Reversible photoswitching of ferromagnetic FePt nanoparticles at room temperature

There has been a great interest in developing photoswitchable magnetic materials because of their possible applications for future high-density information storage media. In fact, however, the examples reported so far did not show ferromagnetic behavior at room temperature. From the viewpoint of their practical application to magnetic recording systems, the ability to fix their magnetic moments such that they still exhibit room-temperature ferromagnetism is an absolute requirement. Here, we have designed reversible photoswitchable ferromagnetic FePt nanoparticles whose surfaces were coated with azobenzene-derivatized ligands. On the surfaces of core particles, reversible photoisomerization of azobenzene in the solid state was realized by using spacer ligands that provide sufficient free volume. These photoisomerizations brought about changes in the electrostatic field around the core-FePt nanoparticles. As a result, we have succeeded in controlling the magnetic properties of these ferromagnetic composite nanoparticles by alternating the photoillumination in the solid state at room temperature.     

Surface-Modified CdS/ZnO Material: Single-Reactor Synthesis and Mechanism of Formation in Aqueous Solution

Method of chemical precipitation from aqueous solutions was used to cover the surface of polycrystalline ZnO nanotubes with a nanostructured CdS layer. The thus synthesized CdS/ZnO composite material was studied by the methods of X-ray diffraction analysis, electron microscopy, and optical spectroscopy. The fundamental time-related aspects of the process of CdS formation on the ZnO surface were examined. It was found that the amount of deposited CdS nanoparticles is independent of the deposition duration. The morphological specific features of ZnO nanotubes are preserved upon a prolonged keeping of ZnO in solution. The photocatalytic activity of CdS/ZnO under visible and UV light was examined in the reaction of hydroquinone oxidation. A possible mechanism of how the CdS/ZnO composite is formed in an aqueous solution in the course of growth of a layer constituted by CdS nanoparticles on the surface of ZnO nanotubes is suggested on the basis of the experimental data. It is demonstrated that the chemical-precipitation method can be used to obtain surface-active composite materials that are photoactive in the visible spectral range.     

Prussian blue nanoparticles protected by poly(vinylpyrrolidone)

Prussian blue (PB) nanoparticles protected by poly(vinylpyrrolidone) (PVP) were prepared by mixing aqueous Fe2+, Fe(CN)63-, and PVP solutions together and were characterized by UV-vis, IR, XRPD, and TEM. Averaged dimensions of the nanoparticles were controlled between 12 and 27 nm depending on initial Fe ion concentrations and feed ratios of Fe ion to PVP. Solubility of PB bulk in organic solvents is considerably low; nevertheless, formations of the PB nanoparticles dramatically increase the solubility in a variety of organic solvents. It is noteworthy that the PVP-protected PB nanoparticles stably maintain the cluster formations without further aggregations and dissociation in CHCl3 over 1 month. Measurement of the critical temperature (Tc) where PB nanoparticles exhibit a ferromagnetic property showed a gradual decrease of Tc for the nanoparticles as the particle sizes become smaller. This result could be ascribed to the reduction of the averaged numbers of magnetic interacted neighbors.     

Magnetic composites based on ultrafine polytetrafluoroethylene and cobalt containing nanoparticles

Composite materials based on ultrafine polytetrafluoroethylene and cobalt-containing nanoparticles were synthesized by the method of high-speed thermal decomposition of cobalt formate in a pseudoboiling layer of grains of ultrafine polytetrafluoroethylene. It has been found that ultrafine polytetrafluoroethylene is a composite material that consists of a core of polytetrafluoroethylene and a membrane of fluoroalkanes. In the formation of cobalt nanoparticles, interaction between them and the shell of ultrafine polytetrafluoroethylene-fluoroalkanes takes place. The result of the interaction is the formation of cobalt fluoride, which makes a significant contribution to the magnetic properties of composite materials. At room temperature, ferromagnetic behavior is characteristic for materials; the coercive force at 300 K is 700 Oe, while at 77 K it reaches 900 Oe.     

Preparation of ZnS/CdS composite nanoparticles by coprecipitation from reverse micelles using CO2 as antisolvent

The possibility of simultaneously recovering ZnS and CdS particles from reverse micelles by dissolving antisolvent CO2 into the micellar solution was investigated by high-pressure UV-Vis spectra. It was found that all the ZnS and CdS particles in the reverse micelles could be precipitated by compressed CO2 at suitable pressures. The phase structures and morphologies of the obtained composites were characterized by X-ray diffraction and transmission electronic micrographs. The results illustrate that the smaller molar ratio of water to surfactant of the reverse micelles and higher pressure of CO2 are favorable for producing smaller particles. This method has many potential advantages for the production of composite nanoparticles.     

Manipulation of the magnetic properties of magnetite-silica nanocomposite materials by controlled Stober synthesis

The paper describes the synthesis and characterization of the magnetic properties of magnetite/silica nanocomposites using a modified Stober method. Magnetite nanoparticles averaging 8-10 nm in diameter and stabilized with oleic acid in toluene were used as the magnetic component of the nanocomposites. SQUID magnetic measurements and ferromagnetic resonance spectroscopy measurements were performed at each stage of the synthesis to understand the properties of the formed composites. Changes of blocking temperature in ZFC/FC SQUID curves correlated with corresponding changes of the resonance field in the ferromagnetic spectra of the sample at each stage of formation. The paper concludes that it is possible to manipulate the magnetic properties of silica/magnetite composite materials by controlling their surface properties and silica coating thickness.     

Study of poly(N,N-dimethylacrylamide)/CdS nanocomposite organic/inorganic gels

CdS nanoparticles have been synthesized and stabilized in poly(N,N-dimethylacrylamide) hydrogels. The properties of the composite material have been characterized by UV-vis spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and steady-state and time-resolved luminescence spectroscopy. This material can be obtained in three different states: swollen, shrunk, and freeze-dried. The swollen and the freeze-dried states correspond to a nanocomposite organic/inorganic (wet or dry) gel containing CdS nanoparticles of approximately 50 nm diameter while the shrunk state is a two-phase system containing CdS crystals, which precipitate forming interesting geometrical shapes.     

The design of hybrid materials based on magnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles and luminescent CdS nanoparticles for cell visualization

Hybrid nanoparticles based on Fe₃O₄ and CdS combining magnetic and luminescence properties were synthesized. The possibility of visualization of various cells by 3-mercaptopropylsilane-modified CdS nanoparticles and hybrid nanoparticles based on them using a confocal microscope was demonstrated. The synthesized materials did not show a clear-cut cytotoxicity.     

Construction of inorganic nanoparticles by micro-nano-porous structure of cellulose matrix

In our previous work, the CdS nanoparticles/cellulose films exhibited significantly high photocatalytic H₂ production efficiency under visible light irradiation than the ordinary CdS photocatalyst. In present paper, the CdS nanoparticles were synthesized in situ in pores of the regenerated cellulose substrate and the porous structure of cellulose, formation of the CdS nanoparticles and interactions between CdS and cellulose matrix in the composite films were investigated deeply. The experimental results indicated that the micro-nano-porous structure of the cellulose matrix could be used easily to create inorganic nanoparticles, which supplied not only cavities for the formation of nanoparticles, but also a shell (semi-stiff cellulose molecules support the pore wall) to protect their nano-structure. When the cellulose films with porous structure at wet state were immersed into inorganic ions solution, the ions interacted immediately with the –OH groups of cellulose, and then transformed into inorganic composite via another treatment, finally inorganic nanoparticles formed during the dry. The pore size of the cellulose matrix decreased from 180 nm (at wet state) to about 18 nm (at dry state), leading to the formation of nanoparticles. The results revealed that the CdS nanoparticles with a mean particle diameter about 6 nm were dispersed well, and were immobilized tightly in the cellulose matrix, resulting in a portable photocatalyst with high efficiency for photocatalytic for H₂ evolution. This is simple and “green” pathway to prepare the organic–inorganic hybrid materials.     

CdS/石墨烯复合材料的制备及其可见光催化分解水产氢性能

以氧化石墨烯和CdS为原料, 在乙醇水溶液中采用CdS光催化还原法制备了CdS/石墨烯复合光催化材料, 并用透射电子显微镜(TEM)、X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)和瞬态光电流等技术对复合材料的结构和光电性能进行了表征. 可见光照射下(λ≥420 nm), 研究了该复合材料光催化分解水产氢的性能. 结果表明, 可见光照射下CdS的光生电子可有效地还原氧化石墨烯, 得到CdS与石墨烯之间具有强相互作用力的CdS/石墨烯复合材料. 与CdS相比, 复合材料中石墨烯作为良好的电子受体和传递介质, 可明显加快CdS光生电子的迁移速率, 提高光生载流子的分离效率, 从而增强复合材料的光电性能和光催化分解水产氢的活性.     

Novel one-step route for synthesizing CdS/polystyrene nanocomposite hollow spheres

CdS/polystyrene nanocomposite hollow spheres with diameters between 240 and 500 nm were synthesized under ambient conditions by a novel microemulsion method in which the polymerization of styrene and the formation of CdS nanoparticles were initiated by gamma-irradiation. The product was characterized by transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA), which show the walls of the hollow spheres are porous and composed of polystyrene containing homogeneously dispersed CdS nanoparticles. The quantum-confined effect of the CdS/polystyrene nanocomposite hollow spheres is confirmed by the ultraviolet-visible (UV-vis) and photoluminescent (PL) spectra. We propose that the walls of these nanocomposite hollow spheres originate from the simultaneous synthesis of polystyrene and CdS nanoparticles at the interface of microemulsion droplets. This novel method is expected to produce various inorganic/polymer nanocomposite hollow spheres with potential applications in the fields of materials science and biotechnology.     

Dithiol-mediated incorporation of CdS nanoparticles from reverse micellar system into Zn-doped SBA-15 mesoporous silica and their photocatalytic properties

CdS nanoparticles, as prepared in reverse micellar systems, were incorporated into alkanedithiol-modified Zn-doped SBA-15 mesoporous silica (dtz.sbnd;ZnSBA-15; pore diameter, ca. 4 nm), which were themselves prepared via hydrolysis of tetraethylorthosilicate (TEOS) in the presence of Zn(NO(3))(2) and triblock copolymer, as a nonsurfactant template and pore-forming agent, followed by contact with dithiol molecules. A particle-sieving effect for the dtz.sbnd;ZnSBA-15 was observed, in that the incorporation of the nanoparticles was remarkably decreased with increasing the nanoparticle size. The resulting CdSz.sbnd;ZnSBA-15 composite was then used as photocatalysts for the generation of H(2) from 2-propanol aqueous solution. Under UV irradiation (lambda>300 nm), a high photocatalytic activity was observed for this composite material. This is effected by electron transfer from the photoexcited ZnS (dithiol-bonded Zn on SBA-15) to CdS nanoparticles. The photocatalytic activity is increased with a decrease in the number of methylene groups in the dithiol molecules, according to the rank order 1,10-decanedithiol < 1,6-hexanedithiol < 1,2-ethanedithiol.     

Mechanism of the formation of photosensitive nanostructured TiO<Subscript>2</Subscript> with low content of CdS nanoparticles

A method for synthesizing a CdS/TiO₂ composite material, active in the visible region, was described. The CdS/TiO₂ composite was obtained by the sol–gel synthesis of nanostructured TiO₂ in a medium of a stable colloidal solution of CdS nanoparticles. The TiO₂ matrix produced by the sol–gel process is amorphous and contains a nanocrystalline anatase phase, the content of which depends on the Ti(OBu)₄ hydrolysis rate. The content of CdS nanoparticles forming in the colloidal solution and participating in the TiO₂ matrix sensitization is determined by the initial CdS: Ti(OBu)₄ ratio. Although the content of CdS nanoparticles in the composite is low (no more than 3 wt %), the composite demonstrates catalytic activity in the visible region, thus proving the possibility of reducing the content of toxic CdS nanoparticles in the TiO₂ matrix without decreasing the photosensitivity of the CdS/TiO₂ composite.     

Synthesis and characterization of ternary nanocomposites of TiO2/rGO/CdS as an efficient catalyst for photo-degradation of methyl orange

Novel ternary composite photocatalysts have been successfully prepared by TiO₂ nanofibers, reduced graphene oxide, and CdS nanoparticles (TiO₂/rGO/CdS) by using electrospinning technique with easy chemical methods. The structures and their properties are examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscope (FESEM). The structural characterization of the composite reveals that pure TiO₂ NFs and CdS NPs crystalline very well and the reduced graphene oxide is tightly composed with TiO₂ NFs and CdS Nps. The photodegradation of methyl orange (MO) under UV light illumination is significantly enhanced compared with that of bare materials. This ternary composite degrades methyl orange within 75 min. The enhanced photocatalytic degradation performance resulted from effective separation of e–h pairs with rGO sheets and also contributed for high rate degradation efficiency. This novel ternary composite has a potential application of wastewater purification and utilization for energy conversions.     

内嵌硫化镉与上转换纳米颗粒的二氧化钛复合纳米管用于近红外光驱动光催化

由于近红外光在太阳光谱中占44%,因此,近红外光驱动的光催化剂的研制具有十分重要的意义.上转换发光材料可将低能量的近红外光子转换为高能光子,这种高能光子可以通过构建荧光共振转移系统将能量转移并活化量子效率较高的半导体材料,对于太阳能的转化利用具有潜在的应用前景.在本文中,通过胶体化学的过程在电纺丝制备的内嵌CdS纳米颗粒以及上转换荧光纳米颗粒(UCNPs)的二氧化硅复合纳米纤维表面外延生长一层二氧化钛层,通过高温煅烧得到二氧化钛复合纳米管.我们通过二氧化硅结构将CdS纳米颗粒与上转换荧光纳米颗粒紧紧束缚在一起,实现较高的荧光共振能量转移.而且,选择β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)作为纳米能量转换器,替代以前研究工作中使用的β-NaYF4:Yb(30%),Tm(0.5%)或者β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4纳米颗粒,来进一步提高近红外光的转换效率.通过透射电子显微镜照片很清楚的观察到制备的TiO2复合纳米管内部内嵌有大量的CdS与上转换纳米颗粒.通过X-射线衍射以及X-射线光电子能谱能仪器对产物的物相以及表面的化学组成进行了细致的表征.结果显示,通过本实验方法已经成功获得了TiO2复合纳米管.用稳态与瞬态荧光仪研究了最终样品的荧光性质.研究结果揭示,与上转换纳米颗粒以及二氧化硅复合纳米纤维相比,复合二氧化钛纳米管可以将上转换荧光纳米颗粒的(UV-Vis)部分荧光完全淬灭了.特别是,铒离子的荧光(650 nm)也被有效淬灭转移,说明本研究采用β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)纳米能量转换器,可以提高近红外光的转换效率,紫外-可见吸收光谱证实,这种二氧化钛纳米管在紫外-可见光区中的吸收光谱与β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)纳米颗粒的荧光光谱具有较大的重叠,使得上转换荧光纳米颗粒与CdS以及二氧化钛组分之间的荧光共振转移的效率大大提高,进而会显著提高光催化的效果.以罗丹明染料作为污染物为模型,我们研究了罗丹明染料在氙灯下或者近红外光光照下的光催化分解实验.研究结果表明,90%的罗丹明染料分子在20 min内就被降解掉,效率高于其它的近红外光催化剂.上转换荧光纳米颗粒的能量转换效率可以得到大幅度提高,本研究工作中制备的光催化剂利用太阳能的效率将会得到极大提高,在未来为能源危机以及环境保护提供一种可供选择的方法与技术.     

Relationship between size of cadmium sulfide nanoparticles and water pool diameter in reverse micelles

Preparation of CdS nanoparticles in water-sodium bis(2-ethylhexyl) sulfosuccinate-isooctane reverse micelles with various water contents is studied. A direct correlation between the water pool diameter in the reverse micelles and the mean size of CdS nanoparticles is found.     

Preparation of cadmium sulfide nanoparticles in self-reproducing reversed micelles

Octyl octanoate (O-OL) underwent hydrolysis in sodium octanoate (NaOA) reversed micelles in 85:15 = isooctane:octanol (OL) (v/v), containing w = [H2O]/[NaOA] = 40. The products of the hydrolysis, octanoic acid (OA) and octanol (OL), lead to the formation of additional (albeit smaller) reversed micelles; hence the process is considered to be self-reproducing. Self-reproduction was found to be catalyzed by lithium hydroxide, solubilized in the water pools, as well as by hydrogen sulfide, added to the solution of the reversed micelles. Addition of hydrogen sulfide to cadmium perchlorate containing self-reproducing reversed micelles resulted in the formation of cadmium sulfide (CdS) nanoparticles. Diameters of the CdS containing nanoparticles could be altered from 5.4 to 1.8 nm by changing the [Cd2+]/[H2S] ratios from 0.25 to 10. The CdS nanoparticles formed were capped by mercaptopropionic acid, isolated as solids, and could be repeatedly redispersed in water without changing their sizes. Additional CdS nanoparticles were generated in the supernatants removed from the precipitated capped CdS nanoparticles.     

Solid state morphology and band gap studies of ETS-10 supported CdS nanoparticles

Engelhard titanosilicate (ETS-10) supported cadmium sulphide (CdS) nanoparticles were synthesized and characterized by various solid state techniques including: XRD, DR UV-Vis, TEM and FESEM. The effect of different synthesis routes of CdS nanoparticles on its physicochemical character was studied. It was observed that CdS nanoparticles prepared by both in situ sulphur reduction (CdS-IS) and reverse micelle (CdS-RM) methods showed similar roperties. However, CdS-IS nanoparticles are more feasible and economically practical. The reflectance measurements of the as-synthesized CdS nanoparticles are apparently blue-shifted compared to bulk CdS. This phenomenon of blue-shifted absorption edge has been ascribed to an increase in bandgap energy with a decrease in particle sizes. The bandgap of the as-synthesized CdS samples was calculated from the linear correlation of [F(R) hν]² and hν. The bandgap of CdS in ETS-10 was noticeably slightly reduced when compared with the as-synthesized CdS (8 nm) due to the formation of cluster arrays on the pores of ETS-10.     

TiO2-CdS-MCM-41复合纳米材料的合成和表征

利用γ-巯丙基三甲氧基硅烷及表面预吸附水解技术在MCM-41介孔分子筛孔道内部以化学键合的形式依次引入了CdS和TiO2纳米粒子.紫外-可见吸收光谱结果表明,借助于巯基的络合能力,MCM-41能有效地从反胶束中萃取CdS纳米粒子.利用小角XRD谱图成功地跟踪观察到了MCM-41介孔分子筛随纳米粒子的引入而产生的孔径变化.     

Distinct visible-light response of composite films with CdS electrodeposited on TiO2 nanorod and nanotube arrays

Thorough infiltration of CdS nanoparticles into spaces of titania nanorod and nanotube arrays was achieved by an ac electrodeposition technique to construct composite films of CdS over titania. The substrate affected not only the electrodeposition rate but also the oriented growth of CdS. A photocurrent much larger than the simple summation of those arising from the two component layers of CdS and titania was detected for both composite films under visible-light illumination. Such an enhancement in the photocurrent was even more prominent for the composite film based on the titania nanorod arrays, which was contributed to the higher charge separation rate arising from the nearly single-crystalline nanorods when compared with the polycrystalline nanotubes.