Highly Luminescent CdSe/ZnS Nanocrystals Synthesized Using a Single‐Molecular ZnS Source in a Microfluidic Reactor

An air‐stable, low‐toxicity, single‐molecular source for ZnS is demonstrated to be an appropriate reagent to synthesize highly luminescent ZnS‐capped CdSe with a narrow size distribution. A photoluminescence quantum yield of above 50 % and a photoluminescence peak full width at half maximum of around 32 nm could be obtained after synthesis using a microreactor. The surface of the ZnS‐capped CdSe nanocrystals can be hydrophilic, while retaining the high quantum yield. Microscopic observation shows that accurate time control, which could be achieved by using a microreactor, is important to avoid the formation of many isolated ZnS particles and the deterioration of the luminescence.     

Organically Doped Metals—A New Approach to Metal Catalysis: Enhanced Ag‐Catalyzed Oxidation of Methanol

We report here a new approach for the modification of the performance of metal catalysts: organic doping of the metal. Specifically, we report that the doping of Ag with Congo Red (CR@Ag) significantly improves the performance of Ag as a catalyst for methanol oxidation to formaldehyde, outperforming both pure Ag and CR‐coated Ag (CR/Ag) in terms of lowering the temperature needed for maximal conversion by 100 °C, lowering the temperature by 200 °C to reach the maximal selectivity (aldehyde formation), and increasing the maximal space velocity by a factor of two. We were led to this discovery by a detailed investigation of the thermal behavior (thermogravimetric and differential thermal analysis and mass spectroscopy) of CR@Ag under an oxidative atmosphere, which has indicated that the metal is strongly catalyzing the CR oxidation, and which pointed to the relevant temperature for activation of the catalyst.     

Red Phosphorescent Iridium Complex Containing Carbazole‐Functionalized β‐Diketonate for Highly Efficient Nondoped Organic Light‐Emitting Diodes

A novel red phosphorescent iridium complex containing a carbazole‐functionalized β‐diketonate, Ir(DBQ)₂(CBDK) (bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐diketonate)) is designed, synthesized, and characterized. The electrophosphorescence properties of a nondoped device using the title complex as an emitter with a device configuration of indium tin oxide (ITO)/N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)‐1,1′‐diphenyl‐4,4′‐diamine (NPB; 20 nm)/iridium complex (20 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 5 nm)/tris(8‐hydroxyquinoline) (AlQ; 30 nm)/Mg_0.9Ag_0.1 (200 nm)/Ag (80 nm) are examined. The results show that the nondoped device achieves a maximum lumen efficiency as high as 3.49 lm W^–1. To understand this excellent result observed, two reference complexes Ir(DBQ)₂(acac), where acac is the acetyl acetonate anion, and Ir(DBQ)₂(FBDK), [bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(9‐methyl‐fluoren‐9‐yl)‐6,6‐dimethylheptane‐3,5‐diketonate)], have also been synthesized, and as emitters they were examined under the same device configuration. The maximum lumen efficiency of the former compound is found to be 0.26 lm W^–1 while that for the latter is 0.37 lm W^–1, suggesting that the excellent performance of Ir(DBQ)₂(CBDK) can be attributed mainly to an improved hole‐transporting property that benefits the exciton transport. In addition, a bulky diketonate group separates the emitter centers from each other, which is also important for organic light‐emitting diodes.     

Carbon‐Decorated FePt Nanoparticles

FePt magnetic nanoparticles are an important candidate material for many future magnetic applications. FePt exists as two main phases, that is, a disordered face‐centered cubic (fcc) structure, which is generally prepared by chemical methods at low temperatures, and the high‐temperature chemically ordered face‐centered tetragonal (fct) structure. The fcc FePt, with low coercivity but associated with superparamagnetic properties, may find applications as a magnetic fluid or as a nanoscale carrier for chemical or biochemical species in biomedical areas, while fct FePt is proposed for use in ultrahigh‐density magnetic recording applications. However, for both of these applications an enhancement of the intrinsically weak magnetic properties, the avoidance of magnetic interferences from neighbor particles, and the improved stability of the small magnetic body remain key practical issues. We report a simple synthetic method for producing FePt nanoparticles that involves hydrothermal treatment of Fe and Pt precursors in glucose followed by calcination at 900 °C. This new method produces thermally stable spheroidal graphite nanoparticles (large and fullerene‐like) that encapsulate or decorate FePt particles of ca. 5 nm with no severe macroscopic particle coalescence. Also, a low coercivity of the material is recorded; indicative of small magnetic interference from neighboring carbon‐coated particles. Thus, this simple synthetic method involves the use of a more environmentally acceptable glucose/aqueous phase to offer a protective coating for FePt nanoparticles. It is also believed that such a synthetic protocol can be readily extended to the preparation of other graphite‐coated magnetic iron alloys of controlled size, stoichiometry, and physical properties.     

Efficient Photosensitization and High Optical Gain in a Novel Quantum‐Dot‐Sensitized Hybrid Photorefractive Nanocomposite at a Telecommunications Wavelength

A high‐performance hybrid polymeric photorefractive nanocomposite operating at the telecommunications wavelength of 1.34 μm is presented. The photorefractive nanocomposite is sensitized with PbS nanocrystals synthesized via a hot colloidal route. Photoconductivity experiments confirm and quantify the photocharge‐generation quantum efficiency of the nanocrystals. A pronounced two‐beam coupling effect at the operation wavelength is observed, leading to very high optical gains. Temporal evolution of the photorefractive growth process is also studied.     

A New Sol–Gel Material Doped with an Erbium Complex and Its Potential Optical‐Amplification Application

The crystal structure of a ternary Er(DBM)₃phen complex (DBM = dibenzoylmethane; phen = 1,10‐phenanthroline) and its in‐situ synthesis via a sol–gel process are reported. The infrared (IR), diffuse reflectance (DR), and fluorescence spectra of the pure complex and the Er³⁺/DBM/phen co‐doped luminescent hybrid gel, formed via an in‐situ method (ErDP gel), have been investigated. The results reveal that the erbium complex is successfully synthesized in situ in the ErDP gel. Excitation at the maximum absorption wavelength of the ligands resulted in the typical near‐IR luminescence (centered at around 1.54 μm) resulting from the ⁴I_13/2 → ⁴I_15/2 transition of the Er³⁺ ion, which contributes to the efficient energy transfer from the ligands to the Er³⁺ ion in both the Er(DBM)₃phen complex and the ErDP gel (an antenna effect). The full width at half maximum (FWHM) centered at 1541 nm in the emission spectrum of the ErDP gel is 72 nm, which has potential for optical‐amplification applications. Further theoretical analysis on the Er³⁺ ion in the ErDP gel shows that it appears to be a promising candidate for tunable lasers and planar optical amplifiers.     

Doping‐Induced Charge Trapping in Organic Light‐Emitting Devices

By using pyran‐containing donor–acceptor dyes as doping molecules in organic light‐emitting devices (OLEDs), we scrutinize the effects of charge trapping and polarization induced by the guest molecules in the electro‐active host material. Laser dyes 4‐(dicyanomethylene)‐2‐methyl‐6‐[2‐(julolidin‐9‐yl)phenyl]ethenyl]‐4H‐pyran (DCM2) and the novel 4‐(dicyanomethylene)‐2‐methyl‐6‐{2‐[(4‐diphenylamino)phenyl]ethenyl}‐4H‐pyran (DCM‐TPA) are used as model compounds. The emission color of these polar dyes depends strongly on doping concentration, which we have attributed to polarization effects induced by the doping molecules themselves. Their frontier orbital energy levels are situated within the bandgap of the tris(8‐hydroxyquinoline)aluminum (Alq₃) host matrix and allow the investigation of either electron trapping or both electron and hole trapping. In the case of DCM‐TPA doping, we were able to show that electron trapping leads to a partial shift of the recombination zone out of the doped Alq₃ region. To impede charge‐recombination processes taking place in the undoped host matrix, a charge‐blocking layer efficiently confines the recombination zone inside the doped zone and gives rise to increased luminous efficiency. For a doping concentration of 1 wt.‐% we obtain a maximum luminous efficiency of 10.4 cd A^–1. At this doping concentration, the yellow emission spectrum shows excellent color saturation with CIE chromaticity coordinates x, y of 0.49 and 0.50, respectively. In the case of DCM2 the recombination zone is much less affected for the same doping concentrations, which is ascribed to the fact that both electrons and holes are being trapped. The experimental findings are corroborated with a numerical simulation of the doped multilayer devices.     

CdS‐Nanoparticle/Polymer Composite Shells Grown on Silica Nanospheres by Atom‐Transfer Radical Polymerization

In this paper we describe the combined use of surface‐initiated atom transfer radical polymerization (ATRP) and a gas/solid reaction in the direct preparation of CdS‐nanoparticle/block‐copolymer composite shells on silica nanospheres. The block copolymer, consisting of poly(cadmium dimethacrylate) (PCDMA) and poly(methyl methacrylate) (PMMA), is obtained by repeatedly performing the surface‐initiated ATRP procedures in N,N‐dimethylformamide (DMF) solution at room temperature, using cadmium dimethacrylate (CDMA) and methyl methacrylate (MMA) as the monomers. CdS nanoparticles with an average size of about 3 nm are generated in situ by exposing the silica nanospheres coated with block‐copolymer shells to H₂S gas. These synthetic core–shell nanospheres were characterized using transmission electron microscopy (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA), diffuse reflectance UV‐vis spectroscopy, X‐ray photoelectron spectroscopy (XPS), and powder X‐ray diffraction (XRD). These composite nanospheres exhibit strong red photoluminescence in the solid state at room temperature.     

Evidence of Interfacial Charge Transfer upon UV‐Light Irradiation in Novel Titanium Oxide Gel

We report on the combined magnetization and electron paramagnetic resonance characterization of a novel Ti‐O organic–inorganic gel hybrid and the related electron–hole generation process upon UV illumination. We find that electrons are injected into the conduction band of the Ti‐O framework, photoreducing Ti^IV to Ti^III. Ti^III sites are mainly located on the surface, owing to the nanometric dimensions of the inorganic component. Surprisingly, the symmetry of the TiO₆ octahedra depends on the level of illumination: in the lightly UV‐exposed samples Ti^III is sited in the weakly distorted TiO₆ octahedra to which methanoate groups are bonded, as suggested by electron spin echo envelope modulation (ESEEM) experiments. Extensive illumination causes structural rearrangements, leading to enhanced tetragonal TiO₆ distortion and shifting the Ti^III interaction towards the hydroxide groups or water. The results provide clear evidence for an interfacial charge transfer between the quantum‐size TiO lattice and coordinated species upon in situ and ex situ UV illumination at temperatures from room temperature to 5 K.     

Synthesis and Assembly of Gold Nanoparticles in Quasi‐Linear Lysine–Keggin‐Ion Colloidal Particles

The formation of fiber‐like colloidal particles of the amino acid lysine complexed with Keggin ions is demonstrated. The lysine–phosphotungstic acid (PTA) colloidal particles act as excellent templates for the synthesis and assembly of gold nanoparticles wherein the lysine‐PTA complex acts as a UV‐switchable reducing agent for gold ions. This novel bio‐organic–inorganic template shows excellent potential as a regulated nanoreactor for application in programmed nanoparticle synthesis and assembly in a single step.     

Fabrication of Hollow Inorganic Microspheres by Chemically Induced Self‐Transformation

Two contrasting approaches, involving either polymer‐mediated or fluoride‐mediated self‐transformation of amorphous solid particles, are described as general routes to the fabrication of hollow inorganic microspheres. Firstly, calcium carbonate and strontium tungstate hollow microspheres are fabricated in high yield using sodium poly(4‐styrenesulfonate) as a stabilizing agent for the formation and subsequent transformation of amorphous primary particles. Transformation occurs with retention of the bulk morphology by localized Ostwald ripening, in which preferential dissolution of the particle interior is coupled to the deposition of a porous external shell of loosely packed nanocrystals. Secondly, the fabrication process is extended to relatively stable amorphous microspheres, such as TiO₂ and SnO₂, by increasing the surface reactivity of the solid precursor particles. For this, fluoride ions, in the form of NH₄F and SnF₂, are used to produce well‐defined hollow spheroids of nanocrystalline TiO₂ and SnO₂, respectively. Our results suggest that the chemical self‐transformation of precursor objects under morphologically invariant conditions could be of general applicability in the preparation of a wide range of nanoparticle‐based hollow architectures for technological and biomedical applications.     

Composition‐ and Shape‐Controlled Synthesis and Optical Properties of ZnxCd1–xS Alloyed Nanocrystals

Composition‐tunable Zn_xCd_1–xS alloyed nanocrystals have been synthesized by a new approach consisting of thermolyzing a mixture of cadmium ethylxanthate (Cd(exan)₂) and zinc ethylxanthate (Zn(exan)₂) precursors in hot, coordinating solvents at relatively low temperatures (180–210 °C). The composition of the alloyed nanocrystals was accurately adjusted by controlling the molar ratio of Cd(exan)₂ to Zn(exan)₂ in the mixed reactants. The alloyed Zn_xCd_1–xS nanocrystals prepared in HDA/TOP (HDA: hexadecylamine; TOP: trioctylphosphine) solution exhibit composition‐dependent shape and phase structures as well as composition‐dependent optical properties. The shape of the Zn_xCd_1–xS nanocrystals changed from dot to single‐armed rod then to multi‐armed rod with a decrease of Zn content in the ternary nanoparticles. The alloying nature of the Zn_xCd_1–xS nanocrystals was consistently confirmed by the results of high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), and UV‐vis absorption and photoluminescence (PL) spectroscopy. Further, the shape‐controlled synthesis of the ternary alloyed nanocrystals was realized by selecting appropriate solvents. Uniform nanodots in the whole composition range were obtained from TOPO/TOP solution, (TOPO: trioctylphosphine oxide) and uniform nanorods in the whole composition range were prepared from HDA/OA solution (OA: octylamine). The effect of the reaction conditions, such as solvent, reaction temperature, and reaction time, on the PL spectra of the alloyed Zn_xCd_1–xS nanocrystals was also systematically studied, and the reaction conditions were optimized for improving the PL properties of the nanocrystals.     

Mixed‐Valence‐Driven Quasi‐1D SnIISnIVS3 with Highly Polarization‐Sensitive UV–vis–NIR Photoresponse

Mixed‐valence states can bring unexpected unique phenomena, especially novel anisotropic physics, due to structural asymmetry, which originate from the discrepant distribution of atoms with different valence. This study reports an unexploited mixed‐valence‐driven quasi‐1D Sn^IISn^IVS₃ crystal, which exhibits widely and distinctively anisotropic polarized‐light absorption reaching ≈3.4 from the deep ultraviolet to near‐infrared region (250–850 nm). The fabricated polarization‐sensitive photodetectors based on highly air‐stable Sn^IISn^IVS₃ nanowires display strong linear dichroism among the UV–vis–NIR spectrum with responsivity exceeding ≈150 A W^?1. Furthermore, the devices are further constructed onto a flexible polyethylene terephthalate (PET) substrate and the photoresponse remains roughly unchanged after repeated bending. This work based on novel mixed‐valence‐driven quasi‐1D ternary sulfide Sn^IISn^IVS₃ excites interest in low‐symmetry semiconductors for developing broadly spectral polarization‐sensitive photodetectors with environmental stability and mechanical flexibility.     

Thioether‐bridged Mesoporous Organosilicas: Mesophase Transformations Induced by the Bridged Organosilane Precursor

The achievement of structural control over thioether‐bridged mesoporous organosilicas is reported. The mesoporous materials have been synthesized by co‐condensation of bis[3‐(triethoxysilyl)propyl]tetrasulfide (TESPTS) and tetramethoxysilane (TMOS) in acetic acid/sodium acetate buffer solution (HAc–NaAc, pH 4.4), using the nonionic surfactant P123 as a template. The mesostructure of the material is mainly controlled by the molar ratio of TESPTS/TMOS in the initial gel mixture. A mesophase transformation, progressing from a highly ordered 2D hexagonal structure via a vesiclelike structure to a mesostructured cellular foam, can be clearly observed when the molar ratio of TESPTS/TMOS is increased in increments. Solid‐state NMR results show that TESPTS is not completely hydrolyzed and condensed at the applied buffer conditions. At low concentrations, the unhydrolyzed TESPTS can penetrate into the core of the surfactant micelles and change the packing parameter of the P123 surfactant. Above a certain concentration, the TESPTS can form a microemulsion with P123 surfactant molecules. Therefore, the vesiclelike structure or cellular foam structure can be synthesized by simply controlling the molar ratio of TESPTS/TMOS. This approach provides a novel method for the facile synthesis of organic–inorganic hybrid materials with a controllable mesostructure under mild synthetic conditions.     

Thermo‐Mechanical Responses of Liquid‐Crystal Networks with a Splayed Molecular Organization

Films of liquid‐crystal networks with a splayed molecular alignment over their cross‐section display a well‐controlled deformation as a function of temperature. The deformation can be explained in terms of differences in thermal expansion depending on the average molecular orientation of the mesogenic centers of the monomeric units. The thermal expansion of the anisotropic polymers has been characterized as a function of their molecular structure and the polymerization conditions. As a reference, films with an in‐plane 90° twist have also been studied and compared with the splayed, out‐of‐plane molecular rotation. The twisted films show a complex macroscopic deformation owing to the formation of saddle‐like geometries, whereas the deformation of the splayed structured is smooth and well controlled. The deformation behavior is anticipated to be of relevance for polymer‐based microelectromechanical system (MEMS) technology.     

Biomimetic Formation of Hydroxyapatite Nanorods by a Single‐Crystal‐to‐Single‐Crystal Transformation

Uniform nanorods of hydroxyapatite (HAP) with an unusual orthorhombic shape have been synthesized from homogeneous solutions of Ca²⁺ and HPO₄^2– in the presence of gelatin and urea. The lengths of the nanorods are in the range of hundreds of micrometers, and the widths are about 100 nm. The HAP phase is generated by the transformation from its precursor phase of octacalcium phosphate (OCP), which has been monitored by X‐ray diffraction, NMR spectroscopy, scanning electron microscopy, and transmission electron microscopy. The rise in pH due to the decomposition of urea drives the OCP transformation to HAP. In the presence of gelatin, nanorods of OCP phase formed first and then transformed into the HAP phase, preserving the single‐crystal morphology. On the other hand, blade‐like OCP crystals form from the solution in the absence of gelatin. On increasing the pH of the solution, the large, blade‐like OCP crystals tend to crash into irregular, hexagonal HAP crystallites. A single‐crystal‐to‐single‐crystal topochemical transformation may be attributed to the evolution of HAP nanorods from the precursor OCP phase. This gives a strong indication as to the OCP to HAP transformation mechanism in the mineralization of biological apatite in tooth enamel and bone.     

Microwave‐Assisted Synthesis of Nanocrystalline MgO and Its Use as a Bacteriocide

Nanocrystalline particles of MgO were synthesized using microwave radiation in an ethylene glycol solution. The antibacterial activities of the MgO nanoparticles were tested by treating Escherichia coli (Gram negative) and Staphylococcus aureus (Gram positive) cultures with 1 mg mL^–1 of the nanoparticles. We have examined the importance of the size effect, pH, and the form of the active MgO species as a bactericidal agent. A clear size dependence of the nanoparticles is observed where the amount of eradicated bacteria was strongly dependent on the particle size.     

Hydrogen Adsorption in Metal–Organic Frameworks: Cu‐MOFs and Zn‐MOFs Compared

Hydrogen adsorption in two different metal–organic frameworks (MOFs), MOF‐5 and Cu‐BTC (BTC: benzene‐1,3,5‐tricarboxylate), with Zn²⁺ and Cu²⁺ as central metal ions, respectively, is investigated at temperatures ranging from 77 K to room temperature. The process responsible for hydrogen storage in these MOFs is pure physical adsorption with a heat of adsorption of approximately –4 kJ mol^–1. With a saturation value of 5.1 wt.‐% for the hydrogen uptake at high pressures and 77 K, MOF‐5 shows the highest storage capacity ever reported for crystalline microporous materials. However, at low pressures Cu‐BTC shows a higher hydrogen uptake than MOF‐5, making Cu‐based MOFs more promising candidates for potential storage materials. Furthermore, the hydrogen uptake is correlated with the specific surface area for crystalline microporous materials, as shown for MOFs and zeolites.     

Nanocrystalline Metal Oxides from the Injection of Metal Oxide Sols in Coordinating Solutions: Synthesis,Characterization, Thermal Stabilization,Device Processing,and Gas‐Sensing Properties

Metal oxide (SnO₂, TiO₂, In₂O₃, ZnO) sols are prepared by various sol–gel processes in such a way as to hinder the condensation reactions. The obtained sols are injected at 160 °C into a solution of tetradecene and dodecylamine, and kept under heating for different periods of time. Depending on the starting sol, variously crystallized oxide nanoparticles are obtained, whose phase compositions and chemical structure have been studied by X‐ray diffraction (XRD) and Fourier transform IR spectroscopy. The elimination of the organic residuals has been carried out by thermal treatment, and the thermal evolution of the nanoparticles has been studied by thermal analyses and Raman spectroscopy. High‐resolution transmission electron microscopy studies coupled with XRD measurements show that the thermal treatment does not markedly affect the particle size, which remains in the nanometer‐sized regime (from 3.5 to 8.5 nm, depending on the system), except in the case of ZnO. The thermally purified and stabilized powders, drop‐coated onto alumina substrates with pre‐deposited electrical contacts, have been tested as gas‐sensing devices, displaying outstanding sensing properties even at room temperature.