One‐Step Preparation of Coaxial CdS–ZnS and Cd1–xZnxS–ZnS Nanowires

Preparation of coaxial (core–shell) CdS–ZnS and Cd_1–xZn_xS–ZnS nanowires has been achieved via a one‐step metal–organic chemical vapor deposition (MOCVD) process with co‐fed single‐source precursors of CdS and ZnS. Single‐source precursors of CdS and ZnS of sufficient reactivity difference were prepared and paired up to form coaxial nanostructures in a one‐step process. The sequential growth of ZnS on CdS nanowires was also conducted to demonstrate the necessity and advantages of the precursor co‐feeding practice for the formation of well‐defined coaxial nanostructures. The coaxial nanostructure was characterized and confirmed by high‐resolution transmission electron microscopy and corresponding energy dispersive X‐ray spectrometry analyses. The photoluminescence efficiencies of the resulting coaxial CdS–ZnS and Cd_1–xZn_xS–ZnS nanowires were significantly enhanced compared to those of the plain CdS and plain Cd_1–xZn_xS nanowires, respectively, owing to the effective passivation of the surface electronic states of the core materials by the ZnS shell.     

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.     

Efficient and Photostable ZnS‐Passivated CdS:Mn Luminescent Nanocrystals

Efficient and photostable ZnS‐passivated CdS:Mn (CdS:Mn/ZnS core/shell) nanocrystals were synthesized using reverse micelle chemistry. CdS:Mn/ZnS core/shell nanocrystals exhibited much improved luminescent properties (quantum yield and photostability) over organically (n‐dodecanethiol‐) capped CdS:Mn nanocrystals. This is the result of effective, robust passivation of CdS surface states by the ZnS shell and consequent suppression of non‐radiative recombination transitions. The dependence of photoluminescence (PL) intensity has been observed as a function of UV irradiation time for both organically and inorganically capped CdS:Mn nanocrystals. Whereas organically capped CdS:Mn nanocrystals exhibit a significant reduction of PL intensity, CdS:Mn/ZnS core/shell nanocrystals exhibit an increased PL intensity with UV irradiation. XPS (X‐ray photoelectron spectroscopy) studies reveal that UV irradiation of CdS:Mn/ZnS nanocrystals in air atmosphere induces the photo‐oxidation of the ZnS shell surface, leading to the formation of ZnSO₄. This photo‐oxidation product is presumably responsible for the enhanced PL emission, serving as a passivating layer.     

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.     

Quantification of Grafting Densities Achieved via Modular “Grafting‐to” Approaches onto Divinylbenzene Microspheres

The surface modification of divinylbenzene (DVB)‐based microspheres is performed via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization and rapid hetero‐Diels–Alder (HDA) chemistry with the aim of quantifying the grafting densities achieved using this “grafting‐to” method. Two variants of the RAFT‐HDA concept are employed to achieve the functionalization of the microspheres. In the first approach, the microspheres are functionalized with a highly reactive diene, i.e., cyclopentadiene, and are subsequently reacted with polystyrene chains (number‐averaged molecular weight, M_n = 4200 g mol^?1; polydispersity index, PDI = 1.12.) that carry a thiocarbonyl moiety functioning as a dienophile. The functionalization of the microspheres is achieved rapidly under ambient conditions, without the aid of an external catalyst. The surface grafting densities obtained are close to 1.2 × 10²⁰ chains per gram of microspheres. In the second approach, the functionalization proceeds via the double bonds inherently available on the microspheres, which are reacted with poly(isobornyl acrylate) chains carrying a highly dienophilic thiocarbonyl functionality; two molecular weights (M_n = 6000 g mol^?1, PDI = 1.25; M_n = 26 000 g mol^?1, PDI = 1.26) are used. Due to the less reactive nature of the dienes in the second approach, functionalization is carried out at elevated temperatures (T = 60 °C) yet in the absence of a catalyst. In this case the surface grafting density is close to 7 chains nm^?2 for M_n = 6000 g mol^?1 and 4 chains nm^?2 for M_n = 26 000 g mol^?1, or 2.82 × 10¹⁹ and 1.38 × 10¹⁹ chains g^?1, respectively. The characterization of the microspheres at various functionalization stages is performed via elemental analysis for the quantification of the grafting densities and attenuated total reflectance (ATR) IR spectroscopy as well as confocal microscopy for the analysis of the surface chemistry.     

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.     

Synthesis of Magnetic,Up‐Conversion Luminescent,and Mesoporous Core–Shell‐Structured Nanocomposites as Drug Carriers

The synthesis (by a facile two‐step sol–gel process), characterization, and application in controlled drug release is reported for monodisperse core–shell‐structured Fe₃O₄@nSiO₂@mSiO₂@NaYF₄: Yb³⁺, Er³⁺/Tm³⁺ nanocomposites with mesoporous, up‐conversion luminescent, and magnetic properties. The nanocomposites show typical ordered mesoporous characteristics and a monodisperse spherical morphology with narrow size distribution (around 80 nm). In addition, they exhibit high magnetization (38.0 emu g^?1, thus it is possible for drug targeting under a foreign magnetic field) and unique up‐conversion emission (green for Yb³⁺/Er³⁺ and blue for Yb³⁺/Tm³⁺) under 980 nm laser excitation even after loading with drug molecules. Drug release tests suggest that the multifunctional nanocomposites have a controlled drug release property. Interestingly, the up‐conversion emission intensity of the multifunctional carrier increases with the released amount of model drug, thus allowing the release process to be monitored and tracked by the change of photoluminescence intensity. This composite can act as a multifunctional drug carrier system, which can realize the targeting and monitoring of drugs simultaneously.     

Water‐Stable,Magnetic Silica–Cobalt/Cobalt Oxide–Silica Multishell Submicrometer Spheres

A method to produce monodisperse magnetic composite spheres with diameters from less than 100 nm to more than 1 μm in water solution is reported. The spheres consist of a dielectric silica core and a cobalt/cobalt oxide shell which can be protected from further oxidation with an outer shell of silica or, alternatively, they can be covered with the polymer polyvinylpyrrolidone as a stabilizer. The formation of a uniform magnetic shell proceeds with the adsorption of metallic cobalt seeds, produced by the reduction of cobalt chloride with sodium borohydride, on a self‐assembled layer of polyelectrolytes on the silica core. In the second step, an outer silica shell can be formed by the hydrolysis and condensation of (3‐aminopropyl)trimethoxysilane and tetraethoxysilane. The double‐shell composite spheres show excellent sphericity, monodispersity, and a magnetic hysteresis loop at room temperature.     

The Huang–Rhys factor and the strength of exciton–LO phonon coupling in ZnO/Mg0.15Zn0.85O superlattices

The temperature dependence of the photoluminescence full width at half maximum and the Huang–Rhys S factor is investigated in ZnO/Mg_0.15Zn_0.85O superlattices. The coupling strength between excitons and longitudinal–optical phonons, which calculated from the temperature dependence of the photoluminescence full width at half maximum, is closely related to the exciton binding energies when the wellwidth is small.     

Hybrid ZnO–Dye Hollow Spheres with New Optical Properties by a Self‐Assembly Process Based on Evans Blue Dye and Cetyltrimethylammonium Bromide

A facile one‐step process for the fabrication of hybrid ZnO–dye hollow spheres with novel optical properties has been discovered. Addition of Evans blue (EB) dye to cetyltrimethylammonium bromide (CTAB) results in the formation of CTAB‐EB micelles through an ionic self‐assembly process, and the resulting material acts as a soft template for the crystallization of ZnO upon addition of a zinc salt and ammonia under mild refluxing conditions. The formation mechanism of such hollow spheres has been investigated. These new hybrid ZnO–dye hollow spheres display distinct optical properties that differ from properties observed for the pure ZnO and dye components. This approach is a new and effective method for fabricating novel semiconductor–dye hybrids with unique electronic and optical properties and is expected to provide access to additional inorganic–organic materials with novel structures and unusual functionalities.     

Synthesis of Semiconducting Functional Materials in Solution: From II‐VI Semiconductor to Inorganic–Organic Hybrid Semiconductor Nanomaterials

This Feature Article provides a brief overview of the latest development and emerging new synthesis solution strategies for II–VI semiconducting nanomaterials and inorganic‐organic semiconductor hybrid materials. Research on the synthesis of II–VI semiconductor nanomaterials and inorganic–organic hybrid semiconducting materials via solution strategies has made great progress in the past few years. A variety of II–VI semiconductor and a new family of [MQ(L)_0.5] (M = Mn, Zn, Cd; Q = S, Se, Te; L = diamine, deta) hybrid nanostructures can be generated using solution synthetic routes. Recent advances have demonstrated that the solution strategies in pure solvent and a mixed solvent can not only determine the crystal size, shape, composition, structure and assembly properties, but also the crystallization pathway, and act as a matrix for the formation of a variety of different II–VI semiconductor and hybrid nanocomposites with diverse morphologies. These II–VI semiconductor nanostructures and their hybrid nanocomposites display obvious quantum size effects, unique and tunable optical properties.     

A Novel Cathode Material with a Concentration‐Gradient for High‐Energy and Safe Lithium‐Ion Batteries

A high‐energy functional cathode material with an average composition of Li[Ni_0.72Co_0.18Mn_0.10]O₂, mainly comprising a core material Li[Ni_0.8Co_0.2]O₂ encapsulated completely within a stable manganese‐rich concentration‐gradient shell is successfully synthesized by a co‐precipitation process. The Li[Ni_0.72Co_0.18Mn_0.10]O₂ with a concentration‐gradient shell has a shell thickness of about 1 µm and an outer shell composition rich in manganese, Li[Ni_0.55Co_0.15Mn_0.30]O₂. The core material can deliver a very high capacity of over 200 mA h g^?1, while the manganese‐rich concentration‐gradient shell improves the cycling and thermal stability of the material. These improvements are caused by a gradual and continuous increase of the stable tetravalent Mn in the concentration‐gradient shell layer. The electrochemical and thermal properties of this cathode material are found to be far superior to those of the core Li[Ni_0.8Co_0.2]O₂ material alone. Electron microscopy also reveals that the original crystal structure of this material remains intact after cycling.     

Yolk–Shell Hybrid Materials with a Periodic Mesoporous Organosilica Shell: Ideal Nanoreactors for Selective Alcohol Oxidation

This contribution describes the preparation of multifunctional yolk–shell nanoparticles (YSNs) consisting of a core of silica spheres and an outer shell based on periodic mesoporous organosilica (PMO) with perpendicularly aligned mesoporous channels. The new yolk–shell hybrid materials were synthesised through a dual mesophase and vesicle soft templating method. The mesostructure of the shell, the dimension of the hollow space (4～52 nm), and the shell thickness (16～34 nm) could be adjusted by precise tuning of the synthesis parameters, as evidenced by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen sorption investigations. Various metal nanoparticles (e.g., Au, Pt, and Pd) were encapsulated and confined in the void space between the core and the shell using impregnation and reduction of adequate metal precursors. The selective oxidation of various alcohol substrates was then carried out to illustrate the benefits of such an architecture in catalysis. High conversion (～100%) and excellent selectivity (～99%) were obtained over Pd nanoparticles encapsulated in the hybrid PMO yolk–shell structures.     

Wavelength‐Dependent Photosensitivity in a Germanium‐Doped Sol–Gel Hybrid Material for Direct Photopatterning

Photosensitivity, as evident in permanent changes in refractive index and volume upon light exposure, is observed in a germanium‐doped methacrylate hybrid material (hybrimer) and found to depend on the wavelength of the UV light. Exposure to short‐wavelength UV illumination (220–260 nm) results in very high photosensitivity with changes in refractive index (Δn ≈ 0.0164) and film thickness (Δt ≈ –40 %) that are mainly a result of photopolymerization and Ge‐related densification. In contrast, the hybrimer is hardly photosensitive to light in the long UV‐wavelength range (350–390 nm). Direct photopatterning of a single circle on the hybrimer film creates a concave lens‐like topography upon illumination with UV light of short wavelength and a convex lens‐like one upon illumination with UV light of long wavelength.     

In Situ Preparation of Sandwich MoO3/C Hybrid Nanostructures for High‐Rate and Ultralong‐Life Supercapacitors

This work presents a design of sandwich MoO₃/C hybrid nanostructure via calcination of the dodecylamine‐intercalated layered α‐MoO₃, leading to the in situ production of the interlayered graphene layer. The sample with a high degree of graphitization of graphene layer and more interlayered void region exhibits the most outstanding energy storage performance. The obtained material is capable of delivering a high specific capacitance of 331 F g^?1 at a current density of 1 A g^?1 and retained 71% capacitance at 10 A g^?1. In addition, nearly no discharge capacity decay between 1000 and 10 000 continuous charge–discharge cycles is observed at a high current density of 10 A g^?1, indicating an excellent specific capacitance retention ability. The exceptional rate capability endows the electrode with a high energy density of 41.2 W h kg^?1 and a high power density of 12.0 kW kg^?1 simultaneously. The excellent performance is attributed to the sandwich hybrid nanostructure of MoO₃/C with broad ion diffusion pathway, low charge‐transfer resistance, and robust structure at high current density for long‐time cycling. The present work provides an insight into the fabrication of novel electrode materials with both enhanced rate capability and cyclability for potential use in supercapacitor and other energy storage devices.     

Hybrids of Magnetic Nanoparticles with Double‐Hydrophilic Core/Shell Cylindrical Polymer Brushes and Their Alignment in a Magnetic Field

The synthesis of double‐hydrophilic core/shell cylindrical polymer brushes (CPBs), their hybrids with magnetite nanoparticles, and the directed alignment of these magnetic hybrid cylinders by a magnetic field are demonstrated. Consecutive grafting from a polyinitiator poly(2‐(2‐bromoisobutyryloxy)ethyl methacrylate) (PBIEM) of tert‐butyl methacrylate (tBMA) and oligo(ethylene glycol) methacrylate (OEGMA) using atom‐transfer radical polymerization (ATRP) and further de‐protection yields core/shell CPBs with poly(methacrylic acid) (PMAA) as the core and POEGMA as the shell, which is evidenced by ¹H NMR, gel permeation chromatography (GPC), and dynamic and static light scattering (DLS and SLS). The resulting core/shell brush is well soluble in water and shows a pH responsiveness because of its weak polyelectrolyte core. Pearl‐necklace structures are observed by cryogenic transmission electron microscopy (cryo‐TEM) at pH 4, while at pH 7, these structures disappear owing to the ionization of the core. A similar morphology is also found for the polychelate of the core/shell CPBs with Fe³⁺ ions. Superparamagnetic magnetite nanoparticles have also been prepared and introduced into the core of the brushes. The hybrid material retains the superparamagnetic property of the magnetite nanoparticles, which is verified by superconducting quantum interference device (SQUID) magnetization measurements. Large‐scale alignment of the hybrid cylinders in relatively low magnetic fields (40–300 mT) can easily be performed when deposited on a surface. which is clearly revealed by the atomic force microscopy (AFM) and TEM measurements.     

Preparation of Secondary Mesopores in Mesoporous Anatase–Silica Nanocomposites with Unprecedented‐High Photocatalytic Degradation Performances

In this article, a simple and mild preparation of secondary pores are reported, for the first time, with uniform and tunable sizes (in a wide range of 0.9–4.8 nm) in the walls highly connecting the primary mesochannels in 3D mesopore networks. The uniform secondary pores are obtained by using ordered 2D hexagonal mesoporous anatase TiO₂–SiO₂ nanocomposites as precursors, NaOH as an etchant via an “extracting SiO₂” approach. The strategy here adopts diluted NaOH solution, appropriate extraction temperature, and solid/liquid ratio. The photocatalytic degradation rates of Rhodamine B (0.347 min^–1), Acid Red 1 (0.0487 min^–1), microcystin–LR (1.66 min^–1) on the representative resultant nanocomposite are very high, which are 4.63, 11.7, 1.84 times that of the precursor without secondary mesopores; even up to 18.9, 8.21, 4.66 times that of P25, respectively. These results clearly demonstrate that the secondary mesopores play an overwhelming role to the increments of activities. The mesoporous anatase–silica nanocomposites with secondary mesopores present unprecedented‐high degradation activities to various organic pollutants in the mesoporous metal‐oxides‐based materials reported up to now and are considerably stable and reusable. It is believed that the fundamentals in this study will provide new insights for rational design and preparation of 3D highly interconnected mesoporous metal‐oxides‐based materials with super‐high performances.     

Formation Mechanism of Epitaxial Palladium–Platinum Core–Shell Nanocatalysts in a One‐Step Supercritical Synthesis

The scarcity of platinum group metals provides a strong incentive to optimize the catalytic activity and stability, e.g., through nanoalloys or core–shell nanoparticles. Here, time‐resolved X‐ray total scattering and transmission electron microscopy characterization are used to study the formation of palladium–platinum core–shell nanoparticles under solvothermal conditions. It is shown that Pd rapidly forms small (5–10 nm), disordered primary particles, which agglomerate and crystallize when reaching 20–25 nm. The primary Pd particles provide nucleation sites for Pt, and, with extended reaction time, the Pd cores become fully covered with Pt shells. The observed core–shell material is surprising when considering the Pt–Pd phase diagram and relative surface energies, but it can be rationalized through the kinetics of precursor conversion. To bridge the gap between scientific studies and industrial demand for large‐scale production, the synthesis process is successfully transferred to a continuous flow supercritical reactor providing a simple scalable and green process for production of bimetallic nanocatalysts.