On the possibility of room temperature ferromagnetism on chunk-shape BaSnO3/ZnO core/shell nanostructures

NASA Astrophysics Data System (ADS)

Rajamanickam, N.; Jayakumar, K.; Ramachandran, K.

2018-04-01

Core/shell BaSnO3/ZnO (BS-ZO) nanostructures were prepared by oxalate precipitation method and wet-chemical method. BaSnO3 (BSO) cubic perovskite structure and ZnO hexagonal wurtzite structure were confirmed by X-ray diffraction (XRD). The crystallite sizes is 23 nm, 29 nm and 27 nm for BSO, ZnO and BS-ZO, respectively. Chunk-shape and cuboids morphology observed from scanning electron microscopy (SEM) analysis. The magnetic properties were studied by VSM for bare and core-shell nano systems and the room temperature ferromagnetism observed for core-shell nanostructures. The BSO/ZnO shows enhanced coercivity and saturated magnetization as compared with BSO and ZnO nanostructures.

Liquid-phase pulsed laser ablation synthesis of graphitized carbon-encapsulated palladium core-shell nanospheres for catalytic reduction of nitrobenzene to aniline

NASA Astrophysics Data System (ADS)

Kim, Yu-jin; Ma, Rory; Reddy, D. Amaranatha; Kim, Tae Kyu

2015-12-01

Graphitized carbon-encapsulated palladium (Pd) core-shell nanospheres were produced via pulsed laser ablation of a solid Pd foil target submerged in acetonitrile. The microstructural features and optical properties of these nanospheres were characterized via high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. Microstructural analysis indicated that the core-shell nanostructures consisted of single-crystalline cubic metallic Pd spheres that serve as the core material, over which graphitized carbon was anchored as a heterogeneous shell. The absorbance spectrum of the synthesized nanostructures exhibited a broad (absorption) band at ∼264 nm; this band corresponded to the typical inter-band transition of a metallic system and resulted possibly from the absorbance of the ionic Pd2+. The catalytic properties of the Pd and Pd@C core-shell nanostructures were investigated using the reduction of nitrobenzene to aniline by an excess amount of NaBH4 in an aqueous solution at room temperature, as a model reaction. Owing to the graphitized carbon-layered structure and the high specific surface area, the resulting Pd@C nanostructures exhibited higher conversion efficiencies than their bare Pd counterparts. In fact, the layered structure provided access to the surface of the Pd nanostructures for the hydrogenation reaction, owing to the synergistic effect between graphitized carbon and the nanostructures. Their unique structure and excellent catalytic performance render Pd@C core-shell nanostructures highly promising candidates for catalysis applications.

Magnetic response of hybrid ferromagnetic and antiferromagnetic core-shell nanostructures

NASA Astrophysics Data System (ADS)

Khan, U.; Li, W. J.; Adeela, N.; Irfan, M.; Javed, K.; Wan, C. H.; Riaz, S.; Han, X. F.

2016-03-01

The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required.The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07946b

Boron-based nanostructures: Synthesis, functionalization, and characterization

NASA Astrophysics Data System (ADS)

Bedasso, Eyrusalam Kifyalew

Boron-based nanostructures have not been explored in detail; however, these structures have the potential to revolutionize many fields including electronics and biomedicine. The research discussed in this dissertation focuses on synthesis, functionalization, and characterization of boron-based zero-dimensional nanostructures (core/shell and nanoparticles) and one-dimensional nanostructures (nanorods). The first project investigates the synthesis and functionalization of boron-based core/shell nanoparticles. Two boron-containing core/shell nanoparticles, namely boron/iron oxide and boron/silica, were synthesized. Initially, boron nanoparticles with a diameter between 10-100 nm were prepared by decomposition of nido-decaborane (B10H14) followed by formation of a core/shell structure. The core/shell structures were prepared using the appropriate precursor, iron source and silica source, for the shell in the presence of boron nanoparticles. The formation of core/shell nanostructures was confirmed using high resolution TEM. Then, the core/shell nanoparticles underwent a surface modification. Boron/iron oxide core/shell nanoparticles were functionalized with oleic acid, citric acid, amine-terminated polyethylene glycol, folic acid, and dopamine, and boron/silica core/shell nanoparticles were modified with 3-(amino propyl) triethoxy silane, 3-(2-aminoethyleamino)propyltrimethoxysilane), citric acid, folic acid, amine-terminated polyethylene glycol, and O-(2-Carboxyethyl)polyethylene glycol. A UV-Vis and ATR-FTIR analysis established the success of surface modification. The cytotoxicity of water-soluble core/shell nanoparticles was studied in triple negative breast cancer cell line MDA-MB-231 and the result showed the compounds are not toxic. The second project highlights optimization of reaction conditions for the synthesis of boron nanorods. This synthesis, done via reduction of boron oxide with molten lithium, was studied to produce boron nanorods without any contamination and with a uniform size distribution. Various reaction parameters such as temperature, reaction time, and sonication were altered to find the optimal reaction conditions. Once these conditions were determined, boron nanorods were produced then functionalized with amine-terminated polyethylene glycol.

Magnetic response of hybrid ferromagnetic and antiferromagnetic core-shell nanostructures.

PubMed

Khan, U; Li, W J; Adeela, N; Irfan, M; Javed, K; Wan, C H; Riaz, S; Han, X F

2016-03-21

The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3[combining macron]. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ∼25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required.

Enhanced exchange bias and improved ferromagnetic properties in Permalloy–BiFe0.95Co0.05O3 core–shell nanostructures

PubMed Central

Javed, K.; Li, W. J.; Ali, S. S.; Shi, D. W.; Khan, U.; Riaz, S.; Han, X. F.

2015-01-01

Hybrid core–shell nanostructures consisting of permalloy (Ni80Fe20) and multiferroic(BiFeO3, BFO/BiFe0.95Co0.05O3, BFC) materials were synthesized by a two-step method, based on wet chemical impregnation and subsequent electrodeposition within porous alumina membranes. Structural and magnetic characterizations have been done to investigate doping effect on magnetic properties and exchange bias. The magnetometry analysis revealed significant enhancements of the exchange bias and coercivity in NiFe-BFC core-shell nanostructures as compared with NiFe-BFO core-shell nanostructures. The enhancements can be attributed to the effective reduction of ferromagnet domain sizes between adjacent layers of core-shell structure. It indicates that it is possible to improve properties of multiferroic composites by site-engineering method. Our approach opens a pathway to obtain optimized nanostructured multiferroic composites exhibiting tunable magnetic properties. PMID:26658956

Porous Core-Shell Nanostructures for Catalytic Applications

NASA Astrophysics Data System (ADS)

Ewers, Trevor David

Porous core-shell nanostructures have recently received much attention for their enhanced thermal stability. They show great potential in the field of catalysis, as reactant gases can diffuse in and out of the porous shell while the core particle is protected from sintering, a process in which particles coalesce to form larger particles. Sintering is a large problem in industry and is the primary cause of irreversible deactivation. Despite the obvious advantages of high thermal stability, porous core-shell nanoparticles can be developed to have additional interactive properties from the combination of the core and shell together, rather than just the core particle alone. This dissertation focuses on developing new porous core-shell systems in which both the core and shell take part in catalysis. Two types of systems are explored; (1) yolk-shell nanostructures with reducible oxide shells formed using the Kirkendall effect and (2) ceramic-based porous oxide shells formed using sol-gel chemistry. Of the Kirkendall-based systems, Au FexOy and Cu CoO were synthesized and studied for catalytic applications. Additionally, ZnO was explored as a potential shelling material. Sol-gel work focused on optimizing synthetic methods to allow for coating of small gold particles, which remains a challenge today. Mixed metal oxides were explored as a shelling material to make dual catalysts in which the product of a reaction on the core particle becomes a reactant within the shell.

Construction of Hierarchical α-MnO2 Nanowires@Ultrathin δ-MnO2 Nanosheets Core-Shell Nanostructure with Excellent Cycling Stability for High-Power Asymmetric Supercapacitor Electrodes.

PubMed

Ma, Zhipeng; Shao, Guangjie; Fan, Yuqian; Wang, Guiling; Song, Jianjun; Shen, Dejiu

2016-04-13

Poor electrical conductivity and mechanical instability are two major obstacles to realizing high performance of MnO2 as pseudocapacitor material. The construction of unique hierarchical core-shell nanostructures, therefore, plays an important role in the efficient enhancement of the rate capacity and the stability of this material. We herein report the fabrication of a hierarchical α-MnO2 nanowires@ultrathin δ-MnO2 nanosheets core-shell nanostructure by adopting a facile and practical solution-phase technique. The novel hierarchical nanostructures are composed of ultrathin δ-MnO2 nanosheets with a few atomic layers growing well on the surface of the ultralong α-MnO2 nanowires. The first specific capacitance of hierarchical core-shell nanostructure reached 153.8 F g(-1) at the discharge current density of as high as 20 A g(-1), and the cycling stability is retained at 98.1% after 10,000 charge-discharge cycles, higher than those in the literature. The excellent rate capacity and stability of the hierarchical core-shell nanostructures can be attributed to the structural features of the two MnO2 crystals, in which a 1D α-MnO2 nanowire core provides a stable structural backbone and the ultrathin 2D δ-MnO2 nanosheet shell creates more reactive active sites. The synergistic effects of different dimensions also contribute to the superior rate capability.

Ethanol Gas Detection Using a Yolk-Shell (Core-Shell) α-Fe2O3 Nanospheres as Sensing Material.

PubMed

Wang, LiLi; Lou, Zheng; Deng, Jianan; Zhang, Rui; Zhang, Tong

2015-06-17

Three-dimensional (3D) nanostructures of α-Fe2O3 materials, including both hollow sphere-shaped and yolk-shell (core-shell)-shaped, have been successfully synthesized via an environmentally friendly hydrothermal approach. By expertly adjusting the reaction time, the solid, hollow, and yolk-shell shaped α-Fe2O3 can be selectively synthesized. Yolk-shell α-Fe2O3 nanospheres display outer diameters of 350 nm, and the interstitial hollow spaces layer is intimately sandwiched between the inner and outer shell of α-Fe2O3 nanostructures. The possible growth mechanism of the yolk-shell nanostructure is proposed. The results showed that the well-defined bilayer interface effectively enhanced the sensing performance of the α-Fe2O3 nanostructures (i.e., yolk-shell α-Fe2O3@α-Fe2O3), owing predominantly to the unique nanostructure, thus facilitated the transport rate and augmented the adsorption quantity of the target gas molecule under gas detection.

Synthesis of Co 2SnO 4@C core-shell nanostructures with reversible lithium storage

NASA Astrophysics Data System (ADS)

Qi, Yue; Du, Ning; Zhang, Hui; Wu, Ping; Yang, Deren

This paper reports the synthesis of Co 2SnO 4@C core-shell nanostructures through a simple glucose hydrothermal and subsequent carbonization approach. The as-synthesized Co 2SnO 4@C core-shell nanostructures have been applied as anode materials for lithium-ion batteries, which exhibit improved cyclic performance compared to pure Co 2SnO 4 nanocrystals. The carbon matrix has good volume buffering effect and high electronic conductivity, which may be responsible for the improved cyclic performance.

Merging of Kirkendall Growth and Ostwald Ripening: CuO@MnO2 Core-shell Architectures for Asymmetric Supercapacitors

PubMed Central

Huang, Ming; Zhang, Yuxin; Li, Fei; Wang, Zhongchang; Alamusi; Hu, Ning; Wen, Zhiyu; Liu, Qing

2014-01-01

Fabricating hierarchical core-shell nanostructures is currently the subject of intensive research in the electrochemical field owing to the hopes it raises for making efficient electrodes for high-performance supercapacitors. Here, we develop a simple and cost-effective approach to prepare CuO@MnO2 core-shell nanostructures without any surfactants and report their applications as electrodes for supercapacitors. An asymmetric supercapacitor with CuO@MnO2 core-shell nanostructure as the positive electrode and activated microwave exfoliated graphite oxide (MEGO) as the negative electrode yields an energy density of 22.1 Wh kg−1 and a maximum power density of 85.6 kW kg−1; the device shows a long-term cycling stability which retains 101.5% of its initial capacitance even after 10000 cycles. Such a facile strategy to fabricate the hierarchical CuO@MnO2 core-shell nanostructure with significantly improved functionalities opens up a novel avenue to design electrode materials on demand for high-performance supercapacitor applications. PMID:24682149

Optimization and photomodification of extremely broadband optical response of plasmonic core-shell obscurants.

PubMed

de Silva, Vashista C; Nyga, Piotr; Drachev, Vladimir P

2016-12-15

Plasmonic resonances of the metallic shells depend on their nanostructure and geometry of the core, which can be optimized for the broadband extinction normalized by mass. The fractal nanostructures can provide a broadband extinction. It allows as well for a laser photoburning of holes in the extinction spectra and consequently windows of transparency in a controlled manner. The studied core-shell microparticles synthesized using colloidal chemistry consist of gold fractal nanostructures grown on precipitated calcium carbonate (PCC) microparticles or silica (SiO 2 ) microspheres. The optimization includes different core sizes and shapes, and shell nanostructures. It shows that the rich surface of the PCC flakes is the best core for the fractal shells providing the highest mass normalized extinction over the extremely broad spectral range. The mass normalized extinction cross section up to 3m 2 /g has been demonstrated in the broad spectral range from the visible to mid-infrared. Essentially, the broadband response is a characteristic feature of each core-shell microparticle in contrast to a combination of several structures resonant at different wavelengths, for example nanorods with different aspect ratios. The photomodification at an IR wavelength makes the window of transparency at the longer wavelength side. Copyright © 2016 Elsevier Inc. All rights reserved.

Exciton in a spherical core/shell nanostructure: Influence of surface ligand

NASA Astrophysics Data System (ADS)

Anitha, B.; Nithiananthi, P.

2018-04-01

Studies on exciton in an inverted type I spherical GaAs/Al0.3Ga0.7As core/shell nanostructure (CSN) are made using variational method. Dielectric constant and effective mass mismatches of the core and shell materials are considered. The effect of core and the shell dimensions on the exciton binding energy (BE) are analyzed for different shell (Rs) and core radii (Rc). It is observed that with the core and the shell inducement, significant change in BE can be achieved. In addition, the influence of ligand enclosureon the BE as a function of shell thickness (ST) is reviewed. The result exhibits that the presence of ligand considerably affects the BE. Further the transmission probability of exciton for various Rc and Rs are reported. The notable changes are compared and examined with and without ligand inclusion.

Fabrication and characterization of optical sensors using metallic core-shell thin film nanoislands for ozone detection

NASA Astrophysics Data System (ADS)

Addanki, Satish; Nedumaran, D.

2017-07-01

Core-Shell nanostructures play a vital role in the sensor field owing to their performance improvements in sensing characteristics and well-established synthesis procedures. These nanostructures can be ingeniously tuned to achieve tailored properties for a particular application of interest. In this work, an Ag-Au core-shell thin film nanoislands with APTMS (3-Aminopropyl trimethoxysilane) and PVA (Polyvinyl alcohol) binding agents was modeled, synthesized and characterized. The simulation results were used to fabricate the sensor through chemical route. The results of this study confirmed that the APTMS based Ag-Au core-shell thin film nanoislands offered a better performance over the PVA based Ag-Au core-shell thin film nanoislands. Also, the APTMS based Ag-Au core-shell thin film nanoislands exhibited better sensitivity towards ozone sensing over the other types, viz., APTMS/PVA based Au-Ag core-shell and standalone Au/Ag thin film nanoislands.

Polarization effects on spectra of spherical core/shell nanostructures: Perturbation theory against finite difference approach

NASA Astrophysics Data System (ADS)

Ibral, Asmaa; Zouitine, Asmaa; Assaid, El Mahdi; El Achouby, Hicham; Feddi, El Mustapha; Dujardin, Francis

2015-02-01

Poisson equation is solved analytically in the case of a point charge placed anywhere in a spherical core/shell nanostructure, immersed in aqueous or organic solution or embedded in semiconducting or insulating matrix. Conduction and valence band-edge alignments between core and shell are described by finite height barriers. Influence of polarization charges induced at the surfaces where two adjacent materials meet is taken into account. Original expressions of electrostatic potential created everywhere in the space by a source point charge are derived. Expressions of self-polarization potential describing the interaction of a point charge with its own image-charge are deduced. Contributions of double dielectric constant mismatch to electron and hole ground state energies as well as nanostructure effective gap are calculated via first order perturbation theory and also by finite difference approach. Dependencies of electron, hole and gap energies against core to shell radii ratio are determined in the case of ZnS/CdSe core/shell nanostructure immersed in water or in toluene. It appears that finite difference approach is more efficient than first order perturbation method and that the effect of polarization charge may in no case be neglected as its contribution can reach a significant proportion of the value of nanostructure gap.

One-pot facile synthesis of reusable tremella-like M1@M2@M1(OH)2 (M1 = Co, Ni, M2 = Pt/Pd, Pt, Pd and Au) three layers core-shell nanostructures as highly efficient catalysts

NASA Astrophysics Data System (ADS)

Liu, Yadong; Fang, Zhen; Kuai, Long; Geng, Baoyou

2014-07-01

In this work, a general, facile, successive and eco-friendly method for multilayer nanostructures has been established for the first time. We take full advantage of the structural and compositional character of M1@M2 (M1 = Co, Ni, M2 = Pt/Pd, Pt, Pd and Au) core-shell nanostructures to prepare a series of reusable tremella-like M1@M2@M1(OH)2 three layer core-shell or yolk-shell nanocomposites with a magnetic core, a porous noble metal shell, and an ultrathin cobalt or nickel hydroxide shell. We evaluated their catalytic performance using a model reaction based on the reduction of 4-nitrophenol. These novel M1@M2@M1(OH)2 nanomaterials with a unique internal micro environment promoted the efficiency of the catalytic reaction, prolonged the service life of the catalyst and enhanced the overall activity of the catalyst in the catalytic process. The novel three layer core-shell nanocomposites can be extended to other applications such as biomedical detection, energy conversion and storage systems.In this work, a general, facile, successive and eco-friendly method for multilayer nanostructures has been established for the first time. We take full advantage of the structural and compositional character of M1@M2 (M1 = Co, Ni, M2 = Pt/Pd, Pt, Pd and Au) core-shell nanostructures to prepare a series of reusable tremella-like M1@M2@M1(OH)2 three layer core-shell or yolk-shell nanocomposites with a magnetic core, a porous noble metal shell, and an ultrathin cobalt or nickel hydroxide shell. We evaluated their catalytic performance using a model reaction based on the reduction of 4-nitrophenol. These novel M1@M2@M1(OH)2 nanomaterials with a unique internal micro environment promoted the efficiency of the catalytic reaction, prolonged the service life of the catalyst and enhanced the overall activity of the catalyst in the catalytic process. The novel three layer core-shell nanocomposites can be extended to other applications such as biomedical detection, energy conversion and storage systems. Electronic supplementary information (ESI) available: Fig. S1-S6. See DOI: 10.1039/c4nr01470g

Novel of core-shell AlOOH/Cu nanostructures: Synthesis, characterization, antimicrobial activity and in vitro toxicity in Neuro-2a cells

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

Bakina, O. V., E-mail: ovbakina@ispms.tsc.ru; Fomenko, A. N., E-mail: alserova@ispms.tsc.ru; Korovin, M. S., E-mail: msk@ispms.tsc.ru

Core-shell micro/nanostructures were fabricated by the reaction of Al/Cu bimetallic nanoparticles with water. Al/Cu nanoparticles have been obtained using the method of simultaneous electrical explosion of a pair of the corresponding metal wires in an argon atmosphere. The nanoparticles are chemically active and interact with water at 60°C to form core-shell micro/nanostructures. The obtained products were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering and the nitrogen adsorption method. The antibacterial activity of the synthesized structures was investigated against E. coli and St. aureus. The toxic effect of these nanostructures against themore » Neuro-2a neuroblastoma cell line was investigated. AlOOH/Cu nanostructures are shown to inhibit cell proliferation. The AlOOH/Cu nanostructures are good candidates for medical applications.« less

Novel of core-shell AlOOH/Cu nanostructures: Synthesis, characterization, antimicrobial activity and in vitro toxicity in Neuro-2a cells

NASA Astrophysics Data System (ADS)

Bakina, O. V.; Fomenko, A. N.; Korovin, M. S.; Glazkova, E. A.; Svarovskaya, N. V.

2016-08-01

Core-shell micro/nanostructures were fabricated by the reaction of Al/Cu bimetallic nanoparticles with water. Al/Cu nanoparticles have been obtained using the method of simultaneous electrical explosion of a pair of the corresponding metal wires in an argon atmosphere. The nanoparticles are chemically active and interact with water at 60°C to form core-shell micro/nanostructures. The obtained products were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering and the nitrogen adsorption method. The antibacterial activity of the synthesized structures was investigated against E. coli and St. aureus. The toxic effect of these nanostructures against the Neuro-2a neuroblastoma cell line was investigated. AlOOH/Cu nanostructures are shown to inhibit cell proliferation. The AlOOH/Cu nanostructures are good candidates for medical applications.

Investigation of magnetic and magneto-transport properties of ferromagnetic-charge ordered core-shell nanostructures

NASA Astrophysics Data System (ADS)

Das, Kalipada

2017-10-01

In our present study, we address in detail the magnetic and magneto-transport properties of ferromagnetic-charge ordered core-shell nanostructures. In these core-shell nanostructures, well-known half metallic La0.67Sr0.33MnO3 nanoparticles (average particle size, ˜20 nm) are wrapped by the charge ordered antiferromagnetic Pr0.67Ca0.33MnO3 (PCMO) matrix. The intrinsic properties of PCMO markedly modify it into such a core-shell form. The robustness of the PCMO matrix becomes fragile and melts at an external magnetic field (H) of ˜20 kOe. The analysis of magneto-transport data indicates the systematic reduction of the electron-electron and electron-magnon interactions in the presence of an external magnetic field in these nanostructures. The pronounced training effect appears in this phase separated compound, which was analyzed by considering the second order tunneling through the grain boundaries of the nanostructures. Additionally, the analysis of low field magnetoconductance data supports the second order tunneling and shows the close value of the universal limit (˜1.33).

A Strategy for Fabricating Porous PdNi@Pt Core-shell Nanostructures and Their Enhanced Activity and Durability for the Methanol Electrooxidation

PubMed Central

Liu, Xinyu; Xu, Guangrui; Chen, Yu; Lu, Tianhong; Tang, Yawen; Xing, Wei

2015-01-01

Three-dimensionally (3D) porous morphology of nanostructures can effectively improve their electrocatalytic activity and durability for various electrochemical reactions owing to big surface area and interconnected structure. Cyanogel, a jelly-like inorganic polymer, can be used to synthesize various three-dimensionally (3D) porous alloy nanomaterials owing to its double-metal property and particular 3D backbone. Here, 3D porous PdNi@Pt core-shell nanostructures (CSNSs) are facilely synthesized by first preparing the Pd-Ni alloy networks (Pd-Ni ANWs) core via cyanogel-reduction method followed by a galvanic displacement reaction to generate the Pt-rich shell. The as-synthesized PdNi@Pt CSNSs exhibit a much improved catalytic activity and durability for the methanol oxidation reaction (MOR) in the acidic media compared to the commercial used Pt black because of their specific structural characteristics. The facile and mild method described herein is highly attractive for the synthisis of 3D porous core-shell nanostructures. PMID:25557190

Hierarchical α-MnO2 nanowires@Ni1-x Mnx Oy nanoflakes core-shell nanostructures for supercapacitors.

PubMed

Wang, Hsin-Yi; Xiao, Fang-Xing; Yu, Le; Liu, Bin; Lou, Xiong Wen David

2014-08-13

A facile two-step solution-phase method has been developed for the preparation of hierarchical α-MnO2 nanowires@Ni1-x Mnx Oy nanoflakes core-shell nanostructures. Ultralong α-MnO2 nanowires were synthesized by a hydrothermal method in the first step. Subsequently, Ni1-x Mnx Oy nanoflakes were grown on α-MnO2 nanowires to form core-shell nanostructures using chemical bath deposition followed by thermal annealing. Both solution-phase methods can be easily scaled up for mass production. We have evaluated their application in supercapacitors. The ultralong one-dimensional (1D) α-MnO2 nanowires in hierarchical core-shell nanostructures offer a stable and efficient backbone for charge transport; while the two-dimensional (2D) Ni1-x Mnx Oy nanoflakes on α-MnO2 nanowires provide high accessible surface to ions in the electrolyte. These beneficial features enable the electrode with high capacitance and reliable stability. The capacitance of the core-shell α-MnO2 @Ni1-x Mnx Oy nanostructures (x = 0.75) is as high as 657 F g(-1) at a current density of 250 mA g(-1) , and stable charging-discharging cycling over 1000 times at a current density of 2000 mA g(-1) has been realized. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of fullerene@gold core-shell nanostructures.

PubMed

Ren, Yupeng; Paira, Priyankar; Nayak, Tapas Ranjan; Ang, Wee Han; Pastorin, Giorgia

2011-07-21

A "direct encapsulation" method was developed for the synthesis of highly stable water-soluble fullerene@gold core-shell nanostructures, with gold nanoshells showing either closed or porous morphology. This gold nano-shell coating formed a "nano-oven", capable of decomposing encapsulated fullerene molecules rapidly when irradiated by laser. We envisaged this being a useful tool for chemical reactions as well as a novel scaffold for nano-material synthesis.

Theoretical investigation of geometries, stabilities, electronic and optical properties for advanced Ag{sub n}@(ZnO){sub 42} (n=6-18) hetero-nanostructure

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

Cheng, Hai-Xia; Department of Physics, National University of Singapore, 117542; Wang, Xiao-Xu

The structural properties of Ag{sub n}@(ZnO){sub 42} (n=6-18) core-shell nanoparticles have been investigated by the first principles calculations, and the core-shell nanostructure with n=13 is proved to be the most stable one for the first time. Ag{sub 13}@(ZnO){sub 42} core-shell nanostructure possesses higher chemistry activity and shows a red shift phenomenon in the light of the absorption spectrum compare to the (ZnO){sub 48}, this can be confirmed by the calculated electron structure. The visible-light could be absorbed by Ag{sub 13}@(ZnO){sub 42} to improve the photo-catalysis of (ZnO){sub 48} nanostructure. Our results show good agreement with experiments.

Atomistic simulations of activated processes in nanoparticles synthesis

NASA Astrophysics Data System (ADS)

Giberti, Federico; Galli, Giulia

Core-shell and Janus nanopartices are promising building blocks for new, highly efficient solar cells. One of the most common synthetic pathways to produce such nanostructures is the use of cation exchange reactions. Although widely used, these procedures are not completely understood. We employed classical Molecular Dynamics and Monte Carlo simulations to understand these transformation at the molecular level; in particular we investigated the conversion from CdSe (sphalerite) to PbSe (rocksalt) NPs with 2-3 nm diameter. In order to recover the equilibrium free energy surfaces we used state of the art enhanced sampling techniques, including Metadynamics. The formation of hybrid core-shell structures resulted to be an activated process, where the limiting step is the transition of a sphalerite to a rocksalt PbSe nucleus. We found that the barrier height and the stability of the two phases depend on the size of the PbSe nucleus, suggesting that the process could proceed via a two step mechanism, where a small sphalerite nucleus is formed first, and it then transforms to a rocksalt nucleus. Our results give insight into possible manipulation processes at the molecular scale, which could be used to stabilize metastable NPs and tune their physical and chemical properties. This work was supported by the DOE Grant No. DE-FG02-06ER46262.

Scalable Super-Resolution Synthesis of Core-Vest Composites Assisted by Surface Plasmons.

PubMed

Montazeri, A O; Kim, Y; Fang, Y S; Soheilinia, N; Zaghi, G; Clark, J K; Maboudian, R; Kherani, N P; Carraro, C

2018-02-15

The behavior of composite nanostructures depends on both size and elemental composition. Accordingly, concurrent control of size, shape, and composition of nanoparticles is key to tuning their functionality. In typical core-shell nanoparticles, the high degree of symmetry during shell formation results in fully encapsulated cores with severed access to the surroundings. We commingle light parameters (wavelength, intensity, and pulse duration) with the physical properties of nanoparticles (size, shape, and composition) to form hitherto unrealized core-vest composite nanostructures (CVNs). Unlike typical core-shells, the plasmonic core of the resulting CVNs selectively maintains physical access to its surrounding. Tunable variations in local temperature profiles ≳50 °C are plasmonically induced over starburst-shaped nanoparticles as small as 50-100 nm. These temperature variations result in CVNs where the shell coverage mirrors the temperature variations. The precision thus offered individually tailors access pathways of the core and the shell.

Fabrication and characterization of ZnS/ZnO core shell nanostructures on silver wires

NASA Astrophysics Data System (ADS)

Kao, Chyuan Haur; Su, Wei Ming; Li, Cheng Yuan; Weng, Wei Chih; Weng, Chen Yuan; Cheng, Chin-Chi; Lin, Yung-Sen; Lin, Chia Feng; Chen, Hsiang

2018-06-01

In this research, ZnS nanoparticles were synthesized on ZnO/silver wires to form ZnS/ZnO core shell structures. Various outward appearance and colors could be observed by different ZnO growth and sulfurization conditions. To evaluate the properties of these nanostructures, optical properties and chemical bindings were analyzed by photoluminescence, Raman analysis, and X-ray photoelectron spectroscopy. Furthermore, material characterizations including transmission electron microscopy and X-ray diffraction confirmed that cubic ZnS (311)/ZnO nanostructures were grown on silver wires for the first time. ZnS/ZnO core shell structures on silver wires are promising for future optoelectronic and biomedical applications.

Synthesis and gas sensing properties of α-Fe(2)O(3)@ZnO core-shell nanospindles.

PubMed

Zhang, Jun; Liu, Xianghong; Wang, Liwei; Yang, Taili; Guo, Xianzhi; Wu, Shihua; Wang, Shurong; Zhang, Shoumin

2011-05-06

α-Fe(2)O(3)@ZnO core-shell nanospindles were synthesized via a two-step hydrothermal approach, and characterized by means of SEM/TEM/XRD/XPS. The ZnO shell coated on the nanospindles has a thickness of 10-15 nm. Considering that both α-Fe(2)O(3) and ZnO are good sensing materials, we have investigated the gas sensing performances of the core-shell nanocomposite using ethanol as the main probe gas. It is interesting to find that the gas sensor properties of the core-shell nanospindles are significantly enhanced compared with pristine α-Fe(2)O(3). The enhanced sensor properties are attributed to the unique core-shell nanostructure. The detailed sensing mechanism is discussed with respect to the energy band structure and the electron depletion theory. The core-shell nanostructure reported in this work provides a new path to fabricate highly sensitive materials for gas sensing applications.

Scalable Synthesis of Triple-Core-Shell Nanostructures of TiO2 @MnO2 @C for High Performance Supercapacitors Using Structure-Guided Combustion Waves.

PubMed

Shin, Dongjoon; Shin, Jungho; Yeo, Taehan; Hwang, Hayoung; Park, Seonghyun; Choi, Wonjoon

2018-03-01

Core-shell nanostructures of metal oxides and carbon-based materials have emerged as outstanding electrode materials for supercapacitors and batteries. However, their synthesis requires complex procedures that incur high costs and long processing times. Herein, a new route is proposed for synthesizing triple-core-shell nanoparticles of TiO 2 @MnO 2 @C using structure-guided combustion waves (SGCWs), which originate from incomplete combustion inside chemical-fuel-wrapped nanostructures, and their application in supercapacitor electrodes. SGCWs transform TiO 2 to TiO 2 @C and TiO 2 @MnO 2 to TiO 2 @MnO 2 @C via the incompletely combusted carbonaceous fuels under an open-air atmosphere, in seconds. The synthesized carbon layers act as templates for MnO 2 shells in TiO 2 @C and organic shells of TiO 2 @MnO 2 @C. The TiO 2 @MnO 2 @C-based electrodes exhibit a greater specific capacitance (488 F g -1 at 5 mV s -1 ) and capacitance retention (97.4% after 10 000 cycles at 1.0 V s -1 ), while the absence of MnO 2 and carbon shells reveals a severe degradation in the specific capacitance and capacitance retention. Because the core-TiO 2 nanoparticles and carbon shell prevent the deformation of the inner and outer sides of the MnO 2 shell, the nanostructures of the TiO 2 @MnO 2 @C are preserved despite the long-term cycling, giving the superior performance. This SGCW-driven fabrication enables the scalable synthesis of multiple-core-shell structures applicable to diverse electrochemical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced charge storage capability of Ge/GeO(2) core/shell nanostructure.

PubMed

Yuan, C L; Lee, P S

2008-09-03

A Ge/GeO(2) core/shell nanostructure embedded in an Al(2)O(3) gate dielectrics matrix was produced. A larger memory window with good data retention was observed in the fabricated metal-insulator-semiconductor (MIS) capacitor for Ge/GeO(2) core/shell nanoparticles compared to Ge nanoparticles only, which is due to the high percentage of defects located on the surface and grain boundaries of the GeO(2) shell. We believe that the findings presented here provide physical insight and offer useful guidelines to controllably modify the charge storage properties of indirect semiconductors through defect engineering.

Controlled Growth of Ordered III-Nitride Core-Shell Nanostructure Arrays for Visible Optoelectronic Devices

DOE PAGES

Rishinaramangalam, Ashwin K.; Mishkat Ul Masabih, Saadat; Fairchild, Michael N.; ...

2014-10-21

In our paper, we demonstrate the growth of ordered arrays of nonpolar {101 ¯ 0} core–shell nanowalls and semipolar {101 ¯ 1} core–shell pyramidal nanostripes on c-plane (0001) sapphire substrates using selective-area epitaxy and metal organic chemical vapor deposition. The nanostructure arrays are controllably patterned into LED mesa regions, demonstrating a technique to impart secondary lithography features into the arrays. Moreover, we study the dependence of the nanostructure cores on the epitaxial growth conditions and show that the geometry and morphology are strongly influenced by growth temperature, V/III ratio, and pulse interruption time. We also demonstrate the growth of InGaNmore » quantum well shells on the nanostructures and characterize the structures by using micro-photoluminescence and cross-section scanning tunneling electron microscopy.« less

Ag@Aggregation-induced emission dye core/shell nanostructures with enhanced one- and two-photon fluorescence

NASA Astrophysics Data System (ADS)

Wang, Cheng; Li, Yang; Xu, Qiujin; Luo, Liang

2017-10-01

Combining plasmonic nanostructures with two-photon fluorescence materials is a promising way to significantly enhance two-photon fluorescence. Ag@1,4-bis(2-cyano-2-phenylethenyl) benzene (BCPEB) core/shell nanostructures were fabricated by simply incubating the isolated Ag nanoparticles with BCPEB microrods in ethanol. BCPEB was chosen as the fluorescent organic molecule owing to the aggregation-induced-emission (AIE) nature which would reduce the emission loss as being practically applied in solid phase. By utilizing the match of the extinction spectrum of Ag nanoparticles and BCPEB's absorption band, the target Ag@BCPEB core/shell nanostructures showed an enhanced one-photon (12×) fluorescence, integrating with SERS signal as well. Moreover, the resultant second harmonic generation of Ag nanoparticles under two-photon excitation also well matched with the absorption band of BCPEB, and significant enhanced two-photon (17×) fluorescence was obtained. The confocal images of NIH-3T3 cells with these nanostructures under one- and two-photon excitation showed good contrast and brightness for bio-imaging.

Synthesis of parallel and antiparallel core-shell triangular nanoparticles

NASA Astrophysics Data System (ADS)

Bhattacharjee, Gourab; Satpati, Biswarup

2018-04-01

Core-shell triangular nanoparticles were synthesized by seed mediated growth. Using triangular gold (Au) nanoparticle as template, we have grown silver (Ag) shellto get core-shell nanoparticle. Here by changing the chemistry we have grown two types of core-shell structures where core and shell is having same symmetry and also having opposite symmetry. Both core and core-shell nanoparticles were characterized using transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) to know the crystal structure and composition of these synthesized core-shell nanoparticles. From diffraction pattern analysis and energy filtered TEM (EFTEM) we have confirmed the crystal facet in core is responsible for such two dimensional growth of core-shell nanostructures.

Efficient synthetic access to thermo-responsive core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Dine, Enaam Jamal Al; Ferjaoui, Zied; Roques-Carmes, Thibault; Schjen, Aleksandra; Meftah, Abdelaziz; Hamieh, Tayssir; Toufaily, Joumana; Schneider, Raphaël; Gaffet, Eric; Alem, Halima

2017-03-01

Core/shell nanostructures based on silica, fluorescent ZnO quantum dots (QDs) and superparamagnetic Fe3O4 nanoparticles (NPs) were prepared and fully characterized by the combination of different techniques and the physical properties of the nanostructures were studied. We demonstrate the efficiency of the atom transfer radical polymerization with activators regenerated by electron transfer process to graft (co-)polymers of different structures and polarity at the surface of metal oxide NPs. The influence of the polymer chain configuration on the optical properties of the ZnO/polymer core/shell QDs was enlightened. Concerning the magnetic properties of the Fe3O4/polymer nanostructures, only the amount of the grafted polymer plays a role on the saturation magnetization of the NPs and no influence of the aggregation was evidenced. The simple and fast process described in this work is efficient for the grafting of copolymers from surfaces and the derived NPs display the combination of the physical properties of the core and the macromolecular behavior of the shell.

Efficient synthetic access to thermo-responsive core/shell nanoparticles.

PubMed

Dine, Enaam Jamal Al; Ferjaoui, Zied; Roques-Carmes, Thibault; Schjen, Aleksandra; Meftah, Abdelaziz; Hamieh, Tayssir; Toufaily, Joumana; Schneider, Raphaël; Gaffet, Eric; Alem, Halima

2017-03-24

Core/shell nanostructures based on silica, fluorescent ZnO quantum dots (QDs) and superparamagnetic Fe 3 O 4 nanoparticles (NPs) were prepared and fully characterized by the combination of different techniques and the physical properties of the nanostructures were studied. We demonstrate the efficiency of the atom transfer radical polymerization with activators regenerated by electron transfer process to graft (co-)polymers of different structures and polarity at the surface of metal oxide NPs. The influence of the polymer chain configuration on the optical properties of the ZnO/polymer core/shell QDs was enlightened. Concerning the magnetic properties of the Fe 3 O 4 /polymer nanostructures, only the amount of the grafted polymer plays a role on the saturation magnetization of the NPs and no influence of the aggregation was evidenced. The simple and fast process described in this work is efficient for the grafting of copolymers from surfaces and the derived NPs display the combination of the physical properties of the core and the macromolecular behavior of the shell.

Design of Janus nanoparticles with atomic precision: tungsten-doped gold nanostructures.

PubMed

Sun, Qiang; Wang, Qian; Jena, Puru; Kawazoe, Yoshiyuki

2008-02-01

Janus nanoparticles, characterized by their anisotropic structure and interactions, have added a new dimension to nanoscience because of their potential applications in biomedicine, sensors, catalysis, and assembled materials. The technological applications of these nanoparticles, however, have been limited as the current chemical, physical, and biosynthetic methods lack sufficient size and shape selectivity. We report a technique where gold clusters doped with tungsten can serve as a seed that facilitates the natural growth of anisotropic nanostructures whose size and shape can be controlled with atomic precision. Using ab initio simulated annealing and molecular dynamics calculations on AunW (n > 12) clusters, we discovered that the W@Au12 cage cluster forms a very stable core with the remaining Au atoms forming patchy structures on its surface. The anisotropic geometry gives rise to anisotropies in vibrational spectra, charge distributions, electronic structures, and reactivity, thus making it useful to have dual functionalities. In particular, the core-patch structure is shown to possess a hydrophilic head and a hydrophobic tail. The W@Au12 clusters can also be used as building blocks of a nanoring with novel properties.

Rapid Synthesis and Formation Mechanism of Core-Shell-Structured La-Doped SrTiO3 with a Nb-Doped Shell

PubMed Central

Park, Nam-Hee; Akamatsu, Takafumi; Itoh, Toshio; Izu, Noriya; Shin, Woosuck

2015-01-01

To provide a convenient and practical synthesis process for metal ion doping on the surface of nanoparticles in an assembled nanostructure, core-shell-structured La-doped SrTiO3 nanocubes with a Nb-doped surface layer were synthesized via a rapid synthesis combining a rapid sol-precipitation and hydrothermal process. The La-doped SrTiO3 nanocubes were formed at room temperature by a rapid dissolution of NaOH pellets during the rapid sol-precipitation process, and the Nb-doped surface (shell) along with Nb-rich edges formed on the core nanocubes via the hydrothermal process. The formation mechanism of the core-shell-structured nanocubes and their shape evolution as a function of the Nb doping level were investigated. The synthesized core-shell-structured nanocubes could be arranged face-to-face on a SiO2/Si substrate by a slow evaporation process, and this nanostructured 10 μm thick thin film showed a smooth surface. PMID:28793420

TiO2 -coated fluoride nanoparticles for dental multimodal optical imaging.

PubMed

Braz, Ana K S; Moura, Diógenes S; Gomes, Anderson S L; Ohulchanskyy, Tymish Y; Chen, Guanying; Liu, Maixian; Damasco, Jossana; de Araujo, Renato E; Prasad, Paras N

2018-04-01

Core-shell nanostructures associated with photonics techniques have found innumerous applications in diagnostics and therapy. In this work, we introduce a novel core-shell nanostructure design that serves as a multimodal optical imaging contrast agent for dental adhesion evaluation. This nanostructure consists of a rare-earth-doped (NaYF 4 :Yb 60%, Tm 0.5%)/NaYF 4 particle as the core (hexagonal prism, ~51 nm base side length) and the highly refractive TiO 2 material as the shell (~thickness of 15 nm). We show that the TiO 2 shell provides enhanced contrast for optical coherence tomography (OCT), while the rare-earth-doped core upconverts excitation light from 975 nm to an emission peaked at 800 nm for photoluminescence imaging. The OCT and the photoluminescence wide-field images of human tooth were demonstrated with this nanoparticle core-shell contrast agent. In addition, the described core-shell nanoparticles (CSNps) were dispersed in the primer of a commercially available dental bonding system, allowing clear identification of dental adhesive layers with OCT. We evaluated that the presence of the CSNp in the adhesive induced an enhancement of 67% scattering coefficient to significantly increase the OCT contrast. Moreover, our results highlight that the upconversion photoluminescence in the near-infrared spectrum region is suitable for image of deep dental tissue. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design, synthesis and applications of core-shell, hollow core, and nanorattle multifunctional nanostructures.

PubMed

El-Toni, Ahmed Mohamed; Habila, Mohamed A; Labis, Joselito Puzon; ALOthman, Zeid A; Alhoshan, Mansour; Elzatahry, Ahmed A; Zhang, Fan

2016-02-07

With the evolution of nanoscience and nanotechnology, studies have been focused on manipulating nanoparticle properties through the control of their size, composition, and morphology. As nanomaterial research has progressed, the foremost focus has gradually shifted from synthesis, morphology control, and characterization of properties to the investigation of function and the utility of integrating these materials and chemical sciences with the physical, biological, and medical fields, which therefore necessitates the development of novel materials that are capable of performing multiple tasks and functions. The construction of multifunctional nanomaterials that integrate two or more functions into a single geometry has been achieved through the surface-coating technique, which created a new class of substances designated as core-shell nanoparticles. Core-shell materials have growing and expanding applications due to the multifunctionality that is achieved through the formation of multiple shells as well as the manipulation of core/shell materials. Moreover, core removal from core-shell-based structures offers excellent opportunities to construct multifunctional hollow core architectures that possess huge storage capacities, low densities, and tunable optical properties. Furthermore, the fabrication of nanomaterials that have the combined properties of a core-shell structure with that of a hollow one has resulted in the creation of a new and important class of substances, known as the rattle core-shell nanoparticles, or nanorattles. The design strategies of these new multifunctional nanostructures (core-shell, hollow core, and nanorattle) are discussed in the first part of this review. In the second part, different synthesis and fabrication approaches for multifunctional core-shell, hollow core-shell and rattle core-shell architectures are highlighted. Finally, in the last part of the article, the versatile and diverse applications of these nanoarchitectures in catalysis, energy storage, sensing, and biomedicine are presented.

Ag@ZnO core-shell nanoparticles study by first principle: The structural, magnetic and optical properties

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

Cheng, Hai-Xia; Wang, Xiao-Xu; Beijing Computing Center, Beijing 100094

Ag@ZnO core-shell nanoparticles of around 72 atoms have been investigated by the density functional theory, revealing proving for the first time that the core-shell structure exhibits a shrinkage phenomenon from outer shell in agreement with the other studies in literatures. Our calculations predict that the Ag@ZnO core-shell structure is a ferromagnetic spin polarized state, and the magnetism mainly stems from the spin splitting of 2p electrons of O atoms. In addition, the total and partial DOS of Ag@ZnO indicate that the nanostructure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. Furthermore, the optical properties calculations showmore » that the absorption edge of Ag@ZnO have a red shift and good photocatalysis compare to that of the bulk ZnO. These results of the Ag@ZnO core-shell structure obtain a well agreement with the experimental measurement. - Graphical abstract: Geometric structure of (a) Ag@ZnO core-shell nanostructure; (b) the core of Ag; (c) the shell of ZnO The core-shell nanoparticle Ag@ZnO contains Ag inner core of radius of 4 Å and ZnO outer shell with thickness of 2 Å. Ag@ZnO core-shell nanoparticles of around 72 atoms have been proved for the first time that the core-shell structure exhibit a shrinkage phenomenon from outer shell. Our calculations predict that the Ag@ZnO core-shell structure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. The absorption edge of Ag@ZnO have a red shift and get good photo-catalysis compare to that of the bulk ZnO.« less

Core/shell structured Zn/ZnO nanoparticles synthesized by gaseous laser ablation with enhanced photocatalysis efficiency

NASA Astrophysics Data System (ADS)

Song, Lu; Wang, Yafei; Ma, Jing; Zhang, Qinghua; Shen, Zhijian

2018-06-01

Zinc oxide (ZnO) is a competitive candidate in semiconductor photocatalysts, only if the efficiency could be fully optimized especially by tailored nanostructures. Here we report a kind of core/shell structured Zn/ZnO nanoparticles with enhanced photocatalysis efficiency, which were synthesized by a highly-productive gaseous laser ablation method. The nanodroplets generated by laser ablation would be reduced to zinc in the protective atmosphere, and further be oxidized at surface to form a specific core/shell structured Zn/ZnO nanoparticles within seconds. Thanks to the formation of this Zn-ZnO Schottky junction, the photocatalysis degradation efficiency of such core/shell Zn/ZnO nanostructure is significantly improved owing to the enhanced visible light absorption and inhibited carrier recombination by introducing the metallic zinc.

Deformation Behavior of Al/a-Si Core-shell Nanostructures

NASA Astrophysics Data System (ADS)

Fleming, Robert

Al/a-Si core-shell nanostructures (CSNs), consisting of a hemispherical Al core surrounded by a hard shell of a-Si, have been shown to display unusual mechanical behavior in response to compression loading. Most notably, these nanostructures exhibit substantial deformation recovery, even when loaded much beyond the elastic limit. Nanoindentation measurements revealed a unique mechanical response characterized by discontinuous signatures in the load-displacement data. In conjunction with the indentation signatures, nearly complete deformation recovery is observed. This behavior is attributed to dislocation nucleation and annihilation events enabled by the 3-dimensional confinement of the Al core. As the core confinement is reduced, either through an increase in confined core volume or a change in the geometrical confinement, the indentation signatures and deformation resistance are significantly reduced. Complimentary molecular dynamics simulations show that a substantial amount of dislocation egression occurs in the core of CSNs during unloading as dislocations annihilate at the core/shell interface. Smaller core diameters correlate with the development of a larger back-stress within the core during unloading, which further correlates with improved dislocation annihilation after unloading. Furthermore, dislocations nucleated in the core of core-shell nanorods are not as effectively removed as compared to CSNs. Nanostructure-textured surfaces (NSTSs) composed of Al/a-Si CSNs have improved tribological properties compared surfaces patterned with Al nanodots and a flat (100) Si surface. NSTSs have a coefficient of friction (COF) as low as 0.015, exhibit low adhesion with adhesion forces on the order of less than 1 microN, and are highly deformation resistant, with no apparent surface deformation after nanoscratch testing, even at contact forces up to 8000 microN. In comparison, (100) Si has substantially higher adhesion and COF ( 10 microN and 0.062, respectively), while the Al nanodots have both higher friction (COF 0.044) and are deformed when subjected to contact loads as low as 250 microN. This integrated experimental and computational study elucidates the mechanisms that contribute to the novel properties of Al/a-Si CSNs and characterizes the tribological properties of surface composed of these nanostructures, which provides a foundation for the rational design of novel technologies based on CSNs.

The effect of operational parameters on the photocatalytic degradation of Congo red organic dye using ZnO-CdS core-shell nano-structure coated on glass by Doctor Blade method.

PubMed

Habibi, Mohammad Hossein; Rahmati, Mohammad Hossein

2015-02-25

Photocatalytic degradation of Congo red was investigated using ZnO-CdS core-shell nano-structure coated on glass by Doctor Blade method in aqueous solution under irradiation. Field-emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) techniques were used for the morphological and structural characterization of ZnO-CdS core-shell nanostructures. XRD results showed diffractions of wurtzite zinc oxide core and wurtzite cadmium sulfide shell. FESEM results showed that nanoparticles are nearly hexagonal with an average diameter of about 50 nm. The effect of catalyst loading, UV-light irradiation time and solution pH on photocatalytic degradation of Congo red was studied and optimized values were obtained. Results showed that the employment of efficient photocatalyst and selection of optimal operational parameters may lead to complete decolorization of dye solutions. It was found that ZnO-CdS core-shell nano-structure is more favorable for the degradation of Congo red compare to pure ZnO or pure CdS due to lower electron hole recombination. The results showed that the photocatalytic degradation rate of Congo red is enhanced with increasing the content of ZnO up to ZnO(0.2 M)/CdS(0.075 M) which is reached 88.0% within 100 min irradiation. Copyright © 2014 Elsevier B.V. All rights reserved.

Facile preparation of gold nanocages and hollow gold nanospheres via solvent thermal treatment and their surface plasmon resonance and photothermal properties.

PubMed

Wang, Haifei; Han, Jing; Lu, Wensheng; Zhang, Jianping; Li, Jinru; Jiang, Long

2015-02-15

Although template etching method is one of the most common ways of preparation of hollow gold nanostructures, this approach still requires further improvements to avoid the collapse of gold shells after the cores were removed. In this work, an improved template etching method, with which hollow gold nanostructure is fabricated by etching Polystyrene (PS) cores from PS@Au core-shell nanospheres with solvent thermal treatment in N,N-Dimethylformamide (DMF), is demonstrated. When PS cores were removed by a thermal treatment process, gold nanoshells reconstruct and the collapse of the nanoshells is avoided. Gold nanocages and hollow gold nanospheres are easily obtained from the various structures of PS@Au core-shell nanospheres. These hollow nanostructures represent special near infrared (NIR) optical property and photothermal property. Compared with hollow gold nanospheres, the gold nanocages show higher temperature increase at the same particle concentration. Copyright © 2014 Elsevier Inc. All rights reserved.

Fabrication of CuO-Pt core-shell nanohooks by in situ reconstructing the Pt-shells.

PubMed

Cao, Fan; Zheng, He; Zhao, Ligong; Huang, Rui; Jia, Shuangfeng; Liu, Huihui; Li, Lei; Wang, Zhao; Hu, Yongming; Gu, Haoshuang; Wang, Jianbo

2018-05-25

The design of various nanostructures with specific compositions and shapes is highly demanded due to the widespread use of micro/nano electro-mechanical systems. In this work, one-dimensional CuO-Pt core-shell nanowires (NWs) are acquired by depositing Pt nanoparticles onto CuO NWs and then mechanically-shaped into nanohooks. Subsequently, the hook-like shape is maintained by the Pt-shell which is reconstructed via Joule heat and re-solidified after cooling down, during which the elastic strain energy is stored in the CuO-core. The results provide a simple strategy to design nanostructures with various compositions and shapes, implying the potential applications in mechanical energy storage and shape memory nanodevices.

Energy-Cascaded Upconversion in an Organic Dye-Sensitized Core/Shell Fluoride Nanocrystal.

PubMed

Chen, Guanying; Damasco, Jossana; Qiu, Hailong; Shao, Wei; Ohulchanskyy, Tymish Y; Valiev, Rashid R; Wu, Xiang; Han, Gang; Wang, Yan; Yang, Chunhui; Ågren, Hans; Prasad, Paras N

2015-11-11

Lanthanide-doped upconversion nanoparticles hold promises for bioimaging, solar cells, and volumetric displays. However, their emission brightness and excitation wavelength range are limited by the weak and narrowband absorption of lanthanide ions. Here, we introduce a concept of multistep cascade energy transfer, from broadly infrared-harvesting organic dyes to sensitizer ions in the shell of an epitaxially designed core/shell inorganic nanostructure, with a sequential nonradiative energy transfer to upconverting ion pairs in the core. We show that this concept, when implemented in a core-shell architecture with suppressed surface-related luminescence quenching, yields multiphoton (three-, four-, and five-photon) upconversion quantum efficiency as high as 19% (upconversion energy conversion efficiency of 9.3%, upconversion quantum yield of 4.8%), which is about ~100 times higher than typically reported efficiency of upconversion at 800 nm in lanthanide-based nanostructures, along with a broad spectral range (over 150 nm) of infrared excitation and a large absorption cross-section of 1.47 × 10(-14) cm(2) per single nanoparticle. These features enable unprecedented three-photon upconversion (visible by naked eye as blue light) of an incoherent infrared light excitation with a power density comparable to that of solar irradiation at the Earth surface, having implications for broad applications of these organic-inorganic core/shell nanostructures with energy-cascaded upconversion.

Biogenic Growth of Alloys and Core-Shell Nanostructures Using Urease as a Nanoreactor at Ambient Conditions

PubMed Central

Sharma, Bhagwati; Mandani, Sonam; Sarma, Tridib K.

2013-01-01

Biomineralization is an extremely efficient biologically guided process towards the advancement of nano-bio integrated materials. As a prime module of the natural world, enzymes are expected to play a major role in biogenic growth of inorganic nanostructures. Although there have been developments in designing enzyme-responsive nanoparticle systems or generation of inorganic nanostructures in an enzyme-stimulated environment, reports regarding action of enzymes as reducing agents themselves for the growth of inorganic nanoparticles still remains elusive. Here we present a mechanistic investigation towards the synthesis of metal and metallic alloy nanoparticles using a commonly investigated enzyme, Jack bean urease (JBU), as a reducing as well as stabilizing agent under physiological conditions. The catalytic functionality of urease was taken advantage of towards the development of metal-ZnO core-shell nanocomposites, making urease an ideal bionanoreactor for synthesizing higher order nanostructures such as alloys and core- shell under ambient conditions. PMID:24018831

Temperature dependence Infrared and Raman studies of III-V/II-VI core-shell nanostructures

NASA Astrophysics Data System (ADS)

Manciu, Felicia S.; McCombe, Bruce D.; Lucey, Derrick

2005-03-01

The temperature dependence (8 K < T < 300 K) of optical phonon modes confined in InP/II-VI core-shell nanostructures have been investigated by far-infrared (FIR) and Raman scattering spectroscopies. The core-shell nanostructures were fabricated by colloidal chemistry and characterized by transmission electron microscopy and X-ray diffraction prior to being embedded in a polycrystalline CsI matrix for the present studies. The FIR measurements of InP/ZnSe sample exhibits three absorption features, one clearly due to the Froelich mode of the InP cores, and the others related to modes associated with the shell layer and its coupling to the matrix. Strong mixing of the characteristic vibrations of each constituent material was observed for InP/ZnS sample. Raman scattering (457.9 nm excitation) features were determined without polarization selection in the backscattering geometry. Interesting T-dependent resonant Raman effect of the surface optical phonon modes has been discovered in InP/ZnSe sample. Reasonable agreement is obtained between the Raman and FIR results, as well as with theoretical calculations.

Plasmonic nanostructures for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Jiang, Ruiqian

In the last three decades, a large number of different plasmonic nanostructures have attracted much attention due to their unique optical properties. Those plasmonic nanostructures include nanoparticles, nanoholes and metal nanovoids. They have been widely utilized in optical devices and sensors. When the plasmonic nanostructures interact with the electromagnetic wave and their surface plasmon frequency match with the light frequency, the electrons in plasmonic nanostructures will resonate with the same oscillation as incident light. In this case, the plasmonic nanostructures can absorb light and enhance the light scattering. Therefore, the plasmonic nanostructures can be used as substrate for surface-enhanced Raman spectroscopy to enhance the Raman signal. Using plasmonic nanostructures can significantly enhance Raman scattering of molecules with very low concentrations. In this thesis, two different plasmonic nanostructures Ag dendrites and Au/Ag core-shell nanoparticles are investigated. Simple methods were used to produce these two plasmonic nanostructures. Then, their applications in surface enhanced Raman scattering have been explored. Ag dendrites were produced by galvanic replacement reaction, which was conducted using Ag nitrate aqueous solution and copper metal. Metal copper layer was deposited at the bottom side of anodic aluminum oxide (AAO) membrane. Silver wires formed inside AAO channels connected Ag nitrate on the top of AAO membrane and copper layer at the bottom side of AAO. Silver dendrites were formed on the top side of AAO. The second plasmonic nanostructure is Au/Ag core-shell nanoparticles. They were fabricated by electroless plating (galvanic replacement) reaction in a silver plating solution. First, electrochemically evolved hydrogen bubbles were used as template through electroless deposition to produce hollow Au nanoparticles. Then, the Au nanoparticles were coated with Cu shells in a Cu plating solution. In the following step, a AgCN based plating solution was used to replace Cu shell to form Au/Ag core-shell nanoparticles. These two plasmonic nanostructures were tested as substrates for Raman spectroscopy. It demonstrated that these plasmonic nanostructures could enhance Raman signal from the molecules on their surface. The results indicate that these plasmonic nanostructures could be utilized in many fields, such as such as biological and environmental sensors.

Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission

NASA Astrophysics Data System (ADS)

Li, Gong Ping; Chen, Rui; Guo, Dong Lai; Wong, Lai Mun; Wang, Shi Jie; Sun, Han Dong; Wu, Tom

2011-08-01

Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications.Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications. Electronic supplementary information (ESI) available: Representative SEM and TEM images of 700 °C annealed ZnO/MgO core/shell NWs, a TEM image of an individual MgO nanocrystal inside the MgO NTs and SEM images of SnO2 NP chains embedded in MgO NTs and comb-shaped MgO hollow nanostructures. See DOI: 10.1039/c1nr10352k

Fabrication and investigation of effect of core size in heterostructure PbS/CdS core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Das, D.; Hussain, A. M. P.

2018-04-01

PbS/CdS core/shell (CS) nanoparticles (NPs) were fabricated with three different concentrations of PbS core and CdS shell. Formation of core/shell heterostructure was confirmed from X-ray diffraction studies. The diffraction patterns exhibited formation of cubic phase and polycrystalline core/shell nanostructure. The crystalline sizes calculated from Williamson-Hall plot exhibited increase with molar concentration of precursors with decrease in strain. High resolution electron microscopy studies also confirm the formation of core/shell structure with particle size around 10 nm. A large blue-shift for PbS core compared to its bulk and small red-shift for the PbS/CdS core/shell as compared to the core is being observed in absorption spectra.

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.

Hybride magnetic nanostructure based on amino acids functionalized polypyrrole

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

Nan, Alexandrina, E-mail: alexandrina.nan@itim-cj.ro; Bunge, Alexander; Turcu, Rodica

Conducting polypyrrole is especially promising for many commercial applications because of its unique optical, electric, thermal and mechanical properties. We report the synthesis and characterization of novel pyrrole functionalized monomers and core-shell hybrid nanostructures, consisting of a conjugated polymer layer (amino acids functionalized pyrrole copolymers) and a magnetic nanoparticle core. For functionalization of the pyrrole monomer we used several amino acids: tryptophan, leucine, phenylalanine, serine and tyrosine. These amino acids were linked via different types of hydrophobic linkers to the nitrogen atom of the pyrrole monomer. The magnetic core-shell hybrid nanostructures are characterized by various methods such as FTIR spectroscopy,more » transmission electron microscopy (TEM) and magnetic measurements.« less

Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in Novel Donor-Acceptor Core-Shell Nanostructures for Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Strain, Jacob; Jamhawi, Abdelqader; Abeywickrama, Thulitha M.; Loomis, Wendy; Rathnayake, Hemali; Liu, Jinjun

2016-06-01

Novel donor-acceptor nanostructures were synthesized via covalent synthesis and/or UV cross-linking method. Their photoinduced dynamics were investigated with ultrafast transient absorption (TA) spectroscopy. These new nanostructures are made with the strategy in mind to reduce manufacturing steps in the process of fabricating an organic photovoltaic cell. By imitating the heterojunction interface within a fixed particle domain, several fabrication steps can be bypassed reducing cost and giving more applicability to other film deposition methods. Such applications include aerosol deposition and ink-jet printing. The systems that were studied by TA spectroscopy include PDIB core, PDIB-P3HT core-shell, and PDIB-PANT core-shell which range in size from 60 to 130 nm. Within the experimentally accessible spectra range there resides a region of ground state bleaching, stimulated emission, and excited-state absorption of both neutrals and anions. Control experiments have been carried out to assign these features. At high pump fluences the TA spectra of PDIB core alone also indicate an intramolecular charge separation. The TA spectroscopy results thus far suggest that the core-shells resemble the photoinduced dynamics of a standard film although the particles are dispersed in solution, which indicates the desired outcome of the work.

When lithography meets self-assembly: a review of recent advances in the directed assembly of complex metal nanostructures on planar and textured surfaces

NASA Astrophysics Data System (ADS)

Hughes, Robert A.; Menumerov, Eredzhep; Neretina, Svetlana

2017-07-01

One of the foremost challenges in nanofabrication is the establishment of a processing science that integrates wafer-based materials, techniques, and devices with the extraordinary physicochemical properties accessible when materials are reduced to nanoscale dimensions. Such a merger would allow for exacting controls on nanostructure positioning, promote cooperative phenomenon between adjacent nanostructures and/or substrate materials, and allow for electrical contact to individual or groups of nanostructures. With neither self-assembly nor top-down lithographic processes being able to adequately meet this challenge, advancements have often relied on a hybrid strategy that utilizes lithographically-defined features to direct the assembly of nanostructures into organized patterns. While these so-called directed assembly techniques have proven viable, much of this effort has focused on the assembly of periodic arrays of spherical or near-spherical nanostructures comprised of a single element. Work directed toward the fabrication of more complex nanostructures, while still at a nascent stage, has nevertheless demonstrated the possibility of forming arrays of nanocubes, nanorods, nanoprisms, nanoshells, nanocages, nanoframes, core-shell structures, Janus structures, and various alloys on the substrate surface. In this topical review, we describe the progress made in the directed assembly of periodic arrays of these complex metal nanostructures on planar and textured substrates. The review is divided into three broad strategies reliant on: (i) the deterministic positioning of colloidal structures, (ii) the reorganization of deposited metal films at elevated temperatures, and (iii) liquid-phase chemistry practiced directly on the substrate surface. These strategies collectively utilize a broad range of techniques including capillary assembly, microcontact printing, chemical surface modulation, templated dewetting, nanoimprint lithography, and dip-pen nanolithography and employ a wide scope of chemical processes including redox reactions, alloying, dealloying, phase separation, galvanic replacement, preferential etching, template-mediated reactions, and facet-selective capping agents. Taken together, they highlight the diverse toolset available when fabricating organized surfaces of substrate-supported nanostructures.

Broadband absorption and enhanced photothermal conversion property of octopod-like Ag@Ag2S core@shell structures with gradually varying shell thickness.

PubMed

Jiang, Qian; Zeng, Wenxia; Zhang, Canying; Meng, Zhaoguo; Wu, Jiawei; Zhu, Qunzhi; Wu, Daxiong; Zhu, Haitao

2017-12-19

Photothermal conversion materials have promising applications in many fields and therefore they have attracted tremendous attention. However, the multi-functionalization of a single nanostructure to meet the requirements of multiple photothermal applications is still a challenge. The difficulty is that most nanostructures have specific absoprtion band and are not flexible to different demands. In the current work, we reported the synthesis and multi-band photothermal conversion of Ag@Ag 2 S core@shell structures with gradually varying shell thickness. We synthesized the core@shell structures through the sulfidation of Ag nanocubes by taking the advantage of their spatially different reactivity. The resulting core@shell structures show an octopod-like mopgorlogy with a Ag 2 S bulge sitting at each corner of the Ag nanocubes. The thickness of the Ag 2 S shell gradually increases from the central surface towards the corners of the structure. The synthesized core@shell structures show a broad band absorption spectrum from 300 to 1100 nm. Enhanced photothermal conversion effect is observed under the illuminations of 635, 808, and 1064 nm lasers. The results indicate that the octopod-like Ag@Ag 2 S core@shell structures have characteristics of multi-band photothermal conversion. The current work might provide a guidance for the design and synthesis of multifunctional photothermal conversion materials.

Structural Basis for Near Unity Quantum Yield Core/Shell Nanostructures

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

McBride, James; Treadway, Joe; Pennycook, Stephen J

2006-01-01

Aberration-corrected Z-contrast scanning transmission electron microscopy of core/shell nanocrystals shows clear correlations between structure and quantum efficiency. Uniform shell coverage is obtained only for a graded CdS/ZnS shell material and is found to be critical to achieving near 100% quantum yield. The sublattice sensitivity of the images confirms that preferential growth takes place on the anion-terminated surfaces. This explains the three-dimensional "nanobullet" shape observed in the case of core/shell nanorods.

Rare-Earth-Free Permanent Magnets for Electrical Vehicle Motors and Wind Turbine Generators: Hexagonal Symmetry Based Materials Systems Mn-Bi and M-type Hexaferrite

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

Hong, Yang-Ki; Haskew, Timothy; Myryasov, Oleg

2014-06-05

The research we conducted focuses on the rare-earth (RE)-free permanent magnet by modeling, simulating, and synthesizing exchange coupled two-phase (hard/soft) RE-free core-shell nano-structured magnet. The RE-free magnets are made of magnetically hard core materials (high anisotropy materials including Mn-Bi-X and M-type hexaferrite) coated by soft shell materials (high magnetization materials including Fe-Co or Co). Therefore, our research helps understand the exchange coupling conditions of the core/shell magnets, interface exchange behavior between core and shell materials, formation mechanism of core/shell structures, stability conditions of core and shell materials, etc.

Incredible antibacterial activity of noble metal functionalized magnetic core-zeolitic shell nanostructures.

PubMed

Padervand, M; Janatrostami, S; Karanji, A Kiani; Gholami, M R

2014-02-01

Functionalized magnetic core-zeolitic shell nanostructures were prepared by hydrothermal and coprecipitation methods. The products were characterized by Vibrating Sample Magnetometer (VSM), X-ray powder diffraction (XRD), Fourier Transform Infrared (FTIR) spectra, nitrogen adsorption-desorption isotherms, and Transmission Electron Microscopy (TEM). The growth of mordenite nanoparticles on the surface of silica coated nickel ferrite nanoparticles in the presence of organic templates was also confirmed. Antibacterial activity of the prepared nanostructures was investigated by the inactivation of Escherichia coli as a gram negative bacterium. A new mechanism was proposed for inactivation of E. coli over the prepared samples. In addition, the Minimum Inhibitory Concentration (MIC) and reuse ability were studied. TEM images of the destroyed cell wall after the treatment time were performed to illustrate the inactivation mechanism. According to the experimental results, the core-shell nanostructures which were modified by organic agents and then functionalized with noble metal nanoparticles were the most active. The interaction of the noble metals with the organic components on the surface of nanostructures was studied theoretically and the obtained results were used to interpret the experimental results. © 2013. Published by Elsevier B.V. All rights reserved.

Fabrication of Fe3O4@mSiO2 Core-Shell Composite Nanoparticles for Drug Delivery Applications

NASA Astrophysics Data System (ADS)

Uribe Madrid, Sergio I.; Pal, Umapada; Kang, Young Soo; Kim, Junghoon; Kwon, Hyungjin; Kim, Jungho

2015-05-01

We report the synthesis of Fe3O4@mSiO2 nanostructures of different meso-silica (mSiO2) shell thickness, their biocompatibility and behaviors for loading and release of a model drug ibuprofen. The composite nanostructures have superparamagnetic magnetite cores of 208 nm average size and meso-silica shells of 15 to 40 nm thickness. A modified Stöber method was used to grow the meso-silica shells over the hydrothermally grown monodispersed magnetite particles. The composite nanoparticles show very promising drug holding and releasing behaviors, which depend on the thickness of meso-silica shell. The biocompatibility of the meso-silica-coated and uncoated magnetite nanoparticles was tested through cytotoxicity assay on breast cancer (MCF-7), ovarian cancer (SKOV3), normal human lung fibroblasts MRC-5, and IMR-90 cells. The high drug holding capacity and reasonable biocompatibility of the nanostructures make them ideal agents for targeted drug delivery applications in human body.

Physical property control in core/shell inorganic nanostructures for fluorescence and magnetic targeting applications

NASA Astrophysics Data System (ADS)

Roberts, Stephen K.

Nanomaterials show immense promise for the future in numerous areas of application. Properties that are unique from the bulk material and are tunable allow for innovation in material design. This thesis will focus on controlling the physical properties of core/shell nanostructures to enhance the utility of the materials. The first focus is on the impact of different solvent mixtures during the shell growth phase of SILAR based core/shell quantum dot synthesis is studied. Gaining insight into the mechanism for SILAR growth of core/shell nanoparticles allows improved synthetic yields and precursor binding, providing enhanced control to synthesis of core/shell nanoparticles. The second focus of this thesis is exploring the use of magnetic nanoparticles for magnetic drug targeting for cardiovascular conditions. Magnetic targeting for drug delivery enables increased local drug concentration, while minimizing non-specific interactions. In order to be effective for magnetic targeting, it must be shown that low magnetic strength is sufficient to capture flowing nanoparticles. By demonstrating the binding of a therapeutic agent to the surface at medicinal levels, the viability for use as a nanoparticle drug delivery system is improved.

Interface engineered ferrite@ferroelectric core-shell nanostructures: A facile approach to impart superior magneto-electric coupling

NASA Astrophysics Data System (ADS)

Abraham, Ann Rose; Raneesh, B.; Das, Dipankar; Oluwafemi, Oluwatobi Samuel; Thomas, Sabu; Kalarikkal, Nandakumar

2018-04-01

The electric field control of magnetism in multiferroics is attractive for the realization of ultra-fast and miniaturized low power device applications like nonvolatile memories. Room temperature hybrid multiferroic heterostructures with core-shell (0-0) architecture (ferrite core and ferroelectric shell) were developed via a two-step method. High-Resolution Transmission Electron Microscopy (HRTEM) images confirm the core-shell structure. The temperature dependant magnetization measurements and Mossbauer spectra reveal superparamagnetic nature of the core-shell sample. The ferroelectric hysteresis loops reveal leaky nature of the samples. The results indicate the promising applications of the samples for magneto-electric memories and spintronics.

Magnetic carbon nanostructures: microwave energy-assisted pyrolysis vs. conventional pyrolysis.

PubMed

Zhu, Jiahua; Pallavkar, Sameer; Chen, Minjiao; Yerra, Narendranath; Luo, Zhiping; Colorado, Henry A; Lin, Hongfei; Haldolaarachchige, Neel; Khasanov, Airat; Ho, Thomas C; Young, David P; Wei, Suying; Guo, Zhanhu

2013-01-11

Magnetic carbon nanostructures from microwave assisted- and conventional-pyrolysis processes are compared. Unlike graphitized carbon shells from conventional heating, different carbon shell morphologies including nanotubes, nanoflakes and amorphous carbon were observed. Crystalline iron and cementite were observed in the magnetic core, different from a single cementite phase from the conventional process.

Thermosensitive polymer stabilized core-shell AuNR@Ag nanostructures as "smart" recyclable catalyst

NASA Astrophysics Data System (ADS)

Li, Dongxiang; Liu, Na; Gao, Yuanyuan; Lin, Weihong; Li, Chunfang

2017-11-01

Core-shell AuNR@Ag nanostructures were synthesized and surface-grafted with thermosensitive poly( N-isopropylacrylamide) to enhance stability and endow stimuli-responsive property. The AuNR cores showed average dimensions of 8-nm diameter and 33-nm length, while the anisotropic silver shells displayed 1-2 nm thin side and maximal 8 nm fat side. The obtained polymer-stabilized AuNR@Ag nanostructures as catalysts showed normal Arrhenius change of apparent rate constant, k app, in catalyzed reaction between 20 and 30 °C, but displayed a decrease of k app with respect to the temperature increasing between 32.5-40 °C, showing self-inhibition of the observed catalytic activity. Such "smart" self-inhibition of catalytic activity at enhanced temperature can be attributed to the thermosensitive response of the grafted polymer molecules and should be significant to control the reaction rate and avoid superheat for exothermic reactions. Such polymer-stabilized nanocatalyst also could be recovered and reused in the catalytic system. [Figure not available: see fulltext.

Self-monitored photothermal nanoparticles based on core-shell engineering

NASA Astrophysics Data System (ADS)

Ximendes, Erving C.; Rocha, Uéslen; Jacinto, Carlos; Kumar, Kagola Upendra; Bravo, David; López, Fernando J.; Rodríguez, Emma Martín; García-Solé, José; Jaque, Daniel

2016-01-01

The continuous development of nanotechnology has resulted in the actual possibility of the design and synthesis of nanostructured materials with pre-tailored functionabilities. Nanostructures capable of simultaneous heating and local thermal sensing are in strong demand as they would constitute a revolutionary solution to several challenging problems in bio-medicine, including the achievement of real time control during photothermal therapies. Several approaches have been demonstrated to achieve simultaneous heating and thermal sensing at the nanoscale. Some of them lack of sufficient thermal sensitivity and others require complicated synthesis procedures for heterostructure fabrication. In this study, we demonstrate how single core/shell dielectric nanoparticles with a highly Nd3+ ion doped shell and an Yb3+,Er3+ codoped core are capable of simultaneous thermal sensing and heating under an 808 nm single beam excitation. The spatial separation between the heating shell and sensing core provides remarkable values of the heating efficiency and thermal sensitivity, enabling their application in single beam-controlled heating experiments in both aqueous and tissue environments.

Glycerol capped PbS/CdS core/shell nanoparticles at different molar ratio and its application in biosensors: An optical properties study

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

Das, D., E-mail: ddasphy014@gmail.com; Hussain, A. M. P.

2016-05-06

Glycerol capped PbS/CdS core/shell type nanoparticles fabricated with two different molar ratios are characterized for study of structural and optical properties. The X-ray diffraction (XRD) pattern exhibits cubic phased polycrystalline nanocrystals. The calculated grain sizes from Williamson-Hall plot were found to be around 6 nm with increased strain. HRTEM investigation confirms the formation of core/shell nanostructures and the sizes of the particles were found to be around 7 nm which is in good agreement with the results of the W-H plot. An increase of band gap with the decrease in precursor concentration is confirmed from the blue shift in the absorption spectramore » and also from Tauc plot. A clear blue shifted intense emission is observed in the photoluminescence spectra with decrease in particle size. Intense luminescence from the core/shell nanostructure may be applied in bio labelling and biosensors.« less

Self-assembly of star micelle into vesicle in solvents of variable quality: the star micelle retains its core-shell nanostructure in the vesicle.

PubMed

Liu, Nijuan; He, Qun; Bu, Weifeng

2015-03-03

Intra- and intermolecular interactions of star polymers in dilute solutions are of fundamental importance for both theoretical interest and hierarchical self-assembly into functional nanostructures. Here, star micelles with a polystyrene corona and a small ionic core bearing platinum(II) complexes have been regarded as a model of star polymers to mimic their intra- and interstar interactions and self-assembled behaviors in solvents of weakening quality. In the chloroform/methanol mixture solvents, the star micelles can self-assemble to form vesicles, in which the star micelles shrink significantly and are homogeneously distributed on the vesicle surface. Unlike the morphological evolution of conventional amphiphiles from micellar to vesicular, during which the amphiphilic molecules are commonly reorganized, the star micelles still retain their core-shell nanostructures in the vesicles and the coronal chains of the star micelle between the ionic cores are fully interpenetrated.

Short-Range Correlated Magnetic Core-Shell CrO₂/Cr₂O₃ Nanorods: Experimental Observations and Theoretical Considerations.

PubMed

Gandhi, Ashish C; Li, Tai-Yue; Chan, Ting Shan; Wu, Sheng Yun

2018-05-09

With the evolution of synthesis and the critical characterization of core-shell nanostructures, short-range magnetic correlation is of prime interest in employing their properties to develop novel devices and widespread applications. In this regard, a novel approach of the magnetic core-shell saturated magnetization (CSSM) cylinder model solely based on the contribution of saturated magnetization in one-dimensional CrO₂/Cr₂O₃ core-shell nanorods (NRs) has been developed and applied for the determination of core-diameter and shell-thickness. The nanosized effect leads to a short-range magnetic correlation of ferromagnetic core-CrO₂ extracted from CSSM, which can be explained using finite size scaling method. The outcome of this study is important in terms of utilizing magnetic properties for the critical characterization of core-shell nanomagnetic materials.

Non-aqueous synthesis of water-dispersible Fe3O4-Ca3(PO4)2 core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Liu, HongLing; Wu, JunHua; Min, Ji Hyun; Hou, Peng; Song, Ah-Young; Kim, Young Keun

2011-02-01

The Fe3O4-Ca3(PO4)2 core-shell nanoparticles were prepared by one-pot non-aqueous nanoemulsion with the assistance of a biocompatible triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO), integrating the magnetic properties of Fe3O4 and the bioactive functions of Ca3(PO4)2 into single entities. The Fe3O4 nanoparticles were pre-formed first by thermal reduction of Fe(acac)3 and then the Ca3(PO4)2 layer was coated by simultaneous deposition of Ca2 + and PO43 - . The characterization shows that the combination of the two materials into a core-shell nanostructure retains the magnetic properties and the Ca3(PO4)2 shell forms an hcp phase (a = 7.490 Å, c = 9.534 Å) on the Fe3O4 surface. The magnetic hysteresis curves of the nanoparticles were further elucidated by the Langevin equation, giving an estimation of the effective magnetic dimension of the nanoparticles and reflecting the enhanced susceptibility response as a result of the surface covering. Fourier transform infrared (FTIR) analysis provides the characteristic vibrations of Ca3(PO4)2 and the presence of the polymer surfactant on the nanoparticle surface. Moreover, the nanoparticles could be directly transferred to water and the aqueous dispersion-collection process of the nanoparticles was demonstrated for application readiness of such core-shell nanostructures in an aqueous medium. Thus, the construction of Fe3O4 and Ca3(PO4)2 in the core-shell nanostructure has conspicuously led to enhanced performance and multi-functionalities, offering various possible applications of the nanoparticles.

Controlled Synthesis and Utilization of Metal and Oxide Hybrid Nanoparticles

NASA Astrophysics Data System (ADS)

Crane, Cameron

This dissertation reports the development of synthetic methods concerning rationally-designed, hybrid, and multifunctional nanomaterials. These methods are based on a wet chemical, solution phase approach that utilizes the knowledge of synthetic organic and inorganic chemistry to generate building blocks in solution for the growth of nanocrystals and hybrid nanostructures. This work builds on the prior knowledge of shape-controlled synthesis of noble metal nanocrystals and expands into the challenging realm of the more reactive first row transition metals. Specifically, a microemulsion sol-gel method was developed to synthesize Au-SiO2 dimers as precursors for the synthesis of segmented heterostructures of noble metals that can be used for catalysis. This microemulsion sol-gel method was modified to synthesize an aqueous suspension of oxidation-resistant Cu-SiO2 core-shell nanoparticles that can be used for sensing and catalysis. A thermal decomposition approach was developed, wherein zero-valence metal precursor complexes in the presence of seed nanoparticles produced metal-metal oxide core-shell structures with well-controlled shell thickness. This method was demonstrated on AuCu 3-Fe3O4, AuCu3-NiO, and AuCu3 -MnO core-shell systems. Switching the core from AuCu3 alloy to pure Cu, this method could extend to Cu-Fe3O4 and Cu-MnO systems. Further etching the Cu core in these core-shell structures led to the formation of the hollow metal oxides which provides a versatile route to hollow nanostructures of metal oxides. This work develops the synthetic library of tools for the production of hybrid nanostructures with multiple functionalities.

Direct Observation of the Growth of Au-Pd Core-Shell Nanoparticles Using in situ Low-Dose Liquid Cell STEM imaging

DOE PAGES

Bhattarai, Nabraj; Prozorov, Tanya

2016-07-25

Bimetallic core-shell nanoparticles are widely used as catalysts in several industrial reactions, with core-shell structures permitting facile surface modification and allowing increased stability and durability, and cost-effectiveness of the catalysts. We report, for the first time, on observing the early stages of the formation of Au-Pd core-shell bimetallic nanoparticles via the seed-mediated growth in the presence of reducing agent, while employing the low-dose scanning transmission electron microscopy imaging with the fluid cell in situ. Use of the continuous flow in situ fluid cell platform allows for delivery of reagent solutions and generation of near-native reaction environment in the reaction chamber,more » and permits direct visualization of the early stages of formation of Au-Pd core-shell structures at low dose rate (0.1 e -/(Å 2s)) in the presence of ascorbic acid. No core-shell structures were detected in the absence of reducing agent at the electron dose of 32.6 e -/Å 2. While the core-shell structures formed in situ under the low-dose imaging closely resemble those obtained in solution synthesis, the reaction kinetics in the fluid cell is affected by the radiolysis of liquid reagents induced by electron beam, altering the rate-determining reaction steps. The enhanced reduction of Pd ions leads to initial rapid growth of the nascent Pd shell along the <111> direction at the Au interface, followed by a slower rearrangement of the outer Pd layer. The latter becomes the rate-determining step in the in situ reaction and appears to follow the oriented attachment-like movement to yield a remodeled, compact and stable Au-Pd core-shell nanostructure. Our findings highlight the differences between the two reaction pathways and aid in understanding the mechanism of formation of the core-shell nanostructure in situ.« less

Core-shell microspheres with porous nanostructured shells for liquid chromatography.

PubMed

Ahmed, Adham; Skinley, Kevin; Herodotou, Stephanie; Zhang, Haifei

2018-01-01

The development of new stationary phases has been the key aspect for fast and efficient high-performance liquid chromatography separation with relatively low backpressure. Core-shell particles, with a solid core and porous shell, have been extensively investigated and commercially manufactured in the last decade. The excellent performance of core-shell particles columns has been recorded for a wide range of analytes, covering small and large molecules, neutral and ionic (acidic and basic), biomolecules and metabolites. In this review, we first introduce the advance and advantages of core-shell particles (or more widely known as superficially porous particles) against non-porous particles and fully porous particles. This is followed by the detailed description of various methods used to fabricate core-shell particles. We then discuss the applications of common silica core-shell particles (mostly commercially manufactured), spheres-on-sphere particles and core-shell particles with a non-silica shell. This review concludes with a summary and perspective on the development of stationary phase materials for high-performance liquid chromatography applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-Controlled Synthesis of Magnetic Iron Oxide@SiO₂-Au@C Particles with Core-Shell Nanostructures.

PubMed

Li, Mo; Li, Xiangcun; Qi, Xinhong; Luo, Fan; He, Gaohong

2015-05-12

The preparation of nonspherical magnetic core-shell nanostructures with uniform sizes still remains a challenge. In this study, magnetic iron oxide@SiO2-Au@C particles with different shapes, such as pseduocube, ellipsoid, and peanut, were synthesized using hematite as templates and precursors of magnetic iron oxide. The as-obtained magnetic particles demonstrated uniform sizes, shapes, and well-designed core-shell nanostructures. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) analysis showed that the Au nanoparticles (AuNPs) of ∼6 nm were uniformly distributed between the silica and carbon layers. The embedding of the metal nanocrystals into the two different layers prevented the aggregation and reduced the loss of the metal nanocrystals during recycling. Catalytic performance of the peanut-like particles kept almost unchanged without a noticeable decrease in the reduction of 4-nitrophenol (4-NP) in 8 min even after 7 cycles, indicating excellent reusability of the particles. Moreover, the catalyst could be readily recycled magnetically after each reduction by an external magnetic field.

Laser ablation of a silicon target in chloroform: formation of multilayer graphite nanostructures

NASA Astrophysics Data System (ADS)

Abderrafi, Kamal; García-Calzada, Raúl; Sanchez-Royo, Juan F.; Chirvony, Vladimir S.; Agouram, Saïd; Abargues, Rafael; Ibáñez, Rafael; Martínez-Pastor, Juan P.

2013-04-01

With the use of high-resolution transmission electron microscopy, selected area electron diffraction and x-ray photoelectron spectroscopy methods of analysis we show that the laser ablation of a Si target in chloroform (CHCl3) by nanosecond UV pulses (40 ns, 355 nm) results in the formation of about 50-80 nm core-shell nanoparticles with a polycrystalline core composed of small (5-10 nm) Si and SiC mono-crystallites, the core being coated by several layers of carbon with the structure of graphite (the shell). In addition, free carbon multilayer nanostructures (carbon nano-onions) are also found in the suspension. On the basis of a comparison with similar laser ablation experiments implemented in carbon tetrachloride (CCl4), where only bare (uncoated) Si nanoparticles are produced, we suggest that a chemical (solvent decomposition giving rise to highly reactive CH-containing radicals) rather than a physical (solvent atomization followed by carbon nanostructure formation) mechanism is responsible for the formation of graphitic shells. The silicon carbonization process found for the case of laser ablation in chloroform may be promising for silicon surface protection and functionalization.

Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission.

PubMed

Li, Gong Ping; Chen, Rui; Guo, Dong Lai; Wong, Lai Mun; Wang, Shi Jie; Sun, Han Dong; Wu, Tom

2011-08-01

Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO(2) and In(2)O(3) are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications. This journal is © The Royal Society of Chemistry 2011

Tuning exchange bias in Fe/γ-Fe{sub 2}O{sub 3} core-shell nanoparticles: Impacts of interface and surface spins

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

Khurshid, Hafsa, E-mail: hkhurshi@usf.edu, E-mail: phanm@usf.edu, E-mail: sharihar@usf.edu; Phan, Manh-Huong, E-mail: hkhurshi@usf.edu, E-mail: phanm@usf.edu, E-mail: sharihar@usf.edu; Mukherjee, Pritish

A comparative study has been performed of the exchange bias (EB) effect in Fe/γ-Fe{sub 2}O{sub 3} core-shell nanoparticles with the same thickness of the γ-Fe{sub 2}O{sub 3} shell (∼2 nm) and the diameter of the Fe core varying from 4 nm to 11 nm. Transmission electron microscopy (TEM) and high-resolution TEM confirmed the high quality of the core-shell nanostructures. A systematic analysis of magnetization versus magnetic field measurements under zero-field-cooled and field-cooled regimes using the Meiklejohn-Bean model and deconvoluting superparamagnetic and paramagnetic contribution to the total magnetic moment Langevin function shows that there exists a critical particle size (∼10 nm), above which the spinsmore » at the interface between Fe and γ-Fe{sub 2}O{sub 3} contribute primarily to the EB, but below which the surface spin effect is dominant. Our finding yields deeper insight into the collective contributions of interface and surface spins to the EB in core-shell nanoparticle systems, knowledge of which is the key to manipulating EB in magnetic nanostructures for spintronics applications.« less

Controlling energy flow in multimetallic nanostructures for plasmonic catalysis

NASA Astrophysics Data System (ADS)

Aslam, Umar; Chavez, Steven; Linic, Suljo

2017-10-01

It has been shown that photoexcitation of plasmonic metal nanoparticles (Ag, Au and Cu) can induce direct photochemical reactions. However, the widespread application of this technology in catalysis has been limited by the relatively poor chemical reactivity of noble metal surfaces. Despite efforts to combine plasmonic and catalytic metals, the physical mechanisms that govern energy transfer from plasmonic metals to catalytic metals remain unclear. Here we show that hybrid core-shell nanostructures in which a core plasmonic metal harvests visible-light photons can selectively channel that energy into catalytically active centres on the nanostructure shell. To accomplish this, we developed a synthetic protocol to deposit a few monolayers of Pt onto Ag nanocubes. This model system allows us to conclusively separate the optical and catalytic functions of the hybrid nanomaterial and determine that the flow of energy is strongly biased towards the excitation of energetic charge carriers in the Pt shell. We demonstrate the utility of these nanostructures for photocatalytic chemical reactions in the preferential oxidation of CO in excess H2. Our data demonstrate that the reaction occurs exclusively on the Pt surface.

Enhanced linear photonic nanojet generated by core-shell optical microfibers

NASA Astrophysics Data System (ADS)

Liu, Cheng-Yang; Yen, Tzu-Ping; Chen, Chien-Wen

2017-05-01

The generation of linear photonic nanojet using core-shell optical microfiber is demonstrated numerically and experimentally in the visible light region. The power flow patterns for the core-shell optical microfiber are calculated by using the finite-difference time-domain method. The focusing properties of linear photonic nanojet are evaluated in terms of length and width along propagation and transversal directions. In experiment, the silica optical fiber is etched chemically down to 6 μm diameter and coated with metallic thin film by using glancing angle deposition. We show that the linear photonic nanojet is enhanced clearly by metallic shell due to surface plasmon polaritons. The large-area superresolution imaging can be performed by using a core-shell optical microfiber in the far-field system. The potential applications of this core-shell optical microfiber include micro-fluidics and nano-structure measurements.

General route to multifunctional uniform yolk/mesoporous silica shell nanocapsules: a platform for simultaneous cancer-targeted imaging and magnetically guided drug delivery.

PubMed

Zhang, Lingyu; Wang, Tingting; Yang, Lei; Liu, Cong; Wang, Chungang; Liu, Haiyan; Wang, Y Andrew; Su, Zhongmin

2012-09-24

Hollow mesoporous SiO(2) (mSiO(2)) nanostructures with movable nanoparticles (NPs) as cores, so-called yolk-shell nanocapsules (NCs), have attracted great research interest. However, a highly efficient, simple and general way to produce yolk-mSiO(2) shell NCs with tunable functional cores and shell compositions is still a great challenge. A facile, general and reproducible strategy has been developed for fabricating discrete, monodisperse and highly uniform yolk-shell NCs under mild conditions, composed of mSiO(2) shells and diverse functional NP cores with different compositions and shapes. These NPs can be Fe(3)O(4) NPs, gold nanorods (GNRs), and rare-earth upconversion NRs, endowing the yolk-mSiO(2) shell NCs with magnetic, plasmonic, and upconversion fluorescent properties. In addition, multifunctional yolk-shell NCs with tunable interior hollow spaces and mSiO(2) shell thickness can be precisely controlled. More importantly, fluorescent-magnetic-biotargeting multifunctional polyethyleneimine (PEI)-modified fluorescent Fe(3)O(4)@mSiO(2) yolk-shell nanobioprobes as an example for simultaneous targeted fluorescence imaging and magnetically guided drug delivery to liver cancer cells is also demonstrated. This synthetic approach can be easily extended to the fabrication of multifunctional yolk@mSiO(2) shell nanostructures that encapsulate various functional movable NP cores, which construct a potential platform for the simultaneous targeted delivery of drug/gene/DNA/siRNA and bio-imaging. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and Characterization of WS2@SiO2 and WS2@PANI Core-Shell Nanocomposites

PubMed Central

Sade, Hagit

2018-01-01

Two tungsten disulfide (WS2)-based core-shell nanocomposites were fabricated using readily available reagents and simple procedures. The surface was pre-treated with a surfactant couple in a layer-by-layer approach, enabling good dispersion of the WS2 nanostructures in aqueous media and providing a template for the polymerization of a silica (SiO2) shell. After a Stöber-like reaction, a conformal silica coating was achieved. Inspired by the resulting nanocomposite, a second one was prepared by reacting the surfactant-modified WS2 nanostructures with aniline and an oxidizing agent in an aqueous medium. Here too, a conformal coating of polyaniline (PANI) was obtained, giving a WS2@PANI nanocomposite. Both nanocomposites were analyzed by electron microscopy, energy dispersive X-ray spectroscopy (EDS) and FTIR, verifying the core-shell structure and the character of shells. The silica shell was amorphous and mesoporous and the surface area of the composite increases with shell thickness. Polyaniline shells slightly differ in their morphologies dependent on the acid used in the polymerization process and are amorphous like the silica shell. Electron paramagnetic resonance (EPR) spectroscopy of the WS2@PANI nanocomposite showed variation between bulk PANI and the PANI shell. These two nanocomposites have great potential to expand the use of transition metals dichalcogenides (TMDCs) for new applications in different fields. PMID:29534426

Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications

PubMed Central

Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

2016-01-01

Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m−3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells. PMID:27734945

Nano-structured silica coated mesoporous carbon micro-granules for potential application in water filtration

NASA Astrophysics Data System (ADS)

Das, Avik; Sen, D.; Mazumder, S.; Ghosh, A. K.

2017-05-01

A novel nano-composite spherical micro-granule has been synthesized using a facile technique of solvent evaporation induced assembly of nanoparticles for potential application in water filtration. The spherical micro-granule is comprised of nano-structured shell of hydrophilic silica encapsulating a hydrophobic mesoporous carbon at the core. Hierarchical structure of such core-shell micro-granules has been rigorously characterized using small-angle neutron and X-ray scattering techniques and complemented with scanning electron microscopy. The hydrophilic silica envelope around the carbon core helps in incorporation of such granules into the hydrophilic polymeric ultra-filtration membrane. The interstitial micro-pores present in the silica shell can serve as water transport channels and the mesoporus carbon core enhances the separation performance due its well adsorption characteristics. It has been found that the incorporation of such granules inside the ultra-filtration membrane indeed enhances the water permeability as well as the separation performance in a significant way.

Synthesis of silver-titanium dioxide nanocomposites for antimicrobial applications

NASA Astrophysics Data System (ADS)

Yang, X. H.; Fu, H. T.; Wang, X. C.; Yang, J. L.; Jiang, X. C.; Yu, A. B.

2014-08-01

Silver-titanium dioxide (Ag-TiO2) nanostructures have attracted increasing attention because of unique functional properties and potential applications in many areas such as photocatalysis, antibacterial, and self-cleaning coatings. In this study, Ag@TiO2 core-shell nanostructures and Ag-decorated TiO2 particles (TiO2@Ag) (the size of these two nanoparticles is ranging from 200-300 nm) have been synthesized by a developed facile but efficient method. These two types of hybrid nanostructures, characterized by various advanced techniques (TEM, XRD, BET and others), exhibit unique functional properties particularly in antibacterial toward Gram negative Escherichia coli, as a case study. Specifically: (i) the TiO2@Ag nanoparticles are superior in bacterial growth inhibition in standard culture conditions (37 °C incubator) to the Ag@TiO2 core-shell ones, in which silver may dominate the antibacterial performance; (ii) while after UV irradiation treatment, the Ag@TiO2 core-shell nanoparticles exhibit better performance in killing grown bacteria than the TiO2@Ag ones, probably because of the Ag cores facilitating charge separation for TiO2, and thus produce more hydroxyl radicals on the surface of the TiO2 particles; and (iii) without UV irradiation, both TiO2@Ag and Ag@TiO2 nanostructures show poor capabilities in killing mature bacteria. These findings would be useful for designing hybrid metal oxide nanocomposites with desirable functionalities in bioapplications in terms of sterilization, deodorization, and water purification.

Distance-Dependent Plasmon-Enhanced Singlet Oxygen Production and Emission for Bacterial Inactivation.

PubMed

Planas, Oriol; Macia, Nicolas; Agut, Montserrat; Nonell, Santi; Heyne, Belinda

2016-03-02

Herein, we synthesized a series of 10 core-shell silver-silica nanoparticles with a photosensitizer, Rose Bengal, tethered to their surface. Each nanoparticle possesses an identical silver core of about 67 nm, but presents a different silica shell thickness ranging from 5 to 100 nm. These hybrid plasmonic nanoparticles thus afford a plasmonic nanostructure platform with a source of singlet oxygen ((1)O2) at a well-defined distance from the metallic core. Via time-resolved and steady state spectroscopic techniques, we demonstrate the silver core exerts a dual role of enhancing both the production of (1)O2, through enhanced absorption of light, and its radiative decay, which in turn boosts (1)O2 phosphorescence emission to a greater extent. Furthermore, we show both the production and emission of (1)O2 in vitro to be dependent on proximity to the plasmonic nanostructure. Our results clearly exhibit three distinct regimes as the plasmonic nanostructure moves apart from the (1)O2 source, with a greater enhancement for silica shell thicknesses ranging between 10 and 20 nm. Moreover, these hybrid plasmonic nanoparticles can be delivered to both Gram-positive and Gram-negative bacteria boosting both photoantibacterial activity and detection limit of (1)O2 in cells.

Transient Micromotors That Disappear When No Longer Needed.

PubMed

Chen, Chuanrui; Karshalev, Emil; Li, Jinxing; Soto, Fernando; Castillo, Roxanne; Campos, Isaac; Mou, Fangzhi; Guan, Jianguo; Wang, Joseph

2016-11-22

Transient self-destroyed micromotors that autonomously disappear in biological media at controlled rates upon completing their task, without leaving a toxic residue, are presented. The propulsion and degradation characteristics of the self-destroyed Mg/ZnO, Mg/Si, and Zn/Fe Janus micromotors and single-component Zn micromotors are described. The degradation of the Janus micromotors relies on the different corrosion rates of their core-shell components. Inductively coupled plasma optical emission spectrometry measurements are used to probe the time-dependent degradation of the different constituents of the micromotors. The toxicity of the transient micromotors is discussed toward their potential use in biomedical applications. This concept of transient micromotors offers considerable potential for diverse practical applications in the near future.

Janus dendrimersomes coassembled from fluorinated, hydrogenated, and hybrid Janus dendrimers as models for cell fusion and fission.

PubMed

Xiao, Qi; Sherman, Samuel E; Wilner, Samantha E; Zhou, Xuhao; Dazen, Cody; Baumgart, Tobias; Reed, Ellen H; Hammer, Daniel A; Shinoda, Wataru; Klein, Michael L; Percec, Virgil

2017-08-22

A three-component system of Janus dendrimers (JDs) including hydrogenated, fluorinated, and hybrid hydrogenated-fluorinated JDs are reported to coassemble by film hydration at specific ratios into an unprecedented class of supramolecular Janus particles (JPs) denoted Janus dendrimersomes (JDSs). They consist of a dumbbell-shaped structure composed of an onion-like hydrogenated vesicle and an onion-like fluorinated vesicle tethered together. The synthesis of dye-tagged analogs of each JD component enabled characterization of JDS architectures with confocal fluorescence microscopy. Additionally, a simple injection method was used to prepare submicron JDSs, which were imaged with cryogenic transmission electron microscopy (cryo-TEM). As reported previously, different ratios of the same three-component system yielded a variety of structures including homogenous onion-like vesicles, core-shell structures, and completely self-sorted hydrogenated and fluorinated vesicles. Taken together with the JDSs reported herein, a self-sorting pathway is revealed as a function of the relative concentration of the hybrid JD, which may serve to stabilize the interface between hydrogenated and fluorinated bilayers. The fission-like pathway suggests the possibility of fusion and fission processes in biological systems that do not require the assistance of proteins but instead may result from alterations in the ratios of membrane composition.

Chemical insights into the roles of nanowire cores on the growth and supercapacitor performances of Ni-Co-O/Ni(OH)2 core/shell electrodes

PubMed Central

Yin, Xuesong; Tang, Chunhua; Zhang, Liuyang; Yu, Zhi Gen; Gong, Hao

2016-01-01

Nanostructured core/shell electrodes have been experimentally demonstrated promising for high-performance electrochemical energy storage devices. However, chemical insights into the significant roles of nanowire cores on the growth of shells and their supercapacitor behaviors still remain as a research shortfall. In this work, by substituting 1/3 cobalt in the Co3O4 nanowire core with nickel, a 61% enhancement of the specific mass-loading of the Ni(OH)2 shell, a tremendous 93% increase of the volumetric capacitance and a superior cyclability were achieved in a novel NiCo2O4/Ni(OH)2 core/shell electrode in contrast to a Co3O4/Ni(OH)2 one. A comparative study suggested that not only the growth of Ni(OH)2 shells but also the contribution of cores were attributed to the overall performances. Importantly, their chemical origins were revealed through a theoretical simulation of the core/shell interfacial energy changes. Besides, asymmetric supercapacitor devices and applications were also explored. The scientific clues and practical potentials obtained in this work are helpful for the design and analysis of alternative core/shell electrode materials. PMID:26857606

Chemical insights into the roles of nanowire cores on the growth and supercapacitor performances of Ni-Co-O/Ni(OH)₂ core/shell electrodes.

PubMed

Yin, Xuesong; Tang, Chunhua; Zhang, Liuyang; Yu, Zhi Gen; Gong, Hao

2016-02-09

Nanostructured core/shell electrodes have been experimentally demonstrated promising for high-performance electrochemical energy storage devices. However, chemical insights into the significant roles of nanowire cores on the growth of shells and their supercapacitor behaviors still remain as a research shortfall. In this work, by substituting 1/3 cobalt in the Co3O4 nanowire core with nickel, a 61% enhancement of the specific mass-loading of the Ni(OH)2 shell, a tremendous 93% increase of the volumetric capacitance and a superior cyclability were achieved in a novel NiCo2O4/Ni(OH)2 core/shell electrode in contrast to a Co3O4/Ni(OH)2 one. A comparative study suggested that not only the growth of Ni(OH)2 shells but also the contribution of cores were attributed to the overall performances. Importantly, their chemical origins were revealed through a theoretical simulation of the core/shell interfacial energy changes. Besides, asymmetric supercapacitor devices and applications were also explored. The scientific clues and practical potentials obtained in this work are helpful for the design and analysis of alternative core/shell electrode materials.

Ballistic anisotropic magnetoresistance in core-shell nanowires and rolled-up nanotubes

NASA Astrophysics Data System (ADS)

Chang, Ching-Hao; Ortix, Carmine

2017-01-01

In ferromagnetic nanostructures, the ballistic anisotropic magnetoresistance (BAMR) is a change in the ballistic conductance with the direction of magnetization due to spin-orbit interaction. Very recently, a directional dependent ballistic conductance has been predicted to occur in a number of newly synthesized nonmagnetic semiconducting nanostructures subject to externally applied magnetic fields, without necessitating spin-orbit coupling. In this paper, we review past works on the prediction of this BAMR effect in core-shell nanowires (CSN) and rolled-up nanotubes (RUNTs). This is complemented by new results, we establish for the transport properties of tubular nanosystems subject to external magnetic fields.

An electrochemical aptasensor for thrombin using synergetic catalysis of enzyme and porous Au@Pd core-shell nanostructures for signal amplification.

PubMed

Xu, Wenju; Yi, Huayu; Yuan, Yali; Jing, Pei; Chai, Yaqin; Yuan, Ruo; Wilson, George S

2015-02-15

In this work, a sensitive electrochemical aptasensor for thrombin (TB) based on synergetic catalysis of enzyme and porous Au@Pd core-shell nanostructure has been constructed. With the advantages of large surface area and outstanding catalytic performance, porous Au@Pd core-shell nanostructures were firstly employed as the nanocarrier for the immobilization of electroactive toluidine blue (Tb), hemin/G-quadruplex formed by intercalating hemin into the TB aptamer (TBA) and glucose oxidase (GOx). As a certain amount of glucose was added into the detection cell, GOx rapidly catalyzed the oxidation of glucose, coupling with the local generation of H2O2 in the presence of dissolved O2. Then, porous Au@Pd nanoparticles and hemin/G-quadruplex as the peroxidase mimics efficiently catalyzed the reduction of H2O2, amplifying the electrochemical signal and improving the sensitivity. Finally, a detection limit of 0.037pM for TB was achieved. The excellent performance of the aptasensor indicated its promising prospect as a valuable tool in simple and cost-effective TB detection in clinical application. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of ZnO core electrodeposition conditions on electrochemical and photocatalytic properties of polypyrrole-graphene oxide shelled nanoarrays

NASA Astrophysics Data System (ADS)

Pruna, A.; Shao, Q.; Kamruzzaman, M.; Li, Y. Y.; Zapien, J. A.; Pullini, D.; Busquets Mataix, D.; Ruotolo, A.

2017-01-01

Novel hybrid core-shell nanoarchitectures were fabricated by a simple two-step electrochemical approach: first ZnO nanorod core was electrodeposited from Zn(NO3)2 solution; further, the core nanoarray was coated with a shell based on polypyrrole hybridized with graphene oxide by electropolymerization. The properties of the core/shell nanoarchitectures were studied as a function of the core properties induced by electrodeposition parameters. The ZnO nanostructures showed improved crystallinity and c-axis preferred orientation with increasing cathodic deposition potential while the increased deposition duration resulted in a morphology transition from nanorod to pyramidal shape. The electrochemical activity of the core/shell arrays was found to increase with the deposition potential of ZnO core but decreased when morphology changed from nanorod to pyramid shape. The photocatalytic results showed improved activity for the core/hybrid shell nanoarrays with respect to ZnO and ZnO/PPy ones. The degradation rate for methylene blue decreased with prolonged deposition duration of the core. The obtained results highlight the importance of electrochemical tuning of ZnO-based core/shell nanoarrays for improved performance in electrochemical and photocatalytic applications.

Hierarchically assembled theranostic nanostructures for siRNA delivery and imaging applications.

PubMed

Shrestha, Ritu; Elsabahy, Mahmoud; Luehmann, Hannah; Samarajeewa, Sandani; Florez-Malaver, Stephanie; Lee, Nam S; Welch, Michael J; Liu, Yongjian; Wooley, Karen L

2012-10-24

Dual functional hierarchically assembled nanostructures, with two unique functions of carrying therapeutic cargo electrostatically and maintaining radiolabeled imaging agents covalently within separate component building blocks, have been developed via the supramolecular assembly of several spherical cationic shell cross-linked nanoparticles clustered around a central anionic shell cross-linked cylinder. The shells of the cationic nanoparticles and the hydrophobic core domain of the anionic central cylindrical nanostructure of the assemblies were utilized to complex negatively charged nucleic acids (siRNA) and to undergo radiolabeling, respectively, for potential theranostic applications. The assemblies exhibited exceptional cell transfection and radiolabeling efficiencies, providing an overall advantage over the individual components, which could each facilitate only one or the other of the functions.

Nano-engineering of three-dimensional core/shell nanotube arrays for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Grote, Fabian; Wen, Liaoyong; Lei, Yong

2014-06-01

Large-scale arrays of core/shell nanostructures are highly desirable to enhance the performance of supercapacitors. Here we demonstrate an innovative template-based fabrication technique with high structural controllability, which is capable of synthesizing well-ordered three-dimensional arrays of SnO2/MnO2 core/shell nanotubes for electrochemical energy storage in supercapacitor applications. The SnO2 core is fabricated by atomic layer deposition and provides a highly electrical conductive matrix. Subsequently a thin MnO2 shell is coated by electrochemical deposition onto the SnO2 core, which guarantees a short ion diffusion length within the shell. The core/shell structure shows an excellent electrochemical performance with a high specific capacitance of 910 F g-1 at 1 A g-1 and a good rate capability of remaining 217 F g-1 at 50 A g-1. These results shall pave the way to realize aqueous based asymmetric supercapacitors with high specific power and high specific energy.

Study of the effect of varying core diameter, shell thickness and strain velocity on the tensile properties of single crystals of Cu-Ag core-shell nanowire using molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sarkar, Jit; Das, D. K.

2018-01-01

Core-shell type nanostructures show exceptional properties due to their unique structure having a central solid core of one type and an outer thin shell of another type which draw immense attention among researchers. In this study, molecular dynamics simulations are carried out on single crystals of copper-silver core-shell nanowires having wire diameter ranging from 9 to 30 nm with varying core diameter, shell thickness, and strain velocity. The tensile properties like yield strength, ultimate tensile strength, and Young's modulus are studied and correlated by varying one parameter at a time and keeping the other two parameters constant. The results obtained for a fixed wire size and different strain velocities were extrapolated to calculate the tensile properties like yield strength and Young's modulus at standard strain rate of 1 mm/min. The results show ultra-high tensile properties of copper-silver core-shell nanowires, several times than that of bulk copper and silver. These copper-silver core-shell nanowires can be used as a reinforcing agent in bulk metal matrix for developing ultra-high strength nanocomposites.

Core–shell nanoparticles: synthesis and applications in catalysis and electrocatalysis

EPA Science Inventory

Core–shell nanoparticles (CSNs) are a class of nanostructured materials that have recently received increased attention owing to their interesting properties and broad range of applications in catalysis, biology, materials chemistry and sensors. By rationally tuning the cores as ...

Polyethylenimine-immobilized core-shell nanoparticles: synthesis, characterization, and biocompatibility test.

PubMed

Ratanajanchai, Montri; Soodvilai, Sunhapas; Pimpha, Nuttaporn; Sunintaboon, Panya

2014-01-01

Herein, we prepared PEI-immobilized core-shell particles possessing various types of polymer cores via a visible light-induced surfactant-free emulsion polymerization (SFEP) of three vinyl monomers: styrene (St), methyl methacrylate (MMA), and 2-hydroxyethyl methacrylate (HEMA). An effect of monomers on the polymerization and characteristics of resulting products was investigated. Monomers with high polarity can provide high monomer conversion, high percentage of grafted PEI, stable particles with uniform size distribution but less amino groups per particles. All prepared nanoparticles exhibited a core-shell nanostructure, containing PEI on the shell with hydrodynamic size around 140-230nm. For in-vitro study in Caco-2 cells, we found that the incorporation of PEI into these core-shell nanoparticles can significantly reduce its cytotoxic effect and also be able to internalized within the cells. Accordingly, these biocompatible particles would be useful for various biomedical applications, including gene transfection and intracellular drug delivery. © 2013.

Biomimetic synthesis of raspberry-like hybrid polymer-silica core-shell nanoparticles by templating colloidal particles with hairy polyamine shell.

PubMed

Pi, Mengwei; Yang, Tingting; Yuan, Jianjun; Fujii, Syuji; Kakigi, Yuichi; Nakamura, Yoshinobu; Cheng, Shiyuan

2010-07-01

The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core-shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core-shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 degrees C for 2.5h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA-silica hybrid shell. The resulting hybrid silica core-shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core-shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA-silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core-shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. 2010 Elsevier B.V. All rights reserved.

Large-area super-resolution optical imaging by using core-shell microfibers

NASA Astrophysics Data System (ADS)

Liu, Cheng-Yang; Lo, Wei-Chieh

2017-09-01

We first numerically and experimentally report large-area super-resolution optical imaging achieved by using core-shell microfibers. The particular spatial electromagnetic waves for different core-shell microfibers are studied by using finite-difference time-domain and ray tracing calculations. The focusing properties of photonic nanojets are evaluated in terms of intensity profile and full width at half-maximum along propagation and transversal directions. In experiment, the general optical fiber is chemically etched down to 6 μm diameter and coated with different metallic thin films by using glancing angle deposition. The direct imaging of photonic nanojets for different core-shell microfibers is performed with a scanning optical microscope system. We show that the intensity distribution of a photonic nanojet is highly related to the metallic shell due to the surface plasmon polaritons. Furthermore, large-area super-resolution optical imaging is performed by using different core-shell microfibers placed over the nano-scale grating with 150 nm line width. The core-shell microfiber-assisted imaging is achieved with super-resolution and hundreds of times the field-of-view in contrast to microspheres. The possible applications of these core-shell optical microfibers include real-time large-area micro-fluidics and nano-structure inspections.

Surface functionalization of magnetite nanoparticle: A new approach using condensation of alkoxysilanes

NASA Astrophysics Data System (ADS)

Rodriguez, A. F. R.; Costa, T. P.; Bini, R. A.; Faria, F. S. E. D. V.; Azevedo, R. B.; Jafelicci, M.; Coaquira, J. A. H.; Martínez, M. A. R.; Mantilla, J. C.; Marques, R. F. C.; Morais, P. C.

2017-09-01

In this study we report on successful production of two samples (BR15 and BR16) comprising magnetite (Fe3O4) nanoparticles ( 10 nm) surface-functionalized via hydrolysis and condensation of alkoxysilane agents, namely 3-aminopropyl-trimethoxisilane (APTS) and N-propyl-trimethoxisilane (NPTS). The as-produced samples were characterized using transmission electron microscopy (TEM), x-ray diffraction (XRD), magnetization measurements (5 K and 300 K hysteresis cycles and zero field-cooled/field-cooled measurements), and Mössbauer spectroscopy (77 and 297 K). The Mössbauer data supported the model picture of a core-shell magnetite-based system. This material system shows shell properties influenced by the surface-coating design, either APTS-coated (BR15) or APTS+NPTS-coated (sample BR16). Analyses of the Mössbauer spectra indicates that the APTS-coated sample presents Fe(III)-rich core and Fe(II)-rich shell with strong hyperfine field; whereas, the APTS+NPTS-coated sample leads to a mixture of two main nanostructures, one essentially surface-terminated with APTS whereas the other surface-terminated with NPTS, both presenting weak hyperfine fields compared with the single surface-coated sample. Magnetization measurements support the core-shell picture built from the analyses of the Mössbauer data. Our findings emphasize the capability of the Mössbauer spectroscopy in assessing subtle differences in surface-functionalized iron-based core-shell nanostructures.

Eosin-Y sensitized core-shell TiO2-ZnO nano-structured photoanodes for dye-sensitized solar cell applications.

PubMed

Manikandan, V S; Palai, Akshaya K; Mohanty, Smita; Nayak, Sanjay K

2018-06-01

In the current investigation, TiO 2 and TiO 2 -ZnO (core-shell) spherical nanoparticles were synthesized by simple combined hydrolysis and refluxing method. A TiO 2 core nanomaterial on the shell material of ZnO was synthesized by utilizing variable ratios of ZnO. The structural characterization of TiO 2 -ZnO core/shell nanoparticles were done by XRD analysis. The spherical structured morphology of the TiO 2 -ZnO has been confirmed through field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) studies. The UV-visible spectra of TiO 2 -ZnO nanostructures were also compared with the pristine TiO 2 to investigate the shift of wavelength. The TiO 2 -ZnO core/shell nanoparticles at the interface efficiently collect the photogenarated electrons from ZnO and also ZnO act a barrier for reduced charge recombination of electrolyte and dye-nanoparticles interface. This combination improved the light absorption which induced the charge transfer ability and dye loading capacity of core-shell nanoparticles. An enhancement in the short circuit current (J sc ) from 1.67 mA/cm 2 to 2.1 mA/cm 2 has been observed for TiO 2 -ZnObased photoanode (with platinum free counter electrode), promises an improvement in the energy conversion efficiency by 57% in comparison with that of the DSSCs based on the pristine TiO 2 . Henceforth, TiO 2 -ZnO photoelectrode in ZnO will effectively act as barrier at the interface of TiO 2 -ZnO and TiO 2 , ensuring the potential for DSSC application. Copyright © 2018 Elsevier B.V. All rights reserved.

Dopamine Polymerization in Liquid Marbles: A General Route to Janus Particle Synthesis.

PubMed

Sheng, Yifeng; Sun, Guanqing; Ngai, To

2016-04-05

Coating a liquid with a particle shell not only renders a droplet superhydrophobic but also isolates a well-confined microenvironment for miniaturized chemical processes. Previously, we have demonstrated that particles at the liquid marble interface provide an ideal platform for the site-selective modification of superhydrophobic particles. However, the need for a special chemical reaction limits their potential use for the fabrication of Janus particles with various properties. Herein, we combine the employment of liquid marbles as microreactors with the remarkable adhesive ability of polydopamine to develop a general route for the synthesis of Janus particles from micrometer-sized superhydrophobic particles. We demonstrate that dopamine polymerization and deposition inside liquid marbles could be used for the selective surface modification of microsized silica particles, resulting in the formation of Janus particles. Moreover, it is possible to manipulate the Janus balance of the particles via the addition of surfactants and/or organic solvents to tune the interfacial energy. More importantly, owing to the many functional groups in polydopamine, we show that versatile strategies could be introduced to use these partially polydopamine-coated silica particles as platforms for further modification, including nanoparticle immobilization, metal ion chelation and reduction, as well as for chemical reactions. Given the flexibility in the choice of cores and the modification strategies, this developed method is distinctive in its high universality, good controllability, and great practicability.

Highly aqueous soluble CaF2:Ce/Tb nanocrystals: effect of surface functionalization on structural, optical band gap, and photoluminescence properties.

PubMed

Ansari, Anees A; Parchur, Abdul K; Kumar, Brijesh; Rai, S B

2016-12-01

The design of nanostructured materials with highly stable water-dispersion and luminescence efficiency is an important concern in nanotechnology and nanomedicine. In this paper, we described the synthesis and distinct surface modification on the morphological structure and optical (optical absorption, band gap energy, excitation, emission, decay time, etc.) properties of highly crystalline water-dispersible CaF 2 :Ce/Tb nanocrystals (core-nanocrystals). The epitaxial growth of inert CaF 2 and silica shell, respectively, on their surface forming as CaF 2 :Ce/Tb@CaF 2 (core/shell) and CaF 2 :Ce/Tb@CaF 2 @SiO 2 (core/shell/SiO 2 ) nanoarchitecture. X-ray diffraction and transmission electron microscope image shows that the nanocrystals were in irregular spherical phase, highly crystalline (~20 nm) with narrow size distribution. The core/shell nanocrystals confirm that the surface coating is responsible in the change of symmetrical nanostructure, which was determined from the band gap energy and luminescent properties. It was found that an inert inorganic shell formation effectively enhances the luminescence efficiency and silica shell makes the nanocrystals highly water-dispersible. In addition, Ce 3+ /Tb 3+ -co-doped CaF 2 nanocrystals show efficient energy transfer from Ce 3+ to Tb 3+ ion and strong green luminescence of Tb 3+ ion at 541 nm( 5 D 4 → 7 F 5 ). Luminescence decay curves of core and core/shell nanocrystals were fitted using mono and biexponential equations, and R 2 regression coefficient criteria were used to discriminate the goodness of the fitted model. The lifetime values for the core/shell nanocrystals are higher than core-nanocrystals. Considering the high stable water-dispersion and intensive luminescence emission in the visible region, these luminescent core/shell nanocrystals could be potential candidates for luminescent bio-imaging, optical bio-probe, displays, staining, and multianalyte optical sensing. A newly designed CaF 2 :Ce/Tb nanoparticles via metal complex decomposition rout shows high dispersibility in aqueous solvents with enhanced photoluminescence. The epitaxial growth of inert CaF 2 shell and further amorphous silica, respectively, enhanced their optical and luminescence properties, which is highly usable for luminescent biolabeling, and optical bioprobe etc.

Fabrication of CuO–Pt core–shell nanohooks by in situ reconstructing the Pt-shells

NASA Astrophysics Data System (ADS)

Cao, Fan; Zheng, He; Zhao, Ligong; Huang, Rui; Jia, Shuangfeng; Liu, Huihui; Li, Lei; Wang, Zhao; Hu, Yongming; Gu, Haoshuang; Wang, Jianbo

2018-05-01

The design of various nanostructures with specific compositions and shapes is highly demanded due to the widespread use of micro/nano electro-mechanical systems. In this work, one-dimensional CuO–Pt core–shell nanowires (NWs) are acquired by depositing Pt nanoparticles onto CuO NWs and then mechanically-shaped into nanohooks. Subsequently, the hook-like shape is maintained by the Pt-shell which is reconstructed via Joule heat and re-solidified after cooling down, during which the elastic strain energy is stored in the CuO-core. The results provide a simple strategy to design nanostructures with various compositions and shapes, implying the potential applications in mechanical energy storage and shape memory nanodevices.

The synthesis of four-layer gold-silver-polymer-silver core-shell nanomushroom with inbuilt Raman molecule for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Jiang, Tao; Wang, Xiaolong; Zhou, Jun

2017-12-01

A facial two-step reduction method was proposed to synthesize four-layer gold-silver-polymer-silver (Au@Ag@PSPAA@Ag) core-shell nanomushrooms (NMs) with inbuilt Raman molecule. The surface-enhanced Raman scattering (SERS) intensity of 4MBA adhered on the surface of Au core gradually increased with the modification of middle Ag shell and then Ag mushroom cap due to the formation of two kinds of ultra-small interior nanogap. Compared with the initial Au nanoparticles, the SERS enhancement ratio of the Au@Ag@PSPAA@Ag NMs approached to nearly 40. The novel core-shell NMs also exhibited homogeneous SERS signals for only one sample and reproducible signals for 10 different samples, certified by the low relative standard deviation values of less than 10% and 15% for the character peaks of 4-mercaptobenzoic acid, respectively. Such a novel four-layer core-shell nanostructure with reliable SERS performance has great potential application in quantitative SERS-based immunoassay.

Efficient tungsten oxide/bismuth oxyiodide core/shell photoanode for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Ma, Haipeng; Zhang, Jing; Liu, Zhifeng

2017-11-01

The novel WO3 nanorods (NRs)/BiOI core/shell structure composite is used as an efficient photoanode applied in photoelectrochemical (PEC) water splitting for the first time. It is synthesized via facile hydrothermal method and, successive ionic layer adsorption and reaction (SILAR) process. This facile synthesis route can achieve uniform WO3/BiOI core/shell composite nanostructures and obtain varied BiOI morphologies simultaneously. The WO3 NRs/BiOI-20 composite exhibits enhanced PEC activity compared to pristine WO3 with a photocurrent density of 0.79 mA cm-2 measured at 0.8 V vs. RHE under AM 1.5G. This excellent performance benefits from the broader absorption spectrum and suppressed electron-hole recombination. This novel core/shell composite may provide insight in developing more efficient solar driven photoelectrodes.

Hypersonic vibrations of Ag@SiO2 (cubic core)-shell nanospheres.

PubMed

Sun, Jing Ya; Wang, Zhi Kui; Lim, Hock Siah; Ng, Ser Choon; Kuok, Meng Hau; Tran, Toan Trong; Lu, Xianmao

2010-12-28

The intriguing optical and catalytic properties of metal-silica core-shell nanoparticles, inherited from their plasmonic metallic cores together with the rich surface chemistry and increased stability offered by their silica shells, have enabled a wide variety of applications. In this work, we investigate the confined vibrational modes of a series of monodisperse Ag@SiO(2) (cubic core)-shell nanospheres synthesized using a modified Stöber sol-gel method. The particle-size dependence of their mode frequencies has been mapped by Brillouin light scattering, a powerful tool for probing hypersonic vibrations. Unlike the larger particles, the observed spheroidal-like mode frequencies of the smaller ones do not scale with inverse diameter. Interestingly, the onset of the deviation from this linearity occurs at a smaller particle size for higher-energy modes than for lower-energy ones. Finite element simulations show that the mode displacement profiles of the Ag@SiO(2) core-shells closely resemble those of a homogeneous SiO(2) sphere. Simulations have also been performed to ascertain the effects that the core shape and the relative hardness of the core and shell materials have on the vibrations of the core-shell as a whole. As the vibrational modes of a particle have a bearing on its thermal and mechanical properties, the findings would be of value in designing core-shell nanostructures with customized thermal and mechanical characteristics.

Magnetically Recoverable Pd/Fe 3O 4 Core-Shell Nanowire Clusters with Increased Hydrogenation Activity

DOE PAGES

Watt, John; Kotula, Paul G.; Huber, Dale L.

2017-02-06

Core-shell nanostructures are promising candidates for the next generation of catalysts due to synergistic effects which can arise from having two active species in close contact, leading to increased activity. Likewise, catalysts displaying added functionality, such as a magnetic response, can increase their scientific and industrial potential. Here, we synthesize Pd/Fe 3O 4 core-shell nanowire clusters and apply them as hydrogenation catalysts for an industrially important hydrogenation reaction; the conversion of acetophenone to 1-phenylethanol. During synthesis, the palladium nanowires self-assemble into clusters which act as a high surface area framework for the growth of a magnetic iron oxide shell. Wemore » demonstrate excellent catalytic activity due to the presence of palladium while the strong magnetic properties provided by the iron oxide shell enable facile catalyst recovery.« less

Structural and photoluminescence studies on catalytic growth of silicon/zinc oxide heterostructure nanowires

PubMed Central

2013-01-01

Silicon/zinc oxide (Si/ZnO) core-shell nanowires (NWs) were prepared on a p-type Si(111) substrate using a two-step growth process. First, indium seed-coated Si NWs (In/Si NWs) were synthesized using a plasma-assisted hot-wire chemical vapor deposition technique. This was then followed by the growth of a ZnO nanostructure shell layer using a vapor transport and condensation method. By varying the ZnO growth time from 0.5 to 2 h, different morphologies of ZnO nanostructures, such as ZnO nanoparticles, ZnO shell layer, and ZnO nanorods were grown on the In/Si NWs. The In seeds were believed to act as centers to attract the ZnO molecule vapors, further inducing the lateral growth of ZnO nanorods from the Si/ZnO core-shell NWs via a vapor-liquid-solid mechanism. The ZnO nanorods had a tendency to grow in the direction of [0001] as indicated by X-ray diffraction and high resolution transmission electron microscopy analyses. We showed that the Si/ZnO core-shell NWs exhibit a broad visible emission ranging from 400 to 750 nm due to the combination of emissions from oxygen vacancies in ZnO and In2O3 structures and nanocrystallite Si on the Si NWs. The hierarchical growth of straight ZnO nanorods on the core-shell NWs eventually reduced the defect (green) emission and enhanced the near band edge (ultraviolet) emission of the ZnO. PMID:23590803

He-Ion Microscopy as a High-Resolution Probe for Complex Quantum Heterostructures in Core-Shell Nanowires.

PubMed

Pöpsel, Christian; Becker, Jonathan; Jeon, Nari; Döblinger, Markus; Stettner, Thomas; Gottschalk, Yeanitza Trujillo; Loitsch, Bernhard; Matich, Sonja; Altzschner, Marcus; Holleitner, Alexander W; Finley, Jonathan J; Lauhon, Lincoln J; Koblmüller, Gregor

2018-06-13

Core-shell semiconductor nanowires (NW) with internal quantum heterostructures are amongst the most complex nanostructured materials to be explored for assessing the ultimate capabilities of diverse ultrahigh-resolution imaging techniques. To probe the structure and composition of these materials in their native environment with minimal damage and sample preparation calls for high-resolution electron or ion microscopy methods, which have not yet been tested on such classes of ultrasmall quantum nanostructures. Here, we demonstrate that scanning helium ion microscopy (SHeIM) provides a powerful and straightforward method to map quantum heterostructures embedded in complex III-V semiconductor NWs with unique material contrast at ∼1 nm resolution. By probing the cross sections of GaAs-Al(Ga)As core-shell NWs with coaxial GaAs quantum wells as well as short-period GaAs/AlAs superlattice (SL) structures in the shell, the Al-rich and Ga-rich layers are accurately discriminated by their image contrast in excellent agreement with correlated, yet destructive, scanning transmission electron microscopy and atom probe tomography analysis. Most interestingly, quantitative He-ion dose-dependent SHeIM analysis of the ternary AlGaAs shell layers and of compositionally nonuniform GaAs/AlAs SLs reveals distinct alloy composition fluctuations in the form of Al-rich clusters with size distributions between ∼1-10 nm. In the GaAs/AlAs SLs the alloy clustering vanishes with increasing SL-period (>5 nm-GaAs/4 nm-AlAs), providing insights into critical size dimensions for atomic intermixing effects in short-period SLs within a NW geometry. The straightforward SHeIM technique therefore provides unique benefits in imaging the tiniest nanoscale features in topography, structure and composition of a multitude of diverse complex semiconductor nanostructures.

Janus structured Pt–FeNC nanoparticles as a catalyst for the oxygen reduction reaction

DOE PAGES

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Park, Gu -Gon; ...

2017-01-03

Here, we present a new Janus structured catalyst consisting of Pt nanoparticles on Fe–N–C nanoparticles encapsulated by graphene layers for the ORR. The ORR activity of the catalyst increases under potential cycling as the unique Janus nanostructure is further bonded due to a synergetic effect. The present study describes an important advanced approach for the future design of efficient, stable, and low-cost Pt-based electrocatalytic systems.

Nano Titanium Monoxide Crystals and Unusual Superconductivity at 11 K.

PubMed

Xu, Jijian; Wang, Dong; Yao, Heliang; Bu, Kejun; Pan, Jie; He, Jianqiao; Xu, Fangfang; Hong, Zhanglian; Chen, Xiaobo; Huang, Fuqiang

2018-03-01

Nano TiO 2 is investigated intensely due to extraordinary photoelectric performances in photocatalysis, new-type solar cells, etc., but only very few synthesis and physical properties have been reported on nanostructured TiO or other low valent titanium-containing oxides. Here, a core-shell nanoparticle made of TiO core covered with a ≈5 nm shell of amorphous TiO 1+ x is newly constructed via a controllable reduction method to synthesize nano TiO core and subsequent soft oxidation to form the shell (TiO 1+ x ). The physical properties measurements of electrical transport and magnetism indicate these TiO@TiO 1+ x nanocrystals are a type-ІІ superconductor of a recorded T c onset = 11 K in the binary Ti-O system. This unusual superconductivity could be attributed to the interfacial effect due to the nearly linear gradient of O/Ti ratio across the outer amorphous layer. This novel synthetic method and enhanced superconductivity could open up possibilities in interface superconductivity of nanostructured composites with well-controlled interfaces. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural properties of CuAu nanoparticles with different type. Molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Chepkasov, I. V.; Baidyshev, V. S.; Baev, A. Y.

2018-05-01

The paper is devoted to the thermal stability of a CuAu nanoparticles structure (D=5 nm) of various type (binary alloy, core-shell, "Janus" type) and of various percentage of copper atoms. The simulation was carried out with molecular dynamics, using the embedded atom potential. The authors defined the most preferable structural options from the standpoint of thermodynamics, as well as studied in detail the influence of different temperatures on the structural stability of CuAu nanoparticles.

Complete Au@ZnO core-shell nanoparticles with enhanced plasmonic absorption enabling significantly improved photocatalysis

NASA Astrophysics Data System (ADS)

Sun, Yiqiang; Sun, Yugang; Zhang, Tao; Chen, Guozhu; Zhang, Fengshou; Liu, Dilong; Cai, Weiping; Li, Yue; Yang, Xianfeng; Li, Cuncheng

2016-05-01

Nanostructured ZnO exhibits high chemical stability and unique optical properties, representing a promising candidate among photocatalysts in the field of environmental remediation and solar energy conversion. However, ZnO only absorbs the UV light, which accounts for less than 5% of total solar irradiation, significantly limiting its applications. In this article, we report a facile and efficient approach to overcome the poor wettability between ZnO and Au by carefully modulating the surface charge density on Au nanoparticles (NPs), enabling rapid synthesis of Au@ZnO core-shell NPs at room temperature. The resulting Au@ZnO core-shell NPs exhibit a significantly enhanced plasmonic absorption in the visible range due to the Au NP cores. They also show a significantly improved photocatalytic performance in comparison with their single-component counterparts, i.e., the Au NPs and ZnO NPs. Moreover, the high catalytic activity of the as-synthesized Au@ZnO core-shell NPs can be maintained even after many cycles of photocatalytic reaction. Our results shed light on the fact that the Au@ZnO core-shell NPs represent a promising class of candidates for applications in plasmonics, surface-enhanced spectroscopy, light harvest devices, solar energy conversion, and degradation of organic pollutants.Nanostructured ZnO exhibits high chemical stability and unique optical properties, representing a promising candidate among photocatalysts in the field of environmental remediation and solar energy conversion. However, ZnO only absorbs the UV light, which accounts for less than 5% of total solar irradiation, significantly limiting its applications. In this article, we report a facile and efficient approach to overcome the poor wettability between ZnO and Au by carefully modulating the surface charge density on Au nanoparticles (NPs), enabling rapid synthesis of Au@ZnO core-shell NPs at room temperature. The resulting Au@ZnO core-shell NPs exhibit a significantly enhanced plasmonic absorption in the visible range due to the Au NP cores. They also show a significantly improved photocatalytic performance in comparison with their single-component counterparts, i.e., the Au NPs and ZnO NPs. Moreover, the high catalytic activity of the as-synthesized Au@ZnO core-shell NPs can be maintained even after many cycles of photocatalytic reaction. Our results shed light on the fact that the Au@ZnO core-shell NPs represent a promising class of candidates for applications in plasmonics, surface-enhanced spectroscopy, light harvest devices, solar energy conversion, and degradation of organic pollutants. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00933f

Lanthanide-doped NaGdF4 core-shell nanoparticles for non-contact self-referencing temperature sensors.

PubMed

Zheng, Shuhong; Chen, Weibo; Tan, Dezhi; Zhou, Jiajia; Guo, Qiangbing; Jiang, Wei; Xu, Cheng; Liu, Xiaofeng; Qiu, Jianrong

2014-06-07

We report that non-contact self-referencing temperature sensors can be realized with the use of core-shell nanostructures. These lanthanide-based nanothermometers (NaGdF4:Yb(3+)/Tm(3+)@Tb(3+)/Eu(3+)) exhibit higher sensitivity in a wide range from 125 to 300 K based on two emissions of Tb(3+) at 545 nm and Eu(3+) at 615 nm under near-infrared laser excitation.

Reconfigurable Polymer Shells on Shape-Anisotropic Gold Nanoparticle Cores.

PubMed

Kim, Juyeong; Song, Xiaohui; Kim, Ahyoung; Luo, Binbin; Smith, John W; Ou, Zihao; Wu, Zixuan; Chen, Qian

2018-05-03

Reconfigurable hybrid nanoparticles made by decorating flexible polymer shells on rigid inorganic nanoparticle cores can provide a unique means to build stimuli-responsive functional materials. The polymer shell reconfiguration has been expected to depend on the local core shape details, but limited systematic investigations have been undertaken. Here, two literature methods are adapted to coat either thiol-terminated polystyrene (PS) or polystyrene-poly(acrylic acid) (PS-b-PAA) shells onto a series of anisotropic gold nanoparticles of shapes not studied previously, including octahedron, concave cube, and bipyramid. These core shapes are complex, rendering shell contours with nanoscale details (e.g., local surface curvature, shell thickness) that are imaged and analyzed quantitatively using the authors' customized analysis codes. It is found that the hybrid nanoparticles based on the chosen core shapes, when coated with the above two polymer shells, exhibit distinct shell segregations upon a variation in solvent polarity or temperature. It is demonstrated for the PS-b-PAA-coated hybrid nanoparticles, the shell segregation is maintained even after a further decoration of the shell periphery with gold seeds; these seeds can potentially facilitate subsequent deposition of other nanostructures to enrich structural and functional diversity. These synthesis, imaging, and analysis methods for the hybrid nanoparticles of anisotropically shaped cores can potentially aid in their predictive design for materials reconfigurable from the bottom up. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rational design and synthesis of yolk-shell ZnGa2O4@C nanostructure with enhanced lithium storage properties

NASA Astrophysics Data System (ADS)

Han, Nao; Xia, Yuguo; Han, Yanyang; Jiao, Xiuling; Chen, Dairong

2018-03-01

The ability to create hybrid nanostructure with synergistic effect and confined morphology to achieve high performance and long-term stability is high desirable in lithium ion batteries. Although transition metal oxides as anode material reveal high theoretical capacities, the significant volume changes during repeated lithium insertion and extraction cause pulverization of electrode materials, resulting in rapid fade in capacity. Herein, yolk-shell nanostructure of ZnGa2O4 encapsulated by amorphous carbon is rationally designed and synthesized through two-step surface coating followed by thermal treatment and etching process. It is noteworthy that ZnGa2O4@C with yolk-shell structure is superior to pristine ZnGa2O4 and ZnGa2O4@C with core-shell structure in term of lithium storage. The stable reversible capacity of yolk-shell ZnGa2O4@C can be retained at 657.2 mAh g-1 at current density of 1 A g-1 after completion of 300 cycles, which also reveals superior rate performance. The appropriate carbon shell and void space involved in the yolk-shell structure are considered to be the crucial factor in accommodating volume expansion as well as preserving the structural integrity of yolk-shell ZnGa2O4@C.

Designing Hollow Nano Gold Golf Balls

PubMed Central

2015-01-01

Hollow/porous nanoparticles, including nanocarriers, nanoshells, and mesoporous materials have applications in catalysis, photonics, biosensing, and delivery of theranostic agents. Using a hierarchical template synthesis scheme, we have synthesized a nanocarrier mimicking a golf ball, consisting of (i) solid silica core with a pitted gold surface and (ii) a hollow/porous gold shell without silica. The template consisted of 100 nm polystyrene beads attached to a larger silica core. Selective gold plating of the core followed by removal of the polystyrene beads produced a golf ball-like nanostructure with 100 nm pits. Dissolution of the silica core produced a hollow/porous golf ball-like nanostructure. PMID:24937196

Thiolated DNA-based chemistry and control in the structure and optical properties of plasmonic nanoparticles with ultrasmall interior nanogap.

PubMed

Oh, Jeong-Wook; Lim, Dong-Kwon; Kim, Gyeong-Hwan; Suh, Yung Doug; Nam, Jwa-Min

2014-10-08

The design, synthesis and control of plasmonic nanostructures, especially with ultrasmall plasmonically coupled nanogap (∼1 nm or smaller), are of significant interest and importance in chemistry, nanoscience, materials science, optics and nanobiotechnology. Here, we studied and established the thiolated DNA-based synthetic principles and methods in forming and controlling Au core-nanogap-Au shell structures [Au-nanobridged nanogap particles (Au-NNPs)] with various interior nanogap and Au shell structures. We found that differences in the binding affinities and modes among four different bases to Au core, DNA sequence, DNA grafting density and chemical reagents alter Au shell growth mechanism and interior nanogap-forming process on thiolated DNA-modified Au core. Importantly, poly A or poly C sequence creates a wider interior nanogap with a smoother Au shell, while poly T sequence results in a narrower interstitial interior gap with rougher Au shell, and on the basis of the electromagnetic field calculation and experimental results, we unraveled the relationships between the width of the interior plasmonic nanogap, Au shell structure, electromagnetic field and surface-enhanced Raman scattering. These principles and findings shown in this paper offer the fundamental basis for the thiolated DNA-based chemistry in forming and controlling metal nanostructures with ∼1 nm plasmonic gap and insight in the optical properties of the plasmonic NNPs, and these plasmonic nanogap structures are useful as strong and controllable optical signal-generating nanoprobes.

Synthesis of carbon core–shell pore structures and their performance as supercapacitors

DOE PAGES

Ariyanto, Teguh; Dyatkin, Boris; Zhang, Gui-Rong; ...

2015-07-15

High-power supercapacitors require excellent electrolyte mobility within the pore network and high electrical conductivity for maximum capacitance and efficiency. Achieving high power typically requires sacrificing energy densities, as the latter demands a high specific surface area and narrow porosity that impedes ion transport. Here, we present a novel solution for this optimization problem: a nanostructured core–shell carbonaceous material that exhibits a microporous carbon core surrounded by a mesoporous, graphitic shell. The tunable synthesis parameters yielded a structure that features either a sharp or a gradual transition between the core and shell sections. Electrochemical supercapacitor testing using organic electrolyte revealed thatmore » these novel core–shell materials outperform carbons with homogeneous pore structures. The hybrid core–shell materials showed a combination of good capacitance retention, typical for the carbon present in the shell and high specific capacitance, typical for the core material. These materials achieved power densities in excess of 40 kW kg -1 at energy densities reaching 27 Wh kg -1.« less

The design and synthesis of heterostructured quantum dots with dual emission in the visible and infrared

DOE PAGES

Lin, Qianglu; Makarov, Nikolay S.; Koh, Weon-kyu; ...

2014-11-26

The unique optical properties exhibited by visible emitting core/shell quantum dots with especially thick shells are the focus of widespread study, but have yet to be realized in infrared (IR) -active nanostructures. We apply an effective-mass model to identify PbSe/CdSe core/shell quantum dots as a promising system for achieving this goal. We then synthesize colloidal PbSe/CdSe quantum dots with shell thicknesses of up to 4 nm that exhibit unusually slow hole intra-band relaxation from shell to core states, as evidenced by the emergence of dual emission, i.e., IR photoluminescence from the PbSe core observed simultaneously with visible emission from themore » CdSe shell. In addition to the large shell thickness, the development of slowed intraband relaxation is facilitated by the existence of a sharp core-shell interface without discernible alloying. Growth of thick shells without interfacial alloying or incidental formation of homogenous CdSe nanocrystals was accomplished using insights attained via a systematic study of the dynamics of the cation-exchange synthesis of both PbSe/CdSe as well as the related system PbS/CdS. Finally, we show that the efficiency of the visible photoluminescence can be greatly enhanced by inorganic passivation.« less

Template-Free Hydrothermal Synthesis, Mechanism, and Photocatalytic Properties of Core-Shell CeO2 Nanospheres

NASA Astrophysics Data System (ADS)

Li, Huijie; Meng, Fanming; Gong, Jinfeng; Fan, Zhenghua; Qin, Rui

2018-03-01

CeO2 nanospheres with the core-shell nanostructure have been successfully synthesized by a template-free hydrothermal method. The structures, morphologies and optical properties of core-shell CeO2 nanospheres were analyzed by X-ray diffraction (XRD), TG, Fourier transform infrared spectroscopy, XRD, EDS, SAED, scanning electron microscopy and transmission electron microscopy, UV-Vis diffuse reflectance spectra, Raman analyses. The degradation efficiencies of core-shell CeO2 nanospheres for methyl orange were as high as 93.49, 95.67 and 98.28% within 160 min, and the rates of photo degradation of methyl orange by core-shell CeO2 nanospheres under UV-light were 0.01693, 0.01782 and 0.02375 min-1. Methyl orange was degraded in photocatalytic oxidation processes, which mainly gave the credit to a large number of reactive species including h+, surface superoxide species ·O2 -, and ·OH radicals. The core-shell structure, small crystallite size and the conversion between Ce3+ and Ce4+ of CeO2 nanospheres were of importance for its catalytic activity. These results demonstrated the possibility of improving the efficient catalysts of the earth abundant CeO2 catalysts.

An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

DOE PAGES

Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; ...

2015-09-11

Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO 2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO 2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic propertiesmore » and thermal stabilities compared with those prepared with organic capping agents. As a result, this inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties.« less

Synthesis of Fe5C2@SiO2 core@shell nanoparticles as a potential candidate for biomedical application

NASA Astrophysics Data System (ADS)

Ahmadpoor, Fatemeh; Shojaosadati, Seyed Abbas; Delavari H, Hamid; Christiansen, Gunna; Saber, Reza

2018-05-01

A new strategy for water-dispersibility of hydrophobic carbide nanostructures was proposed. In this regard, hydrophobic Fe5C2 nanoparticles (NPs) with size ranging 25–40 nm were synthesized and coated with 12–15 nm silica shell for biomedical applications. X-ray diffraction (XRD) results revealed that Fe5C2 NPs with monoclinic structure were successfully prepared. The crystalline structure of Fe5C2 NPs was remained unchanged and saturation magnetization of core remained nearly constant after coating with silica shell. Moreover, Raman spectroscopy identified D-band of amorphous carbon shells which was also confirmed by transmission electron microscopy (TEM). Finally, Fe5C2@SiO2 core@shell NPs demonstrated no significant cytotoxicity and appropriate heat generating which makes them a promising candidate for magnetic fluid hyperthermia applications.

Synthesis of upconversion nanoparticles conjugated with graphene oxide quantum dots and their use against cancer cell imaging and photodynamic therapy.

PubMed

Choi, Seung Yoo; Baek, Seung Hoon; Chang, Sung-Jin; Song, Yohan; Rafique, Rafia; Lee, Kang Taek; Park, Tae Jung

2017-07-15

Multifunctional nanocomposite has a huge potential for cell imaging, drug delivery, and improving therapeutic effect with less side effects. To date, diverse approaches have been demonstrated to endow a single nanostructure with multifunctionality. Herein, we report the synthesis and application of core-shell nanoparticles composed with upconversion nanoparticle (UCNP) as a core and a graphene oxide quantum dot (GOQD) as a shell. The UCNP was prepared and applied for imaging-guided analyses of upconversion luminescence. GOQD was prepared and employed as promising drug delivery vehicles to improve anti-tumor therapy effect in this study. Unique properties of UCNPs and GOQDs were incorporated into a single nanostructure to provide desirable functions for cell imaging and drug delivery. In addition, hypocrellin A (HA) was loaded on GOQDs for photo-dynamic therapy (PDT). HA, a commonly used chemotherapy drug and a photo-sensitizer, was conjugated with GOQD by π-π interaction and loaded on PEGylated UCNP without complicated synthetic process, which can break structure of HA. Applying these core-shell nanoparticles to MTT assay, we demonstrated that the UCNPs with GOQD shell loaded with HA could be excellent candidates as multifunctional agents for cell imaging, drug delivery and cell therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of core/shell structures based on CdTe and GaAs nanocrystalline layers deposited on SnO2 microwires

NASA Astrophysics Data System (ADS)

Ghimpu, L.; Ursaki, V. V.; Pantazi, A.; Mesterca, R.; Brâncoveanu, O.; Shree, Sindu; Adelung, R.; Tiginyanu, I. M.; Enachescu, M.

2018-04-01

We report the fabrication and characterization of SnO2/CdTe and SnO2/GaAs core/shell microstructures. CdTe or GaAs shell layers were deposited by radio-frequency (RF) magnetron sputtering on core SnO2 microwires synthesized by a flame-based thermal oxidation method. The produced structures were characterized by scanning electron microscopy (SEM), high-resolution scanning transmission electron microscope (HR-STEM), X-ray diffraction (XRD), Raman scattering and FTIR spectroscopy. It was found that the SnO2 core is of the rutile type, while the shells are composed of CdTe or GaAs nanocrystallites of zincblende structure with the dimensions of crystallites in the range of 10-20 nm. The Raman scattering investigations demonstrated that the quality of the porous nanostructured shell is improved by annealing at temperatures of 420-450 °C. The prospects of implementing these microstructures in intrinsic type fiber optic sensors are discussed.

Twin-mediated epitaxial growth of highly lattice-mismatched Cu/Ag core-shell nanowires.

PubMed

Weng, Wei-Lun; Hsu, Chin-Yu; Lee, Jheng-Syun; Fan, Hsin-Hsin; Liao, Chien-Neng

2018-05-31

Lattice-mismatch is an important factor for the heteroepitaxial growth of core-shell nanostructures. A large lattice-mismatch usually leads to a non-coherent interface or a polycrystalline shell layer. In this study, a conformal Ag layer is coated on Cu nanowires with dense nanoscale twin boundaries through a galvanic replacement reaction. Despite a large lattice mismatch between Ag and Cu (∼12.6%), the Ag shell replicates the twinning structure in Cu nanowires and grows epitaxially on the nanotwinned Cu nanowire. A twin-mediated growth mechanism is proposed to explain the epitaxy of high lattice-mismatch bimetallic systems in which the misfit dislocations are accommodated by coherent twin boundaries.

Fabrication of core-shell nanostructures via silicon on insulator dewetting and germanium condensation: towards a strain tuning method for SiGe-based heterostructures in a three-dimensional geometry.

PubMed

Naffouti, Meher; David, Thomas; Benkouider, Abdelmalek; Favre, Luc; Cabie, Martiane; Ronda, Antoine; Berbezier, Isabelle; Abbarchi, Marco

2016-07-29

We report on a novel method for the implementation of core-shell SiGe-based nanocrystals combining silicon on insulator dewetting in a molecular beam epitaxy reactor with an ex situ Ge condensation process. With an in situ two-step process (annealing and Ge deposition) we produce two families of islands on the same sample: Si-rich, formed during the first step and, all around them, Ge-rich formed after Ge deposition. By increasing the amount of Ge deposited on the annealed samples from 0 to 18 monolayers, the islands' shape in the Si-rich zones can be tuned from elongated and flat to more symmetric and with a larger vertical aspect ratio. At the same time, the spatial extension of the Ge-rich zones is progressively increased as well as the Ge content in the islands. Further processing by ex situ rapid thermal oxidation results in the formation of a core-shell composition profile in both Si and Ge-rich zones with atomically sharp heterointerfaces. The Ge condensation induces a Ge enrichment of the islands' shell of up to 50% while keeping a pure Si core in the Si-rich zones and a ∼25% SiGe alloy in the Ge-rich ones. The large lattice mismatch between core and shell, the absence of dislocations and the islands' monocrystalline nature render this novel class of nanostructures a promising device platform for strain-based band-gap engineering. Finally, this method can be used for the implementation of ultralarge scale meta-surfaces with dielectric Mie resonators for light manipulation at the nanoscale.

Controllable synthesis of Au@SnO2 core-shell nanohybrids with enhanced photocatalytic activities

NASA Astrophysics Data System (ADS)

Zhang, Shaofeng; Hao, Jinggang; Ren, Feng; Wu, Wei; Xiao, Xiangheng

2017-05-01

Combination of semiconductors with plasmonic nanostructures is an effective route to promote the solar light harvesting as well as the efficiency of photocatalysis. In the present work, the Au@SnO2 hybrid nanostructures with Au nanorods as the cores and highly crystallized SnO2 nanoparticles as the shells were fabricated by a facile hydrothermal method. A critical factor, which influences the coating state of the SnO2 shells over Au NRs, was found to be the concentration of CTAB agent in the system and the corresponding mechanism was also proposed. The photocatalytic activities of the Au@SnO2 nanohybrids were examined by degradation of rhodamine B (RhB) dyes at room temperature. The Au@SnO2 nanohybrids exhibited much higher catalytic activities than that of the commercial SnO2 NPs, which could be attributed to the localized electric field enhancement effect of Au nanorods plasmon and charges transfer between the Au nanorods and SnO2.

Light absorption and plasmon – exciton interaction in three-layer nanorods with a gold core and outer shell composed of molecular J- and H-aggregates of dyes

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

Shapiro, B I; Tyshkunova, E S; Kondorskiy, A D

2015-12-31

Optical properties of hybrid rod-like nanoparticles, consisting of a gold core, an intermediate passive organic layer (spacer) and outer layer of ordered molecular cyanine dye aggregates, are experimentally and theoretically investigated. It is shown that these dyes can form not only ordered J-aggregates but also H-aggregates (differing by the packing angle of dye molecules in an aggregate and having other spectral characteristics) in the outer shell of the hybrid nanostructure. Absorption spectra of synthesised three-layer nanorods are recorded, and their sizes are determined. The optical properties of the composite nanostructures under study are found to differ significantly, depending on themore » type of the molecular aggregate formed in the outer shell. The experimental data are quantitatively explained based on computer simulation using the finite-difference time-domain (FDTD) method, and characteristic features of the plasmon – exciton interaction in the systems under study are revealed. (nanophotonics)« less

Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

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

Kaur, Maninder; Qiang, You, E-mail: youqiang@uidaho.edu; Dai, Qilin

2013-11-11

Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr (<10 at. %) were selected in order to inhibit the complete conversion of the Fe-oxide shell to Cr{sub 2}O{sub 3} and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (∼25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of σ-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs.

Core-shell chromium silicide-silicon nanopillars: a contact material for future nanosystems.

PubMed

Chang, Mu-Tung; Chen, Chih-Yen; Chou, Li-Jen; Chen, Lih-Juann

2009-11-24

Chromium silicide nanostructures are fabricated inside silicon nanopillars grown by the vapor-liquid-solid mechanism. The remarkable field-emission behavior of these nanostructures results from extensive improvement of carrier transport due to the reduced energy barrier between the metal and semiconductor layers. The results warrant consideration of chromium silicide as a potentially important contact material in future nanosystems.

Spectroscopic, structural and in vitro cytotoxicity evaluation of luminescent, lanthanide doped core@shell nanomaterials GdVO4:Eu(3+)5%@SiO2@NH2.

PubMed

Szczeszak, Agata; Ekner-Grzyb, Anna; Runowski, Marcin; Szutkowski, Kosma; Mrówczyńska, Lucyna; Kaźmierczak, Zuzanna; Grzyb, Tomasz; Dąbrowska, Krystyna; Giersig, Michael; Lis, Stefan

2016-11-01

The luminescent GdVO4:Eu(3+)5%@SiO2@NH2 core@shell nanomaterials were obtained via co-precipitation method, followed by hydrolysis and co-condensation of silane derivatives: tetraethyl orthosilicate and 3-aminopropyltriethoxysilane. Their effect on human erythrocytes sedimentation and on proliferation of human lung microvascular endothelial cells was examined and discussed. The luminescent nanoparticles were synthesized in the presence of polyacrylic acid or glycerin in order to minimalize the agglomeration and excessive growth of nanostructures. Surface coating with amine functionalized silica shell improved their biocompatibility, facilitated further organic conjugation and protected the internal core. Magnetic measurements revealed an enhanced T1-relaxivity for the synthesized GdVO4:Eu(3+)5% nanostructures. Structure, morphology and average grain size of the obtained nanomaterials were determined by X-ray diffraction, transmission electron microscopy and dynamic light scattering analysis. The qualitative elemental composition of the nanomaterials was established using energy-dispersive X-ray spectroscopy. The spectroscopic characteristic of red emitting core@shell nanophosphors was completed by measuring luminescence spectra and decays. The emission spectra revealed characteristic bands of Eu(3+) ions related to the transitions (5)D0-(7)F0,1,2,3,4 and (5)D1-(7)F1. The luminescence lifetimes consisted of two components, associated with the presence of Eu(3+) ions located at the surface of the crystallites and in the bulk. Copyright © 2016 Elsevier Inc. All rights reserved.

Advanced nanomaterials–sustainable preparation and their catalytic applications

EPA Science Inventory

Sustainable nanomaterials have attracted great attention as highly functionalized nanocatalysts in diverse forms including solid-supported nanocatalysts, graphene materials, and core-shell catalysts among other nanostructures. Technology advancements in last decades have allowed ...

Fabrication of hollow boron-doped diamond nanostructure via electrochemical corrosion of a tungsten oxide template.

PubMed

Lim, Young-Kyun; Lee, Eung-Seok; Lee, Choong-Hyun; Lim, Dae-Soon

2018-08-10

In the study, a hollow boron-doped diamond (BDD) nanostructure electrode is fabricated to increase the reactive surface area for electrochemical applications. Tungsten oxide nanorods are deposited on the silicon substrate as a template by the hot filament chemical vapor deposition (HFCVD) method. The template is coated with a 100 nm BDD layer deposited by HFCVD to form a core-shell nanostructure. The WO x core is finally electrochemically dissolved to form hollow BDD nanostructure. The fabricated hollow BDD nanostructure electrode is investigated via scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The specific surface areas of the electrodes were analyzed and compared by using Brunauer-Emmett-Teller method. Furthermore, cyclic voltammetry and chronocoulometry are used to investigate the electrochemical characteristics and the reactive surface area of the as-prepared hollow BDD nanostructure electrode. A hollow BDD nanostructure electrode exhibits a reactive area that is 15 times that of a planar BDD thin electrode.

Metal-core/semiconductor-shell nanocones for broadband solar absorption enhancement.

PubMed

Zhou, Lin; Yu, Xiaoqiang; Zhu, Jia

2014-02-12

Nanostructure-based photovoltaic devices have exhibited several advantages, such as reduced reflection, extraordinary light trapping, and so forth. In particular, semiconductor nanostructures provide optical modes that have strong dependence on the size and geometry. Metallic nanostructures also attract a lot of attention because of the appealing plasmonic effect on the near-field enhancement. In this study, we propose a novel design, the metal-core/semiconductor-shell nanocones with the core radius varying in a linearly gradient style. With a thin layer of semiconductor absorber coated on a metallic cone, such a design can lead to significant and broadband absorption enhancement across the entire visible and near-infrared solar spectrum. As an example of demonstration, a layer of 16 nm thick crystalline silicon (c-Si) coated on a silver nanocone can absorb 27% of standard solar radiation across a broad spectral range of 300-1100 nm, which is equivalent to a 700 nm thick flat c-Si film. Therefore, the absorption enhancement factor approaching the Yablonovitch limit is achieved with this design. The significant absorption enhancement can be ascribed to three types of optical modes, that is, Fabry-Perot modes, plasmonic modes, and hybrid modes that combine the features of the previous two. In addition, the unique nanocone geometry enables the linearly gradient radius of the semiconductor shell, which can support multiple optical resonances, critical for the broadband absorption. Our design may find general usage as elements for the low cost, high efficiency solar conversion and water-splitting devices.

Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency

PubMed Central

Pihosh, Yuriy; Turkevych, Ivan; Mawatari, Kazuma; Uemura, Jin; Kazoe, Yutaka; Kosar, Sonya; Makita, Kikuo; Sugaya, Takeyoshi; Matsui, Takuya; Fujita, Daisuke; Tosa, Masahiro; Kondo, Michio; Kitamori, Takehiko

2015-01-01

Efficient photocatalytic water splitting requires effective generation, separation and transfer of photo-induced charge carriers that can hardly be achieved simultaneously in a single material. Here we show that the effectiveness of each process can be separately maximized in a nanostructured heterojunction with extremely thin absorber layer. We demonstrate this concept on WO3/BiVO4+CoPi core-shell nanostructured photoanode that achieves near theoretical water splitting efficiency. BiVO4 is characterized by a high recombination rate of photogenerated carriers that have much shorter diffusion length than the thickness required for sufficient light absorption. This issue can be resolved by the combination of BiVO4 with more conductive WO3 nanorods in a form of core-shell heterojunction, where the BiVO4 absorber layer is thinner than the carrier diffusion length while it’s optical thickness is reestablished by light trapping in high aspect ratio nanostructures. Our photoanode demonstrates ultimate water splitting photocurrent of 6.72 mA cm−2 under 1 sun illumination at 1.23 VRHE that corresponds to ~90% of the theoretically possible value for BiVO4. We also demonstrate a self-biased operation of the photoanode in tandem with a double-junction GaAs/InGaAsP photovoltaic cell with stable water splitting photocurrent of 6.56 mA cm−2 that corresponds to the solar to hydrogen generation efficiency of 8.1%. PMID:26053164

Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency

NASA Astrophysics Data System (ADS)

Pihosh, Yuriy; Turkevych, Ivan; Mawatari, Kazuma; Uemura, Jin; Kazoe, Yutaka; Kosar, Sonya; Makita, Kikuo; Sugaya, Takeyoshi; Matsui, Takuya; Fujita, Daisuke; Tosa, Masahiro; Kondo, Michio; Kitamori, Takehiko

2015-06-01

Efficient photocatalytic water splitting requires effective generation, separation and transfer of photo-induced charge carriers that can hardly be achieved simultaneously in a single material. Here we show that the effectiveness of each process can be separately maximized in a nanostructured heterojunction with extremely thin absorber layer. We demonstrate this concept on WO3/BiVO4+CoPi core-shell nanostructured photoanode that achieves near theoretical water splitting efficiency. BiVO4 is characterized by a high recombination rate of photogenerated carriers that have much shorter diffusion length than the thickness required for sufficient light absorption. This issue can be resolved by the combination of BiVO4 with more conductive WO3 nanorods in a form of core-shell heterojunction, where the BiVO4 absorber layer is thinner than the carrier diffusion length while it’s optical thickness is reestablished by light trapping in high aspect ratio nanostructures. Our photoanode demonstrates ultimate water splitting photocurrent of 6.72 mA cm-2 under 1 sun illumination at 1.23 VRHE that corresponds to ~90% of the theoretically possible value for BiVO4. We also demonstrate a self-biased operation of the photoanode in tandem with a double-junction GaAs/InGaAsP photovoltaic cell with stable water splitting photocurrent of 6.56 mA cm-2 that corresponds to the solar to hydrogen generation efficiency of 8.1%.

Plasmonic Switches and Sensors Based on PANI-Coated Gold Nanostructures

NASA Astrophysics Data System (ADS)

Jiang, Nina

Gold nanostructures have been received intense and growing attention due to their unique properties associated with localized surface plasmon resonance (LSPR). The frequency and strength of the LSPR are highly dependent on the dielectric properties of the surrounding environment around gold nanostructures. Such dependence offers the essential basis for the achievement of plasmonic switching and sensing. While the plasmonic response of gold nanostructures is tuned by changing their dielectric environment, the external stimuli inducing the changes in the dielectric environment will be read out through the plasmonic response of gold nanostructures. As a consequence, plasmonic sensors and switches can be engineered by integrating active media that can respond to external stimuli with gold nanostructures. In this thesis research, I have achieved the coating of polyaniline (PANI) ' a conductive polymer, on gold nanostructures, and exploited the application of the core/shell nanostructures in plasmonic switching and sensing. Large modulation of the longitudinal plasmon resonance of single gold nanorods is achieved by coating PANI shell onto gold nanorods to produce colloidal plasmonic switches. The dielectric properties of PANI shell can be tuned by changing the proton-doping levels, which allows for the modulation of the plasmonic response of gold nanorods. The coated nanorods are sparsely housed in a simple microfluidic chamber. HCl and NaOH solutions are alternately pumped through the chamber for the realization of proton doping and dedoping. The plasmonic switching behavior is examined by monitoring the single-particle scattering spectra under the proton-doped and dedoped state of PANI. The coated nanorods exhibit a remarkable switching performance, with the modulation depth and scattering peak shift reaching 10 dB and 100 nm, respectively. Electrodynamic simulations are employed to confirm the plasmon switching behavior. I have further investigated the modulation of a macroscale array of PANI-coated gold nanorods immobilized on glass slides, whose performance is as good as that of the individual PANI-coated gold nanorods. With much smaller amounts of materials, my core/shell nanorod arrays show peak extinction values and maximal modulation depths that are comparable to those of PANI films with micrometer-scale thicknesses. Switching coupled surface plasmon relative to uncoupled one affords the possibility to achieve the modulation over a wide spectral band and with wealthy plasmonic responses. Thus, I have studied the active control of plasmon coupling in homodimers and homotrimers of PANI-coated gold nanospheres (PGNSs). The dimers and trimers are obtained by reducing the surfactant concentration in the polymerization process of PANI. The reversible proton-doping of PANI enables the control of plasmon coupling to succeed. When the plasmon coupling of the dimers is switched, the wavelength shift of the strongest scattering peak shows an exponential increase with the decrease of the interparticle gap distance. A giant wavelength shift of 231 nm is observed for the dimer with a shell thickness of 10 nm and a gap distance of 0.5 nm. Electrodynamic calculations ascertain that the wavelength shift of the strongest scattering peak originates from the tuning of the dipolar bonding plasmon resonance mode in the dimers. The quadrupolar bonding plasmon resonance mode is turned on and off by switching the doped and undoped state of the dimers with gap distances of less than 3 nm. The active tuning of plasmon coupling is further demonstrated with the trimers of PGNSs, which is sensitive to their configurations. In the triangular configuration, larger vertex angles lead to larger wavelength shifts for the plasmonic tuning. Another strategy for controlling the dielectric properties of PANI shell around gold nanostructures is to change its oxidation level. The variation of the oxidation state of PANI leads to the plasmonic peak wavelength shift. Based on this principle, I have fabricated (gold nanosphere core)/(oxidized PANI shell) plasmonic sensors. The sensors have great potential for sensing chemical and biological molecules with reducibility. By using ascorbic acid (AA) as a target analyte, the plasmonic sensor presents high sensing capability. The limit of detection is 0.5 muM, and the linear response range is from 0.5 muM to 10 muM. The limit of detection for my plasmonic sensor is lower than the lowest limit for AA sensors based on liquid chromatography, electrophoresis, and electrochemical method. The sensing performance of my plasmonic sensors is expected to be further improved by optimizing the amount of (gold nanosphere core)/(oxidized PANI shell) structures, or employing other gold nanostructures with higher refractive index sensitivities. I believe that the colloidal (metal core)/(PANI shell) nanostructures pave the way for the fabrication of high-performance, low-cost plasmonic switches as well as for the preparation of advanced, programmable chromic materials for a wide variety of applications, such as smart windows, military anti-counterfeiting and camouflage, environmental sensors and indicators. (Abstract shortened by UMI.).

Biocompatible magnetic core-shell nanocomposites for engineered magnetic tissues

NASA Astrophysics Data System (ADS)

Rodriguez-Arco, Laura; Rodriguez, Ismael A.; Carriel, Victor; Bonhome-Espinosa, Ana B.; Campos, Fernando; Kuzhir, Pavel; Duran, Juan D. G.; Lopez-Lopez, Modesto T.

2016-04-01

The inclusion of magnetic nanoparticles into biopolymer matrixes enables the preparation of magnetic field-responsive engineered tissues. Here we describe a synthetic route to prepare biocompatible core-shell nanostructures consisting of a polymeric core and a magnetic shell, which are used for this purpose. We show that using a core-shell architecture is doubly advantageous. First, gravitational settling for core-shell nanocomposites is slower because of the reduction of the composite average density connected to the light polymer core. Second, the magnetic response of core-shell nanocomposites can be tuned by changing the thickness of the magnetic layer. The incorporation of the composites into biopolymer hydrogels containing cells results in magnetic field-responsive engineered tissues whose mechanical properties can be controlled by external magnetic forces. Indeed, we obtain a significant increase of the viscoelastic moduli of the engineered tissues when exposed to an external magnetic field. Because the composites are functionalized with polyethylene glycol, the prepared bio-artificial tissue-like constructs also display excellent ex vivo cell viability and proliferation. When implanted in vivo, the engineered tissues show good biocompatibility and outstanding interaction with the host tissue. Actually, they only cause a localized transitory inflammatory reaction at the implantation site, without any effect on other organs. Altogether, our results suggest that the inclusion of magnetic core-shell nanocomposites into biomaterials would enable tissue engineering of artificial substitutes whose mechanical properties could be tuned to match those of the potential target tissue. In a wider perspective, the good biocompatibility and magnetic behavior of the composites could be beneficial for many other applications.The inclusion of magnetic nanoparticles into biopolymer matrixes enables the preparation of magnetic field-responsive engineered tissues. Here we describe a synthetic route to prepare biocompatible core-shell nanostructures consisting of a polymeric core and a magnetic shell, which are used for this purpose. We show that using a core-shell architecture is doubly advantageous. First, gravitational settling for core-shell nanocomposites is slower because of the reduction of the composite average density connected to the light polymer core. Second, the magnetic response of core-shell nanocomposites can be tuned by changing the thickness of the magnetic layer. The incorporation of the composites into biopolymer hydrogels containing cells results in magnetic field-responsive engineered tissues whose mechanical properties can be controlled by external magnetic forces. Indeed, we obtain a significant increase of the viscoelastic moduli of the engineered tissues when exposed to an external magnetic field. Because the composites are functionalized with polyethylene glycol, the prepared bio-artificial tissue-like constructs also display excellent ex vivo cell viability and proliferation. When implanted in vivo, the engineered tissues show good biocompatibility and outstanding interaction with the host tissue. Actually, they only cause a localized transitory inflammatory reaction at the implantation site, without any effect on other organs. Altogether, our results suggest that the inclusion of magnetic core-shell nanocomposites into biomaterials would enable tissue engineering of artificial substitutes whose mechanical properties could be tuned to match those of the potential target tissue. In a wider perspective, the good biocompatibility and magnetic behavior of the composites could be beneficial for many other applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00224b

Synthesis and Catalytic Properties of Au Pd Nanoflowers

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

Xu, Jianguang; Wilson, Adria; Howe, Jane Y

2011-01-01

Reduction of Pd ions by hydroquinone in the presence of gold nanoparticles and polyvinylpyrrolidone resulted in the formation of nanoflowers with a Au core and Pd petals. Addition of HCl to the synthesis halted the reduction by hydroquinone and enabled the acquisition of snapshots of the nanoflowers at different stages of growth. TEM images of the reaction after 10 s show that the nanoflower morphology resulted from the homogeneous nucleation of Pd clusters in solution and their subsequent attachment to gold seeds coated with a thin (0.8 0.1 nm) shell of Pd. UV visible spectra also indicate Pd clusters formedmore » in the early stages of the reaction and disappeared as the nanoflowers grew. The speed at which this reaction can be halted is useful not only for producing a variety of bimetallic nanostructures with precisely controlled dimensions and morphologies but also for understanding the growth mechanism of these structures. The ability of the AuPd core shell structure to catalyze the Suzuki coupling reaction of iodobenzene to phenylboronic acid was probed and compared against the activity of Pd nanocubes and thin-shelled AuPd core shell nanoparticles. The results of this study suggest that Suzuki coupling was not affected by the surface structure or subsurface composition of the nanoparticles, but instead was primarily catalyzed by molecular Pd species that leached from the nanostructures.« less

Synthesis of Au-Pd Nanoflowers Through Nanocluster Assembly

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

Xu, Jianguang; Howe, Jane Y; Chi, Miaofang

2011-01-01

Reduction of Pd ions by hydroquinone in the presence of gold nanoparticles and polyvinylpyrrolidone resulted in the formation of nanoflowers with a Au core and Pd petals. Addition of HCl to the synthesis halted the reduction by hydroquinone and enabled the acquisition of snapshots of the nanoflowers at different stages of growth. TEM images of the reaction after 10 s show that the nanoflower morphology resulted from the homogeneous nucleation of Pd clusters in solution and their subsequent attachment to gold seeds coated with a thin (0.8 {+-} 0.1 nm) shell of Pd. UV-visible spectra also indicate Pd clusters formedmore » in the early stages of the reaction and disappeared as the nanoflowers grew. The speed at which this reaction can be halted is useful not only for producing a variety of bimetallic nanostructures with precisely controlled dimensions and morphologies but also for understanding the growth mechanism of these structures. The ability of the AuPd core-shell structure to catalyze the Suzuki coupling reaction of iodobenzene to phenylboronic acid was probed and compared against the activity of Pd nanocubes and thin-shelled AuPd core-shell nanoparticles. The results of this study suggest that Suzuki coupling was not affected by the surface structure or subsurface composition of the nanoparticles, but instead was primarily catalyzed by molecular Pd species that leached from the nanostructures.« less

Synthesis of core-shell iron nanoparticles via a new (novel) approach

NASA Astrophysics Data System (ADS)

Chaudhary, Rakesh P.; Koymen, Ali R.

2014-03-01

Carbon-encapsulated iron (Fe) nanoparticles were synthesized by a newly developed method in toluene. Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) of the as prepared sample reveal that core-shell nanostructures have been formed with Fe as core and graphitic carbon as shell. Fe nanoparticles with diameter 11nm to 102 nm are encapsulated by 6-8 nm thick graphitic carbon layers. There was no iron carbide formation observed between the Fe core and the graphitic shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. The magnetic hysteresis loop of the as synthesized powder at room temperature showed a saturation magnetization of 9 Am2 kg-1. After thermal treatment crystalline order of the samples improved and hence saturation magnetization increased to 24 Am2kg-1. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and Photothermal cancer therapy.

Localized surface plasmon mediated energy transfer in the vicinity of core-shell nanoparticle

NASA Astrophysics Data System (ADS)

Shishodia, Manmohan Singh; Juneja, Soniya

2016-05-01

Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. The theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.

Nanowebs and nanocables of silicon carbide

NASA Astrophysics Data System (ADS)

Shim, Hyun Woo; Huang, Hanchen

2007-08-01

This paper presents two novel hierarchical structures of SiC-SiO2 core-shell nanowires: (a) nanocables in the form of multi-core and single shell and (b) nanowebs in the form of intersecting nanowires and nanocables, augmented by variable amounts of SiO2 membranes. The two structures are controllable through variations of substrate temperature and source chemistry. The hierarchical nanostructures, together with the controllability, may offer superb mechanical properties in composite applications. Finally, the authors propose a model of nanowebs and nanocables formation, as a result of nanowires intersection and alignment.

Designing artificial enzymes from scratch: Experimental study and mesoscale simulation

NASA Astrophysics Data System (ADS)

Komarov, Pavel V.; Zaborina, Olga E.; Klimova, Tamara P.; Lozinsky, Vladimir I.; Khalatur, Pavel G.; Khokhlov, Alexey R.

2016-09-01

We present a new concept for designing biomimetic analogs of enzymatic proteins; these analogs are based on the synthetic protein-like copolymers. α-Chymotrypsin is used as a prototype of the artificial catalyst. Our experimental study shows that in the course of free radical copolymerization of hydrophobic and hydrophilic monomers the target globular nanostructures of a "core-shell" morphology appear in a selective solvent. Using a mesoscale computer simulation, we show that the protein-like globules can have a large number of catalytic centers located at the hydrophobic core/hydrophilic shell interface.

Controlled Release from Core-Shell Nanoporous Silica Particles for Corrosion Inhibition of Aluminum Alloys

DOE PAGES

Jiang, Xingmao; Jiang, Ying-Bing; Liu, Nanguo; ...

2011-01-01

Ceriumore » m (Ce) corrosion inhibitors were encapsulated into hexagonally ordered nanoporous silica particles via single-step aerosol-assisted self-assembly. The core/shell structured particles are effective for corrosion inhibition of aluminum alloy AA2024-T3. Numerical simulation proved that the core-shell nanostructure delays the release process. The effective diffusion coefficient elucidated from release data for monodisperse particles in water was 1.0 × 10 − 14  m 2 s for Ce 3+ compared to 2.5 × 10 − 13  m 2 s for NaCl. The pore size, pore surface chemistry, and the inhibitor solubility are crucial factors for the application. Microporous hydrophobic particles encapsulating a less soluble corrosion inhibitor are desirable for long-term corrosion inhibition.« less

Piezo-phototronic effect enhanced UV photodetector based on CuI/ZnO double-shell grown on flexible copper microwire.

PubMed

Liu, Jingyu; Zhang, Yang; Liu, Caihong; Peng, Mingzeng; Yu, Aifang; Kou, Jinzong; Liu, Wei; Zhai, Junyi; Liu, Juan

2016-12-01

In this work, we present a facile, low-cost, and effective approach to fabricate the UV photodetector with a CuI/ZnO double-shell nanostructure which was grown on common copper microwire. The enhanced performances of Cu/CuI/ZnO core/double-shell microwire photodetector resulted from the formation of heterojunction. Benefiting from the piezo-phototronic effect, the presentation of piezocharges can lower the barrier height and facilitate the charge transport across heterojunction. The photosensing abilities of the Cu/CuI/ZnO core/double-shell microwire detector are investigated under different UV light densities and strain conditions. We demonstrate the I-V characteristic of the as-prepared core/double-shell device; it is quite sensitive to applied strain, which indicates that the piezo-phototronic effect plays an essential role in facilitating charge carrier transport across the CuI/ZnO heterojunction, then the performance of the device is further boosted under external strain.

One-dimensional coaxial Sb and carbon fibers with enhanced electrochemical performance for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Zhu, Mengnan; Kong, Xiangzhong; Yang, Hulin; Zhu, Ting; Liang, Shuquan; Pan, Anqiang

2018-01-01

Antimony (Sb) has been intensively investigated as a promising anode material for sodium ion batteries (SIBs) in recent years. However, bulk Sb particles usually suffer from excessive volume expansion thus leading to dramatic capacity decay after cycling. To address this issue, Sb has been uniformly decorated on Polyacrylonitrile (PAN) derived carbon nanofibers (PCFs) via a simple chemical deposition strategy to form a one-dimensional (1D) core-shell nanostructure of Sb@PCFs. PCFs were first derived from electrospun PAN fibers and treated with subsequent calcination. The PCFs constructed an interwoven carbon network were later employed for Sb deposition, which can effectively alleviate aggregation or further cracking of Sb nanoparticles occurred in electrochemical kinetic process. The as-obtained Sb@PCFs nanocomposites demonstrated excellent cycling stability with good rate performances. This carefully designed core-shell nanostructure of antimony nanoparticles wrapped PCFs are responsible for good electrochemical Na-ion storage. Moreover, the 1D nanostructure manage to pave pathways for fast ions transfer during charge-discharge, which could extra contribute to the enhanced SIBs performances.

Facile synthesis of hierarchical Co3O4@MnO2 core-shell arrays on Ni foam for asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Huang, Ming; Zhang, Yuxin; Li, Fei; Zhang, Lili; Wen, Zhiyu; Liu, Qing

2014-04-01

Hierarchical Co3O4@MnO2 core-shell arrays on Ni foam have been fabricated by a facile hydrothermal approach and further investigated as the electrode for high-performance supercapacitors. Owing to the high conductivity of the well-defined mesoporous Co3O4 nanowire arrays in combination with the large surface area provided by the ultrathin MnO2 nanosheets, the unique designed Co3O4@MnO2 core-shell arrays on Ni foam have exhibited a high specific capacitance (560 F g-1 at a current density of 0.2 A g-1), good rate capability, and excellent cycling stability (95% capacitance retention after 5000 cycles). An asymmetric supercapacitor with Co3O4@MnO2 core-shell nanostructure as the positive electrode and activated microwave exfoliated graphite oxide activated graphene (MEGO) as the negative electrode yielded an energy density of 17.7 Wh kg-1 and a maximum power density of 158 kW kg-1. The rational design of the unique core-shell array architectures demonstrated in this work provides a new and facile approach to fabricate high-performance electrode for supercapacitors.

One-Pot Synthesis of Tunable Crystalline Ni3 S4 @Amorphous MoS2 Core/Shell Nanospheres for High-Performance Supercapacitors.

PubMed

Zhang, Yu; Sun, Wenping; Rui, Xianhong; Li, Bing; Tan, Hui Teng; Guo, Guilue; Madhavi, Srinivasan; Zong, Yun; Yan, Qingyu

2015-08-12

Transition metal sulfides gain much attention as electrode materials for supercapacitors due to their rich redox chemistry and high electrical conductivity. Designing hierarchical nanostructures is an efficient approach to fully utilize merits of each component. In this work, amorphous MoS(2) is firstly demonstrated to show specific capacitance 1.6 times as that of the crystalline counterpart. Then, crystalline core@amorphous shell (Ni(3)S(4)@MoS(2)) is prepared by a facile one-pot process. The diameter of the core and the thickness of the shell can be independently tuned. Taking advantages of flexible protection of amorphous shell and high capacitance of the conductive core, Ni(3)S(4) @amorphous MoS(2) nanospheres are tested as supercapacitor electrodes, which exhibit high specific capacitance of 1440.9 F g(-1) at 2 A g(-1) and a good capacitance retention of 90.7% after 3000 cycles at 10 A g(-1). This design of crystalline core@amorphous shell architecture may open up new strategies for synthesizing promising electrode materials for supercapacitors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnO/Er2O3 core-shell nanorod arrays: Synthesis, properties and growth mechanism

NASA Astrophysics Data System (ADS)

Yang, Jun; Wang, Yongqian; Jiang, Tingting; Li, Yinchang; Yang, Xiande

2015-01-01

In this study, we demonstrated large-scale ZnO/Er2O3 core-shell nanorod arrays, which were successfully synthesized by a facile and simple electrodeposition method. The effect of varying the amount of Er2O3 in the range from 0.2 g to 1.0 g on morphology of ZnO nanorod arrays has been thoroughly investigated. The results indicate that the growth pattern of all the ZnO/Er2O3 shell-core nanorod arrays were along c-axis and perpendicular to the substrate as before, even more vertical. Photoluminescence measurement was carried out and the PL peaks at 382 nm, 438 nm and 462 nm were observed, which are considered to be due to free excitons and donor-bound excitons, respectively. The ZnO/Er2O3 core-shell nanorods exhibited improved optical property, which can be attributed to the enhanced donor density by the covered Er2O3. Finally, a possible growth mechanism of the ZnO nanostructures is discussed. The electrochemical deposition of ZnO/Er2O3 core-shell nanorod arrays including two stages, namely nucleation and growth process.

Hybrid nanomaterial for stabilizing the antibiofilm activity of Eugenia carryophyllata essential oil.

PubMed

Grumezescu, Alexandru Mihai; Chifiriuc, Mariana Carmen; Saviuc, Crina; Grumezescu, Valentina; Hristu, Radu; Mihaiescu, Dan Eduard; Stanciu, George A; Andronescu, Ecaterina

2012-12-01

The aim of the present study was to demonstrate that Fe(3)O(4)/oleic acid core/shell nanostructures could be used as systems for stabilizing the Eugenia carryophyllata essential oil (EO) on catheter surface pellicles, in order to improve their resistance to fungal colonization. EO microwave assisted extraction was performed in a Neo-Clevenger (related) device and its chemical composition was settled by GC-MS analysis. Fe(3)O(4)/oleic acid-core/shell nanoparticles (NP) were obtained by a precipitation method under microwave condition. High resolution transmission electron microscopy (HR-TEM) was used as a primary characterization method. The NPs were processed to achieve a core/shell/EO coated-shell nanosystem further used for coating the inner surface of central venous catheter samples. The tested fungal strains have been recently isolated from different clinical specimens. The biofilm architecture was assessed by confocal laser scanning microscopy (CLSM). Our results claim the usage of hybrid nanomaterial (core/shell/coated-shell) for the stabilization of E. carryophyllata EO, which prevented or inhibited the fungal biofilm development on the functionalized catheter, highlighting the opportunity of using these nanosystems to obtain improved, anti-biofilm coatings for biomedical applications.

Synthesis of suitable SiO2 nano particles as the core in core-shell nanostructured materials.

PubMed

Ghahari, Mehdi; Aghababazadeh, Roya; Ebadzadeh, Touradj; Mirhabibi, Alireza; Brydson, Rik; Fabbri, Paola; Najafi, Farhod

2011-06-01

The effect of surfactant on the luminescent intensity of SiO2 @Y2O3:Eu3+ particles with a core shell structure is described. Core-shell particles are used in phosphor materials and employing spherical particles with a narrow size distribution is vital for the enhancement of luminescent properties. Three kinds of different surfactants were used to synthesis SiO2 nano particles via a sol gel process. The results demonstrated that comb polycarboxylic acid surfactant had a significant influence on the morphology and particle size distribution. Somehow, particles with 100 nm size and narrow size distribution were produced. These particles had relatively uniform packing, unlike particles produced with other surfactants or without surfactant which had irregular assembly. The photoluminescence intensity of SiO2 @Y2O3:Eu3+ particles that was synthesized by comb polycarboxylic acid surfactant was higher than those which were produced without surfactant.

Layered manganese oxides-decorated and nickel foam-supported carbon nanotubes as advanced binder-free supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Huang, Ming; Mi, Rui; Liu, Hao; Li, Fei; Zhao, Xiao Li; Zhang, Wei; He, Shi Xuan; Zhang, Yu Xin

2014-12-01

Three-dimensional carbon nanotubes@MnO2 core-shell nanostructures grown on Ni foam for binder-free capacitor electrodes have been fabricated by a floating catalyst chemical vapor deposition process and a facile hydrothermal approach. Ultrathin layered MnO2 nanosheets are uniformly coated on the surface of the carbon nanotubes (CNTs), directly grown on Ni foam. This unique well-designed binder-free electrode exhibits a high specific capacitance (325.5 F g-1 at a current density of 0.3 A g-1), good rate capability (70.7% retention), and excellent cycling stability (90.5% capacitance retention after 5000 cycles), due to the high conductivity of the close contact between CNTs and Ni foam, as well as the moderate specific surface area of the CNTs@MnO2 core-shell nanostructures. The developed synthetic strategy may provide design guidelines for constructing advanced binder-free supercapacitors electrode.

Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

PubMed

Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

2012-11-01

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

Generation of reactive oxygen species and charge carriers in plasmonic photocatalytic Au@TiO2 nanostructures with enhanced activity.

PubMed

He, Weiwei; Cai, Junhui; Jiang, Xiumei; Yin, Jun-Jie; Meng, Qingbo

2018-06-13

The combination of semiconductor and plasmonic nanostructures, endowed with high efficiency light harvesting and surface plasmon confinement, has been a promising way for efficient utilization of solar energy. Although the surface plasmon resonance (SPR) assisted photocatalysis has been extensively studied, the photochemical mechanism, e.g. the effect of SPR on the generation of reactive oxygen species and charge carriers, is not well understood. In this study, we take Au@TiO2 nanostructures as a plasmonic photocatalyst to address this critical issue. The Au@TiO2 core/shell nanostructures with tunable SPR property were synthesized by the templating method with post annealing thermal treatment. It was found that Au@TiO2 nanostructures exhibit enhanced photocatalytic activity in either sunlight or visible light (λ > 420 nm). Electron spin resonance spectroscopy with spin trapping and spin labeling was used to investigate the enhancing effect of Au@TiO2 on the photo-induced reactive oxygen species and charge carriers. The formation of Au@TiO2 core/shell nanostructures resulted in a dramatic increase in light-induced generation of hydroxyl radicals, singlet oxygen, holes and electrons, as compared with TiO2 alone. This enhancement under visible light (λ > 420 nm) irradiation may be dominated by SPR induced local electrical field enhancement, while the enhancement under sunlight irradiation is dominated by the higher electron transfer from TiO2 to Au. These results unveiled that the superior photocatalytic activity of Au@TiO2 nanostructures correlates with enhanced generation of reactive oxygen species and charge carriers.

A novel "modularized" optical sensor for pH monitoring in biological matrixes.

PubMed

Liu, Xun; Zhang, Shang-Qing; Wei, Xing; Yang, Ting; Chen, Ming-Li; Wang, Jian-Hua

2018-06-30

A novel core-shell structure optical pH sensor is developed with upconversion nanoparticles (UCNPs) serving as the core and silica as the shell, followed by grafting bovineserumalbumin (BSA) as another shell via glutaraldehyde cross-linking. The obtained core-shell-shell structure is shortly termed as UCNPs@SiO 2 @BSA, and its surface provides a platform for loading various pH sensitive dyes, which are alike "modules" to make it feasible for measuring pHs within different pH ranges by simply regulating the type of dyes. Generally, a single pH sensitive dye is adopted to respond within a certain pH range. This study employs bromothymol blue (BTB) and rhodamine B (RhB) to facilitate their responses to pH variations within two ranges, i.e., pH 5.99-8.09 and pH 4.98-6.40, respectively, with detection by ratio-fluorescence protocol. The core-shell-shell structure offers superior sensitivity, which is tens of times more sensitive than those achieved by ratio-fluorescence approaches based on various nanostructures, and favorable stability is achieved in high ionic strength medium. In addition, this sensor exhibits superior photostability under continuous excitation at 980 nm. Thanks to the near infrared excitation in the core-shell-shell structure, it effectively avoids the self-fluorescence from biological samples and thus facilitates accurate sensing of pH in various biological sample matrixes. Copyright © 2018 Elsevier B.V. All rights reserved.

Double anisotropic electrically conductive flexible Janus-typed membranes.

PubMed

Li, Xiaobing; Ma, Qianli; Tian, Jiao; Xi, Xue; Li, Dan; Dong, Xiangting; Yu, Wensheng; Wang, Xinlu; Wang, Jinxian; Liu, Guixia

2017-12-07

Novel type III anisotropic conductive films (ACFs), namely flexible Janus-typed membranes, were proposed, designed and fabricated for the first time. Flexible Janus-typed membranes composed of ordered Janus nanobelts were constructed by electrospinning, which simultaneously possess fluorescence and double electrically conductive anisotropy. For the fabrication of the Janus-typed membrane, Janus nanobelts comprising a conductive side and an insulative-fluorescent side were primarily fabricated, and then the Janus nanobelts are arranged into parallel arrays using an aluminum rotary drum as the collector to obtain a single anisotropically conductive film. Subsequently, a secondary electrospinning process was applied to the as-prepared single anisotropically conductive films to acquire the final Janus-typed membrane. For this Janus-typed membrane, namely its left-to-right structure, anisotropic electrical conduction synchronously exists on both sides, and furthermore, the two electrically conductive directions are perpendicular. By modulating the amount of Eu(BA) 3 phen complex and conducting polyaniline (PANI), the characteristics and intensity of the fluorescence-electricity dual-function in the membrane can be tuned. The high integration of this peculiar Janus-typed membrane with simultaneous double electrically conductive anisotropy-fluorescent dual-functionality is successfully realized in this study. This design philosophy and preparative technique will provide support for the design and construction of new types of special nanostructures with multi-functionality.

Sonochemical Synthesis of Zinc Oxide Nanostructures for Sensing and Energy Harvesting

NASA Astrophysics Data System (ADS)

Vabbina, Phani Kiran

Semiconductor nanostructures have attracted considerable research interest due to their unique physical and chemical properties at nanoscale which open new frontiers for applications in electronics and sensing. Zinc oxide nanostructures with a wide range of applications, especially in optoelectronic devices and bio sensing, have been the focus of research over the past few decades. However ZnO nanostructures have failed to penetrate the market as they were expected to, a few years ago. The two main reasons widely recognized as bottleneck for ZnO nanostructures are (1) Synthesis technique which is fast, economical, and environmentally benign which would allow the growth on arbitrary substrates and (2) Difficulty in producing stable p-type doping. The main objective of this research work is to address these two bottlenecks and find a solution that is inexpensive, environmentally benign and CMOS compatible. To achieve this, we developed a Sonochemical method to synthesize 1D ZnO Nanorods, core-shell nanorods, 2D nanowalls and nanoflakes on arbitrary substrates which is a rapid, inexpensive, CMOS compatible and environmentally benign method and allows us to grow ZnO nanostructures on any arbitrary substrate at ambient conditions while most other popular methods used are either very slow or involve extreme conditions such as high temperatures and low pressure. A stable, reproducible p-type doping in ZnO is one of the most sought out application in the field of optoelectronics. Here in this project, we doped ZnO nanostructures using sonochemical method to achieve a stable and reproducible doping in ZnO. We have fabricated a homogeneous ZnO radial p-n junction by growing a p-type shell around an n-type core in a controlled way using the sonochemical synthesis method to realize ZnO homogeneous core-shell radial p-n junction for UV detection. ZnO has a wide range of applications from sensing to energy harvesting. In this work, we demonstrate the successful fabrication of an electrochemical immunosensor using ZnO nanoflakes to detect Cortisol and compare their performance with that of ZnO nanorods. We have explored the use of ZnO nanorods in energy harvesting in the form of Dye Sensitized Solar Cells (DSSC) and Perovskite Solar Cells.

The structural, magnetic and optical properties of TMn@(ZnO)42 (TM = Fe, Co and Ni) hetero-nanostructure.

PubMed

Hu, Yaowen; Ji, Chuting; Wang, Xiaoxu; Huo, Jinrong; Liu, Qing; Song, Yipu

2017-11-28

The magnetic transition-metal (TM) @ oxide nanoparticles have been of great interest due to their wide range of applications, from medical sensors in magnetic resonance imaging to photo-catalysis. Although several studies on small clusters of TM@oxide have been reported, the understanding of the physical electronic properties of TM n @(ZnO) 42 is far from sufficient. In this work, the electronic, magnetic and optical properties of TM n @(ZnO) 42 (TM = Fe, Co and Ni) hetero-nanostructure are investigated using the density functional theory (DFT). It has been found that the core-shell nanostructure Fe 13 @(ZnO) 42 , Co 15 @(ZnO) 42 and Ni 15 @(ZnO) 42 are the most stable structures. Moreover, it is also predicted that the variation of the magnetic moment and magnetism of Fe, Co and Ni in TM n @ZnO 42 hetero-nanostructure mainly stems from effective hybridization between core TM-3d orbitals and shell O-2p orbitals, and a magnetic moment inversion for Fe 15 @(ZnO) 42 is investigated. Finally, optical properties studied by calculations show a red shift phenomenon in the absorption spectrum compared with the case of (ZnO) 48 .

Mechanism of ultrasonic energy-assisted formation of V-, Y-shaped nano-structures in conjugated polymers.

PubMed

Majumdar, D; Maiti, R P; Basu, S; Saha, S K

2009-12-01

Recently, hydrocarbon-nanostructures from organic solvent using ultrasonic energy were reported. However, their formation-dynamics remained unexplored. Here, we describe a new technique to synthesize controlled nanostructures (V-, Y-shape) from nanorods of conducting polyaniline applying ultrasonic energy. To characterize the conducting state (emaraldine) of these polyaniline nanorods, electrical measurements have been carried out from which it is seen that there is a crossover from metallic to semiconductor as temperature increases. The observed crossover has been explained by the core-shell structure of the nanorods with core resistivity much higher than the shell resistivity. The nonlinear current-voltage behavior is attributed to the formation of alternate ordered/disordered chain segments along the length of the nanorods. We also propose a model to explore the mechanism of formation of these V-, Y-shaped nanostructures. It is believed that bubble-formation occurs in liquid due to ultrasonic vibration; and asymmetry in the bubble is created when formed near the solid surface leading to jet formation. Liquid jets of collapsing bubble move with incredible velocity (400 km/h); collide with the nanorod to cause fragmentations followed by V-, Y-shaped structure formation when the imparted kinetic energy of jets is comparable with elastic energy of fragments.

Modes of interaction between nanostructured metal and a conducting mirror as a function of separation and incident polarization

NASA Astrophysics Data System (ADS)

Bonnie, F.; Arnold, M. D.; Smith, G. B.; Gentle, A. R.

2013-09-01

The optical resonances that occur in nanostructured metal layers are modulated in thin film stacks if the nanostructured layer is separated from a reflecting conducting layer by various thicknesses of thin dielectric. We have measured and modeled the optical response of interacting silver layers, with alumina spacer thickness ranging from a few nm to 50 nm, for s- and p-polarized incident light, and a range of incident angles. Standard thin film models, including standard effective medium models for the nanostructured layer, will break down for spacer thickness below a critical threshold. For example, with polarisation in the film plane and some nano-islands, it may occur at around 10 nm depending on spacer refractive index. Of particular interest here are novel effects observed with the onset of percolation in the nanolayer. Hot spot effects can be modified by nearby mirrors. Other modes to consider include (a) a two-particle mode involving a particle and its mirror image (b) A Fano resonance from hybridisation of localized and de-localised plasmon modes (c) a Babinet's core-(partial) shell particle with metal core-dielectric shell in metal (d) spacing dependent phase modulation (e) the impact of field gradients induced by the mirror at the nano-layer.

Effect of Surface Functionalization on Structural and Optical Properties of Luminescent LaF₃:Sm Nanoparticles.

PubMed

Ansari, Anees A

2018-02-01

Samarium (Sm3+)-doped LaF3 nanoparticles (NPs) subsequently encapsulated with inert crystalline LaF3 and amorphous silica layers were prepared by polyol and sol-gel chemical process, respectively. These surface modified core/shell/SiO2-nanostructured were characterized by X-ray diffraction (XRD), FE-transmission electron microscopy (TEM), thermal analysis, FTIR, UV/Vis absorption, bang gap energy and photoluminescence spectroscopy. The FETEM, EDX and FTIR spectral studies clearly revealed that the silica layer has been formed surrounding the core-NPs. Comparative spectral analysis indicated that core/shell/SiO2-NPs revealed high solubility in aqueous and non-aqueous solvents. The decrease in band gap energy after surface growth of an inert LaF3 and silica shells is directly correlated to the increase in grain size. On comparing the emission intensity, a significant enhancement was observed after inert layer coating, whereas, it suppress after silica encapsulation due to the non-radiative transitions. The increase luminescent intensity after inert shell growth indicates that a significant amount of non-radiative centers existing on the surface of core/shell nanoparticles can be eliminated by the shielding effect of LaF3 shells. These observed results indicate that the as-prepared core/shell/SiO2-NPs could be highly useful in broad photonic based applications such as optical sensor/optical bio-probe and light emitting diode.

ZnO@MnO2 Core-Shell Nanofiber Cathodes for High Performance Asymmetric Supercapacitors.

PubMed

Radhamani, A V; Shareef, K M; Rao, M S Ramachandra

2016-11-09

Asymmetric supercapacitors (ASCs) with aqueous electrolyte medium have recently become the focus of increasing research. For high performance ASCs, selection of cathode materials play a crucial role, and core-shell nanostructures are found to be a good choice. We successfully synthesized, ZnO@MnO 2 core-shell nanofibers (NFs) by modification of high-aspect-ratio-electrospun ZnO NFs hydrothermally with MnO 2 nanoflakes. High conductivity of the ZnO NFs and the exceptionally high pseudocapacitive nature of MnO 2 nanoflakes coating delivered a specific capacitance of 907 Fg -1 at 0.6 Ag -1 for the core-shell NFs. A simple and cost-effective ASC construction was demonstrated with ZnO@MnO 2 NFs as a battery-type cathode material and a commercial-quality activated carbon as a capacitor-type anode material. The fabricated device functioned very well in a voltage window of 0-2.0 V, and a red-LED was illuminated using a single-celled fabricated ASC device. It was found to deliver a maximum energy density of 17 Whkg -1 and a power density of 6.5 kWkg -1 with capacitance retention of 94% and Coulombic efficiency of 100%. The novel architecture of the ZnO@MnO 2 core-shell nanofibrous material implies the importance of using simple design of fiber-based electrode material by mere changes of core and shell counterparts.

Designing of luminescent GdPO4:Eu@LaPO4@SiO2 core/shell nanorods: Synthesis, structural and luminescence properties

NASA Astrophysics Data System (ADS)

Ansari, Anees A.; Labis, Joselito P.; Aslam Manthrammel, M.

2017-09-01

GdPO4:Eu3+ (core) and GdPO4:Eu@LaPO4 (core/shell) nanorods (NRs) were successfully prepared by urea based co-precipitation process at ambient conditions which was followed by coating with amorphous silica shell via the sol-gel chemical route. The role of surface coating on the crystal structure, crystallinity, morphology, solubility, surface chemistry and luminescence properties were well investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Fourier Transform Infrared (FTIR), UV-Vis, and photoluminescence spectroscopy. XRD pattern revealed highly purified, well-crystalline, single phase-hexagonal-rhabdophane structure of GdPO4 crystal. The TEM micrographs exhibited highly crystalline and narrow size distributed rod-shaped GdPO4:Eu3+ nanostructures with average width 14-16 nm and typical length 190-220 nm. FTIR spectra revealed characteristic infrared absorption bands of amorphous silica. High absorbance in a visible region of silica modified core/shell/Si NRs in aqueous environment suggests the high solubility along with colloidal stability. The photoluminescence properties were remarkably enhanced after growth of undoped LaPO4 layers due to the reduction of nonradiative transition rate. The advantages of presented high emission intensity and high solubility of core/shell and core/shell/Si NRs indicated the potential applications in monitoring biological events.

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Wu, Wei; Zhang, Shaofeng; Ren, Feng; Xiao, Xiangheng; Zhou, Juan; Jiang, Changzhong

2011-11-01

Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces.Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces. Electronic supplementary information (ESI) available: TEM and HRTEM images of hematite seeds and iron oxide/SnO2 (12 h and 36 h). See DOI: 10.1039/c1nr10728c

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity.

PubMed

Wu, Wei; Zhang, Shaofeng; Ren, Feng; Xiao, Xiangheng; Zhou, Juan; Jiang, Changzhong

2011-11-01

Iron oxide/SnO(2) magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO(2) quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO(2) core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe(2)O(3) seeds and commercial SnO(2) products, mainly owing to the effective electron hole separation at the iron oxides/SnO(2) interfaces.

Tandem Core–Shell Si–Ta 3N 5 Photoanodes for Photoelectrochemical Water Splitting

DOE PAGES

Narkeviciute, Ieva; Chakthranont, Pongkarn; Mackus, Adriaan J. M.; ...

2016-11-22

Here, nanostructured core–shell Si–Ta 3N 5 photoanodes were designed and synthesized to overcome charge transport limitations of Ta 3N 5 for photoelectrochemical water splitting. The core–shell devices were fabricated by atomic layer deposition of amorphous Ta 2O 5 onto nanostructured Si and subsequent nitridation to crystalline Ta 3N 5. Nanostructuring with a thin shell of Ta 3N 5 results in a 10-fold improvement in photocurrent compared to a planar device of the same thickness. In examining thickness dependence of the Ta 3N 5 shell from 10 to 70 nm, superior photocurrent and absorbed-photon-to-current efficiencies are obtained from the thinner Tamore » 3N 5 shells, indicating minority carrier diffusion lengths on the order of tens of nanometers. The fabrication of a heterostructure based on a semiconducting, n-type Si core produced a tandem photoanode with a photocurrent onset shifted to lower potentials by 200 mV. CoTiO x and NiO x water oxidation cocatalysts were deposited onto the Si–Ta 3N 5 to yield active photoanodes that with NiO x retained 50–60% of their maximum photocurrent after 24 h chronoamperometry experiments and are thus among the most stable Ta 3N 5 photoanodes reported to date.« less

Synthesis of hierarchical Co3O4@NiO core-shell nanotubes with a synergistic catalytic activity for peroxidase mimicking and colorimetric detection of dopamine.

PubMed

Zhu, Yun; Yang, Zezhou; Chi, Maoqiang; Li, Meixuan; Wang, Ce; Lu, Xiaofeng

2018-05-01

Fabrication of core-shell nanostructured catalyst is a promising way for tuning its catalytic performance due to the highly active interface and rich redox properties. In this work, hierarchical Co 3 O 4 @NiO core-shell nanotubes are fabricated by the deposition of NiO shells via a chemical bath treatment using electrospun Co-C composite nanofibers as templates, followed by a calcination process in air. The as-prepared Co 3 O 4 @NiO core-shell nanotubes exhibit a uniform and novel hollow structure with Co 3 O 4 nanoparticles attached to the inner wall of NiO nanotubes and excellent catalytic activity toward the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H 2 O 2 . Due to the synergistic effect, the peroxidase-like activity of the Co 3 O 4 @NiO core-shell nanotubes is much higher than that of individual Co 3 O 4 and NiO components. Owing to the superior peroxidase-like activity, a simple and rapid colorimetric approach for the detection of dopamine with a detection limit of 1.21µM and excellent selectivity has been developed. It is anticipated that the prepared Co 3 O 4 @NiO core-shell nanotubes are promising materials applied for biomedical analysis and environmental monitoring. Copyright © 2018 Elsevier B.V. All rights reserved.

Core-shell nanophosphor architecture: toward efficient energy transport in inorganic/organic hybrid solar cells.

PubMed

Li, Qinghua; Yuan, Yongbiao; Chen, Zihan; Jin, Xiao; Wei, Tai-huei; Li, Yue; Qin, Yuancheng; Sun, Weifu

2014-08-13

In this work, a core-shell nanostructure of samarium phosphates encapsulated into a Eu(3+)-doped silica shell has been successfully fabricated, which has been confirmed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution TEM. Moreover, we report the energy transfer process from the Sm(3+) to emitters Eu(3+) that widens the light absorption range of the hybrid solar cells (HSCs) and the strong enhancement of the electron-transport of TiO2/poly(3-hexylthiophene) (P3HT) bulk heterojunction (BHJ) HSCs by introducing the unique core-shell nanoarchitecture. Furthermore, by applying femtosecond transient absorption spectroscopy, we successfully obtain the electron transport lifetimes of BHJ systems with or without incorporating the core-shell nanophosphors (NPs). Concrete evidence has been provided that the doping of core-shell NPs improves the efficiency of electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 16.7 ps, i.e., more than 44% faster than pure TiO2 acceptor. Consequently, a notable power conversion efficiency of 3.30% for SmPO4@Eu(3+):SiO2 blended TiO2/P3HT HSCs is achieved at 5 wt % as compared to 1.98% of pure TiO2/P3HT HSCs. This work indicates that the core-shell NPs can efficiently broaden the absorption region, facilitate electron-transport of BHJ, and enhance photovoltaic performance of inorganic/organic HSCs.

Au/CdS Hybrid Nanoparticles in Block Copolymer Micellar Shells.

PubMed

Koh, Haeng-Deog; Changez, Mohammad; Lee, Jae-Suk

2010-10-18

A polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) micellar structure with a P2VP core containing 5 nm CdS nanoparticles (NPs) and a PS shell formed in toluene that is a good solvent for PS block undergoes the core-shell inversion by excess addition of methanol that is a good solvent for P2VP block. It leads to the formation of micellar shell-embedded CdS NPs in the methanol major phase. The spontaneous crystalline growth of Au NPs on the CdS surfaces positioned at micellar shells without a further reduction process is newly demonstrated. The nanostructure of Au/CdS/PS-b-P2VP hybrid NPs is confirmed by transmission electron microscopy, energy-dispersive X-ray, and UV-Vis absorption. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast excited-state dynamics in shape- and composition-controlled gold–silver bimetallic nanostructures

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

Zarick, Holly F.; Boulesbaa, Abdelaziz; Talbert, Eric M.

In this paper, we have examined the ultrafast dynamics of shape- and composition-controlled bimetallic Au/Ag core/shell nanostructures with transient absorption spectroscopy (TAS) as a function of Ag layer thickness (0–15 nm) and pump excitation fluence (50–500 nJ/pulse). Our synthesis approach generated both bimetallic nanocubes and nanopyramids with distinct dipolar plasmon resonances and plasmon dephasing behavior at the resonance. Lifetimes obtained from TAS at low powers (50 nJ/pulse) demonstrated minimal dependence on the Ag layer thickness, whereas at high power (500 nJ/pulse) a rise in electron–phonon coupling lifetime (τ 1) was observed with increasing Ag shell thickness for both nanocubes andmore » nanopyramids. This is attributable to the stronger absorption of the 400 nm pump pulse with higher Ag content, which induced higher electron temperatures. The phonon–phonon scattering lifetime (τ 2) also rises with increasing Ag layer, contributed both by the increasing size of the Au/Ag nanostructures as well as by surface chemistry effects. Further, we observed that even the thinnest, 2 nm, Ag shell strongly impacts both τ 1 and τ 2 at high power despite minimal change in overall size, indicating that the nanostructure composition also strongly impacts the thermalization temperature following absorption of 400 nm light. We also observed a shape-dependent trend at high power, where τ 2 increased for the nanopyramids with increasing Ag shell thickness and nanostructure size, but bimetallic nanocubes demonstrated an unexpected decrease in τ 2 for the thickest, 15 nm, Ag shell. This was attributed to the larger number of corners and edges in the nanocubes relative to the nanopyramids.« less

High-temperature-stable and regenerable catalysts: platinum nanoparticles in aligned mesoporous silica wells.

PubMed

Xiao, Chaoxian; Maligal-Ganesh, Raghu V; Li, Tao; Qi, Zhiyuan; Guo, Zhiyong; Brashler, Kyle T; Goes, Shannon; Li, Xinle; Goh, Tian Wei; Winans, Randall E; Huang, Wenyu

2013-10-01

We report the synthesis, structural characterization, thermal stability study, and regeneration of nanostructured catalysts made of 2.9 nm Pt nanoparticles sandwiched between a 180 nm SiO2 core and a mesoporous SiO2 shell. The SiO2 shell consists of 2.5 nm channels that are aligned perpendicular to the surface of the SiO2 core. The nanostructure mimics Pt nanoparticles that sit in mesoporous SiO2 wells (Pt@MSWs). By using synchrotron-based small-angle X-ray scattering, we were able to prove the ordered structure of the aligned mesoporous shell. By using high-temperature cyclohexane dehydrogenation as a model reaction, we found that the Pt@MSWs of different well depths showed stable activity at 500 °C after the induction period. Conversely, a control catalyst, SiO2 -sphere-supported Pt nanoparticles without a mesoporous SiO2 shell (Pt/SiO2 ), was deactivated. We deliberately deactivated the Pt@MSWs catalyst with a 50 nm deep well by using carbon deposition induced by a low H2 /cyclohexane ratio. The deactivated Pt@MSWs catalyst was regenerated by calcination at 500 °C with 20 % O2 balanced with He. After the regeneration treatments, the activity of the Pt@MSWs catalyst was fully restored. Our results suggest that the nanostructured catalysts-Pt nanoparticles confined inside mesoporous SiO2 wells-are stable and regenerable for treatments and reactions that require high temperatures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversibility of Pt-Skin and Pt-Skeleton Nanostructures in Acidic Media.

PubMed

Durst, Julien; Lopez-Haro, Miguel; Dubau, Laetitia; Chatenet, Marian; Soldo-Olivier, Yvonne; Guétaz, Laure; Bayle-Guillemaud, Pascale; Maillard, Frédéric

2014-02-06

Following a well-defined series of acid and heat treatments on a benchmark Pt3Co/C sample, three different nanostructures of interest for the electrocatalysis of the oxygen reduction reaction were tailored. These nanostructures could be sorted into the "Pt-skin" structure, made of one pure Pt overlayer, and the "Pt-skeleton" structure, made of 2-3 Pt overlayers surrounding the Pt-Co alloy core. Using a unique combination of high-resolution aberration-corrected STEM-EELS, XRD, EXAFS, and XANES measurements, we provide atomically resolved pictures of these different nanostructures, including measurement of the Pt-shell thickness forming in acidic media and the resulting changes of the bulk and core chemical composition. It is shown that the Pt-skin is reverted toward the Pt-skeleton upon contact with acid electrolyte. This change in structure causes strong variations of the chemical composition.

Novel multi-layered 1-D nanostructure exhibiting the theoretical capacity of silicon for a super-enhanced lithium-ion battery

NASA Astrophysics Data System (ADS)

Lee, Byoung-Sun; Yang, Ho-Sung; Jung, Heechul; Jeon, Seung-Yeol; Jung, Changhoon; Kim, Sang-Won; Bae, Jihyun; Choong, Chwee-Lin; Im, Jungkyun; Chung, U.-In; Park, Jong-Jin; Yu, Woong-Ryeol

2014-05-01

Silicon/carbon (Si/C) nanocomposites have recently received much attention as Li-ion battery negative electrodes due to their mutual synergetic effects in capacity and mechanical integrity. The contribution of Si to the total capacity of the Si/C nanocomposites determines their structural efficiency. Herein, we report on a multi-layered, one-dimensional nanostructure that exhibits the theoretical specific capacity of Si in the nanocomposite. Concentrically tri-layered, compartmentalized, C-core/Si-medium/C-shell nanofibers were fabricated by triple coaxial electrospinning. The pulverization of Si was accommodated inside the C-shell, whereas the conductive pathway of the Li-ions and electrons was provided by the C-core, which was proven by ex situ Raman spectroscopy. The compartmentalized Si in between the C-core and C-shell led to excellent specific capacity at a high current rate (>820 mA h g-1 at 12000 mA g-1) and the realization of the theoretical specific capacity of the Li15Si4 phase of Si nanoparticles (3627 mA h g-1). The electrochemical characterization and inductively coupled plasma-atomic emission spectrometry provided direct evidence of full participation of Si in the electrochemical reactions.Silicon/carbon (Si/C) nanocomposites have recently received much attention as Li-ion battery negative electrodes due to their mutual synergetic effects in capacity and mechanical integrity. The contribution of Si to the total capacity of the Si/C nanocomposites determines their structural efficiency. Herein, we report on a multi-layered, one-dimensional nanostructure that exhibits the theoretical specific capacity of Si in the nanocomposite. Concentrically tri-layered, compartmentalized, C-core/Si-medium/C-shell nanofibers were fabricated by triple coaxial electrospinning. The pulverization of Si was accommodated inside the C-shell, whereas the conductive pathway of the Li-ions and electrons was provided by the C-core, which was proven by ex situ Raman spectroscopy. The compartmentalized Si in between the C-core and C-shell led to excellent specific capacity at a high current rate (>820 mA h g-1 at 12000 mA g-1) and the realization of the theoretical specific capacity of the Li15Si4 phase of Si nanoparticles (3627 mA h g-1). The electrochemical characterization and inductively coupled plasma-atomic emission spectrometry provided direct evidence of full participation of Si in the electrochemical reactions. Electronic supplementary information (ESI) available: Simulation details, quantitative measurement of Si content in the nanofibers and ex situ Raman characterization sample preparation procedures are demonstrated. See DOI: 10.1039/c4nr00318g

Tunable luminescent emission characterization of type-I and type-II systems in CdS-ZnSe core-shell nanoparticles: Raman and photoluminescence study.

PubMed

Ca, Nguyen Xuan; Lien, V T K; Nghia, N X; Chi, T T K; Phan, The-Long

2015-11-06

We used wet chemical methods to synthesize core-shell nanocrystalline samples CdS(d)/ZnSe N , where d = 3-6 nm and N = 1-5 are the size of CdS cores and the number of monolayers grown on the cores, respectively. By annealing typical CdS(d)/ZnSe N samples (with d = 3 and 6 nm and N = 2) at 300 °C for various times t an = 10-600 min, we created an intermediate layer composed of Zn1-x Cd x Se and Cd1-x Zn x S alloys with various thicknesses. The formation of core-shell structures and intermediate layers was monitored by Raman scattering and UV-vis absorption spectrometers. Careful photoluminescence studies revealed that the as-prepared CdS(d)/ZnSe N samples with d = 5 nm and N = 2-4, and the annealed samples CdS(3 nm)/ZnSe2 with t an ≤ 60 min and CdS(6 nm)/ZnSe2 with t an ≤ 180 min, show the emission characteristics of type-II systems. Meanwhile, the other samples show the emission characteristics of type-I systems. These results prove that the partial separation of photoexcited carriers between the core and shell is dependent strongly on the engineered core-shell nanostructures, meaning the sizes of the core, shell, and intermediate layers. With the tunable luminescence properties, CdS-ZnSe-based core-shell materials are considered as promising candidates for multiple-exciton generation and single-photon sources.

Melting and solidification behavior of Cu/Al and Ti/Al bimetallic core/shell nanoparticles during additive manufacturing by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Rahmani, Farzin; Jeon, Jungmin; Jiang, Shan; Nouranian, Sasan

2018-05-01

Molecular dynamics (MD) simulations were performed to investigate the role of core volume fraction and number of fusing nanoparticles (NPs) on the melting and solidification of Cu/Al and Ti/Al bimetallic core/shell NPs during a superfast heating and slow cooling process, roughly mimicking the conditions of selective laser melting (SLM). One recent trend in the SLM process is the rapid prototyping of nanoscopically heterogeneous alloys, wherein the precious core metal maintains its particulate nature in the final manufactured part. With this potential application in focus, the current work reveals the fundamental role of the interface in the two-stage melting of the core/shell alloy NPs. For a two-NP system, the melting zone gets broader as the core volume fraction increases. This effect is more pronounced for the Ti/Al system than the Cu/Al system because of a larger difference between the melting temperatures of the shell and core metals in the former than the latter. In a larger six-NP system (more nanoscopically heterogeneous), the melting and solidification temperatures of the shell Al roughly coincide, irrespective of the heating or cooling rate, implying that in the SLM process, the part manufacturing time can be reduced due to solidification taking place at higher temperatures. The nanostructure evolution during the cooling of six-NP systems is further investigated. [Figure not available: see fulltext.

High-quality metal oxide core/shell nanowire arrays on conductive substrates for electrochemical energy storage.

PubMed

Xia, Xinhui; Tu, Jiangping; Zhang, Yongqi; Wang, Xiuli; Gu, Changdong; Zhao, Xin-Bing; Fan, Hong Jin

2012-06-26

The high performance of a pseudocapacitor electrode relies largely on a scrupulous design of nanoarchitectures and smart hybridization of bespoke active materials. We present a powerful two-step solution-based method for the fabrication of transition metal oxide core/shell nanostructure arrays on various conductive substrates. Demonstrated examples include Co(3)O(4) or ZnO nanowire core and NiO nanoflake shells with a hierarchical and porous morphology. The "oriented attachment" and "self-assembly" crystal growth mechanisms are proposed to explain the formation of the NiO nanoflake shell. Supercapacitor electrodes based on the Co(3)O(4)/NiO nanowire arrays on 3D macroporous nickel foam are thoroughly characterized. The electrodes exhibit a high specific capacitance of 853 F/g at 2 A/g after 6000 cycles and an excellent cycling stability, owing to the unique porous core/shell nanowire array architecture, and a rational combination of two electrochemically active materials. Our growth approach offers a new technique for the design and synthesis of transition metal oxide or hydroxide hierarchical nanoarrays that are promising for electrochemical energy storage, catalysis, and gas sensing applications.

Synthesis, Surface Studies, Composition and Structural Characterization of CdSe, Core/Shell, and Biologically Active Nanocrystals

PubMed Central

Rosenthal, Sandra J.; McBride, James; Pennycook, Stephen J.; Feldman, Leonard C.

2011-01-01

Nanostructures, with their very large surface to volume ratio and their non-planar geometry, present an important challenge to surface scientists. New issues arise as to surface characterization, quantification and interface formation. This review summarizes the current state of the art in the synthesis, composition, surface and interface control of CdSe nanocrystal systems, one of the most studied and useful nanostructures. PMID:21479151

Electrochemical synthesis of 1D core-shell Si/TiO2 nanotubes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Kowalski, Damian; Mallet, Jeremy; Thomas, Shibin; Nemaga, Abirdu Woreka; Michel, Jean; Guery, Claude; Molinari, Michael; Morcrette, Mathieu

2017-09-01

Silicon negative electrode for lithium ion battery was designed in the form of self-organized 1D core-shell nanotubes to overcome shortcomings linked to silicon volume expansion upon lithiation/delithiation typically occurring with Si nanoparticles. The negative electrode was formed on TiO2 nanotubes in two step electrochemical synthesis by means of anodizing of titanium and electrodeposition of silicon using ionic liquid electrolytes. Remarkably, it was found that the silicon grows perpendicularly to the z-axis of nanotube and therefore its thickness can be precisely controlled by the charge passed in the electrochemical protocol. Deposited silicon creates a continuous Si network on TiO2 nanotubes without grain boundaries and particle-particle interfaces, defining its electrochemical characteristics under battery testing. In the core-shell system the titania nanotube play a role of volume expansion stabilizer framework holding the nanostructured silicon upon lithiation/delithiation. The nature of Si shell and presence of titania core determine stable performance as negative electrode tested in half cell of CR2032 coin cell battery.

Mechanochemical Synthesis of Li2MnO3 Shell/LiMO2 (M = Ni, Co, Mn) Core-Structured Nanocomposites for Lithium-Ion Batteries

PubMed Central

Noh, Jae-Kyo; Kim, Soo; Kim, Haesik; Choi, Wonchang; Chang, Wonyoung; Byun, Dongjin; Cho, Byung-Won; Chung, Kyung Yoon

2014-01-01

Core/shell-like nanostructured xLi2MnO3·(1−x)LiMO2 (M = Ni, Co, Mn) composite cathode materials are successfully synthesized through a simple solid-state reaction using a mechanochemical ball-milling process. The LiMO2 core is designed to have a high-content of Ni, which increases the specific capacity. The detrimental surface effects arising from the high Ni-content are countered by the Li2MnO3 shell, which stabilizes the nanoparticles. The electrochemical performances and thermal stabilities of the synthesized nanocomposites are compared with those of bare LiMO2. In particular, the results of time-resolved X-ray diffraction (TR-XRD) analyses of xLi2MnO3·(1−x)LiMO2 nanocomposites as well as their differential scanning calorimetry (DSC) profiles demonstrate that the Li2MnO3 shell is effective in stabilizing the LiMO2 core at high temperatures, making the nanocomposites highly suitable from a safety viewpoint. PMID:24784478

Localized surface plasmon mediated energy transfer in the vicinity of core-shell nanoparticle

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

Shishodia, Manmohan Singh, E-mail: manmohan@gbu.ac.in; Juneja, Soniya

2016-05-28

Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. Themore » theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.« less

Facile synthesis of Zn1-xCoxO/ZnO core/shell nanostructures and their application to dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Manthina, Venkata; Agrios, Alexander G.

2017-04-01

Heterostructures consisting of Co-doped ZnO nanorod cores encased in an undoped ZnO shell were successfully synthesized to serve as photoanodes for dye-sensitized solar cells (DSSCs) by a two-step chemical bath deposition (CBD) technique. This yields a highly favorable structure in which electrons injected from the dye into the ZnO then step down in energy into the Co-doped core, where the electron is transported to the collector while the ZnO shell acts as a barrier to recombination with the electrolyte. Incorporation of the core/shell structures into DSSCs resulted in large improvements in photocurrent and photovoltage in comparison to pure ZnO nanorod-based DSSCs. SEM and XRD characterization indicate incorporation of the Co2+ into the ZnO matrix, without separation of the Co into other phases, providing no energy barriers. In addition, the ability of these heterostructures to reduce recombination rates in redox couples with fast recombination rates was probed by comparing DSSC device performance in both iodide/triiodide-based and ferrocene/ferrocenium-based electrolytes.

Highly stable multi-wall carbon nanotubes@poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) core-shell composites with three-dimensional porous nano-network for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Zhou, Haihan; Han, Gaoyi; Chang, Yunzhen; Fu, Dongying; Xiao, Yaoming

2015-01-01

A facile and feasible electrochemical polymerization method has been used to construct the multi-wall carbon nanotubes@poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (MWCNTs@PEDOT/PSS) core-shell composites with three-dimensional (3D) porous nano-network microstructure. The composites are characterized with Fourier transform infrared spectroscopy, scanning electron microscope, and transmission electron microscopy. This special core-shell nanostructure can significantly reduce the ions diffusion distance and the 3D porous nano-network microstructure effectively enlarges the electrode/electrolyte interface. The electrochemical tests including cyclic voltammetry, galvanostatic charge/discharge measurements, and electrochemical impedance spectroscopy tests are performed, the results manifest the MWCNTs@PEDOT/PSS core-shell composites have superior capacitive behaviors and excellent cyclic stability, and a high areal capacitance of 98.1 mF cm-2 is achieved at 5 mV s-1 cyclic voltammetry scan. Furthermore, the MWCNTs@PEDOT/PSS composites exhibit obviously superior capacitive performance than that of PEDOT/PSS and PEDOT/Cl electrodes, indicating the effective composite of MWCNTs and PEDOT noticeably boosts the capacitive performance of PEDOT-based electrodes for electrochemical energy storage. Such a highly stable core-shell 3D network structural composite is very promising to be used as electrode materials for the high-performance electrochemical capacitors.

Plasmon enhanced water splitting mediated by hybrid bimetallic Au-Ag core-shell nanostructures.

PubMed

Erwin, William R; Coppola, Andrew; Zarick, Holly F; Arora, Poorva; Miller, Kevin J; Bardhan, Rizia

2014-11-07

In this work, we employed wet chemically synthesized bimetallic Au-Ag core-shell nanostructures (Au-AgNSs) to enhance the photocurrent density of mesoporous TiO2 for water splitting and we compared the results with monometallic Au nanoparticles (AuNPs). While Au-AgNSs incorporated photoanodes give rise to 14× enhancement in incident photon to charge carrier efficiency, AuNPs embedded photoanodes result in 6× enhancement. By varying nanoparticle concentration in the photoanodes, we observed ∼245× less Au-AgNSs are required relative to AuNPs to generate similar photocurrent enhancement for solar fuel conversion. Power-dependent measurements of Au-AgNSs and AuNPs showed a first order dependence to incident light intensity, relative to half-order dependence for TiO2 only photoanodes. This indicated that plasmonic nanostructures enhance charge carriers formed on the surface of the TiO2 which effectively participate in photochemical reactions. Our experiments and simulations suggest the enhanced near-field, far-field, and multipolar resonances of Au-AgNSs facilitating broadband absorption of solar radiation collectively gives rise to their superior performance in water splitting.

Electroformation of Janus and patchy capsules

NASA Astrophysics Data System (ADS)

Rozynek, Zbigniew; Mikkelsen, Alexander; Dommersnes, Paul; Fossum, Jon Otto

2014-05-01

Janus and patchy particles have designed heterogeneous surfaces that consist of two or several patches with different materials properties. These particles are emerging as building blocks for a new class of soft matter and functional materials. Here we introduce a route for forming heterogeneous capsules by producing highly ordered jammed colloidal shells of various shapes with domains of controlled size and composition. These structures combine the functionalities offered by Janus or patchy particles, and those given by permeable shells such as colloidosomes. The simple assembly route involves the synergetic action of electro-hydrodynamic flow and electro-coalescence. We demonstrate that the method is robust and straightforwardly extendable to production of multi-patchy capsules. This forms a starting point for producing patchy colloidosomes with domains of anisotropic chemical surface properties, permeability or mixed liquid-solid phase domains, which could be exploited to produce functional emulsions, light and hollow supra-colloidosome structures, or scaffolds.

Nanocrystal doped matrixes

DOEpatents

Parce, J. Wallace; Bernatis, Paul; Dubrow, Robert; Freeman, William P.; Gamoras, Joel; Kan, Shihai; Meisel, Andreas; Qian, Baixin; Whiteford, Jeffery A.; Ziebarth, Jonathan

2010-01-12

Matrixes doped with semiconductor nanocrystals are provided. In certain embodiments, the semiconductor nanocrystals have a size and composition such that they absorb or emit light at particular wavelengths. The nanocrystals can comprise ligands that allow for mixing with various matrix materials, including polymers, such that a minimal portion of light is scattered by the matrixes. The matrixes of the present invention can also be utilized in refractive index matching applications. In other embodiments, semiconductor nanocrystals are embedded within matrixes to form a nanocrystal density gradient, thereby creating an effective refractive index gradient. The matrixes of the present invention can also be used as filters and antireflective coatings on optical devices and as down-converting layers. Processes for producing matrixes comprising semiconductor nanocrystals are also provided. Nanostructures having high quantum efficiency, small size, and/or a narrow size distribution are also described, as are methods of producing indium phosphide nanostructures and core-shell nanostructures with Group II-VI shells.

Functionalized magnetic iron oxide/alginate core-shell nanoparticles for targeting hyperthermia

PubMed Central

Liao, Shih-Hsiang; Liu, Chia-Hung; Bastakoti, Bishnu Prasad; Suzuki, Norihiro; Chang, Yung; Yamauchi, Yusuke; Lin, Feng-Huei; Wu, Kevin C-W

2015-01-01

Hyperthermia is one of the promising treatments for cancer therapy. However, the development of a magnetic fluid agent that can selectively target a tumor and efficiently elevate temperature while exhibiting excellent biocompatibility still remains challenging. Here a new core-shell nanostructure consisting of inorganic iron oxide (Fe3O4) nanoparticles as the core, organic alginate as the shell, and cell-targeting ligands (ie, D-galactosamine) decorated on the outer surface (denoted as Fe3O4@Alg-GA nanoparticles) was prepared using a combination of a pre-gel method and coprecipitation in aqueous solution. After treatment with an AC magnetic field, the results indicate that Fe3O4@Alg-GA nanoparticles had excellent hyperthermic efficacy in a human hepatocellular carcinoma cell line (HepG2) owing to enhanced cellular uptake, and show great potential as therapeutic agents for future in vivo drug delivery systems. PMID:26005343

Polydopamine and MnO2 core-shell composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Hou, Ding; Tao, Haisheng; Zhu, Xuezhen; Li, Maoguo

2017-10-01

Polydopamine and MnO2 core-shell composites (PDA@MnO2) for high-performance supercapacitors had been successfully synthesized by a facile and fast method. The morphology, crystalline phase and chemical composition of PDA@MnO2 composites are characterized using SEM, TEM, XRD, EDS and XPS. The performance of PDA@MnO2 composites are further investigated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy in 1 M Na2SO4 electrolyte. The PDA@MnO2 core-shell nanostructure composites exhibit a high capacitance of 193 F g-1 at the current density of 1A g-1 and retained over 81.2% of its initial capacitance after 2500 cycles of charge-discharge at 2 A g-1. The results manifest that the PDA@MnO2 composites can be potentially applied in supercapacitors.

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.

Synthesis of triaxial LiFePO4 nanowire with a VGCF core column and a carbon shell through the electrospinning method.

PubMed

Hosono, Eiji; Wang, Yonggang; Kida, Noriyuki; Enomoto, Masaya; Kojima, Norimichi; Okubo, Masashi; Matsuda, Hirofumi; Saito, Yoshiyasu; Kudo, Tetsuichi; Honma, Itaru; Zhou, Haoshen

2010-01-01

A triaxial LiFePO4 nanowire with a multi wall carbon nanotube (VGCF:Vapor-grown carbon fiber) core column and an outer shell of amorphous carbon was successfully synthesized through the electrospinning method. The carbon nanotube core oriented in the direction of the wire played an important role in the conduction of electrons during the charge-discharge process, whereas the outer amorphous carbon shell suppressed the oxidation of Fe2+. An electrode with uniformly dispersed carbon and active materials was easily fabricated via a single process by heating after the electrospinning method is applied. Mossbauer spectroscopy for the nanowire showed a broadening of the line width, indicating a disordered coordination environment of the Fe ion near the surface. The electrospinning method was proven to be suitable for the fabrication of a triaxial nanostructure.

Functionalized magnetic iron oxide/alginate core-shell nanoparticles for targeting hyperthermia.

PubMed

Liao, Shih-Hsiang; Liu, Chia-Hung; Bastakoti, Bishnu Prasad; Suzuki, Norihiro; Chang, Yung; Yamauchi, Yusuke; Lin, Feng-Huei; Wu, Kevin C-W

2015-01-01

Hyperthermia is one of the promising treatments for cancer therapy. However, the development of a magnetic fluid agent that can selectively target a tumor and efficiently elevate temperature while exhibiting excellent biocompatibility still remains challenging. Here a new core-shell nanostructure consisting of inorganic iron oxide (Fe3O4) nanoparticles as the core, organic alginate as the shell, and cell-targeting ligands (ie, D-galactosamine) decorated on the outer surface (denoted as Fe3O4@Alg-GA nanoparticles) was prepared using a combination of a pre-gel method and coprecipitation in aqueous solution. After treatment with an AC magnetic field, the results indicate that Fe3O4@Alg-GA nanoparticles had excellent hyperthermic efficacy in a human hepatocellular carcinoma cell line (HepG2) owing to enhanced cellular uptake, and show great potential as therapeutic agents for future in vivo drug delivery systems.

Freestanding three-dimensional core-shell nanoarrays for lithium-ion battery anodes.

PubMed

Tan, Guoqiang; Wu, Feng; Yuan, Yifei; Chen, Renjie; Zhao, Teng; Yao, Ying; Qian, Ji; Liu, Jianrui; Ye, Yusheng; Shahbazian-Yassar, Reza; Lu, Jun; Amine, Khalil

2016-06-03

Structural degradation and low conductivity of transition-metal oxides lead to severe capacity fading in lithium-ion batteries. Recent efforts to solve this issue have mainly focused on using nanocomposites or hybrids by integrating nanosized metal oxides with conducting additives. Here we design specific hierarchical structures and demonstrate their use in flexible, large-area anode assemblies. Fabrication of these anodes is achieved via oxidative growth of copper oxide nanowires onto copper substrates followed by radio-frequency sputtering of carbon-nitride films, forming freestanding three-dimensional arrays with core-shell nano-architecture. Cable-like copper oxide/carbon-nitride core-shell nanostructures accommodate the volume change during lithiation-delithiation processes, the three-dimensional arrays provide abundant electroactive zones and electron/ion transport paths, and the monolithic sandwich-type configuration without additional binders or conductive agents improves energy/power densities of the whole electrode.

Hydrogenated CoOx nanowire@Ni(OH)2 nanosheet core-shell nanostructures for high-performance asymmetric supercapacitors.

PubMed

Zhu, Jianxiao; Huang, Lei; Xiao, Yuxiu; Shen, Leo; Chen, Qi; Shi, Wangzhou

2014-06-21

We report a facile strategy to prepare 3D core-shell nanowire heterostructures with microporous hydrogenated CoOx (H-CoOx) nanowires as the conducting scaffold to support Ni(OH)2 nanosheets. Benefiting from the H-CoOx nanowire core to provide the effective pathway for charge transport and the core-shell heterostructures with synergistic effects, the H-CoOx@Ni(OH)2 core-shell nanowire electrode achieved the specific capacitance of 2196 F g(-1) (areal capacitance of 5.73 F cm(-2)), which is approximately a 1.4-fold enhancement compared with the Co3O4@Ni(OH)2 core-shell nanowires. An aqueous asymmetric supercapacitor (ASC) device was fabricated by using H-CoOx@Ni(OH)2 nanowires as the positive electrode and reduced graphene oxide @Fe3O4 nanocomposites as the negative electrode. The ASCs achieved high energy density (∼ 45.3 W h kg(-1) at 1010 W kg(-1)), high power density (∼ 7080 W kg(-1) at 23.4 W h kg(-1)) and high cycling stability. Furthermore, after charging for ∼ 1 min, one such 22 cm(2) ASC device demonstrated to be able to drive a small windmill (0.8 V, 0.1 W) for 20 min. Two such ASCs connected in series can power up a seven-color LED (3.2 V) efficiently.

Fast-Response Single-Nanowire Photodetector Based on ZnO/WS2 Core/Shell Heterostructures.

PubMed

Butanovs, Edgars; Vlassov, Sergei; Kuzmin, Alexei; Piskunov, Sergei; Butikova, Jelena; Polyakov, Boris

2018-04-25

The surface plays an exceptionally important role in nanoscale materials, exerting a strong influence on their properties. Consequently, even a very thin coating can greatly improve the optoelectronic properties of nanostructures by modifying the light absorption and spatial distribution of charge carriers. To use these advantages, 1D/1D heterostructures of ZnO/WS 2 core/shell nanowires with a-few-layers-thick WS 2 shell were fabricated. These heterostructures were thoroughly characterized by scanning and transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. Then, a single-nanowire photoresistive device was assembled by mechanically positioning ZnO/WS 2 core/shell nanowires onto gold electrodes inside a scanning electron microscope. The results show that a few layers of WS 2 significantly enhance the photosensitivity in the short wavelength range and drastically (almost 2 orders of magnitude) improve the photoresponse time of pure ZnO nanowires. The fast response time of ZnO/WS 2 core/shell nanowire was explained by electrons and holes sinking from ZnO nanowire into WS 2 shell, which serves as a charge carrier channel in the ZnO/WS 2 heterostructure. First-principles calculations suggest that the interface layer i-WS 2 , bridging ZnO nanowire surface and WS 2 shell, might play a role of energy barrier, preventing the backward diffusion of charge carriers into ZnO nanowire.

From harmful Microcystis blooms to multi-functional core-double-shell microsphere bio-hydrochar materials.

PubMed

Bi, Lei; Pan, Gang

2017-11-13

Harmful algal blooms (HABs) induced by eutrophication is becoming a serious global environmental problem affecting public health and aquatic ecological sustainability. A novel strategy for the utilization of biomass from HABs was developed by converting the algae cells into hollow mesoporous bio-hydrochar microspheres via hydrothermal carbonization method. The hollow microspheres were used as microreactors and carriers for constructing CaO 2 core-mesoporous shell-CaO 2 shell microspheres (OCRMs). The CaO 2 shells could quickly increase dissolved oxygen to extremely anaerobic water in the initial 40 min until the CaO 2 shells were consumed. The mesoporous shells continued to act as regulators restricting the release of oxygen from CaO 2 cores. The oxygen-release time using OCRMs was 7 times longer than when directly using CaO 2 . More interestingly, OCRMs presented a high phosphate removal efficiency (95.6%) and prevented the pH of the solution from rising to high levels in comparison with directly adding CaO 2 due to the OH - controlled-release effect of OCRMs. The distinct core-double-shell micro/nanostructure endowed the OCRMs with triple functions for oxygen controlled-release, phosphorus removal and less impact on water pH. The study is to explore the possibility to prepare smarter bio-hydrochar materials by utilizing algal blooms.

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

Zaera, Francisco; Bardeen, Christopher J.; Yin, Yadong

The overall goal of this project has been to develop new a new and novel class of well-characterized nanostructured Metal@TiO 2 core-shell and yolk-shell photocatalysts to address two fundamental issues presently limiting this field: (1) the fast recombination of electron-hole pairs once generated by light absorption, and (2) the recombination of H 2 and O 2 on the metal surface once produced. These model samples are also used to study the fundamentals of the photocatalytic processes.

Optically enhanced SnO{sub 2}/CdSe core/shell nanostructures grown by sol-gel spin coating method

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

Kumar, Vijay, E-mail: vijaynadda83@gmail.com; Goswami, Y. C.; Rajaram, P.

2015-08-28

Synthesis of SnO{sub 2}/CdSe metal oxide/ chalcogenide nanostructures on glass micro slides using ultrasonic sol-gel process followed by spin coating has been reported. Stannous chloride, cadmium chloride and selenium dioxide compounds were used for Sn, Cd and Se precursors respectively. Ethylene glycol was used as complexing agent. The samples were characterized by XRD, SEM, AFM and UV-spectrophotometer. All the peaks shown in diffractograms are identified for SnO{sub 2}. Peak broadening observed in core shell due to stress behavior of CdSe lattice. Scanning electron microscope and AFM exhibits the conversion of cluster in to nanorods structures forms. Atomic force microscope showsmore » the structures in nanorods form and a roughness reduced 1.5194 nm by the deposition of CdSe. Uv Visible spectra shows a new absorption edge in the visible region make them useful for optoelectronic applications.« less

Toward hybrid Au nanorods @ M (Au, Ag, Pd and Pt) core-shell heterostructures for ultrasensitive SERS probes

NASA Astrophysics Data System (ADS)

Xie, Xiaobin; Gao, Guanhui; Kang, Shendong; Lei, Yanhua; Pan, Zhengyin; Shibayama, Tamaki; Cai, Lintao

2017-06-01

Being able to precisely control the morphologies of noble metallic nanostructures is of essential significance for promoting the surface-enhanced Raman scattering (SERS) effect. Herein, we demonstrate an overgrowth strategy for synthesizing Au @ M (M = Au, Ag, Pd, Pt) core-shell heterogeneous nanocrystals with an orientated structural evolution and highly improved properties by using Au nanorods as seeds. With the same reaction condition system applied, we obtain four well-designed heterostructures with diverse shapes, including Au concave nanocuboids (Au CNs), Au @ Ag crystalizing face central cube nanopeanuts, Au @ Pd porous nanocuboids and Au @ Pt nanotrepangs. Subsequently, the exact overgrowth mechanism of the above heterostructural building blocks is further analysed via the systematic optimiziation of a series of fabrications. Remarkably, the well-defined Au CNs and Au @ Ag nanopeanuts both exhibit highly promoted SERS activity. We expect to be able to supply a facile strategy for the fabrication of multimetallic heterogeneous nanostructures, exploring the high SERS effect and catalytic activities.

Simultaneous Detection and Removal of Formaldehyde at Room Temperature: Janus Au@ZnO@ZIF-8 Nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Dawei; Li, Zhiwei; Zhou, Jian; Fang, Hong; He, Xiang; Jena, Puru; Zeng, Jing-Bin; Wang, Wei-Ning

2018-03-01

The detection and removal of volatile organic compounds (VOCs) are of great importance to reduce the risk of indoor air quality concerns. This study reports the rational synthesis of a dual-functional Janus nanostructure and its feasibility for simultaneous detection and removal of VOCs. The Janus nanostructure was synthesized via an anisotropic growth method, composed of plasmonic nanoparticles, semiconductors, and metal organic frameworks (e.g., Au@ZnO@ZIF-8). It exhibits excellent selective detection to formaldehyde (HCHO, as a representative VOC) at room temperature over a wide range of concentrations (from 0.25 to 100 ppm), even in the presence of water and toluene molecules as interferences. In addition, HCHO was also found to be partially oxidized into non-toxic formic acid simultaneously with detection. The mechanism underlying this technology was unraveled by both experimental measurements and theoretical calculations: ZnO maintains the conductivity, while ZIF-8 improves the selective gas adsorption; the plasmonic effect of Au nanorods enhances the visible-light-driven photocatalysis of ZnO at room temperature. [Figure not available: see fulltext.

Simultaneous Detection and Removal of Formaldehyde at Room Temperature: Janus Au@ZnO@ZIF-8 Nanoparticles

DOE PAGES

Wang, Dawei; Li, Zhiwei; Zhou, Jian; ...

2017-10-09

The detection and removal of volatile organic compounds (VOCs) are of great importance to reduce the risk of indoor air quality concerns. Our study reports the rational synthesis of a dual-functional Janus nanostructure and its feasibility for simultaneous detection and removal of VOCs. The Janus nanostructure was synthesized via an anisotropic growth method, composed of plasmonic nanoparticles, semiconductors, and metal organic frameworks (e.g., Au@ZnO@ZIF-8). It exhibits excellent selective detection to formaldehyde (HCHO, as a representative VOC) at room temperature over a wide range of concentrations (from0.25 to 100 ppm), even in the presence of water and toluene molecules as interferences.more » Additionally, HCHOwas also found to be partially oxidized into non-toxic formic acid simultaneously with detection. The mechanism underlying this technology was unraveled by both experimental measurements and theoretical calculations: ZnO maintains the conductivity, while ZIF-8 improves the selective gas adsorption; the plasmonic effect of Au nanorods enhances the visible-light-driven photocatalysis of ZnO at room temperature.« less

Simultaneous Detection and Removal of Formaldehyde at Room Temperature: Janus Au@ZnO@ZIF-8 Nanoparticles

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

Wang, Dawei; Li, Zhiwei; Zhou, Jian

The detection and removal of volatile organic compounds (VOCs) are of great importance to reduce the risk of indoor air quality concerns. Our study reports the rational synthesis of a dual-functional Janus nanostructure and its feasibility for simultaneous detection and removal of VOCs. The Janus nanostructure was synthesized via an anisotropic growth method, composed of plasmonic nanoparticles, semiconductors, and metal organic frameworks (e.g., Au@ZnO@ZIF-8). It exhibits excellent selective detection to formaldehyde (HCHO, as a representative VOC) at room temperature over a wide range of concentrations (from0.25 to 100 ppm), even in the presence of water and toluene molecules as interferences.more » Additionally, HCHOwas also found to be partially oxidized into non-toxic formic acid simultaneously with detection. The mechanism underlying this technology was unraveled by both experimental measurements and theoretical calculations: ZnO maintains the conductivity, while ZIF-8 improves the selective gas adsorption; the plasmonic effect of Au nanorods enhances the visible-light-driven photocatalysis of ZnO at room temperature.« less

Enhancing capacitance behaviour of CoOOH nanostructures using transition metal dopants by ambient oxidation.

PubMed

Chen, Yanhui; Zhou, Junfeng; Maguire, Pierce; O'Connell, Robert; Schmitt, Wolfgang; Li, Yonghe; Yan, Zhengguang; Zhang, Yuefei; Zhang, Hongzhou

2016-02-08

Cobalt hydrate and doped binary Co0.9M0.1OOH (M = Ni, Mn, Fe) nanorings of 100-300 nm were fabricated in solution through a facile ambient oxidation method. A transformation from Co0.9Ni0.1(OH)2 nanodiscs to hollow Co0.9Ni0.1OOH nanorings was observed with prolonged reaction time. Core-shell nanodiscs have elemental segregation with a Co(OH)2 core and Ni(OH)2 shell. Co0.9Ni0.1OOH nanorings displayed a higher electrochemical capacitance than Mn and Fe doped nanorings materials or materials with disc-like geometries.

Enhancing the methanol tolerance of platinum nanoparticles for the cathode reaction of direct methanol fuel cells through a geometric design.

PubMed

Feng, Yan; Ye, Feng; Liu, Hui; Yang, Jun

2015-11-18

Mastery over the structure of nanoparticles might be an effective way to enhance their performance for a given application. Herein we demonstrate the design of cage-bell nanostructures to enhance the methanol tolerance of platinum (Pt) nanoparticles while remaining their catalytic activity for oxygen reduction reaction. This strategy starts with the synthesis of core-shell-shell nanoparticles with Pt and silver (Ag) residing respectively in the core and inner shell regions, which are then agitated with saturated sodium chloride (NaCl) solution to eliminate the Ag component from the inner shell region, leading to the formation of bimetallic nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a metal shell with nano-channels, which exhibit superior methanol-tolerant property in catalyzing oxygen reduction reaction due to the different diffusion behaviour of methanol and oxygen in the porous metal shell of cage-bell structured nanoparticles. In particular, the use of remarkably inexpensive chemical agent (NaCl) to promote the formation of cage-bell structured particles containing a wide spectrum of metal shells highlights its engineering merit to produce highly selective electrocatalysts on a large scale for the cathode reaction of direct methanol fuel cells.

Importance of polypyrrole in constructing 3D hierarchical carbon nanotube@MnO2 perfect core-shell nanostructures for high-performance flexible supercapacitors.

PubMed

Zhou, Jinyuan; Zhao, Hao; Mu, Xuemei; Chen, Jiayi; Zhang, Peng; Wang, Yaling; He, Yongmin; Zhang, Zhenxing; Pan, Xiaojun; Xie, Erqing

2015-09-21

This study reports the preparation of 3D hierarchical carbon nanotube (CNT) @MnO2 core-shell nanostructures under the assistance of polypyrrole (PPy). The as-prepared CNT@PPy@MnO2 core-shell structures show a perfect coating of MnO2 on each CNT and, more importantly, a robust bush-like pseudocapacitive shell to effectively increase the specific surface area and enhance the ion accessibility. As expected, a high specific capacity of 490-530 F g(-1) has been achieved from CNT@PPy@MnO2 single electrodes. And about 98.5% of the capacity is retained after 1000 charge/discharge cycles at a current density of 5 A g(-1). Furthermore, the assembled asymmetric CNT@PPy@MnO2//AC capacitors show the maximum energy density of 38.42 W h kg(-1) (2.24 mW h cm(-3)) at a power density of 100 W kg(-1) (5.83 mW cm(-3)), and they maintain 59.52% of the initial value at 10,000 W kg(-1) (0.583 W cm(-3)). In addition, the assembled devices show high cycling stabilities (89.7% after 2000 cycles for asymmetric and 87.2% for symmetric), and a high bending stability (64.74% after 200 bending tests). This ability to obtain high energy densities at high power rates while maintaining high cycling stability demonstrates that this well-designed structure could be a promising electrode material for high-performance supercapacitors.

Mean-field and linear regime approach to magnetic hyperthermia of core-shell nanoparticles: can tiny nanostructures fight cancer?

PubMed

Carrião, Marcus S; Bakuzis, Andris F

2016-04-21

The phenomenon of heat dissipation by magnetic materials interacting with an alternating magnetic field, known as magnetic hyperthermia, is an emergent and promising therapy for many diseases, mainly cancer. Here, a magnetic hyperthermia model for core-shell nanoparticles is developed. The theoretical calculation, different from previous models, highlights the importance of heterogeneity by identifying the role of surface and core spins on nanoparticle heat generation. We found that the most efficient nanoparticles should be obtained by selecting materials to reduce the surface to core damping factor ratio, increasing the interface exchange parameter and tuning the surface to core anisotropy ratio for each material combination. From our results we propose a novel heat-based hyperthermia strategy with the focus on improving the heating efficiency of small sized nanoparticles instead of larger ones. This approach might have important implications for cancer treatment and could help improving clinical efficacy.

Hierarchically structured nanowires on and nanosticks in ZnO microtubes

PubMed Central

Rivaldo-Gómez, C. M.; Cabrera-Pasca, G. A.; Zúñiga, A.; Carbonari, A. W.; Souza, J. A.

2015-01-01

We report both coaxial core-shell structured microwires and ZnO microtubes with growth of nanosticks in the inner and nanowires on the outer surface as a novel hierarchical micro/nanoarchitecture. First, a core-shell structure is obtained—the core is formed by metallic Zn and the semiconducting shell is comprised by a thin oxide layer covered with a high density of nanowires. Such Zn/ZnO core-shell array showed magnetoresistance effect. It is suggested that magnetic moments in the nanostructured shell superimposes to the external magnetic field enhancing the MR effect. Second, microtubes decorated with nanowires on the external surface are obtained. In an intermediate stage, a hierarchical morphology comprised of discrete nanosticks in the inner surface of the microtube has been found. Hyperfine interaction measurements disclosed the presence of confined metallic Zn regions at the interface between linked ZnO grains forming a chain and a ZnO thicker layer. Surprisingly, the metallic clusters form highly textured thin flat regions oriented parallel to the surface of the microtube as revealed by the electrical field gradient direction. The driving force to grow the internal nanosticks has been ascribed to stress-induced migration of Zn ions due to compressive stress caused by the presence of these confined regions. PMID:26456527

Catalyst-free fabrication of novel ZnO/CuO core-Shell nanowires heterojunction: Controlled growth, structural and optoelectronic properties

NASA Astrophysics Data System (ADS)

Khan, Muhammad Arif; Wahab, Yussof; Muhammad, Rosnita; Tahir, Muhammad; Sakrani, Samsudi

2018-03-01

Development of controlled growth and vertically aligned ZnO/CuO core-shell heterojunction nanowires (NWs) with large area by a catalyst free vapor deposition and oxidation approach has been investigated. Structural characterization reveals successful fabrication of a core ZnO nanowire having single crystalline hexagonal wurtzite structure along [002] direction and CuO nanostructure shell with thickness (8-10 nm) having polycrystalline monoclinic structure. The optical property analysis suggests that the reflectance spectrum of ZnO/CuO heterostructure nanowires is decreased by 18% in the visible range, which correspondingly shows high absorption in this region as compared to pristine ZnO nanowires. The current-voltage (I-V) characteristics of core-shell heterojunction nanowires measured by conductive atomic force microscopy (C-AFM) shows excellent rectifying behavior, which indicates the characteristics of a good p-n junction. The high-resolution transmission electron microscopy (HRTEM) has confirmed the sharp junction interface between the core-shell heterojunction nanowire arrays. The valence band offset and conduction band offset at ZnO/CuO heterointerfaces are measured to be 2.4 ± 0.05 and 0.23 ± 0.005 eV respectively, using X-ray photoelectron spectroscopy (XPS) and a type-II band alignment structure is found. The results of this study contribute to the development of new advanced device heterostructures for solar energy conversion and optoelectronics applications.

Synthesis of basalt fiber@Zn1-xMgxO core/shell nanostructures for selective photoreduction of CO2 to CO

NASA Astrophysics Data System (ADS)

Kwak, Byeong Sub; Kim, Kang Min; Park, Sun-Min; Kang, Misook

2017-06-01

This study focused on the development of a catalyst for converting carbon dioxide, the main cause of global warming, into a beneficial energy source. Core@shell structured particles, BF@ZnO and BF@Zn1-xMgxO, are synthesized in order to selectively obtain CO gas from the photoreduction of CO2. A modified sol-gel process is used to synthesize the core@shell structures with a three-dimensional microstructure, which are subsequently characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDAX), ultraviolet (UV)-vis absorption, photoluminescence (PL), and photocurrent density analysis. The CO2 adsorption abilities of the core@shell particles are estimated through CO2-temperature programmed desorption (TPD). The core@shell structured BF@Zn1-xMgxO particles including the Mg ingredient significantly increased the adsorption of CO2 gas at the microfiber/nanoparticle interface. Both the BF@ZnO and BF@Zn1-xMgxO particles selectively reduce the carbon dioxide to carbon monoxide, with almost no other reduced products being observed. These results are attributed to the effective adsorption of CO2 gas and inhibited recombination of the photogenerated electron-hole pairs. BF@Zn0.75Mg0.25O exhibited superior photocatalytic behavior and selectively produced 5.0 μmolgcat-1 L-1 of CO gas after 8 h of reaction.

In-situ synthetize multi-walled carbon nanotubes@MnO2 nanoflake core-shell structured materials for supercapacitors

NASA Astrophysics Data System (ADS)

Zheng, Huajun; Wang, Jiaoxia; Jia, Yi; Ma, Chun'an

2012-10-01

A new type of core-shell structured material consisting of multi-walled carbon nanotubes (MWCNTs) and manganese dioxide (MnO2) nanoflake is synthesized using an in-situ co-precipitation method. By scanning electron microscopy and transition electron microscope, it is confirmed that the core-shell nanostructure is formed by the uniform incorporation of birnessite-type MnO2 nanoflake growth round the surface of the activated-MWCNTs. That core-shell structured material electrode presents excellent electrochemical capacitance properties with the specific capacitance reaching 380 F g-1 at the current density of 5 A g-1 in 0.5 M Na2SO4 electrolyte. In addition, the electrode also exhibits good performance (the power density: 11.28 kW kg-1 at 5 A g-1) and long-term cycling stability (retaining 82.7% of its initial capacitance after 3500 cycles at 5 A g-1). It mainly attributes to MWCNTs not only providing considerable specific surface area for high mass loading of MnO2 nanoflakes to ensure effective utilization of MnO2 nanoflake, but also offering an electron pathway to improve electrical conductivity of the electrode materials. It is clearly indicated that such core-shell structured materials including MWCNTs and MnO2 nanoflake may find important applications for supercapacitors.

Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution.

PubMed

Salem, Mohamed A; Bakr, Eman A; El-Attar, Heba G

2018-01-05

Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17nm for Pt@Ag and 8.8nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH 4 ) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH 4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes. Copyright © 2017. Published by Elsevier B.V.

Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution

NASA Astrophysics Data System (ADS)

Salem, Mohamed A.; Bakr, Eman A.; El-Attar, Heba G.

2018-01-01

Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17 nm for Pt@Ag and 8.8 nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH4) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes.

Engineering Nano-Structured Multiferroic Thin Films

NASA Astrophysics Data System (ADS)

Cheung, Pui Lam

Multiferroics exhibit remarkable tunabilities in their ferromagnetic, ferroelectric and magnetoelectric properties that provide the potential in enabling the control of magnetizations by electric field for the next generation non-volatile memories, antennas and motors. In recent research and developments in integrating single-phase ferroelectric and ferromagnetic materials, multiferroic composite demonstrated a promising magnetoelectric (ME) coupling for future applications. Atomic layer deposition (ALD) technique, on the other hand, allows fabrications of complex multiferroic nanostructures to investigate interfacial coupling between the two materials. In this work, radical-enhanced ALD of cobalt ferrite (CFO) and thermal ALD of lead zirconate titanate (PZT) were combined in fabricating complex multiferroic architectures in investigating the effect of nanostructuring and magnetic shape anisotropy on improving ME coupling. In particular, 1D CFO nanotubes and nanowires; 0D-3D CFO/PZT mesoporous composite; and 1D-1D CFO/PZT core-shell nanowire composite were studied. The potential implementation of nanostructured multiferroic composites into functioning devices was assessed by quantifying the converse ME coupling coefficient. The synthesis of 1D CFO nanostructures was realized by ALD of CFO in anodic aluminum oxide (AAO) membranes. This work provided a simple and inexpensive route to create parallel and high aspect ratio ( 55) magnetic nanostructures. The change in magnetic easy axis of (partially filled) CFO nanotubes from perpendicular to parallel in (fully-filled) nanowires indicated the significance of the geometric factor in controlling magnetizations and ME coupling. The 0D-3D CFO/PZT mesoporous composite demonstrated the optimizations of the strain transfer could be achieved by precise thickness control. 100 nm of mesoporous PZT was synthesized on Pt/TiOx/SiO2/Si using amphiphilic diblock copolymers as a porous ferroelectric template (10 nm pore diameter) for ALD CFO growth. The increased filling of CFO decreased the mechanical flexibility of the composite for electric field induced strain, hence the converse ME coupling was mitigated. The highest converse ME coefficient of 1.2 10-5 Oe-cm/mV was achieved with a 33% pore filling of CFO, in compare to 1 x 10-5 Oe-cm/mV from mesoporous CFO filled with 3 nm of PZT in literature (Chien 2016). Highly directional 1D-1D PZT-core CFO-shell composite in AAO demonstrated the magnetic shape anisotropy could be modulated. The CFO shell thickness allowed the tuning of magnetic easy axis and saturation magnetizations; whereas the PZT volume allowed the optimization of electric field induced strain of the composite. Enhanced converse ME coupling of 1.3 x 10-4 Oe-cm/mV was realized by 5 nm CFO shell on 30 nm of PZT core. In summary, the work has demonstrated nanostructuring of multiferroic composite is an effective pathway to engineer converse ME coupling through optimizations of magnetic shape anisotropy and interfacial strain transfer.

Nanorice Particles: Hybrid Plasmonic Nanostructures

NASA Technical Reports Server (NTRS)

Le, Fei (Inventor); Halas, Nancy J. (Inventor); Nordlander, Peter (Inventor); Brandl, Daniel (Inventor); Wang, Hui (Inventor)

2010-01-01

A new hybrid nanoparticle, i.e., a nanorice particle, which combines the intense local fields of nanorods with the highly tunable plasmon resonances of nanoshells, is described herein. This geometry possesses far greater structural tunability than previous nanoparticle geometries, along with much larger local field enhancements and far greater sensitivity as a surface plasmon resonance (SPR) nanosensor than presently known dielectric-conductive material nanostructures. In an embodiment, a nanoparticle comprises a prolate spheroid-shaped core having a first aspect ratio. The nanoparticle also comprises at least one conductive shell surrounding said prolate spheroid-shaped core. The nanoparticle has a surface plasmon resonance sensitivity of at least 600 nm RIU(sup.-1). Methods of making the disclosed nanorice particles are also described herein.

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

Mumin, Md Abdul, E-mail: pcharpentier@eng.uwo.ca; Akhter, Kazi Farida, E-mail: pcharpentier@eng.uwo.ca; Charpentier, Paul A., E-mail: pcharpentier@eng.uwo.ca

Semiconductor nanocrystals (NCs) (also known as quantum dots, QDs) have attracted immense attention for their size-tunable optical properties that makes them impressive candidates for solar cells, light emitting devices, lasers, as well as biomedical imaging. However monodispersity, high and consistent photoluminescence, photostability, and biocompatibility are still major challenges. This work focuses on optimizing the photophysical properties and biocompatibility of QDs by forming core-shell nanostructures and their encapsulation by a carrier. Highly luminescent CdS and CdS-ZnS core-shell QDs with 5 nm sizes were synthesized using a facile approach based on pyrolysis of the single molecule precursors. After capping the CdS QDsmore » with a thin layer of ZnS to reduce toxicity, the photoluminescence and photostability of the core-shell QDs was significantly enhanced. To make both the bare and core/shell structure QDs more resistant against photochemical reactions, a mesoporous silica layer was grown on the QDs through a reverse microemulsion technique based on hydrophobic interaction. This encapsulation enhanced the quantum yield and photostability compared to the bare QDs by providing much stronger resistance to oxidation and Oswald ripening of QDs. Encapsulation also improved biocompatibility of QDs that was evaluated with human umbilical vein endothelial cell lines (HUVEC)« less

Ultrafast Three-Dimensional Integrated Imaging of Strain in Core/Shell Semiconductor/Metal Nanostructures

DOE PAGES

Cherukara, Mathew J.; Sasikumar, Kiran; DiChiara, Anthony; ...

2017-11-07

Visualizing the dynamical response of material heterointerfaces is increasingly important for the design of hybrid materials and structures with tailored properties for use in functional devices. In situ characterization of nanoscale heterointerfaces such as metal-semiconductor interfaces, which exhibit a complex interplay between lattice strain, electric potential, and heat transport at subnanosecond time scales, is particularly challenging. Here in this work, we use a laser pump/X-ray probe form of Bragg coherent diffraction imaging (BCDI) to visualize in three-dimension the deformation of the core of a model core/shell semiconductor-metal (ZnO/Ni) nanorod following laser heating of the shell. We observe a rich interplaymore » of radial, axial, and shear deformation modes acting at different time scales that are induced by the strain from the Ni shell. We construct experimentally informed models by directly importing the reconstructed crystal from the ultrafast experiment into a thermo-electromechanical continuum model. The model elucidates the origin of the deformation modes observed experimentally. Our integrated imaging approach represents an invaluable tool to probe strain dynamics across mixed interfaces under operando conditions.« less

Ultrafast Three-Dimensional Integrated Imaging of Strain in Core/Shell Semiconductor/Metal Nanostructures

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

Cherukara, Mathew J.; Sasikumar, Kiran; DiChiara, Anthony

Visualizing the dynamical response of material heterointerfaces is increasingly important for the design of hybrid materials and structures with tailored properties for use in functional devices. In situ characterization of nanoscale heterointerfaces such as metal-semiconductor interfaces, which exhibit a complex interplay between lattice strain, electric potential, and heat transport at subnanosecond time scales, is particularly challenging. Here in this work, we use a laser pump/X-ray probe form of Bragg coherent diffraction imaging (BCDI) to visualize in three-dimension the deformation of the core of a model core/shell semiconductor-metal (ZnO/Ni) nanorod following laser heating of the shell. We observe a rich interplaymore » of radial, axial, and shear deformation modes acting at different time scales that are induced by the strain from the Ni shell. We construct experimentally informed models by directly importing the reconstructed crystal from the ultrafast experiment into a thermo-electromechanical continuum model. The model elucidates the origin of the deformation modes observed experimentally. Our integrated imaging approach represents an invaluable tool to probe strain dynamics across mixed interfaces under operando conditions.« less

Ultrafast Three-Dimensional Integrated Imaging of Strain in Core/Shell Semiconductor/Metal Nanostructures.

PubMed

Cherukara, Mathew J; Sasikumar, Kiran; DiChiara, Anthony; Leake, Steven J; Cha, Wonsuk; Dufresne, Eric M; Peterka, Tom; McNulty, Ian; Walko, Donald A; Wen, Haidan; Sankaranarayanan, Subramanian K R S; Harder, Ross J

2017-12-13

Visualizing the dynamical response of material heterointerfaces is increasingly important for the design of hybrid materials and structures with tailored properties for use in functional devices. In situ characterization of nanoscale heterointerfaces such as metal-semiconductor interfaces, which exhibit a complex interplay between lattice strain, electric potential, and heat transport at subnanosecond time scales, is particularly challenging. In this work, we use a laser pump/X-ray probe form of Bragg coherent diffraction imaging (BCDI) to visualize in three-dimension the deformation of the core of a model core/shell semiconductor-metal (ZnO/Ni) nanorod following laser heating of the shell. We observe a rich interplay of radial, axial, and shear deformation modes acting at different time scales that are induced by the strain from the Ni shell. We construct experimentally informed models by directly importing the reconstructed crystal from the ultrafast experiment into a thermo-electromechanical continuum model. The model elucidates the origin of the deformation modes observed experimentally. Our integrated imaging approach represents an invaluable tool to probe strain dynamics across mixed interfaces under operando conditions.

Nanocrystalline p-hydroxyacetanilide (paracetamol) and gold core-shell structure as a model drug deliverable organic-inorganic hybrid nanostructure

NASA Astrophysics Data System (ADS)

Das, Subhojit; Paul, Anumita; Chattopadhyay, Arun

2013-09-01

We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release.We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release. Electronic supplementary information (ESI) available: See DOI: 10.1039/c3nr03566b

Nanostructured microtubes based on TiO2 doped by Zr and Hf oxides with the anatase structure

NASA Astrophysics Data System (ADS)

Zheleznov, VV; Voit, EI; Sushkov, YV; Sarin, SA; Kuryavyi, VG; Opra, DP; Gnedenkov, SV; Sinebryukhov, SL; Sokolov, AA

2016-01-01

The nanostructured microtubes based on TiO2 have been prepared on the carbon fiber template using the sol-gel method. The microtubes consist of nanoparticles of metal oxides: TiO2/ZrO2 and TiO2/HfO2. The dependence of microtubes morphology and nanoparticles structure on the synthesis conditions has been studied using the methods of SEM, SAXS, and Raman spectroscopy. It has been demonstrated that at the stoichiometric ratio of up to 0.04 for Zr/Ti and up to 0.06 for Hf/Ti microtubes consist of uniform nanoparticles with the anatase structure. Along with further increase of the dopants content in the microtubes composition, nanoparticles acquire the core-shell structure. It has been suggested that nanoparticles have a core composed of the solid solutions Ti1-xZrxO2 or Ti1-xHfxO2 and a shell consisting of zirconium or hafnium titanate. The fabricated Zr- and Hf-doped TiO2 materials were investigated in view of their possible use as anode materials for Li-ion batteries. Charge- discharge measurements showed that the doped samples manifested significantly higher reversibility in comparison with the undoped TiO2. The method opens new prospects in synthesis of nanostructured materials for Li-ion batteries application.

Surface-Enhanced Raman Scattering Active Plasmonic Nanoparticles with Ultrasmall Interior Nanogap for Multiplex Quantitative Detection and Cancer Cell Imaging.

PubMed

Li, Jiuxing; Zhu, Zhi; Zhu, Bingqing; Ma, Yanli; Lin, Bingqian; Liu, Rudi; Song, Yanling; Lin, Hui; Tu, Song; Yang, Chaoyong

2016-08-02

Due to its large enhancement effect, nanostructure-based surface-enhanced Raman scattering (SERS) technology had been widely applied for bioanalysis and cell imaging. However, most SERS nanostructures suffer from poor signal reproducibility, which hinders the application of SERS nanostructures in quantitative detection. We report an etching-assisted approach to synthesize SERS-active plasmonic nanoparticles with 1 nm interior nanogap for multiplex quantitative detection and cancer cell imaging. Raman dyes and methoxy poly(ethylene glycol) thiol (mPEG-SH) were attached to gold nanoparticles (AuNPs) to prepare gold cores. Next, Ag atoms were deposited on gold cores in the presence of Pluronic F127 to form a Ag shell. HAuCl4 was used to etch the Ag shell and form an interior nanogap in Au@AgAuNPs, leading to increased Raman intensity of dyes. SERS intensity distribution of Au@AgAuNPs was found to be more uniform than that of aggregated AuNPs. Finally, Au@AgAuNPs were used for multiplex quantitative detection and cancer cell imaging. With the advantages of simple and rapid preparation of Au@AgAuNPs with highly uniform, stable, and reproducible Raman intensity, the method reported here will widen the applications of SERS-active nanoparticles in diagnostics and imaging.

Single-step synthesis of Er3+ and Yb3+ ions doped molybdate/Gd2O3 core-shell nanoparticles for biomedical imaging

NASA Astrophysics Data System (ADS)

Kamińska, Izabela; Elbaum, Danek; Sikora, Bożena; Kowalik, Przemysław; Mikulski, Jakub; Felcyn, Zofia; Samol, Piotr; Wojciechowski, Tomasz; Minikayev, Roman; Paszkowicz, Wojciech; Zaleszczyk, Wojciech; Szewczyk, Maciej; Konopka, Anna; Gruzeł, Grzegorz; Pawlyta, Mirosława; Donten, Mikołaj; Ciszak, Kamil; Zajdel, Karolina; Frontczak-Baniewicz, Małgorzata; Stępień, Piotr; Łapiński, Mariusz; Wilczyński, Grzegorz; Fronc, Krzysztof

2018-01-01

Nanostructures as color-tunable luminescent markers have become major, promising tools for bioimaging and biosensing. In this paper separated molybdate/Gd2O3 doped rare earth ions (erbium, Er3+ and ytterbium, Yb3+) core-shell nanoparticles (NPs), were fabricated by a one-step homogeneous precipitation process. Emission properties were studied by cathodo- and photoluminescence. Scanning electron and transmission electron microscopes were used to visualize and determine the size and shape of the NPs. Spherical NPs were obtained. Their core-shell structures were confirmed by x-ray diffraction and energy-dispersive x-ray spectroscopy measurements. We postulated that the molybdate rich core is formed due to high segregation coefficient of the Mo ion during the precipitation. The calcination process resulted in crystallization of δ/ξ (core/shell) NP doped Er and Yb ions, where δ—gadolinium molybdates and ξ—molybdates or gadolinium oxide. We confirmed two different upconversion mechanisms. In the presence of molybdenum ions, in the core of the NPs, Yb3+-{{{{MoO}}}4}2- (∣2F7/2, 3T2〉) dimers were formed. As a result of a two 980 nm photon absorption by the dimer, we observed enhanced green luminescence in the upconversion process. However, for the shell formed by the Gd2O3:Er, Yb NPs (without the Mo ions), the typical energy transfer upconversion takes place, which results in red luminescence. We demonstrated that the NPs were transported into cytosol of the HeLa and astrocytes cells by endocytosis. The core-shell NPs are sensitive sensors for the environment prevailing inside (shorter luminescence decay) and outside (longer luminescence decay) of the tested cells. The toxicity of the NPs was examined using MTT assay.

Novel highly ordered core–shell nanoparticles

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

Dey, Sonal; Hossain, Mohammad D.; Mayanovic, Robert A.

2016-10-26

Core–shell nanoparticles have potential for a wide range of applications due to the tunability of their magnetic, catalytic, electronic, optical, and other physicochemical properties. A frequent drawback in the design of core–shell nanoparticles and nanocrystals is the lack of control over an extensive, disordered, and compositionally distinct interface that occurs due to the dissimilarity of structural and compositional phases of the core and shell. In this work, we demonstrate a new hydrothermal nanophase epitaxy (HNE) technique to synthesize highly structurally ordered α-Cr 2O 3@α-Co 0.38Cr 1.62O 2.92 inverted core–shell nanoparticles (CSNs) with evidence for the nanoscale growth of corundum structuremore » beginning from the core and extending completely into the shell of the CSNs with minimal defects at the interface. The high-resolution TEM results show a sharp interface exhibiting epitaxial atomic registry of shell atoms over highly ordered core atoms. The XPS and Co K-edge XANES analyses indicate the +2 oxidation state of cobalt is incorporated in the shell of the CSNs. Our XPS and EXAFS results are consistent with oxygen vacancy formation in order to maintain charge neutrality upon substitution of the Co 2+ ion for the Cr 3+ ion in the α-Co 0.38Cr 1.62O 2.92 shell. Furthermore, the CSNs exhibit the magnetic exchange bias effect, which is attributed to the exchange anisotropy at the interface made possible by the nanophase epitaxial growth of the α-Co 0.38Cr 1.62O 2.92 shell on the α-Cr 2O 3 core of the nanoparticles. The combination of a well-structured, sharp interface and novel nanophase characteristics is highly desirable for nanostructures having enhanced magnetic properties.« less

Silica nanoparticle stability in biological media revisited.

PubMed

Yang, Seon-Ah; Choi, Sungmoon; Jeon, Seon Mi; Yu, Junhua

2018-01-09

The stability of silica nanostructure in the core-silica shell nanomaterials is critical to understanding the activity of these nanomaterials since the exposure of core materials due to the poor stability of silica may cause misinterpretation of experiments, but unfortunately reports on the stability of silica have been inconsistent. Here, we show that luminescent silver nanodots (AgNDs) can be used to monitor the stability of silica nanostructures. Though relatively stable in water and phosphate buffered saline, silica nanoparticles are eroded by biological media, leading to the exposure of AgNDs from AgND@SiO 2 nanoparticles and the quenching of nanodot luminescence. Our results reveal that a synergistic effect of organic compounds, particularly the amino groups, accelerates the erosion. Our work indicates that silica nanostructures are vulnerable to cellular medium and it may be possible to tune the release of drug molecules from silica-based drug delivery vehicles through controlled erosion.

Graphene-based copper oxide thin film nanostructures as high-efficiency photocathode for p-type dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Kilic, Bayram; Turkdogan, Sunay; Astam, Aykut; Baran, Sümeyra Seniha; Asgin, Mansur; Cebeci, Hulya; Urk, Deniz

2017-10-01

Graphene-based p-type dye-sensitized solar cells (p-DSSCs) have been proposed and fabricated using copper oxide urchin-like nanostructures (COUN) as photocathode with an FeS2 counter electrode (CE). COUN composed of Cu2O core sphere and CuO shell nanorods with overall diameters of 2 to 4 μm were grown by a simple hydrothermal method with self-assemble nucleation. It was figured out that the formation of copper oxide core/shell structures could be adjusted by an ammonia additive leading to pH change of the precursor solution. In addition to a photocathode, we also demonstrated FeS2 thin films as an efficient CE material alternative to the conventional Pt CEs in DSSCs. FeS2 nanostructures, with diameters of 50 to 80 nm, were synthesized by a similar hydrothermal approach. FeS2 nanostructures are demonstrated to be an outstanding CE material in p-DSSCs. We report graphene/COUN as photocathode and Pt/FeS2 as CE in p-DSSCs, and results show that the synergetic combination of electrodes in each side (increased interconnectivity between COUN and graphene layer, high surface area, and high catalytic activity of FeS2) increased the power conversion efficiency from 1.56% to 3.14%. The excellent performances of COUN and FeS2 thin film in working and CEs, respectively, make them unique choices among the various photocathode and CE materials studied.

Dual Functional Core-Shell Fluorescent Ag2S@Carbon Nanostructure for Selective Assay of E. coli O157:H7 and Bactericidal Treatment.

PubMed

Wang, Ning; Wei, Xing; Zheng, An-Qi; Yang, Ting; Chen, Ming-Li; Wang, Jian-Hua

2017-03-24

A dual functional fluorescent core-shell Ag 2 S@Carbon nanostructure is prepared by a hydrothermally assisted multi-amino synthesis approach with folic acid (FA), polyethylenimine (PEI), and mannoses (Mans) as carbon and nitrogen sources (FA-PEI-Mans-Ag 2 S nanocomposite shortly as Ag 2 S@C). The nanostructure exhibits strong fluorescent emission at λ ex /λ em = 340/450 nm with a quantum yield of 12.57 ± 0.52%. Ag 2 S@C is bound to E. coli O157:H7 via strong interaction with the Mans moiety in Ag 2 S@C with FimH proteins on the fimbriae tip in E. coli O157:H7. Fluorescence emission from Ag 2 S@C/E. coli conjugate is closely related to the content of E. coli O157:H7. Thus, a novel procedure for fluorescence assay of E. coli O157:H7 is developed, offering a detection limit of 330 cfu mL -1 . Meanwhile, the Ag 2 S@C nanostructure exhibits excellent antibacterial performance against E. coli O157:H7. A 99.9% sterilization rate can be readily achieved for E. coli O157:H7 at a concentration of 10 6 -10 7 cfu mL -1 with 3.3 or 10 μg mL -1 of Ag 2 S@C with an interaction time of 5 or 0.5 min, respectively.

Reversible photo-chem-electrotriggered three-state luminescence switching based on core-shell nanostructures

NASA Astrophysics Data System (ADS)

Zhai, Yanling; Zhu, Zhijun; Zhu, Chengzhou; Zhu, Jinbo; Ren, Jiangtao; Wang, Erkang; Dong, Shaojun

2013-05-01

Reversible three-state fluorescence switches triggered by light, electricity and chemical inputs based on ``sponges'' of Pyronin Y-doped silica nanoparticles (PYDS) and polyoxometalate K14[Na(H2O)P5W30O110] (Na-POMs) core-shell nanostructures were realized. Under one or two signal inputs, the system exhibited distinct three-state interconvertible automaton, achieving reversible ``on'' and ``off'' luminescence switches via the related luminescence quenching effect. The features of the system correspond to the equivalent circuitry of an IMPLICATION logic gate performing the Boolean operation by using potential and chemical as inputs. Such a multi-chromic device with novel structure possesses several advantages, such as relative low operation voltage, large reproducibility and reversibility, apparent fluorescence contrast, and long-time stability, which make it a suitable candidate for nonvolatile memory devices. In addition, the current protocol for the hybrid film fabrication can be easily extended from the polyoxometalate and organic dyes to other novel nanostructures matched multifunctional stimulus-responsive species and fluorescence materials in the future.Reversible three-state fluorescence switches triggered by light, electricity and chemical inputs based on ``sponges'' of Pyronin Y-doped silica nanoparticles (PYDS) and polyoxometalate K14[Na(H2O)P5W30O110] (Na-POMs) core-shell nanostructures were realized. Under one or two signal inputs, the system exhibited distinct three-state interconvertible automaton, achieving reversible ``on'' and ``off'' luminescence switches via the related luminescence quenching effect. The features of the system correspond to the equivalent circuitry of an IMPLICATION logic gate performing the Boolean operation by using potential and chemical as inputs. Such a multi-chromic device with novel structure possesses several advantages, such as relative low operation voltage, large reproducibility and reversibility, apparent fluorescence contrast, and long-time stability, which make it a suitable candidate for nonvolatile memory devices. In addition, the current protocol for the hybrid film fabrication can be easily extended from the polyoxometalate and organic dyes to other novel nanostructures matched multifunctional stimulus-responsive species and fluorescence materials in the future. Electronic supplementary information (ESI) available: Experimental details and instrumentation; electrochemical, fluorescence and absorption spectra characterizations of hybrid films. See DOI: 10.1039/c3nr00254c

Design of Ultrathin Pt-Based Multimetallic Nanostructures for Efficient Oxygen Reduction Electrocatalysis.

PubMed

Lai, Jianping; Guo, Shaojun

2017-12-01

Nanocatalysts with high platinum (Pt) utilization efficiency are attracting extensive attention for oxygen reduction reactions (ORR) conducted at the cathode of fuel cells. Ultrathin Pt-based multimetallic nanostructures show obvious advantages in accelerating the sluggish cathodic ORR due to their ultrahigh Pt utilization efficiency. A focus on recent important developments is provided in using wet chemistry techniques for making/tuning the multimetallic nanostructures with high Pt utilization efficiency for boosting ORR activity and durability. First, new synthetic methods for multimetallic core/shell nanoparticles with ultrathin shell sizes for achieving highly efficient ORR catalysts are reviewed. To obtain better ORR activity and stability, multimetallic nanowires or nanosheets with well-defined structure and surface are further highlighted. Furthermore, ultrathin Pt-based multimetallic nanoframes that feature 3D molecularly accessible surfaces for achieving more efficient ORR catalysis are discussed. Finally, the remaining challenges and outlooks for the future will be provided for this promising research field. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth of GaN@InGaN Core-Shell and Au-GaN Hybrid Nanostructures for Energy Applications

DOE PAGES

Kuykendall, Tevye; Aloni, Shaul; Jen-La Plante, Ilan; ...

2009-01-01

We demonstrated a method to control the bandgap energy of GaN nanowires by forming GaN@InGaN core-shell hybrid structures using metal organic chemical vapor deposition (MOCVD). Furthermore, we show the growth of Au nanoparticles on the surface of GaN nanowires in solution at room temperature. The work shown here is a first step toward engineering properties that are crucial for the rational design and synthesis of a new class of photocatalytic materials. The hybrid structures were characterized by various techniques, including photoluminescence (PL), energy dispersive x-ray spectroscopy (EDS), transmission and scanning electron microscopy (TEM and SEM), and x-ray diffraction (XRD).

Enhancing capacitance behaviour of CoOOH nanostructures using transition metal dopants by ambient oxidation

PubMed Central

Chen, Yanhui; Zhou, Junfeng; Maguire, Pierce; O’Connell, Robert; Schmitt, Wolfgang; Li, Yonghe; Yan, Zhengguang; Zhang, Yuefei; Zhang, Hongzhou

2016-01-01

Cobalt hydrate and doped binary Co0.9M0.1OOH (M = Ni, Mn, Fe) nanorings of 100–300 nm were fabricated in solution through a facile ambient oxidation method. A transformation from Co0.9Ni0.1(OH)2 nanodiscs to hollow Co0.9Ni0.1OOH nanorings was observed with prolonged reaction time. Core-shell nanodiscs have elemental segregation with a Co(OH)2 core and Ni(OH)2 shell. Co0.9Ni0.1OOH nanorings displayed a higher electrochemical capacitance than Mn and Fe doped nanorings materials or materials with disc-like geometries. PMID:26853105

Hierarchical nanostructured hollow spherical carbon with mesoporous shell as a unique cathode catalyst support in proton exchange membrane fuel cell.

PubMed

Fang, Baizeng; Kim, Jung Ho; Kim, Minsik; Kim, Minwoo; Yu, Jong-Sung

2009-03-07

Hierarchical nanostructured spherical carbon with hollow macroporous core in combination with mesoporous shell has been explored to support Pt cathode catalyst with high metal loading in proton exchange membrane fuel cell (PEMFC). The hollow core-mesoporous shell carbon (HCMSC) has unique structural characteristics such as large specific surface area and mesoporous volume, ensuring uniform dispersion of the supported high loading (60 wt%) Pt nanoparticles with small particle size, and well-developed three-dimensionally interconnected hierarchical porosity network, facilitating fast mass transport. The HCMSC-supported Pt(60 wt%) cathode catalyst has demonstrated markedly enhanced catalytic activity toward oxygen reduction and greatly improved PEMFC polarization performance compared with carbon black Vulcan XC-72 (VC)-supported ones. Furthermore, the HCMSC-supported Pt(40 wt%) or Pt(60 wt%) outperforms the HCMSC-supported Pt(20 wt%) even at a low catalyst loading of 0.2 mg Pt cm(-2) in the cathode, which is completely different from the VC-supported Pt catalysts. The capability of supporting high loading Pt is supposed to accelerate the commercialization of PEMFC due to the anticipated significant reduction in the amount of catalyst support required, diffusion layer thickness and fabricating cost of the supported Pt catalyst electrode.

Synthesis and magnetic property of T4 virus-supported gold-coated iron ternary nanocomposite

NASA Astrophysics Data System (ADS)

Xu, Ziming; Sun, Hongjing; Gao, Faming; Hou, Li; Li, Na

2012-12-01

Herein, we present a novel method based on the use of the symmetrical T4 bacteriophage capsid as a scaffold for preparing the gold-coated iron ternary core/shell nanostructure. Results showed that the thick gold shell was obtained to effectively protect Fe core from oxidation. Magnetic measurements showed that the nanocomposites were superparamagnetic at room temperature with a blocking temperature of about 35 K. At 3 K, its coercivity of 1142.86 Oe was larger than the existing experimental values. The magnetic property of Au/T4 was also tested, demonstrating the source of the magnetic sample arising from the Fe core only. The absorption spectrum of the Fe@Au/T4 complex was measured and compared with gold/virus. Different thickness gold shells were controlled in the synthesis by tuning the Au salt addition. On the basis of results and discussion, we further speculated the general growing mechanism of the template-supported Fe@Au process.

Synthesis and characterization of core-shell gold nanoparticles with poly(vinyl pyrrolidone) from a new precursor salt

NASA Astrophysics Data System (ADS)

Behera, M.; Ram, S.

2013-02-01

In this article, we report a facile one-step chemical synthesis of gold (Au) nanoparticles (GNPs) from a new precursor salt i.e., gold hydroxide in the presence of poly(vinyl pyrrolidone) (PVP) polymer. The non-aqueous dispersion of GNPs was comprehensively characterized by UV-Visible, FTIR, zeta potential, and transmission electron microscope (TEM). A strong surface plasmon resonance band at 529 nm in the UV-Visible spectrum confirms the formation of GNPs in the Au colloid. The FTIR spectroscopic results showed that PVP molecules get chemisorbed onto the surface of GNP via O-atom of carbonyl group. A negative zeta potential of (-)16 mV reveals accumulation of nonbonding electrons of O-atom of carbonyl group of PVP molecules on the nanosurface of GNP. TEM images demonstrate a core-shell nanostructure with an Au-crystalline core covered by a thin amorphous PVP-shell. PVP-capped GNPs could be a potential candidate for bio-sensing, catalysis, and other applications.

Synthesis of bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles

PubMed Central

Li, Xue-Mei; Liu, Hong-Ling; Liu, Xiao; Fang, Ning; Wang, Xian-Hong; Wu, Jun-Hua

2015-01-01

Bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles were synthesized by a modified nanoemulsion process using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The morphology and crystal structure of the nanoparticles were studied by TEM/HRTEM and XRD. The nanoparticles manifest soft ferromagnetic and/or near superparamagnetic behavior with a small coercivity of ~19 Oe at room temperature. The corresponding magnetic hysteresis curves were elucidated by the modified Langevin equation. The FTIR study confirms the PEO-PPO-PEO molecules on the surface of the nanoparticles. The UV-vis and PL results reveal the well-behaved absorption bands including surface plasmon resonance and multiple visible fingerprint photoluminescent emissions of the nanoparticles dispersed in both hydrophilic and hydrophobic solvents. Moreover, the processes of solvent dispersion-collection of the nanoparticles were demonstrated for application readiness of such core-shell nanostructures. PMID:26548369

Supramolecular core-shell nanoparticles for photoconductive device applications

NASA Astrophysics Data System (ADS)

Cheng, Chih-Chia; Chen, Jem-Kun; Shieh, Yeong-Tarng; Lee, Duu-Jong

2016-08-01

We report a breakthrough discovery involving supramolecular-based strategies to construct novel core-shell heterojunction nanoparticles with hydrophilic adenine-functionalized polythiophene (PAT) as the core and hydrophobic phenyl-C61-butyric acid methyl ester (PCBM) as the shell, which enables the conception of new functional supramolecular assemblies for constructing functional nanomaterials for applications in optoelectronic devices. The generated nanoparticles exhibit uniform spherical shape, well-controlled tuning of particle size with narrow size distributions, and excellent electrochemical stability in solution and the solid state owing to highly efficient energy transfer from PAT to PCBM. When the PAT/PCBM nanoparticles were fabricated into a photoconducting layer in an electronic device, the resulting device showed excellent electric conduction characteristics, including an electrically-tunable voltage-controlled switch, and high short-circuit current and open-circuit voltage. These observations demonstrate how the self-assembly of PAT/PCBM into specific nanostructures may help to promote efficient charge generation and transport processes, suggesting potential for a wide variety of applications as a promising candidate material for bulk heterojunction polymer devices.

Synthesis of bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles

NASA Astrophysics Data System (ADS)

Li, Xue-Mei; Liu, Hong-Ling; Liu, Xiao; Fang, Ning; Wang, Xian-Hong; Wu, Jun-Hua

2015-11-01

Bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles were synthesized by a modified nanoemulsion process using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The morphology and crystal structure of the nanoparticles were studied by TEM/HRTEM and XRD. The nanoparticles manifest soft ferromagnetic and/or near superparamagnetic behavior with a small coercivity of ~19 Oe at room temperature. The corresponding magnetic hysteresis curves were elucidated by the modified Langevin equation. The FTIR study confirms the PEO-PPO-PEO molecules on the surface of the nanoparticles. The UV-vis and PL results reveal the well-behaved absorption bands including surface plasmon resonance and multiple visible fingerprint photoluminescent emissions of the nanoparticles dispersed in both hydrophilic and hydrophobic solvents. Moreover, the processes of solvent dispersion-collection of the nanoparticles were demonstrated for application readiness of such core-shell nanostructures.

Graphene-Encapsulated Nanosheet-Assembled Zinc-Nickel-Cobalt Oxide Microspheres for Enhanced Lithium Storage.

PubMed

Zhang, Qiaobao; Chen, Huixin; Han, Xiang; Cai, Junjie; Yang, Yong; Liu, Meilin; Zhang, Kaili

2016-01-01

The appropriate combination of hierarchical transition-metal oxide (TMO) micro-/nanostructures constructed from porous nanobuilding blocks with graphene sheets (GNS) in a core/shell geometry is highly desirable for high-performance lithium-ion batteries (LIBs). A facile and scalable process for the fabrication of 3D hierarchical porous zinc-nickel-cobalt oxide (ZNCO) microspheres constructed from porous ultrathin nanosheets encapsulated by GNS to form a core/shell geometry is reported for improved electrochemical performance of the TMOs as an anode in LIBs. By virtue of their intriguing structural features, the produced ZNCO/GNS core/shell hybrids exhibit an outstanding reversible capacity of 1015 mA h g(-1) at 0.1 C after 50 cycles. Even at a high rate of 1 C, a stable capacity as high as 420 mA h g(-1) could be maintained after 900 cycles, which suggested their great potential as efficient electrodes for high-performance LIBs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale Seebeck effect at hot metal nanostructures

NASA Astrophysics Data System (ADS)

Ly, Aboubakry; Majee, Arghya; Würger, Alois

2018-02-01

We theoretically study the electrolyte Seebeck effect in the vicinity of a heated metal nanostructure, such as the cap of an active Janus colloid in an electrolyte, or gold-coated interfaces in optofluidic devices. The thermocharge accumulated at the surface varies with the local temperature, thus modulating the diffuse part of the electric double layer. On a conducting surface with non-uniform temperature, the isopotential condition imposes a significant polarization charge within the metal. Surprisingly, this does not affect the slip velocity, which takes the same value on insulating and conducting surfaces. Our results for specific-ion effects agree qualitatively with recent observations for Janus colloids in different electrolyte solutions. Comparing the thermal, hydrodynamic, and ion diffusion time scales, we expect a rich transient behavior at the onset of thermally powered swimming, extending to microseconds after switching on the heating.

Direct Fabrication of Monodisperse Silica Nanorings from Hollow Spheres - A Template for Core-Shell Nanorings.

PubMed

Zhong, Kuo; Li, Jiaqi; Liu, Liwang; Brullot, Ward; Bloemen, Maarten; Volodin, Alexander; Song, Kai; Van Dorpe, Pol; Verellen, Niels; Clays, Koen

2016-04-27

We report a new type of nanosphere colloidal lithography to directly fabricate monodisperse silica (SiO2) nanorings by means of reactive ion etching of hollow SiO2 spheres. Detailed TEM, SEM, and AFM structural analysis is complemented by a model describing the geometrical transition from hollow sphere to ring during the etching process. The resulting silica nanorings can be readily redispersed in solution and subsequently serve as universal templates for the synthesis of ring-shaped core-shell nanostructures. As an example we used silica nanorings (with diameter of ∼200 nm) to create a novel plasmonic nanoparticle topology, a silica-Au core-shell nanoring, by self-assembly of Au nanoparticles (<20 nm) on the ring's surface. Spectroscopic measurements and finite difference time domain simulations reveal high quality factor multipolar and antibonding surface plasmon resonances in the near-infrared. By loading different types of nanoparticles on the silica core, hybrid and multifunctional composite nanoring structures could be realized for applications such as MRI contrast enhancement, catalysis, drug delivery, plasmonic and magnetic hyperthermia, photoacoustic imaging, and biochemical sensing.

Synthesis of NiO-TiO2 hybrids/mSiO2 yolk-shell architectures embedded with ultrasmall gold nanoparticles for enhanced reactivity

NASA Astrophysics Data System (ADS)

Fang, Jiasheng; Zhang, Yiwei; Zhou, Yuming; Zhao, Shuo; Zhang, Chao; Huang, Mengqiu; Gao, Yan

2017-08-01

Novel NiO-TiO2 hybrids/mSiO2 yolk-shell architectures loaded with ultrasmall Au nanoparticles (STNVS-Au) were developed via the rational synthetic strategy. The hierarchical yolk-shell nanostructures (STNVS) with high surface areas were constructed by a facile "bottom-up" assembly process using SiO2 materials and polymer resins as cores/shells and sacrificial templates, accompanied by a simple hydrothermal incorporation of NiO into uniform amorphous TiO2 layers that were converted to NiO-anatase TiO2 p-n heterojunction hybrids. Then, numerous sub-3 nm Au nanoparticles were post encapsulated within STNVS nanostructures through the low-temperature hydrogen reduction based on the unique deposition-precipitation method with Au(en)2Cl3 compounds as gold precursors. The NiO-TiO2 hybrids alloying with Au nanoparticles were effectively protected and entrapped within STNVS architectures, and interacted with outer mSiO2-Au shells, which comprised the powerful STNVS-Au yolk-shell nanoreactors and produced stronger configural synergies in enhancing the heterogeneous catalysis. Into catalyzing the reduction of 4-nitrophenol to 4-aminophenol, the STNVS-Au was shown with outstanding activity and reusability, and its pristine morphology was well retained during the recycling process.

Silica-covered star-shaped Au-Ag nanoparticles as new electromagnetic nanoresonators for Raman characterisation of surfaces.

PubMed

Krajczewski, Jan; Kołątaj, Karol; Pietrasik, Sylwia; Kudelski, Andrzej

2018-03-15

One of the tools used for determining the composition of surfaces of various materials is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). SHINERS is a modification of "standard" surface-enhanced Raman spectroscopy (SERS), in which, before Raman spectra are recorded, the surfaces analysed are covered with a layer of plasmonic nanoparticles protected by a very thin layer of a transparent dielectric. The plasmonic cores of the core-shell nanoparticles used in SHINERS measurements generate a local enhancement of the electric field of the incident electromagnetic radiation, whereas the transparent coatings prevent the metal cores from coming into direct contact with the material being analysed. In this contribution, we propose a new type of SHINERS nanoresonators that contain spiky, star-shaped metal cores (produced from a gold/silver alloy). These spiky, star-shaped Au-Ag nanoparticles have been covered by a layer of silica. The small radii of the ends of the tips of the spikes of these plasmonic nanostructures make it possible to generate a very large enhancement of the electromagnetic field there, with the result that such SHINERS nanoresonators are significantly more efficient than the standard semi-spherical nanostructures. The Au-Ag alloy nanoparticles were synthesised by the reduction of a solution containing silver nitrate and chloroauric acid by ascorbic acid. The final geometry of the nanostructures thus formed was controlled by changing the ratio between the concentrations of AuCl 4 - and Ag + ions. The shape of the synthesised star-shaped Au-Ag nanoparticles does not change significantly during the two standard procedures for depositing a layer of silica (by the decomposition of sodium silicate or the decomposition of tetraethyl orthosilicate). Copyright © 2017 Elsevier B.V. All rights reserved.

Silica-covered star-shaped Au-Ag nanoparticles as new electromagnetic nanoresonators for Raman characterisation of surfaces

NASA Astrophysics Data System (ADS)

Krajczewski, Jan; Kołątaj, Karol; Pietrasik, Sylwia; Kudelski, Andrzej

2018-03-01

One of the tools used for determining the composition of surfaces of various materials is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). SHINERS is a modification of "standard" surface-enhanced Raman spectroscopy (SERS), in which, before Raman spectra are recorded, the surfaces analysed are covered with a layer of plasmonic nanoparticles protected by a very thin layer of a transparent dielectric. The plasmonic cores of the core-shell nanoparticles used in SHINERS measurements generate a local enhancement of the electric field of the incident electromagnetic radiation, whereas the transparent coatings prevent the metal cores from coming into direct contact with the material being analysed. In this contribution, we propose a new type of SHINERS nanoresonators that contain spiky, star-shaped metal cores (produced from a gold/silver alloy). These spiky, star-shaped Au-Ag nanoparticles have been covered by a layer of silica. The small radii of the ends of the tips of the spikes of these plasmonic nanostructures make it possible to generate a very large enhancement of the electromagnetic field there, with the result that such SHINERS nanoresonators are significantly more efficient than the standard semi-spherical nanostructures. The Au-Ag alloy nanoparticles were synthesised by the reduction of a solution containing silver nitrate and chloroauric acid by ascorbic acid. The final geometry of the nanostructures thus formed was controlled by changing the ratio between the concentrations of AuCl4- and Ag+ ions. The shape of the synthesised star-shaped Au-Ag nanoparticles does not change significantly during the two standard procedures for depositing a layer of silica (by the decomposition of sodium silicate or the decomposition of tetraethyl orthosilicate).

Aspartame-stabilized gold-silver bimetallic biocompatible nanostructures with plasmonic photothermal properties, antibacterial activity, and long-term stability.

PubMed

Fasciani, Chiara; Silvero, M Jazmin; Anghel, Maria Alexandra; Argüello, Gerardo A; Becerra, Maria Cecilia; Scaiano, Juan C

2014-12-17

Gold-silver core-shell nanoparticles stabilized with a common sweetener, aspartame (AuNP@Ag@Asm), combine the antimicrobial properties of silver with the photoinduced plasmon-mediated photothermal effects of gold. The particles were tested with several bacterial strains, while biocompatibility was verified with human dermal fibroblasts.

Visible-light photochemical activity of heterostructured core-shell materials composed of selected ternary titanates and ferrites coated by tiO2.

PubMed

Li, Li; Liu, Xuan; Zhang, Yiling; Nuhfer, Noel T; Barmak, Katayun; Salvador, Paul A; Rohrer, Gregory S

2013-06-12

Heterostructured photocatalysts comprised of microcrystalline (mc-) cores and nanostructured (ns-) shells were prepared by the sol-gel method. The ability of titania-coated ATiO3 (A = Fe, Pb) and AFeO3 (A = Bi, La, Y) catalysts to degrade methylene blue in visible light (λ > 420 nm) was compared. The catalysts with the titanate cores had enhanced photocatalytic activities for methylene blue degradation compared to their components alone, whereas the catalysts with ferrite cores did not. The temperature at which the ns-titania shell is crystallized influences the photocatalytic dye degradation. mc-FeTiO3/ns-TiO2 annealed at 500 °C shows the highest reaction rate. Fe-doped TiO2, which absorbs visible light, did not show enhanced photocatalytic activity for methylene blue degradation. This result indicates that iron contamination is not a decisive factor in the reduced reactivity of the titania coated ferrite catalysts. The higher reactivity of materials with the titanate cores suggests that photogenerated charge carriers are more easily transported across the titanate-titanate interface than the ferrite-titanate interface and this provides guidance for materials selection in composite catalyst design.

In-depth understanding of core-shell nanoarchitecture evolution of g-C3N4@C, N co-doped anatase/rutile: Efficient charge separation and enhanced visible-light photocatalytic performance

NASA Astrophysics Data System (ADS)

Mohamed, Mohamad Azuwa; Jaafar, Juhana; M. Zain, M. F.; Minggu, Lorna Jeffery; Kassim, Mohammad B.; Rosmi, Mohamad Saufi; Alias, Nur Hashimah; Mohamad Nor, Nor Azureen; W. Salleh, W. N.; Othman, Mohd Hafiz Dzarfan

2018-04-01

Herein, we demonstrated the simultaneous formation of multi-component heterojunction consisting graphitic carbon nitride (g-C3N4) and C, N co-doped anatase/rutile mixed phase by using facile sol-gel assisted heat treatment. The evolution of core-shell nanostructures heterojunction formation was elucidated by varying the temperature of heat treatment from 300 °C to 600 °C. Homogeneous heterojunction formation between g-C3N4 and anatase/rutile mixed phase was observed in gT400 with C and N doping into TiO2 lattice by O substitution. The core-shell nanoarchitectures between g-C3N4 as shell, and anatase/rutile mixed phase as core with C and N atoms are doped at the interstitial positions of TiO2 lattice was observed in gT500. The result indicated that core-shell nanoarchitectures photocatalyst (gT500) prepared at 500 ◦C exhibited the highest photocatalytic activity in the degradation of methyl orange under visible light irradiation. Meanwhile, the possible mechanisms of charge generation, migration, action species and reaction that probably occur at the gT500 sample were also proposed. The photodegradation results of gT500 correlated completely with the results of the PEC and photoluminescence analysis, which directly evidenced improved charge separation and migration as the crucial parameters governing photocatalysis. It is worthy to note that, the simultaneous formation of multicomponent heterojunction with core-shell structure provided an enormous impact in designing highly active photocatalyst with superior interfacial charge transfer.

Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid

NASA Astrophysics Data System (ADS)

Zhang, Guojun; Zheng, Hongmei; Shen, Ming; Wang, Lei; Wang, Xiaosan

2015-06-01

In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core-shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl4- and PtCl62-, where the AuCl4- ions are preferentially reduced to Au cores and the PtCl62- ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl4/H2PtCl6, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core-shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH4 reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core-shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.

Metal Nanoshells for Plasmonically Enhanced Solar-to-Fuel Photocatalytic Conversion

DTIC Science & Technology

2014-05-09

Final 3. DATES COVERED (From - To) 04/16/2013 – 04/15/2014 4. TITLE AND SUBTITLE Metal Nanoshells for Plasmonically Enhanced Solar -to...following experiments, the core-shell of nanoshell@SiO2, as well as the nanostructure of photocatalyst, were further investigated. Solar energy in the...nanoshells as the core can absorb the solar energy in the IR and visible-light region ranging from 500 nm to 900 nm. Our data showed that the plasmonic

Importance of polypyrrole in constructing 3D hierarchical carbon nanotube@MnO2 perfect core-shell nanostructures for high-performance flexible supercapacitors

NASA Astrophysics Data System (ADS)

Zhou, Jinyuan; Zhao, Hao; Mu, Xuemei; Chen, Jiayi; Zhang, Peng; Wang, Yaling; He, Yongmin; Zhang, Zhenxing; Pan, Xiaojun; Xie, Erqing

2015-08-01

This study reports the preparation of 3D hierarchical carbon nanotube (CNT) @MnO2 core-shell nanostructures under the assistance of polypyrrole (PPy). The as-prepared CNT@PPy@MnO2 core-shell structures show a perfect coating of MnO2 on each CNT and, more importantly, a robust bush-like pseudocapacitive shell to effectively increase the specific surface area and enhance the ion accessibility. As expected, a high specific capacity of 490-530 F g-1 has been achieved from CNT@PPy@MnO2 single electrodes. And about 98.5% of the capacity is retained after 1000 charge/discharge cycles at a current density of 5 A g-1. Furthermore, the assembled asymmetric CNT@PPy@MnO2//AC capacitors show the maximum energy density of 38.42 W h kg-1 (2.24 mW h cm-3) at a power density of 100 W kg-1 (5.83 mW cm-3), and they maintain 59.52% of the initial value at 10 000 W kg-1 (0.583 W cm-3). In addition, the assembled devices show high cycling stabilities (89.7% after 2000 cycles for asymmetric and 87.2% for symmetric), and a high bending stability (64.74% after 200 bending tests). This ability to obtain high energy densities at high power rates while maintaining high cycling stability demonstrates that this well-designed structure could be a promising electrode material for high-performance supercapacitors.This study reports the preparation of 3D hierarchical carbon nanotube (CNT) @MnO2 core-shell nanostructures under the assistance of polypyrrole (PPy). The as-prepared CNT@PPy@MnO2 core-shell structures show a perfect coating of MnO2 on each CNT and, more importantly, a robust bush-like pseudocapacitive shell to effectively increase the specific surface area and enhance the ion accessibility. As expected, a high specific capacity of 490-530 F g-1 has been achieved from CNT@PPy@MnO2 single electrodes. And about 98.5% of the capacity is retained after 1000 charge/discharge cycles at a current density of 5 A g-1. Furthermore, the assembled asymmetric CNT@PPy@MnO2//AC capacitors show the maximum energy density of 38.42 W h kg-1 (2.24 mW h cm-3) at a power density of 100 W kg-1 (5.83 mW cm-3), and they maintain 59.52% of the initial value at 10 000 W kg-1 (0.583 W cm-3). In addition, the assembled devices show high cycling stabilities (89.7% after 2000 cycles for asymmetric and 87.2% for symmetric), and a high bending stability (64.74% after 200 bending tests). This ability to obtain high energy densities at high power rates while maintaining high cycling stability demonstrates that this well-designed structure could be a promising electrode material for high-performance supercapacitors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03426d

Construction of Core-Shell NiMoO4@Ni-Co-S Nanorods as Advanced Electrodes for High-Performance Asymmetric Supercapacitors.

PubMed

Chen, Chao; Yan, Dan; Luo, Xin; Gao, Wenjia; Huang, Guanjie; Han, Ziwu; Zeng, Yan; Zhu, Zhihong

2018-02-07

In this work, hierarchical core-shell NiMoO 4 @Ni-Co-S nanorods were first successfully grown on nickel foam by a facile two-step method to fabricate a bind-free electrode. The well-aligned electrode wrapped by Ni-Co-S nanosheets displays excellent nanostructural properties and outstanding electrochemical performance, owing to the synergistic effects of both nickel molybdenum oxides and nickel cobalt sulfides. The prepared core-shell nanorods in a three-electrode cell yielded a high specific capacitance of 2.27 F cm -2 (1892 F g -1 ) at a current density of 5 mA cm -2 and retained 91.7% of the specific capacitance even after 6000 cycles. Their electrochemical performance was further investigated for their use as positive electrode for asymmetric supercapacitors. Notably, the energy density of the asymmetric supercapacitor device reached 2.45 mWh cm -3 at a power density of 0.131 W cm -3 , and still retained a remarkable 80.3% of the specific capacitance after 3500 cycles. There is great potential for the electrode composed of the core-shell NiMoO 4 @Ni-Co-S nanorods for use in an all-solid-state asymmetric supercapacitor device.

Rational design of octahedron and nanowire CeO2@MnO2 core-shell heterostructures with outstanding rate capability for asymmetric supercapacitors.

PubMed

Zhu, Shi Jin; Jia, Jia Qi; Wang, Tian; Zhao, Dong; Yang, Jian; Dong, Fan; Shang, Zheng Guo; Zhang, Yu Xin

2015-10-14

Two kinds of novel CeO2@MnO2 nanostructures have been synthesized via a self-assembly strategy. The as-prepared CeO2 nanowire@MnO2 nanostructures exhibited unprecedented pseudocapacitance performance (255 F g(-1)) with outstanding rate capability. A new mechanism based on the synergistic effect between CeO2 and MnO2 was proposed to interpret this phenomenon. When assembled as an asymmetric supercapacitor, an energy density of 27.5 W h kg(-1) with a maximum power density of 1.6 kW kg(-1) was achieved for CeO2 nanowire@MnO2 nanostructures.

Local Crystalline Structure in an Amorphous Protein Dense Phase

PubMed Central

Greene, Daniel G.; Modla, Shannon; Wagner, Norman J.; Sandler, Stanley I.; Lenhoff, Abraham M.

2015-01-01

Proteins exhibit a variety of dense phases ranging from gels, aggregates, and precipitates to crystalline phases and dense liquids. Although the structure of the crystalline phase is known in atomistic detail, little attention has been paid to noncrystalline protein dense phases, and in many cases the structures of these phases are assumed to be fully amorphous. In this work, we used small-angle neutron scattering, electron microscopy, and electron tomography to measure the structure of ovalbumin precipitate particles salted out with ammonium sulfate. We found that the ovalbumin phase-separates into core-shell particles with a core radius of ∼2 μm and shell thickness of ∼0.5 μm. Within this shell region, nanostructures comprised of crystallites of ovalbumin self-assemble into a well-defined bicontinuous network with branches ∼12 nm thick. These results demonstrate that the protein gel is comprised in part of nanocrystalline protein. PMID:26488663

Plasmonic Nanodiamonds – Targeted Core-shell Type Nanoparticles for Cancer Cell Thermoablation

PubMed Central

Rehor, Ivan; Lee, Karin L.; Chen, Kevin; Hajek, Miroslav; Havlik, Jan; Lokajova, Jana; Masat, Milan; Slegerova, Jitka; Shukla, Sourabh; Heidari, Hamed; Bals, Sara

2015-01-01

Targeted biocompatible nanostructures with controlled plasmonic and morphological parameters are promising materials for cancer treatment based on selective thermal ablation of cells. Here, core-shell plasmonic nanodiamonds consisting of a silica-encapsulated diamond nanocrystal coated in a gold shell is designed and synthesized. The architecture of particles is analyzed and confirmed in detail using 3-dimensional transmission electron microscope tomography. The particles are biocompatibilized using a PEG polymer terminated with bioorthogonally reactive alkyne groups. Azide-modified transferrin is attached to these particles, and their high colloidal stability and successful targeting to cancer cells overexpressing the transferrin receptor is demonstrated. The particles are nontoxic to the cells and they are readily internalized upon binding to the transferrin receptor. The high plasmonic cross section of the particles in the near-infrared region is utilized to quantitatively ablate the cancer cells with a short, one-minute irradiation by a pulse 750-nm laser. PMID:25336437

Magnetic core/shell nanoparticle thin films deposited by MAPLE: Investigation by chemical, morphological and in vitro biological assays

NASA Astrophysics Data System (ADS)

Cristescu, R.; Popescu, C.; Socol, G.; Iordache, I.; Mihailescu, I. N.; Mihaiescu, D. E.; Grumezescu, A. M.; Balan, A.; Stamatin, I.; Chifiriuc, C.; Bleotu, C.; Saviuc, C.; Popa, M.; Chrisey, D. B.

2012-09-01

We report on thin film deposition of nanostructured Fe3O4/oleic acid/ceftriaxone and Fe3O4/oleic acid/cefepime nanoparticles (core/shell/adsorption-shell) were fabricated by matrix assisted pulsed laser evaporation (MAPLE) onto inert substrates. The thin films were characterized by profilometry, Fourier transform infrared spectroscopy, atomic force microscopy, and investigated by in vitro biological assays. The biological properties tested included the investigation of the microbial viability and the microbial adherence to the glass coverslip nanoparticle film, using Gram-negative and Gram-positive bacterial strains with known antibiotic susceptibility behavior, the microbial adherence to the HeLa cells monolayer grown on the nanoparticle pellicle, and the cytotoxicity on eukaryotic cells. The proposed system, based on MAPLE, could be used for the development of novel anti-microbial materials or strategies for fighting pathogenic biofilms frequently implicated in the etiology of biofilm associated chronic infections.

Hierarchical paramecium-like hollow and solid Au/Pt bimetallic nanostructures constructed using goethite as template

NASA Astrophysics Data System (ADS)

Liu, Wei; Repo, Eveliina; Heikkilä, Mikko; Leskelä, Markku; Sillanpää, Mika

2010-10-01

Novel hollow and solid paramecium-like hierarchical Au/Pt bimetallic nanostructures were constructed using goethite as template via a seed-mediated growth method. Transmission electron microscopy (TEM), ξ-potential measurement, UV-vis spectroscopy, energy dispersive x-ray spectroscopy (EDS), ICP-AES measurement, x-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) were utilized to systematically characterize the bimetallic nanostructures. It is found that the core structure of the paramecium-like bimetallic nanomaterial is closely related to reducing agent. When ascorbic acid is used as reducing agent, goethite serves as in situ sacrificed template and hollow paramecium-like bimetallic structure is obtained. When NH2OH·HCl is used, solid nanostructure with preserved goethite core is produced. Heating the reaction solution is necessary to obtain the paramecium-like morphology with rough interconnected Pt cilia shell. The thickness of Pt cilia layer can be controlled by adjusting the molar ratio of H2PtCl6 to Au nanoseeds. The overgrowth of the rough Pt cilia is proposed to be via an autocatalytic and three-dimensional heterogeneous nucleation process first through flower-like morphology. Both the hollow and solid hierarchical paramecium-like Au/Pt bimetallic nanostructures show good catalytic activities.

Hierarchical paramecium-like hollow and solid Au/Pt bimetallic nanostructures constructed using goethite as template.

PubMed

Liu, Wei; Repo, Eveliina; Heikkilä, Mikko; Leskelä, Markku; Sillanpää, Mika

2010-10-01

Novel hollow and solid paramecium-like hierarchical Au/Pt bimetallic nanostructures were constructed using goethite as template via a seed-mediated growth method. Transmission electron microscopy (TEM), xi-potential measurement, UV-vis spectroscopy, energy dispersive x-ray spectroscopy (EDS), ICP-AES measurement, x-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) were utilized to systematically characterize the bimetallic nanostructures. It is found that the core structure of the paramecium-like bimetallic nanomaterial is closely related to reducing agent. When ascorbic acid is used as reducing agent, goethite serves as in situ sacrificed template and hollow paramecium-like bimetallic structure is obtained. When NH(2)OH.HCl is used, solid nanostructure with preserved goethite core is produced. Heating the reaction solution is necessary to obtain the paramecium-like morphology with rough interconnected Pt cilia shell. The thickness of Pt cilia layer can be controlled by adjusting the molar ratio of H(2)PtCl(6) to Au nanoseeds. The overgrowth of the rough Pt cilia is proposed to be via an autocatalytic and three-dimensional heterogeneous nucleation process first through flower-like morphology. Both the hollow and solid hierarchical paramecium-like Au/Pt bimetallic nanostructures show good catalytic activities.

Quantitative 3D determination of self-assembled structures on nanoparticles using small angle neutron scattering.

PubMed

Luo, Zhi; Marson, Domenico; Ong, Quy K; Loiudice, Anna; Kohlbrecher, Joachim; Radulescu, Aurel; Krause-Heuer, Anwen; Darwish, Tamim; Balog, Sandor; Buonsanti, Raffaella; Svergun, Dmitri I; Posocco, Paola; Stellacci, Francesco

2018-04-09

The ligand shell (LS) determines a number of nanoparticles' properties. Nanoparticles' cores can be accurately characterized; yet the structure of the LS, when composed of mixture of molecules, can be described only qualitatively (e.g., patchy, Janus, and random). Here we show that quantitative description of the LS' morphology of monodisperse nanoparticles can be obtained using small-angle neutron scattering (SANS), measured at multiple contrasts, achieved by either ligand or solvent deuteration. Three-dimensional models of the nanoparticles' core and LS are generated using an ab initio reconstruction method. Characteristic length scales extracted from the models are compared with simulations. We also characterize the evolution of the LS upon thermal annealing, and investigate the LS morphology of mixed-ligand copper and silver nanoparticles as well as gold nanoparticles coated with ternary mixtures. Our results suggest that SANS combined with multiphase modeling is a versatile approach for the characterization of nanoparticles' LS.

Au@TiO2 yolk-shell nanostructures for enhanced performance in both photoelectric and photocatalytic solar conversion

NASA Astrophysics Data System (ADS)

He, Qinrong; Sun, Hang; Shang, Yinxing; Tang, Yanan; She, Ping; Zeng, Shan; Xu, Kongliang; Lu, Guolong; Liang, Song; Yin, Shengyan; Liu, Zhenning

2018-05-01

Solar energy conversion is an important field gaining increasing interest. Herein, bio-inspired Au@TiO2 yolk-shell nanoparticles (NPs) have been prepared via a facial one-pot hydrothermal approach. The Au@TiO2 yolk-shell NPs can self-assemble into 3D-structure to form photoelectrode for photoelectric conversion. The obtained photoelectrode demonstrates a swift and stable photocurrent of 3.5 μA/cm2, which is 4.2 and 1.6 times higher than those of the photocurrents generated by the counterparts of commercial TiO2 and Au@TiO2 core-shell NPs, respectively. Moreover, compared to the commercial TiO2 and Au@TiO2 core-shell NPs, the Au@TiO2 yolk-shell NPs also exhibit superior photocatalytic activity, delivering a H2 evolution rate of 4.92 mmol/g h. The performance improvement observed for the Au@TiO2 yolk-shell NPs is likely contributed by two synergistic factors, i.e. the incorporation of AuNPs and the unique hollow structure, which benefit the activity by simultaneously enhancing light utilization, charge separation and reaction site accessibility. The rational design and fabrication of Au@TiO2 yolk-shell NPs hold great promise for future application in efficient solar energy conversion.

Fabrication of Silica-Coated Hollow Carbon Nanospheres Encapsulating Fe3O4 Cluster for Magnetical and MR Imaging Guided NIR Light Triggering Hyperthermia and Ultrasound Imaging.

PubMed

Huang, Yun-Kai; Su, Chia-Hao; Chen, Jiu-Jeng; Chang, Chun-Ting; Tsai, Yu-Hsin; Syu, Sheng-Fu; Tseng, Tsu-Ting; Yeh, Chen-Sheng

2016-06-15

Iron oxide nanoparticles (IONPs)-carbon (C) hybrid zero-dimensional nanostructures normally can be categorized into core-shell and yolk-shell architectures. Although IONP-C is a promising theranostic nanoagent, the in vivo study has surprisingly been less described. In addition, little effort has strived toward the fabrication of yolk-shell compared to the core-shell structures. In this context, we synthesized a yolk-shell type of the silica-coated hollow carbon nanospheres encapsulating IONPs cluster, which can be dispersed in aqueous solution for systemic studies in vivo, via the preparation involving the mixed micellization, polymerization/hollowing, sol-gel (hydration-condensation), and pyrolysis processes. Through a surface modification of the polyethylenimine followed by the sol-gel process, the silica shell coating was able to escape from condensing and sintering courses resulting in aggregation, due to the annealing. Not limited to the well-known functionalities in magnetical targeting and magnetic resonance (MR) imaging for IONP-C hybrid structures, we expanded this yolk-shell NPs as a near-infrared (NIR) light-responsive echogenic nanoagent giving an enhanced ultrasound imaging. Overall, we fabricated the NIR sensitive yolk-shell IONP-C to activate ultrasound imaging and photothermal ablation under magnetically and MR imaging guided therapy.

Solvent-Tuned Self-Assembled Nanostructures of Chiral l/d-Phenylalanine Derivatives of Protoporphyrin IX

PubMed Central

Bobe, Mr Sharad R; Al Kobaisi, Mohammad; Bhosale, Sheshanath V; Bhosale, Sidhanath V

2015-01-01

Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π–π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine. PMID:26478848

Solvent-Tuned Self-Assembled Nanostructures of Chiral l/d-Phenylalanine Derivatives of Protoporphyrin IX.

PubMed

Bobe, Mr Sharad R; Al Kobaisi, Mohammad; Bhosale, Sheshanath V; Bhosale, Sidhanath V

2015-08-01

Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π-π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine.

Synthesis, characterization, and photocatalytic properties of core/shell mesoporous silica nanospheres supporting nanocrystalline titania

NASA Astrophysics Data System (ADS)

Cendrowski, K.; Chen, X.; Zielinska, B.; Kalenczuk, R. J.; Rümmeli, M. H.; Büchner, B.; Klingeler, R.; Borowiak-Palen, E.

2011-11-01

The facile bulk synthesis of silica nanospheres makes them an attractive support for the transport of chemical compounds such as nanocrystalline titanium dioxide. In this contribution we present a promising route for the synthesis of mesoporous silica nanospheres (m-SiO2) with diameter in range 200 nm, which are ideal supports for nanocrystalline titanium dioxide (TiO2). The detailed microscopic and spectroscopic characterizations of core/shell structure (m-SiO2/TiO2) were conducted. Moreover, the photocatalytic potential of the nanostructures was investigated via phenol decomposition and hydrogen generation. A clear enhancement of photoactivity in both reactions as compared to commercial TiO2-Degussa P25 catalyst is detected.

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.

Inorganic Janus particles for biomedical applications

PubMed Central

Schick, Isabel; Lorenz, Steffen; Gehrig, Dominik; Tenzer, Stefan; Storck, Wiebke; Fischer, Karl; Strand, Dennis; Laquai, Frédéric

2014-01-01

Summary Based on recent developments regarding the synthesis and design of Janus nanoparticles, they have attracted increased scientific interest due to their outstanding properties. There are several combinations of multicomponent hetero-nanostructures including either purely organic or inorganic, as well as composite organic–inorganic compounds. Janus particles are interconnected by solid state interfaces and, therefore, are distinguished by two physically or chemically distinct surfaces. They may be, for instance, hydrophilic on one side and hydrophobic on the other, thus, creating giant amphiphiles revealing the endeavor of self-assembly. Novel optical, electronic, magnetic, and superficial properties emerge in inorganic Janus particles from their dimensions and unique morphology at the nanoscale. As a result, inorganic Janus nanoparticles are highly versatile nanomaterials with great potential in different scientific and technological fields. In this paper, we highlight some advances in the synthesis of inorganic Janus nanoparticles, focusing on the heterogeneous nucleation technique and characteristics of the resulting high quality nanoparticles. The properties emphasized in this review range from the monodispersity and size-tunability and, therefore, precise control over size-dependent features, to the biomedical application as theranostic agents. Hence, we show their optical properties based on plasmonic resonance, the two-photon activity, the magnetic properties, as well as their biocompatibility and interaction with human blood serum. PMID:25551063

Copper, gold, and silver decorated magnetic core-polymeric shell nanostructures for destruction of pathogenic bacteria

NASA Astrophysics Data System (ADS)

Padervand, Mohsen; Karanji, Ahmad Kiani; Elahifard, Mohammad Reza

2017-05-01

Fe3O4 magnetic nanoparticles (MNPs) were prepared by co-precipitation method. The nanoparticles were silica coated using TEOS, and then modified by the polymeric layers of polypropylene glycol (PPG) and polyethylene glycol (PEG). Finally, the core-shell samples were decorated with Ag, Au, and Cu nanoparticles. The products were characterized by vibrating sample magnetometry (VSM), TGA, SEM, XRD, and FTIR methods. The antibacterial activity of the prepared samples was evaluated in inactivation of E. coli and S. aureus microorganisms, representing the Gram-negative and Gram-positive species, respectively. The effect of solid dosage, bacteria concentration and type of polymeric modifier on the antibacterial activity was investigated. TEM images of the bacteria were recorded after the treatment time and according to the observed changes in the cell wall, the mechanism of antibacterial action was discussed. The prepared nanostructures showed high antibacterial activity against both Gram-negative and Gram-positive bacteria. This was due to the leaching of metal ions which subsequently led to the lysis of bacteria. A theoretical investigation was also done by studying the interaction of loaded metals with the nucleotide components of the microorganism DNA, and the obtained results were used to explain the experimental data. Finally, based on the observed inactivation curves, we explain the antibacterial behavior of the prepared nanostructures mathematically.

Spectrally-resolved internal quantum efficiency and carrier dynamics of semipolar [Formula: see text] core-shell triangular nanostripe GaN/InGaN LEDs.

PubMed

Okur, Serdal; Rishinaramangalam, Ashwin K; Mishkat-Ul-Masabih, Saadat; Nami, Mohsen; Liu, Sheng; Brener, Igal; Brueck, Steven R J; Feezell, Daniel F

2018-06-08

We investigate the spectrally resolved internal quantum efficiency (IQE) and carrier dynamics in semipolar [Formula: see text] core-shell triangular nanostripe light-emitting diodes (TLEDs) using temperature-dependent photoluminescence (TDPL) and time-resolved photoluminescence (TRPL) at various excitation energy densities. Using electroluminescence, photoluminescence, and cathodoluminescence measurements, we verify the origins of the broad emission spectra from the nanostructures and confirm that localized regions of high-indium-content InGaN exist along the apex of the nanostructures. Spectrally resolved IQE measurements are then performed, with the spectra integrated from 400-450 nm and 450-500 nm to obtain the IQE of the QWs mainly near the sidewalls and apex of the TLEDs, respectively. TDPL and TRPL are used to decouple the radiative and non-radiative carrier lifetimes for different regions of the emission spectra. We observe that the IQE is higher for the spectral region between 450 nm and 500 nm compared to the IQE between 400 and 450 nm. This result is in contrast to the typical observation that the IQE of planar GaN-based LEDs is lower for longer wavelengths (i.e., higher indium contents). We also observe a longer non-radiative recombination lifetime for the longer wavelength portion of the spectrum. Several explanations are proposed for the improved IQE and longer non-radiative lifetime observed near the apex of the nanostructures. The results show that nanostructures may be leveraged to design more efficient green LEDs, potentially addressing a long-standing challenge in GaN-based materials.

Manipulating the optical properties of symmetrically branched Au/Pd nanocrystals through interior design.

PubMed

DeSantis, Christopher J; Skrabalak, Sara E

2014-05-25

Au/Pd octopods with hollow, cubic interiors and Oh symmetry were synthesized for the first time by etching core@shell Pd@Au/Pd octopods to selectively remove their Pd interiors. Integration of multiple architectural features - in this case branching symmetry, composition, and interior design - into one nanostructure provides design strategies to new plasmonic colloids.

New insights into micro/nanoscale combined probes (nanoAuger, μXPS) to characterize Ag/Au@SiO2 core-shell assemblies

NASA Astrophysics Data System (ADS)

Ledeuil, J. B.; Uhart, A.; Soulé, S.; Allouche, J.; Dupin, J. C.; Martinez, H.

2014-09-01

This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (~12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies.This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (~12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03211j

Nanoscale Au-In alloy-oxide core-shell particles as electrocatalysts for efficient hydroquinone detection

DOE PAGES

Sutter, E.; Tong, X.; Medina-Plaza, C.; ...

2015-10-09

The presence of hydroquinone (HQ), a phenol ubiquitous in nature and widely used in industry, needs to be monitored because of its toxicity to the environment. Here we demonstrate efficient detection of HQ using simple, fast, and noninvasive electrochemical measurements on indium tin oxide (ITO) electrodes modified with nanoparticles comprising bimetallic Au–In cores and mixed Au–In oxide shells. Whereas bare ITO electrodes show very low activity for the detection of HQ, their modification with Au–In core–shell nanoparticles induces a pronounced shift of the oxidation peak to lower potentials, i.e., facilitated oxidation. The response of the different electrodes was correlated withmore » the initial composition of the bimetallic nanoparticle cores, which in turn determined the amount of Au and In stabilized on the surface of the amorphous Au–In oxide shells available for the electrochemical reaction. While adding core–shell nanostructures with different compositions of the alloy core facilitates the electrocatalytic (reduction-) oxidation of HQ, the activity is highest for particles with AuIn cores (i.e., a Au:In ratio of 1). This optimal system is found to follow a single pathway, the two-electron oxidation of the quinone–hydroquinone couple, which gives rise to high oxidation peaks and is most effective in facilitating the electrode-to-analyte charge transfer and thus detection. The limits of detection (LOD) decreased when increasing the amount of Au exposed on the surface of the amorphous Au–In oxide shells. As a result the LODs were in the range of 10 –5 – 10 –6 M and were lower than those obtained using bulk Au.« less

Strategies Toward Well-Defined Polymer Nanoparticles Inspired by Nature: Chemistry versus Versatility

PubMed Central

Elsabahy, Mahmoud; Wooley, Karen L.

2014-01-01

Polymeric nanoparticles are promising delivery platforms for various biomedical applications. One of the main challenges toward the development of therapeutic nanoparticles is the premature disassembly and release of the encapsulated drug. Among the different strategies to enhance the kinetic stability of polymeric nanoparticles, shell- and core-crosslinking have been shown to provide robust character, while creating a suitable environment for encapsulation of a wide range of therapeutics, including hydrophilic, hydrophobic, metallic, and small and large biomolecules, with gating of their release as well. The versatility of shell- and core-crosslinked nanoparticles is driven from the ease by which the structures of the shell- and core-forming polymers and crosslinkers can be modified. In addition, postmodification with cell-recognition moieties, grafting of antibiofouling polymers, or chemical degradation of the core to yield nanocages allow the use of these robust nanostructures as “smart” nanocarriers. The building principles of these multifunctional nanoparticles borrow analogy from the synthesis, supramolecular assembly, stabilization, and dynamic activity of the naturally driven biological nanoparticles such as proteins, lipoproteins, and viruses. In this review, the chemistry involved during the buildup from small molecules to polymers to covalently stabilized nanoscopic objects is detailed, with contrast of the strategies of the supramolecular assembly of polymer building blocks followed by intramicellar stabilization into shell-, core-, or core–shell-crosslinked knedel-like nanoparticles versus polymerization of polymers into nanoscopic molecular brushes followed by further intramolecular covalent stabilization events. The rational design of shell-crosslinked knedel-like nanoparticles is then elaborated for therapeutic packaging and delivery, with emphasis on the polymer chemistry aspects to accomplish the synthesis of such nanoparticulate systems. PMID:25574072

Mean-field and linear regime approach to magnetic hyperthermia of core-shell nanoparticles: can tiny nanostructures fight cancer?

NASA Astrophysics Data System (ADS)

Carrião, Marcus S.; Bakuzis, Andris F.

2016-04-01

The phenomenon of heat dissipation by magnetic materials interacting with an alternating magnetic field, known as magnetic hyperthermia, is an emergent and promising therapy for many diseases, mainly cancer. Here, a magnetic hyperthermia model for core-shell nanoparticles is developed. The theoretical calculation, different from previous models, highlights the importance of heterogeneity by identifying the role of surface and core spins on nanoparticle heat generation. We found that the most efficient nanoparticles should be obtained by selecting materials to reduce the surface to core damping factor ratio, increasing the interface exchange parameter and tuning the surface to core anisotropy ratio for each material combination. From our results we propose a novel heat-based hyperthermia strategy with the focus on improving the heating efficiency of small sized nanoparticles instead of larger ones. This approach might have important implications for cancer treatment and could help improving clinical efficacy.The phenomenon of heat dissipation by magnetic materials interacting with an alternating magnetic field, known as magnetic hyperthermia, is an emergent and promising therapy for many diseases, mainly cancer. Here, a magnetic hyperthermia model for core-shell nanoparticles is developed. The theoretical calculation, different from previous models, highlights the importance of heterogeneity by identifying the role of surface and core spins on nanoparticle heat generation. We found that the most efficient nanoparticles should be obtained by selecting materials to reduce the surface to core damping factor ratio, increasing the interface exchange parameter and tuning the surface to core anisotropy ratio for each material combination. From our results we propose a novel heat-based hyperthermia strategy with the focus on improving the heating efficiency of small sized nanoparticles instead of larger ones. This approach might have important implications for cancer treatment and could help improving clinical efficacy. Electronic supplementary information (ESI) available: Unit cells per region calculation; core-shell Hamiltonian; magnetisation description functions; energy argument of Brillouin function; polydisperse models; details of experimental procedure; LRT versus core-shell model; model calculation software; and shell thickness study. See DOI: 10.1039/C5NR09093H

Toward highly stable solid-state unconventional thin-film battery-supercapacitor hybrid devices: Interfacing vertical core-shell array electrodes with a gel polymer electrolyte

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Klankowski, Steven A.; Liu, Tao; Wu, Judy; Li, Jun

2017-02-01

A novel solid-state battery-supercapacitor hybrid device is fabricated for high-performance electrical energy storage using a Si anode and a TiO2 cathode in conjunction with a flexible, solid-like gel polymer electrolyte film as the electrolyte and separator. The electrodes were fabricated as three-dimensional nanostructured vertical arrays by sputtering active materials as conformal shells on vertically aligned carbon nanofibers (VACNFs) which serve as the current collector and structural template. Such nanostructured vertical core-shell array-electrodes enable short Li-ion diffusion path and large pseudocapacitive contribution by fast surface reactions, leading to the hybrid features of batteries and supercapacitors that can provide high specific energy over a wide range of power rates. Due to the improved mechanical stability of the infiltrated composite structure, the hybrid cell shows excellent cycling stability and is able to retain more than 95% of the original capacity after 3500 cycles. More importantly, this solid-state device can stably operate in a temperature range from -20 to 60 °C with a very low self-discharge rate and an excellent shelf life. This solid-state architecture is promising for the development of highly stable thin-film hybrid energy storage devices for unconventional applications requiring largely varied power, wider operation temperature, long shelf-life and higher safety standards.

Highly Luminescent Zn(x)Cd(1-x)Se/C Core/Shell Nanocrystals: Large Scale Synthesis, Structural and Cathodoluminescence Studies.

PubMed

Bhattacharyya, Sayan; Estrin, Yevgeni; Moshe, Ofer; Rich, Daniel H; Solovyov, Leonid A; Gedanken, A

2009-07-28

Zn(x)Cd(1-x)Se/C core/shell nanocrystals with 31-39 nm semiconducting core and 11-25 nm carbon shell were synthesized from solid state precursors in large scale amounts. A mixture of spherical and tripod nanostructures were obtained only in the one-step reaction (ZC3), where the Zn- and Cd-precursors were reacted simultaneously, rather than in the two step reactions (ZC1 and ZC2), where largely spherical nanostructures were observed. Rietveld analysis of the X-ray diffraction patterns of the samples prepared in three different ways, all under their autogenic pressure, reveal varying compositions of the Zn(x)Cd(1-x)Se nanocrystal core, where the cubic phases with higher Zn content were dominant compared to the hexagonal phases. Carbon encapsulation offers excellent protection to the nanocrystal core and is an added advantage for biological applications. Cathodoluminescence (CL) measurements with spatially integrated and highly localized excitations show distinct peaks and sharp lines at various wavelengths, representing emissions from single nanostructures possessing different compositions, phases, and sizes. Transmission electron microscopy (TEM) showed striations in the nanocrystals that are indicative of a composition modulation, and possibly reveal a phase separation and spinodal decomposition within the nanocrystals. Thermal quenching of the luminescence for both the near band-edge and defect related emissions were observed in the range 60-300 K. The measured activation energies of ∼50-70 meV were related to the presence of shallow donors or acceptors, deep level emissions, and thermal activation and quenching of the luminescence due to the thermal release of electrons from shallow donors to the conduction band or a thermal release of holes from shallow acceptors to the valence band. Spatially integrated CL spectra revealed the existence of broadening and additional components that are consistent with the presence of a composition modulation in the nanocrystals. Spatial localization of the emission in isolated single nanocrystals was studied using monochromatic CL imaging and local CL spectroscopy. CL spectra acquired by a highly localized excitation of individual nanocrystals showed energy shifts in the excitonic luminescence that are consistent with a phase separation into Zn- and Cd-rich regions. The simultaneous appearance of both structural and compositional phase separation for the synthesis of Zn(x)Cd(1-x)Se nanocrystals reveals the complexity and uniqueness of these results.

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties

NASA Astrophysics Data System (ADS)

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-01

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities. Electronic supplementary information (ESI) available: Synthesis and TEM images of pure ZnO nanocrystals. Photocatalytic testing procedures and degradation curves. SEM and TEM images, SAED pattern and EDS spectra and maps of parts of Cu-ZnO hybrid samples. A schematic image of coincident lattice matching between Cu and ZnO. STEM-EDS elemental maps and XRD pattern of the Cu@CuNi-ZnO sample. Comparative synthetic parameters. See DOI: 10.1039/c6nr02055k

Production of silver-silica core-shell nanocomposites using ultra-short pulsed laser ablation in nanoporous aqueous silica colloidal solutions

NASA Astrophysics Data System (ADS)

Santagata, A.; Guarnaccio, A.; Pietrangeli, D.; Szegedi, Á.; Valyon, J.; De Stefanis, A.; De Bonis, A.; Teghil, R.; Sansone, M.; Mollica, D.; Parisi, G. P.

2015-05-01

Ultra-short pulsed laser ablation of materials in liquid has been demonstrated to be a versatile technique for nanoparticles production. In a previous paper, it has been described, for the first time, how by laser ablation in a liquid system, silver nanoparticles can be loaded onto SBA-15 and MCM-41 supports which show promising catalytic properties for the oxidation of Volatile Organic Compounds (VOCs). The aim of the present research is to demonstrate the formation of stable silver-silica core-shell nanoparticles by direct laser ablation (Ti:Sa; 800 nm pulse duration: 120 fs repetition rate: 1 kHz, pulse energy: 3.6 mJ, fluence: 9 J cm  -  2) of a Ag target submerged in a static colloidal solution of MCM-41 or SBA-15 silica nanoporous materials. In previous studies, it was discovered that a side and negligible product of the laser ablation process of silver performed in water-silica systems, could be related to the formation of silver-silica core-shell nanoparticles. In order to emphasize this side process some modifications to the laser ablation experimental set-up were performed. Among these, the most important one, in order to favor the production of the core-shell systems, was to keep the liquid silica suspension firm. The laser generated nanomaterials were then analyzed using TEM morphologic characterization. By UV-vis absorption spectra the observed features have been related to components of the colloidal solution as well as to the number of the incident laser pulses. In this manner characterizations on both the process and the resulting suspension have been performed. Significant amount of small sized silver-silica core-shell nanoparticles have been detected in the studied systems. The size distribution, polydispersivity, UV-vis plasmonic bands and stability of the produced silver-silica core-shell nanocomposites have been related to the extent of damage induced in the nanoporous silica structure during the ablation procedure adopted here. In presence of SBA-15 the silver-silica core-shell nanoparticles observed by TEM are smaller and more homogeneously dispersed if compared with the core-shell system obtained when the MCM-41 mesoporous silica was used. The outcomes show that the choice of the mesoporous silica material can affect the silica shell thickness in addition to the Ag NPs size distribution. With this regard, TEM images evidence that in MCM-41 the silver-silica core-shell nanostructures display a silica layer thickness between 1-10 nm conversely, for SBA-15, the silver-silica core-shell nanoparticles are finely dispersed and the silica shell shows, when present, an average thickness of about 5 nm.

Core-shell heterojunction of silicon nanowire arrays and carbon quantum dots for photovoltaic devices and self-driven photodetectors.

PubMed

Xie, Chao; Nie, Biao; Zeng, Longhui; Liang, Feng-Xia; Wang, Ming-Zheng; Luo, Linbao; Feng, Mei; Yu, Yongqiang; Wu, Chun-Yan; Wu, Yucheng; Yu, Shu-Hong

2014-04-22

Silicon nanostructure-based solar cells have lately intrigued intensive interest because of their promising potential in next-generation solar energy conversion devices. Herein, we report a silicon nanowire (SiNW) array/carbon quantum dot (CQD) core-shell heterojunction photovoltaic device by directly coating Ag-assisted chemical-etched SiNW arrays with CQDs. The heterojunction with a barrier height of 0.75 eV exhibited excellent rectifying behavior with a rectification ratio of 10(3) at ±0.8 V in the dark and power conversion efficiency (PCE) as high as 9.10% under AM 1.5G irradiation. It is believed that such a high PCE comes from the improved optical absorption as well as the optimized carrier transfer and collection capability. Furthermore, the heterojunction could function as a high-performance self-driven visible light photodetector operating in a wide switching wavelength with good stability, high sensitivity, and fast response speed. It is expected that the present SiNW array/CQD core-shell heterojunction device could find potential applications in future high-performance optoelectronic devices.

Studies on the photo-catalytic activity of semiconductor nanostructures and their gold core-shell on the photodegradation of malathion.

PubMed

Fouad, Dina Mamdouh; Mohamed, Mona Bakr

2011-11-11

This work is devoted to the synthesis of different semiconductor nanoparticles and their metal core-shell nanocomposites such as TiO2, Au/TiO2, ZnO, and Au/ZnO. The morphology and crystal structures of the developed nanomaterials were characterized by transmission electron microscopy (TEM) and x-ray diffraction (XRD). These materials were used as catalysts for the photodegradation of malathion, which is one of the most commonly used pesticides in developing countries. The degradation of 10 ppm malathion under ultraviolet (UV) and visible light in the presence of different synthesized nanocomposites was analyzed using high performance liquid chromatography (HPLC) and UV-visible spectra. A comprehensive study was carried out for the catalytic efficiency of the prepared nanoparticles. Moreover, the effects of different factors that could influence catalytic photodegradation, such as different light sources, surface coverage and the nature of the organic contaminants, were investigated. The results indicate that the core-shell nanocomposite of semiconductor-gold serves as a better catalytic system than the semiconductor nanoparticles themselves.

Tungsten oxide@polypyrrole core-shell nanowire arrays as novel negative electrodes for asymmetric supercapacitors.

PubMed

Wang, Fengmei; Zhan, Xueying; Cheng, Zhongzhou; Wang, Zhenxing; Wang, Qisheng; Xu, Kai; Safdar, Muhammad; He, Jun

2015-02-11

Among active pseudocapacitive materials, polypyrrole (PPy) is a promising electrode material in electrochemical capacitors. PPy-based materials research has thus far focused on its electrochemical performance as a positive electrode rather than as a negative electrode for asymmetric supercapacitors (ASCs). Here high-performance electrochemical supercapacitors are designed with tungsten oxide@PPy (WO3 @PPy) core-shell nanowire arrays and Co(OH)2 nanowires grown on carbon fibers. The WO3 @PPy core-shell nanowire electrode exhibits a high capacitance (253 mF/cm2) in negative potentials (-1.0-0.0 V). The ASCs packaged with CF-Co(OH)2 as a positive electrode and CF-WO3 @PPy as a negative electrode display a high volumetric capacitance up to 2.865 F/cm3 based on volume of the device, an energy density of 1.02 mWh/cm3 , and very good stability performance. These findings promote the application of PPy-based nanostructures as advanced negative electrodes for ASCs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Active ester functional single core magnetic nanostructures as a versatile immobilization matrix for effective bioseparation and catalysis.

PubMed

Gelbrich, Thorsten; Reinartz, Michael; Schmidt, Annette M

2010-03-08

Multifunctional nanocarriers for amino functional targets with a high density of accessible binding sites are obtained in a single polymerization step by grafting from copolymerization of an active ester monomer from superparamagnetic cores. As a result of the brush-like structure of the highly dispersed shell, the nano-objects exhibit an available capture capacity for amines that is found to be up to 2 orders of magnitude higher than for commercial magnetic beads, and the functional brush shell can serve as a template for many types of pendant functional groups and molecules. As comonomer, oligo(ethylene glycol) methacrylate allows for excellent water solubility at room temperature, biocompatibility, and thermoflocculation. We demonstrate the biorelated applicability of the hybrid nanoparticles by two different approaches. In the first approach, the immobilization of trypsin to the core-shell nanoparticles results in highly active, nanoparticulate biocatalysts that can easily be separated magnetically. Second, we demonstrate that the obtained nanoparticles are suitable for the effective labeling of cell membranes, opening a novel pathway for the easy and effective isolation of membrane proteins.

ZnS-Sb2S3@C Core-Double Shell Polyhedron Structure Derived from Metal-Organic Framework as Anodes for High Performance Sodium Ion Batteries.

PubMed

Dong, Shihua; Li, Caixia; Ge, Xiaoli; Li, Zhaoqiang; Miao, Xianguang; Yin, Longwei

2017-06-27

Taking advantage of zeolitic imidazolate framework (ZIF-8), ZnS-Sb 2 S 3 @C core-double shell polyhedron structure is synthesized through a sulfurization reaction between Zn 2+ dissociated from ZIF-8 and S 2- from thioacetamide (TAA), and subsequently a metal cation exchange process between Zn 2+ and Sb 3+ , in which carbon layer is introduced from polymeric resorcinol-formaldehyde to prevent the collapse of the polyhedron. The polyhedron composite with a ZnS inner-core and Sb 2 S 3 /C double-shell as anode for sodium ion batteries (SIBs) shows us a significantly improved electrochemical performance with stable cycle stability, high Coulombic efficiency and specific capacity. Peculiarly, introducing a carbon shell not only acts as an important protective layer to form a rigid construction and accommodate the volume changes, but also improves the electronic conductivity to optimize the stable cycle performance and the excellent rate property. The architecture composed of ZnS inner core and a complex Sb 2 S 3 /C shell not only facilitates the facile electrolyte infiltration to reduce the Na-ion diffusion length to improve the electrochemical reaction kinetics, but also prevents the structure pulverization caused by Na-ion insertion/extraction. This approach to prepare metal sulfides based on MOFs can be further extended to design other nanostructured systems for high performance energy storage devices.

Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites.

PubMed

Zarick, Holly F; Boulesbaa, Abdelaziz; Puretzky, Alexander A; Talbert, Eric M; DeBra, Zachary R; Soetan, Naiya; Geohegan, David B; Bardhan, Rizia

2017-01-26

In this work, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr 3 ) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr 3 perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO 2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.

Nanoparticle Decorated Ultrathin Porous Nanosheets as Hierarchical Co3O4 Nanostructures for Lithium Ion Battery Anode Materials

PubMed Central

Mujtaba, Jawayria; Sun, Hongyu; Huang, Guoyong; Mølhave, Kristian; Liu, Yanguo; Zhao, Yanyan; Wang, Xun; Xu, Shengming; Zhu, Jing

2016-01-01

We report a facile synthesis of a novel cobalt oxide (Co3O4) hierarchical nanostructure, in which crystalline core-amorphous shell Co3O4 nanoparticles with a bimodal size distribution are uniformly dispersed on ultrathin Co3O4 nanosheets. When tested as anode materials for lithium ion batteries, the as-prepared Co3O4 hierarchical electrodes delivered high lithium storage properties comparing to the other Co3O4 nanostructures, including a high reversible capacity of 1053.1 mAhg−1 after 50 cycles at a current density of 0.2 C (1 C = 890 mAg−1), good cycling stability and rate capability. PMID:26846434

New insights into micro/nanoscale combined probes (nanoAuger, μXPS) to characterize Ag/Au@SiO2 core-shell assemblies.

PubMed

Ledeuil, J B; Uhart, A; Soulé, S; Allouche, J; Dupin, J C; Martinez, H

2014-10-07

This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (≈12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies.

Controlled formation of intense hot spots in Pd@Ag core-shell nanooctapods for efficient photothermal conversion

NASA Astrophysics Data System (ADS)

Liu, Maochang; Yang, Yang; Li, Naixu; Du, Yuanchang; Song, Dongxing; Ma, Lijing; Wang, Yi; Zheng, Yiqun; Jing, Dengwei

2017-08-01

Plasmonic Ag nanostructures have been of great interest for such applications in cancer therapy and catalysis, etc. However, the relatively week Ag-Ag interaction and spontaneous atom diffusion make it very difficult to generate concaved or branched structures in Ag nanocrystals with sizes less than 100 nm, which has been considered very favorable for plasmonic effects. Herein, by employing a cubic Pd seed and a specific reducing agent to restrict the surface diffusion of Ag atoms, Pd@Ag core-shell nanooctapod structures where Ag atoms can be selectively deposited onto the corner sites of the Pd cubes were obtained. Such selective decoration enables us to precisely control the locations for the hot spot formation during light irradiation. We find that the branched nanooctapod structure shows strong absorption in the visible-light region and generates intense hot spots around the octapod arms of Ag. As such, the photothermal conversion efficiency could be significantly improved by more than 50% with a colloid solution containing only ppm-level nanooctapods compared with pure water. The reported nanostructure is expected to find extensive applications due to its controlled formation of light-induced hot spots at certain points on the crystal surface.

Crystalline silicon carbide nanoparticles encapsulated in branched wavelike carbon nanotubes: synthesis and optical properties.

PubMed

Xi, Guangcheng; Yu, Shijun; Zhang, Rui; Zhang, Meng; Ma, Dekun; Qian, Yitai

2005-07-14

A novel nanostructure, cubic silicon carbide (3C-SiC) nanoparticles encapsulated in branched wavelike carbon nanotubes have been prepared by a reaction of 1,2-dimenthoxyethane (CH3OCH2CH2OCH3), SiCl4, and Mg in an autoclave at 600 degrees C. According to X-ray powder diffraction, the products are composed of 3C-SiC and carbon. TEM and HRTEM images show that the as-synthesized products are composed of 3C-SiC nanoparticles encapsulated in branched carbon nanotubes with wavelike walls. The diameter of the 3C-SiC cores is approximately 20-40 nm and the thickness of the carbon shells is about 3-5 nm. In Raman scattering spectroscopy, both the TO (Gamma) phonon line and the LO (Gamma) phonon line have red shifts about 6 cm(-1) relative to that for the bulk 3C-SiC. The photoluminescence (PL) spectrum shows that there are two emission peaks: blue light emission (431 nm) and violet light emission (414 nm). A sequential deposition growth process (with cores as the templates for the shells) for the nanostructure was proposed.

Field-induced self-assembly of iron oxide nanoparticles investigated using small-angle neutron scattering.

PubMed

Fu, Zhendong; Xiao, Yinguo; Feoktystov, Artem; Pipich, Vitaliy; Appavou, Marie-Sousai; Su, Yixi; Feng, Erxi; Jin, Wentao; Brückel, Thomas

2016-11-03

The magnetic-field-induced assembly of magnetic nanoparticles (NPs) provides a unique and flexible strategy in the design and fabrication of functional nanostructures and devices. We have investigated the field-induced self-assembly of core-shell iron oxide NPs dispersed in toluene by means of small-angle neutron scattering (SANS). The form factor of the core-shell NPs was characterized and analyzed using SANS with polarized neutrons. Large-scale aggregates of iron oxide NPs formed above 0.02 T as indicated by very-small-angle neutron scattering measurements. A three-dimensional long-range ordered superlattice of iron oxide NPs was revealed under the application of a moderate magnetic field. The crystal structure of the superlattice has been identified to be face-centred cubic.

Hybrid nanostructured coating for increased resistance of prosthetic devices to staphylococcal colonization

NASA Astrophysics Data System (ADS)

Anghel, Ion; Grumezescu, Alexandru Mihai

2013-01-01

Prosthetic medical device-associated infections are responsible for significant morbidity and mortality rates. Novel improved materials and surfaces exhibiting inappropriate conditions for microbial development are urgently required in the medical environment. This study reveals the benefit of using natural Mentha piperita essential oil, combined with a 5 nm core/shell nanosystem-improved surface exhibiting anti-adherence and antibiofilm properties. This strategy reveals a dual role of the nano-oil system; on one hand, inhibiting bacterial adherence and, on the other hand, exhibiting bactericidal effect, the core/shell nanosystem is acting as a controlled releasing machine for the essential oil. Our results demonstrate that this dual nanobiosystem is very efficient also for inhibiting biofilm formation, being a good candidate for the design of novel material surfaces used for prosthetic devices.

Morphology conserving aminopropyl functionalization of hollow silica nanospheres in toluene

NASA Astrophysics Data System (ADS)

Dobó, Dorina G.; Berkesi, Dániel; Kukovecz, Ákos

2017-07-01

Inorganic nanostructures containing cavities of monodisperse diameter distribution find applications in e.g. catalysis, adsorption and drug delivery. One of their possible synthesis routes is the template assisted core-shell synthesis. We synthesized hollow silica spheres around polystyrene cores by the sol-gel method. The polystyrene template was removed by heat treatment leaving behind a hollow spherical shell structure. The surface of the spheres was then modified by adding aminopropyl groups. Here we present the first experimental evidence that toluene is a suitable alternative functionalization medium for the resulting thin shells, and report the comprehensive characterization of the amino-functionalized hollow silica spheres based on scanning electron microscopy, transmission electron microscopy, N2 adsorption, FT-IR spectroscopy, Raman spectroscopy and electrokinetic potential measurement. Both the presence of the amino groups and the preservation of the hollow spherical morphology were unambiguously proven. The introduction of the amine functionality adds amphoteric character to the shell as shown by the zeta potential vs. pH function. Unlike pristine silica particles, amino-functionalized nanosphere aqueous sols can be stable at both acidic and basic conditions.

Ascorbic-acid-assisted growth of high quality M@ZnO: a growth mechanism and kinetics study.

PubMed

Yang, Yun; Han, Shuhua; Zhou, Guangju; Zhang, Lijie; Li, Xingliang; Zou, Chao; Huang, Shaoming

2013-12-07

We present a general route for synthesizing M@ZnO nanoparticles (NPs) by using ascorbic acid (AA) to induce deposition of ZnO on various shaped and structured cationic-surfactant-capped NP surfaces (noble, magnetic, semiconductor, rod-like, spherical, cubic, dendrite, alloy, core@shell). The results show that the complexing (AA and Zn(2+)) and cooperative effects (AA and CTAB) play important roles in the formation of polycrystalline ZnO shells. Besides, the growth kinetics of M@ZnO was systematically studied. It was found that the slow growth rate favors the successful formation of uniform core@ZnO NPs with relatively loose shells. An appropriate growth rate allows achieving high quality M@ZnO NPs with dense shells. However, very fast growth causes significant additional nucleation and the formation of pure ZnO NPs. This general method is suitable for preparing M@ZnO using seed NPs prepared in both water and organic phases. It might be an alternative route for functionalizing NPs for bioapplications (ZnO is biocompatible), modulating material properties as designed, or synthesizing template materials for building other nanostructures.

Investigation on the preparation and luminescence emission of LaF{sub 3}:Eu{sup 3+}@LaF{sub 3}/SiO{sub 2} core-shell nanostructure

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

Shao, Jun, E-mail: jun-shao@snnu.edu.cn; Wang, Zhaojin; Wang, Ruibo

LaF{sub 3}:Eu{sup 3+}, LaF{sub 3}:Eu{sup 3+}@LaF{sub 3}, LaF{sub 3}:Eu{sup 3+}@CeF{sub 3} and LaF{sub 3}:Eu{sup 3+}@SiO{sub 2} nanoparticles were successfully synthesized via hydrothermal route and modified Stöber method. The surface property of LaF{sub 3}:Eu{sup 3+} particle was successfully modified by coating LaF{sub 3} and SiO{sub 2} shell onto the particle, which resulted in the change of the surface property and luminescence emission of LaF{sub 3}:Eu{sup 3+}. It was found that the surface quenchers were decreased and thus the nonradiative pathways were reduced with core/shell structure, which not only enhanced the yellow emission of the sample, but also changed the intensity ratiomore » of the yellow to orange emission. The dependence of the shell property and shell thickness on the luminescence emission spectra were investigated systematically. The current investigation can provide useful information for developing applications in biological imaging, detection, and sensing and other aspects.« less

New insights into the photocatalytic activity of 3-D core-shell P25@silica nanocomposites: impact of mesoporous coating.

PubMed

Gong, Yichao; Wang, Dan Ping; Wu, Renbing; Gazi, Sarifuddin; Soo, Han Sen; Sritharan, Thirumany; Chen, Zhong

2017-04-11

In this report, a three-dimensional (3-D) network of core-shell TiO 2 (P25)-mesoporous SiO 2 (P25@mSiO 2 ) nanocomposites was prepared via a controllable surfactant-assisted sol-gel method. The nanocomposites were investigated for photocatalytic reactions of organic dye degradation, water splitting, and CO 2 reduction to understand the roles of the mSiO 2 shell in these photocatalytic reactions. It was found that the mSiO 2 shell accelerates the photodegradation of the organic dye, but dramatically reduces the photocatalytic activity of P25 in water splitting and CO 2 reduction. The roles played by the mSiO 2 shell in the photocatalytic reactions are summarized as: (1) effective prevention of agglomeration of P25 nanoparticles, (2) facilitating the transfer of uncharged photo-generated ˙OH radicals via the abundant -OH groups on the mesoporous surface, (3) provision of increased reaction sites between ˙OH radicals and dye molecules by its mesoporous nanostructure and large surface area, and (4) prevention of diffusion of the photo-generated charge carriers (photoelectrons and photoholes) because of its insulating nature.

Experimental investigation and micromagnetic simulations of hybrid CoCr2O4/Ni coaxial nanostructures.

PubMed

Li, W J; Wang, C J; Zhang, X M; Irfan, M; Khan, U; Liu, Y W; Han, X F

2018-06-15

Multiphase CoCr 2 O 4 /Ni core-shell nanowires (NWs) have been synthesized within anodic aluminum oxide membranes by the combination of the sol-gel method with electrodeposition techniques. X-ray diffraction and x-ray photoemission spectroscopy results confirmed the formation of a cubic spinel structure of CoCr 2 O 4 shell with space group Fd-3m (227). The morphology and composition of the as-grown NWs were studied by field emission scanning electron microscopy, as well as transmission electron microscopy. The magnetic properties of the CoCr 2 O 4 NT shell and hybrid CoCr 2 O 4 /Ni NWs were measured at low temperature using a physical property measurement system. The temperature dependence of the magnetization curves showed that CoCr 2 O 4 NTs undergo a transition from a paramagnetic state to a ferrimagnetic state at about 90 K and a spiral ordering transition temperature near 22 K. An enhanced coercivity and saturation field were observed for the CoCr 2 O 4 /Ni core-shell NWs compared to the single-phase Ni NWs. Micromagnetic simulation results indicated that there is a strong coupling between the shell and core layers during the magnetization reversal process. The combination of hard CoCr 2 O 4 and soft Ni in a single NW structure may have potential applications in future multifunctional devices.

Characterization of Magnetic Nanostructures Using Off-Axis Electron Holography

NASA Astrophysics Data System (ADS)

Zhang, Desai

This dissertation research has involved microscopic characterization of magnetic nanostructures using off-axis electron holography and Lorentz microscopy. The nanostructures investigated have included Co nanoparticles (NPs), Au/Fe/GaAs shell/core nanowires (NWs), carbon spirals with magnetic cores, magnetic nanopillars, Ni-Zn-Co spinel ferrite and CoFe/Pd multilayers. The studies have confirmed the capability of holography to describe the behavior of magnetic structures at the nanoscale. The phase changes caused by the fringing fields of chains consisting of Co NPs were measured and calculated. The difference between chains with different numbers of Co NPs followed the trend indicated by calculations. Holography studies of Au/Fe/GaAs NWs grown on (110) GaAs substrates with rotationally non-uniform coating confirmed that Fe was present in the shell and that the shell behaved as a bar magnet. No fringing field was observed from NWs with cylindrical coating grown on (111)B GaAs substrates. The most likely explanation is that magnetic fields are confined within the shells and form closed loops. The multiple-magnetic-domain structure of iron carbide cores in carbon spirals was imaged using phase maps of the fringing fields. The strength and range of this fringing field was insufficient for manipulating the carbon spirals with an external applied magnetic field. No magnetism was revealed for CoPd/Fe/CoPd magnetic nanopillars. Degaussing and MFM scans ruled out the possibility that saturated magnetization and sample preparation had degraded the anisotropy, and the magnetism, respectively. The results suggested that these nanopillars were not suitable as candidates for prototypical bit information storage devices. Observations of Ni-Zn-Co spinel ferrite thin films in plan-view geometry indicated a multigrain magnetic domain structure and the magnetic fields were oriented in-plane only with no preferred magnetization distribution. This domain structure helps explain this ferrite's high permeability at high resonance frequency, which is an unusual character. Perpendicular magnetic anisotropy (PMA) of CoFe/Pd multilayers was revealed using holography. Detailed microscopic characterization showed structural factors such as layer waviness and interdiffusion that could contribute to degradation of the PMA. However, these factors are overwhelmed by the dominant effect of the CoFe layer thickness, and can be ignored when considering magnetic domain structure.

Yolk@Shell Nanoarchitectures with Bimetallic Nanocores-Synthesis and Electrocatalytic Applications.

PubMed

Guiet, Amandine; Unmüssig, Tobias; Göbel, Caren; Vainio, Ulla; Wollgarten, Markus; Driess, Matthias; Schlaad, Helmut; Polte, Jörg; Fischer, Anna

2016-10-10

In the present paper, we demonstrate a versatile approach for the one-pot synthesis of metal oxide yolk@shell nanostructures filled with bimetallic nanocores. This novel approach is based on the principles of hydrophobic nanoreactor soft-templating and is exemplified for the synthesis of various AgAu NP @tin-rich ITO (AgAu@ITO TR ) yolk@shell nanomaterials. Hydrophobic nanoreactor soft-templating thereby takes advantage of polystyrene-block-poly(4-vinylpiridine) inverse micelles as two-compartment nanoreactor template, in which the core and the shell of the micelles serve as metal and metal oxide precursor reservoir, respectively. The composition, size and number of AuAg bimetallic nanoparticles incorporated within the ITO TR yolk@shell can easily be tuned. The conductivity of the ITO TR shell and the bimetallic composition of the AuAg nanoparticles, the as-synthesized AuAg NP @ITO TR yolk@shell materials could be used as efficient electrocatalysts for electrochemical glucose oxidation with improved onset potential when compared to their gold counterpart.

Colloidal lithography nanostructured Pd/PdO x core-shell sensor for ppb level H2S detection.

PubMed

Benedict, Samatha; Lumdee, Chatdanai; Dmitriev, Alexandre; Anand, Srinivasan; Bhat, Navakanta

2018-06-22

In this work we report on plasma oxidation of palladium (Pd) to form reliable palladium/palladium oxide (Pd/PdO x ) core-shell sensor for ppb level H 2 S detection and its performance improvement through nanostructuring using hole-mask colloidal lithography (HCL). The plasma oxidation parameters and the sensor operating conditions are optimized to arrive at a sensor device with high sensitivity and repeatable response for H 2 S. The plasma oxidized palladium/palladium oxide sensor shows a response of 43.1% at 3 ppm H 2 S at the optimum operating temperature of 200 °C with response and recovery times of 24 s and 155 s, respectively. The limit of detection (LoD) of the plasma oxidised beam is 10 ppb. We further integrate HCL, a bottom-up and cost-effective process, to create nanodiscs of fixed diameter of 100 nm and varying heights (10, 15 and 20 nm) on 10 nm thin Pd beam which is subsequently plasma oxidized to improve the H 2 S sensing characteristics. The nanostructured Pd/PdO x sensor with nanodiscs of 100 nm diameter and 10 nm height shows an enhancement in sensing performance by 11.8% at same operating temperature and gas concentration. This nanostructured sensor also shows faster response and recovery times (15 s and 100 s, respectively) compared to the unstructured Pd/PdO x counterpart together with an experimental LoD of 10 ppb and the estimated limit going all the way down to 2 ppb. Material characterization of the fabricated Pd/PdO x sensors is done using UV-vis spectroscopy and x-ray photoemission spectroscopy.

Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

PubMed

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Nogami, Masayuki; Ohtaki, Michitaka

2013-07-01

In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next PEMFCs, and DMFCs.

Nanoscale alloys and core-shell materials: Model predictions of the nanostructure and mechanical properties

NASA Astrophysics Data System (ADS)

Zhurkin, E. E.; van Hoof, T.; Hou, M.

2007-06-01

Atomic scale modeling methods are used to investigate the relationship between the properties of clusters of nanometer size and the materials that can be synthesized by assembling them. The examples of very different bimetallic systems are used. The first one is the Ni3Al ordered alloy and the second is the AgCo core-shell system. While the Ni3Al cluster assembled materials modeling is already reported in our previous work, here we focus on the prediction of new materials synthesized by low energy deposition and accumulation of AgCo clusters. It is found that the core-shell structure is preserved by deposition with energies typical of low energy cluster beam deposition, although deposition may induce substantial cluster deformation. In contrast with Ni3Al deposited cluster assemblies, no grain boundary between clusters survives deposition and the silver shells merge into a noncrystalline system with a layered structure, in which the fcc Co grains are embedded. To our knowledge, such a material has not yet been synthesized experimentally. Mechanical properties are discussed by confronting the behaviors of Ni3Al and AgCo under the effect of a uniaxial load. To this end, a molecular dynamics scheme is established in view of circumventing rate effects inherent to short term modeling and thereby allowing to examine large plastic deformation mechanisms. Although the mechanisms are different, large plastic deformations are found to improve the elastic properties of both the Ni3Al and AgCo systems by stabilizing their nanostructure. Beyond this improvement, when the load is further increased, the Ni3Al system displays reduced ductility while the AgCo system is superplastic. The superplasticity is explained by the fact that the layered structure of the Ag system is not modified by the deformation. Some coalescence of the Co grains is identified as a geometrical effect and is suggested to be a limiting factor to superplasticity.

One-dimensional carrier confinement in “Giant” CdS/CdSe excitonic nanoshells

DOE PAGES

Razgoniaeva, Natalia; Moroz, Pavel; Yang, Mingrui; ...

2017-05-23

Here, the emerging generation of quantum dot optoelectronic devices offers an appealing prospect of a size-tunable band gap. The confinement-enabled control over electronic properties, however, requires nanoparticles to be sufficiently small, which leads to a large area of interparticle boundaries in a film. Such interfaces lead to a high density of surface traps which ultimately increase the electrical resistance of a solid. To address this issue, we have developed an inverse energy-gradient core/shell architecture supporting the quantum confinement in nanoparticles larger than the exciton Bohr radius. The assembly of such nanostructures exhibits a relatively low surface-to-volume ratio, which was manifestedmore » in this work through the enhanced conductance of solution-processed films. The reported core/shell geometry was realized by growing a narrow gap semiconductor layer (CdSe) on the surface of a wide-gap core material (CdS) promoting the localization of excitons in the shell domain, as was confirmed by ultrafast transient absorption and emission lifetime measurements. The band gap emission of fabricated nanoshells, ranging from 15 to 30 nm in diameter, has revealed a characteristic size-dependent behavior tunable via the shell thickness with associated quantum yields in the 4.4–16.0% range.« less

One-dimensional carrier confinement in “Giant” CdS/CdSe excitonic nanoshells

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

Razgoniaeva, Natalia; Moroz, Pavel; Yang, Mingrui

Here, the emerging generation of quantum dot optoelectronic devices offers an appealing prospect of a size-tunable band gap. The confinement-enabled control over electronic properties, however, requires nanoparticles to be sufficiently small, which leads to a large area of interparticle boundaries in a film. Such interfaces lead to a high density of surface traps which ultimately increase the electrical resistance of a solid. To address this issue, we have developed an inverse energy-gradient core/shell architecture supporting the quantum confinement in nanoparticles larger than the exciton Bohr radius. The assembly of such nanostructures exhibits a relatively low surface-to-volume ratio, which was manifestedmore » in this work through the enhanced conductance of solution-processed films. The reported core/shell geometry was realized by growing a narrow gap semiconductor layer (CdSe) on the surface of a wide-gap core material (CdS) promoting the localization of excitons in the shell domain, as was confirmed by ultrafast transient absorption and emission lifetime measurements. The band gap emission of fabricated nanoshells, ranging from 15 to 30 nm in diameter, has revealed a characteristic size-dependent behavior tunable via the shell thickness with associated quantum yields in the 4.4–16.0% range.« less

Engineering of lead chalcogenide nanostructures for carrier multiplication: Core/shell, 1D, and 2D

NASA Astrophysics Data System (ADS)

Lin, Qianglu

Near infrared emitting semiconductors have been used widely in industry especially in solar-cell fabrications. The efficiency of single junction solar-cell can reach the Shockley-Queisser limit by using optimum band gap material such as silicon and cadmium telluride. The theoretical efficiency can be further enhanced through carrier multiplication, in which a high energy photon is absorbed and more than one electron-hole pair can be generated, reaching more than 100% quantum efficiency in the high energy region of sunlight. The realization of more than unity external quantum efficiency in lead selenide quantum dots solar cell has motivated vast investigation on lowering the carrier multiplication threshold and further improving the efficiency. This dissertation focuses on synthesis of lead chalcogenide nanostructures for their optical spectroscopy studies. PbSe/CdSe core/shell quantum dots were synthesized by cation exchange to obtain thick shells (up to 14 monolayers) for studies of visible and near infrared dual band emissions and carrier multiplication efficiency. By examining the reaction mechanism, a thermodynamic and a kinetic model are introduced to explain the vacancy driven cation exchange. As indicated by the effective mass model, PbSe/CdSe core/shell quantum dots has quasi-type-II band alignment, possessing electron delocalized through the entire quantum dot and hole localized in the core, which breaks down the symmetry of energy levels in the conduction and valence band, leading to hot-hole-assisted efficient multi-exciton generation and a lower carrier multiplication threshold to the theoretical value. For further investigation of carrier multiplication study, PbTe, possessing the highest efficiency among lead chalcogenides due to slow intraband cooling, is synthesized in one-dimensional and two-dimensional nanostructures. By using dodecanethiol as the surfactant, PbTe NRs can be prepared with high uniformity in width and resulted in fine quantum confinement features. The reaction can be explained by a soft-template assisted process, in which the lamellar lead-thiolate precursor transforms into rod-shape micelle in the existence of telluride anions by electrostatic attraction. Fine tuning the reaction condition by changing the solvent to oleylamine, lead telluride nanowires with length up to 200 nm can be prepared, which bundled together because of the strong dipole-dipole attraction between nanowires. Decreasing the amount of surfactant dodecanethiol in the synthesis produces lead telluride nanorings, which formed by attaching four small particles together, leaving the center void. To prepare two-dimensional nanoplatelets, mixture ligands containing two amines with different carbon chain length were used, which initiate oriented attachment of the nanoparticles to form square-shape nanoplatelets. By further adopting stronger binding ligands such as phosphonic acid, PbTe nanoplatelets with micrometer lateral dimension were prepared with extremely sharp near infrared photoluminescence (less than 40 meV), which has never be achieved in quantum dots and other nanostructures.

Self-generated concentration and modulus gradient coating design to protect Si nano-wire electrodes during lithiation.

PubMed

Kim, Sung-Yup; Ostadhossein, Alireza; van Duin, Adri C T; Xiao, Xingcheng; Gao, Huajian; Qi, Yue

2016-02-07

Surface coatings as artificial solid electrolyte interphases have been actively pursued as an effective way to improve the cycle efficiency of nanostructured Si electrodes for high energy density lithium ion batteries, where the mechanical stability of the surface coatings on Si is as critical as Si itself. However, the chemical composition and mechanical property change of coating materials during the lithiation and delithiation process imposed a grand challenge to design coating/Si nanostructure as an integrated electrode system. In our work, we first developed reactive force field (ReaxFF) parameters for Li-Si-Al-O materials to simulate the lithiation process of Si-core/Al2O3-shell and Si-core/SiO2-shell nanostructures. With reactive dynamics simulations, we were able to simultaneously track and correlate the lithiation rate, compositional change, mechanical property evolution, stress distributions, and fracture. A new mechanics model based on these varying properties was developed to determine how to stabilize the coating with a critical size ratio. Furthermore, we discovered that the self-accelerating Li diffusion in Al2O3 coating forms a well-defined Li concentration gradient, leading to an elastic modulus gradient, which effectively avoids local stress concentration and mitigates crack propagation. Based on these results, we propose a modulus gradient coating, softer outside, harder inside, as the most efficient coating to protect the Si electrode surface and improve its current efficiency.

Plasmonic nanodiamonds: targeted core-shell type nanoparticles for cancer cell thermoablation.

PubMed

Rehor, Ivan; Lee, Karin L; Chen, Kevin; Hajek, Miroslav; Havlik, Jan; Lokajova, Jana; Masat, Milan; Slegerova, Jitka; Shukla, Sourabh; Heidari, Hamed; Bals, Sara; Steinmetz, Nicole F; Cigler, Petr

2015-02-18

Targeted biocompatible nanostructures with controlled plasmonic and morphological parameters are promising materials for cancer treatment based on selective thermal ablation of cells. Here, core-shell plasmonic nanodiamonds consisting of a silica-encapsulated diamond nanocrystal coated in a gold shell are designed and synthesized. The architecture of particles is analyzed and confirmed in detail using electron tomography. The particles are biocompatibilized using a PEG polymer terminated with bioorthogonally reactive alkyne groups. Azide-modified transferrin is attached to these particles, and their high colloidal stability and successful targeting to cancer cells overexpressing the transferrin receptor are demonstrated. The particles are nontoxic to the cells and they are readily internalized upon binding to the transferrin receptor. The high plasmonic cross section of the particles in the near-infrared region is utilized to quantitatively ablate the cancer cells with a short, one-minute irradiation by a pulse 750-nm laser. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sugar-Coated Nanobullet: Growth Inhibition of Cancer Cells Induced by Metformin-Loaded Glyconanoparticles.

PubMed

Qian, Ruo-Can; Lv, Jian; Li, Hao-Wen; Long, Yi-Tao

2017-11-22

Metformin, a widely used drug for treating type-2 diabetes, has now been discovered to reduce cancer cell proliferation. However, further efforts are needed to design effective metformin delivery vehicles, instead of bare metformin. Herein we report a highly efficient transport nanostructure based on core-shell glyconanoparticles (GNPs), with gold as the core and dextran as the shell interspersed with metformin molecules. The dextran shell facilitates the entry of GNPs into living cells, which allows the subsequent release of metformin. Using MCF-7 breast cancer cells as an example, significant cell growth inhibition was observed after treatment of metformin-containing GNPs (MGNPs). Compared with bare metformin or bare GNPs, MGNPs show a stronger capacity for cell growth inhibition with good biocompatibility. Furthermore, inactivation of mitochondria and activation of p53 protein are observed during MGNP treatment, which provides evidence for metformin-induced cell apoptosis pathways. This work provides a new therapeutic tool for the treatment of cancer. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silica-Coated Plasmonic Metal Nanoparticles in Action.

PubMed

Hanske, Christoph; Sanz-Ortiz, Marta N; Liz-Marzán, Luis M

2018-05-07

Hybrid colloids consisting of noble metal cores and metal oxide shells have been under intense investigation for over two decades and have driven progress in diverse research lines including sensing, medicine, catalysis, and photovoltaics. Consequently, plasmonic core-shell particles have come to play a vital role in a plethora of applications. Here, an overview is provided of recent developments in the design and utilization of the most successful class of such hybrid materials, silica-coated plasmonic metal nanoparticles. Besides summarizing common simple approaches to silica shell growth, special emphasis is put on advanced synthesis routes that either overcome typical limitations of classical methods, such as stability issues and undefined silica porosity, or grant access to particularly sophisticated nanostructures. Hereby, a description is given, how different types of silica can be used to provide noble metal particles with specific functionalities. Finally, applications of such nanocomposites in ultrasensitive analyte detection, theranostics, catalysts, and thin-film solar cells are reviewed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanodiamond-Based Composite Structures for Biomedical Imaging and Drug Delivery.

PubMed

Rosenholm, Jessica M; Vlasov, Igor I; Burikov, Sergey A; Dolenko, Tatiana A; Shenderova, Olga A

2015-02-01

Nanodiamond particles are widely recognized candidates for biomedical applications due to their excellent biocompatibility, bright photoluminescence based on color centers and outstanding photostability. Recently, more complex architectures with a nanodiamond core and an external shell or nanostructure which provides synergistic benefits have been developed, and their feasibility for biomedical applications has been demonstrated. This review is aimed at summarizing recent achievements in the fabrication and functional demonstrations of nanodiamond-based composite structures, along with critical considerations that should be taken into account in the design of such structures from a biomedical point of view. A particular focus of the review is core/shell structures of nanodiamond surrounded by porous silica shells, which demonstrate a remarkable increase in drug loading efficiency; as well as nanodiamonds decorated with carbon dots, which have excellent potential as bioimaging probes. Other combinations are also considered, relying on the discussed inherent properties of the inorganic materials being integrated in a way to advance inorganic nanomedicine in the quest for better health-related nanotechnology.

Preparation and Structural Studies on Hybrid Core-Shell Nanoparticles Consisting of Silica Core and Conjugated Block Copolymer Shell Prepared by Surface-Initiated Polymerization

NASA Astrophysics Data System (ADS)

Chatterjee, Sourav; Karam, Tony; Rosu, Cornelia; Li, Xin; Do, Changwoo; Youm, Sang Gil; Haber, Louis; Russo, Paul; Nesterov, Evgueni

Controlled Kumada catalyst-transfer polymerization occurring by chain-growth mechanism was developed for the synthesis of conjugated polymers and block copolymers from the surface of inorganic substrates such as silica nanoparticles. Although synthesis of conjugated polymers via Kumada polymerization became an established method for solution polymerization, carrying out the same reaction in heterogeneous conditions to form monodisperse polymer chains still remains a challenge. We developed and described a simple and efficient approach to the preparation of surface-immobilized layer of catalytic Ni(II) initiator, and demonstrated using it to prepare polymers and block copolymers on silica nanoparticle. The structure of the resulting hybrid nanostructures was thoroughly studied using small-angle neutron and X-ray scattering, thermal analysis, and optical spectroscopy. The photoexcitation energy transfer processes in the conjugated polymer shell were studied via steady-state and time resolved transient absorption spectroscopy. This study uncovered important details of the energy transfer, which will be discussed in this presentation.

Magnetic hybrid magnetite/metal organic framework nanoparticles: facile preparation, post-synthetic biofunctionalization and tracking in vivo with magnetic methods

NASA Astrophysics Data System (ADS)

Tregubov, A. A.; Sokolov, I. L.; Babenyshev, A. V.; Nikitin, P. I.; Cherkasov, V. R.; Nikitin, M. P.

2018-03-01

Multifunctional hybrid nanocomposites remain to be of great interest in biomedicine as a universal tool in a number of applications. As a promising example, the nanoparticles with magnetic core and porous shell have a potential as theranostic agents combining both the diagnostics probe and drug delivery vehicle properties. However, reported methods of the nanostructure preparation are complex and include tedious time-consuming growth of porous shell by means of layer by layer assembly technique. In this study, we develop new way of fabrication of the superparamagnetic magnetite core @ porous metal organic framework shell nanoparticles and demonstrate their application both as a multimodal (MRI contrasting, magnetometric and optical labeling) and multifunctional (in vivo bioimaging, biotargeting by coupled receptors, lateral flow assay) agents. The easiness of fabrication, controllable bioconjugation properties and low level of non-specific binding indicate high potential of the nanoparticles to be employed as multifunctional agents in theranostics, advanced biosensing and bioimaging.

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties.

PubMed

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-02

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.

Band structure engineering strategies of metal oxide semiconductor nanowires and related nanostructures: A review

NASA Astrophysics Data System (ADS)

Piyadasa, Adimali; Wang, Sibo; Gao, Pu-Xian

2017-07-01

The electronic band structure of a solid state semiconductor determines many of its physical and chemical characteristics such as electrical, optical, physicochemical, and catalytic activity. Alteration or modification of the band structure could lead to significant changes in these physical and chemical characteristics, therefore we introduce new mechanisms of creating novel solid state materials with interesting properties. Over the past three decades, research on band structure engineering has allowed development of various methods to modify the band structure of engineered materials. Compared to bulk counterparts, nanostructures generally exhibit higher band structure modulation capabilities due to the quantum confinement effect, prominent surface effect, and higher strain limit. In this review we will discuss various band structure engineering strategies in semiconductor nanowires and other related nanostructures, mostly focusing on metal oxide systems. Several important strategies of band structure modulation are discussed in detail, such as doping, alloying, straining, interface and core-shell nanostructuring.

A nanocomposite of Au-AgI core/shell dimer as a dual-modality contrast agent for x-ray computed tomography and photoacoustic imaging

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

Orza, Anamaria; Wu, Hui; Li, Yuancheng

Purpose: To develop a core/shell nanodimer of gold (core) and silver iodine (shell) as a dual-modal contrast-enhancing agent for biomarker targeted x-ray computed tomography (CT) and photoacoustic imaging (PAI) applications. Methods: The gold and silver iodine core/shell nanodimer (Au/AgICSD) was prepared by fusing together components of gold, silver, and iodine. The physicochemical properties of Au/AgICSD were then characterized using different optical and imaging techniques (e.g., HR- transmission electron microscope, scanning transmission electron microscope, x-ray photoelectron spectroscopy, energy-dispersive x-ray spectroscopy, Z-potential, and UV-vis). The CT and PAI contrast-enhancing effects were tested and then compared with a clinically used CT contrast agentmore » and Au nanoparticles. To confer biocompatibility and the capability for efficient biomarker targeting, the surface of the Au/AgICSD nanodimer was modified with the amphiphilic diblock polymer and then functionalized with transferrin for targeting transferrin receptor that is overexpressed in various cancer cells. Cytotoxicity of the prepared Au/AgICSD nanodimer was also tested with both normal and cancer cell lines. Results: The characterizations of prepared Au/AgI core/shell nanostructure confirmed the formation of Au/AgICSD nanodimers. Au/AgICSD nanodimer is stable in physiological conditions for in vivo applications. Au/AgICSD nanodimer exhibited higher contrast enhancement in both CT and PAI for dual-modality imaging. Moreover, transferrin functionalized Au/AgICSD nanodimer showed specific binding to the tumor cells that have a high level of expression of the transferrin receptor. Conclusions: The developed Au/AgICSD nanodimer can be used as a potential biomarker targeted dual-modal contrast agent for both or combined CT and PAI molecular imaging.« less

A Stable Plasmonic Cu@Cu2 O/ZnO Heterojunction for Enhanced Photocatalytic Hydrogen Generation.

PubMed

Lou, Yongbing; Zhang, Yake; Cheng, Lin; Chen, Jinxi; Zhao, Yixin

2018-05-09

The localized surface plasmon resonance (LSPR) effect has been widely utilized in photocatalysis, but most reported LSPR materials are based on noble metals of gold or silver with high chemical stability. Plasmonic copper nanoparticles that exhibit an LSPR absorbance at 600 nm are promising for many applications, such as photocatalysis. Unfortunately, plasmonic copper nanoparticles are affected by serious surface oxidation in air. Herein, a novel lollipop-shaped Cu@Cu 2 O/ZnO heterojunction nanostructure was designed, for the first time, to stabilize the plasmonic Cu core by decorating Cu@Cu 2 O core-shell structures with ZnO nanorods. This Cu@Cu 2 O/ZnO nanostructure exhibited significantly enhanced stability than that of regular Cu@Cu 2 O, which accounted for the remarkably enhanced photocatalytic H 2 evolution rate through water splitting, relative to pristine ZnO nanorods, over an extended wavelength range due to the plasmonic Cu core. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advances and challenges in the field of plasma polymer nanoparticles

PubMed Central

Pleskunov, Pavel; Nikitin, Daniil; Titov, Valerii; Shelemin, Artem; Vaidulych, Mykhailo; Kuzminova, Anna; Solař, Pavel; Hanuš, Jan; Kousal, Jaroslav; Kylián, Ondřej; Slavínská, Danka; Biederman, Hynek

2017-01-01

This contribution reviews plasma polymer nanoparticles produced by gas aggregation cluster sources either via plasma polymerization of volatile monomers or via radio frequency (RF) magnetron sputtering of conventional polymers. The formation of hydrocarbon, fluorocarbon, silicon- and nitrogen-containing plasma polymer nanoparticles as well as core@shell nanoparticles based on plasma polymers is discussed with a focus on the development of novel nanostructured surfaces. PMID:29046847

Advances and challenges in the field of plasma polymer nanoparticles.

PubMed

Choukourov, Andrei; Pleskunov, Pavel; Nikitin, Daniil; Titov, Valerii; Shelemin, Artem; Vaidulych, Mykhailo; Kuzminova, Anna; Solař, Pavel; Hanuš, Jan; Kousal, Jaroslav; Kylián, Ondřej; Slavínská, Danka; Biederman, Hynek

2017-01-01

This contribution reviews plasma polymer nanoparticles produced by gas aggregation cluster sources either via plasma polymerization of volatile monomers or via radio frequency (RF) magnetron sputtering of conventional polymers. The formation of hydrocarbon, fluorocarbon, silicon- and nitrogen-containing plasma polymer nanoparticles as well as core@shell nanoparticles based on plasma polymers is discussed with a focus on the development of novel nanostructured surfaces.

Highly narrow nanogap-containing Au@Au core-shell SERS nanoparticles: size-dependent Raman enhancement and applications in cancer cell imaging

NASA Astrophysics Data System (ADS)

Hu, Chongya; Shen, Jianlei; Yan, Juan; Zhong, Jian; Qin, Weiwei; Liu, Rui; Aldalbahi, Ali; Zuo, Xiaolei; Song, Shiping; Fan, Chunhai; He, Dannong

2016-01-01

Cellular imaging technologies employing metallic surface-enhanced Raman scattering (SERS) tags have gained much interest toward clinical diagnostics, but they are still suffering from poor controlled distribution of hot spots and reproducibility of SERS signals. Here, we report the fabrication and characterization of high narrow nanogap-containing Au@Au core-shell SERS nanoparticles (GCNPs) for the identification and imaging of proteins overexpressed on the surface of cancer cells. First, plasmonic nanostructures are made of gold nanoparticles (~15 nm) coated with gold shells, between which a highly narrow and uniform nanogap (~1.1 nm) is formed owing to polyA anchored on the Au cores. The well controlled distribution of Raman reporter molecules, such as 4,4'-dipyridyl (44DP) and 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB), are readily encoded in the nanogap and can generate strong, reproducible SERS signals. In addition, we have investigated the size-dependent SERS activity of GCNPs and found that with the same laser wavelength, the Raman enhancement discriminated between particle sizes. The maximum Raman enhancement was achieved at a certain threshold of particle size (~76 nm). High narrow nanogap-containing Au@Au core-shell SERS tags (GCTs) were prepared via the functionalization of hyaluronic acid (HA) on GCNPs, which recognized the CD44 receptor, a tumor-associated surface biomarker. And it was shown that GCTs have a good targeting ability to tumour cells and promising prospects for multiplex biomarker detection.Cellular imaging technologies employing metallic surface-enhanced Raman scattering (SERS) tags have gained much interest toward clinical diagnostics, but they are still suffering from poor controlled distribution of hot spots and reproducibility of SERS signals. Here, we report the fabrication and characterization of high narrow nanogap-containing Au@Au core-shell SERS nanoparticles (GCNPs) for the identification and imaging of proteins overexpressed on the surface of cancer cells. First, plasmonic nanostructures are made of gold nanoparticles (~15 nm) coated with gold shells, between which a highly narrow and uniform nanogap (~1.1 nm) is formed owing to polyA anchored on the Au cores. The well controlled distribution of Raman reporter molecules, such as 4,4'-dipyridyl (44DP) and 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB), are readily encoded in the nanogap and can generate strong, reproducible SERS signals. In addition, we have investigated the size-dependent SERS activity of GCNPs and found that with the same laser wavelength, the Raman enhancement discriminated between particle sizes. The maximum Raman enhancement was achieved at a certain threshold of particle size (~76 nm). High narrow nanogap-containing Au@Au core-shell SERS tags (GCTs) were prepared via the functionalization of hyaluronic acid (HA) on GCNPs, which recognized the CD44 receptor, a tumor-associated surface biomarker. And it was shown that GCTs have a good targeting ability to tumour cells and promising prospects for multiplex biomarker detection. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06919j

High-value utilization of egg shell to synthesize Silver and Gold-Silver core shell nanoparticles and their application for the degradation of hazardous dyes from aqueous phase-A green approach.

PubMed

Sinha, Tanur; Ahmaruzzaman, M

2015-09-01

The common household material, egg shell of Anas platyrhynchos is utilized for the synthesis of Silver and Gold-Silver core shell nanoparticles using greener, environment friendly and economic way. The egg shell extracts were acting as a stabilizing and reducing agents. This method avoids the use of external reducing and stabilizing agents, templates and solvents. The effects of various reaction parameters, such as reaction temperature, concentration in the formation of nanoparticles have also been investigated. The compositional abundance of gelatin may be envisaged for the effective reductive as well as stabilizing potency. The mechanisms for the formation of NPs have also been presented. The synthesized Ag NPs formed were predominantly spherical in nature with an average size of particles in the range of 6-26 nm. While, Au-Ag core shell nanoparticles formed were spherical and oval shaped, within a narrow size spectrum of 9-18 nm. Both the Ag NPs Au-and Ag core shell nanoparticles showed characteristic Bragg's reflection planes of fcc structure and surface plasmon resonance at 430 nm and 365 nm, respectively. The NPs were utilized for the removal of toxic and hazardous dyes, such as Rose Bengal, Methyl Violet 6 B and Methylene Blue from aqueous phase. Approximately 98.2%, 98.4% and 97% degradations of Rose Bengal, Methyl Violet 6 B, and Methylene Blue were observed with Ag NPs, while the percentage degradation of these dyes was 97.3%, 97.6% and 96% with Au-Ag NPs, respectively. Therefore, the present study has opened up an innovative way for synthesizing Ag NPs and Au-Ag bimetallic nanostructures of different morphologies and sizes involving the utilization of egg shell extract. The high efficiency of the NPs as photocatalysts has opened a promising application for the removal of hazardous dyes from the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

Coupling Resonances of Surface Plasmon in Gold Nanorod/Copper Chalcogenide Core-Shell Nanostructures and Their Enhanced Photothermal Effect.

PubMed

Li, Yingying; Pan, Guiming; Liu, Qiyu; Ma, Liang; Xie, Ying; Zhou, Li; Hao, Zhonghua; Wang, Ququan

2018-06-04

Dual plasmonic Au@Cu 2-x S core-shell nanorods (NRs) have been fabricated by using a hydrothermal method and plasmon-coupled effect between the Au core and Cu 2-x S shell in the near-infrared (NIR) region. The extinction spectrum of Au@Cu 2-x S NRs is dominated by the surface plasmon resonance (SPR) of the Cu 2-x S shell, the transverse surface plasmon resonance (TSPR), and the longitudinal surface plasmon resonance (LSPR) of the Au NRs. With the Cu 2-x S shell increasing (fixed Au NRs), the TSPR peak slightly redshifts and the LSPR and SPR peaks blueshift, owing to competition between the redshift of the refractive index effect and blueshift from the plasmon coupled effect. Although, for Au@Cu 2 S NRs, only TSPR and LSPR peaks can be seen and a redshift arises with the increasing Cu 2 S shell thickness, implying that no plasmonic coupling between Au NRs and Cu 2 S shell occurred. The extinction spectrum of the Au@Cu 2-x S NRs with three coupled resonance peaks is simulated by using the FDTD method, taking into account the electron-transfer effect. The dispersion properties of the coupling of Au@Cu 2-x S NRs with the LSPR of the initial Au core are studied experimentally by changing the length of the Au NRs, which are explained theoretically by the coupled harmonic oscillator model. The calculated coupled coefficients between SPR of the Cu 2-x S shell and LSPR of the Au NRs is 180 meV, which is much stronger than that of TSPR of Au NRs of 55 meV. Finally, the enhanced photothermal effect of Au@Cu 2-x S NRs has been demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Ganesh, Panchapakesan; Kent, Paul R; Mochalin, Vadym N

We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbon nanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core ofmore » the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbon nanostructure appears, with a shell-shell spacing of about {approx}3.4 {angstrom} for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large ({approx}29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less

Theoretical model for plasmonic photothermal response of gold nanostructures solutions

NASA Astrophysics Data System (ADS)

Phan, Anh D.; Nga, Do T.; Viet, Nguyen A.

2018-03-01

Photothermal effects of gold core-shell nanoparticles and nanorods dispersed in water are theoretically investigated using the transient bioheat equation and the extended Mie theory. Properly calculating the absorption cross section is an extremely crucial milestone to determine the elevation of solution temperature. The nanostructures are assumed to be randomly and uniformly distributed in the solution. Compared to previous experiments, our theoretical temperature increase during laser light illumination provides, in various systems, both reasonable qualitative and quantitative agreement. This approach can be a highly reliable tool to predict photothermal effects in experimentally unexplored structures. We also validate our approach and discuss itslimitations.

Double NIR laser stimulation and enhancing the thermal sensitivity of Er3+/Tm3+/Nd3+ doped multilayer core-shell nanoparticles.

PubMed

Ba, Zhaojing; Hu, Min; Zhao, Yiming; Wang, Yiqing; Wang, Jing; Zhang, Zhenxi

2018-08-31

Non-contact thermal sensors are important devices to study cellular processes and monitor temperature in vivo. Herein, a novel highly sensitive nanothermometer based on NaYF 4 :Yb,Er@ NaYF 4 @NaYF 4 :Yb,Tm@ NaYF 4 :Nd (denoted as Er@Y@Tm@Nd) was prepared by a facile solvothermal method. When excited by the near-infrared (NIR) light of 808 and 980 nm, the as-prepared Er@Y@Tm@Nd nanoparticles could emit both blue and green light, respectively, since the lanthanide cations responsible for these emissions are gathered inside this nanostructure. The green and blue light intensity ratio exhibits obvious temperature dependence in the range of the physiological temperature. Additionally, the fluorescence intensity of Er 3+ and Tm 3+ are also greatly enhanced due to the multilayer structure that implies avoiding the Er 3+ and Tm 3+ energy cross-relaxation by introduction of a NaYF 4 wall between them. The as-prepared core-shell-shell-shell structure with Er 3+ and Tm 3+ in different layers improves dozens of times of the thermal sensitivity based on the non-thermal coupling levels of the probe: the maximum values for the sensitivity are 2.95% K -1 (I Er-521 /I Tm-450 ) and 6.30% K -1 (I Tm-474 /I Er-541 ) when excited by 980 and 808 nm laser sources, respectively. These values are well above those previously reported (<0.7% K -1 ), indicating that the prepared nanostructures are temperature sensors with excellent thermal sensitivity and sensitive to NIR wavelength excitation that makes them highly preferred for thermal detection.

Optical and Photothermal Behaviors of Colloidal and Self-Assembled Magnetic-Plasmonic Nanostructures

NASA Astrophysics Data System (ADS)

Liu, Kai

This dissertation is based on numerous efforts in exploring the capabilties of numerical simulation for investigating novel optical phenomena in different colloidal plasmonic systems. The dissertation includes five chapters. Chapter 1 contains a general introduction to the fundamentals of plasmonic behaviors in colloidal clusters and bottom-up self-assembly methods for manufacturing colloidal clusters which include magnetic based and DNA-assisted pathways. Chapter 2 presents a systematic comparison of optical and thermodynamic properties of near-infrared colloidal nanoparticles, including SiO2 Au core-shell, Au nanocage and Au nanorod, and an example of the nanobubble-based photothermal therapy application. In Chapter 3, a optical phenomenon named Fano resonance is demonstrated in a colloidal heptamer design which consists of seven Fe 3O4 Au core-shell nanoparticles. The incorporation of the magnetic core enables a magnetic-assisted self-assembly process which will be discussed after the photonic analysis. In Chapter 4, the optical behaviors in a 1D magnetic-plasmonic chain are explored. A demonstration of the magnetic-based self-assembly of this 1D chain is given. Chapter 5 is focused on the study of the chiral optical responses in a helical nanoscale system which follows a 3D helical arrangement of Fe3O4 Au core-shell nanoparticles.

The biodistribution of gold nanoparticles designed for renal clearance

NASA Astrophysics Data System (ADS)

Alric, Christophe; Miladi, Imen; Kryza, David; Taleb, Jacqueline; Lux, François; Bazzi, Rana; Billotey, Claire; Janier, Marc; Perriat, Pascal; Roux, Stéphane; Tillement, Olivier

2013-06-01

Owing to their tunable optical properties and their high absorption cross-section of X- and γ-ray, gold nanostructures appear as promising agents for remotely controlled therapy. Since the efficiency of cancer therapy is not limited to the eradication of the tumour but rests also on the sparing of healthy tissue, a biodistribution study is required in order to determine whether the behaviour of the nanoparticles after intravenous injection is safe (no accumulation in healthy tissue, no uptake by phagocytic cell-rich organs (liver, spleen) and renal clearance). The biodistribution of Au@DTDTPA nanoparticles which are composed of a gold core and a DTDTPA (dithiolated polyaminocarboxylate) shell can be established by X-ray imaging (owing to the X-ray absorption of the gold core) and by magnetic resonance imaging (MRI) since the DTDTPA shell was designed for the immobilization of paramagnetic gadolinium ions. However scintigraphy appears better suited for a biodistribution study owing to a great sensitivity. The successful immobilization of radioelements (99mTc, 111In) in the DTDTPA shell, instead of gadolinium ions, renders possible the follow up of Au@DTDTPA by scintigraphy which showed that Au@DTDTPA nanoparticles exhibit a safe behaviour after intravenous injection to healthy rats.Owing to their tunable optical properties and their high absorption cross-section of X- and γ-ray, gold nanostructures appear as promising agents for remotely controlled therapy. Since the efficiency of cancer therapy is not limited to the eradication of the tumour but rests also on the sparing of healthy tissue, a biodistribution study is required in order to determine whether the behaviour of the nanoparticles after intravenous injection is safe (no accumulation in healthy tissue, no uptake by phagocytic cell-rich organs (liver, spleen) and renal clearance). The biodistribution of Au@DTDTPA nanoparticles which are composed of a gold core and a DTDTPA (dithiolated polyaminocarboxylate) shell can be established by X-ray imaging (owing to the X-ray absorption of the gold core) and by magnetic resonance imaging (MRI) since the DTDTPA shell was designed for the immobilization of paramagnetic gadolinium ions. However scintigraphy appears better suited for a biodistribution study owing to a great sensitivity. The successful immobilization of radioelements (99mTc, 111In) in the DTDTPA shell, instead of gadolinium ions, renders possible the follow up of Au@DTDTPA by scintigraphy which showed that Au@DTDTPA nanoparticles exhibit a safe behaviour after intravenous injection to healthy rats. Electronic supplementary information (ESI) available: Planar scintigraphy image. See DOI: 10.1039/c3nr00012e

Reduction of HAuCl 4 by Na 2S revisited: The case for Au nanoparticle aggregates and against Au 2S/Au core/shell particles

DOE PAGES

Schwartzberg, A. M.; Grant, C. D.; van Buuren, Tony; ...

2007-03-10

The reaction of sodium sulfide with chloroauric acid has been surrounded by a controversy over the structure of the resulting product. The original report proposed a Au 2S/Au core/shell structure based on strong near-IR resonance and limited transmission electron microscopy. Subsequent reports used the same model without further attempts to determine the structure of the products. With a significant body of experimental work compiled over a period of several years, we have shown that the major product of this reaction is aggregated spherical nanoparticles of gold with a minority component consisting of triangular and rod-like structures. This is in contradictionmore » to the core/shell structures as originally proposed. Recently, there have been additional reports that again suggest a Au 2S/Au core/shell structure or irregularly shaped Au nanoparticles as an explanation for the near-IR resonance. To help resolve this issue, we have carried out further experiments to determine how the reaction products may depend on experimental conditions such as concentration and aging of the reactants, particularly Na 2S. It has been determined that sodium thiosulfate is the likely product from Na 2S aging. In addition, persistent spectral hole burning experiments have been conducted on gold nanoparticle aggregate (GNA) samples at excitation intensities that are lower than that required to melt the nanostructures. We have observed a decrease in optical absorption on resonance with the excitation laser wavelength, with simultaneous increases in absorption to the blue and red of this wavelength region. However, in the presence of the stabilizer poly(vinyl pyrrolidone) (PVP), no increase in absorbance was observed but rather a blue shifting and decrease in intensity of the near-IR plasmon resonance. These results imply that the non-stabilized GNAs are able to break apart and reform into off resonant aggregate structures. In contrast, this behavior is suppressed in PVP stabilized GNAs because of the presence of polymer which quickly passivates the individual nanoparticles that comprise the GNAs after they are disrupted by laser irradiation. These results would be very difficult to explain if the nanostructures were core/shell. Furthermore, these new results again support the model of GNAs as the best possible explanation for the product of the HAuCl 4 and Na 2S reaction.« less

Evaluating Dimethyldiethoxysilane for use in Polyurethane Crosslinked Silica Aerogels

NASA Technical Reports Server (NTRS)

Randall, Jason P.; Meador, Mary Ann B.; Jana, Sadhan C.

2008-01-01

Silica aerogels are highly porous materials which exhibit exceptionally low density and thermal conductivity. Their "pearl necklace" nanostructure, however, is inherently weak; most silica aerogels are brittle and fragile. The strength of aerogels can be improved by employing an additional crosslinking step using isocyanates. In this work, dimethyldiethoxysilane (DMDES) is evaluated for use in the silane backbone of polyurethane crosslinked aerogels. Approximately half of the resulting aerogels exhibited a core/shell morphology of hard crosslinked aerogel surrounding a softer, uncrosslinked center. Solid state NMR and scanning electron microscopy results indicate the DMDES incorporated itself as a conformal coating around the outside of the secondary silica particles, in much the same manner as isocyanate crosslinking. Response surface curves were generated from compression data, indicating levels of reinforcement comparable to that in previous literature, despite the core/shell morphology.

Synthesis and characterization of Pd(0), PdS, and Pd-PdO core-shell nanoparticles by solventless thermolysis of a Pd-thiolate cluster

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

Jose, Deepa; Jagirdar, Balaji R., E-mail: jagirdar@ipc.iisc.ernet.i

2010-09-15

Colloids of palladium nanoparticles have been prepared by the solvated metal atom dispersion (SMAD) method. The as-prepared Pd colloid consists of particles with an average diameter of 2.8{+-}0.1 nm. Digestive ripening of the as-prepared Pd colloid, a process involving refluxing the as-prepared colloid at or near the boiling point of the solvent in the presence of a passivating agent, dodecanethiol resulted in a previously reported Pd-thiolate cluster, [Pd(SC{sub 12}H{sub 25}){sub 2}]{sub 6} but did not render the expected narrowing down of the particle size distribution. Solventless thermolysis of the Pd-thiolate complex resulted in various Pd systems such as Pd(0), PdS,more » and Pd-PdO core-shell nanoparticles thus demonstrating its versatility. These Pd nanostructures have been characterized using high-resolution electron microscopy and powder X-ray diffraction methods. - Graphical abstract: Solventless thermolysis of a single palladium-thiolate cluster affords various Pd systems such as Pd(0), Pd-PdO core-shell, and PdS nanoparticles demonstrating the versatility of the precursor and the methodology.« less

Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites

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

Zarick, Holly; Boulesbaa, Abdelaziz; Puretzky, Alexander A

In this paper, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr 3) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr3more » perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO 2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.« less

Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites

DOE PAGES

Zarick, Holly; Boulesbaa, Abdelaziz; Puretzky, Alexander A; ...

2016-12-14

In this paper, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr 3) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr3more » perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO 2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.« less

Emission Behavior of Fluorescently Labeled Silver Nanoshell: Enhanced Self-Quenching by Metal Nanostructure.

PubMed

Zhang, Jian; Fu, Yi; Lakowicz, Joseph R

2007-02-08

Labeled silica beads with an average diameter of 100 nm were synthesized by incorporating with 20-600 μM Ru(bpy)(3) (2+) complexes. Silver shells were deposited on the beads layer-by-layer with the shell thickness of 5-50 nm. The emission band became narrower and the intensity was enhanced depending on the shell thickness. Self-quenching of the probe was observed at high concentration. Poisson statistics were employed to analyze self-quenching of the fluorophores. The estimated quenching distance was extended from 6 to 16 nm with shell growth from 0 to 50 nm. Moreover, the silver shells were also labeled with Rhodamine 6G. Fluorescence enhancement and reduced lifetime were also observed for silver-silica shell containing R6G. We found that by adjustment of probe concentration and silver shell thickness, a Ru(bpy)(3) (2+)-labeled particle could be 600 times brighter than an isolated Ru(bpy)(3) (2+) molecule. We expect labeled metal core-shell structures can become useful probes for high sensitivity and/or single particle assay.

Oxidative degradation of the antibiotic oxytetracycline by Cu@Fe3O4 core-shell nanoparticles.

PubMed

Pham, Van Luan; Kim, Do-Gun; Ko, Seok-Oh

2018-08-01

A core-shell nanostructure composed of zero-valent Cu (core) and Fe 3 O 4 (shell) (Cu@Fe 3 O 4 ) was prepared by a simple reduction method and was evaluated for the degradation of oxytetracycline (OTC), an antibiotic. The Cu core and the Fe 3 O 4 shell were verified by X-ray diffractometry (XRD) and transmission electron microscopy. The optimal molar ratio of [Cu]/[Fe] (1/1) in Cu@Fe 3 O 4 created an outstanding synergic effect, leading to >99% OTC degradation as well as H 2 O 2 decomposition within 10min at the reaction conditions of 1g/L Cu@Fe 3 O 4 , 20mg/L OTC, 20mM H 2 O 2 , and pH3.0 (and even at pH9.0). The OTC degradation rate by Cu@Fe 3 O 4 was higher than obtained using single nanoparticle of Cu or Fe 3 O 4 . The results of the study using radical scavengers showed that OH is the major reactive oxygen species contributing to the OTC degradation. Finally, good stability, reusability, and magnetic separation were obtained with approximately 97% OTC degradation and no notable change in XRD patterns after the Cu@Fe 3 O 4 catalyst was reused five times. These results demonstrate that Cu@Fe 3 O 4 is a novel prospective candidate for the pharmaceutical and personal care products degradation in the aqueous phase. Copyright © 2018 Elsevier B.V. All rights reserved.

Iron Oxide and Gold Based Magneto-Plasmonic Nanostructures for Medical Applications: A Review

PubMed Central

Mammeri, Fayna; Ammar, Souad

2018-01-01

Iron oxide and gold-based magneto-plasmonic nanostructures exhibit remarkable optical and superparamagnetic properties originating from their two different components. As a consequence, they have improved and broadened the application potential of nanomaterials in medicine. They can be used as multifunctional nanoprobes for magneto-plasmonic heating as well as for magnetic and optical imaging. They can also be used for magnetically assisted optical biosensing, to detect extreme traces of targeted bioanalytes. This review introduces the previous work on magneto-plasmonic hetero-nanostructures including: (i) their synthesis from simple “one-step” to complex “multi-step” routes, including seed-mediated and non-seed-mediated methods; and (ii) the characterization of their multifunctional features, with a special emphasis on the relationships between their synthesis conditions, their structures and their properties. It also focuses on the most important progress made with regard to their use in nanomedicine, keeping in mind the same aim, the correlation between their morphology—namely spherical and non-spherical, core-satellite and core-shell, and the desired applications. PMID:29518969

Application of Direct Current Atmospheric Pressure Glow Microdischarge Generated in Contact with a Flowing Liquid Solution for Synthesis of Au-Ag Core-Shell Nanoparticles.

PubMed

Dzimitrowicz, Anna; Jamroz, Piotr; Nyk, Marcin; Pohl, Pawel

2016-04-06

A direct current atmospheric pressure glow microdischarge (dc-μAPGD) generated between an Ar nozzle microjet and a flowing liquid was applied to produce Au-Ag core-shell nanoparticles (Au@AgCSNPs) in a continuous flow system. Firstly, operating dc-μAPGD with the flowing solution of the Au(III) ions as the cathode, the Au nanoparticles (AuNPs) core was produced. Next, to produce the core-shell nanostructures, the collected AuNPs solution was immediately mixed with an AgNO₃ solution and passed through the system with the reversed polarity to fabricate the Ag nanoshell on the AuNPs core. The formation of Au@AgCSNPs was confirmed using ultraviolet-visible (UV-Vis) absorbance spectrophotometry, transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). Three localized surface plasmon resonance absorption bands with wavelengths centered at 372, 546, and 675 nm were observed in the UV-Vis spectrum of Au@AgCSNPs, confirming the reduction of both the Au(III) and Ag(I) ions. The right configuration of metals in Au@AgCSNPs was evidenced by TEM. The Au core diameter was 10.2 ± 2.0 nm, while the thickness of the Ag nanoshell was 5.8 ± 1.8 nm. The elemental composition of the bimetallic nanoparticles was also confirmed by EDS. It is possible to obtain 90 mL of a solution containing Au@AgCSNPs per hour using the applied microdischarge system.

Rational growth of branched nanowire heterostructures with synthetically encoded properties and function

PubMed Central

Jiang, Xiaocheng; Tian, Bozhi; Xiang, Jie; Qian, Fang; Zheng, Gengfeng; Wang, Hongtao; Mai, Liqiang; Lieber, Charles M.

2011-01-01

Branched nanostructures represent unique, 3D building blocks for the “bottom-up” paradigm of nanoscale science and technology. Here, we report a rational, multistep approach toward the general synthesis of 3D branched nanowire (NW) heterostructures. Single-crystalline semiconductor, including groups IV, III–V, and II–VI, and metal branches have been selectively grown on core or core/shell NW backbones, with the composition, morphology, and doping of core (core/shell) NWs and branch NWs well controlled during synthesis. Measurements made on the different composition branched NW structures demonstrate encoding of functional p-type/n-type diodes and light-emitting diodes (LEDs) as well as field effect transistors with device function localized at the branch/backbone NW junctions. In addition, multibranch/backbone NW structures were synthesized and used to demonstrate capability to create addressable nanoscale LED arrays, logic circuits, and biological sensors. Our work demonstrates a previously undescribed level of structural and functional complexity in NW materials, and more generally, highlights the potential of bottom-up synthesis to yield increasingly complex functional systems in the future. PMID:21730174

Laser-induced transformation of supramolecular complexes: approach to controlled formation of hybrid multi-yolk-shell Au-Ag@a-C:H nanostructures

PubMed Central

Manshina, A. A.; Grachova, E. V.; Povolotskiy, A. V.; Povolotckaia, A. V.; Petrov, Y. V.; Koshevoy, I. O.; Makarova, A. A.; Vyalikh, D. V.; Tunik, S. P.

2015-01-01

In the present work an efficient approach of the controlled formation of hybrid Au–Ag–C nanostructures based on laser-induced transformation of organometallic supramolecular cluster compound is suggested. Herein the one-step process of the laser-induced synthesis of hybrid multi-yolk-shell Au-Ag@a-C:H nanoparticles which are bimetallic gold-silver subnanoclusters dispersed in nanospheres of amorphous hydrogenated a-C:H carbon is reported in details. It has been demonstrated that variation of the experimental parameters such as type of the organometallic precursor, solvent, deposition geometry and duration of laser irradiation allows directed control of nanoparticles’ dimension and morphology. The mechanism of Au-Ag@a-C:H nanoparticles formation is suggested: the photo-excitation of the precursor molecule through metal-to-ligand charge transfer followed by rupture of metallophilic bonds, transformation of the cluster core including red-ox intramolecular reaction and aggregation of heterometallic species that results in the hybrid metal/carbon nanoparticles with multi-yolk-shell architecture formation. It has been found that the nanoparticles obtained can be efficiently used for the Surface-Enhanced Raman Spectroscopy label-free detection of human serum albumin in low concentration solution. PMID:26153347

A pressure tuned stop-flow atomic layer deposition process for MoS2 on high porous nanostructure and fabrication of TiO2/MoS2 core/shell inverse opal structure

NASA Astrophysics Data System (ADS)

Li, Xianglin; Puttaswamy, Manjunath; Wang, Zhiwei; Kei Tan, Chiew; Grimsdale, Andrew C.; Kherani, Nazir P.; Tok, Alfred Iing Yoong

2017-11-01

MoS2 thin films are obtained by atomic layer deposition (ALD) in the temperature range of 120-150 °C using Mo(CO)6 and dimethyl disulfide (DMDS) as precursors. A pressure tuned stop-flow ALD process facilitates the precursor adsorption and enables the deposition of MoS2 on high porous three dimensional (3D) nanostructures. As a demonstration, a TiO2/MoS2 core/shell inverse opal (TiO2/MoS2-IO) structure has been fabricated through ALD of TiO2 and MoS2 on a self-assembled multilayer polystyrene (PS) structure template. Due to the self-limiting surface reaction mechanism of ALD and the utilization of pressure tuned stop-flow ALD processes, the as fabricated TiO2/MoS2-IO structure has a high uniformity, reflected by FESEM and FIB-SEM characterization. A crystallized TiO2/MoS2-IO structure can be obtained through a post annealing process. As a 3D photonic crystal, the TiO2/MoS2-IO exhibits obvious stopband reflecting peaks, which can be adjusted through changing the opal diameters as well as the thickness of MoS2 layer.

Interference of Steroidogenesis by Gold Nanorod Core/Silver Shell Nanostructures: Implications for Reproductive Toxicity of Silver Nanomaterials.

PubMed

Jiang, Xiumei; Wang, Liming; Ji, Yinglu; Tang, Jinglong; Tian, Xin; Cao, Mingjing; Li, Jingxuan; Bi, Shuying; Wu, Xiaochun; Chen, Chunying; Yin, Jun-Jie

2017-03-01

As a widely used nanomaterial in daily life, silver nanomaterials may cause great concern to female reproductive system as they are found to penetrate the blood-placental barrier and gain access to the ovary. However, it is largely unknown about how silver nanomaterials influence ovarian physiology and functions such as hormone production. This study performs in vitro toxicology study of silver nanomaterials, focusing especially on cytotoxicity and steroidogenesis and explores their underlying mechanisms. This study exposes primary rat granulosa cells to gold nanorod core/silver shell nanostructures (Au@Ag NRs), and compares outcomes with cells exposed to gold nanorods. The Au@Ag NRs generate more reactive oxygen species and reduce mitochondrial membrane potential and less production of adenosine triphosphate. Au@Ag NRs promote steroidogenesis, including progesterone and estradiol, in a time- and dose-dependent manner. Chemical reactivity and transformation of Au@Ag NRs are then studied by electron spin resonance spectroscopy and X-ray absorption near edge structure, which analyze the generation of free radical and intracellular silver species. Results suggest that both particle-specific activity and intracellular silver ion release of Au@Ag NR contribute to the toxic response of granulosa cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size-controlled synthesis of superparamagnetic iron oxide nanoparticles and their surface coating by gold for biomedical applications

NASA Astrophysics Data System (ADS)

Maleki, H.; Simchi, A.; Imani, M.; Costa, B. F. O.

2012-11-01

The size mono-dispersity, saturation magnetization, and surface chemistry of magnetic nanoparticles (NPs) are recognized as critical factors for efficient biomedical applications. Here, we performed modified water-in-oil inverse nano-emulsion procedure for preparation of stable colloidal superparamagnetic iron oxide NPs (SPIONs) with high saturation magnetization. To achieve mono-dispersed SPIONs, optimization process was probed on several important factors including molar ratio of iron salts [Fe3+ and Fe2+], the concentration of ammonium hydroxide as reducing agent, and molar ratio of water to surfactant. The biocompatibility of the obtained NPs, at various concentrations, was evaluated via MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay and the results showed that the NPs were non-toxic at concentrations <0.1 mg/mL. Surface functionalization was performed by conformal coating of the NPs with a thin shell of gold (˜4 nm) through chemical reduction of attached gold salts at the surface of the SPIONs. The Fe3O4 core/Au shell particles demonstrate strong plasmon resonance absorption and can be separated from solution using an external magnetic field. Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, phase components, core-shell surface composition, and magnetic properties have confirmed the formation of the mono-dispersed core-shell nanostructure.

Forging Colloidal Nanostructures via Cation Exchange Reactions

PubMed Central

2016-01-01

Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

Forging Colloidal Nanostructures via Cation Exchange Reactions.

PubMed

De Trizio, Luca; Manna, Liberato

2016-09-28

Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

Core-shell-corona polymeric micelles as a versatile template for synthesis of inorganic hollow nanospheres.

PubMed

Sasidharan, Manickam; Nakashima, Kenichi

2014-01-21

Hollow, inorganic nanoscale capsules have many applications, from the delivery of encapsulated products for cosmetic and medicinal purposes to use as lightweight composite materials. Early methods for producing inorganic hollow nanospheres using hard templates suffered from low product yield and shell weakness upon template removal. In the past decade, researchers have turned to amphiphilic copolymers to synthesize hollow nanostructures and ordered mesoporous materials. Amphiphilic molecules self-assemble into well-defined nanostructures including spherical micelles. Micelles formed from simple, two-component AB diblock and ABA triblock copolymers, however, have been difficult to work with to construct inorganic hollow nanoparticles, because the corona of the micelle, which serves as the template for the shell, becomes unstable as it absorbs inorganic shell precursors, causing aggregates to form. Newly developed, three-component ABC triblock copolymers may solve this problem. They provide nanoassemblies with more diverse morphological and functional features than AB diblock and ABA triblock copolymers. Micelles formed from ABC triblock copolymers in selective solvents that dissolve only one or two of the blocks provide templates for these improved nanoassemblies. By manipulating individual polymer blocks, one can "encode" additional features at the molecular level. For instance, modifying the functional groups or substitution patterns of the blocks allows better morphological and size control. Insights into polymer self-assembly gained over years of work in our group have set the stage to systematically engineer inorganic spherical hollow nanoparticles using ABC triblock copolymers. In this Account, we report our recent progress in producing diverse, inorganic hollow spherical nanospheres from asymmetric triblock copolymeric micelles with core-shell-corona architecture as templates. We discuss three classes of polymeric micelles-with neutral, cationic, and anionic shell structures-that allow fabrication of a variety of hollow nanoparticles. Importantly, we synthesized all of these particles in water, avoiding use of hazardous organic solvents. We have designed the precursor of the inorganic material to be selectively sorbed into the shell domain, leaving the corona free from the inorganic precursors that would destabilize the micelle. The core, meanwhile, is the template for the formation of the hollow void. By rationally tailoring experimental parameters, we readily and selectively obtained a variety of hollow nanoparticles including silica, hybrid silicas, metal-oxides, metal-carbonates, metal-sulfates, metal-borates, and metal-phosphates. Finally, we highlight the state-of-the-art techniques we used to characterize these nanoparticles, and describe experiments that demonstrate the potential of these hollow particles in drug delivery, and as anode and cathode materials for lithium-ion batteries.

Electronic, Optical, and Thermal Properties of Reduced-Dimensional Semiconductors

NASA Astrophysics Data System (ADS)

Huang, Shouting

Reduced-dimensional materials have attracted tremendous attention because of their new physics and exotic properties, which are of great interests for fundamental science. More importantly, the manipulation and engineering of matter on an atomic scale yield promising applications for many fields including nanoelectronics, nanobiotechnology, environments, and renewable energy. Because of the unusual quantum confinement and enhanced surface effect of reduced-dimensional materials, traditional empirical models suffer from necessary but unreliable parameters extracted from previously-studied bulk materials. In this sense, quantitative, parameter-free approaches are highly useful for understanding properties of reduced-dimensional materials and, furthermore, predicting their novel applications. The first-principles density functional theory (DFT) is proven to be a reliable and convenient tool. In particular, recent progress in many-body perturbation theory (MBPT) makes it possible to calculate excited-state properties, e.g., quasiparticle (QP) band gap and optical excitations, by the first-principles approach based on DFT. Therefore, during my PhD study, I employed first-principles calculations based on DFT and MBPT to systematically study fundamental properties of typical reduced-dimensional semiconductors, i.e., the electronic structure, phonons, and optical excitations of core-shell nanowires (NWs) and graphene-like two-dimensional (2D) structures of current interests. First, I present first-principles studies on how to engineer band alignments of nano-sized radial heterojunctions, Si/Ge core-shell NWs. Our calculation reveals that band offsets in these one-dimensional (1D) nanostructures can be tailored by applying axial strain or varying core-shell sizes. In particular, the valence band offset can be efficiently tuned across a wide range and even be diminished via applied strain. Two mechanisms contribute to this tuning of band offsets. Furthermore, varying the size of Si/Ge core-shell NWs and corresponding quantum confinement is shown to be efficient for modifying both valence and conduction band offsets simultaneously. Our proposed approaches to control band offsets in nano-sized heterojunctions may be of practical interest for nanoelectronic and photovoltaic applications. Additionally, I also studied the lattice vibrational modes of Si/Ge core-shell N-Ws. Our calculations show that the internal strain induced by the lattice mismatch between core and shell plays an important role in significantly shifting the frequency of characteristic optical modes of core-shell NWs. In particular, our simulation demonstrates that these frequency shifts can be detected by Raman-scattering experiments, giving rise to a convenient and nondestructive way to obtain structural information of core-shell materials. Meanwhile, another type of collective modes, the radial breathing modes (RBM), is identified in Si-core/Ge-shell NWs and their frequency dependence is explained by an elastic media model. Our studied vibrational modes and their frequency evolution are useful for thermoelectric applications based on core-shell nanostructures. Then I studied optical properties and exciton spectra of 2D semiconducting carbon structures. The energy spectra and wavefunctions of excitons in the 2D graphene derivatives, i.e., graphyne and graphane, are found to be strongly modified by quantum confinement, making them qualitatively different from the usual Rydberg series. However, their parity and optical selection rules are preserved. Thus a one-parameter hydrogenic model is applied to quantitatively explain the ab initio exciton spectra, and allows one to extrapolate the electron-hole binding energy from optical spectroscopies of 2D semiconductors without costly simulations. Meanwhile, our calculated optical absorption spectrum and enhanced spin singlet-triplet splitting project graphyne, an allotrope of graphene, as a good candidate for intriguing energy and biomedical applications. Lastly, we report first-principles results on electronic structures of 2D graphene-like system, i.e., silicene. For planar and simply buckled silicene structures, we confirm their zero-gap nature and show a significant renormalization of their Fermi velocity by including many-electron effects. However, the other two recently proposed silicene structures exhibit a finite band gap, indicating that they are gapped semiconductors instead of expected Dirac-fermion semimetals. This finite band gap of the latter two structures is preserved even with the Ag substrate included. The gap opening is explained by the symmetry breaking of the buckled structures. Moreover, our GW calculation reveals enhanced many-electron effects in these 2D structures. Finally the band gap of the latter two structures can be tuned in a wide range by applying strain.

Formation, characterization and dynamics of onion like carbon structures from nanodiamonds using reactive force-fields for electrical energy storage

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

Kent, Paul R

We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbon nanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core ofmore » the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbon nanostructure appears, with a shell-shell spacing of about {approx}3.4 {angstrom} for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large ({approx}29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less

Core-Shell PdPb@Pd Aerogels with Multiply-Twinned Intermetallic Nanostructures: Facile Synthesis with Accelerated Gelation Kinetics and Their Enhanced Electrocatalytic Properties

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

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang

2018-04-04

Delicately engineering the well-defined noble metal aerogels with favorable structural and compositional features is of vital importance for wide applications. Here, we reported one-pot and facile method for synthesizing core-shell PdPb@Pd hydrogels/aerogels with multiply-twinned grains and ordered intermetallic phase using sodium hypophosphite as a multifunctional reducing agent. Due to the accelerated gelation kinetics induced by increased reaction temperature and specific function of sodium hypophosphite, the formation of hydrogels can be completed within 4 hrs, far faster than the previous reports. Owe to their unique porous structure and favorable geometric and electronic effects, the optimized PdPb@Pd aerogels exhibit enhanced electrochemical performancemore » towards ethylene glycol oxidation with a mass activity of 5.8 times higher than Pd black.« less

Core/shell CuO/Al Nanorods Thermite Film Based on Electrochemical Anodization.

PubMed

Yu, Chunpei; Zhang, Wenchao; Hu, Bin; Ni, Debin; Zheng, Zilong; Liu, Jingping; Ma, Kefeng; Ren, Wei

2018-06-13

In this study, a new method was reported for the fabrication of the nanostructured CuO/Al thermite film on the Cu substrate. The CuO nanorods (NRs) arrays vertically grew from the Cu surfaces by electrochemical anodization processes, followed by the deposition of an Al layer on the CuO NRs via magnetron sputtering to form a core/shell CuO/Al nanothermite film, whose component, structure and morphology were subsequently characterized. In addition, the energy-release characteristics of the obtained nanothermite film was investigated using thermal analyses and laser ignition tests. All evidences demonstrate that the obtained CuO/Al is of a uniform structure and superb energy performance. Impressively, this resulted material is potentially useful in the applications of functional energetic chips due to its easy integration with microelectromechanical systems (MEMS) technologies. © 2018 IOP Publishing Ltd.

SERS microscopy: plasmonic nanoparticle probes and biomedical applications

NASA Astrophysics Data System (ADS)

Gellner, M.; Schütz, M.; Salehi, M.; Packeisen, J.; Ströbel, P.; Marx, A.; Schmuck, C.; Schlücker, S.

2010-08-01

Nanoparticle probes for use in targeted detection schemes and readout by surface-enhanced Raman scattering (SERS) comprise a metal core, Raman reporter molecules and a protective shell. One design of SERS labels specifically optimized for biomedical applications in conjunction with red laser excitation is based on tunable gold/silver nanoshells, which are completely covered by a self-assembled monolayer (SAM) of Raman reporters. A shell around the SAM-coated metal core stabilizes the colloid and prevents particle aggregation. The optical properties and SERS efficiencies of these plasmonic nanostructures are characterized both experimentally and theoretically. Subsequent bioconjugation of SERS probes to ligands such as antibodies is a prerequisite for the selective detection of the corresponding target molecule via the characteristic Raman signature of the label. Biomedical imaging applications of SERS-labeled antibodies for tumor diagnostics by SERS microscopy are presented, using the localization of the tumor suppressor p63 in prostate tissue sections as an example.

Magnetic field induced mixing of light hole excitonic states in (Cd, Mn)Te/(Cd, Mg)Te core/shell nanowires

NASA Astrophysics Data System (ADS)

Płachta, Jakub; Grodzicka, Emma; Kaleta, Anna; Kret, Sławomir; Baczewski, Lech T.; Pietruczik, Aleksiej; Wiater, Maciej; Goryca, Mateusz; Kazimierczuk, Tomasz; Kossacki, Piotr; Karczewski, Grzegorz; Wojtowicz, Tomasz; Wojnar, Piotr

2018-05-01

A detailed magneto-photoluminescence study of individual (Cd, Mn)Te/(Cd, Mg)Te core/shell nanowires grown by molecular beam epitaxy is performed. First of all, an enhancement of the Zeeman splitting due to sp-d exchange interaction between band carriers and Mn-spins is evidenced in these nanostructures. Then, it is found that the value of this splitting depends strongly on the magnetic field direction with respect to the nanowire axis. The largest splitting is observed when the magnetic field is applied perpendicular and the smallest when it is applied parallel to the nanowire axis. This effect is explained in terms of magnetic field induced valence band mixing and evidences the light hole character of the excitonic emission. The values of the light and heavy hole splitting are determined for several individual nanowires based on the comparison of experimental results to theoretical calculations.

Facile fabrication and characterization of poly(tetrafluoroethylene)@polypyrrole/nano-silver composite membranes with conducting and antibacterial property

NASA Astrophysics Data System (ADS)

Shi, Zhiquan; Zhou, Hui; Qing, Xutang; Dai, Tingyang; Lu, Yun

2012-06-01

Porous poly(tetrafluoroethylene) (PTFE) membranes play an important role in air purification and separation engineering. To achieve the bi-functionality of conducting and antibacterial property, two kinds of poly(tetrafluoroethylene)@ polypyrrole/nano-silver composite membranes have been prepared. One involves hydrophobic polypyrrole/nano-silver composite with hollow capsule nanostructures immobilized on the surface of the PTFE membranes. The other is a type of composite membranes with polypyrrole/nano-silver composite wholly packed on the fibrils of the expand PTFE membrane to form core/shell coaxial cable structures. The structure and morphology of the two kinds of composite membranes have been characterized by FTIR, UV-vis, XRD, TGA and SEM measurements. Possible formation mechanisms of the hollow capsules and the core/shell nanocable structures have been discussed in detail. The antibacterial effects of composite membranes are also briefly investigated.

Fabrication and magnetic properties of Ni nanospheres encapsulated in a fullerene-like carbon.

PubMed

Pol, S V; Pol, V G; Frydman, A; Churilov, G N; Gedanken, A

2005-05-19

A very simple, efficient, and economical synthetic technique, which produces fascinating fullerene-like Ni-C (graphitic) core-shell nanostructures at a relatively low temperature, is reported. The thermal dissociation of Ni acetylacetonate is carried out in a closed vessel cell (Swagelok) that was heated at 700 degrees C for 3 h. The encapsulation of ferromagnetic Ni nanospheres into the onion structured graphitic layers is obtained in a one-stage, single precursor reaction, without a catalyst, that possesses interesting magnetic properties. The magnetoresistance (MR) property of Ni nanospheres encapsulated in a fullerene-like carbon was measured, which shows large negative MR, of the order of 10%. The proposed mechanism for the formation of the Ni-C core-shell system is based on the segregation and the surface flux formed in the Ni and carbon particles during the reaction under autogenic pressure at elevated temperature.

Carrier states and optical response in core-shell-like semiconductor nanostructures

NASA Astrophysics Data System (ADS)

Duque, C. M.; Mora-Ramos, M. E.; Duque, C. A.

2017-02-01

The charge carrier states in a GaAs/Al?Ga?As axially symmetric core-shell quantum wire are calculated in the effective mass approximation via a spectral method. The possible presence of externally applied electric and magnetic fields is taken into account, together with the variation in the characteristic in-plane dimensions of the structure. The obtained energy spectrum is used to evaluate the optical response through the coefficients of intersubband optical absorption and relative refractive index change. The particular geometry of the system also allows to use the same theoretical model in order to determine the photoluminescence peak energies associated to correlated electron-hole states in double GaAs/Al?Ga?As quantum rings, showing a good agreement when they are compared with recent experimental reports. This agreement may validate the use of both the calculation process and the approximate model of abrupt, circularly shaped cross section geometry for the system.

Magnetic field induced mixing of light hole excitonic states in (Cd, Mn)Te/(Cd, Mg)Te core/shell nanowires.

PubMed

Płachta, Jakub; Grodzicka, Emma; Kaleta, Anna; Kret, Sławomir; Baczewski, Lech T; Pietruczik, Aleksiej; Wiater, Maciej; Goryca, Mateusz; Kazimierczuk, Tomasz; Kossacki, Piotr; Karczewski, Grzegorz; Wojtowicz, Tomasz; Wojnar, Piotr

2018-05-18

A detailed magneto-photoluminescence study of individual (Cd, Mn)Te/(Cd, Mg)Te core/shell nanowires grown by molecular beam epitaxy is performed. First of all, an enhancement of the Zeeman splitting due to sp-d exchange interaction between band carriers and Mn-spins is evidenced in these nanostructures. Then, it is found that the value of this splitting depends strongly on the magnetic field direction with respect to the nanowire axis. The largest splitting is observed when the magnetic field is applied perpendicular and the smallest when it is applied parallel to the nanowire axis. This effect is explained in terms of magnetic field induced valence band mixing and evidences the light hole character of the excitonic emission. The values of the light and heavy hole splitting are determined for several individual nanowires based on the comparison of experimental results to theoretical calculations.

Single-particle studies of band alignment effects on electron transfer dynamics from semiconductor hetero-nanostructures to single-walled carbon nanotubes.

PubMed

Yuan, Chi-Tsu; Wang, Yong-Gang; Huang, Kuo-Yen; Chen, Ting-Yu; Yu, Pyng; Tang, Jau; Sitt, Amit; Banin, Uri; Millo, Oded

2012-01-24

We utilize single-molecule spectroscopy combined with time-correlated single-photon counting to probe the electron transfer (ET) rates from various types of semiconductor hetero-nanocrystals, having either type-I or type-II band alignment, to single-walled carbon nanotubes. A significantly larger ET rate was observed for type-II ZnSe/CdS dot-in-rod nanostructures as compared to type-I spherical CdSe/ZnS core/shell quantum dots and to CdSe/CdS dot-in-rod structures. Furthermore, such rapid ET dynamics can compete with both Auger and radiative recombination processes, with significance for effective photovoltaic operation. © 2011 American Chemical Society

Interface induce growth of intermediate layer for bandgap engineering insights into photoelectrochemical water splitting

PubMed Central

Zhang, Jian; Zhang, Qiaoxia; Wang, Lianhui; Li, Xing’ao; Huang, Wei

2016-01-01

A model of interface induction for interlayer growing is proposed for bandgap engineering insights into photocatalysis. In the interface of CdS/ZnS core/shell nanorods, a lamellar solid solution intermediate with uniform thickness and high crystallinity was formed under interface induction process. Merged the novel charge carrier transfer layer, the photocurrent of the core/shell/shell nanorod (css-NR) array was significantly improved to 14.0 mA cm−2 at 0.0 V vs. SCE, nearly 8 times higher than that of the perfect CdS counterpart and incident photon to electron conversion efficiency (IPCE) values above 50% under AM 1.5G irradiation. In addition, this array photoelectrode showed excellent photocatalytic stability over 6000 s. These results suggest that the CdS/Zn1−xCdxS/ZnS css-NR array photoelectrode provides a scalable charge carrier transfer channel, as well as durability, and therefore is promising to be a large-area nanostructured CdS-based photoanodes in photoelectrochemical (PEC) water splitting system. PMID:27250648

Simultaneous tracking of drug molecules and carriers using aptamer-functionalized fluorescent superstable gold nanorod-carbon nanocapsules during thermo-chemotherapy

NASA Astrophysics Data System (ADS)

Wang, Xue-Wei; Gao, Wei; Fan, Huanhuan; Ding, Ding; Lai, Xiao-Fang; Zou, Yu-Xiu; Chen, Long; Chen, Zhuo; Tan, Weihong

2016-04-01

Controlling and monitoring the drug delivery process is critical to its intended therapeutic function. Many nanocarrier systems for drug delivery have been successfully developed. However, biocompatibility, stability, and simultaneously tracing drugs and nanocarriers present significant limitations. Herein, we have fabricated a multifunctional nanocomposite by coating the gold nanorod (AuNR) with a biocompatible, superstable and fluorescent carbon layer, obtaining the AuNR@carbon core-shell nanocapsule. In this system, the carbon shell, originally obtained in aqueous glucose solutions and, therefore, biocompatible in physiological environments, could be simply loaded with cell-specific aptamers and therapeutic molecules through π-π interactions, a useful tool for cancer-targeted cellular imaging and therapy. Moreover, such a stable and intrinsic fluorescence effect of the AuNR@carbon enabled simultaneous tracking of released therapeutic molecules and nanocarriers under thermo-chemotherapy. The AuNR@carbons had high surface areas and stable shells, as well as unique optical and photothermal properties, making them promising nanostructures for biomedical applications.Controlling and monitoring the drug delivery process is critical to its intended therapeutic function. Many nanocarrier systems for drug delivery have been successfully developed. However, biocompatibility, stability, and simultaneously tracing drugs and nanocarriers present significant limitations. Herein, we have fabricated a multifunctional nanocomposite by coating the gold nanorod (AuNR) with a biocompatible, superstable and fluorescent carbon layer, obtaining the AuNR@carbon core-shell nanocapsule. In this system, the carbon shell, originally obtained in aqueous glucose solutions and, therefore, biocompatible in physiological environments, could be simply loaded with cell-specific aptamers and therapeutic molecules through π-π interactions, a useful tool for cancer-targeted cellular imaging and therapy. Moreover, such a stable and intrinsic fluorescence effect of the AuNR@carbon enabled simultaneous tracking of released therapeutic molecules and nanocarriers under thermo-chemotherapy. The AuNR@carbons had high surface areas and stable shells, as well as unique optical and photothermal properties, making them promising nanostructures for biomedical applications. Electronic supplementary information (ESI) available: Experimental details and characterization data for all new compounds. See DOI: 10.1039/c6nr00369a

As(V) removal capacity of FeCu bimetallic nanoparticles in aqueous solutions: The influence of Cu content and morphologic changes in bimetallic nanoparticles.

PubMed

Sepúlveda, Pamela; Rubio, María A; Baltazar, Samuel E; Rojas-Nunez, J; Sánchez Llamazares, J L; Garcia, Alejandra García; Arancibia-Miranda, Nicolás

2018-08-15

In this study, bimetallic nanoparticles (BMNPs) with different mass ratios of Cu and Fe were evaluated. The influence of the morphology on the removal of pollutants was explored through theoretical and experimental studies, which revealed the best structure for removing arsenate (As(V)) in aqueous systems. To evidence the surface characteristics and differences among BMNPs with different mass proportions of Fe and Cu, several characterization techniques were used. Microscopy techniques and molecular dynamics simulations were applied to determine the differences in morphology and structure. In addition, X-ray diffraction (XRD) was used to determine the presence of various oxides. Finally, the magnetization response was evaluated, revealing differences among the materials. Our cumulative data show that BMNPs with low amounts of Cu (Fe 0.9 Cu 0.1 ) had a non-uniform core-shell structure with agglomerate-type chains of magnetite, whereas a Janus-like structure was observed in BMNPs with high amounts of Cu (Fe 0.5 Cu 0.5 ). However, a non-uniform core-shell structure (Fe 0.9 Cu 0.1 ) facilitated electron transfer among Fe, Cu and As, which increased the adsorption rate (k), capacity (q e ) and intensity (n). The mechanism of As removal was also explored in a comparative study of the phase and morphology of BMNPs pre- and post-sorption. Copyright © 2018 Elsevier Inc. All rights reserved.

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.

Improving Light Harvesting in Dye-Sensitized Solar Cells Using Hybrid Bimetallic Nanostructures

DOE PAGES

Zarick, Holly F.; Erwin, William R.; Boulesbaa, Abdelaziz; ...

2016-01-25

In this paper, we demonstrate improved light trapping in dye-sensitized solar cells (DSSCs) with hybrid bimetallic gold core/silver shell nanostructures. Silica-coated bimetallic nanostructures (Au/Ag/SiO 2 NSs) integrated in the active layer of DSSCs resulted in 7.51% power conversion efficiency relative to 5.97% for reference DSSCs, giving rise to 26% enhancement in device performance. DSSC efficiencies were governed by the particle density of Au/Ag/SiO 2 NSs with best performing devices utilizing only 0.44 wt % of nanostructures. We performed transient absorption spectroscopy of DSSCs with variable concentrations of Au/Ag/SiO 2 NSs and observed an increase in amplitude and decrease in lifetimemore » with increasing particle density relative to reference. Finally, we attributed this trend to plasmon resonant energy transfer and population of the singlet excited states of the sensitizer molecules at the optimum concentration of NSs promoting enhanced exciton generation and rapid charge transfer into TiO 2.« less

Preparation of hollow mesoporous carbon spheres and their performances for electrochemical applications

NASA Astrophysics Data System (ADS)

Ariyanto, T.; Zhang, G. R.; Kern, A.; Etzold, B. J. M.

2018-03-01

Hollow carbon materials have received intensive attention for energy storage/conversion applications due to their attractive properties of high conductivity, high surface area, large void and short diffusion pathway. In this work, a novel hollow mesoporous material based on carbide-derived carbon (CDC) is presented. CDC is a new class of carbon material synthesized by the selective extraction of metals from metal carbides. With a two-stage extraction procedure of carbides with chlorine, firstly hybrid core-shell carbon particles were synthesized, i.e. mesoporous/graphitic carbon shells covering microporous/amorphous carbon cores. The amorphous cores were then selectively removed from particles by a careful oxidative treatment utilizing its low thermal characters while the more stable carbon shells remained, thus resulting hollow particles. The characterization methods (e.g. N2 sorption, Raman spectroscopy, temperature-programmed oxidation and SEM) proved the successful synthesis of the aspired material. In electric double-layer capacitor (EDLC) testing, this novel hollow core material showed a remarkable enhancement of EDLC’s rate handling ability (75% at a high scan rate) with respect to an entirely solid-mesoporous material. Furthermore, as a fuel cell catalyst support the material showed higher Pt mass activity (a factor of 1.8) compared to a conventional carbon support for methanol oxidation without noticeably decreasing activity in a long-term testing. Therefore, this carbon nanostructure shows great promises as efficient electrode materials for energy storage and conversion systems.

Mechanistic profiling of the siRNA delivery dynamics of lipid-polymer hybrid nanoparticles.

PubMed

Colombo, Stefano; Cun, Dongmei; Remaut, Katrien; Bunker, Matt; Zhang, Jianxin; Martin-Bertelsen, Birte; Yaghmur, Anan; Braeckmans, Kevin; Nielsen, Hanne M; Foged, Camilla

2015-03-10

Understanding the delivery dynamics of nucleic acid nanocarriers is fundamental to improve their design for therapeutic applications. We investigated the carrier structure-function relationship of lipid-polymer hybrid nanoparticles (LPNs) consisting of poly(DL-lactic-co-glycolic acid) (PLGA) nanocarriers modified with the cationic lipid dioleoyltrimethyl-ammoniumpropane (DOTAP). A library of siRNA-loaded LPNs was prepared by systematically varying the nitrogen-to-phosphate (N/P) ratio. Atomic force microscopy (AFM) and cryo-transmission electron microscopy (cryo-TEM) combined with small angle X-ray scattering (SAXS) and confocal laser scanning microscopy (CLSM) studies suggested that the siRNA-loaded LPNs are characterized by a core-shell structure consisting of a PLGA matrix core coated with lamellar DOTAP structures with siRNA localized both in the core and in the shell. Release studies in buffer and serum-containing medium combined with in vitro gene silencing and quantification of intracellular siRNA suggested that this self-assembling core-shell structure influences the siRNA release kinetics and the delivery dynamics. A main delivery mechanism appears to be mediated via the release of transfection-competent siRNA-DOTAP lipoplexes from the LPNs. Based on these results, we suggest a model for the nanostructural characteristics of the LPNs, in which the siRNA is organized in lamellar superficial assemblies and/or as complexes entrapped in the polymeric matrix. Copyright © 2015 Elsevier B.V. All rights reserved.

Designed synthesis of multi-functional PEGylated Yb2O3:Gd@SiO2@CeO2 islands core@shell nanostructure.

PubMed

Li, Junqi; Yao, Shuang; Song, Shuyan; Wang, Xiao; Wang, Yinghui; Ding, Xing; Wang, Fan; Zhang, Hongjie

2016-07-28

Nanomaterials that can restrain or reduce the production of excessive reactive oxygen species such as H2O2 to defend and treat against Alzheimer's disease (AD) have attracted much attention. In this paper, we adopt the strategy of layer-by-layer deposition; namely, first synthesizing available gadolinium-doped ytterbia nanoparticles (Yb2O3:Gd NPs) as cores, and then coating them with silica via the classical Stöber method to prevent leakage and act as a carrier for subsequent ceria deposition and PEGylation, and finally obtain the expected core@shell-structured nanocomposite of PEGylated Yb2O3:Gd@SiO2@CeO2 islands. The nanomaterial has proved not only to be a high-performance dual-modal contrast agent for use in MRI and CT, but also to exhibit excellent catalase mimetic activity, which may help the prognosis, diagnosis and treatment of AD in the future. In addition, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy characterization have revealed the successful design and synthesis of the cores with remarkable size uniformity, with well-distributed CeO2 islands decorated on the surface of SiO2 shells, and tightly immobilized PEG.

Superscattering of light optimized by a genetic algorithm

NASA Astrophysics Data System (ADS)

Mirzaei, Ali; Miroshnichenko, Andrey E.; Shadrivov, Ilya V.; Kivshar, Yuri S.

2014-07-01

We analyse scattering of light from multi-layer plasmonic nanowires and employ a genetic algorithm for optimizing the scattering cross section. We apply the mode-expansion method using experimental data for material parameters to demonstrate that our genetic algorithm allows designing realistic core-shell nanostructures with the superscattering effect achieved at any desired wavelength. This approach can be employed for optimizing both superscattering and cloaking at different wavelengths in the visible spectral range.

Tapered Optical Fiber Probe Assembled with Plasmonic Nanostructures for Surface-Enhanced Raman Scattering Application.

PubMed

Huang, Zhulin; Lei, Xing; Liu, Ye; Wang, Zhiwei; Wang, Xiujuan; Wang, Zhaoming; Mao, Qinghe; Meng, Guowen

2015-08-12

Optical fiber-Raman devices integrated with plasmonic nanostructures have promising potentials for in situ probing remote liquid samples and biological samples. In this system, the fiber probe is required to simultaneously demonstrate stable surface enhanced Raman scattering (SERS) signals and high sensitivity toward the target species. Here we demonstrate a generic approach to integrate presynthesized plasmonic nanostructures with tapered fiber probes that are prepared by a dipping-etching method, through reversed electrostatic attraction between the silane couple agent modified silica fiber probe and the nanostructures. Using this approach, both negatively and positively charged plasmonic nanostructures with various morphologies (such as Au nanosphere, Ag nanocube, Au nanorod, Au@Ag core-shell nanorod) can be stably assembled on the tapered silica fiber probes. Attributed to the electrostatic force between the plasmonic units and the fiber surface, the nanostructures do not disperse in liquid samples easily, making the relative standard deviation of SERS signals as low as 2% in analyte solution. Importantly, the detection sensitivity of the system can be optimized by adjusting the cone angle (from 3.6° to 22°) and the morphology of nanostructures assembled on the fiber. Thus, the nanostructures-sensitized optical fiber-Raman probes show great potentials in the applications of SERS-based environmental detection of liquid samples.

In Situ Hydrothermally Grown TiO2@C Core-Shell Nanowire Coating for Highly Sensitive Solid Phase Microextraction of Polycyclic Aromatic Hydrocarbons.

PubMed

Wang, Fuxin; Zheng, Juan; Qiu, Junlang; Liu, Shuqin; Chen, Guosheng; Tong, Yexiang; Zhu, Fang; Ouyang, Gangfeng

2017-01-18

Nanostructured materials have great potential for solid phase microextraction (SPME) on account of their tiny size, distinct architectures and superior physical and chemical properties. Herein, a core-shell TiO 2 @C fiber for SPME was successfully fabricated by the simple hydrothermal reaction of a titanium wire and subsequent amorphous carbon coating. The readily hydrothermal procedure afforded in situ synthesis of TiO 2 nanowires on a titanium wire and provided a desirable substrate for further coating of amorphous carbon. Benefiting from the much larger surface area of subsequent TiO 2 and good adsorption property of the amorphous carbon coating, the core-shell TiO 2 @C fiber was utilized for the SPME device for the first time and proved to have better performance in extraction of polycyclic aromatic hydrocarbons. In comparison to the polydimethylsiloxane (PDMS) and PDMS/divinylbenzene (DVB) fiber for commercial use, the TiO 2 @C fiber obtained gas chromatography responses 3-8 times higher than those obtained by the commercial 100 μm PDMS and 1-9 times higher than those obtained by the 65 μm PDMS/DVB fiber. Under the optimized extraction conditions, the low detection limits were obtained in the range of 0.4-7.1 ng L -1 with wider linearity in the range of 10-2000 ng L -1 . Moreover, the fiber was successfully used for the determination of polycyclic aromatic hydrocarbons in Pearl River water, which demonstrated the applicability of the core-shell TiO 2 @C fiber.

Nd3+/Yb3+ cascade-sensitized single-band red upconversion emission in active-core/active-shell nanocrystals.

PubMed

Ding, M Y; Hou, J J; Yuan, Y J; Bai, W F; Lu, C H; Xi, J H; Ji, Z G; Chen, D Q

2018-08-24

Lanthanide-doped upconversion nanomaterials (UCNMs) have promoted extensive interest for its biological research and biomedical applications, benefiting from low autofluorescence background, deep light penetration depth, and minimal photo-damage to biological tissues. However, owing to the 980 nm laser-induced overheating issue and the attenuation effect associated with conventional multi-peak emissions, the usage of UCNMs as fluorescent bioprobes is still limited. To address these issues, an effective strategy has been proposed to tune both the excitation and emission peaks of UCNMs into the first biological window (650 ∼ 900 nm), where the light absorption by water and hemoglobin in biological tissues is minimal. Based on the Nd 3+ /Yb 3+ cascade-sensitized upconversion process and efficient exchange-energy transfer between Mn 2+ and Er 3+ in conjunction with the active-core@active-shell nanostructured design, we have developed a new class of upconversion nanoparticles (UCNPs) that exhibit strong single-band red emission upon excitation of an 808 nm near-infrared laser. Hopefully, the well-designed KMnF 3 :Yb/Er/Nd@ KMnF 3 :Yb/Nd core-shell nanocrystals will be considered a promising alternative to conventionally used UCNPs for biolabeling applications without the concern of the overheating issue and the attenuation constraints.

Hybrid Core-Shell (HyCoS) Nanoparticles produced by Complex Coacervation for Multimodal Applications

NASA Astrophysics Data System (ADS)

Vecchione, D.; Grimaldi, A. M.; Forte, E.; Bevilacqua, Paolo; Netti, P. A.; Torino, E.

2017-03-01

Multimodal imaging probes can provide diagnostic information combining different imaging modalities. Nanoparticles (NPs) can contain two or more imaging tracers that allow several diagnostic techniques to be used simultaneously. In this work, a complex coacervation process to produce core-shell completely biocompatible polymeric nanoparticles (HyCoS) for multimodal imaging applications is described. Innovations on the traditional coacervation process are found in the control of the reaction temperature, allowing a speeding up of the reaction itself, and the production of a double-crosslinked system to improve the stability of the nanostructures in the presence of a clinically relevant contrast agent for MRI (Gd-DTPA). Through the control of the crosslinking behavior, an increase up to 6 times of the relaxometric properties of the Gd-DTPA is achieved. Furthermore, HyCoS can be loaded with a high amount of dye such as ATTO 633 or conjugated with a model dye such as FITC for in vivo optical imaging. The results show stable core-shell polymeric nanoparticles that can be used both for MRI and for optical applications allowing detection free from harmful radiation. Additionally, preliminary results about the possibility to trigger the release of a drug through a pH effect are reported.

Controllable Construction of Core-Shell Polymer@Zeolitic Imidazolate Frameworks Fiber Derived Heteroatom-Doped Carbon Nanofiber Network for Efficient Oxygen Electrocatalysis.

PubMed

Zhao, Yingxuan; Lai, Qingxue; Zhu, Junjie; Zhong, Jia; Tang, Zeming; Luo, Yan; Liang, Yanyu

2018-05-01

Designing rational nanostructures of metal-organic frameworks based carbon materials to promote the bifunctional catalytic activity of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is highly desired but still remains a great challenge. Herein, an in situ growth method to achieve 1D structure-controllable zeolitic imidazolate frameworks (ZIFs)/polyacrylonitrile (PAN) core/shell fiber (PAN@ZIFs) is developed. Subsequent pyrolysis of this precursor can obtain a heteroatom-doped carbon nanofiber network as an efficient bifunctional oxygen electrocatalyst. The electrocatalytic performance of derived carbon nanofiber is dominated by the structures of PAN@ZIFs fiber, which is facilely regulated by efficiently controlling the nucleation and growth process of ZIFs on the surface of polymer fiber as well as optimizing the components of ZIFs. Benefiting from the core-shell structures with appropriate dopants and porosity, as-prepared catalysts show brilliant bifunctional ORR/OER catalytic activity and durability. Finally, the rechargeable Zn-air battery assembled from the optimized catalyst (CNF@Zn/CoNC) displays a peak power density of 140.1 mW cm -2 , energy density of 878.9 Wh kg Zn -1 , and excellent cyclic stability over 150 h, giving a promising performance in realistic application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailored Emission Properties of ZnTe/ZnTe:O/ZnO Core-Shell Nanowires Coupled with an Al Plasmonic Bowtie Antenna Array.

PubMed

Nie, Kui-Ying; Tu, Xuecou; Li, Jing; Chen, Xuanhu; Ren, Fang-Fang; Zhang, Guo-Gang; Kang, Lin; Gu, Shulin; Zhang, Rong; Wu, Peiheng; Zheng, Youdou; Tan, Hark Hoe; Jagadish, Chennupati; Ye, Jiandong

2018-06-14

The ability to manipulate light-matter interaction in semiconducting nanostructures is fascinating for implementing functionalities in advanced optoelectronic devices. Here, we report the tailoring of radiative emissions in a ZnTe/ZnTe:O/ZnO core-shell single nanowire coupled with a one-dimensional aluminum bowtie antenna array. The plasmonic antenna enables changes in the excitation and emission processes, leading to an obvious enhancement of near band edge emission (2.2 eV) and subgap excitonic emission (1.7 eV) bound to intermediate band states in a ZnTe/ZnTe:O/ZnO core-shell nanowire as well as surface-enhanced Raman scattering at room temperature. The increase of emission decay rate in the nanowire/antenna system, probed by time-resolved photoluminescence spectroscopy, yields an observable enhancement of quantum efficiency induced by local surface plasmon resonance. Electromagnetic simulations agree well with the experimental observations, revealing a combined effect of enhanced electric near-field intensity and the improvement of quantum efficiency in the ZnTe/ZnTe:O/ZnO nanowire/antenna system. The capability of tailoring light-matter interaction in low-efficient emitters may provide an alternative platform for designing advanced optoelectronic and sensing devices with precisely controlled response.

Facile Synthesis of Core/Shell-like NiCo2O4-Decorated MWCNTs and its Excellent Electrocatalytic Activity for Methanol Oxidation

PubMed Central

Ko, Tae-Hoon; Devarayan, Kesavan; Seo, Min-Kang; Kim, Hak-Yong; Kim, Byoung-Suhk

2016-01-01

The design and development of an economic and highly active non-precious electrocatalyst for methanol electrooxidation is challenging due to expensiveness of the precursors as well as processes and non-ecofriendliness. In this study, a facile preparation of core-shell-like NiCo2O4 decorated MWCNTs based on a dry synthesis technique was proposed. The synthesized NiCo2O4/MWCNTs were characterized by infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and selected area energy dispersive spectrum. The bimetal oxide nanoparticles with an average size of 6 ± 2 nm were homogeneously distributed onto the surface of the MWCNTs to form a core-shell-like nanostructure. The NiCo2O4/MWCNTs exhibited excellent electrocatalytic activity for the oxidation of methanol in an alkaline solution. The NiCo2O4/MWCNTs exhibited remarkably higher current density of 327 mA/cm2 and a lower onset potential of 0.128 V in 1.0 M KOH with as high as 5.0 M methanol. The impressive electrocatalytic activity of the NiCo2O4/MWCNTs is promising for development of direct methanol fuel cell based on non-Pt catalysts. PMID:26828633

Three-dimensional hierarchical NiCo2O4 nanowire@Ni3S2 nanosheet core/shell arrays for flexible asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Bo; Kong, Dezhi; Huang, Zhi Xiang; Mo, Runwei; Wang, Ye; Han, Zhaojun; Cheng, Chuanwei; Yang, Hui Ying

2016-05-01

Three-dimensional (3D) hierarchical NiCo2O4@Ni3S2 core/shell arrays on Ni foam were synthesized by a facile, stepwise synthesis approach. The 3D heterogeneous NiCo2O4 nanostructure forms an interconnected web-like scaffold and serves as the core for the Ni3S2 shell. The as-prepared NiCo2O4@Ni3S2 nanowire array (NWA) electrodes exhibited excellent electrochemical performance, such as high specific areal capacitance and excellent cycling stability. The specific areal capacitance of 3.0 F cm-2 at a current density of 5 mA cm-2 is among the highest values and the only 6.7% capacitance decay after 10 000 cycles demonstrates the excellent cycling stability. A flexible asymmetric supercapacitor (ASC) was fabricated with activated carbon (AC) as the anode and the obtained NiCo2O4@Ni3S2 NWAs as the cathode. The ASC device exhibited a high energy density of 1.89 mW h cm-3 at 5.81 W cm-3 and a high power density of 56.33 W cm-3 at 0.94 mW h cm-3. As a result, the hybrid nanoarchitecture opens a new way to design high performance electrodes for electrochemical energy storage applications.Three-dimensional (3D) hierarchical NiCo2O4@Ni3S2 core/shell arrays on Ni foam were synthesized by a facile, stepwise synthesis approach. The 3D heterogeneous NiCo2O4 nanostructure forms an interconnected web-like scaffold and serves as the core for the Ni3S2 shell. The as-prepared NiCo2O4@Ni3S2 nanowire array (NWA) electrodes exhibited excellent electrochemical performance, such as high specific areal capacitance and excellent cycling stability. The specific areal capacitance of 3.0 F cm-2 at a current density of 5 mA cm-2 is among the highest values and the only 6.7% capacitance decay after 10 000 cycles demonstrates the excellent cycling stability. A flexible asymmetric supercapacitor (ASC) was fabricated with activated carbon (AC) as the anode and the obtained NiCo2O4@Ni3S2 NWAs as the cathode. The ASC device exhibited a high energy density of 1.89 mW h cm-3 at 5.81 W cm-3 and a high power density of 56.33 W cm-3 at 0.94 mW h cm-3. As a result, the hybrid nanoarchitecture opens a new way to design high performance electrodes for electrochemical energy storage applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02600a

Application of Direct Current Atmospheric Pressure Glow Microdischarge Generated in Contact with a Flowing Liquid Solution for Synthesis of Au-Ag Core-Shell Nanoparticles

PubMed Central

Dzimitrowicz, Anna; Jamroz, Piotr; Nyk, Marcin; Pohl, Pawel

2016-01-01

A direct current atmospheric pressure glow microdischarge (dc-μAPGD) generated between an Ar nozzle microjet and a flowing liquid was applied to produce Au-Ag core-shell nanoparticles (Au@AgCSNPs) in a continuous flow system. Firstly, operating dc-μAPGD with the flowing solution of the Au(III) ions as the cathode, the Au nanoparticles (AuNPs) core was produced. Next, to produce the core-shell nanostructures, the collected AuNPs solution was immediately mixed with an AgNO3 solution and passed through the system with the reversed polarity to fabricate the Ag nanoshell on the AuNPs core. The formation of Au@AgCSNPs was confirmed using ultraviolet-visible (UV-Vis) absorbance spectrophotometry, transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). Three localized surface plasmon resonance absorption bands with wavelengths centered at 372, 546, and 675 nm were observed in the UV-Vis spectrum of Au@AgCSNPs, confirming the reduction of both the Au(III) and Ag(I) ions. The right configuration of metals in Au@AgCSNPs was evidenced by TEM. The Au core diameter was 10.2 ± 2.0 nm, while the thickness of the Ag nanoshell was 5.8 ± 1.8 nm. The elemental composition of the bimetallic nanoparticles was also confirmed by EDS. It is possible to obtain 90 mL of a solution containing Au@AgCSNPs per hour using the applied microdischarge system. PMID:28773393

Kinetic trapping through coalescence and the formation of patterned Ag-Cu nanoparticles

NASA Astrophysics Data System (ADS)

Grammatikopoulos, Panagiotis; Kioseoglou, Joseph; Galea, Antony; Vernieres, Jerome; Benelmekki, Maria; Diaz, Rosa E.; Sowwan, Mukhles

2016-05-01

In recent years, due to its inherent flexibility, magnetron-sputtering has been widely used to synthesise bi-metallic nanoparticles (NPs) via subsequent inert-gas cooling and gas-phase condensation of the sputtered atomic vapour. Utilising two separate sputter targets allows for good control over composition. Simultaneously, it involves fast kinetics and non-equilibrium processes, which can trap the nascent NPs into metastable configurations. In this study, we observed such configurations in immiscible, bi-metallic Ag-Cu NPs by scanning transmission electron microscopy (S/TEM) and electron energy-loss spectroscopy (EELS), and noticed a marked difference in the shape of NPs belonging to Ag- and Cu-rich samples. We explained the formation of Janus or Ag@Cu core/shell metastable structures on the grounds of in-flight mixed NP coalescence. We utilised molecular dynamics (MD) and Monte Carlo (MC) computer simulations to demonstrate that such configurations cannot occur as a result of nanoalloy segregation. Instead, sintering at relatively low temperatures can give rise to metastable structures, which eventually can be stabilised by subsequent quenching. Furthermore, we compared the heteroepitaxial diffusivities along various surfaces of both Ag and Cu NPs, and emphasised the differences between the sintering mechanisms of Ag- and Cu-rich NP compositions: small Cu NPs deform as coherent objects on large Ag NPs, whereas small Ag NPs dissolve into large Cu NPs, with their atoms diffusing along specific directions. Taking advantage of this observation, we propose controlled NP coalescence as a method to engineer mixed NPs of a unique, patterned core@partial-shell structure, which we refer to as a ``glass-float'' (ukidama) structure.In recent years, due to its inherent flexibility, magnetron-sputtering has been widely used to synthesise bi-metallic nanoparticles (NPs) via subsequent inert-gas cooling and gas-phase condensation of the sputtered atomic vapour. Utilising two separate sputter targets allows for good control over composition. Simultaneously, it involves fast kinetics and non-equilibrium processes, which can trap the nascent NPs into metastable configurations. In this study, we observed such configurations in immiscible, bi-metallic Ag-Cu NPs by scanning transmission electron microscopy (S/TEM) and electron energy-loss spectroscopy (EELS), and noticed a marked difference in the shape of NPs belonging to Ag- and Cu-rich samples. We explained the formation of Janus or Ag@Cu core/shell metastable structures on the grounds of in-flight mixed NP coalescence. We utilised molecular dynamics (MD) and Monte Carlo (MC) computer simulations to demonstrate that such configurations cannot occur as a result of nanoalloy segregation. Instead, sintering at relatively low temperatures can give rise to metastable structures, which eventually can be stabilised by subsequent quenching. Furthermore, we compared the heteroepitaxial diffusivities along various surfaces of both Ag and Cu NPs, and emphasised the differences between the sintering mechanisms of Ag- and Cu-rich NP compositions: small Cu NPs deform as coherent objects on large Ag NPs, whereas small Ag NPs dissolve into large Cu NPs, with their atoms diffusing along specific directions. Taking advantage of this observation, we propose controlled NP coalescence as a method to engineer mixed NPs of a unique, patterned core@partial-shell structure, which we refer to as a ``glass-float'' (ukidama) structure. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08256k

Low temperature oxidation synthesis of carbon encapsulated Cr2O3 nanocrystals and its lithium storage performance

NASA Astrophysics Data System (ADS)

Zhou, Yun; Liu, Boyang; Shao, Yingfeng; Fan, Chunhua; Fan, Runhua; Wen, Bosheng

A highly efficient and convenient strategy is developed for the one-step in-situ synthesis of carbon encapsulated Cr2O3 nanocrystals with core-shell structure (Cr2O3@C). The explosive reaction of chromocene with ammonium persulfate in an autoclave at 200∘C is crucial for the formation of this nanostructure. The Cr2O3 nanocrystals have a diameter of 5 to 20nm, which are entirely encapsulated by the amorphous carbon shell. The Cr2O3@C anode can retain a stable reversible capacity of 397mAhg-1 after 50 cycles at a current density of 119mA g-1.

Tuning structural motifs and alloying of bulk immiscible Mo-Cu bimetallic nanoparticles by gas-phase synthesis

NASA Astrophysics Data System (ADS)

Krishnan, Gopi; Verheijen, Marcel A.; Ten Brink, Gert H.; Palasantzas, George; Kooi, Bart J.

2013-05-01

Nowadays bimetallic nanoparticles (NPs) have emerged as key materials for important modern applications in nanoplasmonics, catalysis, biodiagnostics, and nanomagnetics. Consequently the control of bimetallic structural motifs with specific shapes provides increasing functionality and selectivity for related applications. However, producing bimetallic NPs with well controlled structural motifs still remains a formidable challenge. Hence, we present here a general methodology for gas phase synthesis of bimetallic NPs with distinctively different structural motifs ranging at a single particle level from a fully mixed alloy to core-shell, to onion (multi-shell), and finally to a Janus/dumbbell, with the same overall particle composition. These concepts are illustrated for Mo-Cu NPs, where the precise control of the bimetallic NPs with various degrees of chemical ordering, including different shapes from spherical to cube, is achieved by tailoring the energy and thermal environment that the NPs experience during their production. The initial state of NP growth, either in the liquid or in the solid state phase, has important implications for the different structural motifs and shapes of synthesized NPs. Finally we demonstrate that we are able to tune the alloying regime, for the otherwise bulk immiscible Mo-Cu, by achieving an increase of the critical size, below which alloying occurs, closely up to an order of magnitude. It is discovered that the critical size of the NP alloy is not only affected by controlled tuning of the alloying temperature but also by the particle shape.Nowadays bimetallic nanoparticles (NPs) have emerged as key materials for important modern applications in nanoplasmonics, catalysis, biodiagnostics, and nanomagnetics. Consequently the control of bimetallic structural motifs with specific shapes provides increasing functionality and selectivity for related applications. However, producing bimetallic NPs with well controlled structural motifs still remains a formidable challenge. Hence, we present here a general methodology for gas phase synthesis of bimetallic NPs with distinctively different structural motifs ranging at a single particle level from a fully mixed alloy to core-shell, to onion (multi-shell), and finally to a Janus/dumbbell, with the same overall particle composition. These concepts are illustrated for Mo-Cu NPs, where the precise control of the bimetallic NPs with various degrees of chemical ordering, including different shapes from spherical to cube, is achieved by tailoring the energy and thermal environment that the NPs experience during their production. The initial state of NP growth, either in the liquid or in the solid state phase, has important implications for the different structural motifs and shapes of synthesized NPs. Finally we demonstrate that we are able to tune the alloying regime, for the otherwise bulk immiscible Mo-Cu, by achieving an increase of the critical size, below which alloying occurs, closely up to an order of magnitude. It is discovered that the critical size of the NP alloy is not only affected by controlled tuning of the alloying temperature but also by the particle shape. Electronic supplementary information (ESI) available: Experimental details including schematics of the gas phase synthesis set up, target arrangement, synthesis condition for various structures, and TEM images of alloy, core-shell and Mo-Cu-Mo onion nanoparticles. See DOI: 10.1039/c3nr00565h

Radiation Shielding System Using a Composite of Carbon Nanotubes Loaded with Electropolymers

NASA Technical Reports Server (NTRS)

McKay, Chris; Chen, Bin

2012-01-01

Single-wall carbon nanotubes (SWCNTs) coated with a hydrogen-rich, electrically conducting polymer such as polyethylene, receive and dissipate a portion of incoming radiation pulse energy to electrical signals that are transmitted along the CNT axes, and are received at energy-dissipating terminals. In this innovation, an array of highly aligned nanowires is grown using a strong electric field or another suitable orientation procedure. Polyethylene (PE), polymethymlethacrylate (PMMA), or other electrically conducting polymer is spin-coated onto the SWCNTs with an average thickness of a few hundred nanometers to a few tenths of micrometers to form a PE/SWCNT composite. Alternatively, the polymer is spin-coated onto the nanowire array or an anodized alumina membrane (AAM) to form a PE/metal core shell structure, or PE can be electropolymerized using the SWCNTs or the metal nanowires as an electrode to form a PE/SWCNT core shell structure. The core shell structures can be extruded as anisotropic fibers. A monomer can be polymerized in the presence of SWCNTs to form highly cross-linked PE/SWCNT films. Alternatively, Pb colloid solution can be impregnated into a three-dimensional PE/SWCNT nanostructure to form a PW/SWCNT/Pb composite structure. A face-centered cubic (FCC) arrangement provides up to 12 interconnection channels connected to each core, with transverse channel dimensions up to 20 nm, with adequate mechanical compressive strength, and with an associated electrical conductivity of around 3 Seimens/cm for currents ranging from 0.01 to 10 mA. This threedimensional nanostructure is used as a host material to house appropriate radiation shielding material such as hydrogen- rich polymer/CNT structures, metal nanoparticles, and nanowires. Thicknesses of this material required to attenuate 10 percent, 50 percent, and 90 percent of an incident beam (gamma, X-ray, ultraviolet, neutron, proton, and electron) at energies in the range of 0 440 MeV are being determined, for example, by measuring fluence rate reduction. For example, a radiation field arrives first at an exposed surface of the innovation and produces an associated first electric field within the metal-like fingers of the three-dimensional nanostructure. This field is intensified near the exposed tips of the fingers, and this intensified field generates an intensified second electric field near the adjacent exposed tips of the coated CNSs. This generates an associated electrical current in the CNSs, and the associated electropolymer coating. The current is received by the second substrate transport component and is transported to the dissipation mechanism located contiguously to the second substrate.

Nanostructured Silicon Used for Flexible and Mobile Electricity Generation.

PubMed

Sun, Baoquan; Shao, Mingwang; Lee, Shuitong

2016-12-01

The use of nanostructured silicon for the generation of electricity in flexible and mobile devices is reviewed. This field has attracted widespread interest in recent years due to the emergence of plastic electronics. Such developments are likely to alter the nature of power sources in the near future. For example, flexible photovoltaic cells can supply electricity to rugged and collapsible electronics, biomedical devices, and conformable solar panels that are integrated with the curved surfaces of vehicles or buildings. Here, the unique optical and electrical properties of nanostructured silicon are examined, with regard to how they can be exploited in flexible photovoltaics, thermoelectric generators, and piezoelectric devices, which serve as power generators. Particular emphasis is placed on organic-silicon heterojunction photovoltaic devices, silicon-nanowire-based thermoelectric generators, and core-shell silicon/silicon oxide nanowire-based piezoelectric devices, because they are flexible, lightweight, and portable. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-Dimensional NiCo2O4@MnMoO4 Core-Shell Nanoarrays for High-Performance Asymmetric Supercapacitors.

PubMed

Yuan, Yuliang; Wang, Weicheng; Yang, Jie; Tang, Haichao; Ye, Zhizhen; Zeng, Yujia; Lu, Jianguo

2017-10-10

Design of new materials with sophisticated nanostructure has been proven to be an efficient strategy to improve their properties in many applications. Herein, we demonstrate the successful combination of high electron conductive materials of NiCo 2 O 4 with high capacitance materials of MnMoO 4 by forming a core-shell nanostructure. The NiCo 2 O 4 @MnMoO 4 core-shell nanoarrays (CSNAs) electrode possesses high capacitance of 1169 F g -1 (4.24 F cm -2 ) at a current density of 2.5 mA cm -2 , obviously larger than the pristine NiCo 2 O 4 electrode. The asymmetric supercapacitors (ASCs), assembled with NiCo 2 O 4 @MnMoO 4 CSNAs as binder-free cathode and active carbon (AC) as anode, exhibit high energy density of 15 Wh kg -1 and high power density of 6734 W kg -1 . Cycle performance of NiCo 2 O 4 @MnMoO 4 CSNAs//AC ASCs, conducted at current density of 20 mA cm -2 , remain 96.45% of the initial capacitance after 10,000 cycles, demonstrating its excellent long-term cycle stability. Kinetically decoupled analysis reveals that the capacitive capacitance is dominant in the total capacitance of NiCo 2 O 4 @MnMoO 4 CSNAs electrode, which may be the reason for ultra long cycle stability of ASCs. Our assembled button ASC can easily light up a red LED for 30 min and a green LED for 10 min after being charged for 30 s. The remarkable electrochemical performance of NiCo 2 O 4 @MnMoO 4 CSNAs//AC ASCs is attributed to its enhanced surface area, abundant electroactive sites, facile electrolyte infiltration into the 3D NiCo 2 O 4 @MnMnO 4 nanoarrays and fast electron and ion transport path.

Interfacial redox reaction-directed synthesis of silver@cerium oxide core-shell nanocomposites as catalysts for rechargeable lithium-air batteries

NASA Astrophysics Data System (ADS)

Liu, Ying; Wang, Man; Cao, Lu-Jie; Yang, Ming-Yang; Ho-Sum Cheng, Samson; Cao, Chen-Wei; Leung, Kwan-Lan; Chung, Chi-Yuen; Lu, Zhou-Guang

2015-07-01

A facile oxidation-reduction reaction method has been implemented to prepare pomegranate-like Ag@CeO2 multicore-shell structured nanocomposites. Under Ar atmosphere, redox reaction automatically occurs between AgNO3 and Ce(NO3)3 in an alkaline solution, where Ag+ is reduced to Ag nanopartilces and Ce3+ is simultaneously oxidized to form CeO2, followed by the self-assembly to form the pomegranate-like multicore-shell structured Ag@CeO2 nanocomposites driven by thermodynamic equilibrium. No other organic amines or surfactants are utilized in the whole reaction system and only NaOH instead of organic reducing agent is used to prevent the introduction of a secondary reducing byproduct. The as-obtained pomegranate-like Ag@CeO2 multicore-shell structured nanocomposites have been characterized as electro-catalysts for the air cathode of lithium-air batteries operated in a simulated air environment. Superior electrochemical performance with high discharge capacity of 3415 mAh g-1 at 100 mA g-1, stable cycling and small charge/discharge polarization voltage is achieved, which is much better than that of the CeO2 or simple mixture of CeO2 and Ag. The enhanced properties can be primarily attributed to the synergy effect between the Ag core and the CeO2 shell resulting from the unique pomegranate-like multicore-shell nanostructures possessing plenty of active sites to promote the facile formation and decomposition of Li2O2.

One-dimensional fossil-like γ-Fe2O3@carbon nanostructure: preparation, structural characterization and application as adsorbent for fast and selective recovery of gold ions from aqueous solution

NASA Astrophysics Data System (ADS)

Gunawan, Poernomo; Xiao, Wen; Hao Chua, Marcus Wen; Poh-Choo Tan, Cheryl; Ding, Jun; Zhong, Ziyi

2016-10-01

One-dimensional (1D) magnetic nanostructures with high thermal stability have important industrial applications, but their fabrication remains a big challenge. Herein we demonstrate a scalable approach for the preparation of stable 1D γ-Fe2O3@carbon, which is also applicable for other metal oxide-core and carbon-shell nanostructures, such as 1D TiO2@carbon. One-dimensional ferric oxyhydroxide (α-FeO(OH)) was initially prepared by a hydrothermal method, followed by carbon coating through hydrothermal treatment of the resulting metal oxide in glucose solution. After calcination in N2 gas at 500 °C and subsequent exposure to air, the initial carbon-coated 1D α-Fe2O3 was converted to 1D γ-Fe2O3@carbon, which was very stable without any observed changes even after 1.5 years of storage under ambient conditions. The materials were then used as adsorbents and found to be highly selective towards Au (III) adsorption, of which the maximum adsorption capacity is about 600 mg Au/g sorbent (1132 mg Au/g carbon). The spent sorbent containing Au after adsorption can be readily collected by applying a magnetic field due to the presence of the magnetic core, and the adsorbed Au particles are subsequently recovered after the combustion and dissolution of the sorbent. This work demonstrates not only a facile approach to the fabrication of robust 1D magnetic materials with a stable carbon shell, but also a possible cyanide-free process for the fast and selective recovery of gold from electronic waste and industrial water.

Polyaminoacid-Induced Growth of Metal Nanoparticles on Layer-by-Layer Templates

DTIC Science & Technology

2008-08-21

15,17 In another study, Zhou et al. used tyrosine residues of silk fibroin for growth of 45 nm core-shell colloidal gold- silk fibroin biocongugates at...fungus,28 or silk fiber-templated29 reduction of gold and silver nanostructures. However, despite the increas- ing interest in using organic substrates...not show any particles on the surface after the identical exposure (Figure 2c). (44) Senior, M.; Gorrell, S.; Hamori, E. Biopolymers 1971, 10, 2387

Mechanism of formation and nanostructure of Stöber silica particles

NASA Astrophysics Data System (ADS)

Masalov, V. M.; Sukhinina, N. S.; Kudrenko, E. A.; Emelchenko, G. A.

2011-07-01

The formation of silica nano- and microparticles has been studied during growth by the modified Stöber-Fink-Bohn (SFB) method. It has been experimentally found that the density and fractal structure of particles vary with size as they grow from 70 to 2200 nm. We propose a model of particle structure which is a dense primary particle core and is composed of concentric secondary particle shells terminating in dense primary particle layers.

Microbubble-Triggered Spontaneous Separation of Transparent Thin Films from Substrates Using Evaporable Core-Shell Nanocapsules.

PubMed

Son, Intae; Lee, Byungsun; Kim, Jae Hong; Kim, Chunho; Yoo, Ji Yong; Ahn, Byung Wook; Hwang, Jeongho; Lee, Jonghyuk; Lee, Jun Hyup

2018-05-23

The spontaneous separation of a polymer thin film from a substrate is an innovative technology that will enable material recycling and reduce manufacturing cost in the film industry, and this can be applied in a wide range of applications, from optical films to wearable devices. Here, we present an unprecedented spontaneous strategy for separating transparent polymer films from substrates on the basis of microbubble generation using nanocapsules containing an evaporable material. The core-shell nanocapsules are prepared from poly(methyl methacrylate)-polyethyleneimine nanoparticles via the encapsulation of methylcyclohexane (MCH). A spherical nanostructure with a vaporizable core is obtained, with the heat-triggered gas release ability leading to the formation of microbubbles. Our separation method applied to transparent polymer films doped with a small amount of the nanocapsules encapsulating evaporable MCH enables spontaneous detachment of thin films from substrates via vacuum-assisted rapid vaporization of MCH over a short separation time, and clear detachment of the film is achieved with no deterioration of the inherent optical transparency and adhesive property compared to a pristine film.

Synthesis of Dispersible Mesoporous Nitrogen-Doped Hollow Carbon Nanoplates with Uniform Hexagonal Morphologies for Supercapacitors.

PubMed

Cao, Jie; Jafta, Charl J; Gong, Jiang; Ran, Qidi; Lin, Xianzhong; Félix, Roberto; Wilks, Regan G; Bär, Marcus; Yuan, Jiayin; Ballauff, Matthias; Lu, Yan

2016-11-02

In this study, dispersible mesoporous nitrogen-doped hollow carbon nanoplates have been synthesized as a new anisotropic carbon nanostructure using gibbsite nanoplates as templates. The gibbsite-silica core-shell nanoplates were first prepared before the gibbsite core was etched away. Dopamine as carbon precursor was self-polymerized on the hollow silica nanoplates surface assisted by sonification, which not only favors a homogeneous polymer coating on the nanoplates but also prevents their aggregation during the polymerization. Individual silica-polydopamine core-shell nanoplates were immobilized in a silica gel in an insulated state via a silica nanocasting technique. After pyrolysis in a nanoconfine environment and elimination of silica, discrete and dispersible hollow carbon nanoplates are obtained. The resulted hollow carbon nanoplates bear uniform hexagonal morphology with specific surface area of 460 m 2 ·g -1 and fairly accessible small mesopores (∼3.8 nm). They show excellent colloidal stability in aqueous media and are applied as electrode materials for symmetric supercapacitors. When using polyvinylimidazolium-based nanoparticles as a binder in electrodes, the hollow carbon nanoplates present superior performance in parallel to polyvinylidene fluoride (PVDF) binder.

Facile synthesis, microstructure and photophysical properties of core-shell nanostructured (SiCN)/BN nanocomposites

PubMed Central

Zhang, Qian; Jia, Dechang; Yang, Zhihua; Cai, Delong; Laine, Richard M.; Li, Qian; Zhou, Yu

2017-01-01

Increasing structural complexity at nanoscale can permit superior control over photophysical properties in the precursor-derived semiconductors. We demonstrate here the synthesis of silicon carbonitride (SiCN)/boron nitride (BN) nanocomposites via a polymer precursor route wherein the cobalt polyamine complexes used as the catalyst, exhibiting novel composite structures and photophysical properties. High Resolution Transmission Electron Microscopy (HRTEM) analysis shows that the diameters of SiCN−BN core−shell nanocomposites and BN shells are 50‒400 nm and 5‒25 nm, respectively. BN nanosheets (BNNSs) are also observed with an average sheet size of 5‒15 nm. The photophysical properties of these nanocomposites are characterized using the UV-Vis and photoluminescence (PL) analyses. The as-produced composites have emission behavior including an emission lifetime of 2.5 ns (±20 ps) longer observed in BN doped SiCN than that seen for SiC nanoparticles. Our results suggest that the SiCN/BN nanocomposites act as semiconductor displaying superior width photoluminescence at wavelengths spanning the visible to near-infrared (NIR) spectral range (400‒700 nm), owing to the heterojunction of the interface between the SiC(N) nanowire core and the BN nanosheet shell. PMID:28084300

Multifunctional two-photon active silica-coated Au@MnO Janus particles for selective dual functionalization and imaging.

PubMed

Schick, Isabel; Lorenz, Steffen; Gehrig, Dominik; Schilmann, Anna-Maria; Bauer, Heiko; Panthöfer, Martin; Fischer, Karl; Strand, Dennis; Laquai, Frédéric; Tremel, Wolfgang

2014-02-12

Monodisperse multifunctional and nontoxic Au@MnO Janus particles with different sizes and morphologies were prepared by a seed-mediated nucleation and growth technique with precise control over domain sizes, surface functionalization, and dye labeling. The metal oxide domain could be coated selectively with a thin silica layer, leaving the metal domain untouched. In particular, size and morphology of the individual (metal and metal oxide) domains could be controlled by adjustment of the synthetic parameters. The SiO2 coating of the oxide domain allows biomolecule conjugation (e.g., antibodies, proteins) in a single step for converting the photoluminescent and superparamagnetic Janus nanoparticles into multifunctional efficient vehicles for theranostics. The Au@MnO@SiO2 Janus particles were characterized using high-resolution transmission electron microscopy (HR-)TEM, powder X-ray diffraction (PXRD), optical (UV-vis) spectroscopy, confocal laser fluorescence scanning microscopy (CLSM), and dynamic light scattering (DLS). The functionalized nanoparticles were stable in buffer solution or serum, showing no indication of aggregation. Biocompatibility and potential biomedical applications of the Au@MnO@SiO2 Janus particles were assayed by a cell viability analysis by coincubating the Au@MnO@SiO2 Janus particles with Caki 1 and HeLa cells. Time-resolved fluorescence spectroscopy in combination with CLSM revealed the silica-coated Au@MnO@SiO2 Janus particles to be highly two-photon active; no indication for an electronic interaction between the dye molecules incorporated in the silica shell surrounding the MnO domains and the attached Au domains was found; fluorescence quenching was observed when dye molecules were bound directly to the Au domains.

Super-Poissonian statistics of photon emission from single CdSe-CdS core-shell nanocrystals coupled to metal nanostructures.

PubMed

Park, Young-Shin; Ghosh, Yagnaseni; Chen, Yongfen; Piryatinski, Andrei; Xu, Ping; Mack, Nathan H; Wang, Hsing-Lin; Klimov, Victor I; Hollingsworth, Jennifer A; Htoon, Han

2013-03-15

We demonstrate that photon antibunching observed for individual nanocrystal quantum dots (NQDs) can be transformed into photon bunching characterized by super-Poissonian statistics when they are coupled to metal nanostructures (MNs). This observation indicates that, while the quantum yield of a biexciton (Q(2X)) is lower than that of a single exciton (Q(1X)) in freestanding NQDs, Q(2X) becomes greater than Q(1X) in NQDs coupled to MNs. This unique phenomenon is attributed to metal-induced quenching with a rate that scales more slowly with exciton multiplicity than the radiative decay rate and dominates over other nonradiative decay channels for both single excitons and biexcitons.

Enzyme sensitive smart inulin-dehydropeptide conjugate self-assembles into nanostructures useful for targeted delivery of ornidazole.

PubMed

Shivhare, Kriti; Garg, Charu; Priyam, Ayushi; Gupta, Alka; Sharma, Ashwani Kumar; Kumar, Pradeep

2018-01-01

Molecular self-assembly of biodegradable amphiphilic polymers allows rational design of biocompatible nanomaterials for drug delivery. Use of substituted polysaccharides for such applications offers the ease of design and synthesis, and provides higher biofunctionality and biocompatibility to nanomaterials. The present work focuses on the synthesis, characterization and potential biomedical applications of self-assembled polysaccharide-based materials. We demonstrated that the synthesized amphiphilic inulin self-assembled in aqueous medium into nanostructures with average size in the range of 146-486nm and encapsulated hydrophobic therapeutic molecule, ornidazole. Hydrophophic dehydropeptide was conjugated with inulin via a biocompatible ester linkage. Dehydrophenylalanine, an unusual amino acid, was incorporated in the peptide to make it stable at a broader range of pH as well as against proteases. The resulting core-shell type of nanostructures could encapsulate ornidazole in the hydrophobic core and released it in a controlled fashion. By taking the advantage of inulin, which gets degraded in the colon by colonic bacteria, the effect of enzyme, inulinase, present in the microflora of the large intestine, on inulin-peptide degradation followed by drug release has been studied. Altogether, small peptide conjugated to inulin offers novel scaffold for the future design of nanostructures with potential applications in the field of targeted drug delivery. Copyright © 2017 Elsevier B.V. All rights reserved.

Direct observation of Au/Ga2O3 peapodded nanowires and their plasmonic behaviors.

PubMed

Chen, Po-Han; Hsieh, Chin-Hua; Chen, Sheng-Yu; Wu, Chen-Hwa; Wu, Yi-Jen; Chou, Li-Jen; Chen, Lih-Juann

2010-09-08

Gold-peapodded Ga(2)O(3) nanowires were fabricated successfully in a well-controlled manner by thermal annealing of core-shell gold-Ga(2)O(3) nanowires. During the heating process, the core gold nanowires were broken up into chains of nanoparticles at sufficiently high temperature by the mechanism of Rayleigh instability. In addition, the size, shape, and interspacing between the particles can be manipulated by varying the annealing time and/or the forming gas. The plasmonic behaviors of these nanostructures are investigated by optical spectroscopy. A single nanowire optical device was designed, and its photonic characteristics were investigated. A remarkably high on/off photocurrent ratio in response to a 532 nm Nd:YAG laser light was found. As the size of the particle (pea) increases, the corresponding spectra are red-shifted. In addition, morphological changes of the peas lead to a distinct spectral response. The results may usher in the diverse applications in optoelectronics and biosensing devices with peapod nanostructures.

Au-CeO2 Janus-like nanoparticles fabricated by block copolymer templates and their catalytic activity in the degradation of methyl orange

NASA Astrophysics Data System (ADS)

Yu, Huan; Jiao, Yapei; Li, Na; Pang, Juanjuan; Li, Wenting; Zhang, Xiaokai; Li, Xue; Li, Chunsheng

2018-01-01

A simple approach towards the fabrication of Au-CeO2 Janus-like nanoparticles is presented. Composite micelles of polystyrene-block-poly (ethylene oxide) (PS-b-PEO)/Ce(NO3)3/HAuCl4 with HAuCl4 and Ce(NO3)3 precursors incorporated in the PEO domains are prepared first. By manipulating the pH value of the composite micelles solution, a redox reaction between Au(III) with Ce(III) in the PEO domains occurs and Au-CeO2 Janus-like nanoparticles composed of a porous CeO2 and an Au nanoparticle are generated. X-ray diffraction (XRD), UV-vis spectrum (UV), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are employed to characterize the Janus-like nanoparticles. The catalytic degradation of methyl orange dye (MO) under ultrasonic irradiation is chosen as the test reaction to examine the catalytic activity of the Au-CeO2 Janus-like nanoparticles. It is found that Au-CeO2 Janus-like nanoparticles show higher activity than that of CeO2 nanoparticles or Au-CeO2 composite nanoparticles. The increased catalytic activity of Au-CeO2 Janus-like nanoparticles is attributed to the exposed Au core on one side of the Janus nanoparticles and the Au-CeO2 heterointerfaces.

Influence of plasmon coupling on the photoluminescence of ZnS/Ag nanoparticles obtained by laser irradiation in liquid

NASA Astrophysics Data System (ADS)

Moos, Rafaela; Graff, Ismael L.; de Oliveira, Vinicius S.; Schreiner, Wido H.; Bezerra, Arandi G.

2017-10-01

We investigate the photoluminescence, optical absorption and structural properties of ZnS submitted to laser irradiation in water and isopropyl alcohol. Nanoparticles were produced by irradiating micro-sized ZnS particles dispersed in both liquids, with and without the addition of Ag nanoparticles, taking advantage of the laser-assisted fragmentation effect. When ZnS microparticles are irradiated either in pure water or isopropyl alcohol a considerable size reduction is achieved (from micra to few nanometers). The photoluminescence of these nanoparticles mainly occurs in the UV, centered at 350 nm, and with smaller intensity in the visible, centered at 600 nm. Irradiation of ZnS microparticles dispersed in colloidal silver triggers a reaction between both materials, modifying its optical absorption and photoluminescent properties. After irradiation of ZnS in alcohol containing Ag nanoparticles, a giant increase of the UV photoluminescence is observed. Interestingly, when the irradiation is performed in aqueous Ag nanoparticles colloids, the photoluminescence suffers a red-shift towards the violet-blue. The data show that core-shell (Ag-ZnO) nanostructures are formed after irradiation and the visible emission likely originates from the ZnO shell grown around silver nanoparticles. The presence of Ag nanoparticles in the liquid medium promotes a stronger absorption of the laser beam during irradiation due to the coupling with the surface plasmon resonance, fostering intense reactions among ZnS, Ag nanoparticles, and the liquid medium. Our study shows that with a simple change of the liquid medium wherein the irradiation is conducted the photoluminescence can be tuned from UV to visible and core-shell nanostructures can be obtained.

Excitation of epsilon-near-zero resonance in ultra-thin indium tin oxide shell embedded nanostructured optical fiber.

PubMed

Minn, Khant; Anopchenko, Aleksei; Yang, Jingyi; Lee, Ho Wai Howard

2018-02-05

We report a novel optical waveguide design of a hollow step index fiber modified with a thin layer of indium tin oxide (ITO). We show an excitation of highly confined waveguide mode in the proposed fiber near the wavelength where permittivity of ITO approaches zero. Due to the high field confinement within thin ITO shell inside the fiber, the epsilon-near-zero (ENZ) mode can be characterized by a peak in modal loss of the hybrid waveguide. Our results show that such in-fiber excitation of ENZ mode is due to the coupling of the guided core mode to the thin-film ENZ mode. We also show that the phase matching wavelength, where the coupling takes place, varies depending on the refractive index of the constituents inside the central bore of the fiber. These ENZ nanostructured optical fibers have many potential applications, for example, in ENZ nonlinear and magneto-optics, as in-fiber wavelength-dependent filters, and as subwavelength fluid channel for optical and bio-photonic sensing.

Structure, function, and self-assembly of single network gyroid (I4132) photonic crystals in butterfly wing scales.

PubMed

Saranathan, Vinodkumar; Osuji, Chinedum O; Mochrie, Simon G J; Noh, Heeso; Narayanan, Suresh; Sandy, Alec; Dufresne, Eric R; Prum, Richard O

2010-06-29

Complex three-dimensional biophotonic nanostructures produce the vivid structural colors of many butterfly wing scales, but their exact nanoscale organization is uncertain. We used small angle X-ray scattering (SAXS) on single scales to characterize the 3D photonic nanostructures of five butterfly species from two families (Papilionidae, Lycaenidae). We identify these chitin and air nanostructures as single network gyroid (I4(1)32) photonic crystals. We describe their optical function from SAXS data and photonic band-gap modeling. Butterflies apparently grow these gyroid nanostructures by exploiting the self-organizing physical dynamics of biological lipid-bilayer membranes. These butterfly photonic nanostructures initially develop within scale cells as a core-shell double gyroid (Ia3d), as seen in block-copolymer systems, with a pentacontinuous volume comprised of extracellular space, cell plasma membrane, cellular cytoplasm, smooth endoplasmic reticulum (SER) membrane, and intra-SER lumen. This double gyroid nanostructure is subsequently transformed into a single gyroid network through the deposition of chitin in the extracellular space and the degeneration of the rest of the cell. The butterflies develop the thermodynamically favored double gyroid precursors as a route to the optically more efficient single gyroid nanostructures. Current approaches to photonic crystal engineering also aim to produce single gyroid motifs. The biologically derived photonic nanostructures characterized here may offer a convenient template for producing optical devices based on biomimicry or direct dielectric infiltration.

Structure, function, and self-assembly of single network gyroid (I4132) photonic crystals in butterfly wing scales

PubMed Central

Saranathan, Vinodkumar; Osuji, Chinedum O.; Mochrie, Simon G. J.; Noh, Heeso; Narayanan, Suresh; Sandy, Alec; Dufresne, Eric R.; Prum, Richard O.

2010-01-01

Complex three-dimensional biophotonic nanostructures produce the vivid structural colors of many butterfly wing scales, but their exact nanoscale organization is uncertain. We used small angle X-ray scattering (SAXS) on single scales to characterize the 3D photonic nanostructures of five butterfly species from two families (Papilionidae, Lycaenidae). We identify these chitin and air nanostructures as single network gyroid (I4132) photonic crystals. We describe their optical function from SAXS data and photonic band-gap modeling. Butterflies apparently grow these gyroid nanostructures by exploiting the self-organizing physical dynamics of biological lipid-bilayer membranes. These butterfly photonic nanostructures initially develop within scale cells as a core-shell double gyroid (Ia3d), as seen in block-copolymer systems, with a pentacontinuous volume comprised of extracellular space, cell plasma membrane, cellular cytoplasm, smooth endoplasmic reticulum (SER) membrane, and intra-SER lumen. This double gyroid nanostructure is subsequently transformed into a single gyroid network through the deposition of chitin in the extracellular space and the degeneration of the rest of the cell. The butterflies develop the thermodynamically favored double gyroid precursors as a route to the optically more efficient single gyroid nanostructures. Current approaches to photonic crystal engineering also aim to produce single gyroid motifs. The biologically derived photonic nanostructures characterized here may offer a convenient template for producing optical devices based on biomimicry or direct dielectric infiltration. PMID:20547870

Structural and Optical Properties of Core-Shell TiO2/CdS Prepared by Chemical Bath Deposition

NASA Astrophysics Data System (ADS)

Al-Jawad, Selma M. H.

2017-10-01

Titanium dioxide (TiO2) nanorod arrays (NRAs) sensitized with cadmium sulfide (CdS) nanoparticles (NPs) were deposited by chemical bath deposition (CBD). TiO2 NRAs were also obtained by using the same method on glass substrates coated with fluorine-doped tin oxide (FTO). The structure of the FTO/TiO2/CdS core-shell was characterized by x-ray diffraction (XRD), atomic force microscopy, scanning electron microscopy, ultraviolet-visible (UV-Vis) absorption spectroscopy, photoluminescence, and photoelectrocatalysis of FTO/TiO2 and FTO/TiO2/CdS. The FTO/TiO2 conformed to anatase and rutile phase structures for different pH values and also with annealing. XRD patterns of the FTO/TiO2/CdS sample exhibited two peaks corresponding to hexagonal (100) and (101) for CdS. Scanning electron micrographs showed nanorod structures for the TiO2 thin films deposited at a pH value equal 0.7. Optical results showed the CdS deposited on nanorod TiO2 exhibited increased absorption ability in the visible light, indicating an increased photocatalytic activity for TiO2/CdS core-shell nanorods in the visible light. When illuminated with a UV-Vis light source, the TiO2/CdS core-shell films displayed high responses. A composite exists between the TiO2 nanostructure and CdS NPs because the film absorbs the incident light located in both the visible and UV-Vis regions. A higher response to UV-Vis light was attained with the use of TiO2 NRAs/CdS NPs films prepared by CBD. This approach offers a technique for fabricating photoelectrodes.

A pH and redox dual stimuli-responsive poly(amino acid) derivative for controlled drug release.

PubMed

Gong, Chu; Shan, Meng; Li, Bingqiang; Wu, Guolin

2016-10-01

A pH and redox dual stimuli-responsive poly(aspartic acid) derivative for controlled drug release was successfully developed through progressive ring-opening reactions of polysuccinimide (PSI). Polyethylene glycol (PEG) chains were grafted onto the polyaspartamide backbone via redox-responsive disulfide linkages, providing a sheddable shell for the polymeric micelles in a reductive environment. Phenyl groups were introduced into the polyaspartamide backbone via the aminolysis reaction of PSI to serve as the hydrophobic segment of micelles. The polyaspartamide scaffold was also functionalized with N-(3-aminopropyl)-imidazole to obtain the pH-responsiveness manifesting as a swelling of the core of micelles at a low pH. The polymeric micelles with a core-shell nanostructure forming in neutral media exhibited both pH and redox responsive characteristics. Doxorubicin (DOX) as a model drug was encapsulated into the core of micelles through both hydrophobic and π-π interactions between aromatic rings and the DOX-loaded polymeric micelles exhibited accelerated drug release behaviors in an acidic and reductive environment due to the swelling of hydrophobic cores and the shedding of PEG shells. Furthermore, the cytocompability of the polymer and the cytotoxicity of DOX-loaded micelles towards Hela cells under corresponding conditions were evaluated, and the endocytosis of DOX-loaded polymeric micelles and the intracellular drug release from micelles were observed. All obtained data indicated that the micelle was a promising candidate for controlled drug release. Copyright © 2016 Elsevier B.V. All rights reserved.

Study of Chemistry and Structure-Property Relationship on Tunable Plasmonic Nanostructures

NASA Astrophysics Data System (ADS)

Jing, Hao

In this dissertation, the rational design and controllable fabrication of an array of novel plasmonic nanostructures with geometrically tunable optical properties are demonstrated, including metal-semiconductor hybrid hetero-nanoparticles, bimetallic noble metal nanoparticles and hollow nanostructures (nanobox and nanocage). Firstly, I have developed a robust wet chemistry approach to the geometry control of Ag-Cu2O core-shell nanoparticles through epitaxial growth of Cu2O nanoshells on the surfaces of various Ag nanostructures, such as quasi-spherical nanoparticles, nanocubes, and nanocuboids. Precise control over the core and the shell geometries enables me to develop detailed, quantitative understanding of how the Cu2O nanoshells introduce interesting modifications to the resonance frequencies and the extinction spectral line shapes of multiple plasmon modes of the Ag cores. Secondly, I present a detailed and systematic study of the controlled overgrowth of Pd on Au nanorods. The overgrowth of Pd nanoshells with fine-controlled dimensions and architectures on single-crystalline Au nanorods through seed-mediated growth protocol in the presence of various surfactants is investigated. Thirdly, I have demonstrated that creation of high-index facets on subwavelength metallic nanoparticles provides a unique approach to the integration of desired plasmonic and catalytic properties on the same nanoparticle. Through site-selective surface etching of metallic nanocuboids whose surfaces are dominated by low-index facets, I have controllably fabricated nanorice and nanodumbbell particles, which exhibit drastically enhanced catalytic activities arising from the catalytically active high index facets abundant on the particle surfaces. And the nanorice and nanodumbbell particles also possess appealing tunable plasmonic properties that allow us to gain quantitative insights into nanoparticle-catalyzed reactions with unprecedented sensitivity and detail through time-resolved plasmon-enhanced spectroscopic measurements, such as surface-enhanced Raman scattering (SERS). Last but not least, I have demonstrated that the capability of geometry control over Ag-Pd bimetallic hollow nanostructures through nanoscale galvanic replacement can be greatly enhanced by the use of appropriate mild reducing agents, such as ascorbic acid and formaldehyde. With the aid of mild reducing agents, we have been able to fine-tailor the compositions, interior architectures, and surface morphologies of Ag-Pd bimetallic hollow nanoparticles with increased structural complexity through surface ligand-free galvanic replacement processes at room temperature. This reducing agent-mediated galvanic replacement provides a unique way of achieving both enhanced optical tunability and optimized catalytic activities through deliberate control over the geometries of complex Ag-Pd bimetallic nanoparticles.

Nanoimprinted Hybrid Metal-Semiconductor Plasmonic Multilayers with Controlled Surface Nano Architecture for Applications in NIR Detectors

PubMed Central

Khosroabadi, Akram A.; Gangopadhyay, Palash; Hernandez, Steven; Kim, Kyungjo; Peyghambarian, Nasser; Norwood, Robert A.

2015-01-01

We present a proof of concept for tunable plasmon resonance frequencies in a core shell nano-architectured hybrid metal-semiconductor multilayer structure, with Ag as the active shell and ITO as the dielectric modulation media. Our method relies on the collective change in the dielectric function within the metal semiconductor interface to control the surface. Here we report fabrication and optical spectroscopy studies of large-area, nanostructured, hybrid silver and indium tin oxide (ITO) structures, with feature sizes below 100 nm and a controlled surface architecture. The optical and electrical properties of these core shell electrodes, including the surface plasmon frequency, can be tuned by suitably changing the order and thickness of the dielectric layers. By varying the dimensions of the nanopillars, the surface plasmon wavelength of the nanopillar Ag can be tuned from 650 to 690 nm. Adding layers of ITO to the structure further shifts the resonance wavelength toward the IR region and, depending on the sequence and thickness of the layers within the structure, we show that such structures can be applied in sensing devices including enhancing silicon as a photodetection material. PMID:28793489

Facile synthesis N-doped hollow carbon spheres from spherical solid silica.

PubMed

Wenelska, K; Ottmann, A; Moszyński, D; Schneider, P; Klingeler, R; Mijowska, E

2018-02-01

Nitrogen-doped core/shell carbon nanospheres (NHCS are prepared and their capability as an anode material in lithium-ion batteries is investigated. The synthesis methodology is based on a fast template route. The resulting molecular nanostructures are characterized by X-ray diffraction, transmission electron microscopy, thermal analysis, and nitrogen adsorption/desorption measurement as well as by cyclic voltammetry and galvanostatic cycling. The core/shell structure provides a rapid lithium transport pathway and boasts a highly reversible capacity. For undoped HCS the BET specific surface area is 623m 2 /g which increases up to 1000m 2 /g upon N-doping. While there is no significant effect of N-doping on the electrochemical performance at small scan rates, the doped NHCS shows better specific capacities than the pristine HCS at elevated rates. For instance, the discharge capacities in the 40th cycle, obtained at 1000mA/g, amount to 170mAh/g and 138mAh/g for NHCS and HCS, respectively. Copyright © 2017 Elsevier Inc. All rights reserved.

A Review of the Structure, Preparation, and Application of NLCs, PNPs, and PLNs.

PubMed

Li, Qianwen; Cai, Tiange; Huang, Yinghong; Xia, Xi; Cole, Susan P C; Cai, Yu

2017-05-27

Nanostructured lipid carriers (NLCs) are modified solid lipid nanoparticles (SLNs) that retain the characteristics of the SLN, improve drug stability and loading capacity, and prevent drug leakage. Polymer nanoparticles (PNPs) are an important component of drug delivery. These nanoparticles can effectively direct drug delivery to specific targets and improve drug stability and controlled drug release. Lipid-polymer nanoparticles (PLNs), a new type of carrier that combines liposomes and polymers, have been employed in recent years. These nanoparticles possess the complementary advantages of PNPs and liposomes. A PLN is composed of a core-shell structure; the polymer core provides a stable structure, and the phospholipid shell offers good biocompatibility. As such, the two components increase the drug encapsulation efficiency rate, facilitate surface modification, and prevent leakage of water-soluble drugs. Hence, we have reviewed the current state of development for the NLCs', PNPs', and PLNs' structures, preparation, and applications over the past five years, to provide the basis for further study on a controlled release drug delivery system.

Erythrocyte-like hollow carbon capsules and their application in proton exchange membrane fuel cells.

PubMed

Kim, Jung Ho; Yu, Jong-Sung

2010-12-14

Hierarchical nanostructured erythrocyte-like hollow carbon (EHC) with a hollow hemispherical macroporous core of ca. 230 nm in diameter and 30-40 nm thick mesoporous shell was synthesized and explored as a cathode catalyst support in a proton exchange membrane fuel cell (PEMFC). The morphology control of EHC was successfully achieved using solid core/mesoporous shell (SCMS) silica template and different styrene/furfuryl alcohol mixture compositions by a nanocasting method. The EHC-supported Pt (20 wt%) cathodes prepared have demonstrated markedly enhanced catalytic activity towards oxygen reduction reactions (ORRs) and greatly improved PEMFC polarization performance compared to carbon black Vulcan XC-72 (VC)-supported ones, probably due to the superb structural characteristics of the EHC such as uniform size, well-developed porosity, large specific surface area and pore volume. In particular, Pt/EHC cathodes exhibited ca. 30-60% higher ORR activity than a commercial Johnson Matthey Pt catalyst at a low catalyst loading of 0.2 mg Pt cm(-2).

Preparation of ZnS/ZnO core - Shell nanocomposite and its photocatalytic behaviour for dye degradation

NASA Astrophysics Data System (ADS)

Patil, Bharati N.; Acharya, Smita A.

2018-05-01

In the present work ZnS-ZnO core-shell-type composite nanostructures was prepared by hydrothermal method. The prepared samples were characterized by X-ray diffraction (XRD) for structural confirmation. Microstructural study by scanning electron microscopy (SEM) exhibit nanoscale dimensions of as-synthesized composite. UV/VIS spectra were recorded for evaluation of photophysical properties. The composite was explored as photocatalysts to study dye degradation using methylene blue in aqueous slurry under irradiation of 663 nm wavelength and congo red under irradiation of 493 nm wavelength. Under the same conditions the photocatalytic activity of the individual phases ZnS and ZnO were also examined, just for sake of comparison. The ZnS-ZnO composite is found to be enhancing the rate of photo degradation of toxic dyes in presence of visible light as compared to ZnS and ZnO individual phases. Thus ZnS based metal sulphide/oxide semiconductor nanocomposites are potential material for Photo-degradation of toxic dyes, and act as good photocatalyst.

Engineering firecracker-like beta-manganese dioxides@spinel nickel cobaltates nanostructures for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Kuang, Min; Wen, Zhong Quan; Guo, Xiao Long; Zhang, Sheng Mao; Zhang, Yu Xin

2014-12-01

An effective and rational strategy is developed for large-scale growth of firecracker-like Ni-substituted Co3O4 (NiCo2O4) nanosheets on β-MnO2 nanowires (NWs) with robust adhesion as high-performance electrode for electrochemical capacitors. The NiCo2O4-MnO2 nanostructures display much higher specific capacitance (343 F g-1 at current density of 0.5 A g-1), better rate capability (75.3% capacitance retention from 0.5 A g-1 to 8 A g-1) and excellent cycle stability (5% capacitance loss after 3000 cycles) than Co3O4-MnO2 nanostructures. Moreover, an asymmetric supercapacitor based on NiCo2O4-MnO2 NWs as the positive electrode and activated graphenes (AG) as the negative electrode achieves an energy density of 9.4 Wh kg-1 and a maximum power density of 2.5 kW kg-1. These attractive findings suggest this novel core-shell nanostructure promising for electrochemical applications as an efficient supercapacitive electrode.

Ni/CdS bifunctional Ti@TiO2 core-shell nanowire electrode for high-performance nonenzymatic glucose sensing.

PubMed

Guo, Chunyan; Huo, Huanhuan; Han, Xu; Xu, Cailing; Li, Hulin

2014-01-07

In this work, a Ni/CdS bifunctional Ti@TiO2 core-shell nanowire electrode with excellent electrochemical sensing property was successfully constructed through a hydrothermal and electrodeposition method. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) were employed to confirm the synthesis and characterize the morphology of the as-prepared samples. The results revealed that the CdS layer between Ni and TiO2 plays an important role in the uniform nucleation and the following growth of highly dispersive Ni nanoparticle on the Ti@TiO2 core-shell nanowire surface. The bifunctional nanostructured electrode was applied to construct an electrochemical nonenzymatic sensor for the reliable detection of glucose. Under optimized conditions, this nonenzymatic glucose sensor displayed a high sensitivity up to 1136.67 μA mM(-1) cm(-2), a wider liner range of 0.005-12 mM, and a lower detection limit of 0.35 μM for glucose oxidation. The high dispersity of Ni nanoparticles, combined with the anti-poisoning faculty against the intermediate derived from the self-cleaning ability of CdS under the photoexcitation, was considered to be responsible for these enhanced electrochemical performances. Importantly, favorable reproducibility and long-term performance were also obtained thanks to the robust frameworks. All these results indicate this novel electrode is a promising candidate for nonenzymatic glucose sensing.

Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance

DOE PAGES

Crane, Cameron C.; Wang, Feng; Li, Jun; ...

2017-02-21

Copper nanoparticles exhibit intense and sharp localized surface plasmon resonance (LSPR) in the visible region; however, the LSPR peaks become weak and broad when exposed to air due to the oxidation of Cu. In this work, the Cu nanoparticles are successfully encapsulated in SiO 2 by employing trioctyl-n-phosphine (TOP)-capped Cu nanoparticles for the sol–gel reaction, yielding an aqueous Cu–SiO 2 core–shell suspension with stable and well-preserved LSPR properties of the Cu cores. With the TOP capping, the oxidation of the Cu cores in the microemulsion was significantly reduced, thus allowing the Cu cores to sustain the sol–gel process used formore » coating the SiO 2 protection layer. It was found that the self-assembled TOP-capped Cu nanoparticles were spontaneously disassembled during the sol–gel reaction, thus recovering the LSPR of individual particles. During the disassembling progress, the extinction spectrum of the nanocube agglomerates evolved from a broad extinction profile to a narrow and sharp peak. For a mixture of nanocubes and nanorods, the spectra evolved to two distinct peaks during the dissembling process. The observed spectra match well with the numerical simulations. In conclusion, these Cu–SiO 2 core–shell nanoparticles with sharp and stable LSPR may greatly expand the utilization of Cu nanoparticles in aqueous environments.« less

Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance

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

Crane, Cameron C.; Wang, Feng; Li, Jun

Copper nanoparticles exhibit intense and sharp localized surface plasmon resonance (LSPR) in the visible region; however, the LSPR peaks become weak and broad when exposed to air due to the oxidation of Cu. In this work, the Cu nanoparticles are successfully encapsulated in SiO 2 by employing trioctyl-n-phosphine (TOP)-capped Cu nanoparticles for the sol–gel reaction, yielding an aqueous Cu–SiO 2 core–shell suspension with stable and well-preserved LSPR properties of the Cu cores. With the TOP capping, the oxidation of the Cu cores in the microemulsion was significantly reduced, thus allowing the Cu cores to sustain the sol–gel process used formore » coating the SiO 2 protection layer. It was found that the self-assembled TOP-capped Cu nanoparticles were spontaneously disassembled during the sol–gel reaction, thus recovering the LSPR of individual particles. During the disassembling progress, the extinction spectrum of the nanocube agglomerates evolved from a broad extinction profile to a narrow and sharp peak. For a mixture of nanocubes and nanorods, the spectra evolved to two distinct peaks during the dissembling process. The observed spectra match well with the numerical simulations. In conclusion, these Cu–SiO 2 core–shell nanoparticles with sharp and stable LSPR may greatly expand the utilization of Cu nanoparticles in aqueous environments.« less

Cd-free Cu-Zn-In-S/ZnS quantum dots@SiO2 multiple cores nanostructure: preparation and application for white LEDs

NASA Astrophysics Data System (ADS)

Jiang, Tongtong; Shen, Mohan; Dai, Peng; Wu, Mingzai; Yu, Xinxin; Li, Guang; Xu, Xiaoliang; Zeng, Haibo

2017-10-01

The work reports the fabrication of Cu doped Zn-In-S (CZIS) alloy quantum dots (QDs) using dodecanethiol and oleic acid as stabilizing ligands. With the increase of doped Cu element, the photoluminescence (PL) peak is monotonically red shifted. After coating ZnS shell, the PL quantum yield of CZIS QDs can reach 78%. Using reverse micelle microemulsion method, CZIS/ZnS QDs@SiO2 multi-core nanospheres were synthesized to improve the colloidal stability and avoid the aggregation of QDs. The obtained multi-core nanospheres were dispersed in curing adhesive, and applied as a color conversion layer in down converted light-emitting diodes. After encapsulation in curing adhesive, the newly designed LEDs show artifically regulated color coordinates with varying the weight ratio of green QDs and red QDs, and the concentrations of these two types of QDs. Moreover, natural white and warm white LEDs with correlated color temperature of 5287, 6732, 2731, and 3309 K can be achieved, which indicates that CZIS/ZnS QDs@SiO2 nanostructures are promising color conversion layer material for solid-state lighting application.

Single and multi-layered core-shell structures based on ZnO nanorods obtained by aerosol assisted chemical vapor deposition

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

Sáenz-Trevizo, A.; Amézaga-Madrid, P.; Pizá-Ruiz, P.

2015-07-15

Core–shell nanorod structures were prepared by a sequential synthesis using an aerosol assisted chemical vapor deposition technique. Several samples consisting of ZnO nanorods were initially grown over TiO{sub 2} film-coated borosilicate glass substrates, following the synthesis conditions reported elsewhere. Later on, a uniform layer consisting of individual Al, Ni, Ti or Fe oxides was grown onto ZnO nanorod samples forming the so-called single MO{sub x}/ZnO nanorod core–shell structures, where MO{sub x} was the metal oxide shell. Additionally, a three-layer core–shell sample was developed by growing Fe, Ti and Fe oxides alternately, onto the ZnO nanorods. The microstructure of the core–shellmore » materials was characterized by grazing incidence X-ray diffraction, scanning and transmission electron microscopy. Energy dispersive X-ray spectroscopy was employed to corroborate the formation of different metal oxides. X-ray diffraction outcomes for single core–shell structures showed solely the presence of ZnO as wurtzite and TiO{sub 2} as anatase. For the multi-layered shell sample, the existence of Fe{sub 2}O{sub 3} as hematite was also detected. Morphological observations suggested the existence of an outer material grown onto the nanorods and further microstructural analysis by HR-STEM confirmed the development of core–shell structures in all cases. These studies also showed that the individual Al, Fe, Ni and Ti oxide layers are amorphous; an observation that matched with X-ray diffraction analysis where no apparent extra oxides were detected. For the multi-layered sample, the development of a shell consisting of three different oxide layers onto the nanorods was found. Overall results showed that no alteration in the primary ZnO core was produced during the growth of the shells, indicating that the deposition technique used herein was and it is suitable for the synthesis of homogeneous and complex nanomaterials high in quality and purity. In addition, materials absorptance determined from the total transmittance and reflectance spectra revealed a broader absorption interval including visible light, indicating potential uses of these nanostructures on solar energy appliances. - Graphical abstract: Display Omitted - Highlights: • Uniform ZnO nanorods (core)–metal oxide (shell) were obtained sequentially by AACVD. • Shells were structured of homogeneous single or multi-layered non-mixed metal oxides. • ZnO nanorod core was preserved during the shell synthesis. • Optical absorptance revealed visible interval absorption for FeO{sub x} shell samples. • Materials can be suitable for photocatalytic or photovoltaic applications.« less

Spectrally-resolved internal quantum efficiency and carrier dynamics of semipolar (10\\bar{1}1) core-shell triangular nanostripe GaN/InGaN LEDs

NASA Astrophysics Data System (ADS)

Okur, Serdal; Rishinaramangalam, Ashwin K.; Mishkat-Ul-Masabih, Saadat; Nami, Mohsen; Liu, Sheng; Brener, Igal; Brueck, Steven R. J.; Feezell, Daniel F.

2018-06-01

We investigate the spectrally resolved internal quantum efficiency (IQE) and carrier dynamics in semipolar (10\\bar{1}1) core–shell triangular nanostripe light-emitting diodes (TLEDs) using temperature-dependent photoluminescence (TDPL) and time-resolved photoluminescence (TRPL) at various excitation energy densities. Using electroluminescence, photoluminescence, and cathodoluminescence measurements, we verify the origins of the broad emission spectra from the nanostructures and confirm that localized regions of high-indium-content InGaN exist along the apex of the nanostructures. Spectrally resolved IQE measurements are then performed, with the spectra integrated from 400–450 nm and 450–500 nm to obtain the IQE of the QWs mainly near the sidewalls and apex of the TLEDs, respectively. TDPL and TRPL are used to decouple the radiative and non-radiative carrier lifetimes for different regions of the emission spectra. We observe that the IQE is higher for the spectral region between 450 nm and 500 nm compared to the IQE between 400 and 450 nm. This result is in contrast to the typical observation that the IQE of planar GaN-based LEDs is lower for longer wavelengths (i.e., higher indium contents). We also observe a longer non-radiative recombination lifetime for the longer wavelength portion of the spectrum. Several explanations are proposed for the improved IQE and longer non-radiative lifetime observed near the apex of the nanostructures. The results show that nanostructures may be leveraged to design more efficient green LEDs, potentially addressing a long-standing challenge in GaN-based materials.

Self-assembly of Janus dendrimers into uniform dendrimersomes and other complex architectures.

PubMed

Percec, Virgil; Wilson, Daniela A; Leowanawat, Pawaret; Wilson, Christopher J; Hughes, Andrew D; Kaucher, Mark S; Hammer, Daniel A; Levine, Dalia H; Kim, Anthony J; Bates, Frank S; Davis, Kevin P; Lodge, Timothy P; Klein, Michael L; DeVane, Russell H; Aqad, Emad; Rosen, Brad M; Argintaru, Andreea O; Sienkowska, Monika J; Rissanen, Kari; Nummelin, Sami; Ropponen, Jarmo

2010-05-21

Self-assembled nanostructures obtained from natural and synthetic amphiphiles serve as mimics of biological membranes and enable the delivery of drugs, proteins, genes, and imaging agents. Yet the precise molecular arrangements demanded by these functions are difficult to achieve. Libraries of amphiphilic Janus dendrimers, prepared by facile coupling of tailored hydrophilic and hydrophobic branched segments, have been screened by cryogenic transmission electron microscopy, revealing a rich palette of morphologies in water, including vesicles, denoted dendrimersomes, cubosomes, disks, tubular vesicles, and helical ribbons. Dendrimersomes marry the stability and mechanical strength obtainable from polymersomes with the biological function of stabilized phospholipid liposomes, plus superior uniformity of size, ease of formation, and chemical functionalization. This modular synthesis strategy provides access to systematic tuning of molecular structure and of self-assembled architecture.

Morphology and crystallinity-controlled synthesis of manganese cobalt oxide/manganese dioxides hierarchical nanostructures for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Li, Fei; Li, Gang; Chen, Hao; Jia, Jia Qi; Dong, Fan; Hu, Yao Bo; Shang, Zheng Guo; Zhang, Yu Xin

2015-11-01

We demonstrate a novel preparative strategy for the well-controlled MnCo2O4.5@MnO2 hierarchical nanostructures. Both δ-MnO2 nanosheets and α-MnO2 nanorods can uniformly decorate the surface of MnCo2O4.5 nanowires to form core-shell heterostructures. Detailed electrochemical characterization reveals that MnCo2O4.5@δ-MnO2 pattern exhibits not only high specific capacitance of 357.5 F g-1 at a scan rate of 0.5 A g-1, but also good cycle stability (97% capacitance retention after 1000 cycles at a scan rate of 5 A g-1), which make it have a promising application as a supercapacitor electrode material.

The Morphologies of the Semiconductor Oxides and Their Gas-Sensing Properties

PubMed Central

Lv, Xin; Li, Shuang; Wang, Qingji

2017-01-01

Semiconductor oxide chemoresistive gas sensors are widely used for detecting deleterious gases due to low cost, simple preparation, rapid response and high sensitivity. The performance of gas sensor is greatly affected by the morphology of the semiconductor oxide. There are many semiconductor oxide morphologies, including zero-dimensional, one-dimensional, two-dimensional and three-dimensional ones. The semiconductor oxides with different morphologies significantly enhance the gas-sensing performance. Among the various morphologies, hollow nanostructures and core-shell nanostructures are always the focus of research in the field of gas sensors due to their distinctive structural characteristics and superior performance. Herein the morphologies of semiconductor oxides and their gas-sensing properties are reviewed. This review also proposes a potential strategy for the enhancement of gas-sensing performance in the future. PMID:29189714

Hydrogenated CoOx nanowire@Ni(OH)2 nanosheet core-shell nanostructures for high-performance asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Zhu, Jianxiao; Huang, Lei; Xiao, Yuxiu; Shen, Leo; Chen, Qi; Shi, Wangzhou

2014-05-01

We report a facile strategy to prepare 3D core-shell nanowire heterostructures with microporous hydrogenated CoOx (H-CoOx) nanowires as the conducting scaffold to support Ni(OH)2 nanosheets. Benefiting from the H-CoOx nanowire core to provide the effective pathway for charge transport and the core-shell heterostructures with synergistic effects, the H-CoOx@Ni(OH)2 core-shell nanowire electrode achieved the specific capacitance of 2196 F g-1 (areal capacitance of 5.73 F cm-2), which is approximately a 1.4-fold enhancement compared with the Co3O4@Ni(OH)2 core-shell nanowires. An aqueous asymmetric supercapacitor (ASC) device was fabricated by using H-CoOx@Ni(OH)2 nanowires as the positive electrode and reduced graphene oxide @Fe3O4 nanocomposites as the negative electrode. The ASCs achieved high energy density (~45.3 W h kg-1 at 1010 W kg-1), high power density (~7080 W kg-1 at 23.4 W h kg-1) and high cycling stability. Furthermore, after charging for ~1 min, one such 22 cm2 ASC device demonstrated to be able to drive a small windmill (0.8 V, 0.1 W) for 20 min. Two such ASCs connected in series can power up a seven-color LED (3.2 V) efficiently.We report a facile strategy to prepare 3D core-shell nanowire heterostructures with microporous hydrogenated CoOx (H-CoOx) nanowires as the conducting scaffold to support Ni(OH)2 nanosheets. Benefiting from the H-CoOx nanowire core to provide the effective pathway for charge transport and the core-shell heterostructures with synergistic effects, the H-CoOx@Ni(OH)2 core-shell nanowire electrode achieved the specific capacitance of 2196 F g-1 (areal capacitance of 5.73 F cm-2), which is approximately a 1.4-fold enhancement compared with the Co3O4@Ni(OH)2 core-shell nanowires. An aqueous asymmetric supercapacitor (ASC) device was fabricated by using H-CoOx@Ni(OH)2 nanowires as the positive electrode and reduced graphene oxide @Fe3O4 nanocomposites as the negative electrode. The ASCs achieved high energy density (~45.3 W h kg-1 at 1010 W kg-1), high power density (~7080 W kg-1 at 23.4 W h kg-1) and high cycling stability. Furthermore, after charging for ~1 min, one such 22 cm2 ASC device demonstrated to be able to drive a small windmill (0.8 V, 0.1 W) for 20 min. Two such ASCs connected in series can power up a seven-color LED (3.2 V) efficiently. Electronic supplementary information (ESI) available: Synthetic methods of Co3O4 and RGO, FESEM cross-sectional image of H-CoOx NWs, XRD of Co3O4, H-CoOx and H-CoOx@Ni(OH)2, CVs and charge-discharge curves of the bare Ni foam, calculation of the specific capacitance of H-CoOx@Ni(OH)2, XRD and FESEM of RGO@Fe3O4 nanocomposites, CV, charge-discharge curves and cycling performance of the RGO@Fe3O4 nanocomposite electrode, and pictures showing demonstration of the ASC devices. See DOI: 10.1039/c4nr00771a

Gamma-Ray Bursts in Circumstellar Shells: A Possible Explanation for Flares

NASA Astrophysics Data System (ADS)

Mesler, Robert; Whalen, D. J.; Lloyd-Ronning, N. M.; Fryer, C. L.; Pihlstrom, Y. M.

2012-05-01

It is now generally accepted that long-duration gamma-ray bursts (GRBs) are due to the collapse of massive rotating stars. The precise collapse process itself, however, is not yet fully understood. Strong winds, outbursts, and intense ionizing UV radiation from single stars or strongly interacting binaries are expected to destroy the molecular cloud cores that give birth to them and create highly complex circumburst environments for the explosion. Such environments might imprint features on GRB light curves that uniquely identify the nature of the progenitor and its collapse. We have performed numerical simulations of realistic environments for a variety of long-duration GRB progenitors with ZEUS-MP and have developed an analytical method for calculating detailed GRB light curves in these profiles. We find that, in the context of the standard afterglow model, massive shells around GRBs produce strong signatures in their light curves, and that this clearly distinguishes them from those occurring in uniform media or steady winds. These features can constrain the mass of the shell and the properties of the wind before and after the ejection. Moreover, the interaction of the GRB with the circumburst shell is seen to produce features that are consistent with observed X-ray flares that are often attributed to delayed energy injection by the central engine. Our algorithm for computing light curves is also applicable to GRBs in a variety of environments such as those in high-redshift cosmological halos or protogalaxies, both of which will soon be targets of future surveys such as JANUS or Lobster.

Tunable Non-Thermal Distribution of Hot Electrons in a Semiconductor Injected from a Plasmonic Gold Nanostructure.

PubMed

Cushing, Scott Kevin; Chen, Chih-Jung; Dong, Chung Li; Kong, Xiang-Tian; Govorov, Alexander O; Liu, Ru-Shi; Wu, Nianqiang

2018-06-26

For semiconductors photosensitized with organic dyes or quantum dots, transferred electrons are usually considered thermalized at the conduction band edge. This study suggests that the electrons injected from a plasmonic metal into a thin semiconductor shell can be non-thermal with energy up to the plasmon frequency. In other words, the electrons injected into the semiconductor are still hot carriers. Photomodulated x-ray absorption measurements of the Ti L 2,3 edge are compared before and after excitation of the plasmon in Au@TiO 2 core shell nanoparticles. Comparison with theoretical predictions of the x-ray absorption, which include the heating and state-filling effects from injected hot carriers, suggest that the electrons transferred from the plasmon remain non-thermal in the ~10 nm TiO 2 shell, due in part to a slow trapping in defect states. By repeating the measurements for spherical, rod-like, and star-like metal nanoparticles, the magnitude of the non-thermal distribution, peak energy, and number of injected hot electrons are confirmed to be tuned by the plasmon frequency and the sharp corners of the plasmonic nanostructure. The results suggest that plasmonic photosensitizers can not only extend the sunlight absorption spectral range of semiconductor-based devices, but could also result in increased open circuit voltages and elevated thermodynamic driving forces for solar fuel generation in photoelectrochemical cells.

Hierarchically assembled NiCo@SiO2@Ag magnetic core-shell microspheres as highly efficient and recyclable 3D SERS substrates.

PubMed

Zhang, Maofeng; Zhao, Aiwu; Wang, Dapeng; Sun, Henghui

2015-01-21

The hierarchically nanosheet-assembled NiCo@SiO2@Ag (NSA) core-shell microspheres have been synthesized by a layer-by-layer procedure at ambient temperature. The mean particle size of NSA microspheres is about 1.7 μm, which is made up of some nanosheets with an average thickness of ∼20 nm. The outer silver shell surface structures can be controlled well by adjusting the concentration of Ag(+) ions and the reaction times. The obtained NSA 3D micro/nanostructures show a structure enhanced SERS performance, which can be attributed to the special nanoscale configuration with wedge-shaped surface architecture. We find that NSA microspheres with nanosheet-assembled shell structure exhibit the highest enhancement efficiency and high SERS sensitivity to p-ATP and MBA molecules. We show that the detection limits for both p-ATP and MBA of the optimized NSA microsphere substrates can approach 10(-7) M. And the relative standard deviation of the Raman peak maximum is ∼13%, which indicates good uniformity of the substrate. In addition, the magnetic NSA microspheres with high saturation magnetization show a quick magnetic response, good recoverability and recyclability. Therefore, such NSA microspheres may have great practical potential applications in rapid and reproducible trace detection of chemical, biological and environment pollutants with a simple portable Raman instrument.

Photoelectrochemical performance of NiO-coated ZnO-CdS core-shell photoanode

NASA Astrophysics Data System (ADS)

Iyengar, Pranit; Das, Chandan; Balasubramaniam, K. R.

2017-03-01

A nano-structured core-shell ZnO-CdS photoanode device with a mesoporous NiO co-catalyst layer was fabricated using solution-processing methods. The growth of the sparse ZnO nano-rod film with a thickness of ca. 930 nm was achieved by optimizing parameters such as the thickness of the ZnO seed layer, choice of Zn precursor salt and the salt concentration. CdS was then coated by a combination of spin coating and spin SILAR (Successive Ionic Layer Adsorption and Reaction) methods to completely fill the interspace of ZnO nano-rods. The uniform CdS surface facilitated the growth of a continuous mesoporous NiO layer. Upon illumination of 100 mW·cm-2 AM 1.5 G radiation the device exhibits stable photocurrents of 2.15 mA·cm-2 at 1.23 V and 0.92 mA·cm-2 at 0.00 V versus RHE, which are significantly higher as compared to the bare ZnO-CdS device. The excellent performance of the device can be ascribed to the higher visible region absorption by CdS, and effective separation of the photogenerated charge carriers due to the suitable band alignment and nanostructuring. Additionally, the mesoporous NiO overlayer offered a larger contact area with the electrolyte and promoted the kinetics enabling higher and stable photocurrent even till the 35th min. of testing.

Generalized Ellipsometry on Complex Nanostructures and Low-Symmetry Materials

NASA Astrophysics Data System (ADS)

Mock, Alyssa Lynn

In this thesis, complex anisotropic materials are investigated and characterized by generalized ellipsometry. In recent years, anisotropic materials have gained considerable interest for novel applications in electronic and optoelectronic devices, mostly due to unique properties that originate from reduced crystal symmetry. Examples include white solid-state lighting devices which have become ubiquitous just recently, and the emergence of high-power, high-voltage electronic transistors and switches in all-electric vehicles. The incorporation of single crystalline material with low crystal symmetry into novel device structures requires reconsideration of existing optical characterization approaches. Here, the generalized ellipsometry concept is extended to include applications for materials with monoclinic and triclinic symmetries. A model eigendielectric displacement vector approach is developed, described and utilized to characterize monoclinic materials. Materials are investigated in spectral regions spanning from the far-infrared to the vacuum ultraviolet. Examples are demonstrated for phonon mode determination in cadmium tungstate and yttrium silicate and for band-to-band transitions in gallia (beta-Ga2O3) single crystals. Furthermore, the anisotropic optical properties of an emerging class of spatially coherent heterostructure materials with nanostructure dimensions are investigated. The so-called anisotropic effective medium approximation for slanted columnar thin films is extended to the concept of slanted columnar heterostructure thin films as well as core-shell heterostructure thin films. Examples include the determination of band-to-band transitions, phonon modes and oxidation properties of cobalt-oxide core shell structures and gas-liquid-solid distribution during controlled adsorption of organic solvents in silicon slanted columnar thin films.

Structural and optical characterization of electrodeposited CdSe in mesoporous anatase TiO2 for regenerative quantum-dot-sensitized solar cells.

PubMed

Sauvage, Frédéric; Davoisne, Carine; Philippe, Laetitia; Elias, Jamil

2012-10-05

We investigated CdSe-sensitized TiO(2) solar cells by means of electrodeposition under galvanostatic control. The electrodeposition of CdSe within the mesoporous film of TiO(2) gives rise to a uniform, thickness controlled, conformal layer of nanostructured CdSe particles intimately wrapping the anatase TiO(2) nanoparticles. This technique has the advantage of providing not only a fast method for sensitization ( < 5 min) but also being easily scalable to the sensitization of large-area panels. XRD together with SAED analysis highlight that the deposit of CdSe is exclusively constituted of the hexagonal polymorph. In addition, hierarchical growth has also been shown, starting from the formation of a TiO(2)-CdSe core-shell structure followed by the growth of an assembly of CdSe nanoparticles resembling cauliflowers. This assembly exhibits at its core a mosaic texture with crystallites of about 3 nm in size, in contrast to a shell composed of well-crystallized single crystals between 5 and 10 nm in size. Preliminary results on the photovoltaic performance of such a nanostructured composite of TiO(2) and CdSe show 0.8% power conversion efficiency under A.M.1.5 G conditions-100 mW cm(-2) in association with a new regenerative redox couple based on cobalt(+III/+II) polypyridil complex (V(oc ) = 485 mV, J(sc ) = 4.26 mA cm (-2), ff=0.37).

Nanostructure and Corresponding Quenching Efficiency of Fluorescent DNA Probes.

PubMed

Guo, Wenjuan; Wei, Yanhong; Dai, Zhao; Chen, Guangping; Chu, Yuanyuan; Zhao, Yifei

2018-02-09

Based on the fluorescence resonance energy transfer (FRET) mechanism, fluorescent DNA probes were prepared with a novel DNA hairpin template method, with SiO₂ coated CdTe (CdTe/SiO₂) core/shell nanoparticles used as the fluorescence energy donors and gold (Au) nanoparticles (AuNPs) as the energy acceptors. The nanostructure and energy donor/acceptor ratio in a probe were controlled with this method. The relationship between the nanostructure of the probes and FRET efficiency (quenching efficiency) were investigated. The results indicated that when the donor/acceptor ratios were 2:1, 1:1, and 1:2; the corresponding FRET efficiencies were about 33.6%, 57.5%, and 74.2%, respectively. The detection results indicated that the fluorescent recovery efficiency of the detecting system was linear when the concentration of the target DNA was about 0.0446-2.230 nmol/L. Moreover, the probes showed good sensitivity and stability in different buffer conditions with a low detection limit of about 0.106 nmol/L.

Nanostructure and Corresponding Quenching Efficiency of Fluorescent DNA Probes

PubMed Central

Guo, Wenjuan; Wei, Yanhong; Dai, Zhao; Chen, Guangping; Chu, Yuanyuan; Zhao, Yifei

2018-01-01

Based on the fluorescence resonance energy transfer (FRET) mechanism, fluorescent DNA probes were prepared with a novel DNA hairpin template method, with SiO2 coated CdTe (CdTe/SiO2) core/shell nanoparticles used as the fluorescence energy donors and gold (Au) nanoparticles (AuNPs) as the energy acceptors. The nanostructure and energy donor/acceptor ratio in a probe were controlled with this method. The relationship between the nanostructure of the probes and FRET efficiency (quenching efficiency) were investigated. The results indicated that when the donor/acceptor ratios were 2:1, 1:1, and 1:2; the corresponding FRET efficiencies were about 33.6%, 57.5%, and 74.2%, respectively. The detection results indicated that the fluorescent recovery efficiency of the detecting system was linear when the concentration of the target DNA was about 0.0446–2.230 nmol/L. Moreover, the probes showed good sensitivity and stability in different buffer conditions with a low detection limit of about 0.106 nmol/L. PMID:29425163

Silver nanoparticles with gelatin nanoshells: photochemical facile green synthesis and their antimicrobial activity

NASA Astrophysics Data System (ADS)

Pourjavadi, Ali; Soleyman, Rouhollah

2011-10-01

In the current study, a facile green synthesis of silver-gelatin core-shell nanostructures (spherical, spherical/cubic hybrid, and cubic, DLS diameter: 4.1-6.9 nm) is reported via the wet chemical synthesis procedure. Sunlight-UV as an available reducing agent cause mild reduction of silver ions into the silver nanoparticles (Ag-NPs). Gelatin protein, as an effective capping/shaping agent, was used in the reaction to self-assemble silver nanostructures. The formation of silver nanostructures and their self-assembly pattern was confirmed by SEM, AFM, and TEM techniques. Further investigations were carried out using zeta-potential, UV-Vis, FTIR, GPC, and TGA/DTG/DTA data. The prepared Ag-NPs showed proper and acceptable antimicrobial activity against three classes of microorganisms ( Escherichia coli Gram-negative bacteria, Staphylococcus aureus Gram-positive bacteria, and Candida albicans fungus). The antibacterial and antifungal Ag-NPs exhibit good stability in solution and can be considered as promising candidates for a wide range of biomedical applications.

Novel electrochemical biosensor based on PVP capped CoFe2O4@CdSe core-shell nanoparticles modified electrode for ultra-trace level determination of rifampicin by square wave adsorptive stripping voltammetry.

PubMed

Asadpour-Zeynali, Karim; Mollarasouli, Fariba

2017-06-15

This work introduces a new electrochemical sensor based on polyvinyl pyrrolidone capped CoFe 2 O 4 @CdSe core-shell modified electrode for a rapid detection and highly sensitive determination of rifampicin (RIF) by square wave adsorptive stripping voltammetry. The new PVP capped CoFe 2 O 4 @CdSe with core-shell nanostructure was synthesized by a facile synthesis method for the first time. PVP can act as a capping and etching agent for protection of the outer surface nanoparticles and formation of a mesoporous shell, respectively. Another important feature of this work is the choice of the ligand (1,10-phenanthroline) for precursor cadmium complex that works as a chelating agent in order to increase optical and electrical properties and stability of prepared nanomaterial. The nanoparticles have been characterized by field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), UV-vis, photoluminescence (PL) spectroscopy, FT-IR, and cyclic voltammetry techniques. The PL spectroscopy study of CoFe 2 O 4 @CdSe has shown significant PL quenching by the formation of CoFe 2 O 4 core inside CdSe, this shows that CoFe 2 O 4 NPs are efficient electron acceptors with the CdSe. It is clearly observed that the biosensor can significantly enhance electrocatalytic activity towards the oxidation of RIF, under the optimal conditions. The novelty of this work arises from the new synthesis method for the core-shell of CoFe 2 O 4 @CdSe. Then, the novel electrochemical biosensor was fabricated for ultra-trace level determination of rifampicin with very low detection limit (4.55×10 -17 M) and a wide linear range from 1.0×10 -16 to 1.0×10 -7 M. The fabricated biosensor showed high sensitivity and selectivity, good reproducibility and stability. Therefore, it was successfully applied for the determination of ultra-trace RIF amounts in biological and pharmaceutical samples with satisfactory recovery data. Copyright © 2016 Elsevier B.V. All rights reserved.

Magnetic/NIR-responsive drug carrier, multicolor cell imaging, and enhanced photothermal therapy of gold capped magnetite-fluorescent carbon hybrid nanoparticles

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

Wang, Hui; Cao, Guixin; Gai, Zheng

In our paper reports a type of multifunctional hybrid nanoparticle (NP) composed of gold nanocrystals coated on and/or embedded in a magnetite-fluorescent porous carbon core-shell NP template (Fe 3O 4@PC-CDs-Au) for biomedical applications, including magnetic/NIR-responsive drug release, multicolor cell imaging, and enhanced photothermal therapy. The synthesis of the Fe 3O 4@PC-CDs-Au NPs firstly involves the preparation of core-shell template NPs with magnetite nanocrystals clustered in the cores and fluorescent carbon dots (CDs) embedded in a porous carbon shell, followed by an in situ reduction of silver ions (Ag +) loaded in the porous carbon shell and a subsequent replacement ofmore » Ag NPs with Au NPs through a galvanic replacement reaction using HAuCl 4 as a precursor. Moreover, the Fe 3O 4@PC-CDsAu NPs can enter the intracellular region and light up mouse melanoma B16F10 cells in multicolor mode. The porous carbon shell, anchored with hydrophilic hydroxyl/carboxyl groups, endows the Fe 3O 4@PC-CDs-Au NPs with excellent stability in the aqueous phase and a high loading capacity (719 mg g -1) for the anti-cancer drug doxorubicin (DOX). The superparamagnetic Fe 3O 4@PC-CDs-Au NPs with a saturation magnetization of 23.26 emu g -1 produce localized heat under an alternating magnetic field, which triggers the release of the loaded drug. The combined photothermal effects of the Au nanocrystals and the CDs on/in the carbon shell can not only regulate the release rate of the loaded drug, but also efficiently kill tumor cells under NIR irradiation. Finally, in benefitting from their excellent optical properties, their magnetic field and NIR light-responsive drug release capabilities and their enhanced photothermal effect, such nanostructured Fe 3O 4@PC-CDs-Au hybrid NPs are very promising for simultaneous imaging diagnostics and high efficacy therapy.« less

Magnetic/NIR-responsive drug carrier, multicolor cell imaging, and enhanced photothermal therapy of gold capped magnetite-fluorescent carbon hybrid nanoparticles

DOE PAGES

Wang, Hui; Cao, Guixin; Gai, Zheng; ...

2015-03-25

In our paper reports a type of multifunctional hybrid nanoparticle (NP) composed of gold nanocrystals coated on and/or embedded in a magnetite-fluorescent porous carbon core-shell NP template (Fe 3O 4@PC-CDs-Au) for biomedical applications, including magnetic/NIR-responsive drug release, multicolor cell imaging, and enhanced photothermal therapy. The synthesis of the Fe 3O 4@PC-CDs-Au NPs firstly involves the preparation of core-shell template NPs with magnetite nanocrystals clustered in the cores and fluorescent carbon dots (CDs) embedded in a porous carbon shell, followed by an in situ reduction of silver ions (Ag +) loaded in the porous carbon shell and a subsequent replacement ofmore » Ag NPs with Au NPs through a galvanic replacement reaction using HAuCl 4 as a precursor. Moreover, the Fe 3O 4@PC-CDsAu NPs can enter the intracellular region and light up mouse melanoma B16F10 cells in multicolor mode. The porous carbon shell, anchored with hydrophilic hydroxyl/carboxyl groups, endows the Fe 3O 4@PC-CDs-Au NPs with excellent stability in the aqueous phase and a high loading capacity (719 mg g -1) for the anti-cancer drug doxorubicin (DOX). The superparamagnetic Fe 3O 4@PC-CDs-Au NPs with a saturation magnetization of 23.26 emu g -1 produce localized heat under an alternating magnetic field, which triggers the release of the loaded drug. The combined photothermal effects of the Au nanocrystals and the CDs on/in the carbon shell can not only regulate the release rate of the loaded drug, but also efficiently kill tumor cells under NIR irradiation. Finally, in benefitting from their excellent optical properties, their magnetic field and NIR light-responsive drug release capabilities and their enhanced photothermal effect, such nanostructured Fe 3O 4@PC-CDs-Au hybrid NPs are very promising for simultaneous imaging diagnostics and high efficacy therapy.« less

Expanding the Bethe/Gauge dictionary

NASA Astrophysics Data System (ADS)

Bullimore, Mathew; Kim, Hee-Cheol; Lukowski, Tomasz

2017-11-01

We expand the Bethe/Gauge dictionary between the XXX Heisenberg spin chain and 2d N = (2, 2) supersymmetric gauge theories to include aspects of the algebraic Bethe ansatz. We construct the wave functions of off-shell Bethe states as orbifold defects in the A-twisted supersymmetric gauge theory and study their correlation functions. We also present an alternative description of off-shell Bethe states as boundary conditions in an effective N = 4 supersymmetric quantum mechanics. Finally, we interpret spin chain R-matrices as correlation functions of Janus interfaces for mass parameters in the supersymmetric quantum mechanics.

Cytotoxicity of various types of gold-mesoporous silica nanoparticles in human breast cancer cells

PubMed Central

Liu, Guomu; Li, Qiongshu; Ni, Weihua; Zhang, Nannan; Zheng, Xiao; Wang, Yingshuai; Shao, Dan; Tai, Guixiang

2015-01-01

Recently, gold nanoparticles (AuNPs) have shown promising biological applications due to their unique electronic and optical properties. However, the potential toxicity of AuNPs remains a major hurdle that impedes their use in clinical settings. Mesoporous silica is very suitable for the use as a coating material for AuNPs and might not only reduce the cytotoxicity of cetyltrimethylammonium bromide-coated AuNPs but might also facilitate the loading and delivery of drugs. Herein, three types of rod-like gold-mesoporous silica nanoparticles (termed bare AuNPs, core–shell Au@mSiO2NPs, and Janus Au@mSiO2NPs) were specially designed, and the effects of these AuNPs on cellular uptake, toxic behavior, and mechanism were then systematically studied. Our results indicate that bare AuNPs exerted higher toxicity than the Au@mSiO2NPs and that Janus Au@mSiO2NPs exhibited the lowest toxicity in human breast cancer MCF-7 cells, consistent with the endocytosis capacity of the nanoparticles, which followed the order, bare AuNPs > core–shell Au@mSiO2NPs > Janus Au@mSiO2NPs. More importantly, the AuNPs-induced apoptosis of MCF-7 cells exhibited features that were characteristic of intracellular reactive oxygen species (ROS) generation, activation of c-Jun-N-terminal kinase (JNK) phosphorylation, an enhanced Bax-to-Bcl-2 ratio, and loss of the mitochondrial membrane potential. Simultaneously, cytochrome c was released from mitochondria, and the caspase-3/9 cascade was activated. Moreover, both ROS scavenger (N-acetylcysteine) and JNK inhibitor (SP600125) partly blocked the induction of apoptosis in all AuNPs-treated cells. Taken together, these findings suggest that all AuNPs induce apoptosis through the ROS-/JNK-mediated mitochondrial pathway. Thus, Janus Au@mSiO2NPs exhibit the potential for applications in biomedicine, thus aiding the clinical translation of AuNPs. PMID:26491285

Magnetic and interface properties of the core-shell Fe3O4/Au nanocomposites

NASA Astrophysics Data System (ADS)

Baskakov, A. O.; Solov'eva, A. Yu.; Ioni, Yu. V.; Starchikov, S. S.; Lyubutin, I. S.; Khodos, I. I.; Avilov, A. S.; Gubin, S. P.

2017-11-01

Core-shell Fe3O4/Au nanostructures were obtained with an advanced method of two step synthesis and several complementary methodics were applied for investigation structural and magnetic properties of the samples. Along with X-ray diffraction and transmission electron microscopy, electron diffraction, optical, Raman and Mössbauer spectroscopy were used for nanoparticle characterization. It was established that the physical and structural properties Fe3O4/Au nanocomposites are specific of intrinsic properties of gold and magnetite. Mössbauer and Raman spectroscopy data indicated that magnetite was in a nonstoichiometric state with an excess of trivalent iron both in the initial Fe3O4 nanoparticles and in the Fe3O4/Au nanocomposites. As follows from the Mössbauer data, magnetic properties of iron ions in the internal area (in core) and in the surface layer of magnetite nanoparticles are different due to the rupture of exchange bonds at the particles surface. This leads to decrease in an effective magnetic moment at the surface. Gold atoms at the interface of the composites interact with dangling bonds of magnetite and stabilize the magnetic properties of the surface layers of magnetite.

Facile One-pot Transformation of Iron Oxides from Fe2O3 Nanoparticles to Nanostructured Fe3O4@C Core-Shell Composites via Combustion Waves

PubMed Central

Shin, Jungho; Lee, Kang Yeol; Yeo, Taehan; Choi, Wonjoon

2016-01-01

The development of a low-cost, fast, and large-scale process for the synthesis and manipulation of nanostructured metal oxides is essential for incorporating materials with diverse practical applications. Herein, we present a facile one-pot synthesis method using combustion waves that simultaneously achieves fast reduction and direct formation of carbon coating layers on metal oxide nanostructures. Hybrid composites of Fe2O3 nanoparticles and nitrocellulose on the cm scale were fabricated by a wet impregnation process. We demonstrated that self-propagating combustion waves along interfacial boundaries between the surface of the metal oxide and the chemical fuels enabled the release of oxygen from Fe2O3. This accelerated reaction directly transformed Fe2O3 into Fe3O4 nanostructures. The distinctive color change from reddish-brown Fe2O3 to dark-gray Fe3O4 confirmed the transition of oxidation states and the change in the fundamental properties of the material. Furthermore, it simultaneously formed carbon layers of 5–20 nm thickness coating the surfaces of the resulting Fe3O4 nanoparticles, which may aid in maintaining the nanostructures and improving the conductivity of the composites. This newly developed use of combustion waves in hybridized nanostructures may permit the precise manipulation of the chemical compositions of other metal oxide nanostructures, as well as the formation of organic/inorganic hybrid nanostructures. PMID:26902260

Shape control and compartmentalization in active colloidal cells.

PubMed

Spellings, Matthew; Engel, Michael; Klotsa, Daphne; Sabrina, Syeda; Drews, Aaron M; Nguyen, Nguyen H P; Bishop, Kyle J M; Glotzer, Sharon C

2015-08-25

Small autonomous machines like biological cells or soft robots can convert energy input into control of function and form. It is desired that this behavior emerges spontaneously and can be easily switched over time. For this purpose we introduce an active matter system that is loosely inspired by biology and which we term an active colloidal cell. The active colloidal cell consists of a boundary and a fluid interior, both of which are built from identical rotating spinners whose activity creates convective flows. Similarly to biological cell motility, which is driven by cytoskeletal components spread throughout the entire volume of the cell, active colloidal cells are characterized by highly distributed energy conversion. We demonstrate that we can control the shape of the active colloidal cell and drive compartmentalization by varying the details of the boundary (hard vs. flexible) and the character of the spinners (passive vs. active). We report buckling of the boundary controlled by the pattern of boundary activity, as well as formation of core-shell and inverted Janus phase-separated configurations within the active cell interior. As the cell size is increased, the inverted Janus configuration spontaneously breaks its mirror symmetry. The result is a bubble-crescent configuration, which alternates between two degenerate states over time and exhibits collective migration of the fluid along the boundary. Our results are obtained using microscopic, non-momentum-conserving Langevin dynamics simulations and verified via a phase-field continuum model coupled to a Navier-Stokes equation.

Structural and photoluminescence properties of silicon nanowires extracted by means of a centrifugation process from plasma torch synthesized silicon nanopowder.

PubMed

Le Borgne, Vincent; Agati, Marta; Boninelli, Simona; Castrucci, Paola; De Crescenzi, Maurizio; Dolbec, Richard; El Khakani, My Ali

2017-07-14

We report on a method for the extraction of silicon nanowires (SiNWs) from the by-product of a plasma torch based spheroidization process of silicon. This by-product is a nanopowder which consists of a mixture of SiNWs and silicon particles. By optimizing a centrifugation based process, we were able to extract substantial amounts of highly pure Si nanomaterials (mainly SiNWs and Si nanospheres (SiNSs)). While the purified SiNWs were found to have typical outer diameters in the 10-15 nm range and lengths of up to several μm, the SiNSs have external diameters in the 10-100 nm range. Interestingly, the SiNWs are found to have a thinner Si core (2-5 nm diam.) and an outer silicon oxide shell (with a typical thickness of ∼5-10 nm). High resolution transmission electron microscopy (HRTEM) observations revealed that many SiNWs have a continuous cylindrical core, whereas others feature a discontinuous core consisting of a chain of Si nanocrystals forming a sort of 'chaplet-like' structures. These plasma-torch-produced SiNWs are highly pure with no trace of any metal catalyst, suggesting that they mostly form through SiO-catalyzed growth scheme rather than from metal-catalyzed path. The extracted Si nanostructures are shown to exhibit a strong photoluminescence (PL) which is found to blue-shift from 950 to 680 nm as the core size of the Si nanostructures decreases from ∼5 to ∼3 nm. This near IR-visible PL is shown to originate from quantum confinement (QC) in Si nanostructures. Consistently, the sizes of the Si nanocrystals directly determined from HRTEM images corroborate well with those expected by QC theory.

Structural and photoluminescence properties of silicon nanowires extracted by means of a centrifugation process from plasma torch synthesized silicon nanopowder

NASA Astrophysics Data System (ADS)

Le Borgne, Vincent; Agati, Marta; Boninelli, Simona; Castrucci, Paola; De Crescenzi, Maurizio; Dolbec, Richard; El Khakani, My Ali

2017-07-01

We report on a method for the extraction of silicon nanowires (SiNWs) from the by-product of a plasma torch based spheroidization process of silicon. This by-product is a nanopowder which consists of a mixture of SiNWs and silicon particles. By optimizing a centrifugation based process, we were able to extract substantial amounts of highly pure Si nanomaterials (mainly SiNWs and Si nanospheres (SiNSs)). While the purified SiNWs were found to have typical outer diameters in the 10-15 nm range and lengths of up to several μm, the SiNSs have external diameters in the 10-100 nm range. Interestingly, the SiNWs are found to have a thinner Si core (2-5 nm diam.) and an outer silicon oxide shell (with a typical thickness of ˜5-10 nm). High resolution transmission electron microscopy (HRTEM) observations revealed that many SiNWs have a continuous cylindrical core, whereas others feature a discontinuous core consisting of a chain of Si nanocrystals forming a sort of ‘chaplet-like’ structures. These plasma-torch-produced SiNWs are highly pure with no trace of any metal catalyst, suggesting that they mostly form through SiO-catalyzed growth scheme rather than from metal-catalyzed path. The extracted Si nanostructures are shown to exhibit a strong photoluminescence (PL) which is found to blue-shift from 950 to 680 nm as the core size of the Si nanostructures decreases from ˜5 to ˜3 nm. This near IR-visible PL is shown to originate from quantum confinement (QC) in Si nanostructures. Consistently, the sizes of the Si nanocrystals directly determined from HRTEM images corroborate well with those expected by QC theory.

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

Orfield, Noah J.; McBride, James R.; Wang, Feng

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging,more » rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.« less

Synthesis of Polyvinylpyrrolidone (PVP)-Green Tea Extract Composite Nanostructures using Electrohydrodynamic Spraying Technique

NASA Astrophysics Data System (ADS)

Kamaruddin; Edikresnha, D.; Sriyanti, I.; Munir, M. M.; Khairurrijal

2017-05-01

Green Tea Extract (GTE) as an active substance has successfully loaded to PVP nanostructures using electrohydrodynamic spraying technique. The precursor solution was the mixture of ethanolic polyvinylpyrrolidone (PVP) with a molecular weight of 1,300 kg/mol and ethanolic GTE solutions at a weight concentration of 4 wt.% and 2 wt.%, respectively, and it was estimated that the entanglement number was 2. The electrospraying was conducted at the voltage of 15 kV, the flow rate of 10 µL/min., and the distance between the collector and the tip of the nozzle of 10 cm. The SEM images showed that the PVP/GTE nanostructures had a combination of agglomerated beads (less spherical particles) and nanofibers. This occurred because if the PVP concentration is low, the PVP/GTE composite has weak core structures that cause the shell to be easily agglomerated each other. The intermolecular interaction between PVP and GTE in the PVP/GTE nanostructures occurred as confirmed by the peak at 3396 cm-1, which is the carboxyl group, proving that the PVP/GTE nanostructures contained water, alcohols, and phenols. The peak at 1040 cm-1, which is the stretching of C-O group in amino acid, gave another proof to the intermolecular interaction.

Si/InGaN core/shell hierarchical nanowire arrays and their photoelectrochemical properties.

PubMed

Hwang, Yun Jeong; Wu, Cheng Hao; Hahn, Chris; Jeong, Hoon Eui; Yang, Peidong

2012-03-14

Three-dimensional hierarchical nanostructures were synthesized by the halide chemical vapor deposition of InGaN nanowires on Si wire arrays. Single phase InGaN nanowires grew vertically on the sidewalls of Si wires and acted as a high surface area photoanode for solar water splitting. Electrochemical measurements showed that the photocurrent density with hierarchical Si/InGaN nanowire arrays increased by 5 times compared to the photocurrent density with InGaN nanowire arrays grown on planar Si (1.23 V vs RHE). High-resolution transmission electron microscopy showed that InGaN nanowires are stable after 15 h of illumination. These measurements show that Si/InGaN hierarchical nanostructures are a viable high surface area electrode geometry for solar water splitting. © 2012 American Chemical Society

Controlled Fabrication of Functional Capsules Based on the Synergistic Interaction between Polyphenols and MOFs under Weak Basic Condition.

PubMed

Wang, Hui; Zhu, Wei; Ping, Yuan; Wang, Chen; Gao, Ning; Yin, Xianpeng; Gu, Chen; Ding, Dan; Brinker, C Jeffrey; Li, Guangtao

2017-04-26

Metal-organic coordination materials with controllable nanostructures are of widespread interest due to the coupled benefits of inorganic/organic building blocks and desired architectures. In this work, based on the finding of a synergistic interaction between metal-organic frameworks (MOFs) and natural polyphenols under weak basic condition, a facile strategy has been developed for directly fabricating diverse phenolic-inspired functional materials or metal-phenolic frameworks (MPFs) with controlled hollow nanostructures (polyhedral core-shell, rattle-like, hollow cage, etc.) and controllable size, morphology, and roughness, as well as composition. By further incorporating the diverse functionalities of polyphenols such as low toxicity and therapeutic properties, catalytic activity, and ability to serve as carbon precursors, into the novel assemblies, diverse artificially designed nanoarchitectures with target functionalities have been generated for an array of applications.

Tunable plasmon-enhanced broadband light harvesting for perovskite solar cells

NASA Astrophysics Data System (ADS)

Que, Meidan; Zhu, Liangliang; Yang, Yawei; Liu, Jie; Chen, Peng; Chen, Wei; Yin, Xingtian; Que, Wenxiu

2018-04-01

In this work, we report a reliable method for synthesizing (Au, Au/Ag core)/(TiO2 shell) nanostructures with their plasmonic wavelengths covering the visible light region for perovskite solar cells. The mono- and bi-metallic core-shell nanoparticles exhibit tunable localized surface plasmon resonance wavelength and function as "light tentacle" to improve the photo-electricity conversion efficiency. Plasmonic nanoparticles with different sizes and shapes, different thicknesses of TiO2 shell and Ag interlayer are found to have a strong influence on the localized surface plasmon resonance enhancement effect. The experimental photovoltaic performance of perovskite solar cells is significantly enhanced when the plasmonic nanoparticles are embedded inmesoporous TiO2 scaffolds. A champion photo-electricity conversion efficiency of 17.85% is achieved with nanoparticles (Au/Ag, λLSPR = 650 nm), giving a 18.7% enhancement over that of the pristine device (15.04%). Finite-difference time-domain simulations show that nanorod Au in mesoporus TiO2 scaffold induces the most intense electromagnetic coupling, and provides a novel emitter for photon flux in mesoporous perovskite solar cells. These theoretical results are consistent with the corresponding experimental those. Thus, enhancing the incident light intensities around 650 nm will be most favorable to the improvement of the photo-electricity conversion efficiency of perovskite solar cells.

Aqueous-Based Fabrication of Low-VOC Nanostructured Block Copolymer Films as Potential Marine Antifouling Coatings.

PubMed

Kim, Kris S; Gunari, Nikhil; MacNeil, Drew; Finlay, John; Callow, Maureen; Callow, James; Walker, Gilbert C

2016-08-10

The ability to fabricate nanostructured films by exploiting the phenomenon of microphase separation has made block copolymers an invaluable tool for a wide array of coating applications. Standard approaches to engineering nanodomains commonly involve the application of organic solvents, either through dissolution or annealing protocols, resulting in the release of volatile organic compounds (VOCs). In this paper, an aqueous-based method of fabricating low-VOC nanostructured block copolymer films is presented. The reported procedure allows for the phase transfer of water insoluble triblock copolymer, poly(styrene-block-2 vinylpyridine-block-ethylene oxide) (PS-b-P2VP-b-PEO), from a water immiscible phase to an aqueous environment with the assistance of a diblock copolymeric phase transfer agent, poly(styrene-block-ethylene oxide) (PS-b-PEO). Phase transfer into the aqueous phase results in self-assembly of PS-b-P2VP-b-PEO into core-shell-corona micelles, which are characterized by dynamic light scattering techniques. The films that result from coating the micellar solution onto Si/SiO2 surfaces exhibit nanoscale features that disrupt the ability of a model foulant, a zoospore of Ulva linza, to settle. The multilayered architecture consists of a pH-responsive P2VP-"shell" which can be stimulated to control the size of these features. The ability of these nanostructured thin films to resist protein adsorption and serve as potential marine antifouling coatings is supported through atomic force microscopy (AFM) and analysis of the settlement of Ulva linza zoospore. Field trials of the surfaces in a natural environment show the inhibition of macrofoulants for 1 month.

Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage.

PubMed

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang; Yuan, Changzhou; Lou, Xiong Wen David

2012-10-02

Metal oxide nanostructures are promising electrode materials for lithium-ion batteries and supercapacitors because of their high specific capacity/capacitance, typically 2-3 times higher than that of the carbon/graphite-based materials. However, their cycling stability and rate performance still can not meet the requirements of practical applications. It is therefore urgent to improve their overall device performance, which depends on not only the development of advanced electrode materials but also in a large part "how to design superior electrode architectures". In the article, we will review recent advances in strategies for advanced metal oxide-based hybrid nanostructure design, with the focus on the binder-free film/array electrodes. These binder-free electrodes, with the integration of unique merits of each component, can provide larger electrochemically active surface area, faster electron transport and superior ion diffusion, thus leading to substantially improved cycling and rate performance. Several recently emerged concepts of using ordered nanostructure arrays, synergetic core-shell structures, nanostructured current collectors, and flexible paper/textile electrodes will be highlighted, pointing out advantages and challenges where appropriate. Some future electrode design trends and directions are also discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multibuilding Block Janus Synthesized by Seed-Mediated Self-Assembly for Enhanced Photothermal Effects and Colored Brownian Motion in an Optical Trap.

PubMed

Sansanaphongpricha, Kanokwan; DeSantis, Michael C; Chen, Hongwei; Cheng, Wei; Sun, Kai; Wen, Bo; Sun, Duxin

2017-02-01

The asymmetrical features and unique properties of multibuilding block Janus nanostructures (JNSs) provide superior functions for biomedical applications. However, their production process is very challenging. This problem has hampered the progress of JNS research and the exploration of their applications. In this study, an asymmetrical multibuilding block gold/iron oxide JNS has been generated to enhance photothermal effects and display colored Brownian motion in an optical trap. JNS is formed by seed-mediated self-assembly of nanoparticle-loaded thermocleavable micelles, where the hydrophobic backbones of the polymer are disrupted at high temperatures, resulting in secondary self-assembly and structural rearrangement. The JNS significantly enhances photothermal effects compared to their homogeneous counterpart after near-infrared (NIR) light irradiation. The asymmetrical distribution of gold and iron oxide within JNS also generates uneven thermophoretic force to display active colored Brownian rotational motion in a single-beam gradient optical trap. These properties indicate that the asymmetrical JNS could be employed as a strong photothermal therapy mediator and a fuel-free nanoscale Janus motor under NIR light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mimosa Origami: A nanostructure-enabled directional self-organization regime of materials

PubMed Central

Wong, William S. Y.; Li, Minfei; Nisbet, David R.; Craig, Vincent S. J.; Wang, Zuankai; Tricoli, Antonio

2016-01-01

One of the innate fundamentals of living systems is their ability to respond toward distinct stimuli by various self-organization behaviors. Despite extensive progress, the engineering of spontaneous motion in man-made inorganic materials still lacks the directionality and scale observed in nature. We report the directional self-organization of soft materials into three-dimensional geometries by the rapid propagation of a folding stimulus along a predetermined path. We engineer a unique Janus bilayer architecture with superior chemical and mechanical properties that enables the efficient transformation of surface energy into directional kinetic and elastic energies. This Janus bilayer can respond to pinpoint water stimuli by a rapid, several-centimeters-long self-assembly that is reminiscent of the Mimosa pudica’s leaflet folding. The Janus bilayers also shuttle water at flow rates up to two orders of magnitude higher than traditional wicking-based devices, reaching velocities of 8 cm/s and flow rates of 4.7 μl/s. This self-organization regime enables the ease of fabricating curved, bent, and split flexible channels with lengths greater than 10 cm, demonstrating immense potential for microfluidics, biosensors, and water purification applications. PMID:28861471

Mimosa Origami: A nanostructure-enabled directional self-organization regime of materials.

PubMed

Wong, William S Y; Li, Minfei; Nisbet, David R; Craig, Vincent S J; Wang, Zuankai; Tricoli, Antonio

2016-06-01

One of the innate fundamentals of living systems is their ability to respond toward distinct stimuli by various self-organization behaviors. Despite extensive progress, the engineering of spontaneous motion in man-made inorganic materials still lacks the directionality and scale observed in nature. We report the directional self-organization of soft materials into three-dimensional geometries by the rapid propagation of a folding stimulus along a predetermined path. We engineer a unique Janus bilayer architecture with superior chemical and mechanical properties that enables the efficient transformation of surface energy into directional kinetic and elastic energies. This Janus bilayer can respond to pinpoint water stimuli by a rapid, several-centimeters-long self-assembly that is reminiscent of the Mimosa pudica 's leaflet folding. The Janus bilayers also shuttle water at flow rates up to two orders of magnitude higher than traditional wicking-based devices, reaching velocities of 8 cm/s and flow rates of 4.7 μl/s. This self-organization regime enables the ease of fabricating curved, bent, and split flexible channels with lengths greater than 10 cm, demonstrating immense potential for microfluidics, biosensors, and water purification applications.

Core–shell PdPb@Pd aerogels with multiply-twinned intermetallic nanostructures: facile synthesis with accelerated gelation kinetics and their enhanced electrocatalytic properties

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

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang

Delicately engineering the well-defined noble metal aerogels with favorable structural and compositional features is of vital importance for wide applications. Here, we reported one-pot and facile method for synthesizing core-shell PdPb@Pd hydrogels/aerogels with multiply-twinned grains and ordered intermetallic phase using sodium hypophosphite as a multifunctional reducing agent. Due to the accelerated gelation kinetics induced by increased reaction temperature and specific function of sodium hypophosphite, the formation of hydrogels can be completed within 4 hrs, far faster than the previous reports. Owe to their unique porous structure and favorable geometric and electronic effects, the optimized PdPb@Pd aerogels exhibit enhanced electrochemical performancemore » towards ethylene glycol oxidation with a mass activity of 5.8 times higher than Pd black.Core–shell PdPb@Pd aerogels with multiply-twinned grains and an ordered intermetallic phase was synthesized, which exhibited good electrocatalytic activity towards ethanol oxidation.« less

Enhanced carrier multiplication in engineered quasi-type-II quantum dots

PubMed Central

Cirloganu, Claudiu M.; Padilha, Lazaro A.; Lin, Qianglu; Makarov, Nikolay S.; Velizhanin, Kirill A.; Luo, Hongmei; Robel, Istvan; Pietryga, Jeffrey M.; Klimov, Victor I.

2014-01-01

One process limiting the performance of solar cells is rapid cooling (thermalization) of hot carriers generated by higher-energy solar photons. In principle, the thermalization losses can be reduced by converting the kinetic energy of energetic carriers into additional electron-hole pairs via carrier multiplication (CM). While being inefficient in bulk semiconductors this process is enhanced in quantum dots, although not sufficiently high to considerably boost the power output of practical devices. Here we demonstrate that thick-shell PbSe/CdSe nanostructures can show almost a fourfold increase in the CM yield over conventional PbSe quantum dots, accompanied by a considerable reduction of the CM threshold. These structures enhance a valence-band CM channel due to effective capture of energetic holes into long-lived shell-localized states. The attainment of the regime of slowed cooling responsible for CM enhancement is indicated by the development of shell-related emission in the visible observed simultaneously with infrared emission from the core. PMID:24938462

Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

DOE PAGES

Strickler, Alaina L.; Jackson, Ariel; Jaramillo, Thomas F.

2016-12-28

Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specificmore » and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.« less

Photoswitchable Janus glycodendrimer micelles as multivalent inhibitors of LecA and LecB from Pseudomonas aeruginosa.

PubMed

Hu, Yingxue; Beshr, Ghamdan; Garvey, Christopher J; Tabor, Rico F; Titz, Alexander; Wilkinson, Brendan L

2017-11-01

The first example of the self-assembly and lectin binding properties of photoswitchable glycodendrimer micelles is reported. Light-addressable micelles were assembled from a library of 12 amphiphilic Janus glycodendrimers composed of variable carbohydrate head groups and hydrophobic tail groups linked to an azobenzene core. Spontaneous association in water gave cylindrical micelles with uniform size distribution as determined by dynamic light scattering (DLS) and small angle neutron scattering (SANS). Trans-cis photoisomerization of the azobenzene dendrimer core was used to probe the self-assembly behaviour and lectin binding properties of cylindrical micelles, revealing moderate-to-potent inhibition of lectins LecA and LecB from Pseudomonas aeruginosa. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Novel synthesis and characterization of Ag@TiO2 core shell nanostructure for non-enzymatic glucose sensor

NASA Astrophysics Data System (ADS)

T, Dayakar; Venkateswara Rao, K.; Vinodkumar, M.; Bikshalu, K.; Chakradhar, B.; Ramachandra Rao, K.

2018-03-01

Ag@TiO2 core-shell nano composite (ATCSNC) were synthesized by using Ocimum tenuiflorum leaves extract through a simple one-step hydrothermal route for Non-enzymatic glucose sensing material. The prepared NCs were characterized and found high crystallinity, red shift absorbance, interface-bonding parameters, rough surface and network like microstructure through XRD, Uv-vis, FTIR, SEM, and TEM. The prepared ATCSNC have been used for fabrication of glassy carbon electrode (GCE) and the same was applied to test its electro catalytic activity of glucose in 0.1 M NaOH. The promising results were recorded for ATCSNC/GCE with a high sensitivity (1968.72 μAm M-1cm-2), wide linear range (1 μM-8.1 mM), good response time (3 s), and excellent low detection limit (0.19 μM, S/N = 3). Furthermore, the designed sensor exhibits admirable stability and reproducibility, as well as attractive achievability for real sample analysis. As such, the proposed ATCSNC could be highly beneficial in the development of sustainable and eco-friendly glucose sensing devices.

Potential effect of CuInS2/ZnS core-shell quantum dots on P3HT/PEDOT:PSS heterostructure based solar cell

NASA Astrophysics Data System (ADS)

Jindal, Shikha; Giripunje, S. M.

2018-07-01

Nanostructured quantum dots (QDs) are quite promising in the solar cell application due to quantum confinement effect. QDs possess multiple exciton generation and large surface area. The environment friendly CuInS2/ZnS core-shell QDs were prepared by solvothermal method. Thus, the 3 nm average sized CuInS2/ZnS QDs were employed in the bulk heterojunction device and the active blend layer consisting of the P3HT and CuInS2/ZnS QDs was investigated. The energy level information of CuInS2/ZnS QDs as an electron acceptor was explored by ultra violet photoelectron spectroscopy. Bulk heterojunction hybrid device of ITO/PEDOT:PSS/P3HT: (CuInS2/ZnS QDs)/ZnO/Ag was designed by spin coating approach and its electrical characterization was investigated by solar simulator. Current density - voltage characteristics shows the enhancement in power conversion efficiency with increasing concentration of CuInS2/ZnS QDs in bulk heterojunction device.

Synthesis of core-shell AlOOH hollow nanospheres by reacting Al nanoparticles with water

NASA Astrophysics Data System (ADS)

Lozhkomoev, A. S.; Glazkova, E. A.; Bakina, O. V.; Lerner, M. I.; Gotman, I.; Gutmanas, E. Y.; Kazantsev, S. O.; Psakhie, S. G.

2016-05-01

A novel route for the synthesis of boehmite nanospheres with a hollow core and the shell composed of highly crumpled AlOOH nanosheets by oxidizing Al nanopowder in pure water under mild processing conditions is described. The stepwise events of Al transformation into boehmite are followed by monitoring the pH in the reaction medium. A mechanism of formation of hollow AlOOH nanospheres with a well-defined shape and crystallinity is proposed which includes the hydration of the Al oxide passivation layer, local corrosion of metallic Al accompanied by hydrogen evolution, the rupture of the protective layer, the dissolution of Al from the particle interior and the deposition of AlOOH nanosheets on the outer surface. In contrast to previously reported methods of boehmite nanoparticle synthesis, the proposed method is simple, and environmentally friendly and allows the generation of hydrogen gas as a by-product. Due to their high surface area and high, slit-shaped nanoporosity, the synthesized AlOOH nanostructures hold promise for the development of more effective catalysts, adsorbents, vaccines and drug carriers.

Nanostructured Silica/Gold-Cellulose-Bonded Amino-POSS Hybrid Composite via Sol-Gel Process and Its Properties.

PubMed

Ramesh, Sivalingam; Kim, Heung Soo; Lee, Young-Jun; Hong, Gwang-Wook; Kim, Joo-Hyung

2017-12-01

It is demonstrated in this paper that silica nanoparticles coated with core/shell gold provide efficient thermal, optical, and morphological properties with respect to the cellulose-polyhedral oligomeric silsesquioxanes (POSS) hybrid system. The one-step synthesis of a silica/gold nanocomposite is achieved with a simultaneous hydrolysis and reduction of gold chloride in the presence of formic acid, and the trimethoxysilane group acts as a silica precursor. The focus here comprises the synthesis of cellulose-POSS and silica/gold hybrid nanocomposites using the following two methods: (1) an in situ sol-gel process and (2) a polyvinyl alcohol/tetrakis (hydroxymethyl)phosphonium chloride process. Accordingly, the silica/gold core/shell nanoparticles are synthesized. The growth and attachment of the gold nanoparticles onto the functionalized surface of the silica at the nanometer scale is achieved via both the sol-gel and the tetrakis (hydroxymethyl) phosphonium chloride processes. The cellulose-POSS-silica/gold nanocomposites are characterized according to Fourier transformed infrared spectroscopy, Raman, X-ray diffraction, UV, photoluminescence, SEM, energy-dispersive X-ray spectroscopy, TEM, thermogravimetric, and Brunauer-Emmett-Teller analyses.

Nanostructured Silica/Gold-Cellulose-Bonded Amino-POSS Hybrid Composite via Sol-Gel Process and Its Properties

NASA Astrophysics Data System (ADS)

Ramesh, Sivalingam; Kim, Heung Soo; Lee, Young-June; Hong, Gwang-Wook; Kim, Joo-Hyung

2017-06-01

It is demonstrated in this paper that silica nanoparticles coated with core/shell gold provide efficient thermal, optical, and morphological properties with respect to the cellulose-polyhedral oligomeric silsesquioxanes (POSS) hybrid system. The one-step synthesis of a silica/gold nanocomposite is achieved with a simultaneous hydrolysis and reduction of gold chloride in the presence of formic acid, and the trimethoxysilane group acts as a silica precursor. The focus here comprises the synthesis of cellulose-POSS and silica/gold hybrid nanocomposites using the following two methods: (1) an in situ sol-gel process and (2) a polyvinyl alcohol/tetrakis (hydroxymethyl)phosphonium chloride process. Accordingly, the silica/gold core/shell nanoparticles are synthesized. The growth and attachment of the gold nanoparticles onto the functionalized surface of the silica at the nanometer scale is achieved via both the sol-gel and the tetrakis (hydroxymethyl) phosphonium chloride processes. The cellulose-POSS-silica/gold nanocomposites are characterized according to Fourier transformed infrared spectroscopy, Raman, X-ray diffraction, UV, photoluminescence, SEM, energy-dispersive X-ray spectroscopy, TEM, thermogravimetric, and Brunauer-Emmett-Teller analyses.

Synthesis of superparamagnetic silica-coated magnetite nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Kaur, Navjot; Chudasama, Bhupendra

2015-05-01

Multifunctional superparamagnetic iron oxide nanoparticles (SPIONs) coated with silica are widely researched for biomedical applications such as magnetic resonance imaging, tissue repair, cell separation, hyperthermia, drug delivery, etc. In this article synthesis of magnetite (Fe3O4) nanoparticles and their coating with SiO2 is reported. Fe3O4 nanoparticles were synthesized by chemical co-precipitation and it was coated with silica by hydrolysis and condensation of tetraethylorthosilicate. XRD, FTIR, TEM and VSM techniques were used to characterize bare and coated nanoparticles. Results indicated that the average size of SPIONS was 8.4 nm. X-ray diffraction patterns of silica coated SPIONS were identical to that of SPIONS confirming the inner spinal structure of SPIONS. FTIR results confirmed the binding of silica with the magnetite and the formation of the silica shell around the magnetite core. Magnetic properties of SPIONS and silica coated SPIONS are determined by VSM. They are superparamagnetic. The major conclusion drawn from this study is that the synthesis route yields stable, non-aggregated magnetite-silica core-shell nanostructures with tailored morphology and excellent magnetic properties.

Electrostatics-driven assembly of uni-lamellar catanionic facetted vesicles

NASA Astrophysics Data System (ADS)

Leung, Cheuk-Yui; Palmer, Liam; Kewalramani, Sumit; Sknepnek, Rastko; Vernizzi, Graziano; Greenfield, Megan; Stupp, Samuel; Bedzyk, Michael; Olvera de La Cruz, Monica

2012-02-01

Nature utilizes shape to generate function. Organelle and halophilic bacteria wall envelopes, for example, adopt various polyhedral shapes to compartmentalize matter. The origin of these shapes is unknown. A large variety of shell geometries, either fully faceted polyhedra or mixed Janus-like vesicles with faceted and curved domains that resemble cellular shells can be generated by coassembling water-insoluble anionic (--1) amphiphiles with high valence cationic (+2 and +3) amphiphiles. Electron microscopy, X-ray scattering, theory and simulations demonstrate that the resulting faceted ionic shells are crystalline, and stable at high salt concentrations. The crystallization of the co-assembled single tail amphiphiles is induced by ionic correlations, and modified by the solution pH. This work promotes the design of faceted shapes for various applications and improves our understanding of the origin of polyhedral shells in nature.

Effective Infiltration of Gel Polymer Electrolyte into Silicon-Coated Vertically Aligned Carbon Nanofibers as Anodes for Solid-State Lithium-Ion Batteries.

PubMed

Pandey, Gaind P; Klankowski, Steven A; Li, Yonghui; Sun, Xiuzhi Susan; Wu, Judy; Rojeski, Ronald A; Li, Jun

2015-09-23

This study demonstrates the full infiltration of gel polymer electrolyte into silicon-coated vertically aligned carbon nanofibers (Si-VACNFs), a high-capacity 3D nanostructured anode, and the electrochemical characterization of its properties as an effective electrolyte/separator for future all-solid-state lithium-ion batteries. Two fabrication methods have been employed to form a stable interface between the gel polymer electrolyte and the Si-VACNF anode. In the first method, the drop-casted gel polymer electrolyte is able to fully infiltrate into the open space between the vertically aligned core-shell nanofibers and encapsulate/stabilize each individual nanofiber in the polymer matrix. The 3D nanostructured Si-VACNF anode shows a very high capacity of 3450 mAh g(-1) at C/10.5 (or 0.36 A g(-1)) rate and 1732 mAh g(-1) at 1C (or 3.8 A g(-1)) rate. In the second method, a preformed gel electrolyte film is sandwiched between an Si-VACNF electrode and a Li foil to form a half-cell. Most of the vertical core-shell nanofibers of the Si-VACNF anode are able to penetrate into the gel polymer film while retaining their structural integrity. The slightly lower capacity of 2800 mAh g(-1) at C/11 rate and ∼1070 mAh g(-1) at C/1.5 (or 2.6 A g(-1)) rate have been obtained, with almost no capacity fade for up to 100 cycles. Electrochemical impedance spectroscopy does not show noticeable changes after 110 cycles, further revealing the stable interface between the gel polymer electrolyte and the Si-VACNFs anode. These results show that the infiltrated flexible gel polymer electrolyte can effectively accommodate the stress/strain of the Si shell due to the large volume expansion/contraction during the charge-discharge processes, which is particularly useful for developing future flexible solid-state lithium-ion batteries incorporating Si-anodes.

Simulation of the Impact of Si Shell Thickness on the Performance of Si-Coated Vertically Aligned Carbon Nanofiber as Li-Ion Battery Anode

PubMed Central

Das, Susobhan; Li, Jun; Hui, Rongqing

2015-01-01

Micro- and nano-structured electrodes have the potential to improve the performance of Li-ion batteries by increasing the surface area of the electrode and reducing the diffusion distance required by the charged carriers. We report the numerical simulation of Lithium-ion batteries with the anode made of core-shell heterostructures of silicon-coated carbon nanofibers. We show that the energy capacity can be significantly improved by reducing the thickness of the silicon anode to the dimension comparable or less than the Li-ion diffusion length inside silicon. The results of simulation indicate that the contraction of the silicon electrode thickness during the battery discharge process commonly found in experiments also plays a major role in the increase of the energy capacity. PMID:28347120

Thermoelectric-pyroelectric hybrid energy generation from thermopower waves in core-shell structured carbon nanotube-PZT nanocomposites.

PubMed

Yeo, Taehan; Hwang, Hayoung; Shin, Dongjoon; Seo, Byungseok; Choi, Wonjoon

2017-02-10

There is an urgent need to develop a suitable energy source owing to the rapid development of various innovative devices using micro-nanotechnology. The thermopower wave (TW), which produces a high specific power during the combustion of solid fuel inside micro-nanostructure materials, is a unique energy source for unusual platforms that cannot use conventional energy sources. Here, we report on the significant enhancement of hybrid energy generation of pyroelectrics and thermoelectrics from TWs in carbon nanotube (CNT)-PZT (lead zirconate titanate, P(Z 0.5 -T 0.5 )) composites for the first time. Conventional TWs use only charge carrier transport driven by the temperature gradient along the core materials to produce voltage. In this study, a core-shell structure of CNTs-PZTs was prepared to utilize both the temperature gradient along the core material (thermoelectrics) and the dynamic change in the temperature of the shell structure (pyroelectrics) induced by TWs. The dual mechanism of energy generation in CNT-PZT composites amplified the average peak and duration of the voltage up to 403 mV and 612 ms, respectively, by a factor of 2 and 60 times those for the composites without a PZT layer. Furthermore, dynamic voltage measurements and structural analysis in repetitive TWs confirmed that CNT-PZT composites maintain the original performance in multiple TWs, which improves the reusability of materials. The advanced TWs obtained by the application of a PZT layer as a pyroelectric material contributes to the extension of the usable energy portion as well as the development of TW-based operating devices.

Flow chemistry to control the synthesis of nano and microparticles for biomedical applications.

PubMed

Hassan, Natalia; Oyarzun-Ampuero, Felipe; Lara, Pablo; Guerrero, Simón; Cabuil, Valérie; Abou-Hassan, Ali; Kogan, Marcelo J

2014-03-01

In this article we review the flow chemistry methodologies for the controlled synthesis of different kind of nano and microparticles for biomedical applications. Injection mechanism has emerged as new alternative for the synthesis of nanoparticles due to this strategy allows achieving superior levels of control of self-assemblies, leading to higher-ordered structures and rapid chemical reactions. Self-assembly events are strongly dependent on factors such as the local concentration of reagents, the mixing rates, and the shear forces, which can be finely tuned, as an example, in a microfluidic device. Injection methods have also proved to be optimal to elaborate microsystems comprising polymer solutions. Concretely, extrusion based methods can provide controlled fluid transport, rapid chemical reactions, and cost-saving advantages over conventional reactors. We provide an update of synthesis of nano and microparticles such as core/shell, Janus, nanocrystals, liposomes, and biopolymeric microgels through flow chemistry, its potential bioapplications and future challenges in this field are discussed.

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.

Preparation and electrochemical characteristics of porous hollow spheres of NiO nanosheets as electrodes of supercapacitors

NASA Astrophysics Data System (ADS)

Yu, Wei; Jiang, Xinbing; Ding, Shujiang; Li, Ben Q.

2014-06-01

Porous hollow nanospheres (or spherical shells) made of NiO nanosheets are synthesized and tested for the electrochemical performance of the electrodes made of these materials for supercapacitors. Preparation of the NiO sheet hollow spheres starts with synthesis of polystyrene nanospheres with carboxyl groups (CPS), followed by a two-step activation procedure and the subsequent nucleation and growth by electroless deposition of Ni on the CPS core to obtain CPS@Ni core-shell nanoparticles. The CPS core is eliminated and metallic Ni nanoshell is converted into NiO by calcinations at high temperatures. The material properties of as-prepared hollow NiO nanospheres are characterized by TEM, XRD and N2-absorption measurements. The electrochemical characteristics of the electrodes made of these nanostructured NiO materials are determined by the CV and galvanostatic measurements. These electrochemical tests indicate that electrodes made of the NiO nanosheet hollow spheres exhibit an improved reversible capacitance of 600 F g-1 after 1000 cycles at a high current density of 10 A g-1. It is believed that the good electrochemical performance of these electrodes is attributed to the improved OH- transport in the porous network structures associated with the hollow spheres of randomly oriented NiO nanosheets.

Uniform Fe3O4 coating on flower-like ZnO nanostructures by atomic layer deposition for electromagnetic wave absorption.

PubMed

Wan, Gengping; Wang, Guizhen; Huang, Xianqin; Zhao, Haonan; Li, Xinyue; Wang, Kan; Yu, Lei; Peng, Xiange; Qin, Yong

2015-11-21

An elegant atomic layer deposition (ALD) method has been employed for controllable preparation of a uniform Fe3O4-coated ZnO (ZnO@Fe3O4) core-shell flower-like nanostructure. The Fe3O4 coating thickness of the ZnO@Fe3O4 nanostructure can be tuned by varying the cycle number of ALD Fe2O3. When serving as additives for microwave absorption, the ZnO@Fe3O4-paraffin composites exhibit a higher absorption capacity than the ZnO-paraffin composites. For ZnO@500-Fe3O4, the effective absorption bandwidth below -10 dB can reach 5.2 GHz and the RL values below -20 dB also cover a wide frequency range of 11.6-14.2 GHz when the coating thickness is 2.3 mm, suggesting its potential application in the treatment of the electromagnetic pollution problem. On the basis of experimental observations, a mechanism has been proposed to understand the enhanced microwave absorption properties of the ZnO@Fe3O4 composites.

Insight into induced charges at metal surfaces and biointerfaces using a polarizable Lennard-Jones potential.

PubMed

Geada, Isidro Lorenzo; Ramezani-Dakhel, Hadi; Jamil, Tariq; Sulpizi, Marialore; Heinz, Hendrik

2018-02-19

Metallic nanostructures have become popular for applications in therapeutics, catalysts, imaging, and gene delivery. Molecular dynamics simulations are gaining influence to predict nanostructure assembly and performance; however, instantaneous polarization effects due to induced charges in the free electron gas are not routinely included. Here we present a simple, compatible, and accurate polarizable potential for gold that consists of a Lennard-Jones potential and a harmonically coupled core-shell charge pair for every metal atom. The model reproduces the classical image potential of adsorbed ions as well as surface, bulk, and aqueous interfacial properties in excellent agreement with experiment. Induced charges affect the adsorption of ions onto gold surfaces in the gas phase at a strength similar to chemical bonds while ions and charged peptides in solution are influenced at a strength similar to intermolecular bonds. The proposed model can be applied to complex gold interfaces, electrode processes, and extended to other metals.

Janus and Strawberry-like Particles from Azo Molecular Glass and Polydimethylsiloxane Oligomer.

PubMed

Hsu, Chungen; Du, Yi; Wang, Xiaogong

2017-10-10

This study investigated Janus and strawberry-like particles composed of azo molecular glass and polydimethylsiloxane (PDMS) oligomer, focusing on controllable fabrication and formation mechanism of these unique structures and morphologies. Two materials, the azo molecular glass (IA-Chol) and PDMS oligomer (H 2 pdca-PDMS), were prepared for this purpose. The Janus and strawberry-like particles were obtained from the droplets of a dichloromethane (DCM) solution containing both IA-Chol and H 2 pdca-PDMS, dispersed in water and stabilized by poly(vinyl alcohol). Results show that the structured particles are formed through segregation between the two components induced by gradual evaporation of DCM from the droplets, which is controlled by adding ethylene glycol (EG) into the above dispersion. Without the addition of EG, Janus particles are formed through the full segregation of the two components in the droplets. On the other hand, with the existence of EG in the dispersion, strawberry-like particles instead of Janus particles are formed in the phase separation process. The diffusion of EG molecules from the dispersion medium into the droplets causes the PDMS phase deswelling in the interfacial area due to the poor solvent effect. Caused by the surface coagulation, the coalescence of the isolated IA-Chol domains is jammed in the shell region, which results in the formation of the strawberry-like particles. For the particles separated from the dispersion and dried, the PDMS oligomer phase of the Janus particles can adhere and spread on the substrate to form unique "particle-on-pad" morphology due to its low surface energy and swelling ability, while the strawberry-like particles exist as "standstill" objects on the substrates. Upon irradiation with a linearly polarized laser beam at 488 nm, the azo molecular glass parts in the particles are significantly deformed along the light polarization direction, which show unique and distinct morphologies for these two types of the particles.

Enhanced Photoelectrochemical Behavior of H-TiO2 Nanorods Hydrogenated by Controlled and Local Rapid Thermal Annealing.

PubMed

Wang, Xiaodan; Estradé, Sonia; Lin, Yuanjing; Yu, Feng; Lopez-Conesa, Lluis; Zhou, Hao; Gurram, Sanjeev Kumar; Peiró, Francesca; Fan, Zhiyong; Shen, Hao; Schaefer, Lothar; Braeuer, Guenter; Waag, Andreas

2017-12-01

Recently, colored H-doped TiO 2 (H-TiO 2 ) has demonstrated enhanced photoelectrochemical (PEC) performance due to its unique crystalline core-disordered shell nanostructures and consequent enhanced conduction behaviors between the core-shell homo-interfaces. Although various hydrogenation approaches to obtain H-TiO 2 have been developed, such as high temperature hydrogen furnace tube annealing, high pressure hydrogen annealing, hydrogen-plasma assisted reaction, aluminum reduction and electrochemical reduction etc., there is still a lack of a hydrogenation approach in a controlled manner where all processing parameters (temperature, time and hydrogen flux) were precisely controlled in order to improve the PEC performance of H-TiO 2 and understand the physical insight of enhanced PEC performance. Here, we report for the first time a controlled and local rapid thermal annealing (RTA) approach to prepare hydrogenated core-shell H-TiO 2 nanorods grown on F:SnO 2 (FTO) substrate in order to address the degradation issue of FTO in the typical TiO 2 nanorods/FTO system observed in the conventional non-RTA treated approaches. Without the FTO degradation in the RTA approach, we systematically studied the intrinsic relationship between the annealing temperature, structural, optical, and photoelectrochemical properties in order to understand the role of the disordered shell on the improved photoelectrochemical behavior of H-TiO 2 nanorods. Our investigation shows that the improvement of PEC performance could be attributed to (i) band gap narrowing from 3.0 to 2.9 eV; (ii) improved optical absorption in the visible range induced by the three-dimensional (3D) morphology and rough surface of the disordered shell; (iii) increased proper donor density; (iv) enhanced electron-hole separation and injection efficiency due to the formation of disordered shell after hydrogenation. The RTA approach developed here can be used as a suitable hydrogenation process for TiO 2 nanorods/FTO system for important applications such as photocatalysis, hydrogen generation from water splitting and solar energy conversion.

In-situ laser-induced synthesis of associated YVO4:Eu3+@SiO2@Au-Ag/C nanohybrids with enhanced luminescence

NASA Astrophysics Data System (ADS)

Kolesnikov, I. E.; lvanova, T. Yu.; Ivanov, D. A.; Kireev, A. A.; Mamonova, D. V.; Golyeva, E. V.; Mikhailov, M. D.; Manshina, A. A.

2018-02-01

Associated luminescence/plasmonic nanoparticles were prepared in a single step process as a result of laser illumination (low intensity CW He-Cd laser) of colloidal solution of YVO4:Eu3+@SiO2 mixed with heterometallic supramolecular complex. The results of SEM-EDX analysis, absorption, steady-state luminescence and luminescence decay measurements revealed formation of associated nanohybrids with core/shell morphology. The obtained nanostructures demonstrated metal enhanced luminescence with enhancement factor of 1.6. The theoretical calculations revealed strong correlation of enhancement factor and plasmonic nanoparticles number.

Martensitic transformations in Ag-Au bimetallic core-shell nanoalloys

NASA Astrophysics Data System (ADS)

Chen, Fuyi; Johnston, Roy L.

2008-01-01

Combining the Gupta potential and bond order analysis in a molecular dynamics simulation, a martensitic transformation is observed in the 147-atom AucoreAgshell nanostructure at 328K. The response time for this transformation is about 7ps at 350K. In pure gold clusters, it was previously thought that a similar solid-to-solid transformation is a prelude to melting transitions. In the present case, atomic pathway snapshots show that the heating energy is used to overcome the energy barrier for initiating the spontaneous process. The subsequent twist-deformation propagation and termination are clearly observed.

SiC Nanowires Synthesized by Rapidly Heating a Mixture of SiO and Arc-Discharge Plasma Pretreated Carbon Black.

PubMed

Wang, Feng-Lei; Zhang, Li-Ying; Zhang, Ya-Fei

2008-11-22

SiC nanowires have been synthesized at 1,600 degrees C by using a simple and low-cost method in a high-frequency induction furnace. The commercial SiO powder and the arc-discharge plasma pretreated carbon black were mixed and used as the source materials. The heating-up and reaction time is less than half an hour. It was found that most of the nanowires have core-shell SiC/SiO(2) nanostructures. The nucleation, precipitation, and growth processes were discussed in terms of the oxide-assisted cluster-solid mechanism.

Visible photoelectrochemical water splitting into H 2 and O 2 in a dye-sensitized photoelectrosynthesis cell

DOE PAGES

Alibabaei, Leila; Sherman, Benjamin D.; Norris, Michael R.; ...

2015-04-27

A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO 2/TiO 2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO 3H 2) 2bpy) 2Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH 2)] 4+ ([RuaII-RubII-OH 2] 4+, combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO 2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al 2O 3 or TiO 2 overlayers. Illumination of the resulting fluorine-dopedmore » tin oxide (FTO)|SnO 2/TiO 2|-[Ru a II-Ru b II-OH 2] 4+(Al 2O 3 or TiO 2) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H 2 and O 2. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO 2/TiO 2 core/shell compared with nanoITO/TiO 2 with the same assembly results in photocurrent enhancements of ~5. In conclusion, systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm 2 with 445-nm, ~90-mW/cm 2 illumination in a phosphate buffer at pH 7.« less

Dendritic Core-Frame and Frame Multimetallic Rhombic Dodecahedra: A Comparison Study of Composition and Structure Effects on Electrocatalysis of Methanol Oxidation

DOE PAGES

Mathurin, Leanne E.; Tao, Jing; Xin, Huolin; ...

2017-11-03

The composition and structure of multimetallic nanostructures can be tailored to enhance electrocatalytic properties. This work reports a seed-mediated synthesis of novel multimetallic dendritic core-frame and frame nanostructures with a rhombic dodecahedral shape for enhanced methanol oxidation reaction (MOR). The synthesis involves in situ formation of Cu seeds and the subsequent selective deposition of Pt and Ru on the edges and vertices of the Cu seeds to generate CuPt and CuPtRu dendritic core-frame nanostructures. The core-frame nanostructures undergo a post acetic acid etching process to form the frame nanostructures. While transmission electron microscopy reveals the morphology and elemental distribution ofmore » the nanostructures, X-ray diffraction patterns confirm the alloy compositions of dendritic frames for both the core-frame and frame nanostructures. Compared to the bimetallic CuPt nanostructures, the trimetallic CuPtRu nanostructures lower the onset potential and completely suppress the peak current in the reverse scan for MOR. The CuPtRu alloyed frame nanostructures are the best to prevent Ru leaching compared to the CuPtRu core-frame nanostructures and PtRu catalysts. X-ray photoelectron spectroscopy reveals that all three elements become more electron rich in the frame nanostructures. Thus, further refining the composition ratio of the CuPtRu alloyed dendritic frame nanostructures can lead to more efficient catalysts at a lower cost for MOR.« less

Dendritic Core-Frame and Frame Multimetallic Rhombic Dodecahedra: A Comparison Study of Composition and Structure Effects on Electrocatalysis of Methanol Oxidation

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

Mathurin, Leanne E.; Tao, Jing; Xin, Huolin

The composition and structure of multimetallic nanostructures can be tailored to enhance electrocatalytic properties. This work reports a seed-mediated synthesis of novel multimetallic dendritic core-frame and frame nanostructures with a rhombic dodecahedral shape for enhanced methanol oxidation reaction (MOR). The synthesis involves in situ formation of Cu seeds and the subsequent selective deposition of Pt and Ru on the edges and vertices of the Cu seeds to generate CuPt and CuPtRu dendritic core-frame nanostructures. The core-frame nanostructures undergo a post acetic acid etching process to form the frame nanostructures. While transmission electron microscopy reveals the morphology and elemental distribution ofmore » the nanostructures, X-ray diffraction patterns confirm the alloy compositions of dendritic frames for both the core-frame and frame nanostructures. Compared to the bimetallic CuPt nanostructures, the trimetallic CuPtRu nanostructures lower the onset potential and completely suppress the peak current in the reverse scan for MOR. The CuPtRu alloyed frame nanostructures are the best to prevent Ru leaching compared to the CuPtRu core-frame nanostructures and PtRu catalysts. X-ray photoelectron spectroscopy reveals that all three elements become more electron rich in the frame nanostructures. Thus, further refining the composition ratio of the CuPtRu alloyed dendritic frame nanostructures can lead to more efficient catalysts at a lower cost for MOR.« less

Integrative self-assembly of functional hybrid nanoconstructs by inorganic wrapping of single biomolecules, biomolecule arrays and organic supramolecular assemblies

NASA Astrophysics Data System (ADS)

Patil, Avinash J.; Li, Mei; Mann, Stephen

2013-07-01

Synthesis of functional hybrid nanoscale objects has been a core focus of the rapidly progressing field of nanomaterials science. In particular, there has been significant interest in the integration of evolutionally optimized biological systems such as proteins, DNA, virus particles and cells with functional inorganic building blocks to construct mesoscopic architectures and nanostructured materials. However, in many cases the fragile nature of the biomolecules seriously constrains their potential applications. As a consequence, there is an on-going quest for the development of novel strategies to modulate the thermal and chemical stabilities, and performance of biomolecules under adverse conditions. This feature article highlights new methods of ``inorganic molecular wrapping'' of single or multiple protein molecules, individual double-stranded DNA helices, lipid bilayer vesicles and self-assembled organic dye superstructures using inorganic building blocks to produce bio-inorganic nanoconstructs with core-shell type structures. We show that spatial isolation of the functional biological nanostructures as ``armour-plated'' enzyme molecules or polynucleotide strands not only maintains their intact structure and biochemical properties, but also enables the fabrication of novel hybrid nanomaterials for potential applications in diverse areas of bionanotechnology.

Integrative self-assembly of functional hybrid nanoconstructs by inorganic wrapping of single biomolecules, biomolecule arrays and organic supramolecular assemblies.

PubMed

Patil, Avinash J; Li, Mei; Mann, Stephen

2013-08-21

Synthesis of functional hybrid nanoscale objects has been a core focus of the rapidly progressing field of nanomaterials science. In particular, there has been significant interest in the integration of evolutionally optimized biological systems such as proteins, DNA, virus particles and cells with functional inorganic building blocks to construct mesoscopic architectures and nanostructured materials. However, in many cases the fragile nature of the biomolecules seriously constrains their potential applications. As a consequence, there is an on-going quest for the development of novel strategies to modulate the thermal and chemical stabilities, and performance of biomolecules under adverse conditions. This feature article highlights new methods of "inorganic molecular wrapping" of single or multiple protein molecules, individual double-stranded DNA helices, lipid bilayer vesicles and self-assembled organic dye superstructures using inorganic building blocks to produce bio-inorganic nanoconstructs with core-shell type structures. We show that spatial isolation of the functional biological nanostructures as "armour-plated" enzyme molecules or polynucleotide strands not only maintains their intact structure and biochemical properties, but also enables the fabrication of novel hybrid nanomaterials for potential applications in diverse areas of bionanotechnology.

Quantum Yield Heterogeneity among Single Nonblinking Quantum Dots Revealed by Atomic Structure-Quantum Optics Correlation

DOE PAGES

Orfield, Noah J.; McBride, James R.; Wang, Feng; ...

2016-02-05

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging,more » rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.« less

New Approach to Create TiO2(B)/Carbon Core/Shell Nanotubes: Ideal Structure for Enhanced Lithium Ion Storage.

PubMed

Zhu, Xiaoyi; Yang, Xianfeng; Lv, Chunxiao; Guo, Shaojun; Li, Jianjiang; Zheng, Zhanfeng; Zhu, Huaiyong; Yang, Dongjiang

2016-07-27

To achieve uniform carbon coating on TiO2 nanomaterials, high temperature (>500 °C) annealing treatment is a necessity. However, the annealing treatment inevitably leads to the strong phase transformation from TiO2(B) with high lithium ion storage (LIS) capacity to anatase with low LIS one as well as the damage of nanostructures. Herein, we demonstrate a new approach to create TiO2(B)/carbon core/shell nanotubes (C@TBNTs) using a long-chain silane polymethylhydrosiloxane (PMHS) to bind the TBNTs by forming Si-O-Ti bonds. The key feature of this work is that the introduction of PMHS onto TBNTs can afford TBNTs with very high thermal stability at higher than 700 °C and inhibit the phase transformation from TiO2(B) to anatase. Such a high thermal property of PMHS-TBNTs makes them easily coated with highly graphitic carbon shell via CVD process at 700 °C. The as-prepared C@TBNTs deliver outstanding rate capability and electrochemical stability, i.e., reversible capacity above 250 mAh g(-1) at 10 C and a high specific capacity of 479.2 mAh g(-1) after 1000 cycles at 1 C. As far as we know, the LIS performance of our sample is the highest among the previously reported TiO2(B) anode materials.

Carbon-shell-constrained silicon cluster derived from Al-Si alloy as long-cycling life lithium ion batteries anode

NASA Astrophysics Data System (ADS)

Su, Junming; Zhang, Congcong; Chen, Xiang; Liu, Siyang; Huang, Tao; Yu, Aishui

2018-03-01

Although silicon is the most promising anode material for Li-ion batteries, large volume expansion during lithiation and delithiation is the main obstacle limiting the commercial application of silicon anodes. There are two ways to alleviate volume expansion and prevent further pulverization of a Si anode: fabrication of a rational nanostructure possessing void spaces and uniform distribution of the conducting sites, without a good balance effect in mitigating the limiting factors and enhancing battery performance. In this paper, we propose a novel nanostructure - a carbon-shell-constrained Si cluster (Si/C shell) with both adequate void space and good distribution of electrical contact sites to guarantee homogeneous lithiation in the initial cycle. Benefiting from the ability to maintain electrical conductivity of the outer carbon shell, even after cluster fragmentation, the Si/C shell synthesized from low-cost commercial Al-Si alloy spheres can deliver 0.03% capacity loss from 100th to 1000th cycles at a current density of 1 A g-1. The Si/C shell sample with the dual functional structure mentioned above can also maintain its own nanostructure during cycling and deliver excellent rate performance. It is a concise and scalable strategy which can simplify the preparation of other alloy anode materials for Li-ion batteries.

Gold-Based Magneto/Optical Nanostructures: Challenges for In Vivo Applications in Cancer Diagnostics and Therapy.

PubMed

Melancon, Marites; Lu, Wei; Li, Chun

2009-06-01

Nanoparticles with gold shell and iron core have unique optical and magnetic properties which can be utilized for simultaneous detection and treatment strategies. Several nanoparticles have been synthesized and shown to mediate a variety of potential applications in biomedicine, including cancer molecular optical and magnetic resonance imaging, controlled drug delivery, and photothermal ablation therapy. However, to be effective, these nanoparticles must be delivered efficiently into their targets. In this review, we will provide an updated summary of the gold-shelled magnetic nanoparticles that have been synthesized, methods for characterization, and their potential for cancer diagnosis and treatment. We will also discuss the biological barriers that need to be overcome for the effective delivery of these nanoparticles. The desired nanoparticle characteristics needed to evade these biological barriers were also explained. Hopefully, this review will help researchers in designing nanoparticles by carefully choosing the optimum size, shape, surface charge, and surface coating.

Influences of external vs. core-shell mixing on aerosol optical properties at various relative humidities.

PubMed

Ramachandran, S; Srivastava, Rohit

2013-05-01

Aerosol optical properties of external and core-shell mixtures of aerosol species present in the atmosphere are calculated in this study for different relative humidities. Core-shell Mie calculations are performed using the values of radii, refractive indices and densities of aerosol species that act as core and shell, and the core-shell radius ratio. The single scattering albedo (SSA) is higher when the absorbing species (black carbon, BC) is the core, while for a sulfate core SSA does not vary significantly as the BC in the shell dominates the absorption. Absorption gets enhanced in core-shell mixing of absorbing and scattering aerosols when compared to their external mixture. Thus, SSA is significantly lower for a core-shell mixture than their external mixture. SSA is more sensitive to core-shell ratio than mode radius when BC is the core. The extinction coefficient, SSA and asymmetry parameter are higher for external mixing when compared to BC (core)-water soluble aerosol (shell), and water soluble aerosol (core)-BC (shell) mixtures in the relative humidity range of 0 to 90%. Spectral SSA exhibits the behaviour of the species which acts as a shell in core-shell mixing. The asymmetry parameter for an external mixture of water soluble aerosol and BC is higher than BC (core)-water soluble aerosol (shell) mixing and increases as function of relative humidity. The asymmetry parameter for the water soluble aerosol (core)-BC (shell) is independent of relative humidity as BC is hydrophobic. The asymmetry parameter of the core-shell mixture decreases when BC aerosols are involved in mixing, as the asymmetry parameter of BC is lower. Aerosol optical depth (AOD) of core-shell mixtures increases at a higher rate when the relative humidity exceeds 70% in continental clean and urban aerosol models, whereas AOD remains the same when the relative humidity exceeds 50% in maritime aerosol models. The SSA for continental aerosols varies for core-shell mixing of water soluble aerosol (core)-shell (BC) when compared to their external mixture, while the SSA for maritime aerosols does not vary significantly for different mixing scenarios because of the dominance of sea salt aerosols. Thus, these results confirm that aerosol mixing can modify the physical and optical characteristics of aerosols, which vary as a function of relative humidity. These calculations will be useful in parameterising the effect of core-shell vs. external mixing of aerosols in global climate models, and in the evaluation of aerosol radiative effects.

A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core-Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer

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

Sivanantham, Arumugam; Ganesan, Pandian; Estevez, Luis

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue-derived nitrogen-doped nanocarbon (NC) layer-trapped, cobalt-rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC-loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO2 on nickel foam at 10 mA cm-2 and has a durability of over 400 h. The commercial Pt/C cathode-assisted, core–shell Co@NC–anode water electrolyzer delivers 10more » mA cm-2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO2–anode water electrolyzer. Over the long-term chronopotentiometry durability testing, the IrO2–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell-operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal-rich, core–shell electrocatalysts with enriched active centers.« less

Two-step growth mechanism of supported Co3O4-based sea-urchin like hierarchical nanostructures

NASA Astrophysics Data System (ADS)

Maurizio, Chiara; Edla, Raju; Michieli, Niccolo'; Orlandi, Michele; Trapananti, Angela; Mattei, Giovanni; Miotello, Antonio

2018-05-01

Supported 3D hierarchical nanostructures of transition metal oxides exhibit enhanced photocatalytic performances and long-term stability under working conditions. The growth mechanisms crucially determine their intimate structure, that is a key element to optimize their properties. We report on the formation mechanism of supported Co3O4 hierarchical sea urchin-like nanostructured catalyst, starting from Co-O-B layers deposited by Pulsed Laser Deposition (PLD). The particles deposited on the layer surface, that constitute the seeds for the urchin formation, have been investigated after separation from the underneath deposited layer, by X-ray diffraction, X-ray absorption spectroscopy and scanning electron microscopy. The comparison with PLD deposited layers without O and/or B indicates a crucial role of B for the urchin formation that (i) limits Co oxidation during the deposition process and (ii) induces a chemical reduction of Co, especially in the particle core, in the first step of air annealing (2 h, 500 °C). After 2 h heating Co oxidation proceeds and Co atoms outdiffuse from the Co fcc particle core likely through fast diffusion channel present in the shell and form Co3O4 nano-needles. The growth of nano-needles from the layer beneath the particles is prevented by a faster Co oxidation and a minimum fraction of metallic Co. This investigation shows how diffusion mechanisms and chemical effects can be effectively coupled to obtain hierarchical structures of transition metal oxides.

High-Quality Hollow Closed-Pore Silica Antireflection Coatings Based on Styrene-Acrylate Emulsion @ Organic-Inorganic Silica Precursor.

PubMed

Guo, Zhaolong; Zhao, Haixin; Zhao, Wei; Wang, Tao; Kong, Depeng; Chen, Taojing; Zhang, Xiaoyan

2016-05-11

Making use of a facile and low-cost way for the preparation of a hierarchically organized novel hollow closed-pore silica antireflective coating (CHAR) with tailored optical properties and a mechanical reliability is of great interest in the field of solar photovoltaic technology. The process mainly contains two aspects: (1) a styrene-acrylate emulsion @ organic-inorganic silica precursor (SA@OISP) core/shell hierarchical nanostructure, consisting of a sacrificial styrene-acrylate (SA) primary template, was fabricated using a sol-gel method; (2) the self-assembly of the nanostructures leads to SA@OISP nanospheres forming the high-quality hollow closed-pore silica antireflection coating (CHAR) by a dip-coating process and a subsequent calcination treatment. The resulting SA@OISP nanospheres have a mean diameter of 65.2 nm and contained a SA soft core with a mean diameter of approximately 54.8 nm and an organic-inorganic silica precursor (OISP) shell with a thickness of approximately 6-10 nm. Furthermore, the prepared CHAR film exhibited a high transmittance and good ruggedness. An average transmittance (TAV) of 97.64% was obtained, and the value is close to the ideal single-layered antireflection coating (98.09%) over a broad range of wavelengths (from 380 to 1100 nm). The CHAR film showed a stable TAV, with attenuation values of less than 0.8% and 0.43% after the abrasion test and the damp heat test, respectively. The conversion efficiency of the CHAR coating cover solar modules tends to be increased by 3.75%. The promising results obtained in this study suggest that the CHAR film was considered as an essential component of the solar module and were expected to provide additional solar energy harvest under extreme outdoor climates.

Plasma-Based Synthesis of Nanostructured Materials and their Characterization

NASA Astrophysics Data System (ADS)

Chaudhary, Rakesh P.

The aim of this thesis is to explore the novel cost-effective synthesis technique to develop nanostructured materials and investigate their structural and magnetic properties. Nanomaterials were synthesized by a plasma discharge between desired metal electrodes in the cavitation field of an organic solvent. Multifunctional core-shell magnetic nanoparticles of 3d transition elements (Fe, Ni) and bimetallic (FeNi) were synthesized by varying experimental conditions. The phase, crystallinity and the magnetic properties of the materials synthesized were found to be dependent on experimental reaction parameters such as different solvents, electrodes, the spacing between electrodes, applied voltage, experiment time and high-temperature annealing. Fe and Gd-based nanoparticles were developed for high-performance magnetic resonance imaging (MRI) contrast enhancement. Biocompatible hybrid composite of Fe core - C shell nanoparticles evaluated as negative MRI contrast agents display remarkably high transverse relaxivity (r2) of 70 mM-1S-1 at 7T. In addition to 3d transition magnetic materials, magnetism of multilayer graphene nanosheets with only s and p electrons was investigated to understand and explain the intrinsic origin of ferromagnetism in carbon-based material. Apart from magnetic materials, noble metal Pd nanoparticles were developed using one-step process for hydrogen storage. The role of hydrogen on the dilation of Pd lattice was investigated using the experiment and density functional theory (DFT) studies. This method demonstrates that plasma discharge method using appropriate electrodes and solvents can be used to synthesize desired nanoparticles. This potential emphasizes the importance of adopting this methodology, which offers advantages that include a rapid reaction rate and ability to form very small nanoparticles with narrow size distribution.

Transmission electron microscopy of unstained hybrid Au nanoparticles capped with PPAA (plasma-poly-allylamine): structure and electron irradiation effects.

PubMed

Gontard, Lionel C; Fernández, Asunción; Dunin-Borkowski, Rafal E; Kasama, Takeshi; Lozano-Pérez, Sergio; Lucas, Stéphane

2014-12-01

Hybrid (organic shell-inorganic core) nanoparticles have important applications in nanomedicine. Although the inorganic components of hybrid nanoparticles can be characterized readily using conventional transmission electron microscopy (TEM) techniques, the structural and chemical arrangement of the organic molecular components remains largely unknown. Here, we apply TEM to the physico-chemical characterization of Au nanoparticles that are coated with plasma-polymerized-allylamine, an organic compound with the formula C3H5NH2. We discuss the use of energy-filtered TEM in the low-energy-loss range as a contrast enhancement mechanism for imaging the organic shells of such particles. We also study electron-beam-induced crystallization and amorphization of the shells and the formation of graphitic-like layers that contain both C and N. The resistance of the samples to irradiation by high-energy electrons, which is relevant for optical tuning and for understanding the degree to which such hybrid nanostructures are stable in the presence of biomedical radiation, is also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ocean Drilling Program: Information Services: Database Services

Science.gov Websites

Available Examples of Data Core Photos Logging Database (LDEO-BRG) RIDGE Petrological Database (LDEO from postcruise research All ODP and DSDP core photos All ODP data are available online through Janus proprietary for a period of one year after the end of a cruise and are available only to the participating

Core–shell interaction and its impact on the optical absorption of pure and doped core-shell CdSe/ZnSe nanoclusters

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

Wang, Xinqin; Cui, Yingqi; Zeng, Qun

The structural, electronic, and optical properties of core-shell nanoclusters, (CdSe){sub x}@(CdSe){sub y} and their Zn-substituted complexes of x = 2–4 and y = 16–28, were studied with density functional theory calculations. The substitution was applied in the cores, the shells, and/or the whole clusters. All these clusters are characterized by their core-shell structures in which the core-shell interaction was found different from those in core or in shell, as reflected by their bondlengths, volumes, and binding energies. Moreover, the core and shell combine together to compose a new cluster with electronic and optical properties different from those of separated individuals,more » as reflected by their HOMO-LUMO gaps and optical absorptions. With the substitution of Cd by Zn, the structural, electronic, and optical properties of clusters change regularly. The binding energy increases with Zn content, attributed to the strong Zn–Se bonding. For the same core/shell, the structure with a CdSe shell/core has a narrower gap than that with a ZnSe shell/core. The optical absorption spectra also change accordingly with Zn substitution. The peaks blueshift with increasing Zn concentration, accompanying with shape variations in case large number of Cd atoms are substituted. Our calculations reveal the core-shell interaction and its influence on the electronic and optical properties of the core-shell clusters, suggesting a composition–structure–property relationship for the design of core-shell CdSe and ZnSe nanoclusters.« less

Hollow-structured mesoporous materials: chemical synthesis, functionalization and applications.

PubMed

Li, Yongsheng; Shi, Jianlin

2014-05-28

Hollow-structured mesoporous materials (HMMs), as a kind of mesoporous material with unique morphology, have been of great interest in the past decade because of the subtle combination of the hollow architecture with the mesoporous nanostructure. Benefitting from the merits of low density, large void space, large specific surface area, and, especially, the good biocompatibility, HMMs present promising application prospects in various fields, such as adsorption and storage, confined catalysis when catalytically active species are incorporated in the core and/or shell, controlled drug release, targeted drug delivery, and simultaneous diagnosis and therapy of cancers when the surface and/or core of the HMMs are functionalized with functional ligands and/or nanoparticles, and so on. In this review, recent progress in the design, synthesis, functionalization, and applications of hollow mesoporous materials are discussed. Two main synthetic strategies, soft-templating and hard-templating routes, are broadly sorted and described in detail. Progress in the main application aspects of HMMs, such as adsorption and storage, catalysis, and biomedicine, are also discussed in detail in this article, in terms of the unique features of the combined large void space in the core and the mesoporous network in the shell. Functionalization of the core and pore/outer surfaces with functional organic groups and/or nanoparticles, and their performance, are summarized in this article. Finally, an outlook of their prospects and challenges in terms of their controlled synthesis and scaled application is presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomistic tight-binding computations of the structural and optical properties of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals

NASA Astrophysics Data System (ADS)

Sukkabot, Worasak

2018-05-01

A study of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals is carried out using atomistic tight-binding theory and the configuration interaction method to provide information for applications in bioimaging, biolabeling, display devices and near-infrared electronic instruments. The calculations yield the dependences of the internal and external passivated shells on the natural behaviours of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals. The reduction of the optical band gaps is observed with increasing numbers of monolayers in the external ZnS shell due to quantum confinement. Interestingly, the optical band gaps of CdTe/CdS/ZnS core/shell/shell nanocrystals are greater than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. In the presence of an external ZnS-coated shell, electron-hole wave function overlaps, oscillation strengths, ground-state exchange energies and Stokes shift are improved, whereas ground-state coulomb energies and fine-structure splitting are reduced. The oscillation strengths, Stokes shift and fine-structure splitting are reduced with the increase in external ZnS shell thickness. The oscillation strengths, Stokes shift and fine-structure splitting of CdTe/CdS/ZnS core/shell/shell nanocrystals are larger than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. Reduction of the atomistic electron-hole interactions is observed with increasing external ZnS shell size. The strong electron-hole interactions are more probed in CdTe/CdS/ZnS core/shell/shell nanocrystals than in CdTe/CdSe/ZnS core/shell/shell nanocrystals.

Unravelling the origin of the giant Zn deficiency in wurtzite type ZnO nanoparticles

PubMed Central

Renaud, Adèle; Cario, Laurent; Rocquelfelte, Xavier; Deniard, Philippe; Gautron, Eric; Faulques, Eric; Das, Tilak; Cheviré, François; Tessier, Franck; Jobic, Stéphane

2015-01-01

Owing to its high technological importance for optoelectronics, zinc oxide received much attention. In particular, the role of defects on its physical properties has been extensively studied as well as their thermodynamical stability. In particular, a large concentration of Zn vacancies in ZnO bulk materials is so far considered highly unstable. Here we report that the thermal decomposition of zinc peroxide produces wurtzite-type ZnO nanoparticles with an extraordinary large amount of zinc vacancies (>15%). These Zn vacancies segregate at the surface of the nanoparticles, as confirmed by ab initio calculations, to form a pseudo core-shell structure made of a dense ZnO sphere coated by a Zn free oxo-hydroxide mono layer. In others terms, oxygen terminated surfaces are privileged over zinc-terminated surfaces for passivation reasons what accounts for the Zn off-stoichiometry observed in ultra-fine powdered samples. Such Zn-deficient Zn1-xO nanoparticles exhibit an unprecedented photoluminescence signature suggesting that the core-shell-like edifice drastically influences the electronic structure of ZnO. This nanostructuration could be at the origin of the recent stabilisation of p-type charge carriers in nitrogen-doped ZnO nanoparticles. PMID:26333510