involved in vitro and in vivo methods, and very few human studies. The routes of uptake into the nervous system and mechanisms of nanoparticle uptake by cells are presented with examples. Brain nanoparticle uptake inversely correlates with size. The influence of shape has not been reported. Surface charge has not been clearly shown to affect flux across the blood-brain barrier. There is very little evidence for metal-based nanoparticle distribution into brain parenchyma. Metal-based nanoparticle disruption of the blood-brain barrier and adverse brain changes have been shown, and are more pronounced for spheres than rods. Study concentrations need to be put in exposure contexts. Work with dorsal root ganglion cells and brain cells in vitro show the potential for metal-based nanoparticles to produce toxicity. Interpretation of these results must consider the ability of nanoparticles to distribute across the barriers protecting the nervous system. Effects of the persistence of poorly soluble metal-based nanoparticles are of particular concern. Copyright © 2013 Wiley Periodicals, Inc.

Biomimetic Synthesis of Gelatin Polypeptide-Assisted Noble-Metal Nanoparticles and Their Interaction Study

NASA Astrophysics Data System (ADS)

Liu, Ying; Liu, Xiaoheng; Wang, Xin

2011-12-01

Herein, the generation of gold, silver, and silver-gold (Ag-Au) bimetallic nanoparticles was carried out in collagen (gelatin) solution. It first showed that the major ingredient in gelatin polypeptide, glutamic acid, acted as reducing agent to biomimetically synthesize noble metal nanoparticles at 80°C. The size of nanoparticles can be controlled not only by the mass ratio of gelatin to gold ion but also by pH of gelatin solution. Interaction between noble-metal nanoparticles and polypeptide has been investigated by TEM, UV-visible, fluorescence spectroscopy, and HNMR. This study testified that the degradation of gelatin protein could not alter the morphology of nanoparticles, but it made nanoparticles aggregated clusters array (opposing three-dimensional α-helix folding structure) into isolated nanoparticles stabilized by gelatin residues. This is a promising merit of gelatin to apply in the synthesis of nanoparticles. Therefore, gelatin protein is an excellent template for biomimetic synthesis of noble metal/bimetallic nanoparticle growth to form nanometer-sized device.

Biomimetic Synthesis of Gelatin Polypeptide-Assisted Noble-Metal Nanoparticles and Their Interaction Study

PubMed Central

2011-01-01

Herein, the generation of gold, silver, and silver–gold (Ag–Au) bimetallic nanoparticles was carried out in collagen (gelatin) solution. It first showed that the major ingredient in gelatin polypeptide, glutamic acid, acted as reducing agent to biomimetically synthesize noble metal nanoparticles at 80°C. The size of nanoparticles can be controlled not only by the mass ratio of gelatin to gold ion but also by pH of gelatin solution. Interaction between noble-metal nanoparticles and polypeptide has been investigated by TEM, UV–visible, fluorescence spectroscopy, and HNMR. This study testified that the degradation of gelatin protein could not alter the morphology of nanoparticles, but it made nanoparticles aggregated clusters array (opposing three-dimensional α-helix folding structure) into isolated nanoparticles stabilized by gelatin residues. This is a promising merit of gelatin to apply in the synthesis of nanoparticles. Therefore, gelatin protein is an excellent template for biomimetic synthesis of noble metal/bimetallic nanoparticle growth to form nanometer-sized device. PMID:27502645

Method for producing metal oxide nanoparticles

DOEpatents

Phillips, Jonathan [Santa Fe, NM; Mendoza, Daniel [Santa Fe, NM; Chen, Chun-Ku [Albuquerque, NM

2008-04-15

Method for producing metal oxide nanoparticles. The method includes generating an aerosol of solid metallic microparticles, generating plasma with a plasma hot zone at a temperature sufficiently high to vaporize the microparticles into metal vapor, and directing the aerosol into the hot zone of the plasma. The microparticles vaporize in the hot zone into metal vapor. The metal vapor is directed away from the hot zone and into the cooler plasma afterglow where it oxidizes, cools and condenses to form solid metal oxide nanoparticles.

Fullerene-Like Nickel Oxysulfide Hollow Nanospheres as Bifunctional Electrocatalysts for Water Splitting.

PubMed

Liu, Junli; Yang, Yong; Ni, Bing; Li, Haoyi; Wang, Xun

2017-02-01

Fullerene-like nickel oxysulfide hollow nanospheres with ≈50 nm are constructed by in situ growth on the surface of nickel foam by taking advantage of solvothermal reaction. The as-prepared composite exhibits exhilaratingly high HER and OER performance in 1 m KOH, which opens up a very promising aspect for non-noble metal chalcogenides as bifunctional electrocatalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Chalcogenide Materials for X-ray and Gamma-ray Detection

DTIC Science & Technology

2016-05-01

53 Novel Chalcogenide Materials for x-ray and y-ray Detection Distribution Statement A. Approved for public release; distribution is unlimited. 0...TITLE AND SUBTITLE Sa. CONTRACT NUMBER Novel Chalcogenide Materials for x-ray and y-ray Detection Sb. GRANT NUMBER HDTRA 1-09-1-0044 Sc. PROGRAM...heavy atom chalcogenide family of semiconductors for room temperature gamma radiation detection . Its goal was to accelerate nuclear detector material

High-Purity Glasses Based on Arsenic Chalcogenides

DTIC Science & Technology

2001-06-01

Chemical interaction of chalcogenides and some impurities (CS 2, TeO2 ) with the quartz glass at high temperature leads to the thin layers formation...UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADPO1 1523 TITLE: High-Purity Glasses Based on Arsenic Chalcogenides...Materials Vol. 3, No. 2, June 2001, p. 341 - 349 HIGH-PURITY GLASSES BASED ON ARSENIC CHALCOGENIDES M. F. Churbanov, I. V. Scripachev, G. E. Snopatin, V. S

Poisson's Ratio and the Densification of Glass under High Pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rouxel, T.; Ji, H.; Hammouda, T.

2008-06-06

Because of a relatively low atomic packing density, (C{sub g}) glasses experience significant densification under high hydrostatic pressure. Poisson's ratio ({nu}) is correlated to C{sub g} and typically varies from 0.15 for glasses with low C{sub g} such as amorphous silica to 0.38 for close-packed atomic networks such as in bulk metallic glasses. Pressure experiments were conducted up to 25 GPa at 293 K on silica, soda-lime-silica, chalcogenide, and bulk metallic glasses. We show from these high-pressure data that there is a direct correlation between {nu} and the maximum post-decompression density change.

Supramolecular Assembly of Single-Source Metal-Chalcogenide Nanocrystal Precursors.

PubMed

Smith, Stephanie C; Bryks, Whitney; Tao, Andrea R

2018-05-28

In this Feature Article, we discuss our recent work in the synthesis of novel supramolecular precursors for semiconductor nanocrystals. Metal chalcogenolates that adopt liquid crystalline phases are employed as single-source precursors that template the growth of shaped solid-state nanocrystals. Supramolecular assembly is programmed by both precursor chemical composition and molecular parameters such alkyl chain length, steric bulk, and the intercalation of halide ions. Here, we explore the various design principles that enable the rational synthesis of these single-source precursors, their liquid crystalline phases, and the various semiconductor nanocrystal products that can be generated by thermolysis, ranging from highly anisotropic two-dimensional nanosheets and nanodisks to spheres.

LOW-TEMPERATURE HEAT CAPACITIES AND THERMODYNAMIC FUNCTIONS OF SOME PLATINUM AND PALLADIUM GROUP CHALCOGENIDES. I. MONO-CHALCOGENIDES. Pts, PtTe, AND PdTe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Groenvold, F.; Thurmann-Moe, T.; Westrum, E.F. Jr.

1961-11-01

Heat capacities of platinum monosulfide, platinum monotelluride, and palladium monotelluride were measured in the range 5--350 deg K. They show the normal sigmoidal temperature dependence with no evidence of transivions or other anomalies. The derived heat-capacity equations were integrated. Values of heat capacitles, entropy, and enthalpy increments, and of the free-energy function are tabulated for selected temperatures. Av 298,15 deg K, the third-law entroples are 13,16 cal gfw/sup -1/ deg K/sup -1/ for PtS 19.41 cal gfw/sup -1/ deg K/sup - 1/ for PtTe, and 2l.42 cal gfw/sup -1/ deg K/sup -1/ for PdTe. The new dava on PvS weremore » correlaved wlvh exlstlng decomposlvlonpressure data vo evaluate DELTA Hf, DELTA Ff, and DELTA Sf 298.15 deg K. Entropies for other platlnum-metal monochalcogenides were estimated. (auth)« less

Atomistic origin of an ordered superstructure induced superconductivity in layered chalcogenides.

PubMed

Ang, R; Wang, Z C; Chen, C L; Tang, J; Liu, N; Liu, Y; Lu, W J; Sun, Y P; Mori, T; Ikuhara, Y

2015-01-27

Interplay among various collective electronic states such as charge density wave and superconductivity is of tremendous significance in low-dimensional electron systems. However, the atomistic and physical nature of the electronic structures underlying the interplay of exotic states, which is critical to clarifying its effect on remarkable properties of the electron systems, remains elusive, limiting our understanding of the superconducting mechanism. Here, we show evidence that an ordering of selenium and sulphur atoms surrounding tantalum within star-of-David clusters can boost superconductivity in a layered chalcogenide 1T-TaS2-xSex, which undergoes a superconducting transition in the nearly commensurate charge density wave phase. Advanced electron microscopy investigations reveal that such an ordered superstructure forms only in the x area, where the superconductivity manifests, and is destructible to the occurrence of the Mott metal-insulator transition. The present findings provide a novel dimension in understanding the relationship between lattice and electronic degrees of freedom.

Pulsed laser deposition of chalcogenide sulfides from multi- and single-component targets: the non-stoichiometric material transfer

NASA Astrophysics Data System (ADS)

Schou, Jørgen; Gansukh, Mungunshagai; Ettlinger, Rebecca B.; Cazzaniga, Andrea; Grossberg, Maarja; Kauk-Kuusik, Marit; Canulescu, Stela

2018-01-01

The mass transfer from target to films is incongruent for chalcogenide sulfides in contrast to the expectations of pulsed laser deposition (PLD) as a stoichiometric film growth process. Films produced from a CZTS (Cu2ZnSnS4) multi-component target have no Cu below a fluence threshold of 0.2 J/cm2, and the Cu content is also very low at low fluence from a single-component target. Above this threshold, the Cu content in the films increases almost linearly up to a value above the stoichiometric value, while the ratio of the concentration of the other metals Zn to Sn (Zn/Sn) remains constant. Films of a similar material CTS (Cu2SnS3) have been produced by PLD from a CTS target and exhibits a similar trend in the same fluence region. The results are discussed on the basis of solid-state data and the existing data from the literature.

Applications of UV/Vis Spectroscopy in Characterization and Catalytic Activity of Noble Metal Nanoparticles Fabricated in Responsive Polymer Microgels: A Review.

PubMed

Begum, Robina; Farooqi, Zahoor H; Naseem, Khalida; Ali, Faisal; Batool, Madeeha; Xiao, Jianliang; Irfan, Ahmad

2018-11-02

Noble metal nanoparticles loaded smart polymer microgels have gained much attention due to fascinating combination of their properties in a single system. These hybrid systems have been extensively used in biomedicines, photonics, and catalysis. Hybrid microgels are characterized by using various techniques but UV/Vis spectroscopy is an easily available technique for characterization of noble metal nanoparticles loaded microgels. This technique is widely used for determination of size and shape of metal nanoparticles. The tuning of optical properties of noble metal nanoparticles under various stimuli can be studied using UV/Vis spectroscopic method. Time course UV/Vis spectroscopy can also be used to monitor the kinetics of swelling and deswelling of microgels and hybrid microgels. Growth of metal nanoparticles in polymeric network or growth of polymeric network around metal nanoparticle core can be studied by using UV/Vis spectroscopy. This technique can also be used for investigation of various applications of hybrid materials in catalysis, photonics, and sensing. This tutorial review describes the uses of UV/Vis spectroscopy in characterization and catalytic applications of responsive hybrid microgels with respect to recent research progress in this area.

Electrochemically induced actuation of liquid metal marbles

NASA Astrophysics Data System (ADS)

Tang, Shi-Yang; Sivan, Vijay; Khoshmanesh, Khashayar; O'Mullane, Anthony P.; Tang, Xinke; Gol, Berrak; Eshtiaghi, Nicky; Lieder, Felix; Petersen, Phred; Mitchell, Arnan; Kalantar-Zadeh, Kourosh

2013-06-01

Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads.Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00185g

Metal-based nanoparticle interactions with the nervous system: The challenge of brain entry and the risk of retention in the organism

EPA Science Inventory

This review of metal and metal-oxide based nanoparticles focuses on factors that influence their distribution into the nervous system, evidence that they enter brain parenchyma, and nervous system responses. Emphasis is placed on gold as a model metal-based nanoparticle and for r...

The Effect of Metal Oxide on Nanoparticles from Thermite Reactions

ERIC Educational Resources Information Center

Moore, Lewis Ryan

2006-01-01

The purpose of this research was to determine how metal oxide used in a thermite reaction can impact the production of nanoparticles. The results showed the presence of nanoparticles (less than 1 micron in diameter) of at least one type produced by each metal oxide. The typical particles were metallic spheres, which ranged from 300 nanometers in…

Shape tunable plasmonic nanoparticles

DOEpatents

El-Sayed, Mostafa A.; El-Sayed, Ivan Homer

2017-03-07

Noble metal nanoparticles and methods of their use are provided. Certain aspects provided solid noble metal nanoparticles tuned to the near infrared. The disclosed nanoparticles can be used in molecular imaging, diagnosis, and treatment. Methods for imaging cells are also provided.

Impact of Metal and Metal Oxide Nanoparticles on Plant: A Critical Review

PubMed Central

Rastogi, Anshu; Zivcak, Marek; Sytar, Oksana; Kalaji, Hazem M.; He, Xiaolan; Mbarki, Sonia; Brestic, Marian

2017-01-01

An increasing need of nanotechnology in various industries may cause a huge environment dispersion of nanoparticles in coming years. A concern about nanoparticles interaction with flora and fauna is raised due to a growing load of it in the environment. In recent years, several investigators have shown impact of nanoparticles on plant growth and their accumulation in food source. This review examines the research performed in the last decade to show how metal and metal oxide nanoparticles are influencing the plant metabolism. We addressed here, the impact of nanoparticle on plant in relation to its size, concentration, and exposure methodology. Based on the available reports, we proposed oxidative burst as a general mechanism through which the toxic effects of nanoparticles are spread in plants. This review summarizes the current understanding and the future possibilities of plant-nanoparticle research. PMID:29075626

Water-soluble core/shell nanoparticles for proton therapy through particle-induced radiation

NASA Astrophysics Data System (ADS)

Park, Jeong Chan; Jung, Myung-Hwan; Kim, Maeng Jun; Kim, Kye-Ryung

2015-02-01

Metallic nanoparticles have been used in biomedical applications such as magnetic resonance imaging (MRI), therapy, and drug delivery systems. Metallic nanoparticles as therapeutic tools have been demonstrated using radio-frequency magnetic fields or near-infrared light. Recently, therapeutic applications of metallic nanomaterials combined with proton beams have been reported. Particle-induced radiation from metallic nanoparticles, which can enhance the therapeutic effects of proton therapy, was released when the nanoparticles were bombarded by a high-energy proton beam. Core/shell nanoparticles, especially Au-coated magnetic nanoparticles, have drawn attention in biological applications due to their attractive characteristics. However, studies on the phase transfer of organic-ligand-based core/shell nanoparticles into water are limited. Herein, we demonstrated that hydrophobic core/shell structured nanomaterials could be successfully dispersed in water through chloroform/surfactant mixtures. The effects of the core/shell nanomaterials and the proton irradiation on Escherichia coli (E. coli) were also explored.

Durability improvements of two-dimensional metal nanoparticle sheets by molecular cross-linked structures between nanoparticles

NASA Astrophysics Data System (ADS)

Saito, Noboru; Ryuzaki, Sou; Wang, Pangpang; Park, Susie; Sakai, Nobuyuki; Tatsuma, Tetsu; Okamoto, Koichi; Tamada, Kaoru

2018-03-01

The durability of two-dimensional metal nanoparticle sheets is a crucial factor for realizing next-generation optoelectronic devices based on plasmonics such as organic light-emitting diodes. Here, we report improvements in the durability of Ag nanoparticle sheets by forming alkanedithiol (DT16) cross-linked structures between the nanoparticles. The cross-linked structures in a sheet were fabricated by the self-assembly of DT16-capped Ag nanoparticles with 10% coverage (AgDT16). The durabilities for thermal, organic solvent, and oxidation reactions of AgDT16 sheets were found to be improved owing to the cross-linked structures by comparing Ag nanoparticle sheets without the cross-linked structures. The absorbance spectra revealed that the Ag nanoparticle sheets without the structure are markedly damaged by each durability test, whereas the AgDT16 sheets remain. The molecular cross-linked structures between nanoparticles in two-dimansional metal nanoparticle sheets were found to have the potential to play a key role in the realization of plasmonic optoelectronic devices including metal nanoparticles.

Fabrication, optimization and characterization of noble silver nanoparticles from sugarcane leaves (Saccharum officinarum) extract for antifungal application

USDA-ARS?s Scientific Manuscript database

Metal nanoparticles obtained from green route are gaining significant prominence as a result of their potential applications in nanomedicine and material engineering. Overall metal nanoparticles studied, silver nanoparticles (AgNPs) clutch prominent place in nanoparticles research field. Herein, we ...

Biosynthesis of silver and zinc oxide nanoparticles using Pichia fermentans JA2 and their antimicrobial property

NASA Astrophysics Data System (ADS)

Chauhan, Ritika; Reddy, Arpita; Abraham, Jayanthi

2015-01-01

The development of eco-friendly alternative to chemical synthesis of metal nanoparticles is of great challenge among researchers. The present study aimed to investigate the biological synthesis, characterization, antimicrobial study and synergistic effect of silver and zinc oxide nanoparticles against clinical pathogens using Pichia fermentans JA2. The extracellular biosynthesis of silver and zinc oxide nanoparticles was investigated using Pichia fermentans JA2 isolated from spoiled fruit pulp bought in Vellore local market. The crystalline and stable metallic nanoparticles were characterized evolving several analytical techniques including UV-visible spectrophotometer, X-ray diffraction pattern analysis and FE-scanning electron microscope with EDX-analysis. The biosynthesized metallic nanoparticles were tested for their antimicrobial property against medically important Gram positive, Gram negative and fungal pathogenic microorganisms. Furthermore, the biosynthesized nanoparticles were also evaluated for their increased antimicrobial activities with various commercially available antibiotics against clinical pathogens. The biosynthesized silver nanoparticles inhibited most of the Gram negative clinical pathogens, whereas zinc oxide nanoparticles were able to inhibit only Pseudomonas aeruginosa. The combined effect of standard antibiotic disc and biosynthesized metallic nanoparticles enhanced the inhibitory effect against clinical pathogens. The biological synthesis of silver and zinc oxide nanoparticles is a novel and cost-effective approach over harmful chemical synthesis techniques. The metallic nanoparticles synthesized using Pichia fermentans JA2 possess potent inhibitory effect that offers valuable contribution to pharmaceutical associations.

Strong coupling-like phenomenon in single metallic nanoparticle embedded in molecular J-aggregates

NASA Astrophysics Data System (ADS)

Feng, Xin; Wang, Chen; Ma, Hongjing; Chen, Yuanyuan; Duan, Gaoyan; Zhang, Pengfei; Song, Gang

2018-02-01

Strong coupling-like phenomenon between plasmonic cavities and emitters provides a new way to realize the quantum-like effect controlling at microscale/nanoscale. We investigate the strong coupling-like phenomenon in the structure of single metallic nanoparticle embedded in molecular J-aggregates by the classical simulation method and show that the size of the metallic nanoparticle and the oscillator strength of molecular J-aggregates impact the strong coupling-like phenomenon. The strong coupling-like phenomenon is induced by the interactions between two dipoles formed by the metallic nanoparticle and molecular J-aggregates or the interactions between the dipole generated from molecular J-aggregates and the quadrupole generated from the metallic nanoparticle. The strong coupling-like phenomenon appears evidently with the increase in oscillator strength of molecular J-aggregates. The detuning energy linearly decreases with the increase in radius of the metallic nanoparticle. Our structure has potential applications in quantum networks, quantum key distributions and so on.

Photochemical Fabrication of Transition Metal Nanoparticles Using CdS Template and Their Co-Catalysis Effects for TiO2 Photocatalysis

NASA Astrophysics Data System (ADS)

Badhwar, Nidhi; Gupta, Nidhi; Pal, Bonamali

2013-09-01

Transition metal nanoparticles were prepared by chemical dissolution of CdS template from metal photodeposited CdS nanorod (length = 70-85 nm and width = 5-6 nm) heterocomposites. Size (9-10 nm) of metal nanoparticles obtained after CdS removal was larger than the size (4-6 nm) of metal nanodeposits over CdS template. The obtained Au nanoparticles displayed a broad red shifted absorption band at 660 nm, whereas Pt, Pd and Rh nanoparticles exhibit featureless absorption spectra. Elemental analysis confirms the complete removal of CdS template from Au-CdS (Au — 2.65 at.%) and Ag-CdS (Ag — 2.06 at.%) composites showing no Cd peak. These metal nanoparticles imparted dissimilar co-catalytic activity of TiO2 for photocatalytic degradation of salicylic acid in the order Au > Pt > Pd > Ag > Rh as a function of their nature, electronegativity, redox potential and work function.

Role of Metal and Metal Oxide Nanoparticles as Diagnostic and Therapeutic Tools for Highly Prevalent Viral Infections

PubMed Central

Yadavalli, Tejabhiram; Shukla, Deepak

2016-01-01

Nanotechnology is increasingly playing important roles in various fields including virology. The emerging use of metal or metal oxide nanoparticles in virus targeting formulations shows the promise of improved diagnostic or therapeutic ability of the agents while uniquely enhancing the prospects of targeted drug delivery. Although a number of nanoparticles varying in composition, size, shape, and surface properties have been approved for human use, the candidates being tested or approved for clinical diagnosis and treatment of viral infections are relatively less in number. Challenges remain in this domain due to a lack of essential knowledge regarding the in vivo comportment of nanoparticles during viral infections. This review provides a broad overview of recent advances in diagnostic, prophylactic and therapeutic applications of metal and metal oxide nanoparticles in Human Immunodeficiency Virus, Hepatitis virus, influenza virus and Herpes virus infections. Types of nanoparticles commonly used and their broad applications have been explained in this review. PMID:27575283

Biomolecule/nanomaterial hybrid systems for nanobiotechnology.

PubMed

Tel-Vered, Ran; Yehezkeli, Omer; Willner, Itamar

2012-01-01

The integration of biomolecules with metallic or semiconductor nanoparticles or carbon nanotubes yields new hybrid nanostructures of unique features that combine the properties of the biomolecules and of the nano-elements. These unique features of the hybrid biomolecule/nanoparticle systems provide the basis for the rapid development of the area of nanobiotechnology. Recent advances in the implementation of hybrid materials consisting of biomolecules and metallic nanoparticles or semiconductor quantum dots will be discussed. The following topics will be exemplified: (i) The electrical wiring of redox enzymes with electrodes by means of metallic nanoparticles or carbon nanotubes, and the application of the modified electrodes as amperometric biosensors or for the construction of biofuel cells. (ii) The biocatalytic growth of metallic nanoparticles as a means to construct optical or electrical sensors. (iii) The functionalization of semiconductor quantum dots with biomolecules and the application of the hybrid nanostructures for developing different optical sensors, including intracellular sensor systems. (iv) The use of biomolecule-metallic nanoparticle nanostructures as templates for growing metallic nanowires, and the construction of fuel-driven nano-transporters.

Ballistic-diffusive approximation for the thermal dynamics of metallic nanoparticles in nanocomposite materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirdel-Havar, A. H., E-mail: Amir.hushang.shirdel@gmail.com; Masoudian Saadabad, R.

2015-03-21

Based on ballistic-diffusive approximation, a method is presented to model heat transfer in nanocomposites containing metal nanoparticles. This method provides analytical expression for the temperature dynamics of metallic nanoparticles embedded in a dielectric medium. In this study, nanoparticles are considered as spherical shells, so that Boltzmann equation is solved using ballistic-diffusive approximation to calculate the electron and lattice thermal dynamics in gold nanoparticles, while thermal exchange between the particles is taken into account. The model was used to investigate the influence of particle size and metal concentration of the medium on the electron and lattice thermal dynamics. It is shownmore » that these two parameters are crucial in determining the nanocomposite thermal behavior. Our results showed that the heat transfer rate from nanoparticles to the matrix decreases as the nanoparticle size increases. On the other hand, increasing the metal concentration of the medium can also decrease the heat transfer rate.« less

Metal Nanoparticles as Targeted Carriers Circumventing the Blood-Brain Barrier.

PubMed

Sintov, A C; Velasco-Aguirre, C; Gallardo-Toledo, E; Araya, E; Kogan, M J

2016-01-01

Metal nanoparticles have been proposed as a carrier and a therapeutic agent in biomedical field because of their unique physiochemical properties. Due to these physicochemical properties, they can be used in different fields of biomedicine. In relation to this, plasmonic nanoparticles can be used for detection and photothermal destruction of tumor cells or toxic protein aggregates, and magnetic iron nanoparticles can be used for imaging and for hyperthermia of tumor cells. In addition, both therapy and imaging can be combined in one nanoparticle system, in a process called theranostics. Metal nanoparticles can be synthesized to modulate their size and shape, and conjugated with different ligands, which allow their application in drug delivery, diagnostics, and treatment of central nervous system diseases. This review is focused on the potential applications of metal nanoparticles and their capability to circumvent the blood-brain barrier (BBB). Although many articles have demonstrated delivery of metal nanoparticles to the brain by crossing the BBB after systemic administration, the percentage of the injected dose that reaches this organ is low in comparison to others, especially the liver and spleen. In connection with this drawback, we elaborate the architecture of the BBB and review possible mechanisms to cross this barrier by engineered nanoparticles. The potential uses of metal nanoparticles for treatment of disorders as well as related neurotoxicological considerations are also discussed. Finally, we bring up for discussion a direct and relatively simpler solution to the problem. We discuss this in detail after having proposed the use of the intranasal administration route as a way to circumvent the BBB. This route has not been extensively studied yet for metal nanoparticles, although it could be used as a research tool for mechanistic understanding and toxicity as well as an added value for medical practice. © 2016 Elsevier Inc. All rights reserved.

Imposed Environmental Stresses Facilitate Cell-Free Nanoparticle Formation by Deinococcus radiodurans

PubMed Central

2017-01-01

ABSTRACT The biological synthesis of metal nanoparticles has been examined in a wide range of organisms, due to increased interest in green synthesis and environmental remediation applications involving heavy metal ion contamination. Deinococcus radiodurans is particularly attractive for environmental remediation involving metal reduction, due to its high levels of resistance to radiation and other environmental stresses. However, few studies have thoroughly examined the relationships between environmental stresses and the resulting effects on nanoparticle biosynthesis. In this work, we demonstrate cell-free nanoparticle production and study the effects of metal stressor concentrations and identity, temperature, pH, and oxygenation on the production of extracellular silver nanoparticles by D. radiodurans R1. We also report the synthesis of bimetallic silver and gold nanoparticles following the addition of a metal stressor (silver or gold), highlighting how production of these particles is enabled through the application of environmental stresses. Additionally, we found that both the morphology and size of monometallic and bimetallic nanoparticles were dependent on the environmental stresses imposed on the cells. The nanoparticles produced by D. radiodurans exhibited antimicrobial activity comparable to that of pure silver nanoparticles and displayed catalytic activity comparable to that of pure gold nanoparticles. Overall, we demonstrate that biosynthesized nanoparticle properties can be partially controlled through the tuning of applied environmental stresses, and we provide insight into how their application may affect nanoparticle production in D. radiodurans during bioremediation. IMPORTANCE Biosynthetic production of nanoparticles has recently gained prominence as a solution to rising concerns regarding increased bacterial resistance to antibiotics and a desire for environmentally friendly methods of bioremediation and chemical synthesis. To date, a range of organisms have been utilized for nanoparticle formation. The extremophile D. radiodurans, which can withstand significant environmental stresses and therefore is more robust for metal reduction applications, has yet to be exploited for this purpose. Thus, this work improves our understanding of the impact of environmental stresses on biogenic nanoparticle morphology and composition during metal reduction processes in this organism. This work also contributes to enhancing the controlled synthesis of nanoparticles with specific attributes and functions using biological systems. PMID:28687649

Imposed Environmental Stresses Facilitate Cell-Free Nanoparticle Formation by Deinococcus radiodurans.

PubMed

Chen, Angela; Contreras, Lydia M; Keitz, Benjamin K

2017-09-15

The biological synthesis of metal nanoparticles has been examined in a wide range of organisms, due to increased interest in green synthesis and environmental remediation applications involving heavy metal ion contamination. Deinococcus radiodurans is particularly attractive for environmental remediation involving metal reduction, due to its high levels of resistance to radiation and other environmental stresses. However, few studies have thoroughly examined the relationships between environmental stresses and the resulting effects on nanoparticle biosynthesis. In this work, we demonstrate cell-free nanoparticle production and study the effects of metal stressor concentrations and identity, temperature, pH, and oxygenation on the production of extracellular silver nanoparticles by D. radiodurans R1. We also report the synthesis of bimetallic silver and gold nanoparticles following the addition of a metal stressor (silver or gold), highlighting how production of these particles is enabled through the application of environmental stresses. Additionally, we found that both the morphology and size of monometallic and bimetallic nanoparticles were dependent on the environmental stresses imposed on the cells. The nanoparticles produced by D. radiodurans exhibited antimicrobial activity comparable to that of pure silver nanoparticles and displayed catalytic activity comparable to that of pure gold nanoparticles. Overall, we demonstrate that biosynthesized nanoparticle properties can be partially controlled through the tuning of applied environmental stresses, and we provide insight into how their application may affect nanoparticle production in D. radiodurans during bioremediation. IMPORTANCE Biosynthetic production of nanoparticles has recently gained prominence as a solution to rising concerns regarding increased bacterial resistance to antibiotics and a desire for environmentally friendly methods of bioremediation and chemical synthesis. To date, a range of organisms have been utilized for nanoparticle formation. The extremophile D. radiodurans , which can withstand significant environmental stresses and therefore is more robust for metal reduction applications, has yet to be exploited for this purpose. Thus, this work improves our understanding of the impact of environmental stresses on biogenic nanoparticle morphology and composition during metal reduction processes in this organism. This work also contributes to enhancing the controlled synthesis of nanoparticles with specific attributes and functions using biological systems. Copyright © 2017 American Society for Microbiology.

Metal-doped semiconductor nanoparticles and methods of synthesis thereof

NASA Technical Reports Server (NTRS)

Ren, Zhifeng (Inventor); Wang, Wenzhong (Inventor); Chen, Gang (Inventor); Dresselhaus, Mildred (Inventor); Poudel, Bed (Inventor); Kumar, Shankar (Inventor)

2009-01-01

The present invention generally relates to binary or higher order semiconductor nanoparticles doped with a metallic element, and thermoelectric compositions incorporating such nanoparticles. In one aspect, the present invention provides a thermoelectric composition comprising a plurality of nanoparticles each of which includes an alloy matrix formed of a Group IV element and Group VI element and a metallic dopant distributed within the matrix.

Metal-doped semiconductor nanoparticles and methods of synthesis thereof

DOEpatents

Ren, Zhifeng [Newton, MA; Chen, Gang [Carlisle, MA; Poudel, Bed [West Newton, MA; Kumar, Shankar [Newton, MA; Wang, Wenzhong [Beijing, CN; Dresselhaus, Mildred [Arlington, MA

2009-09-08

The present invention generally relates to binary or higher order semiconductor nanoparticles doped with a metallic element, and thermoelectric compositions incorporating such nanoparticles. In one aspect, the present invention provides a thermoelectric composition comprising a plurality of nanoparticles each of which includes an alloy matrix formed of a Group IV element and Group VI element and a metallic dopant distributed within the matrix.

Nickel and platinum group metal nanoparticle production by Desulfovibrio alaskensis G20.

PubMed

Capeness, M J; Edmundson, M C; Horsfall, L E

2015-12-25

Desulfovibrio alaskensis G20 is an anaerobic sulfate reducing bacteria. While Desulfovibrio species have previously been shown to reduce palladium and platinum to the zero-state, forming nanoparticles in the process; there have been no reports that D. alaskensis is able to form these nanoparticles. Metal nanoparticles have properties that make them ideal for use in many industrial and medical applications, such as their size and shape giving them higher catalytic activity than the bulk form of the same metal. Nanoparticles of the platinum group metals in particular are highly sought after for their catalytic ability and herein we report the formation of both palladium and platinum nanoparticles by D. alaskensis and the biotransformation of solvated nickel ions to nanoparticle form. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Metal ion displacements in noncentrosymmetric chalcogenides La{sub 3}Ga{sub 1.67}S{sub 7}, La{sub 3}Ag{sub 0.6}GaCh{sub 7} (Ch=S, Se), and La{sub 3}MGaSe{sub 7} (M=Zn, Cd)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iyer, Abishek K.; Yin, Wenlong; Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900

The quaternary Ga-containing chalcogenides La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}, La{sub 3}ZnGaSe{sub 7}, and La{sub 3}CdGaSe{sub 7}, as well as the related ternary chalcogenide La{sub 3}Ga{sub 1.67}S{sub 7}, were prepared by reactions of the elements at 950 °C. They adopt noncentrosymmetric hexagonal structures (space group P6{sub 3}, Z=2) with cell parameters (a=10.2 Å, c=6.1 Å for the sulfides; a=10.6 Å, c=6.4 Å for the selenides) that are largely controlled by the geometrical requirements of one-dimensional stacks of Ga-centered tetrahedra separated by the La atoms. Among these compounds, which share the common formulation La{sub 3}M{sub 1–x}GaCh{sub 7} (M=Ga, Ag,more » Zn, Cd; Ch=S, Se), the M atoms occupy sites within a stacking of trigonal antiprisms formed by Ch atoms. The location of the M site varies between extremes with trigonal antiprismatic (CN6) and trigonal planar (CN3) geometry. Partial occupation of these sites and intermediate ones accounts for the considerable versatility of these structures and the occurrence of large metal displacement parameters. The site occupations can be understood in a simple way as being driven by the need to satisfy appropriate bond valence sums for both the M and Ch atoms. Band structure calculations rationalize the substoichiometry observed in the Ag-containing compounds (La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}) as a response to overbonding. X-ray photoelectron spectroscopy supports the presence of monovalent Ag atoms in these compounds, which are not charge-balanced. - Graphical abstract: Partial occupation of metal atoms in multiple sites accounts for versatility in Ga-containing chalcogenides La{sub 3}M{sub 1–x}GaCh{sub 7} with noncentrosymmetric hexagonal structures. - Highlights: • La{sub 3}M{sub 1–x}GaCh{sub 7} (M =Ga, Ag, Zn, Cd; Ch =S, Se) adopt related hexagonal structures. • Large displacements of M atoms originate from partial occupation of multiple sites. • Bond valence sum arguments give a simple explanation for site preference. • XPS studies confirm presence of monovalent Ag in La{sub 3}Ag{sub 0.6}GaCh{sub 7}. • Substoichiometry in La{sub 3}Ag{sub 0.6}GaCh{sub 7} avoids occupation of Ag–Ch antibonding levels.« less

Marine microorganisms as potential biofactories for synthesis of metallic nanoparticles.

PubMed

Manivasagan, Panchanathan; Nam, Seung Yun; Oh, Junghwan

2016-11-01

The use of marine microorganisms as potential biofactories for green synthesis of metallic nanoparticles is a relatively new field of research with considerable prospects. This method is eco-friendly, time saving, and inexpensive and can be easily scaled up for large-scale synthesis. The increasing need to develop simple, nontoxic, clean, and environmentally safe production methods for nanoparticles and to decrease environmental impact, minimize waste, and increase energy productivity has become important in this field. Marine microorganisms are tiny organisms that live in marine ecosystems and account for >98% of biomass of the world's ocean. Marine microorganisms synthesize metallic nanoparticles either intracellularly or extracellularly. Marine microbially-produced metallic nanoparticles have received considerable attention in recent years because of their expected impact on various applications such as medicine, energy, electronic, and space industries. The present review discusses marine microorganisms as potential biofactories for the green synthesis of metallic nanoparticles and their potential applications.

Characterization, sorption, and exhaustion of metal oxide nanoparticles as metal adsorbents

NASA Astrophysics Data System (ADS)

Engates, Karen Elizabeth

Safe drinking water is paramount to human survival. Current treatments do not adequately remove all metals from solution, are expensive, and use many resources. Metal oxide nanoparticles are ideal sorbents for metals due to their smaller size and increased surface area in comparison to bulk media. With increasing demand for fresh drinking water and recent environmental catastrophes to show how fragile water supplies are, new approaches to water conservation incorporating new technologies like metal oxide nanoparticles should be considered as an alternative method for metal contaminant adsorbents from typical treatment methods. This research evaluated the potential of manufactured iron, anatase, and aluminum nanoparticles (Al2O3, TiO2, Fe2O3) to remove metal contaminants (Pb, Cd, Cu, Ni, Zn) in lab-controlled and natural waters in comparison to their bulk counterparts by focusing on pH, contaminant and adsorbent concentrations, particle size, and exhaustive capabilities. Microscopy techniques (SEM, BET, EDX) were used to characterize the adsorbents. Adsorption experiments were performed using 0.01, 0.1, or 0.5 g/L nanoparticles in pH 8 solution. When results were normalized by mass, nanoparticles adsorbed more than bulk particles but when surface area normalized the opposite was observed. Adsorption was pH-dependent and increased with time and solid concentration. Aluminum oxide was found to be the least acceptable adsorbent for the metals tested, while titanium dioxide anatase (TiO2) and hematite (alpha-Fe2O3) showed great ability to remove individual and multiple metals from pH 8 and natural waters. Intraparticle diffusion was likely part of the complex kinetic process for all metals using Fe2O3 but not TiO 2 nanoparticles within the first hour of adsorption. Adsorption kinetics for all metals tested were described by a modified first order rate equation used to consider the diminishing equilibrium metal concentrations with increasing metal oxides, showing faster adsorption rates for nanoparticles compared to bulk particles. Isotherms were best fit with most correlations of r=0.99 or better using the Langmuir-Freundlich equation which describes a heterogeneous surface with monolayer adsorption. Calculated rate constants and distribution coefficients (Kd) showed TiO2 nanoparticles were very good sorbents and more rapid in removing metals than other nanoparticles studied here and reported in the literature. Desorption studies concluded Pb, Cd, and Zn appear to be irreversibly sorbed to TiO2 surfaces at pH 8. TiO2 and Fe2O3 nanoparticles were capable of multiple metal loadings, with exhaustion for both adsorbents at pH 6. Exhaustion studies at pH 8 showed hematite exhausted after four consecutive cycles while anatase showed no exhaustion after 8 cycles. Their bulk counterparts exhausted in earlier cycles indicating the lack of ability to adsorb much of the multiple metals in solution. The increased surface area of TiO2 and Fe 2O3 nanoparticles, coupled with strong adsorption at the pH of most natural waters and resistance to desorption of some metals, may offer a potential remediation method for removal of metals from water in the future.

Processing soft materials for integrated photonic and macroelectronic components and devices

NASA Astrophysics Data System (ADS)

Tsay, Candice Ruth

Incorporating soft materials into micro-fabrication processes opens up new functionalities for fabricated devices, but requires unique processing routes. This thesis presents our development of integrated photonic and macroelectronic structures through processing innovations that unite disparate inorganic/organic, and soft/rigid materials systems. For the integrated photonic system, we focus our efforts on chalcogenide glasses, dielectric materials that exhibit a variety of optical properties that make them desirable for near- and mid-infrared communications and sensing applications. However, processing limitations for these relatively fragile materials have made the direct integration of waveguides with sources or detectors challenging. Here we demonstrate the viability of several additive methods for patterning chalcogenide glass waveguides from solution. In particular, we focus on two complementary soft lithography methods. The first, micro-molding in capillaries (MIMIC), is shown to fabricate multi-mode As2S 3 waveguides which are directly integrated with quantum cascade lasers (QCLs). In a second method, we demonstrate the ability of micro-transfer molding (muTM), to produce arrays of single mode rib waveguides over large areas while maintaining low surface and edge roughness. These methods form a suite of processes that can be applied to chalcogenide solutions to create a diverse array of mid-IR photonic structures ranging from less than 5 to 10's of mum in cross-sectional dimension. Optical characterization, including measurement of waveguide loss by cut-back, is carried out in the mid-IR using QCLs. In addition, materials characterization of the chalcogenide glass structures is carried out to determine loss mechanisms and optimize processing. While we use soft polymeric materials as molds to pattern chalcogenide glasses, we also employ them as substrate material for stretchable electronic systems, which comprise a new class of flexible macroelectronics. These devices must undergo elastic deformation to large strain (>10%), for applications in which electronics are conformally shaped around surfaces of arbitrary shape, like many biological surfaces. We develop strategies for processing stretchable metallic electrodes and study the mechanism of their stretchability via careful observation of thin film micro-structures. Our macroelectronic work culminates in fabrication of stretchable microelectrode arrays that interface with brain tissue, laying the groundwork for future development of advanced bio-electronic interfaces.

Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals

NASA Astrophysics Data System (ADS)

Carey, Benjamin J.; Ou, Jian Zhen; Clark, Rhiannon M.; Berean, Kyle J.; Zavabeti, Ali; Chesman, Anthony S. R.; Russo, Salvy P.; Lau, Desmond W. M.; Xu, Zai-Quan; Bao, Qiaoliang; Kevehei, Omid; Gibson, Brant C.; Dickey, Michael D.; Kaner, Richard B.; Daeneke, Torben; Kalantar-Zadeh, Kourosh

2017-02-01

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (~1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes.

Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals.

PubMed

Carey, Benjamin J; Ou, Jian Zhen; Clark, Rhiannon M; Berean, Kyle J; Zavabeti, Ali; Chesman, Anthony S R; Russo, Salvy P; Lau, Desmond W M; Xu, Zai-Quan; Bao, Qiaoliang; Kevehei, Omid; Gibson, Brant C; Dickey, Michael D; Kaner, Richard B; Daeneke, Torben; Kalantar-Zadeh, Kourosh

2017-02-17

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (∼1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes.

Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals

PubMed Central

Carey, Benjamin J.; Ou, Jian Zhen; Clark, Rhiannon M.; Berean, Kyle J.; Zavabeti, Ali; Chesman, Anthony S. R.; Russo, Salvy P.; Lau, Desmond W. M.; Xu, Zai-Quan; Bao, Qiaoliang; Kavehei, Omid; Gibson, Brant C.; Dickey, Michael D.; Kaner, Richard B.; Daeneke, Torben; Kalantar-Zadeh, Kourosh

2017-01-01

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (∼1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes. PMID:28211538

Nanomaterials derived from metal-organic frameworks

NASA Astrophysics Data System (ADS)

Dang, Song; Zhu, Qi-Long; Xu, Qiang

2018-01-01

The thermal transformation of metal-organic frameworks (MOFs) generates a variety of nanostructured materials, including carbon-based materials, metal oxides, metal chalcogenides, metal phosphides and metal carbides. These derivatives of MOFs have characteristics such as high surface areas, permanent porosities and controllable functionalities that enable their good performance in sensing, gas storage, catalysis and energy-related applications. Although progress has been made to tune the morphologies of MOF-derived structures at the nanometre scale, it remains crucial to further our knowledge of the relationship between morphology and performance. In this Review, we summarize the synthetic strategies and optimized methods that enable control over the size, morphology, composition and structure of the derived nanomaterials. In addition, we compare the performance of materials prepared by the MOF-templated strategy and other synthetic methods. Our aim is to reveal the relationship between the morphology and the physico-chemical properties of MOF-derived nanostructures to optimize their performance for applications such as sensing, catalysis, and energy storage and conversion.

Lithium-aluminum-iron electrode composition

DOEpatents

Kaun, Thomas D.

1979-01-01

A negative electrode composition is presented for use in a secondary electrochemical cell. The cell also includes an electrolyte with lithium ions such as a molten salt of alkali metal halides or alkaline earth metal halides that can be used in high-temperature cells. The cell's positive electrode contains a a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent in an alloy of aluminum-iron. Various binary and ternary intermetallic phases of lithium, aluminum and iron are formed. The lithium within the intermetallic phase of Al.sub.5 Fe.sub.2 exhibits increased activity over that of lithium within a lithium-aluminum alloy to provide an increased cell potential of up to about 0.25 volt.

Metal-chelate dye-controlled organization of Cd32S14(SPh)40(4-) nanoclusters into three-dimensional molecular and covalent open architecture.

PubMed

Zheng, Nanfeng; Lu, Haiwei; Bu, Xianhui; Feng, Pingyun

2006-04-12

Chalcogenide II-VI nanoclusters are usually prepared as isolated clusters and have defied numerous efforts to join them into covalent open-framework architecture with conventional templating methods such as protonated amines or inorganic cations commonly used to direct the formation of porous frameworks. Herein, we report the first templated synthesis of II-VI covalent superlattices from large II-VI tetrahedral clusters (i.e., [Cd32S14(SPh)38]2-). Our method takes advantage of low charge density of metal-chelate dyes that is a unique match with three-dimensional II-VI semiconductor frameworks in charge density, surface hydrophilicity-hydrophobicity, and spatial organization. In addition, metal-chelate dyes also serve to tune the optical properties of resulting dye semiconductor composite materials.

Ultrahigh refractive index chalcogenide based copolymers for infrared optics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Anderson, Laura E.; Namnabat, Soha; Char, Kookheon; Glass, Richard; Norwood, Robert A.; Pyun, Jeffrey

2016-09-01

Current trends in technology development demand increased miniaturization and higher level integration of electronic and photonic components. Such needs arise in emerging imaging systems, optoelectronic devices, optical interconnects and photonic integrated circuits. Compact, integrated photonics requires high refractive index materials, which primarily comprise crystalline and amorphous semiconductors, as well as chalcogenide glasses, which can possess refractive indices higher than 4 and good infrared transparency. There is currently no high refractive index (n 2 or above) that has the low cost production and ease of processing available in optical polymers. Such polymers would potentially cover applications that are not convenient or possible with crystalline and vitreous semiconductors. Examples of such applications include micro lens arrays for image sensors, optical adhesives for bonding and antireflection coatings, and high contrast optical waveguides. While much of the focus has been in the telecommunications transparency regions, significant new opportunities exist for a polymer which is capable of transmitting efficiently in the MWIR region. While there are polymers that have been synthesized with refractive indices as high as 1.75, these polymers are generally conjugated and incorporate heteroatoms such as sulfur or metals, and generally have complex and expensive syntheses. Here we report on new chalcogenide based copolymers with very high refractive index (n 2) that also have good optical transmission properties in the near-, short- and mid-wave infrared up to 5µm. These polymers are rich in sulfur, have low hydrogen content and were made using inverse vulcanization.

Plasmonic efficiencies of nanoparticles made of metal nitrides (TiN, ZrN) compared with gold

PubMed Central

Lalisse, Adrien; Tessier, Gilles; Plain, Jérome; Baffou, Guillaume

2016-01-01

Metal nitrides have been proposed to replace noble metals in plasmonics for some specific applications. In particular, while titanium nitride (TiN) and zirconium nitride (ZrN) possess localized plasmon resonances very similar to gold in magnitude and wavelength, they benefit from a much higher sustainability to temperature. For this reason, they are foreseen as ideal candidates for applications in nanoplasmonics that require high material temperature under operation, such as heat assisted magnetic recording (HAMR) or thermophotovoltaics. This article presents a detailed investigation of the plasmonic properties of TiN and ZrN nanoparticles in comparison with gold nanoparticles, as a function of the nanoparticle morphology. As a main result, metal nitrides are shown to be poor near-field enhancers compared to gold, no matter the nanoparticle morphology and wavelength. The best efficiencies of metal nitrides as compared to gold in term of near-field enhancement are obtained for small and spherical nanoparticles, and they do not exceed 60%. Nanoparticle enlargements or asymmetries are detrimental. These results mitigate the utility of metal nitrides for high-temperature applications such as HAMR, despite their high temperature sustainability. Nevertheless, at resonance, metal nitrides behave as efficient nanosources of heat and could be relevant for applications in thermoplasmonics, where heat generation is not detrimental but desired. PMID:27934890

Plasmonic efficiencies of nanoparticles made of metal nitrides (TiN, ZrN) compared with gold.

PubMed

Lalisse, Adrien; Tessier, Gilles; Plain, Jérome; Baffou, Guillaume

2016-12-09

Metal nitrides have been proposed to replace noble metals in plasmonics for some specific applications. In particular, while titanium nitride (TiN) and zirconium nitride (ZrN) possess localized plasmon resonances very similar to gold in magnitude and wavelength, they benefit from a much higher sustainability to temperature. For this reason, they are foreseen as ideal candidates for applications in nanoplasmonics that require high material temperature under operation, such as heat assisted magnetic recording (HAMR) or thermophotovoltaics. This article presents a detailed investigation of the plasmonic properties of TiN and ZrN nanoparticles in comparison with gold nanoparticles, as a function of the nanoparticle morphology. As a main result, metal nitrides are shown to be poor near-field enhancers compared to gold, no matter the nanoparticle morphology and wavelength. The best efficiencies of metal nitrides as compared to gold in term of near-field enhancement are obtained for small and spherical nanoparticles, and they do not exceed 60%. Nanoparticle enlargements or asymmetries are detrimental. These results mitigate the utility of metal nitrides for high-temperature applications such as HAMR, despite their high temperature sustainability. Nevertheless, at resonance, metal nitrides behave as efficient nanosources of heat and could be relevant for applications in thermoplasmonics, where heat generation is not detrimental but desired.

Ga metal nanoparticle-GaAs quantum molecule complexes for Terahertz generation.

PubMed

Bietti, Sergio; Basso Basset, Francesco; Scarpellini, David; Fedorov, Alexey; Ballabio, Andrea; Esposito, Luca; Elborg, Martin; Kuroda, Takashi; Nemcsics, Akos; Toth, Lajos; Manzoni, Cristian; Vozzi, Caterina; Sanguinetti, Stefano

2018-06-18

A hybrid metal-semiconductor nanosystem for the generation of THz radiation, based on the fabrication of GaAs quantum molecules-Ga metal nanoparticles complexes through a self assembly approach, is proposed. The role of the growth parameters, the substrate temperature, the Ga and As flux during the quantum dot molecule fabrication and the metal nanoparticle alignment is discussed. The tuning of the relative positioning of quantum dot molecules and metal nanoparticles is obtained through the careful control of Ga droplet nucleation sites via Ga surface diffusion. The electronic structure of a typical quantum dot molecule was evaluated on the base of the morphological characterizations performed by Atomic Force Microscopy and cross sectional Scanning Electron Microscopy, and the predicted results confirmed by micro-photoluminescence experiments, showing that the Ga metal nanoparticle-GaAs quantum molecule complexes are suitable for terahertz generation from intraband transition. . © 2018 IOP Publishing Ltd.

Microbially-mediated method for synthesis of non-oxide semiconductor nanoparticles

DOEpatents

Phelps, Tommy J.; Lauf, Robert J.; Moon, Ji Won; Rondinone, Adam J.; Love, Lonnie J.; Duty, Chad Edward; Madden, Andrew Stephen; Li, Yiliang; Ivanov, Ilia N.; Rawn, Claudia Jeanette

2014-06-24

The invention is directed to a method for producing non-oxide semiconductor nanoparticles, the method comprising: (a) subjecting a combination of reaction components to conditions conducive to microbially-mediated formation of non-oxide semiconductor nanoparticles, wherein said combination of reaction components comprises i) anaerobic microbes, ii) a culture medium suitable for sustaining said anaerobic microbes, iii) a metal component comprising at least one type of metal ion, iv) a non-metal component containing at least one non-metal selected from the group consisting of S, Se, Te, and As, and v) one or more electron donors that provide donatable electrons to said anaerobic microbes during consumption of the electron donor by said anaerobic microbes; and (b) isolating said non-oxide semiconductor nanoparticles, which contain at least one of said metal ions and at least one of said non-metals. The invention is also directed to non-oxide semiconductor nanoparticle compositions produced as above and having distinctive properties.

Materials Characterization and Microelectronic Implementation of Metal-insulator Transition Materials and Phase Change Materials

DTIC Science & Technology

2015-03-26

appropriate. Group 16 (VI) contains the following elements: Oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and polonium (Po). They are shown...below in Figure 33. S, Se, and Te are referred to as chalcogens, and their compounds are chalcogenides [68]. Polonium is excluded from the chalcogen...temperature dots and paint were placed on samples on the substrate. Temperature dots are typically used in the transportation of goods such as food in order

Surface functionalization of two-dimensional metal chalcogenides by Lewis acid-base chemistry

NASA Astrophysics Data System (ADS)

Lei, Sidong; Wang, Xifan; Li, Bo; Kang, Jiahao; He, Yongmin; George, Antony; Ge, Liehui; Gong, Yongji; Dong, Pei; Jin, Zehua; Brunetto, Gustavo; Chen, Weibing; Lin, Zuan-Tao; Baines, Robert; Galvão, Douglas S.; Lou, Jun; Barrera, Enrique; Banerjee, Kaustav; Vajtai, Robert; Ajayan, Pulickel

2016-05-01

Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid-base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti4+ to form planar p-type [Ti4+n(InSe)] coordination complexes. Using this strategy, we fabricate planar p-n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B3+, Al3+ and Sn4+) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid-base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device.

The role of interfacial metal silicates on the magnetism in FeCo/SiO 2 and Fe 49% Co 49% V 2% /SiO 2 core/shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desautels, R. D.; Freeland, J. W.; Rowe, M. P.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments havemore » shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell.« less

Pulse laser ablation of Au, Ag, and Cu metal targets in liquid for nanoparticle production

NASA Astrophysics Data System (ADS)

Herbani, Y.; Irmaniar; Nasution, R. S.; Mujtahid, F.; Masse, S.

2018-03-01

We have fabricated metal and oxide nanoparticles using pulse laser ablation of Au, Ag, and Cu metal targets immersed in water. While laser ablation of Au and Ag targets in water produced metal nanoparticles which were stable for a month even without any dispersant, we found CuO nanoparticles for Cu target due to rapid oxidation of Cu in water resulted in its poor stability. Au, Ag, and CuO nanoparticles production were barely identified by naked eyes for their distinctive colour of red, yellow, and dark green colloidal suspensions, respectively. It was also verified using UV-Vis spectrometer that Au, Ag, and CuO colloidal nanoparticles have their respective surface plasmon resonance at 520, 400, and 620 nm. TEM observation showed that particle sizes for all the fabricated nanoparticles were in the range of 20 – 40 nm with crystalline structures.

Toxicity of heavy metals and metal-containing nanoparticles on plants.

PubMed

Mustafa, Ghazala; Komatsu, Setsuko

2016-08-01

Plants are under the continual threat of changing climatic conditions that are associated with various types of abiotic stresses. In particular, heavy metal contamination is a major environmental concern that restricts plant growth. Plants absorb heavy metals along with essential elements from the soil and have evolved different strategies to cope with the accumulation of heavy metals. The use of proteomic techniques is an effective approach to investigate and identify the biological mechanisms and pathways affected by heavy metals and metal-containing nanoparticles. The present review focuses on recent advances and summarizes the results from proteomic studies aimed at understanding the response mechanisms of plants under heavy metal and metal-containing nanoparticle stress. Transport of heavy metal ions is regulated through the cell wall and plasma membrane and then sequestered in the vacuole. In addition, the role of different metal chelators involved in the detoxification and sequestration of heavy metals is critically reviewed, and changes in protein profiles of plants exposed to metal-containing nanoparticles are discussed in detail. Finally, strategies for gaining new insights into plant tolerance mechanisms to heavy metal and metal-containing nanoparticle stress are presented. This article is part of a Special Issue entitled: Plant Proteomics--a bridge between fundamental processes and crop production, edited by Dr. Hans-Peter Mock. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrolysis of a molten semiconductor

PubMed Central

Yin, Huayi; Chung, Brice; Sadoway, Donald R.

2016-01-01

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb2S3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across the cell. As opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO2, CO and SO2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides. PMID:27553525

Electrolysis of a molten semiconductor.

PubMed

Yin, Huayi; Chung, Brice; Sadoway, Donald R

2016-08-24

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb2S3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across the cell. As opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO2, CO and SO2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides.

Electrolysis of a molten semiconductor

NASA Astrophysics Data System (ADS)

Yin, Huayi; Chung, Brice; Sadoway, Donald R.

2016-08-01

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb2S3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across the cell. As opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO2, CO and SO2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides.

Potential application of metal nanoparticles for dosimetric systems: Concepts and perspectives

NASA Astrophysics Data System (ADS)

Guidelli, Eder José; Baffa, Oswaldo

2014-11-01

Metallic nanoparticles increase the delivered dose and consequently enhance tissue radio sensitization during radiation therapy of cancer. The Dose Enhancement Factor (DEF) corresponds to the ratio between the dose deposited on a tissue containing nanoparticles, and the dose deposited on a tissue without nanoparticles. In this sense, we have used electron spin resonance spectroscopy (ESR) to investigate how silver and gold nanoparticles affect the dose deposition in alanine dosimeters, which act as a surrogate of soft tissue. Besides optimizing radiation absorption by the dosimeter, the optical properties of these metal nanoparticles could also improve light emission from materials employed as radiation detectors. Therefore, we have also examined how the plasmonic properties of noble metal nanoparticles could enhance radiation detection using optically stimulated luminescence (OSL) dosimetry. This work will show results on how the use of gold and silver nanoparticles are beneficial for the ESR and OSL dosimetric techniques, and will describe the difficulties we have been facing, the challenges to overcome, and the perspectives.

Mechanochemical activation and patterning of an adhesive surface toward nanoparticle deposition.

PubMed

Baytekin, H Tarik; Baytekin, Bilge; Huda, Sabil; Yavuz, Zelal; Grzybowski, Bartosz A

2015-02-11

Mechanical pulling of adhesive tape creates radicals on the tape's surface. These radicals are capable of reducing metal salts to the corresponding metal nanoparticles. In this way, the mechanically activated tape can be decorated with various types of nanoparticles, including Au, Ag, Pd, or Cu. While retaining their mechanical properties and remaining "sticky," the tapes can exhibit new properties derived from the presence of metal nanoparticles (e.g., bacteriostaticity, increased electrical conductivity). They can also be patterned with nanoparticles only at selective locations of mechanical activation.

Nanoengineered membrane electrode assembly interface

DOEpatents

Song, Yujiang; Shelnutt, John A

2013-08-06

A membrane electrode structure suitable for use in a membrane electrode assembly (MEA) that comprises membrane-affixed metal nanoparticles whose formation is controlled by a photochemical process that controls deposition of the metal nanoparticles using a photocatalyst integrated with a polymer electrolyte membrane, such as an ionomer membrane. Impregnation of the polymer membrane with the photocatalyst prior to metal deposition greatly reduces the required amount of metal precursor in the deposition reaction solution by restricting metal reduction substantially to the formation of metal nanoparticles affixed on or near the surface of the polymer membrane with minimal formation of metallic particles not directly associated with the membrane.

Cellular partitioning of nanoparticulate versus dissolved metals in marine phytoplankton.

PubMed

Bielmyer-Fraser, Gretchen K; Jarvis, Tayler A; Lenihan, Hunter S; Miller, Robert J

2014-11-18

Discharges of metal oxide nanoparticles into aquatic environments are increasing with their use in society, thereby increasing exposure risk for aquatic organisms. Separating the impacts of nanoparticle from dissolved metal pollution is critical for assessing the environmental risks of the rapidly growing nanomaterial industry, especially in terms of ecosystem effects. Metal oxides negatively affect several species of marine phytoplankton, which are responsible for most marine primary production. Whether such toxicity is generally due to nanoparticles or exposure to dissolved metals liberated from particles is uncertain. The type and severity of toxicity depends in part on whether phytoplankton cells take up and accumulate primarily nanoparticles or dissolved metal ions. We compared the responses of the marine diatom, Thalassiosira weissflogii, exposed to ZnO, AgO, and CuO nanoparticles with the responses of T. weissflogii cells exposed to the dissolved metals ZnCl2, AgNO3, and CuCl2 for 7 d. Cellular metal accumulation, metal distribution, and algal population growth were measured to elucidate differences in exposure to the different forms of metal. Concentration-dependent metal accumulation and reduced population growth were observed in T. weissflogii exposed to nanometal oxides, as well as dissolved metals. Significant effects on population growth were observed at the lowest concentrations tested for all metals, with similar toxicity for both dissolved and nanoparticulate metals. Cellular metal distribution, however, markedly differed between T. weissflogii exposed to nanometal oxides versus those exposed to dissolved metals. Metal concentrations were highest in the algal cell wall when cells were exposed to metal oxide nanoparticles, whereas algae exposed to dissolved metals had higher proportions of metal in the organelle and endoplasmic reticulum fractions. These results have implications for marine plankton communities as well as higher trophic levels, since metal may be transferred from phytoplankton through food webs vis à vis grazing by zooplankton or other pathways.

Carbon Materials Embedded with Metal Nanoparticles as Anode in Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Hung, Ching-cheh

2002-01-01

Carbon materials containing metal nanoparticles that can form an alloy with lithium were tested for their capacity and cycle life to store and release lithium electrochemically. Metal nanoparticles may provide the additional lithium storage capacity as well as additional channels to conduct lithium in carbon. The cycle life of this carbon-metal composite can be long because the solid-electrolyte interface (SEI) on the carbon surface may protect both lithium and the metal particles in the carbon interior. In addition, the voids in the carbon interior may accommodate the nanoparticle's volume change, and such volume change may not cause much internal stress due to small sizes of the nanoparticles. This concept of improving carbon's performance to store and release lithium was demonstrated using experimental cells of C(Pd)/0.5M Lil-50/50 (vol.%) EC and DMC/Li, where C(Pd) was graphitized carbon fibers containing palladium nanoparticles, EC was ethylene carbonate, and DMC was dimethyl carbonate. However, such improvement was not observed if the Pd nanoparticles are replaced by aluminum, possibly because the aluminum nanoparticles were oxidized in air during storage, resulting in an inert oxide of aluminum. Further studies are needed to use this concept for practical applications.

Inorganic and metal nanoparticles and their antimicrobial activity in food packaging applications.

PubMed

Hoseinnejad, Mahmoud; Jafari, Seid Mahdi; Katouzian, Iman

2018-03-01

Nanotechnology has revolutionized almost all the fields of science and technology, particularly the food packaging industry. Accordingly, some nanoparticles can be used in food contact materials to preserve food products for longer periods. To date, many inorganic and metal nanoparticles have been implemented to synthesize active food packaging materials and to extend the shelf-life of foods. Packaging with nanocomposites containing these nanoparticles offers advantages, such as reduction in the usage of preservatives and higher rate of reactions to inhibit the microbial growth. Nevertheless, the safety issues of employing the metal and inorganic nanoparticles in food packaging are still a major concern and more studies along with clinical trials need to be carried out prior to the mass production of these promising food containers. In this review, we have evaluated recent studies plus the applications of inorganic and metal nanoparticles mostly in food packaging applications along with their antimicrobial properties and reaction mechanisms. Many examples have been provided with the aim of opening new horizons for researchers to implement inorganic and metal nanoparticles in active food packaging field.

Composite nanoparticles containing rare earth metal and methods of preparation thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kandapallil, Binil Itty Ipe; Krishnan, Lakshmi; Johnson, Francis

The present invention is directed to composite nanoparticles comprising a metal, a rare earth element, and, optionally, a complexing ligand. The invention is also directed to composite nanoparticles having a core-shell structure and to processes for preparation of composite nanoparticles of the invention.

Antimicrobial Polymers with Metal Nanoparticles

PubMed Central

Palza, Humberto

2015-01-01

Metals, such as copper and silver, can be extremely toxic to bacteria at exceptionally low concentrations. Because of this biocidal activity, metals have been widely used as antimicrobial agents in a multitude of applications related with agriculture, healthcare, and the industry in general. Unlike other antimicrobial agents, metals are stable under conditions currently found in the industry allowing their use as additives. Today these metal based additives are found as: particles, ions absorbed/exchanged in different carriers, salts, hybrid structures, etc. One recent route to further extend the antimicrobial applications of these metals is by their incorporation as nanoparticles into polymer matrices. These polymer/metal nanocomposites can be prepared by several routes such as in situ synthesis of the nanoparticle within a hydrogel or direct addition of the metal nanofiller into a thermoplastic matrix. The objective of the present review is to show examples of polymer/metal composites designed to have antimicrobial activities, with a special focus on copper and silver metal nanoparticles and their mechanisms. PMID:25607734

Sol–gel synthesis of SnO{sub 2}–MgO nanoparticles and their photocatalytic activity towards methylene blue degradation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bayal, Nisha; Jeevanandam, P., E-mail: jeevafcy@iitr.ernet.in

2013-10-15

Graphical abstract: - Highlights: • A simple sol–gel method for the synthesis of SnO{sub 2}–MgO nanoparticles is reported. • Band gap of SnO{sub 2} can be tuned by varying the magnesium content in SnO{sub 2}–MgO. • SnO{sub 2}–MgO shows good photocatalytic activity towards degradation of methylene blue. - Abstract: SnO{sub 2}–MgO mixed metal oxide nanoparticles were prepared by a simple sol–gel method. The nanoparticles were characterized by power X-ray diffraction, scanning electron microscopy coupled with energy dispersive X-ray analysis, transmission electron microscopy and UV–vis diffuse reflectance spectroscopy. The XRD results indicate the formation of mixed metal oxide nanoparticles and alsomore » a decrease of SnO{sub 2} crystallite size in the mixed metal oxide nanoparticles with increasing magnesium oxide content. The reflectance spectroscopy results show a blue shift of the band gap of SnO{sub 2} in the mixed metal oxide nanoparticles. The photocatalytic activity of the SnO{sub 2}–MgO nanoparticles was tested using the photodegradation of aqueous methylene blue in the presence of sunlight. The results indicate that the mixed metal oxide nanoparticles possess higher efficiency for the photodegradation of methylene blue compared to pure SnO{sub 2} nanoparticles.« less

Hydrazine-Free Solution-Deposited CuIn(S,Se)2 Solar Cells by Spray Deposition of Metal Chalcogenides.

PubMed

Arnou, Panagiota; van Hest, Maikel F A M; Cooper, Carl S; Malkov, Andrei V; Walls, John M; Bowers, Jake W

2016-05-18

Solution processing of semiconductors, such as CuInSe2 and its alloys (CIGS), can significantly reduce the manufacturing costs of thin film solar cells. Despite the recent success of solution deposition approaches for CIGS, toxic reagents such as hydrazine are usually involved, which introduce health and safety concerns. Here, we present a simple and safer methodology for the preparation of high-quality CuIn(S, Se)2 absorbers from metal sulfide solutions in a diamine/dithiol mixture. The solutions are sprayed in air, using a chromatography atomizer, followed by a postdeposition selenization step. Two different selenization methods are explored resulting in power conversion efficiencies of up to 8%.

Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Bailey, S. G.; McNatt, J. S.; Chandrashekhar, M. V. S.; Harris, J. D.; Rusch, A. W.; Nogales, K. A.; Goettsche, K.V.; Hanson, W.; Amos, D.;

Novel Materials, Processing, and Device Technologies for Space Exploration with Potential Dual-Use Applications

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Bailey, S. G.; McNatt, J. S.; Chandrashekhar, M. V. S.; Harris, J. D.; Rusch, A. W.; Nogales, K. A.; Goettsche, K. V.; Hanson, W.; Amos, D.;

Virus templated metallic nanoparticles

NASA Astrophysics Data System (ADS)

Aljabali, Alaa A. A.; Barclay, J. Elaine; Lomonossoff, George P.; Evans, David J.

2010-12-01

Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron.Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron. Electronic supplementary information (ESI) available: Additional experimental detail, agarose gel electrophoresis results, energy dispersive X-ray spectra, ζ-potential measurements, dynamic light scattering data, nanoparticle tracking analysis and an atomic force microscopy image of Ni-CPMV. See DOI: 10.1039/c0nr00525h

Temperature and size-dependent Hamaker constants for metal nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, K.; Pinchuk, P.

2016-08-01

Theoretical values of the Hamaker constant have been calculated for metal nanoparticles using Lifshitz theory. The theory describes the Hamaker constant in terms of the permittivity of the interacting bodies. Metal nanoparticles exhibit an internal size effect that alters the dielectric permittivity of the particle when its size falls below the mean free path of the conducting electrons. This size dependence of the permittivity leads to size-dependence of the Hamaker constant for metal nanoparticles. Additionally, the electron damping and the plasma frequency used to model the permittivity of the particle exhibit temperature-dependence, which lead to temperature dependence of the Hamaker constant. In this work, both the size and temperature dependence for gold, silver, copper, and aluminum nanoparticles is demonstrated. The results of this study might be of interest for studying the colloidal stability of nanoparticles in solution.

Temperature and size-dependent Hamaker constants for metal nanoparticles.

PubMed

Jiang, K; Pinchuk, P

2016-08-26

Theoretical values of the Hamaker constant have been calculated for metal nanoparticles using Lifshitz theory. The theory describes the Hamaker constant in terms of the permittivity of the interacting bodies. Metal nanoparticles exhibit an internal size effect that alters the dielectric permittivity of the particle when its size falls below the mean free path of the conducting electrons. This size dependence of the permittivity leads to size-dependence of the Hamaker constant for metal nanoparticles. Additionally, the electron damping and the plasma frequency used to model the permittivity of the particle exhibit temperature-dependence, which lead to temperature dependence of the Hamaker constant. In this work, both the size and temperature dependence for gold, silver, copper, and aluminum nanoparticles is demonstrated. The results of this study might be of interest for studying the colloidal stability of nanoparticles in solution.

Enhanced Radiofrequency Ablation With Magnetically Directed Metallic Nanoparticles.

PubMed

Nguyen, Duy T; Tzou, Wendy S; Zheng, Lijun; Barham, Waseem; Schuller, Joseph L; Shillinglaw, Benjamin; Quaife, Robert A; Sauer, William H

2016-05-01

Remote heating of metal located near a radiofrequency ablation source has been previously demonstrated. Therefore, ablation of cardiac tissue treated with metallic nanoparticles may improve local radiofrequency heating and lead to larger ablation lesions. We sought to evaluate the effect of magnetic nanoparticles on tissue sensitivity to radiofrequency energy. Ablation was performed using an ablation catheter positioned with 10 g of force over prepared ex vivo specimens. Tissue temperatures were measured and lesion volumes were acquired. An in vivo porcine thigh model was used to study systemically delivered magnetically guided iron oxide (FeO) nanoparticles during radiofrequency application. Magnetic resonance imaging and histological staining of ablated tissue were subsequently performed as a part of ablation lesion analysis. Ablation of ex vivo myocardial tissue treated with metallic nanoparticles resulted in significantly larger lesions with greater impedance changes and evidence of increased thermal conductivity within the tissue. Magnet-guided localization of FeO nanoparticles within porcine thigh preps was demonstrated by magnetic resonance imaging and iron staining. Irrigated ablation in the regions with greater FeO, after FeO infusion and magnetic guidance, created larger lesions without a greater incidence of steam pops. Metal nanoparticle infiltration resulted in significantly larger ablation lesions with altered electric and thermal conductivity. In vivo magnetic guidance of FeO nanoparticles allowed for facilitated radiofrequency ablation without direct infiltration into the targeted tissue. Further research is needed to assess the clinical applicability of this ablation strategy using metallic nanoparticles for the treatment of cardiac arrhythmias. © 2016 American Heart Association, Inc.

In situ Synthesis of Metal Nanoparticle Embedded Free Standing Multifunctional PDMS Films.

PubMed

Goyal, Anubha; Kumar, Ashavani; Patra, Prabir K; Mahendra, Shaily; Tabatabaei, Salomeh; Alvarez, Pedro J J; John, George; Ajayan, Pulickel M

2009-07-01

We demonstrate a simple one-step method for synthesizing noble metal nanoparticle embedded free standing polydimethylsiloxane (PDMS) composite films. The process involves preparing a homogenous mixture of metal salt (silver, gold and platinum), silicone elastomer and the curing agent (hardener) followed by curing. During the curing process, the hardener crosslinks the elastomer and simultaneously reduces the metal salt to form nanoparticles. This in situ method avoids the use of any external reducing agent/stabilizing agent and leads to a uniform distribution of nanoparticles in the PDMS matrix. The films were characterized using UV-Vis spectroscopy, transmission electron microscopy and X-ray photoemission spectroscopy. The nanoparticle-PDMS films have a higher Young's modulus than pure PDMS films and also show enhanced antibacterial properties. The metal nanoparticle-PDMS films could be used for a number of applications such as for catalysis, optical and biomedical devices and gas separation membranes. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

GO-Cu7S4 catalyzed ortho-aminomethylation of phenol derivatives with N,N-dimethylbenzylamines: site-selective oxidative CDC.

PubMed

Gupta, Sonu; Chandna, Nisha; Dubey, Pooja; Singh, Ajai K; Jain, Nidhi

2018-06-21

Copper chalcogenide nanoparticles (Cu7S4) supported on graphene oxide (GO) have been synthesized for the first time from Cu2S, and used as highly efficient heterogeneous catalysts for oxidative ortho-selective C-H aminomethylation of phenols with N,N-dimethylbenzylamines. The NPs (30-80 nm) have been characterized by HRTEM, SEM-EDX, PXRD, FTIR, Raman, ICP-AES and XPS analyses. The NP catalyzed sp2-sp3 cross dehydrogenative coupling (CDC) features a broad substrate scope, excellent functional group tolerance, high yields, use of an inexpensive and reusable copper catalyst, mild conditions, and no need for pre-functionalization of substrates.

General rules for incorporating noble metal nanoparticles in organic solar cells

NASA Astrophysics Data System (ADS)

Ciesielski, A.; Switlik, D.; Szoplik, T.

2017-05-01

Over the recent years, the influence of the addition of noble metal nanoparticles (Au, Ag, Al, Cu) into the bulk heterojunction (BHJ) solar cells on their efficiency of visible sunlight absorption has been excessively studied. However, several detailed studies were focused on compounds with similar chemical structure, and thus similar optical and electric properties. Such approach provides little help when it comes to admixing metallic nanoparticles into new compound families with different properties. Moreover, theoretical approaches frequently tend to neglect the fact, that nanoparticles have different dispersion relation than bulk material, which may lead to false conclusions. In this work, we consider additional dispersion modes in the metal permittivity due to finite size of the nanoparticles. We use Maxwell-Garnet effective medium approach (EMA), combined with the transfer matrix method, as well as finite-difference time-domain (FDTD) simulations, to create a set of general rules for incorporating noble metal nanoparticles into the active layer. These principles, based on assumed basic properties of the active layer (e.g. real and imaginary part of refractive index, thickness) provide optimal material, size spectrum and fill factor of nanoparticle inclusions in order to ensure the best absorption enhancement. Our results show, that the optimal concentrations for silver nanoparticles are about 50% greater than those determined without taking into account additional components in the permittivity of the metal.

Chalcogenide phase-change thin films used as grayscale photolithography materials.

PubMed

Wang, Rui; Wei, Jingsong; Fan, Yongtao

2014-03-10

Chalcogenide phase-change thin films are used in many fields, such as optical information storage and solid-state memory. In this work, we present another application of chalcogenide phase-change thin films, i.e., as grayscale photolithgraphy materials. The grayscale patterns can be directly inscribed on the chalcogenide phase-change thin films by a single process through direct laser writing method. In grayscale photolithography, the laser pulse can induce the formation of bump structure, and the bump height and size can be precisely controlled by changing laser energy. Bumps with different height and size present different optical reflection and transmission spectra, leading to the different gray levels. For example, the continuous-tone grayscale images of lifelike bird and cat are successfully inscribed onto Sb(2)Te(3) chalcogenide phase-change thin films using a home-built laser direct writer, where the expression and appearance of the lifelike bird and cat are fully presented. This work provides a way to fabricate complicated grayscale patterns using laser-induced bump structures onto chalcogenide phase-change thin films, different from current techniques such as photolithography, electron beam lithography, and focused ion beam lithography. The ability to form grayscale patterns of chalcogenide phase-change thin films reveals many potential applications in high-resolution optical images for micro/nano image storage, microartworks, and grayscale photomasks.

Can microbes mediate nano-transformation?

NASA Astrophysics Data System (ADS)

Prasad, K.; Jha, Anal K.; Prasad, Kamlesh; Kulkarni, A. R.

2010-10-01

A green low-cost and reproducible microbe ( Lactobacillus) and baker's yeast ( Saccharomyces cerevisiae) mediated biosynthesis of metallic and oxide nanoparticles are reported. Silver and copper oxide nanoparticles are synthesized using Lactobacillus sp. and Saccharomyces cerevisiae. The synthesis is performed akin to room temperature in the laboratory ambience. X-ray and transmission electron microscopy analyses are performed to ascertain the formation of metallic and oxide nanoparticles. Individual nanoparticles having the dimensions of 2-6 nm (metallic) and 10-20 nm (oxide) are found. A possible mechanism involved for the synthesis of metallic and oxide nanoparticles has also been proposed in which pH as well as the partial pressure of gaseous hydrogen (r-H2) or redox potential of the culture solution seem to play an important role in the process.

Ion-barrier for memristors/ReRAM and methods thereof

DOEpatents

Haase, Gad S.

2017-11-28

The present invention relates to memristive devices including a resistance-switching element and a barrier element. In particular examples, the barrier element is a monolayer of a transition metal chalcogenide that sufficiently inhibits diffusion of oxygen atoms or ions out of the switching element. As the location of these atoms and ions determine the state of the device, inhibiting diffusion would provide enhanced state retention and device reliability. Other types of barrier elements, as well as methods for forming such elements, are described herein.

The role of interfacial metal silicates on the magnetism in FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desautels, R. D., E-mail: rddesautels@physics.umanitoba.ca; Toyota Research Institute of North America, Ann Arbor, Michigan 48169; Freeland, J. W.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, andmore » vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO{sub 2}-based interfacial shell.« less

Phytosynthesis of nanoparticles: concept, controversy and application

PubMed Central

2014-01-01

Nanotechnology is an exciting and powerful discipline of science; the altered properties of which have offered many new and profitable products and applications. Agriculture, food and medicine sector industries have been investing more in nanotechnology research. Plants or their extracts provide a biological synthesis route of several metallic nanoparticles which is more eco-friendly and allows a controlled synthesis with well-defined size and shape. The rapid drug delivery in the presence of a carrier is a recent development to treat patients with nanoparticles of certain metals. The engineered nanoparticles are more useful in increasing the crop production, although this issue is still in infancy. This is simply due to the unprecedented and unforeseen health hazard and environmental concern. The well-known metal ions such as zinc, iron and copper are essential constituents of several enzymes found in the human system even though the indiscriminate use of similar other metal nanoparticle in food and medicine without clinical trial is not advisable. This review is intended to describe the novel phytosynthesis of metal and metal oxide nanoparticles with regard to their shape, size, structure and diverse application in almost all fields of medicine, agriculture and technology. We have also emphasized the concept and controversial mechanism of green synthesis of nanoparticles. PMID:24910577

Phytosynthesis of nanoparticles: concept, controversy and application

NASA Astrophysics Data System (ADS)

Husen, Azamal; Siddiqi, Khwaja Salahuddin

2014-05-01

Nanotechnology is an exciting and powerful discipline of science; the altered properties of which have offered many new and profitable products and applications. Agriculture, food and medicine sector industries have been investing more in nanotechnology research. Plants or their extracts provide a biological synthesis route of several metallic nanoparticles which is more eco-friendly and allows a controlled synthesis with well-defined size and shape. The rapid drug delivery in the presence of a carrier is a recent development to treat patients with nanoparticles of certain metals. The engineered nanoparticles are more useful in increasing the crop production, although this issue is still in infancy. This is simply due to the unprecedented and unforeseen health hazard and environmental concern. The well-known metal ions such as zinc, iron and copper are essential constituents of several enzymes found in the human system even though the indiscriminate use of similar other metal nanoparticle in food and medicine without clinical trial is not advisable. This review is intended to describe the novel phytosynthesis of metal and metal oxide nanoparticles with regard to their shape, size, structure and diverse application in almost all fields of medicine, agriculture and technology. We have also emphasized the concept and controversial mechanism of green synthesis of nanoparticles.

Microbially-mediated method for synthesis of non-oxide semiconductor nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phelps, Tommy J.; Lauf, Robert J.; Moon, Ji-Won

The invention is directed to a method for producing non-oxide semiconductor nanoparticles, the method comprising: (a) subjecting a combination of reaction components to conditions conducive to microbially-mediated formation of non-oxide semiconductor nanoparticles, wherein said combination of reaction components comprises i) anaerobic microbes, ii) a culture medium suitable for sustaining said anaerobic microbes, iii) a metal component comprising at least one type of metal ion, iv) a non-metal component comprising at least one non-metal selected from the group consisting of S, Se, Te, and As, and v) one or more electron donors that provide donatable electrons to said anaerobic microbes duringmore » consumption of the electron donor by said anaerobic microbes; and (b) isolating said non-oxide semiconductor nanoparticles, which contain at least one of said metal ions and at least one of said non-metals. The invention is also directed to non-oxide semiconductor nanoparticle compositions produced as above and having distinctive properties.« less

A review on radiation-induced nucleation and growth of colloidal metallic nanoparticles

PubMed Central

2013-01-01

This review presents an introduction to the synthesis of metallic nanoparticles by radiation-induced method, especially gamma irradiation. This method offers some benefits over the conventional methods because it provides fully reduced and highly pure nanoparticles free from by-products or chemical reducing agents, and is capable of controlling the particle size and structure. The nucleation and growth mechanism of metallic nanoparticles are also discussed. The competition between nucleation and growth process in the formation of nanoparticles can determine the size of nanoparticles which is influenced by certain parameters such as the choice of solvents and stabilizer, the precursor to stabilizer ratio, pH during synthesis, and absorbed dose. PMID:24225302

Metal nanoparticles (other than gold or silver) prepared using plant extracts for medical applications

NASA Astrophysics Data System (ADS)

Pasca, Roxana-Diana; Santa, Szabolcs; Racz, Levente Zsolt; Racz, Csaba Pal

2016-12-01

There are many modalities to prepare metal nanoparticles, but the reducing of the metal ions with plant extracts is one of the most promising because it is considerate less toxic for the environment, suitable for the use of those nanoparticles in vivo and not very expensive. Various metal ions have been already studied such as: cobalt, copper, iron, platinum, palladium, zinc, indium, manganese and mercury and the number of plant extracts used is continuously increasing. The prepared systems were characterized afterwards with a great number of methods of investigation: both spectroscopic (especially UV-Vis spectroscopy) and microscopic (in principal, electron microscopy-TEM) methods. The applications of the metal nanoparticles obtained are diverse and not completely known, but the medical applications of such nanoparticles occupy a central place, due to their nontoxic components, but some diverse industrial applications do not have to be forgotten.

K(2)MM'(3)Se(6) (M = Cu, Ag; M' = Ga, In), A new series of metal chalcogenides with chain-sublayer-chain slabs: (infinity)(1)[M'Se(4)]-(infinity)(2)[(MSe(4))(M'Se(4))]-(infinity)(1)[M'Se(4)].

PubMed

Ma, Hong-Wei; Guo, Guo-Cong; Wang, Ming-Sheng; Zhou, Guo-Wei; Lin, Shan-Hou; Dong, Zhen-Chao; Huang, Jin-Shun

2003-02-24

A new series of novel isostructural metal chalcogenides, K(2)CuIn(3)Se(6) (1), K(2)CuGa(3)Se(6) (2), and K(2)AgIn(3)Se(6) (3), were obtained by a reactive flux technique and structurally characterized. Compounds 1, 2, and 3 crystallize in the space group C2/c of the monoclinic system with eight formula units in a cell: a = 11.445(2) A, b = 11.495(2) A, c = 21.263(4) A, beta = 97.68(3) degrees, V = 2772(1) A(3), R1/wR2 = 0.0676/0.1652 for 1; a = 11.031(2) A, b = 11.050(4) A, c = 20.808(7) A, beta = 97.71(2) degrees, V = 2513(1) A(3), R1/wR2 = 0.0301/0.0511 for 2; and a = 11.633(1) A, b = 11.587(1) A, c = 21.355(1) A, beta = 98.010(8) degrees, V = 2850.4(4) A(3), R1/wR2 = 0.0471/0.0732 for 3. These isostructural compounds are characterized by a chain-sublayer-chain slab structure. The sublayer, composed of alternative corner-sharing mixed-metal tetrahedra, is sandwiched by parallel corner-sharing tetrahedral chains. Optical absorption spectra of compounds 1, 2, and 3 reveal the presence of a sharp optical gap of 1.68, 1.72, and 1.64 eV, respectively, suggesting that these materials are semiconductors and suitable for efficient absorption of solar radiation in solar cell applications. IR spectra show no obvious absorption in the range 800-4000 cm(-)(1).

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

PubMed

Liu, Lichen; Corma, Avelino

2018-05-23

Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

Synthesis of substantially monodispersed colloids

NASA Technical Reports Server (NTRS)

Stoeva, Savka (Inventor); Klabunde, Kenneth J. (Inventor); Sorensen, Christopher (Inventor)

2003-01-01

A method of forming ligated nanoparticles of the formula Y(Z).sub.x where Y is a nanoparticle selected from the group consisting of elemental metals having atomic numbers ranging from 21-34, 39-52, 57-83 and 89-102, all inclusive, the halides, oxides and sulfides of such metals, and the alkali metal and alkaline earth metal halides, and Z represents ligand moieties such as the alkyl thiols. In the method, a first colloidal dispersion is formed made up of nanoparticles solvated in a molar excess of a first solvent (preferably a ketone such as acetone), a second solvent different than the first solvent (preferably an organic aryl solvent such as toluene) and a quantity of ligand moieties; the first solvent is then removed under vacuum and the ligand moieties ligate to the nanoparticles to give a second colloidal dispersion of the ligated nanoparticles solvated in the second solvent. If substantially monodispersed nanoparticles are desired, the second dispersion is subjected to a digestive ripening process. Upon drying, the ligated nanoparticles may form a three-dimensional superlattice structure.

Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and their Influence on Activity and Selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somorjai, Gabor A.; Park, Jeong Y.

2008-02-13

Recent breakthroughs in synthesis in nanosciences have achieved control of size and shapes of nanoparticles that are relevant for catalyst design. In this article, we review the advance of synthesis of nanoparticles, fabrication of two and three dimensional model catalyst system, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles in the 1-10 nm range permitted us to study the influence of composition, structure, and dynamic properties of monodispersed metal nanoparticle on chemical reactivity and selectivity. We review the importance of size and shape of nanoparticles to determine the reaction selectivity in multi-pathmore » reactions. The influence of metal-support interaction has been studied by probing the hot electron flows through the metal-oxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are discussed.« less

Production of Oxidation-Resistant Cu-Based Nanoparticles by Wire Explosion

PubMed Central

Kawamura, Go; Alvarez, Samuel; Stewart, Ian E.; Catenacci, Matthew; Chen, Zuofeng; Ha, Yoon-Cheol

2015-01-01

The low performance or high cost of commercially available conductive inks limits the advancement of printed electronics. This article studies the explosion of metal wires in aqueous solutions as a simple, low-cost, and environmentally friendly method to prepare metallic nanoparticles consisting of Cu and Cu alloys for use in affordable, highly conductive inks. Addition of 0.2 M ascorbic acid to an aqueous explosion medium prevented the formation of Cu2O shells around Cu nanoparticles, and allowed for the printing of conductive lines directly from these nanoparticles with no post-treatment. Cu alloy nanoparticles were generated from metal wires that were alloyed as purchased, or from two wires of different metals that were twisted together. Cu nanoparticles alloyed with 1% Sn, 5% Ag, 5% Ni and 30% Ni had electrical conductivities similar to Cu but unlike Cu, remained conductive after 24 hrs at 85 °C and 85% RH. PMID:26669447

Coaxial lithography

NASA Astrophysics Data System (ADS)

Ozel, Tuncay; Bourret, Gilles R.; Mirkin, Chad A.

2015-05-01

The optical and electrical properties of heterogeneous nanowires are profoundly related to their composition and nanoscale architecture. However, the intrinsic constraints of conventional synthetic and lithographic techniques have limited the types of multi-compositional nanowire that can be created and studied in the laboratory. Here, we report a high-throughput technique that can be used to prepare coaxial nanowires with sub-10 nm control over the architectural parameters in both axial and radial dimensions. The method, termed coaxial lithography (COAL), relies on templated electrochemical synthesis and can create coaxial nanowires composed of combinations of metals, metal oxides, metal chalcogenides and conjugated polymers. To illustrate the possibilities of the technique, a core/shell semiconductor nanowire with an embedded plasmonic nanoring was synthesized—a structure that cannot be prepared by any previously known method—and its plasmon-excitation-dependent optoelectronic properties were characterized.

Density Functional Theory and Beyond for Band-Gap Screening: Performance for Transition-Metal Oxides and Dichalcogenides.

PubMed

Li, Wenqing; Walther, Christian F J; Kuc, Agnieszka; Heine, Thomas

2013-07-09

The performance of a wide variety of commonly used density functionals, as well as two screened hybrid functionals (HSE06 and TB-mBJ), on predicting electronic structures of a large class of en vogue materials, such as metal oxides, chalcogenides, and nitrides, is discussed in terms of band gaps, band structures, and projected electronic densities of states. Contrary to GGA, hybrid functionals and GGA+U, both HSE06 and TB-mBJ are able to predict band gaps with an appreciable accuracy of 25% and thus allow the screening of various classes of transition-metal-based compounds, i.e., mixed or doped materials, at modest computational cost. The calculated electronic structures are largely unaffected by the choice of basis functions and software implementation, however, might be subject to the treatment of the core electrons.

Modeling of absorption and scattering properties of core -shell nanoparticles for application as nanoantenna in optical domain

NASA Astrophysics Data System (ADS)

Devi, Jutika; Saikia, Rashmi; Datta, Pranayee

2016-10-01

The present paper describes the study of core-shell nanoparticles for application as nanoantenna in the optical domain. To obtain the absorption and extinction efficiencies as well as the angular distribution of the far field radiation pattern and the resonance wavelengths for these metal-dielectric, dielectric-metal and metal-metal core-shell nanoparticles in optical domain, we have used Finite Element Method based COMSOL Multiphysics Software and Mie Theory. From the comparative study of the extinction efficiencies of core-shell nanoparticles of different materials, it is found that for silica - gold core - shell nanoparticles, the resonant wavelength is greater than that of the gold - silver, silver-gold and gold-silica core - shell nanoparticles and also the radiation pattern of the silica-gold core-shell nanoparticle is the most suitable one from the point of view of directivity. The dielectric functions of the core and shell material as well as of the embedded matrix are extremely important and plays a very major role to tune the directivity and resonance wavelength. Such highly controllable parameters of the dielectric - metal core - shell nanoparticles make them suitable for efficient coupling of optical radiation into nanoscale structures for a broad range of applications in the field of communications.

Control of Partial Coalescence of Self-Assembled Metal Nano-Particles across Lyotropic Liquid Crystals Templates towards Long Range Meso-Porous Metal Frameworks Design

PubMed Central

Dumée, Ludovic F.; Lemoine, Jean-Baptiste; Ancel, Alice; Hameed, Nishar; He, Li; Kong, Lingxue

2015-01-01

The formation of purely metallic meso-porous metal thin films by partial interface coalescence of self-assembled metal nano-particles across aqueous solutions of Pluronics triblock lyotropic liquid crystals is demonstrated for the first time. Small angle X-ray scattering was used to study the influence of the thin film composition and processing conditions on the ordered structures. The structural characteristics of the meso-structures formed demonstrated to primarily rely on the lyotropic liquid crystal properties while the nature of the metal nano-particles used as well as the their diameters were found to affect the ordered structure formation. The impact of the annealing temperature on the nano-particle coalescence and efficiency at removing the templating lyotropic liquid crystals was also analysed. It is demonstrated that the lyotropic liquid crystal is rendered slightly less thermally stable, upon mixing with metal nano-particles and that low annealing temperatures are sufficient to form purely metallic frameworks with average pore size distributions smaller than 500 nm and porosity around 45% with potential application in sensing, catalysis, nanoscale heat exchange, and molecular separation. PMID:28347094

Low-temperature nanosolders

DOEpatents

Boyle, Timothy J.; Lu, Ping; Vianco, Paul T.; Chandross, Michael E.

2016-10-11

A nanosolder comprises a first metal nanoparticle core coated with a second metal shell, wherein the first metal has a higher surface energy and smaller atomic size than the second metal. For example, a bimetallic nanosolder can comprise a protective Ag shell "glued" around a reactive Cu nanoparticle. As an example, a 3-D epitaxial Cu-core and Ag-shell structure was generated from a mixture of copper and silver nanoparticles in toluene at temperatures as low as 150.degree. C.

Nanoparticle enhanced ionic liquid heat transfer fluids

DOEpatents

Fox, Elise B.; Visser, Ann E.; Bridges, Nicholas J.; Gray, Joshua R.; Garcia-Diaz, Brenda L.

2014-08-12

A heat transfer fluid created from nanoparticles that are dispersed into an ionic liquid is provided. Small volumes of nanoparticles are created from e.g., metals or metal oxides and/or alloys of such materials are dispersed into ionic liquids to create a heat transfer fluid. The nanoparticles can be dispersed directly into the ionic liquid during nanoparticle formation or the nanoparticles can be formed and then, in a subsequent step, dispersed into the ionic liquid using e.g., agitation.

Liquid metal/metal oxide frameworks with incorporated Ga2O3 for photocatalysis.

PubMed

Zhang, Wei; Naidu, Boddu S; Ou, Jian Zhen; O'Mullane, Anthony P; Chrimes, Adam F; Carey, Benjamin J; Wang, Yichao; Tang, Shi-Yang; Sivan, Vijay; Mitchell, Arnan; Bhargava, Suresh K; Kalantar-Zadeh, Kourosh

2015-01-28

Solvothermally synthesized Ga2O3 nanoparticles are incorporated into liquid metal/metal oxide (LM/MO) frameworks in order to form enhanced photocatalytic systems. The LM/MO frameworks, both with and without incorporated Ga2O3 nanoparticles, show photocatalytic activity due to a plasmonic effect where performance is related to the loading of Ga2O3 nanoparticles. Optimum photocatalytic efficiency is obtained with 1 wt % incorporation of Ga2O3 nanoparticles. This can be attributed to the sub-bandgap states of LM/MO frameworks, contributing to pseudo-ohmic contacts which reduce the free carrier injection barrier to Ga2O3.

Determining the composition of gold nanoparticles: a compilation of shapes, sizes, and calculations using geometric considerations.

PubMed

Mori, Taizo; Hegmann, Torsten

2016-01-01

Size, shape, overall composition, and surface functionality largely determine the properties and applications of metal nanoparticles. Aside from well-defined metal clusters, their composition is often estimated assuming a quasi-spherical shape of the nanoparticle core. With decreasing diameter of the assumed circumscribed sphere, particularly in the range of only a few nanometers, the estimated nanoparticle composition increasingly deviates from the real composition, leading to significant discrepancies between anticipated and experimentally observed composition, properties, and characteristics. We here assembled a compendium of tables, models, and equations for thiol-protected gold nanoparticles that will allow experimental scientists to more accurately estimate the composition of their gold nanoparticles using TEM image analysis data. The estimates obtained from following the routines described here will then serve as a guide for further analytical characterization of as-synthesized gold nanoparticles by other bulk (thermal, structural, chemical, and compositional) and surface characterization techniques. While the tables, models, and equations are dedicated to gold nanoparticles, the composition of other metal nanoparticle cores with face-centered cubic lattices can easily be estimated simply by substituting the value for the radius of the metal atom of interest.

Facile synthesis of Curcuma longa tuber powder engineered metal nanoparticles for bioimaging applications

NASA Astrophysics Data System (ADS)

Sankar, Renu; Rahman, Pattanathu K. S. M.; Varunkumar, Krishnamoorthy; Anusha, Chidambaram; Kalaiarasi, Arunachalam; Shivashangari, Kanchi Subramanian; Ravikumar, Vilwanathan

2017-02-01

Nanomaterials based fluorescent agents are rapidly becoming significant and promising transformative tools for improving medical diagnostics for extensive in vivo imaging modalities. Compared with conventional fluorescent agents, nano-fluorescence has capabilities to improve the in vivo detection and enriched targeting efficiencies. In our laboratory we synthesized fluorescent metal nanoparticles of silver, copper and iron using Curcuma longa tuber powder by simple reduction. The physicochemical properties of the synthesized metal nanoparticles were attained using UV-visible spectrophotometry, scanning electron microscopy with EDAX spectroscopy, dynamic light scattering, Fourier-transform infrared spectroscopy and X-ray diffraction. The Curcuma longa tuber powder has one of the bioactive compound Curcumin might act as a capping agent during the synthesis of nanoparticles. The synthesized metal nanoparticles fluorescence property was confirmed by spectrofluorometry. When compared with copper and iron nanoparticles the silver nanoparticles showed high fluorescence intensity under spectrofluorometry. Moreover, in vitro cell images of the silver nanoparticles in A549 cell lines also correlated with the results of spectrofluorometry. These silver nanoparticles show inspiring cell-imaging applications. They enter into cells without any further modifications, and the fluorescence property can be utilized for fluorescence-based cell imaging applications.

Microscopic Electron Dynamics in Metal Nanoparticles for Photovoltaic Systems.

PubMed

Kluczyk, Katarzyna; Jacak, Lucjan; Jacak, Witold; David, Christin

2018-06-25

Nanoparticles—regularly patterned or randomly dispersed—are a key ingredient for emerging technologies in photonics. Of particular interest are scattering and field enhancement effects of metal nanoparticles for energy harvesting and converting systems. An often neglected aspect in the modeling of nanoparticles are light interaction effects at the ultimate nanoscale beyond classical electrodynamics. Those arise from microscopic electron dynamics in confined systems, the accelerated motion in the plasmon oscillation and the quantum nature of the free electron gas in metals, such as Coulomb repulsion and electron diffusion. We give a detailed account on free electron phenomena in metal nanoparticles and discuss analytic expressions stemming from microscopic (Random Phase Approximation—RPA) and semi-classical (hydrodynamic) theories. These can be incorporated into standard computational schemes to produce more reliable results on the optical properties of metal nanoparticles. We combine these solutions into a single framework and study systematically their joint impact on isolated Au, Ag, and Al nanoparticles as well as dimer structures. The spectral position of the plasmon resonance and its broadening as well as local field enhancement show an intriguing dependence on the particle size due to the relevance of additional damping channels.

Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT

DOEpatents

McCormick, III., Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

2006-11-21

A new, facile, general one-phase method of generating thio-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the stops of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

DOEpatents

McCormick, III, Charles L.; Lowe, Andrew B [Hattiesburg, MS; Sumerlin, Brent S [Pittsburgh, PA

2011-12-27

A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Bioinspired metal-cell wall-metal sandwich structure on an individual bacterial cell scaffold.

PubMed

Zhang, Xiaoliang; Yu, Mei; Liu, Jianhua; Li, Songmei

2012-08-25

Pd nanoparticles were introduced to individual Bacillus cells and dispersedly anchored on both the inside and outside of the cell walls. The anchored nanoparticles served as "seeds" to drive the formation of double metallic layers forming a metal-cell wall-metal sandwich structure at the single-cell level.

Gene transcription patterns and energy reserves in Daphnia magna show no nanoparticle specific toxicity when exposed to ZnO and CuO nanoparticles.

PubMed

Adam, Nathalie; Vergauwen, Lucia; Blust, Ronny; Knapen, Dries

2015-04-01

There is still a lot of contradiction on whether metal ions are solely responsible for the observed toxicity of ZnO and CuO nanoparticles to aquatic species. While most experiments have studied nanoparticle effects at organismal levels (e.g. mortality, reproduction), effects at lower levels of biological organization may clarify the role of metal ions, nanoparticles and nanoparticle aggregates. In this study, the effect of ZnO and CuO nanoparticles was tested at two lower levels: energy reserves and gene transcription and compared with zinc and copper salts. Daphnia magna was exposed during 96h to 10% immobilization concentrations of all chemicals, after which daphnids were sampled for determination of glycogen, lipid and protein concentration and for a differential gene transcription analysis using microarray. The dissolved, nanoparticle and aggregated fraction in the medium was characterized. The results showed that ZnO nanoparticles had largely dissolved directly after addition to the test medium. The CuO nanoparticles mostly formed aggregates, while only a small fraction dissolved. The exposure to zinc (both nano and metal salt) had no effect on the available energy reserves. However, in the copper exposure, the glycogen, lipid and protein concentration in the exposed daphnids was lower than in the unexposed ones. When comparing the nanoparticle (ZnO or CuO) exposed daphnids to the metal salt (zinc or copper salt) exposed daphnids, the microarray results showed no significantly differentially transcribed gene fragments. The results indicate that under the current exposure conditions the toxicity of ZnO and CuO nanoparticles to D. magna is solely caused by toxic metal ions. Copyright © 2015 Elsevier Inc. All rights reserved.

Hybrid nanocatalysts containing enzymes and metallic nanoparticles for ethanol/O2 biofuel cell

NASA Astrophysics Data System (ADS)

Aquino Neto, S.; Almeida, T. S.; Palma, L. M.; Minteer, S. D.; de Andrade, A. R.

2014-08-01

We report the preparation of hybrid nanostructured bioanodes containing the enzyme alcohol dehydrogenase (ADH) with either Au, Pt, or Pt0.75Sn0.25 nanoparticles for use in ethanol/O2 hybrid biofuel cells. We describe two different methodologies for the preparation of the bioanodes: in a first case, multi walled carbon nanotubes (MWCNTs) were employed as a support for the metallic nanoparticles and TBAB-modified Nafion® aided enzyme immobilization. In the second case, we immobilized the enzymes using dendrimers-encapsulated nanoparticles as the agent for enzyme anchoring. The biofuel cell tests showed that the addition of metallic nanoparticles to the bioanode structure enhanced the overall biofuel cell performance. The bioelectrode containing Au nanoparticles displaying the best performance, with an open circuit potential of 0.61 ± 0.05 V and a maximum power density of 155 ± 11 μW cm-2. NADH cyclic voltammetric experiments indicated that Au nanoparticles behaved as a catalyst toward NADH oxidation. Comparing the two protocols we used to synthetized nanoparticles, the sample containing the Au nanoparticles supported on MWCNTs furnished fourfold higher values. Therefore, from the satisfactory results obtained, it can be inferred that the combination of small amounts of metallic nanoparticles with enzymes improve bioanode performance.

Physicochemical model of detonation synthesis of nanoparticles from metal carboxylates

NASA Astrophysics Data System (ADS)

Tolochko, B. P.; Chernyshev, A. P.; Ten, K. A.; Pruuel, E. R.; Zhogin, I. L.; Zubkov, P. I.; Lyakhov, N. Z.; Luk'yanchikov, L. A.; Sheromov, M. A.

2008-02-01

We have shown previously that when metal carboxylates are subjected to a shock-wave action, diamond nanoparticles and nanoparticles of metals (Ag, Bi, Co, Fe, Pb) are formed and their characteristic size is about 30-200 Å. The metal nanoparticles formed are covered by an amorphous-carbon layer up to 20 Å thick. In this work we put forward a physicochemical model of the formation of diamond and metal nanoparticles from metal carboxylates upon shock-wave action. The energy released upon detonation inside the precursor is lower than in regions not occupied by the stearates. The characteristic time of temperature equalization has been estimated to be on the order of ˜10-3 s, which is greater by a factor of ˜103 than the characteristic reaction time. Due to the adiabatic nature of the processes occurring, the typical temperature of a "particle" will be lower than the temperature of the surrounding medium. In the framework of the model suggested, it has been assumed that the growth of metal clusters should occur by the diffusion mechanism; i.e., the "building material" is supplied through diffusion. The calculation using our previous experimental data on the reaction time and average size of metal particles has shown that the diffusion properties of the medium in which the metal nanoparticles are formed are close to those of the liquid state of the substance. The temperature and pressure under detonation conditions markedly exceed the analogous parameters characteristic of experiments on the thermodestruction of metal carboxylates. The small time of existence of the reaction mixture is compensated by the high mobility and concentration of reagents.

Thermally stable nanoparticles on supports

DOEpatents

Roldan Cuenya, Beatriz; Naitabdi, Ahmed R.; Behafarid, Farzad

2012-11-13

An inverse micelle-based method for forming nanoparticles on supports includes dissolving a polymeric material in a solvent to provide a micelle solution. A nanoparticle source is dissolved in the micelle solution. A plurality of micelles having a nanoparticle in their core and an outer polymeric coating layer are formed in the micelle solution. The micelles are applied to a support. The polymeric coating layer is then removed from the micelles to expose the nanoparticles. A supported catalyst includes a nanocrystalline powder, thin film, or single crystal support. Metal nanoparticles having a median size from 0.5 nm to 25 nm, a size distribution having a standard deviation .ltoreq.0.1 of their median size are on or embedded in the support. The plurality of metal nanoparticles are dispersed and in a periodic arrangement. The metal nanoparticles maintain their periodic arrangement and size distribution following heat treatments of at least 1,000.degree. C.

Applications of white rot fungi in bioremediation with nanoparticles and biosynthesis of metallic nanoparticles.

PubMed

He, Kai; Chen, Guiqiu; Zeng, Guangming; Huang, Zhenzhen; Guo, Zhi; Huang, Tiantian; Peng, Min; Shi, Jiangbo; Hu, Liang

2017-06-01

White rot fungi (WRF) are important environmental microorganisms that have been widely applied in many fields. To our knowledge, the application performance of WRF in bioremediation can be greatly improved by the combination with nanotechnology. And the preparation of metallic nanoparticles using WRF is an emerging biosynthesis approach. Understanding the interrelation of WRF and nanoparticles is important to further expand their applications. Thus, this mini-review summarizes the currently related reports mainly from the two different point of views. We highlight that nanoparticles as supports or synergistic agents can enhance the stability and bioremediation performance of WRF in wastewater treatment and the biosynthesis process and conditions of several important metallic nanoparticles by WRF. Furthermore, the potential toxicity of nanoparticles on WRF and challenges encountered are also discussed. Herein, we deem that this mini-review will strengthen the basic knowledge and provide valuable insight for the applications of WRF and nanoparticles.

Method for forming thermally stable nanoparticles on supports

DOEpatents

Roldan Cuenya, Beatriz; Naitabdi, Ahmed R.; Behafarid, Farzad

2013-08-20

An inverse micelle-based method for forming nanoparticles on supports includes dissolving a polymeric material in a solvent to provide a micelle solution. A nanoparticle source is dissolved in the micelle solution. A plurality of micelles having a nanoparticle in their core and an outer polymeric coating layer are formed in the micelle solution. The micelles are applied to a support. The polymeric coating layer is then removed from the micelles to expose the nanoparticles. A supported catalyst includes a nanocrystalline powder, thin film, or single crystal support. Metal nanoparticles having a median size from 0.5 nm to 25 nm, a size distribution having a standard deviation .ltoreq.0.1 of their median size are on or embedded in the support. The plurality of metal nanoparticles are dispersed and in a periodic arrangement. The metal nanoparticles maintain their periodic arrangement and size distribution following heat treatments of at least 1,000.degree. C.

Removal of Metal Nanoparticles Colloidal Solutions by Water Plants

NASA Astrophysics Data System (ADS)

Olkhovych, Olga; Svietlova, Nataliia; Konotop, Yevheniia; Karaushu, Olena; Hrechishkina, Svitlana

2016-11-01

The ability of seven species of aquatic plants ( Elodea canadensis, Najas guadelupensis, Vallisneria spiralis L., Riccia fluitans L., Limnobium laevigatum, Pistia stratiotes L., and Salvinia natans L.) to absorb metal nanoparticles from colloidal solutions was studied. It was established that investigated aquatic plants have a high capacity for removal of metal nanoparticles from aqueous solution (30-100%) which indicates their high phytoremediation potential. Analysis of the water samples content for elements including the mixture of colloidal solutions of metal nanoparticles (Mn, Cu, Zn, Ag + Ag2O) before and after exposure to plants showed no significant differences when using submerged or free-floating hydrophytes so-called pleuston. However, it was found that the presence of submerged hydrophytes in aqueous medium ( E. canadensis, N. guadelupensis, V. spiralis L., and R. fluitans L.) and significant changes in the content of photosynthetic pigments, unlike free-floating hydrophytes ( L. laevigatum, P. stratiotes L., S. natans L.), had occur. Pleuston possesses higher potential for phytoremediation of contaminated water basins polluted by metal nanoparticles. In terms of removal of nanoparticles among studied free-floating hydrophytes, P. stratiotes L. and S. natans L. deserve on special attention.

Enhanced photocatalytic degradation of methylene blue by metal-modified silicon nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brahiti, N., E-mail: dihiabrahiti@yahoo.fr; Université Mouloud MAMMERI de TiziOuzou, Département de Physique, Bastos; Hadjersi, T., E-mail: hadjersi@gmx.com

2015-02-15

Highlights: • SiNWs modified with Pd, Au and Pt were used as photocatalysts to degrade MB. • Yield of photodegardation increases with UV irradiation time. • SiNWs modified with Pd nanoparticles show the best photocatalytic activity. • A degradation of 97% was obtained after 200 min of UV irradiation. - Abstract: Silicon nanowires (SiNWs) modified with Au, Pt and Pd nanoparticles were used as heterogeneous photocatalysts for the photodegradation of methylene blue in water under UV light irradiation. The modification of SiNWs was carried out by deposition of metal nanoparticles using the electroless metal deposition (EMD) technique. The effect ofmore » metal nanoparticles deposition time on the photocatalytic activity was studied. It was found that the photocatalytic activity of modified SiNWs was enhanced when the deposition time of metal nanoparticles was increased. In addition of modified SiNWs with Pt, Au and Pd nanoparticles, oxidized silicon substrate (Ox-Si), oxidized silicon nanowires (Ox-SiNWs) and hydrogen-terminated silicon nanowires (H-SiNWs) were also evaluated for the photodegradation of methylene blue.« less

Enhancement of Thermal Damage to Adenocarcinoma Cells by Iron Nanoparticles Modified with MUC1 Aptamer.

PubMed

Guo, Fangqin; Hu, Yan; Yu, Lianyuan; Deng, Xiaoyuan; Meng, Jie; Wang, Chen; Yang, Xian-Da

2016-03-01

Hyperthermia cancer treatment is an adjunctive therapy that aims at killing the tumor cells with excessive heat that is usually generated by metal contrasts exposed to alternating magnetic field. The efficacy of hyperthermia is often limited by the heat damage to normal tissue due to indiscriminate distribution of the metal contrasts within the body. Tumor-targeting metal contrasts may reduce the toxicity of hyperthermia and improve the efficacy of thermotherapy against cancer. MUC1 is a glycoprotein over expressed in most adenocarcinomas, and represents an attractive therapeutic target. In this study, a MUC1 aptamer is conjugated with iron nanoparticles to construct adenocarcinoma-targeting metal contrasts. DNA hybridization studies confirmed that the aptamers were conjugated to the iron nanoparticles. Importantly, more aptamer-modified nanoparticles attached to the MUC1-positive cancer cells compared with the unmodified nanoparticles. Moreover, aptamer-modified nanoparticles significantly enhanced the targeted hyperthermia damage to MUC1-positive cancer cells in vitro (p < 0.05). The results suggest that MUC1 aptamer-modified metal particles may have potential in development of targeted hyperthermia therapy against adenocarcinomas.

Synthesis of ultrasmall, homogeneously alloyed, bimetallic nanoparticles on silica supports

NASA Astrophysics Data System (ADS)

Wong, A.; Liu, Q.; Griffin, S.; Nicholls, A.; Regalbuto, J. R.

2017-12-01

Supported nanoparticles containing more than one metal have a variety of applications in sensing, catalysis, and biomedicine. Common synthesis techniques for this type of material often result in large, unalloyed nanoparticles that lack the interactions between the two metals that give the particles their desired characteristics. We demonstrate a relatively simple, effective, generalizable method to produce highly dispersed, well-alloyed bimetallic nanoparticles. Ten permutations of noble and base metals (platinum, palladium, copper, nickel, and cobalt) were synthesized with average particle sizes from 0.9 to 1.4 nanometers, with tight size distributions. High-resolution imaging and x-ray analysis confirmed the homogeneity of alloying in these ultrasmall nanoparticles.

Formation and properties of metallic nanoparticles in lithium and sodium fluorides with radiation-induced color centers

NASA Astrophysics Data System (ADS)

Bryukvina, L. I.; Martynovich, E. F.

2012-12-01

The specific features of light- and temperature-induced formation of metallic nanoparticles in γ-irradiated LiF and NaF crystals have been investigated. Atomic force microscope images of nanoparticles of different sizes and in different locations have been presented. The relation between the crystal processing regimes and properties of the nanoparticles formed has been revealed. The optical properties of the processed crystals have been analyzed. The thermo- and light-stimulated processes underlying the formation of metallic nanoparticles in aggregation of the color centers and their decay due to the recovery of the crystal lattice have been studied.

Solution synthesis of metal silicide nanoparticles.

PubMed

McEnaney, Joshua M; Schaak, Raymond E

2015-02-02

Transition-metal silicides are part of an important family of intermetallic compounds, but the high-temperature reactions that are generally required to synthesize them preclude the formation of colloidal nanoparticles. Here, we show that palladium, copper, and nickel nanoparticles react with monophenylsilane in trioctylamine and squalane at 375 °C to form colloidal Pd(2)Si, Cu(3)Si, and Ni(2)Si nanoparticles, respectively. These metal silicide nanoparticles were screened as electrocatalysts for the hydrogen evolution reaction, and Pd(2)Si and Ni(2)Si were identified as active catalysts that require overpotentials of -192 and -243 mV, respectively, to produce cathodic current densities of -10 mA cm(-2).

Environmentally friendly preparation of metal nanoparticles

EPA Science Inventory

The book chapter summarizes the “state of the art” in the exploitation of various environmentally-friendly synthesis approaches, reaction precursors and conditions to manufacture metal and metal oxide nanoparticles for a vast variety of purposes.

Carbon Materials Metal/Metal Oxide Nanoparticle Composite and Battery Anode Composed of the Same

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

2006-01-01

A method of forming a composite material for use as an anode for a lithium-ion battery is disclosed. The steps include selecting a carbon material as a constituent part of the composite, chemically treating the selected carbon material to receive nanoparticles, incorporating nanoparticles into the chemically treated carbon material and removing surface nanoparticles from an outside surface of the carbon material with incorporated nanoparticles. A material making up the nanoparticles alloys with lithium.

From basic physics to mechanisms of toxicity: the "liquid drop" approach applied to develop predictive classification models for toxicity of metal oxide nanoparticles.

PubMed

Sizochenko, Natalia; Rasulev, Bakhtiyor; Gajewicz, Agnieszka; Kuz'min, Victor; Puzyn, Tomasz; Leszczynski, Jerzy

2014-11-21

Many metal oxide nanoparticles are able to cause persistent stress to live organisms, including humans, when discharged to the environment. To understand the mechanism of metal oxide nanoparticles' toxicity and reduce the number of experiments, the development of predictive toxicity models is important. In this study, performed on a series of nanoparticles, the comparative quantitative-structure activity relationship (nano-QSAR) analyses of their toxicity towards E. coli and HaCaT cells were established. A new approach for representation of nanoparticles' structure is presented. For description of the supramolecular structure of nanoparticles the "liquid drop" model was applied. It is expected that a novel, proposed approach could be of general use for predictions related to nanomaterials. In addition, in our study fragmental simplex descriptors and several ligand-metal binding characteristics were calculated. The developed nano-QSAR models were validated and reliably predict the toxicity of all studied metal oxide nanoparticles. Based on the comparative analysis of contributed properties in both models the LDM-based descriptors were revealed to have an almost similar level of contribution to toxicity in both cases, while other parameters (van der Waals interactions, electronegativity and metal-ligand binding characteristics) have unequal contribution levels. In addition, the models developed here suggest different mechanisms of nanotoxicity for these two types of cells.

Wireless Chalcogenide Nanoionic-Based Radio-Frequency Switch

NASA Technical Reports Server (NTRS)

Nessel, James; Miranda, Felix

2013-01-01

A new nonvolatile nanoionic switch is powered and controlled through wireless radio-frequency (RF) transmission. A thin layer of chalcogenide glass doped with a metal ion, such as silver, comprises the operational portion of the switch. For the switch to function, an oxidizable electrode is made positive (anode) with respect to an opposing electrode (cathode) when sufficient bias, typically on the order of a few tenths of a volt or more, is applied. This action causes the metal ions to flow toward the cathode through a coordinated hopping mechanism. At the cathode, a reduction reaction occurs to form a metal deposit. This metal deposit creates a conductive path that bridges the gap between electrodes to turn the switch on. Once this conductive path is formed, no further power is required to maintain it. To reverse this process, the metal deposit is made positive with respect to the original oxidizable electrode, causing the dissolution of the metal bridge thereby turning the switch off. Once the metal deposit has been completely dissolved, the process self-terminates. This switching process features the following attributes. It requires very little to change states (i.e., on and off). Furthermore, no power is required to maintain the states; hence, the state of the switch is nonvolatile. Because of these attributes the integration of a rectenna to provide the necessary power and control is unique to this embodiment. A rectenna, or rectifying antenna, generates DC power from an incident RF signal. The low voltages and power required for the nanoionic switch control are easily generated from this system and provide the switch with a novel capability to be operated and powered from an external wireless device. In one realization, an RF signal of a specific frequency can be used to set the switch into an off state, while another frequency can be used to set the switch to an on state. The wireless, miniaturized, and nomoving- part features of this switch make it suitable for applications such as integration into garments, RFID (radio-frequency identification) tags, and conformal structures (e.g., aircraft wings, sounding rockets contours, etc). In the case of RFID tags the innovation will provide countermeasures to attempts for identity theft and other uninvited attempts for retrieval of information. It could also be applicable to the automotive industry as well as the aerospace industry for collision avoidance and phased array radar systems, respectively

Optical properties of MgF2 nano-composite films dispersed with noble metal nanoparticles synthesized by sol-gel method

NASA Astrophysics Data System (ADS)

Wakaki, Moriaki; Soujima, Nobuaki; Shibuya, Takehisa

2015-03-01

Porous MgF2 films synthesized by a sol-gel method exhibit the lowest refractive index among the dielectric optical materials and are the most useful materials for the anti-reflection coatings. On the other hand, surface plasmon resonance (SPR) absorptions of noble metal nanoparticles in various solid matrices have been extensively studied. New functional materials like a SERS (Surface Enhanced Raman Spectroscopy) tips are expected by synthesizing composite materials between porous MgF2 films featured by the network of MgF2 nanoparticles and noble metal nanoparticles introduced within the network. In this study, fundamental physical properties including morphology and optical properties are characterized for these materials to make clear the potential of the composite system. Composite materials of MgF2 films dispersed with noble metal (Ag, Au) nanoparticles were prepared using the sol-gel technique with various annealing temperatures and densities of noble metal nanoparticles. The structural morphology was analyzed by an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). The size and shape distributions of the metal nanoparticles were observed using a transmission electron microscope (TEM). The optical properties of fabricated composite films were characterized by UV-Vis-NIR and FT-IR spectrophotometers. The absorption spectra due to the surface plasmon resonance (SPR) of the metal nanoparticles were analyzed using the dielectric function considering the effective medium approximation, typically Maxwell-Garnett model. The Raman scattering spectra were also studied to check the enhancement effect of specimen dropped on the MgF2: Ag nano-composite films deposited on Si substrate. Enhancement of the Raman intensity of pyridine solution specimen was observed.

Superior Electrical Conductivity in Hydrogenated Layered Ternary Chalcogenide Nanosheets for Flexible All-Solid-State Supercapacitors.

PubMed

Hu, Xin; Shao, Wei; Hang, Xudong; Zhang, Xiaodong; Zhu, Wenguang; Xie, Yi

2016-05-04

As the properties of ultrathin two-dimensional (2D) crystals are strongly related to their electronic structures, more and more attempts were carried out to tune their electronic structures to meet the high standards for the construction of next-generation smart electronics. Herein, for the first time, we show that the conductive nature of layered ternary chalcogenide with formula of Cu2 WS4 can be switched from semiconducting to metallic by hydrogen incorporation, accompanied by a high increase in electrical conductivity. In detail, the room-temperature electrical conductivity of hydrogenated-Cu2 WS4 nanosheet film was almost 10(10) times higher than that of pristine bulk sample with a value of about 2.9×10(4)  S m(-1) , which is among the best values for conductive 2D nanosheets. In addition, the metallicity in the hydrogenated-Cu2 WS4 is robust and can be retained under high-temperature treatment. The fabricated all-solid-state flexible supercapacitor based on the hydrogenated-Cu2 WS4 nanosheet film shows promising electrochemical performances with capacitance of 583.3 F cm(-3) at a current density of 0.31 A cm(-3) . This work not only offers a prototype material for the study of electronic structure regulation in 2D crystals, but also paves the way in searching for highly conductive electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cubic Dirac fermions in quasi-one-dimensional transition-metal chalcogenide semimetals immune to Peierls distortion

NASA Astrophysics Data System (ADS)

Liu, Qihang; Zunger, Alex

A Cubic Dirac Fermion in condensed-matter physics refers to a band crossing in periodic solids that has 4-fold degeneracy with cubic dispersions in certain directions. Such a crystalline symmetry induced fermion is composed of 6 Weyl fermions where 3 have left-handed and 3 have right-handed chirality, and constitutes one of the ``new fermions'' that have no counterpart in high-energy physics. However, no prediction has yet pointed to a plausible example of a material candidate hosting such a cubically-dispersed Dirac semimetal (CDSM). Here we establish the design principles for CDSM finding that only 2 out of 230 space groups possess the required symmetry elements. Adding the required band occupancy criteria, we conduct a material search using density functional band theory identifying a group of quasi-one-dimensional molybdenum chalcogenide compounds A(MoX)3 (A = Na, K, Rb, In, Tl; X = S, Se, Te) with space group P63/m as ideal CDSM candidates. Studying the stability of the A(MoX)3 family towards a Peierls distortion reveals a few candidates such as Rb(MoTe)3 and Tl(MoTe)3 that are resilliant to Peierls distortion, thus retaining the metallic character. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division under Grant No. DE-FG02-13ER46959 to University of Colorado, Boulder.

Processing and properties of magnesium containing a dense uniform dispersion of nanoparticles.

PubMed

Chen, Lian-Yi; Xu, Jia-Quan; Choi, Hongseok; Pozuelo, Marta; Ma, Xiaolong; Bhowmick, Sanjit; Yang, Jenn-Ming; Mathaudhu, Suveen; Li, Xiao-Chun

2015-12-24

Magnesium is a light metal, with a density two-thirds that of aluminium, is abundant on Earth and is biocompatible; it thus has the potential to improve energy efficiency and system performance in aerospace, automobile, defence, mobile electronics and biomedical applications. However, conventional synthesis and processing methods (alloying and thermomechanical processing) have reached certain limits in further improving the properties of magnesium and other metals. Ceramic particles have been introduced into metal matrices to improve the strength of the metals, but unfortunately, ceramic microparticles severely degrade the plasticity and machinability of metals, and nanoparticles, although they have the potential to improve strength while maintaining or even improving the plasticity of metals, are difficult to disperse uniformly in metal matrices. Here we show that a dense uniform dispersion of silicon carbide nanoparticles (14 per cent by volume) in magnesium can be achieved through a nanoparticle self-stabilization mechanism in molten metal. An enhancement of strength, stiffness, plasticity and high-temperature stability is simultaneously achieved, delivering a higher specific yield strength and higher specific modulus than almost all structural metals.

Non-rare earth magnetic nanoparticles

DOEpatents

Carpenter, Everett E.; Huba, Zachary J.; Carroll, Kyler J.; Farghaly, Ahmed; Khanna, Shiv N.; Qian, Meichun; Bertino, Massimo

2017-09-26

Continuous flow synthetic methods are used to make single phase magnetic metal alloy nanoparticles that do not contain rare earth metals. Soft and hard magnets made from the magnetic nanoparticles are used for a variety of purposes, e.g. in electric motors, communication devices, etc.

Dialkyldiselenophosphinato-metal complexes - a new class of single source precursors for deposition of metal selenide thin films and nanoparticles

NASA Astrophysics Data System (ADS)

Malik, Sajid N.; Akhtar, Masood; Revaprasadu, Neerish; Qadeer Malik, Abdul; Azad Malik, Mohammad

2014-08-01

We report here a new synthetic approach for convenient and high yield synthesis of dialkyldiselenophosphinato-metal complexes. A number of diphenyldiselenophosphinato-metal as well as diisopropyldiselenophosphinato-metal complexes have been synthesized and used as precursors for deposition of semiconductor thin films and nanoparticles. Cubic Cu2-xSe and tetragonal CuInSe2 thin films have been deposited by AACVD at 400, 450 and 500 °C whereas cubic PbSe and tetragonal CZTSe thin films have been deposited through doctor blade method followed by annealing. SEM investigations revealed significant differences in morphology of the films deposited at different temperatures. Preparation of Cu2-xSe and In2Se3 nanoparticles using diisopropyldiselenophosphinato-metal precursors has been carried out by colloidal method in HDA/TOP system. Cu2-xSe nanoparticles (grown at 250 °C) and In2Se3 nanoparticles (grown at 270 °C) have a mean diameter of 5.0 ± 1.2 nm and 13 ± 2.5 nm, respectively.

A Discovery of Strong Metal-Support Bonding in Nanoengineered Au-Fe3O4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy.

PubMed

Han, Chang Wan; Choksi, Tej; Milligan, Cory; Majumdar, Paulami; Manto, Michael; Cui, Yanran; Sang, Xiahan; Unocic, Raymond R; Zemlyanov, Dmitry; Wang, Chao; Ribeiro, Fabio H; Greeley, Jeffrey; Ortalan, Volkan

2017-08-09

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous "strong metal-support bonding" between gold nanoparticles and "nano-engineered" Fe 3 O 4 substrates by in situ microscopy. During in situ vacuum annealing of Au-Fe 3 O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3 O 4 on Au nanoparticles, the gold nanoparticles transform into the gold thin films and wet the surface of nano-Fe 3 O 4 , as the surface reduction of nano-Fe 3 O 4 proceeds. This phenomenon results from a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3 O 4 and the extremely strong adhesion between Au and the reduced Fe 3 O 4 . This strong metal-support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and ultimately for the development of improved catalysts and functional nanostructures.

Mercury mobilization in a flooded soil by incorporation into metallic copper and metal sulfide nanoparticles.

PubMed

Hofacker, Anke F; Voegelin, Andreas; Kaegi, Ralf; Kretzschmar, Ruben

2013-07-16

Mercury is a highly toxic priority pollutant that can be released from wetlands as a result of biogeochemical redox processes. To investigate the temperature-dependent release of colloidal and dissolved Hg induced by flooding of a contaminated riparian soil, we performed laboratory microcosm experiments at 5, 14, and 23 °C. Our results demonstrate substantial colloidal Hg mobilization concomitant with Cu prior to the main period of sulfate reduction. For Cu, we previously showed that this mobilization was due to biomineralization of metallic Cu nanoparticles associated with suspended bacteria. X-ray absorption spectroscopy at the Hg LIII-edge showed that colloidal Hg corresponded to Hg substituting for Cu in the metallic Cu nanoparticles. Over the course of microbial sulfate reduction, colloidal Hg concentrations decreased but continued to dominate total Hg in the pore water for up to 5 weeks of flooding at all temperatures. Transmission electron microscopy (TEM) suggested that Hg became associated with Cu-rich mixed metal sulfide nanoparticles. The formation of Hg-containing metallic Cu and metal sulfide nanoparticles in contaminated riparian soils may influence the availability of Hg for methylation or volatilization processes and has substantial potential to drive Hg release into adjacent water bodies.

Transition metal-substituted cobalt ferrite nanoparticles for biomedical applications.

PubMed

Sanpo, Noppakun; Berndt, Christopher C; Wen, Cuie; Wang, James

2013-03-01

Transition metals of copper, zinc, chromium and nickel were substituted into cobalt ferrite nanoparticles via a sol-gel route using citric acid as a chelating agent. The microstructure and elemental composition were characterized using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. Phase analysis of transition metal-substituted cobalt ferrite nanoparticles was performed via X-ray diffraction. Surface wettability was measured using the water contact angle technique. The surface roughness of all nanoparticles was measured using profilometry. Moreover, thermogravimetric analysis and differential scanning calorimetry were performed to determine the temperature at which the decomposition and oxidation of the chelating agents took place. Results indicated that the substitution of transition metals influences strongly the microstructure, crystal structure and antibacterial property of the cobalt ferrite nanoparticles. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nanosensors based on functionalized nanoparticles and surface enhanced raman scattering

DOEpatents

Talley, Chad E.; Huser, Thomas R.; Hollars, Christopher W.; Lane, Stephen M.; Satcher, Jr., Joe H.; Hart, Bradley R.; Laurence, Ted A.

2007-11-27

Surface-Enhanced Raman Spectroscopy (SERS) is a vibrational spectroscopic technique that utilizes metal surfaces to provide enhanced signals of several orders of magnitude. When molecules of interest are attached to designed metal nanoparticles, a SERS signal is attainable with single molecule detection limits. This provides an ultrasensitive means of detecting the presence of molecules. By using selective chemistries, metal nanoparticles can be functionalized to provide a unique signal upon analyte binding. Moreover, by using measurement techniques, such as, ratiometric received SERS spectra, such metal nanoparticles can be used to monitor dynamic processes in addition to static binding events. Accordingly, such nanoparticles can be used as nanosensors for a wide range of chemicals in fluid, gaseous and solid form, environmental sensors for pH, ion concentration, temperature, etc., and biological sensors for proteins, DNA, RNA, etc.

Spectral dependence of fluorescence near plasmon resonant metal nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Yeechi

The optical properties of fluorophores are significantly modified when placed within the near field (0--100 nm) of plasmon resonant metal nanostructures, due to the competition between increased decay rates and "hotspots" of concentrated electric fields. The decay rates and effective electric field intensities are highly dependent on the relative position of dye and metal and the overlap between plasmon resonance and dye absorption and emission. Understanding these dependencies can greatly improve the performance of biosensing and nanophotonic devices. In this dissertation, the fluorescence intensity of organic dyes and CdSe quantum dots near single metal nanoparticles is studied as a function of the local surface plasmon resonance (LSPR) of the nanoparticle. Single metal nanoparticles have narrow, well-defined, intense local surface plasmon resonances that are tunable across the visible spectrum by changes in size and shape. First, we show that organic dyes can be self-assembled on single silver nanoprisms into known configurations by the hybridization of thiolated DNA oligomers. We correlate the fluorescence intensity of the dyes to the LSPR of the individual nanoprism to which they are attached. For each of three different organic dyes, we observe a strong correlation between the fluorescence intensity of the dye and the degree of spectral overlap with the plasmon resonance of the nanoparticle. On average, we observe the brightest fluorescence from dyes attached to metal nanoparticles that have a LSPR scattering peak 40--120 meV higher in energy than the emission peak of the fluorophore. Second, the plasmon-enhanced fluorescence from CdSe/CdS/CdZnS/ZnS core/shell quantum dots is studied near a variety of silver and gold nanoparticles. With single-particle scattering spectroscopy, the localized surface plasmon resonance spectra of single metal nanoparticles is correlated with the photoluminescence excitation (PLE) spectra of the nearby quantum dots. The PLE spectra closely track the scattering spectra of the metal nanoparticles. By taking advantage of the ability to excite quantum dots across a wide range of wavelengths while detecting a single emission wavelength, we measure an excitation enhancement factor for single metal nanoparticles. The data also provide a calculation of a lower-bound of experimentally attainable enhancement factors solely due to increased near-field excitation. This factor was found to range from ˜3 to 10 for Au spheres, Ag cubes and Ag nanoprisms.

Plasma based formation and deposition of metal and metal oxide nanoparticles using a gas aggregation source

NASA Astrophysics Data System (ADS)

Polonskyi, Oleksandr; Ahadi, Amir Mohammad; Peter, Tilo; Fujioka, Kenji; Abraham, Jan Willem; Vasiliauskaite, Egle; Hinz, Alexander; Strunskus, Thomas; Wolf, Sebastian; Bonitz, Michael; Kersten, Holger; Faupel, Franz

2018-05-01

Metal clusters and nanoparticles (NPs) have been studied intensively due to their unique chemical, physical, electrical, and optical properties, resulting from their dimensions, which provided host of applications in nanoscience and nanotechnology. Formation of new materials by embedding NPs into various matrices (i.e. formation of nanocomposites) further expands the horizon of possible application of such nanomaterials. In the last few decades, the focus was put on the formation of metallic and metal oxide NPs via a so-called gas aggregation nanoparticle source employing magnetron sputtering (i.e. Haberland concept). In this paper, an overview is given of the recent progress in formation and deposition of NPs by the gas aggregation method. Examples range from noble metals (Ag, Au) through reactive metals (Al, Ti) to Si and the respective oxides. Emphasis is placed on the mechanism of nanoparticle growth and the resulting properties. Moreover, kinetic Monte Carlo simulations were developed to explain the growth mechanism and dynamics of nanoparticle formation depending on the experimental conditions. In addition, the role of trace amounts of reactive gases and of pulsed operation of the plasma on the nucleation process is addressed. Finally, the treatment of the NPs in the plasma environment resulting in nanoparticle charging, morphological and chemical modifications is discussed. Contribution to the Topical Issue "Fundamentals of Complex Plasmas", edited by Jürgen Meichsner, Michael Bonitz, Holger Fehske, Alexander Piel.

Optical trapping of metal-dielectric nanoparticle clusters near photonic crystal microcavities.

PubMed

Mejia, Camilo A; Huang, Ningfeng; Povinelli, Michelle L

2012-09-01

We predict the formation of optically trapped, metal-dielectric nanoparticle clusters above photonic crystal microcavities. We determine the conditions on particle size and position for a gold particle to be trapped above the microcavity. We then show that strong field redistribution and enhancement near the trapped gold nanoparticle results in secondary trapping sites for a pair of dielectric nanoparticles.

Comparative study on the uptake and bioimpact of metal nanoparticles released into environment

NASA Astrophysics Data System (ADS)

Andries, Maria; Pricop, Daniela; Grigoras, Marian; Lupu, Nicoleta; Sacarescu, Liviu; Creanga, Dorina; Iacomi, Felicia

2015-12-01

Metallic particles of very small size are ubiquitously released in the air, water and soil from various natural and artificial sources - the last ones with enhanced extent since nanotechnology development accelerated exponentially. In this study we focused on the impact of metal nanoparticles in vegetal species of agroindustrial interest namely the maize (Zea mais L.). Laboratory simulation of environmental pollution was carried out by using engineered nanoparticles of two types: iron oxides with magnetic properties and gold nanoparticles supplied in the form of dilutes stable suspensions in the culture medium of maize seedlings. Magnetic nanoparticle (MNPs) preparation was performed by applying chemical route from iron ferric and ferrous precursor salts in alkali reaction medium at relatively high temperature (over 80 °C). Gold nanoparticles (GNPs) synthesis was accomplished from auric hydrochloride acid in alkali reaction medium in similar temperature conditions. In both types of metallic nanoparticles citrate ions were used as coating shell with role of suspension stabilization. Plantlet response was assessed at the level of assimilatory pigment contents in green tissue of seedlings in early ontogenetic stages.

Fabrication and characterisation of ligand-functionalised ultrapure monodispersed metal nanoparticle nanoassemblies employing advanced gas deposition technique

NASA Astrophysics Data System (ADS)

Geremariam Welearegay, Tesfalem; Cindemir, Umut; Österlund, Lars; Ionescu, Radu

2018-02-01

Here, we report for the first time the fabrication of ligand-functionalised ultrapure monodispersed metal nanoparticles (Au, Cu, and Pt) from their pure metal precursors using the advanced gas deposition technique. The experimental conditions during nanoparticle formation were adjusted in order to obtain ultrafine isolated nanoparticles on different substrates. The morphology and surface analysis of the as-deposited metal nanoparticles were investigated using scanning electron microscopy, x-ray diffraction and Fourier transform infra-red spectroscopy, which demonstrated the formation of highly ordered pure crystalline nanoparticles with a relatively uniform size distribution of ∼10 nm (Au), ∼4 nm (Cu) and ∼3 nm (Pt), respectively. A broad range of organic ligands containing thiol or amine functional groups were attached to the nanoparticles to form continuous networks of nanoparticle-ligand nanoassemblies, which were characterised by scanning electron microscopy and x-ray photoelectron spectroscopy. The electrical resistance of the functional nanoassemblies deposited in the gap spacing of two microfabricated parallel Au electrodes patterned on silicon substrates ranged between tens of kΩ and tens of MΩ, which is suitable for use in many applications including (bio)chemical sensors, surface-enhanced Raman spectroscopy and molecular electronic rectifiers.

Investigation of self-phase modulation based optical regeneration in single mode As2Se3 chalcogenide glass fiber.

PubMed

Fu, L; Rochette, M; Ta'eed, V; Moss, D; Eggleton, B

2005-09-19

We investigate the feasibility of all-optical regeneration based on self-phase modulation in single mode As2Se3 chalcogenide fiber. By combining the chalcogenide fiber with a bandpass filter, we achieve a near step-like power transfer function with no pulse distortion. The device is shown to operate with 5.8 ps duration pulses, thus demonstrating the feasibility of this device operating with high bit-rate data signals. These results are achieved with pulse peak powers <10 W in a fully passive device, including only 2.8 m of chalcogenide fiber. We obtain an excellent agreement between theory and experiment and show that both the high nonlinearity of the chalcogenide glass along with its high normal dispersion near 1550 nm enables a significant device length reduction in comparison with silica-based devices, without compromise on the performance. We find that even for only a few meters of fiber, the large normal dispersion of the chalcogenide glass inhibits spectral oscillations that would appear with self-phase modulation alone. We measure the two photon absorption attenuation coefficient and find that it advantageously affects the device transfer function.

Fabrication of Metal and Metal Oxide Nanoparticles by Algae and their Toxic Effects

NASA Astrophysics Data System (ADS)

Siddiqi, Khwaja Salahuddin; Husen, Azamal

2016-08-01

Of all the aquatic organisms, algae are a good source of biomolecules. Since algae contain pigments, proteins, carbohydrates, fats, nucleic acids and secondary metabolites such as alkaloids, some aromatic compounds, macrolides, peptides and terpenes, they act as reducing agents to produce nanoparticles from metal salts without producing any toxic by-product. Once the algal biomolecules are identified, the nanoparticles of desired shape or size may be fabricated. The metal and metal oxide nanoparticles thus synthesized have been investigated for their antimicrobial activity against several gram-positive and gram-negative bacterial strains and fungi. Their dimension is controlled by temperature, incubation time, pH and concentration of the solution. In this review, we have attempted to update the procedure of nanoparticle synthesis from algae, their characterization by UV-vis, Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, x-ray diffraction, energy-dispersive x-ray spectroscopy, dynamic light scattering and application in cutting-edge areas.

Atomic layer deposition of metal sulfide materials

DOE PAGES

Dasgupta, Neil P.; Meng, Xiangbo; Elam, Jeffrey W.; ...

2015-01-12

The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivatingmore » interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H 2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application space, the benefits and challenges of novel ALD processes are emphasized and common trends are summarized. We conclude with a perspective on potential future directions for metal chalcogenide ALD as well as untapped opportunities. As a result, we consider challenges that must be addressed prior to implementing ALD metal sulfides into future device architectures.« less

1-D Metal Nanobead Arrays within Encapsulated Nanowires via a Red-Ox-Induced Dewetting: Mechanism Study by Atom-Probe Tomography.

PubMed

Sun, Zhiyuan; Tzaguy, Avra; Hazut, Ori; Lauhon, Lincoln J; Yerushalmi, Roie; Seidman, David N

2017-12-13

Metal nanoparticle arrays are excellent candidates for a variety of applications due to the versatility of their morphology and structure at the nanoscale. Bottom-up self-assembly of metal nanoparticles provides an important complementary alternative to the traditional top-down lithography method and makes it possible to assemble structures with higher-order complexity, for example, nanospheres, nanocubes, and core-shell nanostructures. Here we present a mechanism study of the self-assembly process of 1-D noble metal nanoparticles arrays, composed of Au, Ag, and AuAg alloy nanoparticles. These are prepared within an encapsulated germanium nanowire, obtained by the oxidation of a metal-germanium nanowire hybrid structure. The resulting structure is a 1-D array of equidistant metal nanoparticles with the same diameter, the so-called nanobead (NB) array structure. Atom-probe tomography and transmission electron microscopy were utilized to investigate the details of the morphological and chemical evolution during the oxidation of the encapsulated metal-germanium nanowire hybrid-structures. The self-assembly of nanoparticles relies on the formation of a metal-germanium liquid alloy and the migration of the liquid alloy into the nanowire, followed by dewetting of the liquid during shape-confined oxidation where the liquid column breaks-up into nanoparticles due to the Plateau-Rayleigh instability. Our results demonstrate that the encapsulating oxide layer serves as a structural scaffold, retaining the overall shape during the eutectic liquid formation and demonstrates the relationship between the oxide mechanical properties and the final structural characteristics of the 1-D arrays. The mechanistic details revealed here provide a versatile tool-box for the bottom-up fabrication of 1-D arrays nanopatterning that can be modified for multiple applications according to the RedOx properties of the material system components.

Synthesis of branched metal nanostructures with controlled architecture and composition

NASA Astrophysics Data System (ADS)

Ortiz, Nancy

On account of their small size, metal nanoparticles are proven to be outstanding catalysts for numerous chemical transformations and represent promising platforms for applications in the fields of electronics, chemical sensing, medicine, and beyond. Many properties of metal nanoparticles are size-dependent and can be further manipulated through their shape and architecture (e.g., spherical vs. branched). Achieving morphology control of nanoparticles through solution-based techniques has proven challenging due to limited knowledge of morphology development in nanosyntheses. To overcome these complications, a systematic examination of the local ligand environment of metal precursors on nanostructure formation was undertaken to evaluate its contribution to nanoparticle nucleation rate and subsequent growth processes. Specifically, this thesis will provide evidence from ex situ studies---Transmission Electron Microscopy (TEM) and UV-visible spectroscopy (UV-Vis)---that support the hypothesis that strongly coordinated ligands delay burst-like nucleation to generate spherical metal nanoparticles and ligands with intermediate binding affinity regulate the gradual reduction of metal precursors to promote aggregated assembly of nanodendrites. These ex situ studies were coupled with a new in situ perspective, providing detailed understanding of metal precursor transformation, its direct relation to nanoparticle morphology development, and the ligand influence towards the formation of structurally complex metal nanostructures, using in situ synchrotron X-ray Diffraction (XRD) and Ultra Small-Angle X-ray Scattering (USAXS). The principles extracted from the study of monometallic nanostructure formation were also found to be generally applicable to the synthesis of bimetallic nanostructures, e.g., Pd-Pt architectures, with either core-shell or alloyed structures that were readily achieved by ligand selection. These outcomes provide a direct connection between fundamental principles of coordination chemistry and nanoparticle formation, with a stronger foundation for the predictive synthesis of future nanomaterials with controllable structural features.

Metal-organic frameworks as selectivity regulators for hydrogenation reactions

NASA Astrophysics Data System (ADS)

Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

2016-11-01

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

Metal-organic frameworks as selectivity regulators for hydrogenation reactions.

PubMed

Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

2016-11-03

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe 3+ , Cr 3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

The mechanism of metal nanoparticle formation in plants: limits on accumulation

NASA Astrophysics Data System (ADS)

Haverkamp, R. G.; Marshall, A. T.

2009-08-01

Metal nanoparticles have many potential technological applications. Biological routes to the synthesis of these particles have been proposed including production by vascular plants, known as phytoextraction. While many studies have looked at metal uptake by plants, particularly with regard to phytoremediation and hyperaccumulation, few have distinguished between metal deposition and metal salt accumulation. This work describes the uptake of AgNO3, Na3Ag(S2O3)2, and Ag(NH3)2NO3 solutions by hydroponically grown Brassica juncea and the quantitative measurement of the conversion of these salts to silver metal nanoparticles. Using X-ray absorption near edge spectroscopy (XANES) to determine the metal speciation within the plants, combined with atomic absorption spectroscopy (AAS) for total Ag, the quantity of reduction of AgI to Ag0 is reported. Transmission electron microscopy (TEM) showed Ag particles of 2-35 nm. The factors controlling the amount of silver accumulated are revealed. It is found that there is a limit on the amount of metal nanoparticles that may be deposited, of about 0.35 wt.% Ag on a dry plant basis, and that higher levels of silver are obtained only by the concentration of metal salts within the plant, not by deposition of metal. The limit on metal nanoparticle accumulation, across a range of metals, is proposed to be controlled by the total reducing capacity of the plant for the reduction potential of the metal species and limited to reactions occurring at an electrochemical potential greater than 0 V (verses the standard hydrogen electrode).

Novel Quaternary Chalcogenide/Reduced Graphene Oxide-Based Asymmetric Supercapacitor with High Energy Density.

PubMed

Sarkar, Samrat; Howli, Promita; Das, Biswajit; Das, Nirmalya Sankar; Samanta, Madhupriya; Das, G C; Chattopadhyay, K K

2017-07-12

In this work we have synthesized quaternary chalcogenide Cu 2 NiSnS 4 (QC) nanoparticles grown in situ on 2D reduced graphene oxide (rGO) for application as anode material of solid-state asymmetric supercapacitors (ASCs). Thorough characterization of the synthesized composite validates the proper phase, stoichiometry, and morphology. Detailed electrochemical study of the electrode materials and ASCs has been performed. The as-fabricated device delivers an exceptionally high areal capacitance (655.1 mF cm -2 ), which is much superior to that of commercial micro-supercapacitors. Furthermore, a remarkable volumetric capacitance of 16.38 F cm -3 is obtained at a current density of 5 mA cm -2 combined with a very high energy density of 5.68 mW h cm -3 , which is comparable to that of commercially available lithium thin film batteries. The device retains 89.2% of the initial capacitance after running for 2000 cycles, suggesting its long-term capability. Consequently, the enhanced areal and volumetric capacitances combined with decent cycle stability and impressive energy density endow the uniquely decorated QC/rGO composite material as a promising candidate in the arena of energy storage devices. Moreover, Cu 2 NiSnS 4 being a narrow band gap photovoltaic material, this work offers a novel protocol for the development of self-charging supercapacitors in the days to come.

Time-dependent growth of crystalline Au0-nanoparticles in cyanobacteria as self-reproducing bioreactors: 1. Anabaena sp.

NASA Astrophysics Data System (ADS)

Rösken, Liz M.; Körsten, Susanne; Fischer, Christian B.; Schönleber, Andreas; van Smaalen, Sander; Geimer, Stefan; Wehner, Stefan

2014-04-01

Customized metal nanoparticles are highly relevant in industrial processes, where they are used as catalysts and therefore needed on a large scale. An extremely economically and environmentally friendly way to produce metal nanoparticles is microbial biosynthesis, meaning the biosorption and bioreduction of diluted metal ions to zero valent (metal) nanoparticles. To maintain the key advantage of biosynthesis, including eco friendliness, a bioreactor (e.g., bacteria) has to be harmless by itself. Here, the ability of the cyanobacteria Anabaena sp. (SAG 12.82) is shown to fulfill both needs: bioreduction of Au3+ ions to Au0 and the subsequent formation of crystalline Au0-nanoparticles as well as absence of the release of toxic substances (e.g., anatoxin-a). The time-dependent growth of the nanoparticles is recorded by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) over a range of several days. Formation of nanoparticles starts within the first minutes at the heterocyst polysaccharide layer (HEP). After 4 h, the dominating amount of nanoparticles is found in the vegetative cells. The bioproduced nanoparticles are found in both cell types, mainly located along the thylakoid membranes of the vegetative cells and have a final average size of 9 nm within the examined timescale of a few days.

Robust Synthesis of Ciprofloxacin-Capped Metallic Nanoparticles and Their Urease Inhibitory Assay.

PubMed

Nisar, Muhammad; Khan, Shujaat Ali; Qayum, Mughal; Khan, Ajmal; Farooq, Umar; Jaafar, Hawa Z E; Zia-Ul-Haq, Muhammad; Ali, Rashid

2016-03-25

The fluoroquinolone antibacterial drug ciprofloxacin (cip) has been used to cap metallic (silver and gold) nanoparticles by a robust one pot synthetic method under optimized conditions, using NaBH₄ as a mild reducing agent. Metallic nanoparticles (MNPs) showed constancy against variations in pH, table salt (NaCl) solution, and heat. Capping with metal ions (Ag/Au-cip) has significant implications for the solubility, pharmacokinetics and bioavailability of fluoroquinolone molecules. The metallic nanoparticles were characterized by several techniques such as ultraviolet visible spectroscopy (UV), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) methods. The nanoparticles synthesized using silver and gold were subjected to energy dispersive X-ray tests in order to show their metallic composition. The NH moiety of the piperazine group capped the Ag/Au surfaces, as revealed by spectroscopic studies. The synthesized nanoparticles were also assessed for urease inhibition potential. Fascinatingly, both Ag-cip and Au-cip NPs exhibited significant urease enzyme inhibitory potential, with IC50 = 1.181 ± 0.02 µg/mL and 52.55 ± 2.3 µg/mL, compared to ciprofloxacin (IC50 = 82.95 ± 1.62 µg/mL). MNPs also exhibited significant antibacterial activity against selected bacterial strains.

TOXICITY OF SILVER NANOPARTICLES TO DAPHNIA MAGNA

EPA Science Inventory

Relatively little is known regarding toxicity of nanoparticles in the environment. It is widely assumed that the toxicity of nanoparticles will be less than that of their metallic ions. Also the effect of organics on metal toxicity is well established. Presented here are the resu...

Stimuli-Responsive Polymeric Nanoparticles.

PubMed

Liu, Xiaolin; Yang, Ying; Urban, Marek W

2017-07-01

There is increasing evidence that stimuli-responsive nanomaterials have become significantly critical components of modern materials design and technological developments. Recent advances in synthesis and fabrication of stimuli-responsive polymeric nanoparticles with built-in stimuli-responsive components (Part A) and surface modifications of functional nanoparticles that facilitate responsiveness (Part B) are outlined here. The synthesis and construction of stimuli-responsive spherical, core-shell, concentric, hollow, Janus, gibbous/inverse gibbous, and cocklebur morphologies are discussed in Part A, with the focus on shape, color, or size changes resulting from external stimuli. Although inorganic/metallic nanoparticles exhibit many useful properties, including thermal or electrical conductivity, catalytic activity, or magnetic properties, their assemblies and formation of higher order constructs are often enhanced by surface modifications. Section B focuses on selected surface reactions that lead to responsiveness achieved by decorating nanoparticles with stimuli-responsive polymers. Although grafting-to and grafting-from dominate these synthetic efforts, there are opportunities for developing novel synthetic approaches facilitating controllable recognition, signaling, or sequential responses. Many nanotechnologies utilize a combination of organic and inorganic phases to produce ceramic or metallic nanoparticles. One can envision the development of new properties by combining inorganic (metals, metal oxides) and organic (polymer) phases into one nanoparticle designated as "ceramers" (inorganics) and "metamers" (metallic). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic-Resolution Electron Microscopy and Field Evaporation Simulation.

PubMed

Devaraj, Arun; Colby, Robert; Vurpillot, François; Thevuthasan, Suntharampillai

2014-04-17

Oxide-supported metal nanoparticles are widely used in heterogeneous catalysis. The increasingly detailed design of such catalysts necessitates three-dimensional characterization with high spatial resolution and elemental selectivity. Laser-assisted atom probe tomography (APT) is uniquely suited to the task but faces challenges with the evaporation of metal/insulator systems. Correlation of APT with aberration-corrected scanning transmission electron microscopy (STEM), for Au nanoparticles embedded in MgO, reveals preferential evaporation of the MgO and an inaccurate assessment of nanoparticle composition. Finite element field evaporation modeling is used to illustrate the evolution of the evaporation front. Nanoparticle composition is most accurately predicted when the MgO is treated as having a locally variable evaporation field, indicating the importance of considering laser-oxide interactions and the evaporation of various molecular oxide ions. These results demonstrate the viability of APT for analysis of oxide-supported metal nanoparticles, highlighting the need for developing a theoretical framework for the evaporation of heterogeneous materials.

Electromagnetic Field Redistribution in Metal Nanoparticle on Graphene.

PubMed

Li, Keke; Liu, Anping; Wei, Dapeng; Yu, Keke; Sun, Xiaonan; Yan, Sheng; Huang, Yingzhou

2018-04-25

Benefiting from the induced image charge on metal film, the light energy is confined on a film surface under metal nanoparticle dimer, which is called electromagnetic field redistribution. In this work, electromagnetic field distribution of metal nanoparticle monomer or dimer on graphene is investigated through finite-difference time-domain method. The results point out that the electromagnetic field (EM) redistribution occurs in this nanoparticle/graphene hybrid system at infrared region where light energy could also be confined on a monolayer graphene surface. Surface charge distribution was analyzed using finite element analysis, and surface-enhanced Raman spectrum (SERS) was utilized to verify this phenomenon. Furthermore, the data about dielectric nanoparticle on monolayer graphene demonstrate this EM redistribution is attributed to strong coupling between light-excited surface charge on monolayer graphene and graphene plasmon-induced image charge on dielectric nanoparticle surface. Our work extends the knowledge of monolayer graphene plasmon, which has a wide range of applications in monolayer graphene-related film.

Enhanced Antimicrobial Activity Of Antibiotics Mixed With Metal Nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, Sandeep; Kumar, Neeraj; Bhanjana, Gaurav; Thakur, Rajesh; Dilbaghi, Neeraj

2011-12-01

Current producers of antimicrobial technology have a long lasting, environmentally safe, non-leaching, water soluble solution that will eventually replace all poisons and heavy metals. The transition metal ions inevitably exist as metal complexes in biological systems by interaction with the numerous molecules possessing groupings capable of complexation or chelation. Nanoparticles of metal oxides offer a wide variety of potential applications in medicine due to the unprecedented advances in nanobiotechnology research. the bacterial action of antibiotics like penicillin, erythryomycin, ampicillin, streptomycin, kanamycin etc. and that of a mixture of antibiotics and metal and metal oxide nanoparticles like zinc oxide, zirconium, silver and gold on microbes was examined by the agar-well-diffusion method, enumeration of colony-forming units (CFU) and turbidimetry.

Green Synthesis, Characterization and Uses of Palladium/Platinum Nanoparticles

NASA Astrophysics Data System (ADS)

Siddiqi, Khwaja Salahuddin; Husen, Azamal

2016-11-01

Biogenic synthesis of palladium (Pd) and platinum (Pt) nanoparticles from plants and microbes has captured the attention of many researchers because it is economical, sustainable and eco-friendly. Plant and their parts are known to have various kinds of primary and secondary metabolites which reduce the metal salts to metal nanoparticles. Shape, size and stability of Pd and Pt nanoparticles are influenced by pH, temperature, incubation time and concentrations of plant extract and that of the metal salt. Pd and Pt nanoparticles are broadly used as catalyst, as drug, drug carrier and in cancer treatment. They have shown size- and shape-dependent specific and selective therapeutic properties. In this review, we have discussed the biogenic fabrication of Pd/Pt nanoparticles, their potential application as catalyst, medicine, biosensor, medical diagnostic and pharmaceuticals.

Negative differential resistance effect induced by metal ion implantation in SiO2 film for multilevel RRAM application

NASA Astrophysics Data System (ADS)

Wu, Facai; Si, Shuyao; Shi, Tuo; Zhao, Xiaolong; Liu, Qi; Liao, Lei; Lv, Hangbing; Long, Shibing; Liu, Ming

2018-02-01

Pt/SiO2:metal nanoparticles/Pt sandwich structure is fabricated with the method of metal ion (Ag) implantation. The device exhibits multilevel storage with appropriate R off/R on ratio, good endurance and retention properties. Based on transmission electron microscopy and energy dispersive spectrometer analysis, we confirm that Pt nanoparticles are spurted into SiO2 film from Pt bottom electrode by Ag implantation; during electroforming, the local electric field can be enhanced by these Pt nanoparticles, meanwhile the Ag nanoparticles constantly migrate toward the Pt nanoparticles. The implantation induced nanoparticles act as trap sites in the resistive switching layer and play critical roles in the multilevel storage, which is evidenced by the negative differential resistance effect in the current-voltage (I-V) measurements.

Localized Plasmon resonance in metal nanoparticles using Mie theory

NASA Astrophysics Data System (ADS)

Duque, J. S.; Blandón, J. S.; Riascos, H.

2017-06-01

In this work, scattering light by colloidal metal nanoparticles with spherical shape was studied. Optical properties such as diffusion efficiencies of extinction and absorption Q ext and Q abs were calculated using Mie theory. We employed a MATLAB program to calculate the Mie efficiencies and the radial dependence of electric field intensities emitted for colloidal metal nanoparticles (MNPs). By UV-Vis spectroscopy we have determined the LSPR for Cu nanoparticles (CuNPs), Ni nanoparticles (NiNPs) and Co nanoparticles (CoNPs) grown by laser ablation technique. The peaks of resonances appear in 590nm, 384nm and 350nm for CuNPs, NiNPs and CoNPs respectively suspended in water. Changing the medium to acetone and ethanol we observed a shift of the resonance peaks, these values agreed with our simulations results.

Surface plasmon resonances in liquid metal nanoparticles

NASA Astrophysics Data System (ADS)

Ershov, A. E.; Gerasimov, V. S.; Gavrilyuk, A. P.; Karpov, S. V.

2017-06-01

We have shown significant suppression of resonant properties of metallic nanoparticles at the surface plasmon frequency during the phase transition "solid-liquid" in the basic materials of nanoplasmonics (Ag, Au). Using experimental values of the optical constants of liquid and solid metals, we have calculated nanoparticle plasmonic absorption spectra. The effect was demonstrated for single particles, dimers and trimers, as well as for the large multiparticle colloidal aggregates. Experimental verification was performed for single Au nanoparticles heated to the melting temperature and above up to full suppression of the surface plasmon resonance. It is emphasized that this effect may underlie the nonlinear optical response of composite materials containing plasmonic nanoparticles and their aggregates.

Salt-Driven Deposition of Thermoresponsive Polymer-Coated Metal Nanoparticles on Solid Substrates.

PubMed

Zhang, Zhiyue; Maji, Samarendra; da Fonseca Antunes, André B; De Rycke, Riet; Hoogenboom, Richard; De Geest, Bruno G

2016-06-13

Here we report on a simple, generally applicable method for depositing metal nanoparticles on a wide variety of solid surfaces under all aqueous conditions. Noble-metal nanoparticles obtained by citrate reduction followed by coating with thermoresponsive polymers spontaneously form a monolayer-like structure on a wide variety of substrates in presence of sodium chloride whereas this phenomenon does not occur in salt-free medium. Interestingly, this phenomenon occurs below the cloud point temperature of the polymers and we hypothesize that salt ion-induced screening of electrostatic charges on the nanoparticle surface entropically favors hydrophobic association between the polymer-coated nanoparticles and a hydrophobic substrate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An environmentally benign antimicrobial nanoparticle based ...

EPA Pesticide Factsheets

Silver nanoparticles have antibacterial properties but their use has been a cause for concern because they persist in the environment. Here we show that lignin nanoparticles infused with silver ions and coated with a cationic polyelectrolyte layer form a biodegradable and green alternative to silver nanoparticles. The polyelectrolyte layer promotes the adhesion of the particles to bacterial cell membranes and together with silver ions can kill a broad spectrum of bacteria, including Escherichia coli, Pseudomonas aeruginosa and quaternary-amine-resistant Ralstonia sp. Ion depletion studies showed that the bioactivity of these nanoparticles is time-limited because of the desorption of silver ions. High-throughput bioactivity screening did not reveal increased toxicity of the particles when compared to an equivalent mass of metallic silver nanoparticles or silver nitrate solution. Our results demonstrate that the application of green chemistry principles may allow the synthesis of nanoparticles with biodegradable cores that have higher antimicrobial activity and smaller environmental impact than metallic silver nanoparticles. Our results demonstrate that the application of green chemistry principles may allow the synthesis of nanoparticles with biodegradable cores that have higher antimicrobial activity and smaller environmental impact than metallic silver nanoparticles

Generation of Subsurface Voids, Incubation Effect, and Formation of Nanoparticles in Short Pulse Laser Interactions with Bulk Metal Targets in Liquid: Molecular Dynamics Study

PubMed Central

2017-01-01

The ability of short pulse laser ablation in liquids to produce clean colloidal nanoparticles and unusual surface morphology has been employed in a broad range of practical applications. In this paper, we report the results of large-scale molecular dynamics simulations aimed at revealing the key processes that control the surface morphology and nanoparticle size distributions by pulsed laser ablation in liquids. The simulations of bulk Ag targets irradiated in water are performed with an advanced computational model combining a coarse-grained representation of liquid environment and an atomistic description of laser interaction with metal targets. For the irradiation conditions that correspond to the spallation regime in vacuum, the simulations predict that the water environment can prevent the complete separation of the spalled layer from the target, leading to the formation of large subsurface voids stabilized by rapid cooling and solidification. The subsequent irradiation of the laser-modified surface is found to result in a more efficient ablation and nanoparticle generation, thus suggesting the possibility of the incubation effect in multipulse laser ablation in liquids. The simulations performed at higher laser fluences that correspond to the phase explosion regime in vacuum reveal the accumulation of the ablation plume at the interface with the water environment and the formation of a hot metal layer. The water in contact with the metal layer is brought to the supercritical state and provides an environment suitable for nucleation and growth of small metal nanoparticles from metal atoms emitted from the hot metal layer. The metal layer itself has limited stability and can readily disintegrate into large (tens of nanometers) nanoparticles. The layer disintegration is facilitated by the Rayleigh–Taylor instability of the interface between the higher density metal layer decelerated by the pressure from the lighter supercritical water. The nanoparticles emerging from the layer disintegration are rapidly cooled and solidified due to the interaction with water environment, with a cooling rate of ∼2 × 1012 K/s observed in the simulations. The computational prediction of two distinct mechanisms of nanoparticle formation yielding nanoparticles with different characteristic sizes provides a plausible explanation for the experimental observations of bimodal nanoparticle size distributions in laser ablation in liquids. The ultrahigh cooling and solidification rates suggest the possibility for generation of nanoparticles featuring metastable phases and highly nonequilibrium structures. PMID:28798858

Nanoporous metal-carbon composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Worsley, Marcus A.; Satcher, Joe; Kucheyev, Sergei

Described here is a metal-carbon composite, comprising (a) a porous three-dimensional scaffold comprising one or more of carbon nanotubes, graphene and graphene oxide, and (b) metal nanoparticles disposed on said porous scaffold, wherein the metal-carbon composite has a density of 1 g/cm.sup.3 or less, and wherein the metal nanoparticles account for 1 wt. % or more of the metal-carbon composite. Also described are methods for making the metal-carbon composite.

Alkylamine capped metal nanoparticle "inks" for printable SERS substrates, electronics and broadband photodetectors.

PubMed

Polavarapu, Lakshminarayana; Manga, Kiran Kumar; Yu, Kuai; Ang, Priscilla Kailian; Cao, Hanh Duyen; Balapanuru, Janardhan; Loh, Kian Ping; Xu, Qing-Hua

2011-05-01

We report a facile and general method for the preparation of alkylamine capped metal (Au and Ag) nanoparticle "ink" with high solubility. Using these metal nanoparticle "inks", we have demonstrated their applications for large scale fabrication of highly efficient surface enhanced Raman scattering (SERS) substrates by a facile solution processing method. These SERS substrates can detect analytes down to a few nM. The flexible plastic SERS substrates have also been demonstrated. The annealing temperature dependent conductivity of the nanoparticle films indicated a transition temperature above which high conductivity was achieved. The transition temperature could be tailored to the plastic compatible temperatures by using proper alkylamine as the capping agent. The ultrafast electron relaxation studies of the nanoparticle films demonstrated that faster electron relaxation was observed at higher annealing temperatures due to stronger electronic coupling between the nanoparticles. The applications of these highly concentrated alkylamine capped metal nanoparticle inks for the printable electronics were demonstrated by printing the oleylamine capped gold nanoparticles ink as source and drain for the graphene field effect transistor. Furthermore, the broadband photoresponse properties of the Au and Ag nanoparticle films have been demonstrated by using visible and near-infrared lasers. These investigations demonstrate that these nanoparticle "inks" are promising for applications in printable SERS substrates, electronics, and broadband photoresponse devices. © The Royal Society of Chemistry 2011

Influence of support morphology on the bonding of molecules to nanoparticles

PubMed Central

Yim, Chi Ming; Pang, Chi L.; Hermoso, Diego R.; Dover, Coinneach M.; Muryn, Christopher A.; Maccherozzi, Francesco; Dhesi, Sarnjeet S.; Pérez, Rubén; Thornton, Geoff

2015-01-01

Supported metal nanoparticles form the basis of heterogeneous catalysts. Above a certain nanoparticle size, it is generally assumed that adsorbates bond in an identical fashion as on a semiinfinite crystal. This assumption has allowed the database on metal single crystals accumulated over the past 40 years to be used to model heterogeneous catalysts. Using a surface science approach to CO adsorption on supported Pd nanoparticles, we show that this assumption may be flawed. Near-edge X-ray absorption fine structure measurements, isolated to one nanoparticle, show that CO bonds upright on the nanoparticle top facets as expected from single-crystal data. However, the CO lateral registry differs from the single crystal. Our calculations indicate that this is caused by the strain on the nanoparticle, induced by carpet growth across the substrate step edges. This strain also weakens the CO–metal bond, which will reduce the energy barrier for catalytic reactions, including CO oxidation. PMID:26080433

Morphology and dispersion of FeCo alloy nanoparticles dispersed in a matrix of IR pyrolized polyvinyl alcohol

NASA Astrophysics Data System (ADS)

Vasilev, A. A.; Dzidziguri, E. L.; Muratov, D. G.; Zhilyaeva, N. A.; Efimov, M. N.; Karpacheva, G. P.

2018-04-01

Metal-carbon nanocomposites consisting of FeCo alloy nanoparticles dispersed in a carbon matrix were synthesized by the thermal decomposition method of a precursor based on polyvinyl alcohol and metals salts. The synthesized powders were investigated by X-ray diffraction (XRD), X-ray fluorescent spectrometry (XRFS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Surface characteristics of materials were measured by BET-method. The morphology and dispersity of metal nanoparticles were studied depending on the metals ratio in the composite.

Wear mechanisms of the biotribological nanocomposite a-C : H coatings implanted by metallic nanoparticles.

PubMed

Major, L; Janusz, M; Lackner, J M; Kot, M; Dyner, M; Major, B

2017-10-01

Recently, to reduce the residual stress and increase the mechanical properties of a-C:H coatings, metallic nanoparticles have been implanted into their structure. In the present work, to improve the properties of the coating, metallic nanoparticles, including Cu, Nb, Ta, Zr, AgPt and Ag, were inserted into the a-C:H structure. The applied biological and mechanical analysis allowed the optimal biotribological parameters to be indicated for the potential application as protective coatings for metallic medical tools. Wear mechanisms operating at the small length of the designed biotribological coating, such as a-C:H implanted by Zr nanoparticles, were studied by means of transmission electron microscopy (TEM). The TEM analysis confirmed very good coating adhesion to the metallic substrate. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Antimicrobial properties of metal and metal-halide nanoparticles and their potential applications

NASA Astrophysics Data System (ADS)

Torrey, Jason Robert

Heavy metals, including silver and copper, have been known to possess antimicrobial properties against bacterial, fungal, and viral pathogens. Metal nanoparticles (aggregations of metal atoms 1-200 nm in size) have recently become the subject of intensive study for their increased antimicrobial properties. In the current studies, metal and metal-halide nanoparticles were evaluated for their antibacterial efficacy. Silver (Ag), silver bromide (AgBr), silver iodide (AgI), and copper iodide (CuI) nanoparticles significantly reduced bacterial numbers of the Gram-negative Pseudomonas aeruginosa and the Gram-positive Staphylococcus aureus within 24 hours and were more effective against P. aeruginosa. CuI nanoparticles were found to be highly effective, reducing both organisms by >4.43 log 10 within 15 minutes at 60 ppm Cu. CuI nanoparticles formulated with different stabilizers (sodium dodecyl sulfate, SDS; polyvinyl pyrrolidone, PVP) were further tested against representative Gram-positive and Gram-negative bacteria, Mycobacteria, a fungus (Candida albicans ), and a non-enveloped virus (poliovirus). Both nanoparticles caused significant reductions in most of the Gram-negative bacteria within five minutes (>5.09-log10). The Gram-positive bacterial species and C. albicans were more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. In contrast, the acid-fast Mycobacterium smegmatis was more resistant to CuI-SDS than CuI-PVP nanoparticles. Poliovirus was more resistant than the other organisms tested except for Mycobacterium fortuitum, which displayed the greatest resistance to CuI nanoparticles. As an example of a real world antimicrobial application, polymer coatings embedded with various concentrations of CuI nanoparticles were tested for antibacterial efficacy against P. aeruginosa and S. aureus. Polyester-epoxy powder coatings were found to display superior uniformity, stability and antimicrobial properties against both organisms (>4.92 log 10 after six hours at 0.25% Cu). These surfaces were negatively impacted when tested under dry conditions with high organic content. At 0.25% Cu, the antibacterial activity of the powder coatings was not impacted by washing with several commercial cleaners; however, at concentrations of 0.05% Cu, antibacterial activity was reduced by washing with water, WindexRTM , and Pine SolRTM. Ultrasonic cleaning of the coatings appeared to decrease their antimicrobial efficacy. Despite this, CuI nanoparticles were found in all studies to have great potential as a new class of fast-acting, broad-spectrum antimicrobial.

Superconductivity and bandwidth-controlled Mott metal-insulator transition in 1T-TaS2-xSex

NASA Astrophysics Data System (ADS)

Ang, R.; Miyata, Y.; Ieki, E.; Nakayama, K.; Sato, T.; Liu, Y.; Lu, W. J.; Sun, Y. P.; Takahashi, T.

2013-09-01

We have performed high-resolution angle-resolved photoemission spectroscopy (ARPES) of layered chalcogenide 1T-TaS2-xSex to elucidate the electronic states especially relevant to the occurrence of superconductivity. We found a direct evidence for a Ta-5d-derived electron pocket associated with the superconductivity, which is fragile against a Mott-gap opening observed in the insulating ground state for S-rich samples. In particular, a strong electron-electron interaction-induced Mott gap driven by a Ta 5d orbital also exists in the metallic ground state for Se-rich samples, while finite ARPES intensity near the Fermi level likely originating from a Se 4p orbital survives, indicative of the orbital-selective nature of the Mott transition. Present results suggest that effective electron correlation and p-d hybridization play a crucial role to tune the superconductivity and Mott metal-insulator transition.

Effect of high pressure on the electrical resistivity of Ge-Te-In glasses

NASA Astrophysics Data System (ADS)

Prasad, K. N. N.; Varma, G. Sreevidya; Rukmani, K.; Asokan, S.

2015-06-01

The variation in the electrical resistivity of the chalcogenide glasses Ge15Te85-xInx has been studied as a function of high pressure for pressures up to 8.5GPa. All the samples studied undergo a semi-conductor to metallic transition in a continuous manner at pressures between 1.5-2.5GPa. The transition pressure at which the samples turn metallic increases with increase in percentage of Indium. This increase is a direct consequence of the increase in network rigidity with the addition of Indium. At a constant pressure of 0.5GPa, the normalized resistivity shows some signature of the existence of the intermediate phase. Samples recovered after a pressure cycle remain amorphous suggesting that the semi-conductor to metallic transition arises from a reduction of the band gap due to pressure or the movement of the Fermi level into the conduction or valence band.

Stable surface passivation process for compound semiconductors

DOEpatents

Ashby, Carol I. H.

2001-01-01

A passivation process for a previously sulfided, selenided or tellurated III-V compound semiconductor surface. The concentration of undesired mid-gap surface states on a compound semiconductor surface is reduced by the formation of a near-monolayer of metal-(sulfur and/or selenium and/or tellurium)-semiconductor that is effective for long term passivation of the underlying semiconductor surface. Starting with the III-V compound semiconductor surface, any oxidation present thereon is substantially removed and the surface is then treated with sulfur, selenium or tellurium to form a near-monolayer of chalcogen-semiconductor of the surface in an oxygen-free atmosphere. This chalcogenated surface is then contacted with a solution of a metal that will form a low solubility chalcogenide to form a near-monolayer of metal-chalcogen-semiconductor. The resulting passivating layer provides long term protection for the underlying surface at or above the level achieved by a freshly chalcogenated compound semiconductor surface in an oxygen free atmosphere.

77 FR 32942 - Application(s) for Duty-Free Entry of Scientific Instruments

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-04

.... Intended Use: The instrument will be used to fabricate bulk nanostructured metals and metallic glasses, in particular Mg based alloys, CuNb, NiAl, Nb based alloys and metal matrix composites with oxide nanoparticles... oxide nanoparticles during the melting of metals. Suction casting is required to achieve nanocrystalline...

Metal-Folded Single-Chain Nanoparticle: Nanoclusters and Self-Assembled Reduction-Responsive Sub-5-nm Discrete Subdomains.

PubMed

Cao, Hui; Cui, Zhigang; Gao, Pan; Ding, Yi; Zhu, Xuechao; Lu, Xinhua; Cai, Yuanli

2017-09-01

Easy access to discrete nanoclusters in metal-folded single-chain nanoparticles (metal-SCNPs) and independent ultrafine sudomains in the assemblies via coordination-driven self-assembly of hydrophilic copolymer containing 9% imidazole groups is reported herein. 1 H NMR, dynamic light scattering, and NMR diffusion-ordered spectroscopy results demonstrate self-assembly into metal-SCNPs (>70% imidazole-units folded) by neutralization in the presence of Cu(II) in water to pH 4.6. Further neutralization induces self-assembly of metal-SCNPs (pH 4.6-5.0) and shrinkage (pH 5.0-5.6), with concurrent restraining residual imidazole motifs and hydrophilic segment, which organized into constant nanoparticles over pH 5.6-7.5. Atomic force microscopy results evidence discrete 1.2 nm nanoclusters and sub-5-nm subdomains in metal-SCNP and assembled nanoparticle. Reduction of metal center using sodium ascorbate induces structural rearrangement to one order lower than the precursor. Enzyme mimic catalysis required media-tunable discrete ultrafine interiors in metal-SCNPs and assemblies have hence been achieved. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved laser damage threshold for chalcogenide glasses through surface microstructuring

NASA Astrophysics Data System (ADS)

Florea, Catalin; Sanghera, Jasbinder; Busse, Lynda; Shaw, Brandon; Aggarwal, Ishwar

2011-03-01

We demonstrate improved laser damage threshold of chalcogenide glasses with microstructured surfaces as compared to chalcogenide glasses provided with traditional antireflection coatings. The surface microstructuring is used to reduce Fresnel losses over large bandwidths in As2S3 glasses and fibers. The treated surfaces show almost a factor of two of improvement in the laser damage threshold when compared with untreated surfaces.

Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films

NASA Astrophysics Data System (ADS)

Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.

2016-09-01

In this work we report on the formation of lumpy Pd and Pt nanoparticles on fluorine-doped tin oxide/glass (FTO/glass) substrate by a laser-based approach. In general, complex-surface morphology metal nanoparticles can be used in several technological applications exploiting the peculiarities of their physical properties as modulated by nanoscale morphology. For example plasmonic metal nanoparticles presenting a lumpy morphology (i.e. larger particles coated on the surface by smaller particles) can be used in plasmonic solar cell devices providing broadband scattering enhancement over the smooth nanoparticles leading, so, to the increase of the device efficiency. However, the use of plasmonic lumpy nanoparticles remains largely unexplored due to the lack of simply, versatile, low-cost and high-throughput methods for the controllable production of such nanostructures. Starting from these considerations, we report on the observation that nanoscale-thick Pd and Pt films (17.6 and 27.9 nm, 12.1 and 19.5 nm, respectively) deposited on FTO/glass surface irradiated by nanosecond pulsed laser at fluences E in the 0.5-1.5 J/cm2 range, produce Pd and Pt lumpy nanoparticles on the FTO surface. In addition, using scanning electron microscopy analyses, we report on the observation that starting from each metal film of fixed thickness h, the fraction F of lumpy nanoparticles increases with the laser fluence E and saturates at the higher fluences. For each fixed fluence, F was found higher starting from the Pt films (at each starting film thickness h) with respect to the Pd films. For each fixed metal and fluence, F was found to be higher decreasing the starting thickness of the deposited film. To explain the formation of the lumpy Pd and Pt nanoparticles and the behavior of F as a function of E and h both for Pd and Pt, the thermodynamic behavior of the Pd and Pt films and nanoparticles due to the interaction with the nanosecond laser is discussed. In particular, the photothermal vaporization and Coulomb explosion processes of the Pd and Pt nanoparticles are invoked as possible mechanisms for the lumpy nanoparticles formation.

Preparation of PVA/Co/Ag film and evaluation of its magnetic and microstructural properties

NASA Astrophysics Data System (ADS)

Banerjee, M.; Sachdev, Preeti; Mukherjee, G. S.

2012-05-01

PVA/Co/Ag film has been prepared by sputtering Co followed by Ag in polyvinyl alcohol (PVA) matrix film by IBS technique, so as to get a 9 nm (thick) layer of Co metal nanoparticles followed by a protective 4 nm (thick) layer of Ag nanoparticles. Grazing incidence x-ray diffraction (GIXRD) pattern of the film reveals the formation of nanocrystalline Co with hcp phase. GIXRD pattern also indicates that there is no change in the crystalline structure of PVA even after sputtering of the metallic nanoparticles. The average particle size of Co nanoparticles as evaluated using Scherrer formula is found to be about 2.64 nm. UV visible absorption pattern of the film sample showed SPR peaks of Co and Ag metals in their nano size level embedded in the PVA matrix system. XPS study confirms the metallic nature of Co and Ag nanoparticles; and the depth profiling study reveals that both the metal nanoparticles have been embedded in the PVA matrix system. Surface morphology of such film has been studied using AFM; and the magnetic behaviour of the film studied by using MOKE shows soft ferromagnetic behaviour in this PVA/Co/Ag system.

Porous metal oxide particles and their methods of synthesis

DOEpatents

Chen, Fanglin; Liu, Qiang

2013-03-12

Methods are generally disclosed for synthesis of porous particles from a solution formed from a leaving agent, a surfactant, and a soluble metal salt in a solvent. The surfactant congregates to form a nanoparticle core such that the metal salt forms about the nanoparticle core to form a plurality of nanoparticles. The solution is heated such that the leaving agent forms gas bubbles in the solution, and the plurality of nanoparticles congregate about the gas bubbles to form a porous particle. The porous particles are also generally disclosed and can include a particle shell formed about a core to define an average diameter from about 0.5 .mu.m to about 50 .mu.m. The particle shell can be formed from a plurality of nanoparticles having an average diameter of from about 1 nm to about 50 nm and defined by a metal salt formed about a surfactant core.

Electrolysis of a molten semiconductor

DOE PAGES

Yin, Huayi; Chung, Brice; Sadoway, Donald R.

2016-08-24

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb 2S 3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across themore » cell. In conclusion, as opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO 2, CO and SO 2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides.« less

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

PubMed Central

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; Wang, Shibing; Lin, Yu; Zeng, Qiaoshi; Xu, Gang; Liu, Zhenxian; Solanki, G. K.; Patel, K. D.; Cui, Yi; Hwang, Harold Y.; Mao, Wendy L.

2015-01-01

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe2 up to ∼60 GPa using multiple experimental techniques and ab-initio calculations. MoSe2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSe2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides. PMID:26088416

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

DOE PAGES

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; ...

2015-06-19

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe 2 up to ~60 GPa using multiple experimental techniques and ab-initio calculations. MoSe 2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS 2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSemore » 2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides.« less

Dendronized Metal Nanoparticles-Self-Organizing Building Blocks for the Design of New Functional Materials

DTIC Science & Technology

2016-04-01

characterization has just started.       The hybrids that we have synthesized are based on plasmonic gold and  silver   nanoparticles  (NPs) but  the concept  is...AFRL-AFOSR-UK-TR-2016-0010 Dendronized metal nanoparticles - self-organizing building blocks for the design of new functional materials Bertrand...2015 4. TITLE AND SUBTITLE Dendronized metal nanoparticles - self-organizing building blocks for the design of new functional materials 5a. CONTRACT

Facile fabrication of core-in-shell particles by the slow removal of the core and its use in the encapsulation of metal nanoparticles.

PubMed

Choi, Won San; Koo, Hye Young; Kim, Dong-Yu

2008-05-06

Core-in-shell particles with controllable core size have been fabricated from core-shell particles by means of the controlled core-dissolution method. These cores in inorganic shells were employed as scaffolds for the synthesis of metal nanoparticles. After dissolution of the cores, metal nanoparticles embedded in cores were encapsulated into the interior of shell, without any damage or change. This article describes a very simple method for deriving core-in-shell particles with controllable core size and encapsulation of nanoparticles into the interior of shell.

Intense generation of respirable metal nanoparticles from a low-power soldering unit.

PubMed

Gómez, Virginia; Irusta, Silvia; Balas, Francisco; Santamaria, Jesus

2013-07-15

Evidence of intense nanoparticle generation from a low power (45W) flux soldering unit is presented. This is a familiar device often used in daily life, including home repairs and school electronic laboratories. We demonstrate that metal-containing nanoparticles may reach high concentrations (ca. 10(6) particles/cm(3)) within the breathing range of the operator, with initial size distributions centered at 35-60nm The morphological and chemical analysis of nanoparticle agglomerates collected on TEM grids and filters confirms their multiparticle structure and the presence of metals. Copyright © 2013 Elsevier B.V. All rights reserved.

Metallic Films with Fullerene-Like WS2 (MoS2) Nanoparticles: Self-Lubricating Coatings with Potential Applications

NASA Astrophysics Data System (ADS)

Eidelman, O.; Friedman, H.; Tenne, R.

Metallic films impregnated with fullerene-like-WS2 (MoS2) nanoparticles were fabricated on stainless steel and Ti-Ni substrates using galvanic and electroless deposition. The coatings were obtained from aqueous suspensions containing the metallic salts as well as the dispersed nanoparticles. Tribological tests showed that the films have low friction and wear. Such coatings could be useful for numerous civilian and defense-related applications.

Merely Measuring the UV-Visible Spectrum of Gold Nanoparticles Can Change Their Charge State.

PubMed

Navarrete, Jose; Siefe, Chris; Alcantar, Samuel; Belt, Michael; Stucky, Galen D; Moskovits, Martin

2018-02-14

Metallic nanostructures exhibit a strong plasmon resonance at a wavelength whose value is sensitive to the charge density in the nanostructure, its size, shape, interparticle coupling, and the dielectric properties of its surrounding medium. Here we use UV-visible transmission and reflectance spectroscopy to track the shifts of the plasmon resonance in an array of gold nanoparticles buried under metal-oxide layers of varying thickness produced using atomic layer deposition (ALD) and then coated with bulk layers of one of three metals: aluminum, silver, or gold. A significant shift in the plasmon resonance was observed and a precise value of ω p , the plasmon frequency of the gold comprising the nanoparticles, was determined by modeling the composite of gold nanoparticles and metal-oxide layer as an optically homogeneous film of core-shell particles bounded by two substrates: one of quartz and the other being one of the aforementioned metals, then using a Maxwell-Garnett effective medium expression to extract ω p for the gold nanoparticles before and after coating with the bulk metals. Under illumination, the change in the charge density of the gold nanoparticles per particle determined from the change in the values of ω p is found to be some 50-fold greater than what traditional electrostatic contact electrification models compute based on the work function difference of the two conductive materials. Moreover, when using bulk gold as the capping layer, which should have resulted in a negligible charge exchange between the gold nanoparticles and the bulk gold, a significant charge transfer from the bulk gold layer to the nanoparticles was observed as with the other metals. We explain these observations in terms of the "plasmoelectric effect", recently described by Atwater and co-workers, in which the gold nanoparticles modify their charge density to allow their resonant wavelength to match that of the incident light, thereby achieving, a lower value of the chemical potential due to the entropy increase resulting from the conversion of the plasmon's energy to heat. We conclude that even the act of registering the spectrum of nanoparticles is at times sufficient to alter their charge densities and hence their UV-visible spectra.

Biosynthesis and characterization of zinc, magnesium and titanium nanoparticles: an eco-friendly approach

NASA Astrophysics Data System (ADS)

Raliya, Ramesh; Tarafdar, J. C.

2014-02-01

In the present study, zinc (Zn), magnesium (Mg) and titanium (Ti) nanoparticles synthesized using fungus by employing various precursor salts of sulfate salts, nitrate salts, chloride salts and oxide salts. To access the nanoparticle production potential, over a hundreds of fungi were isolated from the soil and tested with precursor salts of the Zn, Mg and Ti. Out of which, only 14 fungal isolates were identified, having potential to reduce metal salt into metal nanoparticles. Upon molecular identification, six were identified as Aspergillus flavus, two each as Aspergillus terreus and Aspergillus tubingensis and one each as Aspergillus niger, Rhizoctonia bataticola, Aspergillus fumigatus, and Aspergillus oryzae. Factors responsible for more production of monodispersed Zn, Mg and Ti nanoparticles were optimized. It was concluded that 0.01 mM precursor salt concentration, 72 h of incubation at pH 5.5 and temperature 28 °C resulted smaller nanoparticles obtained. The biosynthesized functional Zn and Ti nanoparticles can be stored up to 90 days and Mg nanoparticles up to 105 days in its nanoform. Bio-transformed products were analyzed using valid characterization technique i.e. dynamic light scattering, transmission electron microscopy, atomic force microscopy, energy dispersive X-ray spectroscopy to confirm size, shape, surface morphology and elemental composition. It was found that the average size of developed nano Zn was 8.2 nm, with surface charge of -5.70 mV and 98 % particles were of Zn metal only. Similarly, the average size of Mg nanoparticles was 6.4 nm with surface charge of -6.66 and 97.4 % Mg metal yield, whereas, Ti nanoparticles size were found in the ranges between 1.5 and 30 nm with surface charge of -6.25 mV and 98.6 % Ti metal yield.

Current perspectives of nanoparticles in medical and dental biomaterials

PubMed Central

Mohamed Hamouda, Ibrahim

2012-01-01

Nanotechnology is gaining tremendous impetus due to its capability of modulating metals into their nanosize, which drastically changes the chemical, physical and optical properties of metals. Nanoparticles have been introduced as materials with good potential to be extensively used in biological and medical applications. Nanoparticles are clusters of atoms in the size range of 1-100 nm. Inorganic nanoparticles and their nano-composites are applied as good antibacterial agents. Due to the outbreak of infectious diseases caused by different pathogenic bacteria and the development of antibiotic resistance, pharmaceutical companies and researchers are searching for new antibacterial agents. The metallic nanoparticles are the most promising as they show good antibacterial properties due to their large surface area to volume ratios, which draw growing interest from researchers due to increasing microbial resistance against metal ions, antibiotics and the development of resistant strains. Metallic nanoparticles can be used as effective growth inhibitors in various microorganisms and thereby are applicable to diverse medical devices. Nanotechnology discloses the use of elemental nanoparticles as active antibacterial ingredient for dental materials. In dentistry, both restorative materials and oral bacteria are believed to be responsible for restoration failure. Secondary caries is found to be the main reason to restoration failure. Secondary caries is primarily caused by invasion of plaque bacteria (acid-producing bacteria) such as Streptococcus mutans and lactobacilli in the presence of fermentable carbohydrates. To make long-lasting restorations, antibacterial materials should be made. The potential of nanoparticles to control the formation of biofilms within the oral cavity is also coming under increasing scrutiny. Possible uses of nanoparticles as topically applied agents within dental materials and the application of nanoparticles in the control of oral infections are also reviewed. PMID:23554743

Metal nanoparticle deposited inorganic nanostructure hybrids, uses thereof and processes for their preparation

DOEpatents

Tenne, Reshef; Tsverin, Yulia; Burghaus, Uwe; Komarneni, Mallikharjuna Rao

2016-01-26

This invention relates to a hybrid component comprising at least one nanoparticle of inorganic layered compound (in the form of fullerene-like structure or nanotube), and at least one metal nanoparticle, uses thereof as a catalyst, (e.g. photocatalysis) and processes for its preparation.

Low-loss, submicron chalcogenide integrated photonics with chlorine plasma etching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiles, Jeff; Malinowski, Marcin; Rao, Ashutosh

A chlorine plasma etching-based method for the fabrication of high-performance chalcogenide-based integrated photonics on silicon substrates is presented. By optimizing the etching conditions, chlorine plasma is employed to produce extremely low-roughness etched sidewalls on waveguides with minimal penalty to propagation loss. Using this fabrication method, microring resonators with record-high intrinsic Q-factors as high as 450 000 and a corresponding propagation loss as low as 0.42 dB/cm are demonstrated in submicron chalcogenide waveguides. Furthermore, the developed chlorine plasma etching process is utilized to demonstrate fiber-to-waveguide grating couplers in chalcogenide photonics with high power coupling efficiency of 37% for transverse-electric polarized modes.

Space processing of chalcogenide glasses

NASA Technical Reports Server (NTRS)

Larsen, D. C.; Ali, M. A.

1975-01-01

Chalcogenide glasses are discussed as good infrared transmitters, possessing the strength, corrosion resistance, and scale-up potential necessary for large 10.6-micron windows. The disadvantage of earth-produced chalcogenide glasses is shown to be an infrared absorption coefficient which is unacceptably high relative to alkali halides. This coefficient is traced to optical nonhomogeneities resulting from environmental and container contamination. Space processing is considered as a means of improving the infrared transmission quality of chalcogenides and of eliminating the following problems: optical inhomogeneities caused by thermal currents and density fluctuation in the l-g earth environment; contamination from the earth-melting crucible by oxygen and other elements deleterious to infrared transmission; and, heterogeneous nucleation at the earth-melting crucible-glass interface.

Influence of rare earth elements (Nd, Sm, Gd) on the physicochemical properties of ges crystal

NASA Astrophysics Data System (ADS)

Madatov, R. S.; Alekperov, A. S.; Magerramova, Dzh. A.

2015-11-01

Layered semiconductors (including GeS), which are widely used in modern electronics, are of great interest for researchers. New GeS-based devices have been developed for holographic recording, optical processing, and storage of information. In the last few years, American scientists have developed a unique GeS-based device that makes it possible to accumulate an immense amount of solar energy. The introduction of rare earth elements (REEs) facilitates the healing of metal and chalcogenide vacancies, removes polytypism, and enhances interlayer interaction.

Dimensional and compositional change of 1D chalcogen nanostructures leading to tunable localized surface plasmon resonances.

PubMed

Min, Yuho; Seo, Ho Jun; Choi, Jong-Jin; Hahn, Byung-Dong; Moon, Geon Dae

2018-08-24

As part of the oxygen family, chalcogen (Se, Te) nanostructures have been considered important elements for various practical fields and further exploited to constitute metal chalcogenides for each targeted application. Here, we report a controlled synthesis of well-defined one-dimensional chalcogen nanostructures such as nanowries, nanorods, and nanotubes by controlling reduction reaction rate to fine-tune the dimension and composition of the products. Tunable optical properties (localized surface plasmon resonances) of these chalcogen nanostructures are observed depending on their morphological, dimensional, and compositional variation.

A further step towards tuning the properties of metal-chalcogenide nanocapsules by replacing skeletal oxide by sulphide ligands.

PubMed

Schäffer, Christian; Todea, Ana Maria; Bögge, Hartmut; Floquet, Sébastien; Cadot, Emmanuel; Korenev, Vladimir S; Fedin, Vladimir P; Gouzerh, Pierre; Müller, Achim

2013-01-14

Addition of [Mo(2)(V)O(2)(μ-O)(μ-S)(aq)](2+) linker-type units to a solution/dynamic library containing tungstates results via the formation of the complementary pentagonal {(W)W(5)} units logically in the self-assembly of a mixed oxide/sulphide {W(VI)(72)Mo(V)(60)}-type Keplerate, thereby demonstrating the ability to tune the capsule's skeletal softness (the (μ-O)(2) and (μ-S)(2) scenarios are known) and providing options to influence differently important capsule-substrate interactions.

The formation mechanism of binary semiconductor nanomaterials: shared by single-source and dual-source precursor approaches.

PubMed

Yu, Kui; Liu, Xiangyang; Zeng, Qun; Yang, Mingli; Ouyang, Jianying; Wang, Xinqin; Tao, Ye

2013-10-11

One thing in common: The formation of binary colloidal semiconductor nanocrystals from single- (M(EEPPh2 )n ) and dual-source precursors (metal carboxylates M(OOCR)n and phosphine chalcogenides such as E=PHPh2 ) is found to proceed through a common mechanism. For CdSe as a model system (31) P NMR spectroscopy and DFT calculations support a reaction mechanism which includes numerous metathesis equilibriums and Se exchange reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile biological synthetic strategy to morphologically aligned CeO2/ZrO2 core nanoparticles using Justicia adhatoda extract and ionic liquid: Enhancement of its bio-medical properties.

PubMed

Pandiyan, Nithya; Murugesan, Balaji; Sonamuthu, Jegatheeswaran; Samayanan, Selvam; Mahalingam, Sundrarajan

2018-01-01

In this study, a typical green synthesis route has approached for CeO 2 /ZrO 2 core metal oxide nanoparticles using ionic liquid mediated Justicia adhatoda extract. This synthesis method is carried out at simple room temperature condition to obtain the core metal oxide nanoparticles. XRD, SEM and TEM studies employed to study the crystalline and surface morphological properties under nucleation, growth, and aggregation processes. CeO 2 /ZrO 2 core metal oxides display agglomerated nano stick-like structure with 20-45nm size. GC-MS spectroscopy confirms the presence of vasicinone and N,N-Dimethylglycine present in the plant extract, which are capable of converting the corresponding metal ion precursor to CeO 2 /ZrO 2 core metal oxide nanoparticles. In FTIR, the corresponding stretching for Ce-O and Zr-O bands indicated at 498 and 416cm -1 and Raman spectroscopy also supports typical stretching frequencies at 463 and 160cm -1 . Band gap energy of the CeO 2 /ZrO 2 core metal oxide is 3.37eV calculated from UV- DRS spectroscopy. The anti-bacterial studies performed against a set of bacterial strains the result showed that core metal oxide nanoparticles more susceptible to gram-positive (G+) bacteria than gram-negative (G-) bacteria. A unique feature of the antioxidant behaviors core metal oxides reduces the concentration of DPPH radical up to 89%. The CeO 2 /ZrO 2 core metal oxide nanoparticles control the S. marcescent bio-film formation and restrict the quorum sensing. The toxicology behavior of CeO 2 /ZrO 2 core metal oxide NPs is found due to the high oxygen site vacancies, ROS formation, smallest particle size and higher surface area. This type of green synthesis route may efficient and the core metal oxide nanoparticles will possess a good bio-medical agent in future. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts

DOE PAGES

Hunt, Sean T.; Milina, Maria; Alba-Rubio, Ana C.; ...

2016-05-20

Here, we demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti 0.1W 0.9C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading,more » enhance the activity, and increase the stability of noble metal catalysts.« less

The effect of metal (hydr)oxide nano-enabling on intraparticle mass transport of organic contaminants in hybrid granular activated carbon.

PubMed

Garcia, Jose; Markovski, Jasmina; McKay Gifford, J; Apul, Onur; Hristovski, Kiril D

2017-05-15

The overarching goal of this study was to ascertain the changes in intraparticle mass transport rates for organic contaminants resulting from nano-enabled hybridization of commercially available granular activated carbon (GAC). Three different nano-enabled hybrid media were fabricated by in-situ synthesizing titanium dioxide nanoparticles inside the pores of GAC sorbent, characterized, and evaluated for removal of two model organic contaminants under realistic conditions to obtain the intraparticle mass transport (pore and surface diffusion) coefficients. The results validated the two hypotheses that: (H1) the pore diffusion rates of organic contaminants linearly decrease with decrease in cumulative pore volume caused by increase in metal (hydr)oxide nanoparticle content inside the pores of the hybrid GAC sorbent; and (H2) introduction of metal (hydr)oxide nanoparticles initially increases surface diffusivity, but additional loading causes its decrease as the increase in metal (hydr)oxide nanoparticles content continues to reduce the porosity of the GAC sorbent. Nano-enabled hybridization of commercially available GAC with metal (hydr)oxides has the potential to significantly increase the intraparticle mass transport limitations for organic contaminants. Introduction of metal (hydr)oxide nanoparticles inside the pores of a pristine sorbent causes the pore diffusion rates of organic contaminants to decrease as the cumulative pore volume is reduced. In contrast, the introduction of limited amounts of metal (hydr)oxide nanoparticles appears to facilitate the surface diffusion rates of these contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.

Metal Nanoparticles Covered with a Metal-Organic Framework: From One-Pot Synthetic Methods to Synergistic Energy Storage and Conversion Functions.

PubMed

Kobayashi, Hirokazu; Mitsuka, Yuko; Kitagawa, Hiroshi

2016-08-01

Hybrid materials composed of metal nanoparticles and metal-organic frameworks (MOFs) have attracted much attention in many applications, such as enhanced gas storage and catalytic, magnetic, and optical properties, because of the synergetic effects between the metal nanoparticles and MOFs. In this Forum Article, we describe our recent progress on novel synthetic methods to produce metal nanoparticles covered with a MOF (metal@MOF). We first present Pd@copper(II) 1,3,5-benzenetricarboxylate (HKUST-1) as a novel hydrogen-storage material. The HKUST-1 coating on Pd nanocrystals results in a remarkably enhanced hydrogen-storage capacity and speed in the Pd nanocrystals, originating from charge transfer from Pd nanocrystals to HKUST-1. Another material, Pd-Au@Zn(MeIM)2 (ZIF-8, where HMeIM = 2-methylimidazole), exhibits much different catalytic activity for alcohol oxidation compared with Pd-Au nanoparticles, indicating a design guideline for the development of composite catalysts with high selectivity. A composite material composed of Cu nanoparticles and Cr3F(H2O)2O{C6H3(CO2)3}2 (MIL-100-Cr) demonstrates higher catalytic activity for CO2 reduction into methanol than Cu/γ-Al2O3. We also present novel one-pot synthetic methods to produce composite materials including Pd/ZIF-8 and Ni@Ni2(dhtp) (MOF-74, where H4dhtp = 2,5-dihydroxyterephthalic acid).

Spectral properties of nanocomposites based on fluorine-containing polymer and gold nanoparticles

NASA Astrophysics Data System (ADS)

Barmina, E. V.; Mel’nik, N. N.; Rakov, I. I.; Ivanov, V. E.; Simakin, A. V.; Gudkov, S. V.; Shafeev, G. A.

2018-04-01

The optical properties of nanocomposites of gold nanoparticles and fluorine-containing polymer have been studied. Gold nanoparticles were obtained by laser ablation of gold or terbium targets in organic solvents. The thus formed colloidal solutions were used to prepare nanocomposites of gold nanoparticles in polymer matrices of transparent and colorless fluorine-containing polymer. The polymer matrix is found to promote aggregation of nanoparticles of metal under study into elongated chains. In turn, metal nanoparticles influence on the polymer matrix. Gold nanoparticles amplify the Raman signal of the polymer matrix. In addition, the Raman spectra of nanocomposites indicate aggregation of disordered carbon around the nanoparticles obtained by laser ablation in organic solvents.

Polymer Nanocomposite Film with Metal Rich Surface Prepared by In Situ Single-Step Formation of Palladium Nanoparticles: An Interesting Way to Combine Specific Functional Properties.

PubMed

Thompson, David; Kranbuehl, David; Espuche, Eliane

2016-10-18

This paper presents a continuous single-step route that permits preparation of a thermostable polymer/metal nanocomposite film and to combine different functional properties in a unique material. More precisely, palladium nanoparticles are in situ generated in a polyimide matrix thanks to a designed curing cycle which is applied to a polyamic acid/metal precursor solution cast on a glass plate. A metal-rich surface layer which is strongly bonded to the bulk film is formed in addition to homogeneously dispersed metal nanoparticles. This specific morphology leads to obtaining an optically reflective film. The metal nanoparticles act as gas diffusion barriers for helium, oxygen, and carbon dioxide; they induce a tortuosity effect which allows dividing the gas permeation coefficients by a factor near to 2 with respect to the neat polyimide matrix. Moreover, the ability of the in situ synthesized palladium nanoparticles to entrap hydrogen is evidenced. The nanocomposite film properties can be modulated as a function of the location of the film metal-rich surface with respect to the hydrogen feed. The synthesized nanocomposite could represent a major interest for a wide variety of applications, from specific coatings for aerospace or automotive industry, to catalysis applications or sensors.

A Discovery of Strong Metal–Support Bonding in Nanoengineered Au–Fe 3 O 4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Chang Wan; Choksi, Tej; Milligan, Cory

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

A Discovery of Strong Metal–Support Bonding in Nanoengineered Au–Fe 3 O 4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy

DOE PAGES

Han, Chang Wan; Choksi, Tej; Milligan, Cory; ...

2017-06-26

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

Chalcogenide Glass Lasers on Silicon Substrate Integrated Photonics

DTIC Science & Technology

2016-07-08

AFRL-AFOSR-UK-TR-2016-0013 Chalcogenide glass lasers on silicon substrate integrated photonics Clara Dimas MASDAR INSTITUTE OF SCIENCE & TECHNOLOGY...PROJECT NUMBER 5e.  TASK NUMBER 5f.  WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) MASDAR INSTITUTE OF SCIENCE & TECHNOLOGY - MIST...communication by reducing coupling losses, chip size, energy requirements and manufacturing cost. Chalcogenide glass (ChG) light sources doped with rare earth

Raman and CT scan mapping of chalcogenide glass diffusion generated gradient index profiles

NASA Astrophysics Data System (ADS)

Lindberg, G. P.; Berg, R. H.; Deegan, J.; Benson, R.; Salvaggio, P. S.; Gross, N.; Weinstein, B. A.; Gibson, D.; Bayya, S.; Sanghera, J.; Nguyen, V.; Kotov, M.

2016-05-01

Metrology of a gradient index (GRIN) material is non-trivial, especially in the realm of infrared and large refractive index. Traditional methods rely on index matching fluids which are not available for indexes as high as those found in the chalcogenide glasses (2.4-3.2). By diffusing chalcogenide glasses of similar composition one can blend the properties in a continuous way. In an effort to measure this we will present data from both x-ray computed tomography scans (CT scans) and Raman mapping scans of the diffusion profiles. Proof of concept measurements on undiffused bonded sheets of chalcogenide glasses were presented previously. The profiles measured will be of axially stacked sheets of chalcogenide glasses diffused to create a linear GRIN profile and nested tubes of chalcogenide glasses diffused to create a radial parabolic GRIN profile. We will show that the x-ray absorption in the CT scan and the intensity of select Raman peaks spatially measured through the material are indicators of the concentration of the diffusion ions and correlate to the spatial change in refractive index. We will also present finite element modeling (FEM) results and compare them to post precision glass molded (PGM) elements that have undergone CT and Raman mapping.

Oligonucleotide flexibility dictates crystal quality in DNA-programmable nanoparticle superlattices.

PubMed

Senesi, Andrew J; Eichelsdoerfer, Daniel J; Brown, Keith A; Lee, Byeongdu; Auyeung, Evelyn; Choi, Chung Hang J; Macfarlane, Robert J; Young, Kaylie L; Mirkin, Chad A

2014-11-12

The evolution of crystallite size and microstrain in DNA-mediated nanoparticle superlattices is dictated by annealing temperature and the flexibility of the interparticle bonds. This work addresses a major challenge in synthesizing optical metamaterials based upon noble metal nanoparticles by enabling the crystallization of large nanoparticles (100 nm diameter) at high volume fractions (34% metal). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface modification by metal ion implantation forming metallic nanoparticles in an insulating matrix

NASA Astrophysics Data System (ADS)

Salvadori, M. C.; Teixeira, F. S.; Sgubin, L. G.; Cattani, M.; Brown, I. G.

2014-08-01

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We have investigated nanocomposites produced by metal ion implantation into insulating substrates, where the implanted metal self-assembles into nanoparticles. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), which can be estimated by computer simulation using the TRIDYN code. TRIDYN is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study show that the nanoparticles form a bidimentional array buried a few nanometers below the substrate surface. We have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples show that metallic nanoparticles form in the insulating matrix. These nanocomposites have been characterized by measuring the resistivity of the composite layer as a function of the implantation dose. The experimental results are compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement is found between the experimental results and the predictions of the theory. We conclude in that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

Synthesis of nanoparticles using ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jia Xu

The present disclosure relates to methods for producing nanoparticles. The nanoparticles may be made using ethanol as the solvent and the reductant to fabricate noble-metal nanoparticles with a narrow particle size distributions, and to coat a thin metal shell on other metal cores. With or without carbon supports, particle size is controlled by fine-tuning the reduction power of ethanol, by adjusting the temperature, and by adding an alkaline solution during syntheses. The thickness of the added or coated metal shell can be varied easily from sub-monolayer to multiple layers in a seed-mediated growth process. The entire synthesis of designed core-shellmore » catalysts can be completed using metal salts as the precursors with more than 98% yield; and, substantially no cleaning processes are necessary apart from simple rinsing. Accordingly, this method is considered to be a "green" chemistry method.« less

Mesomorphic glass nanocomposites made of metal alkanoates and nanoparticles as emerging nonlinear-optical materials

NASA Astrophysics Data System (ADS)

Garbovskiy, Y.; Klimusheva, G.; Mirnaya, T.

2016-09-01

Mesomorphic metal alkanoates is very promising yet overlooked class of nonlinear-optical materials. Metal alkanoates can exhibit a broad variety of condensed states of matter including solid crystals, plastic crystals, lyotropic and thermotropic ionic liquid crystals, liquids, mesomorphic glasses, and Langmuir-Blodgett films. Glass-forming properties of metal alkanoates combined with their use as nano-reactors and anisotropic host open up simple and efficient way to design various photonic nanomaterials. Despite very interesting physics, the experimental data on optical and nonlinearoptical properties of such materials are scarce. The goal of the present paper is to fill the gap by discussing recent advances in the field of photonic materials made of metal alkanoates, organic dyes, and nanoparticles. Optical and nonlinear-optical properties of the following materials are reviewed: (i) mesomorphic glass doped with organic dyes; (ii) smectic glass composed of cobalt alkanoates; (iii) semiconductor nanoparticles embedded in a glassy host; (iv) metal nanoparticles - glass (the cobalt octanoate) nanocomposites.

Perovskite nanoparticle-sensitized Ga 2O 3 nanorod arrays for CO detection at high temperature

DOE PAGES

Lin, Hui -Jan; Baltrus, John P.; Gao, Haiyong; ...

2016-04-04

Here, noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La 0.8Sr 0.2FeO 3 (LSFO) nanoparticle surface decoration on Ga 2O 3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts wasmore » of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga 2O 3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga 2O 3 nanorod surfaces with faster surface CO oxidation reactions.« less

Perovskite Nanoparticle-Sensitized Ga2O3 Nanorod Arrays for CO Detection at High Temperature.

PubMed

Lin, Hui-Jan; Baltrus, John P; Gao, Haiyong; Ding, Yong; Nam, Chang-Yong; Ohodnicki, Paul; Gao, Pu-Xian

2016-04-13

Noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La(0.8)Sr(0.2)FeO3 (LSFO) nanoparticle surface decoration on Ga2O3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts was of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga2O3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga2O3 nanorod surfaces with faster surface CO oxidation reactions.

Electron-hole pairs generated in ZrO2 nanoparticle resist upon exposure to extreme ultraviolet radiation

NASA Astrophysics Data System (ADS)

Kozawa, Takahiro; Santillan, Julius Joseph; Itani, Toshiro

2018-02-01

Metal oxide nanoparticle resists have attracted much attention as the next-generation resist used for the high-volume production of semiconductor devices. However, the sensitization mechanism of the metal oxide nanoparticle resists is unknown. Understanding the sensitization mechanism is important for the efficient development of resist materials. In this study, the energy deposition in a zirconium oxide (ZrO2) nanoparticle resist was investigated. The numbers of electron-hole pairs generated in a ZrO2 core and an methacrylic acid (MAA) ligand shell upon exposure to 1 mJ cm-2 (exposure dose) extreme ultraviolet (EUV) radiations were theoretically estimated to be 0.16 at most and 0.04-0.17 cm2 mJ-1, respectively. By comparing the calculated distribution of electron-hole pairs with the line-and-space patterns of the ZrO2 nanoparticle resist fabricated by an EUV exposure tool, the number of electron-hole pairs required for the solubility change of the resist films was estimated to be 1.3-2.2 per NP. NP denotes a nanoparticle consisting of a metal oxide core with a ligand shell. In the material design of metal oxide nanoparticle resists, it is important to efficiently use the electron-hole pairs generated in the metal oxide core for the chemical change of ligand molecules.

Synthesis and characterization of Fe-based metal and oxide based nanoparticles: discoveries and research highlights of potential applications in biology and medicine.

PubMed

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Cao, Yanqin; Wu, Haibo; Nogami, Masayuki

2014-01-01

In this review, we have presented the controlled synthesis of Fe-based metal and oxide nanoparticles with large size by chemical methods. The issues of the size, shape and morphology of Fe nanoparticles are discussed in the certain ranges of practical applications in biology and medicine. The homogeneous nanosystems of Fe-based metal and oxide nanoparticles with various sizes and shapes from the nano-to-micro ranges can be used in order to meet the demands of the treatments of dangerous tumors and cancers through magnetic hyperthermia and magnetic resonance imaging (MRI). In this context, the polyhedral Fe-based metal and oxide nanoparticles having large size in the ranges from 1000 nm to 5000 nm can be potentially used in magnetic hyperthermia and MRI in the innovative drug delivery, diagnosis, treatment, and therapy of tumor and cancer diseases because of their very high bio-adaptability. We have suggested that high stability and durability of Fe-based metal and oxide nanoparticles are very crucial to recent magnetic hyperthermia and MRI technology. The roles of various Fe-based nanostructures are focused in biomedical applications of tumors and cancers diagnostics, targeted drug delivery, and magnetic hyperthermia. Finally, Fe-based, α-, β- and γ-Fe2O3, and Fe3O4-based nanoparticles are shortly discussed in various potential applications in catalysis, biology, and medicine.

Quantitation of Surface Coating on Nanoparticles Using Thermogravimetric Analysis.

PubMed

Dongargaonkar, Alpana A; Clogston, Jeffrey D

2018-01-01

Nanoparticles are critical components in nanomedicine and nanotherapeutic applications. Some nanoparticles, such as metallic nanoparticles, consist of a surface coating or surface modification to aid in its dispersion and stability. This surface coating may affect the behavior of nanoparticles in a biological environment, thus it is important to measure. Thermogravimetric analysis (TGA) can be used to determine the amount of coating on the surface of the nanoparticle. TGA experiments run under inert atmosphere can also be used to determine residual metal content present in the sample. In this chapter, the TGA technique and experimental method are described.

Material influence on hot spot distribution in the nanoparticle heterodimer on film

NASA Astrophysics Data System (ADS)

Chen, Fang; Huang, Yingzhou; Wei, Hua; Wang, Shuxia; Zeng, Xiping; Cao, Wenbin; Wen, Weijia

2018-04-01

The metal nanoparticle aggregated on film, as an effective plasma enhancement pathway, has been widely used in various surface plasmon-related fields. In this study, the hot spots on the metal nanoparticle dimer composed of different materials (Agsbnd Au, Agsbnd Pd, and Agsbnd Cu) on metal (Au) film were investigated with finite element method. Based on the results, the hot spot distribution affected by the material can be confirmed by the electric field distribution of the metal nanoparticle dimer on the film. The aggregation effects of Au and Ag nanoparticles in Ausbnd Ag dimer system are not significant. However, for the Pdsbnd Ag dimer system, the hot spot aggregation effect is slightly larger than that of the Pd nanoparticle under the Ag nanoparticle. Besides, the non-uniform hot spots would bring about the light focusing phenomenon that the light intensity under Ag nanoparticle is almost 100 times greater than that under Cu nanoparticle in Agsbnd Cu dimer system. These results were further confirmed by the surface charge distribution, and analyzed based on the plasmonic hybridization theory. The data about the nanoparticle dimer on the dielectric (Si) film demonstrate the importance of induced image charges on the film surface in such a light focusing phenomenon. Our findings can enhance the understanding of the surface plasmon coupling in different materials, which may have great application prospects in surface plasmon-related fields, such as SERS, plasmonic enhanced solar cell, and plasmonic sensoring, etc.

Pyrite-Type Nanomaterials for Advanced Electrocatalysis.

PubMed

Gao, Min-Rui; Zheng, Ya-Rong; Jiang, Jun; Yu, Shu-Hong

2017-09-19

Since being proposed by John Bockris in 1970, hydrogen economy has emerged as a very promising alternative to the current hydrocarbon economy. Access to reliable and affordable hydrogen economy, however, requires cost-effective and highly efficient electrocatalytic materials that replace noble metals (e.g., Pt, Ir, Ru) to negotiate electrode processes such as oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). Although substantial advances in the development of inexpensive catalysts, successful deployment of these materials in fuel cells and electrolyzers will depend on their improved activity and robustness. Recent research has demonstrated that the nanostructuring of Earth-abundant minerals provides access to newly advanced energy materials, particularly for nanostructured pyrites, which are attracting great interest. Crystalline pyrites commonly contain the characteristic dianion units and have cations occurring in octahedral coordination-whose generalized formula is MX 2 , where M can be transition metal of groups 8-12 and X is a chalcogen. The diversity of pyrites that are accessible and their versatile and tunable properties make them attractive for a wide range of applications from photovoltaics to energy storage and electrocatalysis. Pyrite-type structures can be further extended to their ternary analogues, for example, CoAsS (cobaltite), NiAsS (gersdorffite), NiSbS (ullmannite), CoPS, and many others. Moreover, improved properties of pyrites can be realized through grafting them with promoter objects (e.g., metal oxides, metal chalcogenides, noble metals, and carbons), which bring favorable interfaces and structural and electronic modulations, thus leading to performance gains. In recent years, research on the synthesis of pyrite nanomaterials and on related structure understanding has dramatically advanced their applications, which offers new perspectives in the search for efficient and robust electrocatalysts, yet a focused review that concentrates the critical developments is still missing. In this Account, we describe our recent progress on the discoveries and applications of nanostructured pyrite-type materials in the area of electrocatalysis. We first briefly highlight some interesting properties of pyrite-type materials and why they are attractive for modern electrocatalysis. Some recent advances on their synthesis that allows access to highly nanostructured pyrite-type materials are reviewed, along with the grafting of resultant pyrites with foreign materials (e.g., metal oxides, metal chalcogenides, noble metals, and carbons) to enable improved catalytic performances. We finally spotlight the exciting examples where pyrite nanostructures were used as efficient electrocatalysts to drive the OER, HER, and methanol-tolerant ORR. It is reasonable to assume that, with significant efforts and focus, the next few years will bring new advances on the pyrites and other minerals for electrocatalysis.

Natural inorganic nanoparticles--formation, fate, and toxicity in the environment.

PubMed

Sharma, Virender K; Filip, Jan; Zboril, Radek; Varma, Rajender S

2015-12-07

The synthesis, stability, and toxicity of engineered metal nanoparticles (ENPs) have been extensively studied during the past two decades. In contrast, research on the formation, fate, and ecological effects of naturally-occurring nanoparticles (NNPs) has become a focus of attention only recently. The natural existence of metal nanoparticles and their oxides/sulfides in waters, wastewaters, ore deposits, mining regions, and hydrothermal vents, as exemplified by the formation of nanoparticles containing silver and gold (AgNPs and AuNPs), Fe, Mn, pyrite (FeS2), Ag2S, CuS, CdS, and ZnS, is dictated largely by environmental conditions (temperature, pH, oxic/anoxic, light, and concentration and characteristics of natural organic matter (NOM)). Examples include the formation of nanoparticles containing pyrite, Cu and Zn-containing pyrite, and iron in hydrothermal vent black smoker emissions. Metal sulfide nanoparticles can be formed directly from their precursor ions or indirectly by sulfide ion-assisted transformation of the corresponding metal oxides under anaerobic conditions. This tutorial focuses on the formation mechanisms, fate, and toxicity of natural metal nanoparticles. Natural waters containing Ag(I) and Au(III) ions in the presence of NOM generate AgNPs and AuNPs under thermal, non-thermal, and photochemical conditions. These processes are significantly accelerated by existing redox species of iron (Fe(II)/Fe(III)). NOM, metal-NOM complexes, and reactive oxygen species (ROS) such as O2˙(-), ˙OH, and H2O2 are largely responsible for the natural occurrence of nanoparticles. AgNPs and AuNPs emanating from Ag(I)/Au(III)-NOM reactions are stable for several months, thus indicating their potential to be transported over long distances from their point of origin. However, endogenous cations present in natural waters can destabilize the nanoparticles, with divalent cations (e.g., Ca(2+), Mg(2+)) being more influential than their monovalent equivalents (e.g., Na(+), K(+)). The toxicity of NNPs may differ from that of ENPs because of differences in the coatings on the nanoparticle surfaces. An example of this phenomenon is presented and is briefly discussed.

Enhanced absorption with quantum dots, metal nanoparticles, and 2D materials

NASA Astrophysics Data System (ADS)

Simsek, Ergun; Mukherjee, Bablu; Guchhait, Asim; Chan, Yin Thai

2016-03-01

We fabricate and characterize mono- and few- layers of MoS2 and WSe2 on glass and SiO2/Si substrates. PbS quantum dots and/or Au nanoparticles are deposited on the fabricated thin metal dichalcogenide films by controlled drop casting and electron beam evaporation techniques. The reflection spectra of the fabricated structures are measured with a spatially resolved reflectometry setup. Both experimental and numerical results show that surface functionalization with metal nanoparticles can enhance atomically thin transition metal dichalcogenides' absorption and scattering capabilities, however semiconducting quantum dots do not create such effect.

Hierarchical active factors to band gap and nonlinear optical response in Ag-containing quaternary-chalcogenide compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Jun-ben; Xinjiang Key Laboratory of Electronic Information Material and Devices, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, 40-1 South Beijing Road, Urumqi 830011; Mamat, Mamatrishat, E-mail: mmtrxt@xju.edu.cn

In this research work, Ag-containing quaternary-chalcogenide compounds KAg{sub 2}TS{sub 4} (T=P, Sb) (I-II) and RbAg{sub 2}SbS{sub 4} (III) have been studied by means of Density Functional Theory as potential IR nonlinear optical materials. The origin of wide band gap, different optical anisotropy and large SHG response is explained via a combination of density of states, electronic density difference and bond population analysis. It is indicated that the different covalent interaction behavior of P-S and Sb-S bonds dominates the band gap and birefringence. Specifically, the Ag-containing chalcogenide compound KAg{sub 2}PS{sub 4} possesses wide band gap and SHG response comparable with thatmore » of AgGaS{sub 2}. By exploring the origin of the band gap and NLO response for compounds KAg{sub 2}TS{sub 4} (T=P, Sb), we found the determination factor to the properties is different, especially the roles of Ag-d orbitals and bonding behavior of P-S or Sb-S. Thus, the compounds KAg{sub 2}TS{sub 4} (T=P, Sb) and RbAg{sub 2}SbS{sub 4} can be used in infrared (IR) region. - Graphical abstract: Metal thiophosphates RbPbPS{sub 4} and KSbP{sub 2}S{sub 6} have a similar band gap with KAg{sub 2}PS{sub 4}. However, based on first principles calculated results it shown that KAg{sub 2}PS{sub 4} possesses wide band gap (3.02 eV) and relatively large SHG response. Display Omitted.« less

Sustainable Utilization of Bio waste towards the Green Synthesis of Nanoparticles and its Utility in the Naked Eye Detection of Metals Coupled with its Larvicidal and Antimicrobial Properties

NASA Astrophysics Data System (ADS)

Nikhila, P. S.; Satheesh, Namitha; Sreejitha, V. S.; Pillai, Anandu R.; Saritha, A.; Smitha Chandran, S.

2018-02-01

Green synthesis of nanoparticles has become a prominent zone of attention in the field of nanotechnology, as it is a nontoxic, economically feasible and green approach. In the present work we have developed an eco-friendly and zero cost method for the synthesis of silver nanoparticles using common a bio waste banana blossom peel. The well-known characteristic phenomenon of surface Plasmon resonance (SPR) has been exploited towards the characterization of the green synthesized nanoparticles. The aforementioned nanoparticles were characterized by UV spectroscopy and the behaviour of these particles towards naked eye detection of metal ions were observed. The sensitivity of the nanoparticles towards the detection of metal ions was carefully monitored by the shift in the SPR band. Moreover the larvicidal potential of these green synthesized silver nanoparticles were evaluated as per WHO standards. The synthesized silver nanoparticles were found to be an effective antibacterial agent against Gram negative bacteria-E.coli. The method we followed for the synthesis of silver nanoparticles is economically feasible as well as environment friendly and also capable of rapid synthesis of nanoparticles at ambient conditions.

Beet juice utilization: Expeditious green synthesis of nobel metal nanoparticles (Ag, Au, Pt, and Pd) using microwaves

EPA Science Inventory

Metal nanoparticles of Ag, Au, Pt, and Pd were prepared in aqueous solutions via a rapid microwave-assisted green method using beet juice, an abundant sugar-rich agricultural produce, served as both a reducing and a capping reagent. The Ag nanoparticles with capping prepared by b...

Flexible supercapacitor electrodes based on real metal-like cellulose papers.

PubMed

Ko, Yongmin; Kwon, Minseong; Bae, Wan Ki; Lee, Byeongyong; Lee, Seung Woo; Cho, Jinhan

2017-09-14

The effective implantation of conductive and charge storage materials into flexible frames has been strongly demanded for the development of flexible supercapacitors. Here, we introduce metallic cellulose paper-based supercapacitor electrodes with excellent energy storage performance by minimizing the contact resistance between neighboring metal and/or metal oxide nanoparticles using an assembly approach, called ligand-mediated layer-by-layer assembly. This approach can convert the insulating paper to the highly porous metallic paper with large surface areas that can function as current collectors and nanoparticle reservoirs for supercapacitor electrodes. Moreover, we demonstrate that the alternating structure design of the metal and pseudocapacitive nanoparticles on the metallic papers can remarkably increase the areal capacitance and rate capability with a notable decrease in the internal resistance. The maximum power and energy density of the metallic paper-based supercapacitors are estimated to be 15.1 mW cm -2 and 267.3 μWh cm -2 , respectively, substantially outperforming the performance of conventional paper or textile-type supercapacitors.With ligand-mediated layer-by-layer assembly between metal nanoparticles and small organic molecules, the authors prepare metallic paper electrodes for supercapacitors with high power and energy densities. This approach could be extended to various electrodes for portable/wearable electronics.

SINGLE-PARTICLE ICPMS FOR CHARACTERIZING METAL-BASED NANOPARTICLES IN THE ENVIRONMENT - ADVANCES AND CHALLENGES

EPA Science Inventory

As engineered metal-based nanomaterials become widely used in consumer and industrial products, the amount of these materials introduced into the environment by a variety of paths will increase. The concentration of metal associated with these engineered nanoparticles will be s...

Biogenic synthesis of metallic nanoparticles and prospects toward green chemistry.

PubMed

Adil, Syed Farooq; Assal, Mohamed E; Khan, Mujeeb; Al-Warthan, Abdulrahman; Siddiqui, Mohammed Rafiq H; Liz-Marzán, Luis M

2015-06-07

The immense importance of nanoparticles and their applications is a strong motivation for exploring new synthetic techniques. However, due to strict regulations that manage the potential environmental impacts greener alternatives for conventional synthesis are the focus of intense research. In the scope of this perspective, a concise discussion about the use of green reducing and stabilizing agents toward the preparation of metal nanoparticles is presented. Reports on the synthesis of noble metal nanoparticles using plant extracts, ascorbic acid and sodium citrate as green reagents are summarized and discussed, pointing toward an urgent need of understanding the mechanistic aspects of the involved reactions.

Method for removing strongly adsorbed surfactants and capping agents from metal to facilitate their catalytic applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adzic, Radoslav R.; Gong, Kuanping; Cai, Yun

A method of synthesizing activated electrocatalyst, preferably having a morphology of a nanostructure, is disclosed. The method includes safely and efficiently removing surfactants and capping agents from the surface of the metal structures. With regard to metal nanoparticles, the method includes synthesis of nanoparticle(s) in polar or non-polar solution with surfactants or capping agents and subsequent activation by CO-adsorption-induced surfactant/capping agent desorption and electrochemical oxidation. The method produces activated macroparticle or nanoparticle electrocatalysts without damaging the surface of the electrocatalyst that includes breaking, increasing particle thickness or increasing the number of low coordination sites.

Absorption properties of metal-semiconductor hybrid nanoparticles.

PubMed

Shaviv, Ehud; Schubert, Olaf; Alves-Santos, Marcelo; Goldoni, Guido; Di Felice, Rosa; Vallée, Fabrice; Del Fatti, Natalia; Banin, Uri; Sönnichsen, Carsten

2011-06-28

The optical response of hybrid metal-semiconductor nanoparticles exhibits different behaviors due to the proximity between the disparate materials. For some hybrid systems, such as CdS-Au matchstick-shaped hybrids, the particles essentially retain the optical properties of their original components, with minor changes. Other systems, such as CdSe-Au dumbbell-shaped nanoparticles, exhibit significant change in the optical properties due to strong coupling between the two materials. Here, we study the absorption of these hybrids by comparing experimental results with simulations using the discrete dipole approximation method (DDA) employing dielectric functions of the bare components as inputs. For CdS-Au nanoparticles, the DDA simulation provides insights on the gold tip shape and its interface with the semiconductor, information that is difficult to acquire by experimental means alone. Furthermore, the qualitative agreement between DDA simulations and experimental data for CdS-Au implies that most effects influencing the absorption of this hybrid system are well described by local dielectric functions obtained separately for bare gold and CdS nanoparticles. For dumbbell shaped CdSe-Au, we find a shortcoming of the electrodynamic model, as it does not predict the "washing out" of the optical features of the semiconductor and the metal observed experimentally. The difference between experiment and theory is ascribed to strong interaction of the metal and semiconductor excitations, which spectrally overlap in the CdSe case. The present study exemplifies the employment of theoretical approaches used to describe the optical properties of semiconductors and metal nanoparticles, to achieve better understanding of the behavior of metal-semiconductor hybrid nanoparticles.

Electro-Optics Millimeter/Microwave Technology in Japan. Report of DoD Technology Team.

DTIC Science & Technology

1985-05-01

Fiber Technology Hitachi is developing Ge-Se chalcogenide glass infrared optical fibers. Mate- rial development and evaluation has been carried out...chalcogenide glass fibers. The analysis indi- cates that the addition of Sb to Ge-Se chalcogenide glass should yield fibers with a very small absorption...representative of other commercial cables. Fiber is drawn using Vapor Axial Deposition (VAD) with pre-form glass ingots. Multiple fibers are combined

Space processing of chalcogenide glass

NASA Technical Reports Server (NTRS)

Larsen, D. C.; Ali, M. I.

1977-01-01

The manner in which the weightless, containerless nature of in-space processing can be successfully utilized to improve the quality of infrared transmitting chalcogenide glasses is determined. The technique of space processing chalcogenide glass was developed, and the process and equipment necessary to do so was defined. Earthbound processing experiments with As2S3 and G28Sb12Se60 glasses were experimented with. Incorporated into these experiments is the use of an acoustic levitation device.

Index change of chalcogenide materials from precision glass molding processes

NASA Astrophysics Data System (ADS)

Deegan, J.; Walsh, K.; Lindberg, G.; Benson, R.; Gibson, D.; Bayya, S.; Sanghera, J.; Stover, E.

2015-05-01

With the increase in demand for infrared optics for thermal applications and the use of glass molding of chalcogenide materials to support these higher volume optical designs, an investigation of changes to the optical properties of these materials is required. Typical precision glass molding requires specific thermal conditions for proper lens molding of any type of optical glass. With these conditions a change (reduction) of optical index occurs after molding of all oxide glass types and it is presumed that a similar behavior will happen with chalcogenide based materials. We will discuss the effects of a typical molding thermal cycle for use with commercially and newly developed chalcogenide materials and show results of index variation from nominally established material data.

Pressure and temperature induced elastic properties of rare earth chalcogenides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shriya, S.; Sapkale, R., E-mail: sapkale.raju@rediffmail.com; Varshney, Dinesh, E-mail: vdinesh33@rediffmail.com

2016-05-06

The pressure and temperature dependent mechanical properties as Young modulus, Thermal expansion coefficient of rare earth REX (RE = La, Pr, Eu; X = O, S, Se, and Te) chalcogenides are studied. The rare earth chalcogenides showed a structural phase transition (B1–B2). Pressure dependence of Young modulus discerns an increase in pressure inferring the hardening or stiffening of the lattice as a consequence of bond compression and bond strengthening. Suppressed Young modulus as functions of temperature infers the weakening of the lattice results in bond weakening in REX. Thermal expansion coefficient demonstrates that REX (RE = La, Pr, Eu; Xmore » = O, S, Se, and Te) chalcogenides is mechanically stiffened, and thermally softened on applied pressure and temperature.« less

Kinetic Study on the Formation of Bimetallic Core-Shell Nanoparticles via Microemulsions

PubMed Central

Tojo, Concha; Vila-Romeu, Nuria

2014-01-01

Computer calculations were carried out to determine the reaction rates and the mean structure of bimetallic nanoparticles prepared via a microemulsion route. The rates of reaction of each metal were calculated for a particular microemulsion composition (fixed intermicellar exchange rate) and varying reduction rate ratios between both metal and metal salt concentration inside the micelles. Model predictions show that, even in the case of a very small difference in reduction potential of both metals, the formation of an external shell in a bimetallic nanoparticle is possible if a large reactant concentration is used. The modification of metal arrangement with concentration was analyzed from a mechanistic point of view, and proved to be due to the different impact of confinement on each metal: the reaction rate of the faster metal is only controlled by the intermicellar exchange rate but the slower metal is also affected by a cage-like effect. PMID:28788260

Mono and bimetallic nanoparticles of gold, silver and palladium-catalyzed NADH oxidation-coupled reduction of Eosin-Y

NASA Astrophysics Data System (ADS)

Santhanalakshmi, J.; Venkatesan, P.

2011-02-01

Mono metallic (Au, Ag, Pd) and bimetallic (Au-Ag, Ag-Pd, Au-Pd) with 1:1 mol stoichiometry, nanoparticles are synthesized using one-pot, temperature controlled chemical method using cetyltrimethylammonium bromide (CTAB) as the capping agent. The particle sizes (Au = 5.6, Ag = 5.0, Pd = 6.0, Au-Ag = 9.2, Ag-Pd = 9.6, Au-Pd = 9.4 nm) are characterized by UV-Vis, HRTEM, and XRD measurements, respectively. CTAB bindings onto mono and bimetallic nanoparticles are analyzed by FTIR spectra. The catalytic activities of mono and bimetallic nanoparticles are tested on the reaction between NADH oxidation and Eosin-Y reduction. The effects of base, pH, ionic strength, nature of mono and bimetallic catalysts are studied and the reaction conditions are optimized. Bimetallic nanoparticles exhibited better catalysis than the mono metallic nanoparticles, which may be due to the electronic effects of the core to shell metal atoms.

Formation of metal clusters in halloysite clay nanotubes

NASA Astrophysics Data System (ADS)

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; Ivanov, Evgenii V.; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A.; Lvov, Yuri M.

2017-12-01

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length 1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube's central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube's wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

Formation of metal clusters in halloysite clay nanotubes.

PubMed

Vinokurov, Vladimir A; Stavitskaya, Anna V; Chudakov, Yaroslav A; Ivanov, Evgenii V; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A; Lvov, Yuri M

2017-01-01

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c .50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube's central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube's wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

Green Synthesis of Iron Nanoparticles and Their Environmental Applications and Implications

PubMed Central

Saif, Sadia; Tahir, Arifa; Chen, Yongsheng

2016-01-01

Recent advances in nanoscience and nanotechnology have also led to the development of novel nanomaterials, which ultimately increase potential health and environmental hazards. Interest in developing environmentally benign procedures for the synthesis of metallic nanoparticles has been increased. The purpose is to minimize the negative impacts of synthetic procedures, their accompanying chemicals and derivative compounds. The exploitation of different biomaterials for the synthesis of nanoparticles is considered a valuable approach in green nanotechnology. Biological resources such as bacteria, algae fungi and plants have been used for the production of low-cost, energy-efficient, and nontoxic environmental friendly metallic nanoparticles. This review provides an overview of various reports of green synthesised zero valent metallic iron (ZVMI) and iron oxide (Fe2O3/Fe3O4) nanoparticles (NPs) and highlights their substantial applications in environmental pollution control. This review also summarizes the ecotoxicological impacts of green synthesised iron nanoparticles opposed to non-green synthesised iron nanoparticles. PMID:28335338

Plasmon transmutation: inducing new modes in nanoclusters by adding dielectric nanoparticles.

PubMed

Wen, Fangfang; Ye, Jian; Liu, Na; Van Dorpe, Pol; Nordlander, Peter; Halas, Naomi J

2012-09-12

Planar clusters of coupled plasmonic nanoparticles support nanoscale electromagnetic "hot spots" and coherent effects, such as Fano resonances, with unique near and far field signatures, currently of prime interest for sensing applications. Here we show that plasmonic cluster properties can be substantially modified by the addition of individual, discrete dielectric nanoparticles at specific locations on the cluster, introducing new plasmon modes, or transmuting existing plasmon modes to new ones, in the resulting metallodielectric nanocomplex. Depositing a single carbon nanoparticle in the junction between a pair of adjacent nanodisks induces a metal-dielectric-metal quadrupolar plasmon mode. In a ten-membered cluster, placement of several carbon nanoparticles in junctions between multiple adjacent nanoparticles introduces a collective magnetic plasmon mode into the Fano dip, giving rise to an additional subradiant mode in the metallodielectric nanocluster response. These examples illustrate that adding dielectric nanoparticles to metallic nanoclusters expands the number and types of plasmon modes supported by these new mixed-media nanoscale assemblies.

A model for the latent heat of melting in free standing metal nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shin, Jeong-Heon; Deinert, Mark R., E-mail: mdeinert@mail.utexas.edu

2014-04-28

Nanoparticles of many metals are known to exhibit scale dependent latent heats of melting. Analytical models for this phenomenon have so far failed to completely capture the observed phenomena. Here we present a thermodynamic analysis for the melting of metal nanoparticles in terms of their internal energy and a scale dependent surface tension proposed by Tolman. The resulting model predicts the scale dependence of the latent heat of melting and is confirmed using published data for tin and aluminum.

A model for the latent heat of melting in free standing metal nanoparticles

NASA Astrophysics Data System (ADS)

Shin, Jeong-Heon; Deinert, Mark R.

2014-04-01

Nanoparticles of many metals are known to exhibit scale dependent latent heats of melting. Analytical models for this phenomenon have so far failed to completely capture the observed phenomena. Here we present a thermodynamic analysis for the melting of metal nanoparticles in terms of their internal energy and a scale dependent surface tension proposed by Tolman. The resulting model predicts the scale dependence of the latent heat of melting and is confirmed using published data for tin and aluminum.

A model for the latent heat of melting in free standing metal nanoparticles.

PubMed

Shin, Jeong-Heon; Deinert, Mark R

2014-04-28

Nanoparticles of many metals are known to exhibit scale dependent latent heats of melting. Analytical models for this phenomenon have so far failed to completely capture the observed phenomena. Here we present a thermodynamic analysis for the melting of metal nanoparticles in terms of their internal energy and a scale dependent surface tension proposed by Tolman. The resulting model predicts the scale dependence of the latent heat of melting and is confirmed using published data for tin and aluminum.

Subsurface synthesis and characterization of Ag nanoparticles embedded in MgO

NASA Astrophysics Data System (ADS)

Vilayurganapathy, S.; Devaraj, A.; Colby, R.; Pandey, A.; Varga, T.; Shutthanandan, V.; Manandhar, S.; El-Khoury, P. Z.; Kayani, Asghar; Hess, W. P.; Thevuthasan, S.

2013-03-01

Metal nanoparticles exhibit a localized surface plasmon resonance (LSPR) which is very sensitive to the size and shape of the nanoparticle and the surrounding dielectric medium. The coupling between the electromagnetic radiation and the localized surface plasmon in metallic nanoparticles results in a sizable enhancement of the incident fields, making them possible candidates for plasmonic applications. In particular, partially exposed metallic nanoparticles distributed in a dielectric matrix can provide prime locations for LSPR spectroscopy and sensing. We report the synthesis and characterization of a plasmonic substrate consisting of Ag nanoparticles partially buried in MgO. Ag nanoparticles of different shapes and size distributions were synthesized below the surface of MgO by implanting 200 keV Ag+ ions followed by annealing at 1000 °C for 10 and 30 h. A detailed optical and structural characterization was carried out to understand the evolution of the Ag nanoparticle and size distribution inside the MgO matrix. Micro x-ray diffraction (Micro-XRD) was employed to investigate the structural properties and estimate the crystallite size. The nanoparticles evolved from a spherical to a faceted morphology with annealing time, assuming an octahedral shape truncated at the (001) planes, as visualized from aberration-corrected transmission electron microscopy (TEM) images. The nanoparticles embedded in MgO were shown to be pure metallic Ag using atom probe tomography (APT). The nanoparticles were partially exposed to the surface by employing plasma etch techniques to remove the overlaying MgO. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to study the surface morphology and obtain a height distribution for the partially exposed nanoparticles.

Gold and silver nanoparticles from Trianthema decandra: synthesis, characterization, and antimicrobial properties

PubMed Central

Geethalakshmi, R; Sarada, DVL

2012-01-01

Background There is an increasing commercial demand for nanoparticles due to their wide applicability in various markets, including medicine, catalysis, electronics, chemistry, and energy. In this report, a simple and ecofriendly chemical reaction for the synthesis of gold and silver nanoparticles from Trianthema decandra (Aizoaceae) has been developed. Methods and results On treatment of aqueous solutions containing chloroauric acid or silver nitrate with root extract of T. decandra, stable gold or silver nanoparticles were rapidly formed. The kinetics of reduction of gold and silver ions during the reaction was analyzed by ultraviolet-visible spectroscopy. Field emission-scanning electron microscopy showed formation of gold nanoparticles in various shapes, including spherical, cubical, triangular, and hexagonal, while silver nanoparticles were spherical. The size of the gold nanoparticles was 33–65 nm and that of the silver nanoparticles was 36–74 nm. Energy dispersive x-ray and Fourier transform infrared spectroscopy confirmed the presence of metallic gold and metallic silver in the respective nanoparticles. The antimicrobial properties of the synthesized nanoparticles were analyzed using the Kirby-Bauer method. The results show varied susceptibility of microorganisms to the gold and silver nanoparticles. Conclusion It is believed that phytochemicals present in T. decandra extract reduce the silver and gold ions into metallic nanoparticles. This strategy reduces the cost of production and the environmental impact. The silver and gold nanoparticles formed showed strong activity against all microorganisms tested. PMID:23091381

Transition-Metal Oxide (111) Bilayers

DOE PAGES

Okamoto, Satoshi; Xiao, Di

2018-04-15

Correlated electron systems on a honeycomb lattice have emerged as a fertile playground to explore exotic electronic phenomena. Theoretical and experimental work has appeared to realize novel behavior, including quantum Hall effects and valleytronics, mainly focusing on van der Waals compounds, such as graphene, chalcogenides, and halides. Here in this paper, we review our theoretical study on perovskite transition-metal oxides (TMOs) as an alternative system to realize such exotic phenomena. We demonstrate that novel quantum Hall effects and related phenomena associated with the honeycomb structure could be artificially designed by such TMOs by growing their heterostructures along the [111] crystallographicmore » axis. One of the important predictions is that such TMO heterostructures could support two-dimensional topological insulating states. The strong correlation effects inherent to TM d electrons further enrich the behavior.« less

Transition-Metal Oxide (111) Bilayers

NASA Astrophysics Data System (ADS)

Okamoto, Satoshi; Xiao, Di

2018-04-01

Correlated electron systems on a honeycomb lattice have emerged as a fertile playground to explore exotic electronic phenomena. Theoretical and experimental work has appeared to realize novel behavior, including quantum Hall effects and valleytronics, mainly focusing on van der Waals compounds, such as graphene, chalcogenides, and halides. In this article, we review our theoretical study on perovskite transition-metal oxides (TMOs) as an alternative system to realize such exotic phenomena. We demonstrate that novel quantum Hall effects and related phenomena associated with the honeycomb structure could be artificially designed by such TMOs by growing their heterostructures along the [111] crystallographic axis. One of the important predictions is that such TMO heterostructures could support two-dimensional topological insulating states. The strong correlation effects inherent to TM d electrons further enrich the behavior.

Open-framework micro- and meso-structured chalcogenides and their ion exchange properties

NASA Astrophysics Data System (ADS)

Ding, Nan

2007-12-01

Micro- and meso- structured chalcogenides with open inorganic framework have driven tremendous attention and intense work during the last two decades. They belong to a special category of materials possessing multifunctional potential due to their large void space within the atomic skeletons and the novel physical properties brought by the chalcogen elements. The latter are not generally present in typical open-framework oxides. In addition, because of the different size and electronegativity of the chalcogen elements compared to oxygen, many new structural properties were expected to emerge when the work in this dissertation was undertaken. The major body of this work involves group 13 (e.g. Ga, In) or 14 (e.g. Ge, Sn) elements with chalcogen. Transition metals also are incorporated in a few examples. The first two groups of compounds reported belong to the latter case. Unique structure types have been obtained under hydrothermal conditions via the combination of M (M = Zn, Cd), Sn and Q (Q = S, Se) to build microporous A6M4Sn3Q13 (A = K, Rb) based on truncated penta-supertrahedral cluster [M4Sn4Q 17]10-. More surprisingly, the protonation of K 6Cd4Sn3Se13 led to another new compound K14Cd15Sn12Se46 which possesses a labyrinth-like void space within the compact [Cd15Sn12Se 46]14- anionic skeleton. This structural characteristic leads to an unusual stability of the compound in acid. Both the K6Cd 4Sn3Se13 and K14Cd15Sn 12Se46 are fast ion-exchangers and their K+ ions can be replaced by other alkali metal cations and even H+ for the latter. Other work reported was aimed at the heavier analogs of alumiophosphate, i.e. the open-frameworks based on group 13 (Ga, In), 15 (Sb) and chalcogen elements. Two groups of chalcoantimonates with two-dimensional architectures [M5Sb6S19]5- and polymorphic [M2Sb2Q7]2- (M = Ga, In; Q = S, Se) were obtained. With the help of bulky organic structure-directing agents, large windows were formed in some of these anionic slabs. The windows are aligned through each layer, adding a pseudo-3D feature to the compounds. This leads to excellent ion-exchange properties. More remarkably, these compounds showed exceptional selectivity for Cs+ ions than any other alkali metal and alkaline earth metal cations due to the soft acid (Cs +)/soft base (S2-) attraction and the size discrimination imposed by the open windows within the frameworks. These properties point to a new direction of designing compounds for possible radioactive 137Cs+ remediation. With the even larger surfactant molecules in water, metal cations In 3+, Zn2+ and Cd2+ can connect [SbSe 4]3- clusters via coordination chemistry to form cubic and hexagonal mesophases. In addition to the linking effect, these metal cations also played the role of Lewis acids and partially reduced [SbSe4] 3- to [SbSe3]3-, both of which are present in the long-range ordered mesostructures. Short range order in a mesostuctured chalcogenide was approached, when structurally rigid Chevrel clusters [Re 6Se6Br8]2- were linked by triselenide anions via metathesis. Higher angle Bragg reflections of this compound provided an opportunity to build a structural model for the first time for a chalcogen-based mesophase.

Size Selective Green Synthesis of Silver and Gold Nanoparticles: Enhanced Antibacterial Efficacy of Resveratrol Capped Silver Sol.

PubMed

Shukla, Shashi P; Roy, Mainak; Mukherjee, Poulomi; Das, Laboni; Neogy, Suman; Srivastava, Dinesh; Adhikari, Soumyakanti

2016-03-01

In view of potential biomedical application of the noble metal nanoparticles, we report a size controlled yet simple and green synthesis of resveratrol stabilized silver and gold nanoparticles having low polydispersity of size. Here, resveratrol plays two simultaneous roles, reducing the metal ions and providing efficient capping of the small nanoparticles. This gives rise to specific size of silver and gold nanoparticles at specific ratios of metal to resveratrol. The particles have been characterized by XRD and transmission electron microscopy. The nanoparticle sols are stable for months. The UV Visible absorption spectra of the silver sol show the plasmon peak of spherical nanoparticles, presence of which is further reflected in the TEM images. Size of the silver particles obtained is in between 11 to 21 nm depending on the ratio of resveratrol to metal ion used. Resveratrol capped silver nanoparticles exhibit high antibacterial activity against Gram negative wild type E coli BW (25113). The minimum inhibitory concentration (MIC) of nano-silver against the bacterium has been estimated to be 6.48 μg/ml, which is significantly lower than that reported in some earlier as well as recent publications. Reaction of gold ions with resveratrol, on the other hand, produces gold nanoparticles of sizes varying from 7 to 29 nm at different ratios of resveratrol to the metal ions. Particles with higher size and aspect ratio are formed at lower concentration of the capping agent whereas particles with very small size and pseudo-spherical morphology are formed at higher capping concentration. Difference in the formation kinetics of silver and gold nanoparticles has been attributed to the different growth mechanisms in the two cases. Possible modes of anchorage of resveratrol to silver nanoparticles have been investigated using surface enhanced resonance Raman spectroscopy (SERS) which shows that the silver nanoparticles are capped by resveratrol molecule primarily through O-Ag linkages of the p-OH aromatic ring. This, in turn, demonstrates the feasibility of using these nanoparticles as SERS templates.

A universal approach to the synthesis of nanodendrites of noble metals.

PubMed

Feng, Yan; Ma, Xiaohong; Han, Lin; Peng, Zhijian; Yang, Jun

2014-06-07

Nanomaterials usually exhibit structure-dependent catalytic activity, selectivity, and stability. Herein, we report a universal approach for the synthesis of noble metal nanoparticles with a dendritic structure, which is based on the reduction of metal acetylacetonate precursors in oleylamine at a temperature of 160 °C. In this strategy, the metal acetylacetonate precursors are reduced into metal atoms by oleylamine and grow into metal nanoparticles, while oleylamine is simultaneously converted into oleylamide to protect the nanoparticles. The competition between particle aggregation and oleylamide passivation is essential to the formation of a large number of particle aggregates, which eventually grow into nanodendrites via Ostwald ripening process. In particular, in comparison with commercial PtRu/C catalysts, the alloy PtRuOs nanodendrites exhibited superior catalytic activity toward methanol oxidation.

Microwave absorption properties of the core/shell-type iron and nickel nanoparticles

NASA Astrophysics Data System (ADS)

Lu, B.; Dong, X. L.; Huang, H.; Zhang, X. F.; Zhu, X. G.; Lei, J. P.; Sun, J. P.

Iron (Fe) and nickel (Ni) nanoparticles were prepared by the DC arc-discharge method in a mixture of hydrogen and argon gases, using bulk metals as the raw materials. The microstructure of core/shell (metal/metal oxide) in nanoparticle formed after in situ passivation process. The complex electromagnetic parameters (permittivity ɛ=ɛr'+iɛr″ and permeability μ=μr'+iμr″) of the paraffin-mixed nanocomposite samples (paraffin:nanoparticles=1:1 in mass ratio) were measured in the frequency range of 2-18 GHz. The polarization mechanisms of the space charge and dipole coexist in both the Fe and Ni nanoparticles. The orientational polarization is a particular polarization for Fe nanoparticles and brings a relatively higher dielectric loss. Natural resonance is the main reason for magnetic loss and the corresponding frequencies are 11.6 and 5.2 GHz for the Fe and Ni nanoparticles, respectively. The paraffin composite with Fe nanoparticles provided excellent microwave absorption properties (reflection loss <-20 dB) in the range 6.8-16.6 GHz over the absorber thickness of 1.1-2.3 mm.

Real-time cellular and molecular dynamics of bi-metallic self-therapeutic nanoparticle in cancer cells

NASA Astrophysics Data System (ADS)

Vishwakarma, Sandeep Kumar; Bardia, Avinash; Lakkireddy, Chandrakala; Paspala, Syed Ameer Basha; Habeeb, Md. Aejaz; Khan, Aleem Ahmed

2018-02-01

Since last decades various kinds of nanoparticles have been functionalized to improve their biomedical applications. However, the biological effect of un-modified/non-functionalized bi-metallic magnetic nanoparticles remains under investigated. Herein we demonstrate a multifaceted non-functionalized bi-metallic inorganic Gd-SPIO nanoparticle which passes dual high MRI contrast and can kill the cancer cells through several mechanisms. The results of the present study demonstrate that Gd-SPIO nanoparticles have potential to induce cancer cell death by production of reactive oxygen species and apoptotic events. Furthermore, Gd-SPIO nanoparticles also enhance the expression levels of miRNA-199a and miRNA-181a-7p which results in decreased levels of cancer markers such as C-met, TGF-β and hURP. One very interesting finding of this study reveals side scatter-based real-time analysis of nanoparticle uptake in cancer cells using flow cytometry analysis. In conclusion, this study paves a way for future investigation of un-modified inorganic nanoparticles to purport enhanced therapeutic effect in combination with potential anti-tumor drugs/molecules in cancer cells.

WO3/Pt nanoparticles promote light-induced lipid peroxidation and lysosomal instability within tumor cells

NASA Astrophysics Data System (ADS)

Clark, Andrea J.; Petty, Howard R.

2016-02-01

Although metal-metal oxide nanoparticles have attracted considerable interest as catalysts, they have attracted little interest in nanomedicine. This is likely due to the fact that metal oxide semiconductors generally require biologically harmful ultraviolet excitation. In contrast, this study focuses upon WO3/Pt nanoparticles, which can be excited by visible light. To optimize the nanoparticles’ catalytic performance, platinization was performed at alkaline pH. These nanoparticles destroyed organic dyes, consumed dissolved oxygen and produced hydroxyl radicals. 4T1 breast cancer cells internalized WO3/Pt nanoparticles within the membrane-bound endo-lysosomal compartment as shown by electron and fluorescence microscopy. During visible light exposure, but not in darkness, WO3/Pt nanoparticles manufacture reactive oxygen species, promote lipid peroxidation, and trigger lysosomal membrane disruption. As cells of the immune system degrade organic molecules, produce reactive oxygen species, and activate the lipid peroxidation pathway within target cells, these nanoparticles mimic the chemical attributes of immune effector cells. These biomimetic nanoparticles should become useful in managing certain cancers, especially ocular cancer.

Bioselective synthesis of gold nanoparticles from diluted mixed Au, Ir, and Rh ion solution by Anabaena cylindrica

NASA Astrophysics Data System (ADS)

Rochert, Anna S.; Rösken, Liz M.; Fischer, Christian B.; Schönleber, Andreas; Ecker, Dennis; van Smaalen, Sander; Geimer, Stefan; Wehner, Stefan

2017-11-01

Over the last years, an environmentally friendly and economically efficient way of nanoparticle production has been found in the biosynthesis of metal nanoparticles by bacteria and cyanobacteria. In this study, Anabaena cylindrica, a non-toxic cyanobacterium, is deployed in a diluted ionic aqueous mixture of equal concentrations of gold, iridium, and rhodium, of 0.1 mM each, for the selective biosynthesis of metal nanoparticles (NPs). To analyze the cyanobacterial metal uptake, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and inductively coupled plasma mass spectrometry (ICP-MS) were applied. Only gold can be found in crystalline and nanoparticle form inside the cells of A. cylindrica, and it is the only metal for which ICP-MS analyses show a rapid decrease of the concentration in the culture medium. A slight decrease of rhodium and none of iridium was observed in the evaluated timeline of 51 h. The average diameter size of the emerging gold nanoparticles increased over the first few days, but is found to be below 10 nm even after more than 2 days. A new evaluation method was used to determine the spatially resolved distribution of the nanoparticles inside the cyanobacterial cells. This new method was also used to analyze TEM images from earlier studies of A. cylindrica and Anabaena sp., both incubated with an overall concentration of 0.8 mM Au3+ to compare the metal uptake. A. cylindrica was found to be highly selective towards the formation of gold nanoparticles in the presence of rhodium and iridium.

Metallic nanoparticles and their medicinal potential. Part II: aluminosilicates, nanobiomagnets, quantum dots and cochleates.

PubMed

Loomba, Leena; Scarabelli, Tiziano

2013-09-01

Metallic miniaturization techniques have taken metals to nanoscale size where they can display fascinating properties and their potential applications in medicine. In recent years, metal nanoparticles such as aluminium, silicon, iron, cadmium, selenium, indium and calcium, which find their presence in aluminosilicates, nanobiomagnets, quantum dots (Q-dots) and cochleates, have caught attention of medical industries. The increasing impact of metallic nanoparticles in life sciences has significantly advanced the production techniques for these nanoparticles. In this Review, the various methods for the synthesis of nanoparticles are outlined, followed by their physicochemical properties, some recent applications in wound healing, diagnostic imaging, biosensing, assay labeling, antimicrobial activity, cancer therapy and drug delivery are listed, and finally their toxicological impacts are revised. The first half of this article describes the medicinal uses of two noble nanoparticles - gold and silver. This Review provides further information on the ability of aluminum, silicon, iron, selenium, indium, calcium and zinc to be used as nanoparticles in biomedical sciences. Aluminosilicates find their utility in wound healing and antibacterial growth. Iron-oxide nanoparticles enhance the properties of MRI contrast agents and are also used as biomagnets. Cadmium, selenium, tellurium and indium form the core nanostructures of tiny Q-dots used in cellular assay labeling, high-resolution cell imaging and biosensing. Cochleates have the bivalent nano ions calcium, magnesium or zinc imbedded in their structures and are considered to be highly effective agents for drug and gene delivery. The aluminosilicates, nanobiomagnets, Q-dots and cochleates are discussed in the light of their properties, synthesis and utility.

Soluble Lead and Bismuth Chalcogenidometallates: Versatile Solders for Thermoelectric Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hao; Son, Jae Sung; Dolzhnikov, Dmitriy S.

Here we report the syntheses of largely unexplored lead and bismuth chalcogenidometallates in the solution phase. Using N2H4 as the solvent, new compounds such as K6Pb3Te6·7N2H4 were obtained. These soluble molecular compounds underwent cation exchange processes using resin chemistry, replacing Na+ or K+ by decomposable N2H5+ or tetraethylammonium cations. They also transformed into stoichiometric lead and bismuth chalcogenide nanomaterials with the addition of metal salts. Such a versatile chemistry led to a variety of composition-matched solders to join lead and bismuth chalcogenides and tune their charge transport properties at the grain boundaries. Solution-processed thin films composed of Bi0.5Sb1.5Te3 microparticles solderedmore » by (N2H5)6Bi0.5Sb1.5Te6 exhibited thermoelectric power factors (~28 μW/cm K2) comparable to those in vacuum-deposited Bi0.5Sb1.5Te3 films. The soldering effect can also be integrated with attractive fabrication techniques for thermoelectric modules, such as screen printing, suggesting the potential of these solders in the rational design of printable and moldable thermoelectrics.« less

Synthesis, Crystal Structure, and Physical Properties of New Layered Oxychalcogenide La2O2Bi3AgS6

NASA Astrophysics Data System (ADS)

Hijikata, Yudai; Abe, Tomohiro; Moriyoshi, Chikako; Kuroiwa, Yoshihiro; Goto, Yosuke; Miura, Akira; Tadanaga, Kiyoharu; Wang, Yongming; Miura, Osuke; Mizuguchi, Yoshikazu

2017-12-01

We have synthesized a new layered oxychalcogenide La2O2Bi3AgS6. From synchrotron X-ray diffraction and Rietveld refinement, the crystal structure of La2O2Bi3AgS6 was refined using a model of the P4/nmm space group with a = 4.0644(1) Å and c = 19.412(1) Å, which is similar to the related compound LaOBiPbS3, while the interlayer bonds (M2-S1 bonds) are apparently shorter in La2O2Bi3AgS6. The tunneling electron microscopy (TEM) image confirmed the lattice constant derived from Rietveld refinement (c ˜ 20 Å). The electrical resistivity and Seebeck coefficient suggested that the electronic states of La2O2Bi3AgS6 are more metallic than those of LaOBiS2 and LaOBiPbS3. The insertion of a rock-salt-type chalcogenide into the van der Waals gap of BiS2-based layered compounds, such as LaOBiS2, will be a useful strategy for designing new layered functional materials in the layered chalcogenide family.

Rare-earth transition-metal gallium chalcogenides RE3MGaCh7 (M=Fe, Co, Ni; Ch=S, Se)

NASA Astrophysics Data System (ADS)

Rudyk, Brent W.; Stoyko, Stanislav S.; Oliynyk, Anton O.; Mar, Arthur

2014-02-01

Six series of quaternary rare-earth transition-metal chalcogenides RE3MGaCh7 (M=Fe, Co, Ni; Ch=S, Se), comprising 33 compounds in total, have been prepared by reactions of the elements at 1050 °C (for the sulphides) or 900 °C (for the selenides). They adopt noncentrosymmetric hexagonal structures (ordered Ce3Al1.67S7-type, space group P63, Z=2) with cell parameters in the ranges of a=9.5-10.2 Å and c=6.0-6.1 Å for the sulphides and a=10.0-10.5 Å and c=6.3-6.4 Å for the selenides as refined from powder X-ray diffraction data. Single-crystal structures were determined for five members of the sulphide series RE3FeGaS7 (RE=La, Pr, Tb) and RE3CoGaS7 (RE=La, Tb). The highly anisotropic crystal structures consist of one-dimensional chains of M-centred face-sharing octahedra and stacks of Ga-centred tetrahedra all pointing in the same direction. Magnetic measurements on the sulphides reveal paramagnetic behaviour in some cases and long-range antiferromagnetic behaviour with low Néel temperatures (15 K or lower) in others. Ga L-edge XANES spectra support the presence of highly cationic Ga tetrahedral centres with a tendency towards more covalent Ga-Ch character on proceeding from the sulphides to the selenides. Band structure calculations on La3FeGaS7 indicate that the electronic structure is dominated by Fe 3d-based states near the Fermi level.

Synthesis, structural and optical properties of PVP coated transition metal doped ZnS nanoparticles

NASA Astrophysics Data System (ADS)

Desai, N. V.; Shaikh, I. A.; Rawal, K. G.; Shah, D. V.

2018-05-01

The room temperature photoluminescence (PL) of transition metal doped ZnS nanoparticles is investigated in the present study. The PVP coated ZnS nanoparticles doped with transition metals are synthesized by facile wet chemical co-precipitation method with the concentration of impurity 1%. The UV-Vis absorbance spectra have a peak at 324nm which shifts slightly to 321nm upon introduction of the impurity. The incorporation of the transition metal as dopant is confirmed by X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). The particle size and the morphology are characterized by scanning electron microscopy (SEM), XRD and UV-Vis spectroscopy. The average size of synthesized nanoparticles is about 2.6nm. The room temperature photoluminescence (PL) of undoped and doped ZnS nanoparticles show a strong and sharp peak at 782nm and 781.6nm respectively. The intensity of the PL changes with the type of doping having maximum for manganese (Mn).

Environment effect on the acoustic vibration of metal nanoparticles

NASA Astrophysics Data System (ADS)

Voisin, C.; Christofilos, D.; Del Fatti, N.; Vallée, F.

2002-05-01

The impact of the environment on the frequency and damping of the breathing acoustic mode of noble metal nanoparticle is discussed using the model of isotropic homogeneous elastic spheres embedded in an elastic medium. The results are compared to the experimental investigations performed in glass embedded silver nanoparticles and gold colloids using a time-resolved pump-probe technique.

Design and Preparation of Nanoparticle Dimers for SERS Detection

DTIC Science & Technology

2012-09-10

sensitivity afforded by surface enhanced Raman spectroscopy (SERS). Metal nanoparticles dimers were synthesized that incorporate SERS reporters...and antigens, based on the remarkable sensitivity afforded by surface enhanced Raman spectroscopy (SERS). Metal nanoparticles dimers were...Potma, V. A._Apkarian. High Sensitivity Surface-Enhanced Raman Scattering in Solution Using Engineered Silver Nanosphere Dimers, The Journal of

In-vitro bio-fabrication of silver nanoparticle using Adhathoda vasica leaf extract and its anti-microbial activity

NASA Astrophysics Data System (ADS)

Nazeruddin, G. M.; Prasad, N. R.; Prasad, S. R.; Garadkar, K. M.; Nayak, Arpan Kumar

2014-07-01

It is well known that on treating the metallic salt solution with some plant extracts, a rapid reduction occurs leading to the formation of highly stable metal nanoparticles. Extracellular synthesis of metal nanoparticles using extracts of plants like Azadirachta indica (Neem), and Zingiber officinale (Ginger) has been reported to be successfully carried out. In this study we have developed a novel method to synthesize silver nanoparticles by mixing silver salt solution with leaf extract of Adhathoda vasica (Adulsa) without using any surfactant or external energy. By this method physiologically stable, bio-compatible Ag nanoparticles were formed which could be used for a variety of applications such as targeted drug delivery which ensures enhanced therapeutic efficacy and minimal side effects. With this method rapid synthesis of nanoparticles was observed to occur; i.e. reaction time was 1-2 h as compared to 2-4 days required by microorganisms. These nanoparticles were analyzed by various characterization techniques to reveal their morphology, chemical composition, and antimicrobial activity. TEM image of these NPs indicated the formation of spherical, non-uniform, poly-dispersed nanoparticles. A detailed study of anti-microbial activity of nanoparticles was carried out.

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic Resolution Electron Microscopy and Field Evaporation Simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devaraj, Arun; Colby, Robert J.; Vurpillot, F.

2014-03-26

Metal-dielectric composite materials, specifically metal nanoparticles supported on or embedded in metal oxides, are widely used in catalysis. The accurate optimization of such nanostructures warrants the need for detailed three-dimensional characterization. Atom probe tomography is uniquely capable of generating sub-nanometer structural and compositional data with part-per-million mass sensitivity, but there are reconstruction artifacts for composites containing materials with strongly differing fields of evaporation, as for oxide-supported metal nanoparticles. By correlating atom probe tomography with scanning transmission electron microscopy for Au nanoparticles embedded in an MgO support, deviations from an ideal topography during evaporation are demonstrated directly, and correlated with compositionalmore » errors in the reconstructed data. Finite element simulations of the field evaporation process confirm that protruding Au nanoparticles will evolve on the tip surface, and that evaporation field variations lead to an inaccurate assessment of the local composition, effectively lowering the spatial resolution of the final reconstructed dataset. Cross-correlating the experimental data with simulations results in a more detailed understanding of local evaporation aberrations during APT analysis of metal-oxide composites, paving the way towards a more accurate three-dimensional characterization of this technologically important class of materials.« less

Optical properties of metal nanoparticles embedded in amorphous silicon analysed using discrete dipole approximation

NASA Astrophysics Data System (ADS)

Fantoni, Alessandro; Fernandes, Miguel; Vygranenko, Yuri; Vieira, Manuela; Oliveira-Silva, Rui P.; Prazeres, D. M. F.; Ribeiro, Ana P. C.; Alegria, Elisabete C. B. A.

2018-02-01

Localized surface plasmons (LSP) can be excited in metal nanoparticles (NP) by UV, visible or NIR light and are described as coherent oscillation of conduction electrons. Taking advantage of the tunable optical properties of NPs, we propose the realization of a plasmonic structure, based on the LSP interaction of NP with an embedding matrix of amorphous silicon. This study is directed to define the characteristics of NP and substrate necessary to the development of a LSP proteomics sensor that, once provided immobilized antibodies on its surface, will screen the concentration of selected antigens through the determination of LSPR spectra and peaks of light absorption. Metals of interest for NP composition are: Aluminium and Gold. Recent advances in nanoparticle production techniques allow almost full control over shapes and size, permitting full control over their optical and plasmonic properties and, above all, over their responsive spectra. Analytical solution is only possible for simple NP geometries, therefore our analysis, is realized recurring to computer simulation using the Discrete Dipole Approximation method (DDA). In this work we use the free software DDSCAT to study the optical properties of metal nanoparticles embedded in an amorphous silicon matrix, as a function of size, shape, aspect-ratio and metal type. Experimental measurements realized with arrays of metal nanoparticles are compared with the simulations.

The Effects of Toxic Particles in Human Lung Cells - Research Area 8. Life Sciences

DTIC Science & Technology

2016-01-05

Characterization of Metal Nanoparticles 2.1. Synthesis and Characterization of Nanoparticles We generated and tested a silver colloid solution with a mean... silver and gold nanoparticle -induced effects; and 6) Assess metal levels in whale skin biopsies in the Gulf of Mexico. The first five aims focused...We found that silver , gold and titanium dioxide nanoparticles were relatively non-toxic. Only silver 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND

Functionalized Ni@SiO2 core/shell magnetic nanoparticles as a chemosensor and adsorbent for Cu2+ ion in drinking water and human blood.

PubMed

Park, Minsung; Seo, Sungmin; Lee, Soo Jin; Jung, Jong Hwa

2010-11-01

Fluorogenic based nitrobenzofuran-functionalized Ni@SiO(2) core/shell magnetic nanoparticles have been prepared by sol-gel grafting reaction. Their ability to detect and remove metal ions was evaluated by fluorophotometry. The nanoparticles exhibited a high affinity and selectivity for Cu(2+) over competing metal ions. Furthermore, the nanoparticles efficiently removed Cu(2+) in drinking water and human blood.

Effect of Percolation on the Cubic Susceptibility of Metal Nanoparticle Composites

NASA Technical Reports Server (NTRS)

Smith, David D.; Bender, Matthew W.; Boyd, Robert W.

1998-01-01

Generalized two-dimensional and three-dimensional Maxwell Garnett and Bruggeman geometries reveal that a sign reversal in the cubic susceptibility occurs for metal nanoparticle composites near the percolation threshold.

Fabrication and functionalization of carbon nanotube field effect transistors for bio-sensing applications

NASA Astrophysics Data System (ADS)

Zhou, Jianyun

Single walled carbon nanotube based field effect transistors are fabricated using photolithography and electron beam lithography techniques. First catalyst islands are deposited onto the substrate using standard optical lithographic techniques, and the nanotubes are grown by catalytic chemical vapor deposition from the pre-patterned catalyst islands. After imaging the grown nanotubes, the metal contact electrodes are patterned using lithography, followed by metal deposition using a sputtering technique. Both single nanotube devices and nanotube film devices are fabricated using this method. The single nanotube devices can be semiconducting, ambipolar, or metallic, with the resistance ranging from tens of kilo ohms to a few mega ohms, while the film devices are generally metallic, with only a few kilo ohms of resistance. Semiconducting single nanotube devices are functionalized for sensor applications. An electrodeposition technique was developed to functionalize the nanotube with a few materials, including avidin, chitosan, and metal nanoparticles. Among them, metal nanoparticle deposition is the most successful, and both gold and silver nanoparticles have been successfully deposited onto the sidewalls of the nanotubes from an "in situ" sacrificial electrode. The size and density of the nanoparticles, to some extent, can be tailored by controlling the deposition voltage. The gold nanoparticles are generally spherical, while the silver nanoparticles have branching snowflake shapes. These nanoparticles change the ON-state conductance of the nanotube while maintaining its semiconducting characteristics. The gold nanoparticles on the nanotube sidewalls can serve as anchoring sites for thiol-terminated biomolecules to functionalize the device for biosensing purposes. Results have shown that the thiol-terminated molecules can bind to the Au nanoparticles; however, nonspecific binding to the SiO2 surface is still abundant. Therefore, a self assembled monolayer (SAM) of protein-resistant polyethylene glycol (PEG) is deposited onto the SiO 2 surface to provide protein resistance, which results in selective immobilization of bio-receptors to the gold nanoparticles on the nanotube only. This reduces possible noise signals from the nonspecific substrate binding, and is expected to improve the device sensitivity.

Nucleation and Growth of Ordered Arrays of Silver Nanoparticles on Peptide Nanofibers: Hybrid Nanostructures with Antimicrobial Properties.

PubMed

Pazos, Elena; Sleep, Eduard; Rubert Pérez, Charles M; Lee, Sungsoo S; Tantakitti, Faifan; Stupp, Samuel I

2016-05-04

Silver nanoparticles have been of great interest as plasmonic substrates for sensing and imaging, catalysts, or antimicrobial systems. Their physical properties are strongly dependent on parameters that remain challenging to control such as size, chemical composition, and spatial distribution. We report here on supramolecular assemblies of a novel peptide amphiphile containing aldehyde functionality in order to reduce silver ions and subsequently nucleate silver metal nanoparticles in water. This system spontaneously generates monodisperse silver particles at fairly regular distances along the length of the filamentous organic assemblies. The metal-organic hybrid structures exhibited antimicrobial activity and significantly less toxicity toward eukaryotic cells. Metallized organic nanofibers of the type described here offer the possibility to create hydrogels, which integrate the useful functions of silver nanoparticles with controllable metallic content.

Noble Metal Nanoparticles for Biosensing Applications

PubMed Central

Doria, Gonçalo; Conde, João; Veigas, Bruno; Giestas, Leticia; Almeida, Carina; Assunção, Maria; Rosa, João; Baptista, Pedro V.

2012-01-01

In the last decade the use of nanomaterials has been having a great impact in biosensing. In particular, the unique properties of noble metal nanoparticles have allowed for the development of new biosensing platforms with enhanced capabilities in the specific detection of bioanalytes. Noble metal nanoparticles show unique physicochemical properties (such as ease of functionalization via simple chemistry and high surface-to-volume ratios) that allied with their unique spectral and optical properties have prompted the development of a plethora of biosensing platforms. Additionally, they also provide an additional or enhanced layer of application for commonly used techniques, such as fluorescence, infrared and Raman spectroscopy. Herein we review the use of noble metal nanoparticles for biosensing strategies—from synthesis and functionalization to integration in molecular diagnostics platforms, with special focus on those that have made their way into the diagnostics laboratory. PMID:22438731

Semiconductor-metal transition of Se in Ru-Se Catalyst Nanoparticles

NASA Astrophysics Data System (ADS)

Babu, P. K.; Lewera, Adam; Oldfield, Eric; Wieckowski, Andrzej

2009-03-01

Ru-Se composite nanoparticles are promising catalysts for the oxygen reduction reaction (ORR) in fuel cells. Though the role of Se in enhancing the chemical stability of Ru nanoparticles is well established, the microscopic nature of Ru-Se interaction was not clearly understood. We carried out a combined investigation of ^77Se NMR and XPS on Ru-Se nanoparticles and our results indicate that Se, a semiconductor in elemental form, becomes metallic when interacting with Ru. ^77Se spin-lattice relaxation rates are found to be proportional to T, the well-known Korringa behavior characteristic of metals. The NMR results are supported by the XPS binding energy shifts which suggest that a possible Ru->Se charge transfer could be responsible for the semiconductor->metal transition of Se which also makes Ru less susceptible to oxidation during ORR.

Measurement of chalcogenide glass optical dispersion using a mid-infrared prism coupler

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao, Hong; Anheier, Norman C.; Musgraves, Jonathan D.

2011-05-01

Physical properties of chalcogenide glass, including broadband infrared transparency, high refractive index, low glass transition temperature, and nonlinear properties, make them attractive candidates for advanced mid-infrared (3 to 12 {micro}m) optical designs. Efforts focused at developing new chalcogenide glass formulations and processing methods require rapid quantitative evaluation of their optical contents to guide the materials research. However, characterization of important optical parameters such as optical dispersion remains a slow and costly process, generally with limited accuracy. The recent development of a prism coupler at the Pacific Northwest National Laboratory (PNNL) now enables rapid, high precision measurement of refractive indices atmore » discrete wavelengths from the visible to the mid-infrared. Optical dispersion data of several chalcogenide glass families were collected using this method. Variations in the optical dispersion were correlated to glass composition and compared against measurements using other methods. While this work has been focused on facilitating chalcogenide glass synthesis, mid-infrared prism coupler analysis has broader applications to other mid-infrared optical material development efforts, including oxide glasses and crystalline materials.« less

A Genetically Modified Tobacco Mosaic Virus that can Produce Gold Nanoparticles from a Metal Salt Precursor

PubMed Central

Love, Andrew J.; Makarov, Valentine V.; Sinitsyna, Olga V.; Shaw, Jane; Yaminsky, Igor V.; Kalinina, Natalia O.; Taliansky, Michael E.

2015-01-01

We genetically modified tobacco mosaic virus (TMV) to surface display a characterized peptide with potent metal ion binding and reducing capacity (MBP TMV), and demonstrate that unlike wild type TMV, this construct can lead to the formation of discrete 10–40 nm gold nanoparticles when mixed with 3 mM potassium tetrachloroaurate. Using a variety of analytical physicochemical approaches it was found that these nanoparticles were crystalline in nature and stable. Given that the MBP TMV can produce metal nanomaterials in the absence of chemical reductants, it may have utility in the green production of metal nanomaterials. PMID:26617624

Toxicological Assessment of CoO and La2O3 Metal Oxide Nanoparticles in Human Small Airway Epithelial Cells

PubMed Central

Pirela, Sandra V.; Shaffer, Justine; Mihalchik, Amy L.; Chisholm, William P.; Andrew, Michael E.; Schwegler-Berry, Diane; Castranova, Vincent; Demokritou, Philip; Qian, Yong

2016-01-01

Cobalt monoxide (CoO) and lanthanum oxide (La2O3) nanoparticles are 2 metal oxide nanoparticles with different redox potentials according to their semiconductor properties. By utilizing these two nanoparticles, this study sought to determine how metal oxide nanoparticle’s mode of toxicological action is related to their physio-chemical properties in human small airway epithelial cells (SAEC). We investigated cellular toxicity, production of superoxide radicals and alterations in gene expression related to oxidative stress, and cellular death at 6 and 24 h following exposure to CoO and La2O3 (administered doses: 0, 5, 25, and 50 µg/ml) nanoparticles. CoO nanoparticles induced gene expression related to oxidative stress at 6 h. After characterizing the nanoparticles, transmission electron microscope analysis showed SAEC engulfed CoO and La2O3 nanoparticles. CoO nanoparticles were toxic after 6 and 24 h of exposure to 25.0 and 50.0 µg/ml administered doses, whereas, La2O3 nanoparticles were toxic only after 24 h using the same administered doses. Based upon the Volumetric Centrifugation Method in vivo Sedimentation, Diffusion, and Dosimetry, the dose of CoO and La2O3 nanoparticles delivered at 6 and 24 h were determined to be: CoO: 1.25, 6.25, and 12.5 µg/ml; La2O3: 5, 25, and 50 µg/ml and CoO: 4, 20, and 40 µg/ml; and La2O3: 5, 25, 50 µg/ml, respectively. CoO nanoparticles produced more superoxide radicals and caused greater stimulation of total tyrosine and threonine phosphorylation at both 6 and 24 h when compared with La2O3 nanoparticles. Taken together, these data provide evidence that different toxicological modes of action were involved in CoO and La2O3 metal oxide nanoparticle-induced cellular toxicity. PMID:26769336

Synthesis of noble metal/carbon nanotube composites in supercritical methanol.

PubMed

Sun, Zhenyu; Fu, Lei; Liu, Zhimin; Han, Buxing; Liu, Yunqi; Du, Jimin

2006-03-01

A simple and efficient route has been employed to deposit noble metal nanoparticles (Pt, Ru, Pt-Ru, Rh, Ru-Sn) onto carbon nanotubes (CNTs) in supercritical methanol solution. In this method, the inorganic metallic salts acted as metal precursors, and methanol as solvent as well as reductant for the precursors. The as-prepared nanocomposites were structurally and morphologically characterized by X-ray diffraction spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy, and X-ray photoelectron spectroscopy analyses. It was demonstrated that the CNTs were decorated by crystalline metal nanoparticles with uniform sizes and a narrow particle size distribution. The size and loading content of the nanoparticles on CNTs could be tuned by manipulating reaction parameters. Furthermore, the formation mechanism of the composites was also discussed.

Metal nanoparticle-graphene oxide composites: Photophysical properties and sensing applications

NASA Astrophysics Data System (ADS)

Murphy, Sean J.

Composite nanomaterials allow for attractive properties of multiple functional components to be combined. Fundamental understanding of the interaction between different nanomaterials, their surroundings, and nearby molecular species is pertinent for implementation into devices. Metal nanoparticles have been used for their optical properties in many applications including stained glass, cancer therapy, solar steam generation, surface enhanced Raman spectroscopy (SERS), and catalysis. Carbon-based nanomaterials such as graphene and carbon nanotubes show potential for a wide variety of applications including solar energy harvesting, chemical sensors, and electronics. Combining useful and in some cases new properties of composite nanomaterials offers exciting opportunities in fundamental science and device development. In this dissertation, I aim to address understanding photoinduced interaction between porphyrin and silver nanoparticles, inter-sheet interaction between stacked graphene oxide (GO) sheets in thin films, complexation of reduced GO with Raman active target molecule in SERS applications, and efficacy of graphene-metal nanoparticle composites for sensing applications. Molecule-metal nanoparticle composite material made up of photoactive porphyrin and silver nanoparticles was studied using various spectroscopic tools. UV-visible absorption and surface enhanced Raman spectroscopic results suggest formation of a charge-transfer complex for porphyrin-silver nanoparticle composite. Ultrafast transient absorption and fluorescence upconversion spectroscopies further corroborate electronic interaction by providing evidence for excited state electron transfer between porphyrin and silver nanoparticles. Understanding electronic interaction between adsorbed photoactive molecules and metal nanoparticles may be of use for applications in photocatalysis or light-energy harvesting. Graphene oxide (GO) thin films have been prepared and studied using transient absorption microscopy (TAM). Transient absorption microscopy correlated with atomic force microscope allows for the morphological properties of GO thin film to be related to optical properties, namely dynamics of photoexcited carriers in GO. Results suggest short-timescale (ps -- ˜1 ns) dynamics of charge carriers in GO are affected very little by interaction with the glass substrate on which GO is placed. Also, the stack thickness or number of stacked GO sheets does not play a large role in the short-timescale dynamics of GO charge carriers. GO or reduced GO (RGO)-silver nanoparticles composites were produced using different methods: (1) chemical reduction of silver ion precursor and (2) photocatalytic reduction of GO and silver ion using TiO2 nanoparticles. Optical and morphological properties of composites were studied using spectroscopy and electron microscopy revealing a degree of control in metal nanoparticle growth and loading on the surface of RGO. Nanocomposites were shown to be capable of complexing with or adsorbing target molecular species. Complexation and adsorption are corroborated with demonstration that the composite nanomaterials act as effective SERRS sensors taking advantage of localized surface plasmon resonance of metal nanoparticles and the ability of RGO to interact with molecular and ionic species.

Thermal response of chalcogenide microsphere resonators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmad, H; Aryanfar, I; Lim, K S

2012-05-31

A chalcogenide microsphere resonator (CMR) used for temperature sensing is proposed and demonstrated. The CMR is fabricated using a simple technique of heating chalcogenide glass and allowing the molten glass to form a microsphere on the waist of a tapered silica fibre. The thermal responses of the CMR is investigated and compared to that of a single-mode-fibre (SMF) based microsphere resonator. It is observed that the CMR sensitivity to ambient temperature changes is 8 times higher than that of the SMF-based microsphere resonator. Heating the chalcogenide microsphere with a laser beam periodically turned on and off shows periodic shifts inmore » the transmission spectrum of the resonator. By injecting an intensity-modulated cw signal through the resonator a thermal relaxation time of 55 ms is estimated.« less

Effects of Metallic Nanoparticles on Interfacial Intermetallic Compounds in Tin-Based Solders for Microelectronic Packaging

NASA Astrophysics Data System (ADS)

Haseeb, A. S. M. A.; Arafat, M. M.; Tay, S. L.; Leong, Y. M.

2017-10-01

Tin (Sn)-based solders have established themselves as the main alternative to the traditional lead (Pb)-based solders in many applications. However, the reliability of the Sn-based solders continues to be a concern. In order to make Sn-based solders microstructurally more stable and hence more reliable, researchers are showing great interest in investigating the effects of the incorporation of different nanoparticles into them. This paper gives an overview of the influence of metallic nanoparticles on the characteristics of interfacial intermetallic compounds (IMCs) in Sn-based solder joints on copper substrates during reflow and thermal aging. Nanocomposite solders were prepared by mechanically blending nanoparticles of nickel (Ni), cobalt (Co), zinc (Zn), molybdenum (Mo), manganese (Mn) and titanium (Ti) with Sn-3.8Ag-0.7Cu and Sn-3.5Ag solder pastes. The composite solders were then reflowed and their wetting characteristics and interfacial microstructural evolution were investigated. Through the paste mixing route, Ni, Co, Zn and Mo nanoparticles alter the morphology and thickness of the IMCs in beneficial ways for the performance of solder joints. The thickness of Cu3Sn IMC is decreased with the addition of Ni, Co and Zn nanoparticles. The thickness of total IMC layer is decreased with the addition of Zn and Mo nanoparticles in the solder. The metallic nanoparticles can be divided into two groups. Ni, Co, and Zn nanoparticles undergo reactive dissolution during solder reflow, causing in situ alloying and therefore offering an alternative route of alloy additions to solders. Mo nanoparticles remain intact during reflow and impart their influence as discrete particles. Mechanisms of interactions between different types of metallic nanoparticles and solder are discussed.

Formation of metal clusters in halloysite clay nanotubes

DOE PAGES

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; ...

2017-02-16

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9more » wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.« less

Formation of metal clusters in halloysite clay nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9more » wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.« less

Formation of metal clusters in halloysite clay nanotubes

PubMed Central

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; Ivanov, Evgenii V.; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A.; Lvov, Yuri M.

2017-01-01

Abstract We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3–5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10–12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions. PMID:28458738

In Vitro Vascular Toxicity of Manufactured Metal Oxide Nanoparticles: Size Profile Predicts Cellular Specificity, Delivered Dose, and Toxicity

EPA Science Inventory

Metal oxide nanoparticles (NPs) are being used in an expanding range of products and applications due to their unique physicochemical properties. In vivo biokinetic studies have demonstrated the ability of metal oxide NPs to translocate to the distal organs, including the cardiov...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Chang Wan; Choksi, Tej; Milligan, Cory

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

Metal oxide nanoparticle mediated enhanced Raman scattering and its use in direct monitoring of interfacial chemical reactions.

PubMed

Li, Li; Hutter, Tanya; Finnemore, Alexander S; Huang, Fu Min; Baumberg, Jeremy J; Elliott, Stephen R; Steiner, Ullrich; Mahajan, Sumeet

2012-08-08

Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (×10(4)) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.

Transport across the cell-membrane dictates nanoparticle fate and toxicity: a new paradigm in nanotoxicology

NASA Astrophysics Data System (ADS)

Guarnieri, Daniela; Sabella, Stefania; Muscetti, Ornella; Belli, Valentina; Malvindi, Maria Ada; Fusco, Sabato; de Luca, Elisa; Pompa, Pier Paolo; Netti, Paolo A.

2014-08-01

The toxicity of metallic nanoparticles (MNPs) has been fully ascertained, but the mechanisms underlying their cytotoxicity remain still largely unclear. Here we demonstrate that the cytotoxicity of MNPs is strictly reliant on the pathway of cellular internalization. In particular, if otherwise toxic gold, silver, and iron oxide NPs are forced through the cell membrane bypassing any form of active mechanism (e.g., endocytosis), no significant cytotoxic effect is registered. Pneumatically driven NPs across the cell membrane show a different distribution within the cytosol compared to NPs entering the cell by active endocytosis. Specifically, they exhibit free random Brownian motions within the cytosol and do not accumulate in lysosomes. Results suggest that intracellular accumulation of metallic nanoparticles into endo-lysosomal compartments is the leading cause of nanotoxicity, due to consequent nanoparticle degradation and in situ release of metal ions.The toxicity of metallic nanoparticles (MNPs) has been fully ascertained, but the mechanisms underlying their cytotoxicity remain still largely unclear. Here we demonstrate that the cytotoxicity of MNPs is strictly reliant on the pathway of cellular internalization. In particular, if otherwise toxic gold, silver, and iron oxide NPs are forced through the cell membrane bypassing any form of active mechanism (e.g., endocytosis), no significant cytotoxic effect is registered. Pneumatically driven NPs across the cell membrane show a different distribution within the cytosol compared to NPs entering the cell by active endocytosis. Specifically, they exhibit free random Brownian motions within the cytosol and do not accumulate in lysosomes. Results suggest that intracellular accumulation of metallic nanoparticles into endo-lysosomal compartments is the leading cause of nanotoxicity, due to consequent nanoparticle degradation and in situ release of metal ions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr02008a

High resolution SEM imaging of gold nanoparticles in cells and tissues.

PubMed

Goldstein, A; Soroka, Y; Frušić-Zlotkin, M; Popov, I; Kohen, R

2014-12-01

The growing demand of gold nanoparticles in medical applications increases the need for simple and efficient characterization methods of the interaction between the nanoparticles and biological systems. Due to its nanometre resolution, modern scanning electron microscopy (SEM) offers straightforward visualization of metallic nanoparticles down to a few nanometre size, almost without any special preparation step. However, visualization of biological materials in SEM requires complicated preparation procedure, which is typically finished by metal coating needed to decrease charging artefacts and quick radiation damage of biomaterials in the course of SEM imaging. The finest conductive metal coating available is usually composed of a few nanometre size clusters, which are almost identical to the metal nanoparticles employed in medical applications. Therefore, SEM monitoring of metal nanoparticles within cells and tissues is incompatible with the conventional preparation methods. In this work, we show that charging artefacts related to non-conductive biological specimen can be successfully eliminated by placing the uncoated biological sample on a conductive substrate. By growing the cells on glass pre-coated with a chromium layer, we were able to observe the uptake of 10 nm gold nanoparticles inside uncoated and unstained macrophages and keratinocytes cells. Imaging in back scattered electrons allowed observation of gold nanoparticles located inside the cells, while imaging in secondary electron gave information on gold nanoparticles located on the surface of the cells. By mounting a skin cross-section on an improved conductive holder, consisting of a silicon substrate coated with copper, we were able to observe penetration of gold nanoparticles of only 5 nm size through the skin barrier in an uncoated skin tissue. The described method offers a convenient modification in preparation procedure for biological samples to be analyzed in SEM. The method provides high conductivity without application of surface coating and requires less time and a reduced use of toxic chemicals. © 2014 The Authors Journal of Microscopy © 2014 Royal Microscopical Society.

Surface Plasmon Resonance or Biocompatibility—Key Properties for Determining the Applicability of Noble Metal Nanoparticles

PubMed Central

Craciun, Ana Maria; Focsan, Monica; Vulpoi, Adriana

2017-01-01

Metal and in particular noble metal nanoparticles represent a very special class of materials which can be applied as prepared or as composite materials. In most of the cases, two main properties are exploited in a vast number of publications: biocompatibility and surface plasmon resonance (SPR). For instance, these two important properties are exploitable in plasmonic diagnostics, bioactive glasses/glass ceramics and catalysis. The most frequently applied noble metal nanoparticle that is universally applicable in all the previously mentioned research areas is gold, although in the case of bioactive glasses/glass ceramics, silver and copper nanoparticles are more frequently applied. The composite partners/supports/matrix/scaffolds for these nanoparticles can vary depending on the chosen application (biopolymers, semiconductor-based composites: TiO2, WO3, Bi2WO6, biomaterials: SiO2 or P2O5-based glasses and glass ceramics, polymers: polyvinyl alcohol (PVA), Gelatin, polyethylene glycol (PEG), polylactic acid (PLA), etc.). The scientific works on these materials’ applicability and the development of new approaches will be targeted in the present review, focusing in several cases on the functioning mechanism and on the role of the noble metal. PMID:28773196

Systematic investigation of structural and morphological studies on doped TiO2 nanoparticles for solar cell applications

NASA Astrophysics Data System (ADS)

Murugadoss, G.; Jayavel, R.; Rajesh Kumar, M.

2014-12-01

Optical, structural and thermal properties of the doped with different ions (transition metals, other metals or post transition metals, non-metals, alkali metals and lanthanides) in TiO2 nanocrystals were investigated. The doped nanoparticles were synthesized by modified chemical method. Ethanol-deionised water mixer (20:1) was used as solvent for synthesize of the undoped and doped TiO2 nanoparticles. Systematic studies on structural and morphological changes by thermal treatment on TiO2 were examined. It has been observed that with Eu and Al doping TiO2, the phase transition temperature for anatase to rutile phase increased. Blue and red shifting absorptions were observed for doped TiO2 in visible region. Among the dopant, significant blue shift was obtained for Cu, Cd, Ag, Y, Ce and In doped TiO2 and red shift was obtained for Zr, Sm, Al, Na, S, Fe, Ni, Eu and Gd doped TiO2 nanoparticles.

Size dependent studies of metal nanoparticles with bio-fluorophores

NASA Astrophysics Data System (ADS)

Patil, Ajeetkumar; Ballary, Steffy; George, Sajan D.; Chidangil, Santhosh

2017-06-01

Interaction of noble metal nanoparticles (NPs) with fluorophores has been an important research area in the field of material science and biomedical field. In the proximity of a metal nanoparticle, there is a quenching or enhancement in the intrinsic fluorescence of the fluorophore . The conditional quenching of the fluorescence can be used for negative sensing whereas enhancement in the fluorescence can be used to gain greater sensitivity and high signal to noise ratio in the molecular sensing/imaging. The current work deals with the systematic studies to understand the fluorescence quenching for few bio-fluorophores (NADH and FAD) when interacted with different sized silver nano-particles of (10nm, 40nm and 100nm). Home assembled Laser Induced Fluorescence (LIF) set-up was used to study the fluorescence quenching of NADH and FAD for different sized silver nanoparticles.

Plasmonic resonances of nanoparticles from large-scale quantum mechanical simulations

NASA Astrophysics Data System (ADS)

Zhang, Xu; Xiang, Hongping; Zhang, Mingliang; Lu, Gang

2017-09-01

Plasmonic resonance of metallic nanoparticles results from coherent motion of its conduction electrons, driven by incident light. For the nanoparticles less than 10 nm in diameter, localized surface plasmonic resonances become sensitive to the quantum nature of the conduction electrons. Unfortunately, quantum mechanical simulations based on time-dependent Kohn-Sham density functional theory are computationally too expensive to tackle metal particles larger than 2 nm. Herein, we introduce the recently developed time-dependent orbital-free density functional theory (TD-OFDFT) approach which enables large-scale quantum mechanical simulations of plasmonic responses of metallic nanostructures. Using TD-OFDFT, we have performed quantum mechanical simulations to understand size-dependent plasmonic response of Na nanoparticles and plasmonic responses in Na nanoparticle dimers and trimers. An outlook of future development of the TD-OFDFT method is also presented.

Manipulating the architecture of bimetallic nanostructures and their plasmonic properties

NASA Astrophysics Data System (ADS)

DeSantis, Christopher John

There has been much interest in colloidal noble metal nanoparticles due to their fascinating plasmonic and catalytic properties. These properties make noble metal nanoparticles potentially useful for applications such as targeted drug delivery agents and hydrogen storage devices. Historically, shape-controlled noble metal nanoparticles have been predominantly monometallic. Recent synthetic advances provide access to bimetallic noble metal nanoparticles wherein their inherent multifunctionality and ability to fine tune or expand their surface chemistry and light scattering properties of metal nanoparticles make them popular candidates for many applications. Even so, there are currently few synthetic strategies to rationally design shape-controlled bimetallic nanocrystals; for this reason, few architectures are accessible. For example, the "seed-mediated method" is a popular means of achieving monodisperse shape-controlled bimetallic nanocrystals. In this process, small metal seeds are used as platforms for additional metal addition, allowing for conformal core shell nanostructures. However, this method has only been applied to single metal core/single metal shell structures; therefore, the surface compositions and architectures achievable are limited. This thesis expands upon the seed-mediated method by coupling it with co-reduction. In short, two metal precursors are simultaneously reduced to deposit metal onto pre-formed seeds in hopes that the interplay between two metal species facilitates bimetallic shell nanocrystals. Au/Pd was used as a test system due to favorable reduction potentials of metal precursors and good lattice match between Au and Pd. Alloyed shelled Au Au/Pd nanocrystals were achieved using this "seed-mediated co-reduction" approach. Symmetric eight-branched Au/Pd nanocrystals (octopods) are also prepared using this method. This thesis investigates many synthetic parameters that determine the shape outcome in Au/Pd nanocrystals during seed-mediated co-reduction. Plasmonic, catalytic, and assembly properties are also investigated in relation to nanocrystal shape and architecture. This work provides a foundation for the rational design of architecturally defined bimetallic nanostructures.

Fate, behavior, and bioavailability of metal and metal oxide nanomaterials in terrestrial ecosystems

NASA Astrophysics Data System (ADS)

Bertsch, P. M.; Unrine, J. M.; Judy, J.; Tsyusko, O.

2012-12-01

Despite the benefits that are currently being manifested and those transformative breakthroughs that will undoubtedly result from advances in nanotechnology, concerns surrounding the potential negative impacts to the environment and human health and welfare continue to emerge. Information on the transport and fate of manufactured nanomaterials (MNMs) in the environment and on their potential effects to human and ecological receptors is emerging at an increasing rate. Notwithstanding these developments, the research enterprise focused on the environmental implications of nanotechnology is in its infancy and few unifying principles have yet to emerge. This lack of unanimity is related to many factors including, the vast diversity in chemical composition, size, shape, and surface chemical properties of MNMs, as well as the range of receptor species and cell lines investigated. Additionally, the large variation in exposure methodologies employed by various investigators as well as the discrepancies in the amount and quality of characterization data collected to support specific conclusions, provide major challenges for developing unifying concepts and principles. As the utilization of MNMs for a large variety of applications is currently in an exponential growth phase, there is great urgency to develop information that can be used to identify priority areas for assessing risks to humans and the environment, as well as in developing potential mitigation strategies. We have been investigating the fate, behavior, and potential impacts of MNMs released into terrestrial ecosystems by examining the bioavailability and toxicity as well as the trophic transfer of a range of metal and metal oxide nanoparticles (Ag, Au, Cu, TiO2, ZnO, CeO2) to microorganisms, detritivores, and plants. Interdisciplinary studies include the characterization of the nanoparticles and aged nanoparticles in complex media, the distribution of nanoparticles in biological tissues, nanoparticle toxicity as referenced to the free metal ion concentration, and gene and protein expression associated with nanoparticle exposure. The results demonstrate the importance and challenges of characterization of nanoparticles under varying chemical conditions associated with exposure media. We have also demonstrated that metal and metal oxide nanoparticles are bioavailable and can be toxic to microorganisms, plants, nematodes, and earthworms. The results also suggest a different spatial distribution in tissues as well as unique toxicity mechanisms compared to the free metal ion concentration. Ongoing studies are evaluating the propensity for nanoparticles to be transferred from one trophic level to the next by feeding pre-exposed microorganisms (B. vietnamensis) to the nematode, C. elegans, pre-exposed earthworms (E. fetida) to bullfrogs (R. catesbeiana) and pre-exposed tobacco plants (Nicotiana tabacum L. cv Xanthi) to the caterpillar, tobacco horn worm (Manduca sexta), to test the hypothesis that surface modification of nanoparticles by peptides or other biomolecules facilitate the transmembrane transport of nanoparticles, thus enhancing the bioavailability to higher trophic levels.

Static Behavior of Chalcogenide Based Programmable Metallization Cells

NASA Astrophysics Data System (ADS)

Rajabi, Saba

Nonvolatile memory (NVM) technologies have been an integral part of electronic systems for the past 30 years. The ideal non-volatile memory have minimal physical size, energy usage, and cost while having maximal speed, capacity, retention time, and radiation hardness. A promising candidate for next-generation memory is ion-conducting bridging RAM which is referred to as programmable metallization cell (PMC), conductive bridge RAM (CBRAM), or electrochemical metallization memory (ECM), which is likely to surpass flash memory in all the ideal memory characteristics. A comprehensive physics-based model is needed to completely understand PMC operation and assist in design optimization. To advance the PMC modeling effort, this thesis presents a precise physical model parameterizing materials associated with both ion-rich and ion-poor layers of the PMC's solid electrolyte, so that captures the static electrical behavior of the PMC in both its low-resistance on-state (LRS) and high resistance off-state (HRS). The experimental data is measured from a chalcogenide glass PMC designed and manufactured at ASU. The static on- and off-state resistance of a PMC device composed of a layered (Ag-rich/Ag-poor) Ge30Se70 ChG film is characterized and modeled using three dimensional simulation code written in Silvaco Atlas finite element analysis software. Calibrating the model to experimental data enables the extraction of device parameters such as material bandgaps, workfunctions, density of states, carrier mobilities, dielectric constants, and affinities. The sensitivity of our modeled PMC to the variation of its prominent achieved material parameters is examined on the HRS and LRS impedance behavior. The obtained accurate set of material parameters for both Ag-rich and Ag-poor ChG systems and process variation verification on electrical characteristics enables greater fidelity in PMC device simulation, which significantly enhances our ability to understand the underlying physics of ChG-based resistive switching memory.

Viscoelastic properties of chalcogenide glasses and the simulation of their molding processes

NASA Astrophysics Data System (ADS)

Liu, Weiguo; Shen, Ping; Jin, Na

In order to simulate the precision molding process, the viscoelastic properties of chalcogenide glasses under high temperatures were investigated. Thermomechanical analysis were performed to measure and analysis the thermomechanical properties of chalcogenide glasses. The creep responses of the glasses at different temperatures were obtained. Finite element analysis was applied for the simulation of the molding processes. The simulation results were in consistence with previously reported experiment results. Stress concentration and evolution during the molding processes was also described with the simulation results.

Iron chalcogenide superconductors at high magnetic fields

PubMed Central

Lei, Hechang; Wang, Kefeng; Hu, Rongwei; Ryu, Hyejin; Abeykoon, Milinda; Bozin, Emil S; Petrovic, Cedomir

2012-01-01

Iron chalcogenide superconductors have become one of the most investigated superconducting materials in recent years due to high upper critical fields, competing interactions and complex electronic and magnetic phase diagrams. The structural complexity, defects and atomic site occupancies significantly affect the normal and superconducting states in these compounds. In this work we review the vortex behavior, critical current density and high magnetic field pair-breaking mechanism in iron chalcogenide superconductors. We also point to relevant structural features and normal-state properties. PMID:27877518