Effect of incorporated CdS nanoparticles on the crystallinity and morphology of poly(styrene‐b‐ethylene oxide) diblock copolymers

Surface‐modified CdS nanoparticles selectively dispersed in hexagonally packed poly(ethylene oxide) (PEO) cylinders of poly(styrene‐b‐ethylene oxide) (PSEO) block copolymers were prepared. The photoluminescence and ultraviolet–visible characteristics of the presynthesized CdS nanoparticles in N,N‐dimethylformamide and in PEO domains of the PSEO block copolymers were determined. Because of strong interactions between the CdS nanoparticles and PEO chains, as shown by Fourier transform infrared spectroscopy, the incorporation of the CdS nanoparticles prevented the PEO cylinders from properly crystallizing; this was confirmed by differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. The intercylinder distance between the swollen and reduced‐crystallinity CdS/PEO cylinders in turn increased, as confirmed by small‐angle X‐ray scattering and transmission electron microscopy. At a high CdS concentration (43 wt % or 8.3 vol % with respect to PEO), however, the hexagonally packed cylindrical nanostructure of the PSEO diblock copolymers was destroyed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1220–1229, 2005     

A simple CdS nanoparticles cascading approach for boosting N3 dye/ZnO nanoplates DSSCs overall performance

Enhanced photosensitization in presence of CdS nanoparticles is achieved in electrochemically deposited ZnO nanoplates and N3 loaded dye-sensitized solar cells. Chemically embedded CdS nanoparticles act as a sandwiching layer between ZnO nanoplates and dye molecules by overcoming current limiting serious Zn²⁺/dye insulating complex formation and CdS photo-corrosion issues. The X-ray diffraction and the scanning electron microscopy confirm the ZnO with vertically aligned nanoplates, perpendicular to the substrate surface. Amorphous CdS is monitored using electron dispersive X-ray analysis. The low and high resolution transmission electron microscope images confirm the presence of CdS nanoparticles over ZnO nanoplates which later is supported by an increase in optical absorbance and shift in band edge. About 400% increase in solar conversion efficiency with this cascade arrangement is achieved when compared with without CdS which could be fascinating while designing solid state solar cells in presence of suitable p-type layer.     

Synthesis, structural and photocatalytic studies of Mn-doped CdS nanoparticles

Mn-doped CdS nanoparticles (Cd_1?x Mn _x S; where x = 0.00–0.10) were synthesized by a chemical precipitation method. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope, transmission electron microscope (TEM), and UV–Vis spectrometer. The XRD and TEM measurements show that the size of crystallites is in the range of 10–40 nm. Optical measurements indicated a red shift in the absorption band edge upon Mn doping. The direct allowed band gaps of undoped and Mn-doped CdS nanoparticles measured by UV–Vis spectrometer were 2.3 and 2.4 eV at 400 °C, respectively. Photocatalytic activities of CdS and Mn-doped CdS were evaluated by irradiating the solution to ultraviolet light and taking methyl orange (MO) as organic dye. It was found that 5 mol% Mn-doped CdS bleaches MO much faster than undoped CdS upon its exposure to the ultraviolet light. The experiment demonstrated that the photo-degradation efficiency of 5 mol% Mn-doped CdS was significantly higher than that of undoped CdS.     

Synthesis and characterization of CdS nanoparticles prepared by precipitation in the presence of span 20 as surfactant

Cadmium sulfide nanoparticles with average size of ≈16 nm have been synthesized using chemical precipitation reaction of CdCl₂ and Na₂S in the presence of nonionic surfactant stabilized reverse emulsions. Sorbian monolaurate (Span 20) is used for the stabilization of emulsions. The influence of Span 20 on controlling the size and properties of CdS nanoparticles were studied. The obtained CdS nanoparticles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Energy-dispersive x-ray (EDX), and X-ray diffraction (XRD). The optical properties of CdS nanoparticles are investigated systematically by UV-visible absorption spectroscopy. The blue shift in the absorption region and increase in the bandgap to the larger value (2.77 eV) are attributed to the nanosize of the obtained particles.     

Simple and low temperature preparation and characterization of CdS nanoparticles as a highly efficient photocatalyst in presence of a low-cost ionic liquid

A simple and low temperature method is proposed for preparation of CdS nanoparticles in presence of 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM] [EtSO₄], a room-temperature ionic liquid (RTIL). The powder X-ray diffraction (XRD) studies display that the products are excellently crystallized in the form of cubic structure and size of the nanparticles prepared in presence of the RTIL is smaller than that prepared in water. Energy dispersive X-ray spectroscopy (EDX) investigations reveal that the products are very pure and nearly stoichiometric. The results obtained by scanning electron microscopy (SEM) demonstrate that the CdS nanoparticles prepared in presence of the RTIL have lower tendency for aggregation relative to the prepared sample in water. Diffuse reflectance spectra (DRS) of the product prepared in the neat RTIL, shows 1.52 eV blue shift relative to bulk CdS, which can be attributed to quantum confinement effect of the CdS nanoparticles. A possible formation mechanism for CdS nanoparticles in presence of the RTIL is presented. Photocatalytic activity of the CdS nanoparticles towards photodegradation of methylene blue (MB) using UV and visible lights was performed. The results demonstrate that observed firstorder rate constant for photodegradation of MB on CdS nanoparticles prepared in the neat RTIL are about 20 and 6 times greater than the prepared sample in water using visible and UV lights, respectively.     

CdS-containing nano-assemblies of double hydrophilic block copolymers in water

Two samples of poly(sodium(sulfamate-carboxylate)isoprene)-block-poly(ethylene oxide) copolymer (SCIEO-1 and SCIEO-2) differing in molecular weight and relative length of polyelectrolyte blocks have been used as templates for the synthesis of cadmium sulfide (CdS) nanoparticles in aqueous media. The double-hydrophilic copolymer SCIEO has very high 1D charge density, and its polymer chain structure mimics that of polysaccharide heparin. It is soluble in aqueous media, but the addition of cadmium acetate (Cd(Ac)₂) to its aqueous solution causes the formation of micellar aggregates with Cd²⁺containing insoluble cores above the threshold Cd²⁺ concentration. The trapped Cd²⁺ ions can be chemically transformed to CdS nanoparticles. The stability of hybrid SCIEO/CdS micelles depends on the ratio of PEO-to-SCI lengths: it was found that the SCIEO-2 copolymer with sufficiently long PEO block behaves as an effective stabilizer for the synthesis of CdS nanoparticles embedded in micelles, while SCIEO-1 does not. The morphology of aggregates varies with the Cd-to-SCI ratios and ranges from spherical to mixture of spherical and necklace-like micellar aggregates. A number of experimental techniques including static and dynamic light scattering, fluorescence correlation spectroscopy, atomic force and transmission electron microscopy, UV-vis, and fluorescence spectroscopy were employed for the characterization of both CdS containing hybrid micelles and embedded CdS nanoparticles.     

Effect of Surface‐Hydroxylated CdS Nanoparticles on the Morphological Transformation of Polystyrene‐block‐Poly(ethylene oxide) Thin Films

Summary: Polystyrene‐block‐poly(ethylene oxide) (SEO) block copolymer thin films, in which CdS clusters have been sequestered into the PEO domains of the SEO block copolymers, are found to induce the morphological transformation of PEO from cylinders to spheres, as shown by using atomic force microscopy (AFM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). This transformation is caused by the presence of hydrogen‐bonding interactions between surface‐hydroxylated CdS and PEO, as confirmed by nuclear magnetic resonance (NMR) studies.

Morphological transformation of PEO cylinders into CdS/PEO spheres by hydrogen‐bonding interactions between surface‐hydroxylated CdS and PEO.     

Synthesis and characterization of organic–inorganic hybrid materials prepared by sol–gel and containing CdS nanoparticles prepared by a colloidal method using poly(N-vinyl-2-pyrrolidone)

This paper describes the synthesis and characterization of CdS nanoparticles (NPs) stabilized with poly(N-vinyl-2-pyrrolidone) and their further immobilization on a hybrid organic–inorganic matrix produced by the sol–gel process. The production of the hybrid matrix doped with CdS NPs was carried out in two steps. In the first step a precursor, designated diureasil precursor, was synthesized from the reaction between the terminal amine groups of α,ω-diamine-poly(oxyethylene-co-oxypropylene) and the isocyanate group of 3-isocyanatopropyltriethoxysilane. The next step involved the hydrolysis and condensation reactions of ethoxy groups attached to silicon, this step resulting in the formation of a crosslinked siliceous network linked through urea bonds to a poly(oxyethylene)/poly(oxypropylene) chain. The NPs were added to the diureasil precursor before the gelation process to allow a homogeneous dispersion of the NPs within the matrix. The developed method allowed the transfer of colloidal NPs to a solid matrix without the need of exchange the capping agents or the solvent. The materials were characterized by absorption, steady-state photoluminescence spectroscopy and by TEM. The results obtained showed the presence of CdS NPs with quantum size effect dispersed within the diureasil matrix. The obtained nanocomposites show a high transparency in the visible range accounting for the good dispersion of the NPs within the matrix. The TEM analysis confirmed that the NPs are uniformly dispersed within the diureasil matrix.     

Enhanced magnetoconductivity and electrical property of MWCNT-CdS nanocomposite embedded in polyaniline

PANI/MWCNT-CdS nanocomposites with different content of CdS wt.% has been synthesized by the chemical oxidative in-situ polymerization reaction of aniline in the presence of multi-walled carbon nanotubes (MWCNT). TEM, XRD, FTIR, and TGA studies were done for the structural and thermal characterization of the samples respectively. The particle size of CdS nanoparticles distributes in between 2.7 and 4.8 nm. XRD spectrum reveals that the co-existence of MWCNT, CdS in PANI matrix, where CdS forms a hexagonal structure. TGA result shows that nanocomposite becomes more thermally stable with the increase in CdS content. The dc electrical transport property of PANI/MWCNT-CdS nanocomposites has been investigated within a temperature range 77 ≤ T ≤ 300 K. The dc conductivity follows a 3D variable range hopping (VRH) model. A large magnetoconductivity change (19%) is observed for 2 wt% CdS content in PANI/MWCNT-CdS, which is explained by the wave function shrinkage model.     

CdS nanoparticles chemically modified PAN functional materials: Preparation and nonlinear optical properties

The fabrication of nanocomposites by covalent inclusion of inorganic nanoparticles in an organic polymer matrix is highly topical and may find applications in the electronics, optics and energy sectors. Incorporation of CdS nanoparticles into the polyacrylonitrile (PAN) matrices could be expected to display improved or enhanced optoelectronic and optical properties. Using a newly synthesized RAFT agent, i.e., CdS-DDAT nanoparticles (DDAT: S-1-Dodecyl-S′-(α, α′-dimethyl-α′′-acetic acid) trithiocarbonate), CdS covalently functionalized polyacrylonitrile (CdS-PAN) nanocomposite material was prepared in the presence of small amount of AIBN under ultrasonic radiation. This material, which exhibits an induced positive nonlinear absorption of incident light, has been well-characterized by a variety of physical techniques such as GPC, UV/vis, FT-IR, TGA, XRD and Z-scan.     

Study of the effect of formamide and N,N-dimethylformamide on the synthesis of CdS nanoparticles in a SiO2 matrix by sol-gel method

The influence of formamide (F) and N,N-dimethylformamide (DMF) in drying and firing of CdS nanocrystals in SiO₂ glasses by a sol-gel method has been studied. It has been established that pore size distribution and surface area are different with the use of DMF and that influences the quality of the final product. The presence of CdS semiconductor nanoparticles has been demonstrated by transmission electronic microscopy (TEM), and the quantum confinement effect due to the size of nanoparticles is denoted by a blue shift in the visible absorption spectra. From the results obtained in this paper, it is clear that DMF has an influence on final material microstructure.     

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.     

Fabrication of Luminescent CdS Nanoparticles on Short‐Peptide‐Based Hydrogel Nanofibers: Tuning of Optoelectronic Properties

The pH‐induced self‐assembly of three synthetic tripeptides in water medium is used to immobilize luminescent CdS nanoparticles. These peptides form a nanofibrillar network structure upon gelation in aqueous medium at basic pH values (pH 11.0–13.0), and the fabrication of CdS nanoparticles on the gel nanofiber confers the luminescent property to these gels. Atomic force microscopy, field‐emission scanning electron microscopy, and high‐resolution transmission electron microscopy clearly reveal the presence of CdS nanoparticles in a well‐defined array on the gel nanofibers. This is a convenient way to make organic nanofiber–inorganic nanoparticle hybrid nanocomposite systems. The size of the CdS nanoparticles remains almost same before and after deposition on the gel nanofiber. Photoluminescence (PL) measurement of the CdS nanoparticles upon deposition on the gel nanofibers shows a significant blue shift in the emission spectrum of the nanoparticles, and there is a considerable change in the PL gap energy of the CdS nanoparticles after immobilization on different gel nanofibrils. This finding suggests that the optoelectronic properties of CdS nanoparticles can be tuned upon deposition on gel nanofibers without changing the size of the nanoparticles.     

Preparation and optical properties of blue-emitting colloidal CdS nanocrystallines by the solvothermal process using poly (ethylene oxide) as the stabilizer

Blue-emitting colloidal CdS nanocrystals have been synthesized through the solvothermal reaction of cadmium acetate and thiourea in N,N-dimethylformamide using poly(ethylene oxide; PEO) as the stabilizing polymer. The as-prepared CdS colloids were stable at ambient conditions for several weeks. The PEO-stabilized CdS colloids showed a narrow fluorescence band with the maximum at about 420 nm and thus emitting blue fluorescence under the ultraviolet (UV) lamp. A common red shift of fluorescence band is not detected for the prepared CdS colloids in the study, indicating that PEO-stabilized CdS NCs possess few crystalline defects on their surface. In addition, transmission electron microscope micrographs reveal that the sizes of CdS NCs are between 4.4 to 5.4 nm with small standard deviations from 0.5 to 0.7 nm. The particle growth kinetics was studied by monitoring UV-visible absorption onsets versus the reaction time and was found to nearly follow the Lifshitz–Slyozov–Wagner theory for the Ostwald ripening mechanism.     

Preparation of CdS nanoparticles by hydrothermal method in microemulsion

CdS nanoparticles with good crystallinity were prepared by hydrothermal method in microemulsion composed of polyoxyethylene laurylether/water/cyclohexane/butanol. The structure and the size of the CdS nanoparticles were analyzed by TEM and XRD. The UV-Vis optical absorption of the samples was also investigated. The results show that hydrothermal treatment is an effective method to prepare CdS nanoparticles of hexagonal structure at lower temperature. The particles were in dimensional uniformity. The diameter of the CdS nanoparticles decreased with the increase of the molar ratio of water to surfactant. The minimum diameter of the CdS nanoparticles prepared in this work was about 10 nm. Obvious blue shift appeared in the UV-Vis absorption spectra. Translated from Chinese Journal of Inorganic Chemistry, 2006, 22(5): (in Chinese)     

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.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver (Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites, was designed as a photoanode for solar hydrogen generation, with photocurrent density achieving 4.7 mA/cm² at 1.6 V (vs. RHE), which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films, respectively. Additionally, with optical absorption onset extended to ～660 nm, CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-to-current efficiency (IPCE) in the whole optical absorption region, reaching 23.1% and 9.8% at 400 nm and 500 nm, respectively. The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer, and the extended visible-light absorption of CdS nanocrystallites. Moreover, the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability, due to its excellent plasmon resonance effect.     

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.     

Synthesis and barrier properties of a film polymer nanocomposite based on polystyrene and cadmium sulfide nanoparticles

A film polymer nanocomposite with nanoparticles of a chalcogenide semiconductor, CdS, in a polystyrene matrix was prepared on the surface of 08kp steel. The barrier properties of the synthesized two-layer film nanomaterial in a 3 wt % aqueous NaCl solution were evaluated by measuring the electrode potential of coated and uncoated specimens and were compared with those of polymer films without nanofiller and with Fe₃O₄ nanoparticles. Introduction of hydrophobic CdS nanoparticles into the polymer matrix leads to significant enhancement (by ～20%, as compared to Fe₃O₄) of the barrier properties of the polymer nanocomposite.     

巯萘剂表面修饰的CdS纳米微粒的合成及发光特性

用疏萘剂(TN)作为表面修饰剂,在甲醇溶液中合成了CdS/TN纳米微粒,用TEM测得纳米微粒呈球形,其粒径约10nm,吸收光谱和荧光光谱研究表明,[S^2-]/[TN]浓度比、TN和镉离子的浓度对CdS/TN纳米微粒的粒径及发光特性具有显著影响,且随着条件的改变,CdS/TN纳米微粒的发射波长红移100nm,表现出明显的量子尺寸特性.XPS显示所制得表面修饰纳米微粒的核为CdS.