以含铬类水滑石型层状化合物为模板制备硫化物半导体纳米晶

采用类水滑石型混合金属氢氧化物(CdCr-LDH和ZnCdCr-LDH)为前驱体, 通过气-固反应方法, 制备了根植于层状氢氧化物层板中的硫化镉纳米晶和硫化镉/硫化锌复合纳米晶, 通过改变前驱体(CdCr-LDH)中镉和铬的摩尔比可以调控硫化镉纳米晶的粒径.     

Recent advances of lead-free metal halide perovskite single crystals and nanocrystals: synthesis,crystal structure,optical properties,and their diverse applications

Lead halide hybrid perovskites have received massive research attention because of their unique inherent photophysical properties that driven them for potential application in the fields of photovoltaics, light-emitting devices, lasing, X-ray detector, and so on. Perovskite single crystals and nanocrystals are generally synthesized via various low-cost solution-processed techniques. The emergence of simple growth approaches of perovskite structures enable to fabricate low-cost and highly efficient devices. However, toxicity of Pb atoms and instability of perovskite structures obstruct further commercialization of these technologies. Recent efforts have been shifted to discover novel, eco-friendly, and stable lead-free metal halide perovskite (LFHP) materials and exploring their different growth processes for various device applications. This review aims to provide an up-to-date analysis of recent progress report on LFHPs and will mainly focus on their growth processes in the single crystalline and nanocrystalline forms. This review also tries to understand how the perovskite crystal structure impacts on their fundamental properties. In addition, we discuss the current progress in various field of applications and their future aspects.     

Polyol-mediated solvothermal synthesis and luminescence properties of CeF3, and CeF3:Tb nanocrystals

CeF₃ and CeF₃:Tb³⁺ nanocrystals were successfully synthesized through a facile and effective polyol-mediated route with ethylene glycol (EG) as solvent. Various experimental techniques including X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) spectra as well as decay dynamics were used to characterize the samples. The results indicated that the content of NH₄F and reactant concentrations were key factors in the product shape and size. Excessive NH₄F was necessary for the formation of hexagonal nanoplates. The specific morphology of product can be controlled by changing the NH₄F content and reactant concentrations. In addition, Tb³⁺ doped-CeF₃ sample shows strong green emission centered at 544 nm corresponding to the ⁵D₄-⁷F₅ transition of Tb³⁺. Due to the decrease of nonradiative decay rate, the lifetime of ⁵D₄ level of Tb³⁺ become longer gradually upon increasing the size of product.     

Goethite nanorods as anode electrode materials for rechargeable Li-ion batteries

Although various transition metal oxides have been reported to act as low potential Li insertion hosts, the oxyhydroxides have remained unexplored to date. We show here that the hydroxide ions present in transition metal oxyhydroxides do not interfere with the lithium uptake and extraction, permitting very good reversibility of the reduction/oxidation reactions. Goethite (α-FeOOH) nanocrystals can uptake and extract large amount of Li via the conversion reaction mechanism, providing a reversible capacity of 500 mA h g⁻¹ at an average potential of 0.85 V vs. Li/Li⁺. The mechanism was examined using a combination of X-ray diffraction, electron microscopy, and the corresponding selected area electron diffractions (SAEDs). The α-FeOOH is reduced into nanoparticles of metallic Fe⁰ embedded in an amorphous matrix of Li₂O and LiOH in the first discharge; the subsequent cyclings are redox reactions between metallic Fe⁰ and Fe₂O₃ clusters.     

Self‐Assembly Film of Zeolite Y Nanocrystals Loading Palladium on an Au Electrode for Electrochemical Applications

Nano‐scale zeolite Y crystals were synthesized, and palladium nanoparticles were prepared in the supercage of the zeolite by “ship‐in‐a‐bottle” approach. A novel method to fabricate zeolite‐modified electrode (ZME) loading Pd nanoparticles was developed, in which the zeolite Y loading Pd²⁺ ions was self‐assembled on (3‐mercaptopropyl) trimethoxysilane‐attached Au surface to form the stable and density packed multilayers (SAM‐ZME). The structures of zeolite Y and the SAM‐ZME were investigated by using TEM, XRD and SEM techniques. Pd²⁺ ions in the SAM‐ZME were converted into Pd nanoparticles (Pd_n⁰) by two steps consisting of the electrochemical reduction as well as the succeeding admission and release of CO. The redox couple [Fe(CN)₆]^3?/4? was used to probe the electron‐transfer barrier properties during self‐assembling process. Moreover, the special properties of the SAM‐ZME loading Pd_n⁰ were studied by using cyclic voltammetry and CO‐probe in situ FTIR spectroscopy. The results illustrated that Pd_n⁰ in the SAM‐ZME exhibits higher electrocatalytic activity for oxidation of adsorbed CO than that of ZME prepared in our previous study by zeolite coating method. The present study is of importance in design and preparation of SAM‐ZME, which poccesseses excellent properties for the immobilization of electrocatalysts or biomolecules.     

Synthesis of highly fluorescent LaF3:Ln/LaF3 core/shell nanocrystals by a surfactant-free aqueous solution route

A surfactant-free aqueous solution route has been established for the synthesis of LaF₃:Ln³⁺/LaF₃ core/shell nanocrystals (Ln=Ce, Tb, Nd) heated at 75 °C at ambient pressure. All the as-prepared nanocrystals with spherical shape have an average size around 20 nm, and consist of well crystallized hexagonal phases. The X-ray photoelectron spectra was used to confirm that the LaF₃ shells have coated the LaF₃:Ce³⁺, Tb³⁺ cores. Compared with that of the original cores under the same conditions, the emission intensity of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ and LaF₃:Nd³⁺/LaF₃ core/shell nanocrystals increased significantly of 120% and 60%, respectively. The quantum yield of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ core/shell nanocrystals reached about 27% in aqueous solution. These results indicate that a significant reduction of the quenching from the surface of the core nanocrystals can be obtained by the synthesis of the core/shell structures, and this method can provide more desirable lanthanide-doped nanocrystals for potential biological applications.     

AFM of adsorbed polyelectrolytes on cellulose I surfaces spin-coated on silicon wafers

Thin layers of cellulose I nanocrystals were spin-coated onto silicon wafers to give a flat model cellulose surface. A mild heat treatment was required to stabilize the cellulose layer. Interactions of this surface with polyelectrolyte layers and multilayers were probed by atomic force microscopy in water and dilute salt solutions. Deflection–distance curves for standard silicon nitride tips were measured for silicon, cellulose-coated silicon, and for polyelectrolytes adsorbed on the cellulose surface. Transfer of polymer to the tip was checked by running deflection–distance curves against clean silicon. Deflection–distance curves were relatively insensitive to adsorbed polyelectrolyte, but salt addition caused transfer of cationic polyelectrolyte to the tip, and swelling of the polyelectrolyte multilayers.     

Structure and optical features of silicon carbide nanocrystals confined in alumina matrices

Thin films based on silicon carbide and alumina were synthesized by means of rf-sputtering using a co-deposition process. Several nanostructures were created which consist of thin films (∼200 nm thick) with homogeneous distribution of SiC nanocrystals (∼5 nm mean diameter) in the host alumina matrices. Characterization methods including X-ray photoelectrons spectroscopy (XPS), UV-vis absorption and photoluminescence (PL) were used to identify the involved structures, compositions and optical features of these nanostructures. Thus, XPS investigations were relevant to point out the involved chemical bonding in the core SiC nanocrystals and in the host alumina environments. Additionally, mixed bonding such as Si-O-C was also shown and seems to correlate with the SiC-alumina interfaces. Optical properties of the nanostructures films such as UV-vis absorption and photoluminescence (PL) were measured in representative samples and compared to simulated PL responses obtained by a theoretical model.     

A variational multiscale constitutive model for nanocrystalline materials

This paper presents a variational multi-scale constitutive model in the finite deformation regime capable of capturing the mechanical behavior of nanocrystalline (nc) fcc metals. The nc-material is modeled as a two-phase material consisting of a grain interior phase and a grain boundary effected zone (GBAZ). A rate-independent isotropic porous plasticity model is employed to describe the GBAZ, whereas a crystal-plasticity model which accounts for the transition from partial dislocation to full dislocation mediated plasticity is employed for the grain interior. The constitutive models of both phases are formulated in a small strain framework and extended to finite deformation by use of logarithmic and exponential mappings. Assuming the rule of mixtures, the overall behavior of a given grain is obtained via volume averaging. The scale transition from a single grain to a polycrystal is achieved by Taylor-type homogenization where a log-normal grain size distribution is assumed. It is shown that the proposed model is able to capture the inverse Hall-Petch effect, i.e., loss of strength with grain size refinement. Finally, the predictive capability of the model is validated against experimental results on nanocrystalline copper and nickel.     

Increase in rate of electrodeposition and in Ni(II) concentration in the bath as a way to control grain size of amorphous/nanocrystalline Ni-W alloys

Calculations based on the equilibria involved have been carried out to find the conditions of the highest possible solubility of Ni(II) in an ammonia-citrate bath for the electrodeposition of amorphous/nanocrystalline Ni-W alloys. The appropriate increase in the concentration of citrate, followed by the corresponding increase in the concentration of Ni(II), has led, under the conditions of constant current, to the increase in the efficiency of the electrodeposition and therefore the rate of electrodeposition by 3.2 times. The amorphous alloys obtained in solutions of different Ni(II) concentrations had different sizes of nanocrystals (15–100 ?), as determined from X-ray diffractograms, and different alloy compositions (10–19.5 at% of W), but were of similar high hardness. Electronic Publication