Synthesis of beta-cyclodextrin-modified water-dispersible Ag-TiO2 core-shell nanoparticles and their photocatalytic activity

The beta-cyclodextrin-modified Ag-TiO2 core-shell nanoparticles were prepared by sodium borohydrate reduction of AgNO3 and the subsequent hydrolysis of the tetraisopropyl orthotitanate in an aqueous medium. Inversely in the preparation of beta-cyclodextrin-modified TiO2-Ag core-shell nanoparticles, first hydrolysis and then following reduction were carried out. The synthesized spherical core-shell nanoparticles were highly water-dispersible and had an average diameter in the range of 9 to 12 nm. A significant shifting of surface plasmon band was observed for the synthesized Ag-TiO2 and TiO2-Ag core-shell nanoparticles. On a model reaction, namely, the photodegradation of phenol by the UV light irradiation, the photocatalytic property of TiO2 nanoparticles was enhanced, when the Ag nanoparticle was embedded in the core of TiO2 nanoparticles but TiO2 nanoparticles coated by Ag shell decreased the photocatalytic property of TiO2 nanoparticles. The mechanism is ascribed to the surface plasmon characteristics of Ag in the core of the TiO2 nanoparticles under the acceleration by host-guest inclusion characteristics.     

Facile synthesis of near-monodisperse Ag@Ni core-shell nanoparticles and their application for catalytic generation of hydrogen

Magnetically recyclable Ag-Ni core-shell nanoparticles have been fabricated via a simple one-pot synthetic route using oleylamine both as solvent and reducing agent and triphenylphosphine as a surfactant. As characterized by transmission electron microscopy (TEM), the as-synthesized Ag-Ni core-shell nanoparticles exhibit a very narrow size distribution with a typical size of 14.9 ± 1.2 nm and a tunable shell thickness. UV-vis absorption spectroscopy study shows that the formation of a Ni shell on Ag core can damp the surface plasmon resonance (SPR) of the Ag core and lead to a red-shifted SPR absorption peak. Magnetic measurement indicates that all the as-synthesized Ag-Ni core-shell nanoparticles are superparamagnetic at room temperature, and their blocking temperatures can be controlled by modulating the shell thickness. The as-synthesized Ag-Ni core-shell nanoparticles exhibit excellent catalytic properties for the generation of H(2) from dehydrogenation of sodium borohydride in aqueous solutions. The hydrogen generation rate of Ag-Ni core-shell nanoparticles is found to be much higher than that of Ag and Ni nanoparticles of a similar size, and the calculated activation energy for hydrogen generation is lower than that of many bimetallic catalysts. The strategy employed here can also be extended to other noble-magnetic metal systems.     

Optical studies of Au@SnO<Subscript>2</Subscript>/poly-(vinyl) alcohol core-shell nanoparticle thin films

Au@SnO₂ core-shell nanoparticles dispersed in poly-(vinyl) alcohol films were fabricated on glass substrate by employing dip-coating technique. The structure and morphology of the films were investigated by X-ray diffraction technique and field-emission transmission electron microscopy, respectively. Optical properties of the films were studied by UV–visible spectroscopy. Surface plasmon spectrum of the core-shell nanoparticles film remained unaltered with increase in the number of layers. However, gold nanoparticles films have shown peak broadening and shifting with increase in the number of layers. Our investigations showed that the surface plasmon band of the gold nanoparticles could be tailored and preserved by controlled deposition of tin dioxide shell.     

Fe2o3 shell growth on Pt nanoparticles

Fe2O3 shells have been synthesized around Pt cores to create Pt@Fe2O3 core-shell nanoparticles. The synthesis conditions allow control of the shell shape and allow the preparation of both hexagonal shells and spherical shells. 2D cross-sectional TEM images show that the cores are not positioned at the centers of the shells. By rotating the nanoparticles and monitoring the apparent motions of the cores in the 2D cross-sectional images, it is possible to determine quantitatively the radial position of the Pt core with respect to the center of the Fe2O3 shell. The distribution of core positions within the core-shell structures is bimodal. These observations suggest that the Fe2O3 shells grow on the Pt cores by a nucleation process, rather than layer-by-layer growth.     

Tailoring the photoluminescence of MgO nanowires using the Ag shell layers and nanoparticles

We fabricated MgO/Ag core-shell nanowires, where core nanowires were coated with a conformal layer of Ag via sputtering. By subsequent thermal annealing, we generated Ag nanoparticles. Photoluminescence (PL) studies revealed that Ag-shell coating decreased the intensity of blue emission, whereas that of UV emission remained almost invariant. The subsequent annealing has induced an additional green emission band. We discuss here the possible mechanism by which the PL properties have been tailored by Ag-layer coating and by forming nanoparticles. This approach can be applied to tailor and improve the optical properties of different composite nanostructures.     

Low-field magnetoresistance effect in core-shell structured La(0.7) Sr(0.3) CoO(3) nanoparticles

Core-shell structured La(0.7) Sr(0.3) CoO(3) nanoparticles are synthesized and their magnetic and magneto-transport properties are investigated. In these core-shell La(0.7) Sr(0.3) CoO(3) nanoparticles, the cores are single-crystalline and ferromagnetic, whereas the shells are noncrystalline and predominantly paramagnetic. Moreover, the insulating-like shells can serve as a good spin tunneling barrier. Therefore, in such a special core-shell structure, the spin-polarized interparticle tunneling is improved due to the existence of shells, which thus induces an enhanced low-field magnetoresistance effect.     

One-step solvothermal synthesis of Fe3O4@C core-shell nanoparticles with tunable sizes

We report the synthesis of Fe3O4@C core-shell nanoparticles (FCNPs) by using a facile one-step solvothermal method. The FCNPs consisted of Fe3O4 particles as the cores and amorphous uniform carbon shells. The content of Fe3O4 is up to 81.6 wt%. These core-shell nanoparticles are aggregated by primary nanocrystals with a size of 10-12 nm. The FCNPs possess a hollow interior, high magnetization, excellent absorption properties and abundant surface hydroxyl groups. A possible growth mechanism of the FCNPs is proposed. The role of glucose in regulating the grain size and morphology of the particles is discussed. The absorption properties of the FCNPs towards Cr(VI) in aqueous solution is investigated. We demonstrate that the FCNPs can effectively remove more than 90 wt% of Cr(VI) from aqueous solution.     

Large enhancement of fluorescence efficiency from CdSe/ZnS quantum dots induced by resonant coupling to spatially controlled surface plasmons

Nanoengineered fluorescent response is reported from semiconductor core-shell (CdSe/ZnS) quantum dots in proximity to the surface plasmon polariton field of periodic Ag nanoparticle arrays. Tuning the surface plasmon polariton resonance to the quantum dot exciton emission band results in an enhancement of up to approximately 50-fold in the overall fluorescence efficiency, in a design where each Ag nanoparticle is interconnected by a continuous Ag thin film. Propagating modes of surface plasmon resonances have a direct impact on the fluorescence enhancement.     

Low temperature magnetic hardening in self-assembled FePt/Ag core-shell nanoparticles

The FePt/Ag core-shell nanoparticles with different Ag shell thickness have been fabricated using a seed mediated technique. The core-shell nanoparticles are annealed at temperatures ranging from 350 to 600 °C for 30 min in vacuum. The magnetic measurement demonstrates that the FePt/Ag core-shell nanoparticles show a better chemical ordering tendency with a magnetic hardening temperature of 400–450 °C, which is almost 100 °C lower than that of pure FePt nanoparticles. Negative peaks on the δM curves of the annealed FePt/Ag core-shell nanoparticles demonstrate that the predominant interparticle interactions are dipolar type rather than exchange coupling one. Besides, the FePt/Ag core-shell nanoparticles show both sensitive plasmonic and superparamagnetic properties. The present results indicate that our composite nanoparticles are very promising from the viewpoint of the optoelectronics and biomedical applications.     

X-ray photoelectron spectroscopy of silver nanoparticles in phosphate glass

Phosphate glasses doped with silver nanoparticles have been characterized by X-ray photoelectron spectroscopy. A study on the relation of Ag binding energies with the optical properties of the nanocomposites has revealed binding energies for 3d doublets higher than those reported for bulk silver with a tendency towards the bulk value with increasing wavelength of surface plasmon resonance peak position. The data is interpreted in terms of quantum confinement effects in small silver clusters and an increase in particle size with plasmon absorption redshift.     

Synthesis and characterization of Fe/Nd2O3 core-shell nanoparticles by hydrogen plasma-metal reaction

Fe/Nd2O3 core-shell nanoparticles (CSNs) with a mean diameter of 35 nm were produced successfully by using hydrogen plasma-metal reaction (HPMR) method. This core-shell structure was confirmed by high resolution transmission electron microscopy (HRTEM), energy dispersion X-ray spectroscopy (EDS), X-ray photoelectron spectral (XPS), and induction-coupled plasma (ICP) spectroscopy. The magnetic properties were measured by vibrating sample magnetometer (VSM). It was found that the mole ratio of Nd to Fe on the nanoparticle surface is 1.2:1, about 7 times of that of the whole nanoparticle. The saturation magnetization Ms and remanence Mr of Fe/Nd2O3 nanoparticles decrease prominently from Fe nanoparticles, whereas the coercivity Hc drops only less than 5% of Fe nanoparticle. These CSNs have potential applications in magnetic and catalytic fields.     

Synthesis of Fe3O4@PbS hybrid nanoparticles through the combination of surface-initiated atom transfer radical polymerization and acidolysis by H2S

A versatile approach to fabricate nanoparticles with multiple functionalities through the combined use of both surface-initiated ATRP and acidolysis by H2S techniques was demonstrated. The hybrid nanoparticles exhibited the core-shell structure having the magnetite nanoparticles as the core and the polymethacrylate as the shell with PbS nanoparticles distributing in the shell. The structure and morphology of the synthesized nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optical and magnetic properties of the nanoparticles were investigated by UV-Vis spectroscopy, photoluminescence spectroscopy and vibrating sample magnetometer (VSM), respectively. It is observed that the absorption and emission behaviors of the Fe3O4@PbS hybrid nanoparticles were seriously influenced by the ATRP time and the reaction time with H2S. The saturated magnetization (Ms) decreased with the increase of ATRP time due to the formation of thicker shells coating on the surfaces of magnetite nanoparticles.     

Optical response of Ag-Au bimetallic nanoparticles to electron storage in aqueous medium

Composition and structure dependence of the shift in the position of the surface plasmon resonance band upon introduction of NaBH4 to aqueous solutions of gold and silver nanoparticles are presented. Silver and gold nanoalloys in different compositions were prepared by co-reduction of the corresponding salt mixtures using sodium citrate as the reducing agent. After addition of NaBH4 to the resultant nanoalloys, the maximum of their surface plasmon resonance band, ranging between that of pure silver (ca. 400 nm) and of pure gold (ca. 530 nm), is blue-shifted as a result of electron storage on the particles. The extent of this blue shift increases non-linearly with the mole fraction of silver in the nanoparticle, parallel to the trends reported previously for both the frequency and the extinction coefficient of the plasmon band shifts. Gold(core)@silver(shell) nanoparticles were prepared by sequential reduction of gold and silver, where addition of NaBH4 results in relatively large spectral shift in the plasmon resonance band when compared with the nanoalloys having a similar overall composition. The origin of the large plasmon band shift in the core-shell is related with a higher silver surface concentration on these particles. Hence, the chemical nature of the nanoparticle emerges as the dominating factor contributing to the extent of the spectral shift as a result of electron storage in bimetallic systems.     

Effect of inorganic shells on luminescence properties of ZnS:Ag nanoparticles

The hydrothermally synthesized Ag-doped ZnS (ZnS:Ag) nanoparticles have been coated with inorganic shells by a chemical precipitation method. The ZnS:Ag/ZnS, ZnS:Ag/CdS, and ZnS:Ag/ZnO core–shell nanoparticles with different thickness of ZnS, CdS, and ZnO shells have been prepared. The effects of shells on the luminescence properties of ZnS:Ag cores have been investigated through the photoluminescence (PL) spectra and luminescence stabilities of products. In the core–shell nanoparticles involved here, the ZnO shell can most significantly enhance the luminescence of ZnS:Ag cores. The 450 nm emission intensity of ZnS:Ag/ZnO nanoparticles is up to 125 % of that of ZnS:Ag nanoparticles. However, the ZnO shell can hardly influence the luminescence stability under ultraviolet irradiation. The ZnS shell can only increase the luminescence of ZnS:Ag cores to some extent, but it can improve the luminescence stability under ultraviolet irradiation. Although the CdS shell can improve the luminescence stability to some extent, it quenches the luminescence of ZnS:Ag nanoparticles dramatically.     

Manifestation of the silver nanoparticles incorporated into the poly vinyl alcohol matrices

Electrical and optical properties of the silver nanoparticles (Ag NPs) incorporated into the polyvinyl alcohol (PVA) matrices were investigated as a function of Ag NPs. The intensities of FT-Raman bands have a maximum corresponding to the Ag NP amount about 3.6 mg.. The PVA doped with different amounts of Ag NPs shows UV-Visible peaks, were red shifted by Ag NPs increase, while their intensities according well with the FT-Raman spectra. The UV-Visible spectra for the 3.6 mg Ag NPs doped in PVA presented a small red shift and band intensity decrease by increasing temperature.     

Fabrication and properties of flower-shaped Pt@TiO2 core-shell nanoparticles

Flower-shaped core-shell Pt@TiO₂ nanoparticles have been synthesized successfully by a simple hydrothermal route using TiF₄ as precursor. Morphology of the product was investigated by transmission electron microscopy (TEM), selected area electron diffraction (SAED) and X-ray diffraction technique. It has been revealed that the TiO₂ shells of core-shell Pt@TiO₂ nanoparticles are constructed by multiple wedge-shaped petals of TiO₂ crystals with anatase-type crystalline phase. The SAED pattern of TiO₂ shells reflecting the formation of wedge-shaped TiO₂ petals is because of the preferential growth of (004) crystal planes surrounded by (101) facets of TiO₂ crystal planes. The high phototocatalytic performance of flower-shaped core-shell Pt@TiO₂ nanoparticles is also largely attributed to the high Schottky energical barrier within Pt-TiO₂ hetero-interface and the interaction between synchronously vibrated electrons within Pt and electrons in valence band of TiO₂ crystals.     

Single particle model of SnO2 deposition on silver nanoparticles

Silver nanoparticles coated with almost uniform, thin shell of tin oxide are synthesized via a simple colloid chemistry technique, where the reduction of Ag⁴⁺ to Ag⁰ followed by the encapsulation of oxide takes place. The as prepared dispersions of tin oxide coated silver nanocomposite particles display a surface plasmon band, which is significantly red shifted with respect to that of bare Ag. Morphology of the composite nanoparticles was investigated by TEM. Presence of SnO₂ shell on the silver nanoparticles was also supported by XPS results. A theoretical single particle model has been proposed for the formation of tin oxide shell on the silver nanoparticles.     

Phase transfer identification of core-shell structures in Ag-Au bimetallic nanoparticles

The difference between the transfer of poly(vinylpyrrolidone)-protected Au and Ag nanoparticles from an aqueous solution to toluene was used to develop a simple experimental procedure that can positively identify the formation of bimetallic Ag-Au nanoparticles with the core-shell structure. The method was validated by UV-visible spectroscopy, EDX, and TEM measurements. Using this technique, we have found that core-shell nanoparticles of Ag-Au were formed by the seed-mediated growth method using Ag nanoparticles as the seeds. The reversed order of using Au nanoparticles as the seeds, on the contrary, could only produce a physical mixture of Ag-Au core-shell nanoparticles and isolated Ag nanoparticles.     

Synthesis and characterization of Ag@polycarbazole nanoparticles and their novel optical behavior

Ag@polycarbazole as a new 3D nanocomposite material was successfully fabricated using microwave polyol reduction method followed by cations assisted oxidative polymerization of carbazole. The material was characterized by transmission electron microscopes (TEM), scanning electron microscope (SEM), FT-IR, and Raman measurements. The results confirmed that Ag nanoparticles are entirely enclosed by 3,6 polycarbazole. The interfacial study was carried out by X-ray photoelectron spectroscopy, which revealed that Ag surface atoms are intact chemically and blue shifted due to polymer composite formation. The surface plasmon resonance (SPR) and photoluminescence (PL) behavior were found quite sensitive to surface composition of Ag nanoparticles, which is greatly influenced by cations dopant and enclosing polymer in contrary way. The polycarbazole played a contributive role to counterbalance the effect of cations dopant in SPR and PL behaviors along with displaying its luminescence in violet region.     

Photothermal properties of gold nanoparticles under exposure to high optical energies

Photothermal (PT) efficacy and damage thresholds of gold nanoparticles (NP)-spheres, rods and silica-gold shells-were experimentally studied during their excitation with nanosecond laser pulses at the fluence levels at and above the NP damage threshold. The maxima of PT efficacy of gold NPs with near-infrared (NIR) plasmon resonances (gold rods and shells) and the minima of their damage thresholds were found to be shifted from their plasmon resonance NIR wavelengths into non-resonant visible wavelengths. This suppression of PT efficacy of NIR plasmon resonances (bleaching) was found to be up to 18 times for the rods and up to 22 times for the shells. During laser-induced deterioration the NPs maintained their PT properties at least within 40-150?ns after exposure to laser pulses. PT properties of the gold NPs can be enhanced with the pulse train mode within the above time. The PT bubbles generated around superheated NPs were used as their optical markers and allowed us to quantify PT efficacy of plasmon resonance through the bubble parameters under the conditions when other methods of NP detection are not applicable.