Physical properties of Pb doped ZnS thin films prepared by ultrasonic spray technique

In the present work, high quality Pb doped ZnS thin films were deposited on glass substrates at 450°C using spray ultrasonic technique. The dependence of the structural, morphological and optical properties of the films on the lead (Pb) doping amount was investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis–NIR spectrophotometry, and four-point method. The improvement of the obtained Pb:ZnS thin films properties were discussed as a function of Pb concentration (0.5 to 2 at.%). The average crystallite size of Pb:ZnS was found in the range of 25–37 nm. The scanning electron microscopy (SEM) reveals that the films are continuous, homogeneous and dense. The UV–vis–NIR spectroscopy characterizations demonstrated that all the films exhibit good transmittance (60–70%) in the visible region and their optical band gap energy ($E_{\mathrm{g}}$) changes from 3.92 to 3.6 eV. The films electrical resistivity showed an apparent dependence on Pb content.     

La掺杂和空位对ZnS磁性和光学性能影响的第一性原理研究

利用密度泛函理论框架下的平面波超软赝势法,通过第一性原理对La掺杂与Zn空位(V_(Zn))及La掺杂与S空位(V_S)共存的ZnS体系的电子结构、磁性机理、形成能及吸收光谱进行了研究.结果表明, La掺杂与空位(V_(Zn)或V_S)的空间位置最近时,掺杂体系的形成能最低,体系最稳定.另外,La掺杂与Zn空位共存时,体系具有磁性,且体系的净磁矩与La原子与Zn空位的相对位置有关;La掺杂与S空位共存时,掺杂体系无磁性,但此时体系的禁带宽度最窄且吸收光谱红移最显著.     

Separation and quantification of quantum dots and dissolved metal cations by size exclusion chromatography–ICP-MS

The prevalence of engineered metallic nanoparticles within electronic products has evoked a need to assess their occurrence and fate within environmental systems upon potential release of these nanoparticles. Quantum dots (QDs) are mixed-metal nanocrystals with the smallest of particle sizes (2–10 nm) that readily leach heavy metal cations in water, potentially creating a co-occurrence of nanoparticulate and dissolved metal pollutants. In this report, we develop a size exclusion chromatography–inductively coupled plasma–mass spectrometry method (SEC-ICP-MS) for the rapid separation and quantification of ~5-nm-sized CdSe/ZnS QDs and dissolved Cd²⁺ and Zn²⁺ cations in water. The SEC-ICP-MS method provided a wide chromatographic separation of CdSe/ZnS QDs and dissolved Cd²⁺ and Zn²⁺ cations only when using the smallest SEC column pore size available and an eluent composition that prevented loss of metals to column polymer surfaces by using a surfactant to ensure elution of QDs (ammonium lauryl sulfate) and a complexing ligand to ensure elution of metal cations (ethylenediaminetetraacetate). Detection limits were between 0.2 and 2 µg L^–1 for Cd²⁺ and Zn²⁺ among dissolved cation and QD phases, and ranges of linearity covered two to three orders of magnitude. Gold nanoparticles of sizes 5, 10, 20 and 50 nm were also effectively separated from dissolved Au³⁺ cations, illustrating the method applicability to a wide range of nanoparticle sizes and compositions. QD and dissolved metal concentrations measured by SEC-ICP-MS were comparable to those measured using the more conventional method of centrifuge ultrafiltration on split samples for dissolved and total metals. The applicability of the SEC-ICP-MS method to environmental systems was verified by measuring QDs and dissolved metals added to samples of natural waters. The method was also applied to monitoring CdSe/ZnS dissolution kinetics in an urban river water. The SEC-ICP-MS developed here may offer improved automation for characterising heterogeneous suspensions containing >1 µg L^–1 heavy metals.     

Interaction potential models for bulk Zns,Zns nanoparticle,and Zns nanoparticle‐PMMA from first‐principles

An ab initio derived transferable polarizable force‐field has been developed for Zinc sulphide (ZnS) nanoparticle (NP) and ZnS NP‐PMMA nanocomposite. The structure and elastic constants of bulk ZnS using the new force‐field are within a few percent of experimental observables. The new force‐field show remarkable ability to reproduce structures and nucleation energies of nanoclusters (Zn₁S₁‐Zn₁₂S₁₂) as validated with that of the density functional theory calculations. A qualitative agreement of the radial distribution functions of Zn? O, in a ZnS nanocluster‐PMMA system, obtained using molecular mechanics molecular dynamics (MD) and ab initio MD (AIMD) simulations indicates that the ZnS–PMMA interaction through Zn? O bonding is explained satisfactorily by our force‐field. © 2015 Wiley Periodicals, Inc.     

Fe3O4@MIL-100(Fe) modified ZnS nanoparticles with enhanced sonocatalytic degradation of tetracycline antibiotic in water

Sonocatalysis has attracted excellent research attention to eradicate hazardous pollutants from the environment effectively. This work synthesised an organic/inorganic hybrid composite catalyst by coupling Fe₃O₄@MIL-100(Fe) (FM) with ZnS nanoparticles using the solvothermal evaporation method. Remarkably, the composite material delivered significantly enhanced sonocatalytic efficiency for removing tetracycline (TC) antibiotics in the presence of H₂O₂ compared to bare ZnS nanoparticles. By adjusting different parameters such as TC concentration, catalyst dosage and H₂O₂ amount, the optimized composite (20 %Fe₃O₄@MIL-100(Fe)/ZnS) removed 78.25% antibiotic in 20 min at the cost of 1 mL of H₂O₂. These much superior activities are attributed to the efficient interface contact, effective charge transfer, accelerated transport capabilities and strong redox potential for the superior acoustic catalytic performance of FM/ZnS composite systems. Based on various characterization, free radical capture experiments and energy band structures, we proposed a mechanism for the sonocatalytic degradation of tetracycline based on S-scheme heterojunctions and Fenton like reactions. This work will provide an important reference for developing ZnS-based nanomaterials to study sonodegradation of pollutants.     

Facile hydrothermal synthesis of zinc sulfide nanowires for high-performance asymmetric supercapacitor

A facile, single-step hydrothermal route is followed to prepare ZnS nanowires with large aspect ratios. The obtained ZnS nanowires deposited on nickel foam (ZnS/Ni-foam) exhibit a specific capacitance of 781 F/g at a current density of 0.5 A/g. An asymmetric supercapacitor fabricated from ZnS/Ni-foam as a positive electrode and jute derived activated carbon coated on Ni-foam (JAC/Ni-foam) as a negative electrode attains a high specific capacitance of 573 F/g at a current density of 0.5 A/g, with an accompanying high energy density of 51 Wh/kg at a power density of 200 W/kg in an extensive operating potential window of 1.2 V. In addition, the ZnS//JAC asymmetric supercapacitor reveals long-term cyclic stability, after 10,000 GCD cycles the device sustain around ～87 % of the initial specific capacitance. These results shed enlighten a new opportunity for promising electrode materials in supercapacitors.     

高性能量子点编码磁性微球的制备

基于改进的层层组装法,以氯仿/正丁醇混合溶液作为反应溶剂,将油溶性CdSSe/ZnS量子点装载到表面氨基修饰的磁性聚苯乙烯微球(MS)表面,通过调节量子点浓度,制备出高性能CdSSe/ZnS量子点编码磁性微球(CdSSe/ZnS-MBs).研究了氯仿和氯仿/正丁醇混合溶液对CdSSe/ZnS-MBs制备效果的影响.结果表明,氯仿/正丁醇混合溶液不仅能避免氯仿等量子点良溶剂对聚合物微球的形貌破坏,同时能促进CdSSe/ZnS量子点高效地装载到磁性微球表面.所制备的CdSSe/ZnS-MBs在水相具有较好的分散性,荧光强度变异系数(CV)小,形貌均一.该方法为简单、精确可控地制备高编码容量的量子点编码微球提供了新思路.     

Kinetics of the Coordination Transformation for Preparation of Nanosized ZnS in a PVA Film

Abstract

This study was focused on the pervasion process of sulfion in a PVA–Zn²⁺ complex film. A diffusion equation for this process, based on the Fick first diffusion law, is suggested, which was in good agreement with the experimental results. The diffusion constant was 9.92 × 10^?6 cm²/sec, calculated by combining the model and the experimental results.     

Use of Cdse/ZnS quantum dots for sensitive detection and quantification of paraquat in water samples

Based on the highly sensitive fluorescence change of water-soluble CdSe/ZnS core-shell quantum dots (QD) by paraquat herbicide, a simple, rapid and reproducible methodology was developed to selectively determine paraquat (PQ) in water samples. The methodology enabled the use of simple pretreatment procedure based on the simple water solubilization of CdSe/ZnS QDs with hydrophilic heterobifunctional thiol ligands, such as 3-mercaptopropionic acid (3-MPA), using microwave irradiation. The resulting water-soluble QDs exhibit a strong fluorescence emission at 596 nm with a high and reproducible photostability. The proposed analytical method thus satisfies the need for a simple, sensible and rapid methodology to determine residues of paraquat in water samples, as required by the increasingly strict regulations for health protection introduced in recent years. The sensitivity of the method, expressed as detection limits, was as low as 3.0 ng L⁻¹. The lineal range was between 10–5 × 10³ ng L⁻¹. RSD values in the range of 71–102% were obtained. The analytical applicability of proposed method was demonstrated by analyzing water samples from different procedence.     

Structural transition behavior of ZnS nanotetrapods under high pressure

ZnS nanotetrapods synthesized via a solvothermal route have a octahedral core with a zincblende (ZB) structure and four hexprism-shaped arms consisting of alternately stacking ZB and wurtzite (WZ) phases, where the WZ phase has a higher volume percentage. In situ angular-dispersive X-ray diffraction (ADXRD) measurements were carried out to study the structural behavior of ZnS nanotetrapods under high pressure up to 41.3?GPa. The initial WZ structure exhibits a very high mechanical stability to ～11.3?GPa. Both the WZ and ZB structures transform to the rocksalt (RS) structure at ～15.4?GPa. The bulk moduli of the WZ (148.2?±?8.9?GPa) and RS (165.6?±?9.9?GPa) phases are both larger than the previously reported values. These phenomena are discussed based on the alternating epitaxial growth of the WZ and ZB phases in the arms of nanotetrapods. Our study suggests that the internal structure of nanomaterials could also greatly affect their stability and transition behavior.