Formation of ZnO@Cd(OH)2 core-shell nanoparticles by sol-gel method: An approach to modify surface chemistry for stable and enhanced green emission

We report the formation of highly stable and luminescent ZnO@Cd(OH)₂ core-shell nanoparticles by simple introduction of cadmium salt in the initial precursor solution, used to synthesize ZnO nanoparticles by sol-gel route. The cadmium to zinc salt concentration ratio has been also varied to control the growth of ZnO nanoparticles at the smaller particle size. Formation of ZnO@Cd(OH)₂ core-shell nanostructure has been confirmed by X-ray diffraction (XRD), energy dispersive analysis of X-rays (EDAX) and X-ray photoelectron spectroscopy (XPS). UV-vis absorption spectroscopy exhibits blue-shift in absorption edge on increasing cadmium concentrations. The photoluminescence emission spectra showed the remarkably stable and enhanced visible (green) emission from suspended ZnO@Cd(OH)₂ nanoparticles in comparison to bare ZnO nanoparticles. It is postulated that Cd(OH)₂ layer at the surface of ZnO nanoparticles prevents the agglomeration of nanoparticles and efficiently assists the trapping of hole at the surface site, a first step necessary for visible emission. The Fourier transform infrared spectroscopy (FTIR) also supports our assumption about surface chemistry.     

Preparation, optical properties, magnetic properties and thermal stability of core-shell structure cobalt/zinc oxide nanocomposites

Cobalt nanoparticles coated with zinc oxide can form composite spheres with core-shell structure. This coating process was based on the use of silane coupling with agent 3-mercaptopropyltrimethoxysilane (HS-(CH₂)₃Si(OCH₃)₃, MPTS) as a primer to render the cobalt surface vitreophilic, thus it renders cobalt surface compatible with ZnO. X-ray photoelectron spectroscopy (XPS) was used to gain insight into the way in which the MPTS is bound to the surface of the cobalt nanoparticles. The morphological structure, chemical composition, optical properties and magnetic properties of the product were investigated by using transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), photoluminescence (PL) spectroscope and vibrating sample magnetometer (VSM). It was found that the Co/ZnO core-shell structure nanocomposites exhibited both of favorable magnetism and photoluminescence properties. Results of the thermogravimetric analysis (TGA) and differential thermal analysis (DTA) indicated that the thermal stability of cobalt/zinc oxide was better than that of pure cobalt nanoparticles.     

Core/shell structured ZnO/SiO2 nanoparticles: Preparation, characterization and photocatalytic property

ZnO nanoparticles were prepared by a simple chemical synthesis route. Subsequently, SiO₂ layers were successfully coated onto the surface of ZnO nanoparticles to modify the photocatalytic activity in acidic or alkaline solutions. The obtained particles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS) and zeta potential. It was found that ultrafine core/shell structured ZnO/SiO₂ nanoparticles were successfully obtained. The photocatalytic performance of ZnO/SiO₂ core/shell structured nanoparticles in Rhodamine B aqueous solution at varied pH value were also investigated. Compared with uncoated ZnO nanoparticles, core/shell structured ZnO/SiO₂ nanoparticles with thinner SiO₂ shell possess improved stability and relatively better photocatalytic activity in acidic or alkaline solutions, which would broaden its potential application in pollutant treatment.     

Visible-light photocatalytic degradation of methylene blue with laser-induced Ag/ZnO nanoparticles

The preparation of Ag doped ZnO nanoparticles conducted through the method of laser-induction is presented in this work. The Ag/ZnO nanoparticles attained from various weight percentages of added AgNO₃ relative to ZnO were applied under visible-light irradiation for evaluating the heterogeneous photocatalytic degradations of methylene blue (MB) solutions. It was shown that the catalytic behavior of Ag/ZnO nanoparticles in the visible-light range is notably improved through the Ag deposition onto ZnO nanoparticles by the method of laser-induction with a maximum effectiveness of 92% degradation. The properties of the nanoparticles were characterized by the employments of UV-vis spectroscopy (UV-vis), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), and selected-area electron diffraction (SAED).     

Structure evolution of carbon black under ionic-liquid-assisted microwave irradiation

The interactions between the carbon black (CB) and the ionic liquid (IL), 1-butyl-3-methyl-imiazolium hexafluorophosphate ([BMIM⁺][PF₆⁻]), are firstly examined. The CB, mixed with the IL via simple blending, is then subjected to microwave (MW) irradiation to prepare the modified CB. The structure evolutions of the modified CB such as the microcrystalline structure and surface chemistry are revealed by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and pore analysis. After mixing but before MW irradiation, the microcrystalline arrangement of CB turns to be more ordering and microcrystalline size (La) to be a little bigger but with a limited degree. Under MW irradiation, the IL undergoes severe decomposition. The combination of localized high temperature (proposed to be higher than 425 °C) and the decomposition of the IL leads to substantial structure changes of the CB. The graphitization of the CB surface, the disordering of the microcrystalline and the decrease in La are disclosed. In addition, compared with the untreated CB, the CB treated with IL-assisted MW irradiation is found to have much higher volume of the smaller mesopore.     

The structure and magnetic properties of Cu-doped ZnO prepared by sol-gel method

The Cu-doped ZnO and pure ZnO powders were synthesized by sol-gel method. The structural properties of the samples were investigated by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. All the results confirmed that copper ions were well incorporated into the ZnO lattices by substituting Zn sites without changing the wurtzite structure and no secondary phase existed in Cu-doped ZnO nanoparticles. The Zn_0.97Cu_0.03O nanoparticles exhibited ferromagnetism at room temperature, as established by the vibrating sample magnetometer analysis.     

Adsorption of Ionic Liquid onto Halloysite Nanotubes: Mechanism and Reinforcement of the Modified Clay to Rubber

An ionic liquid (IL), 1-butyl-3-methyl-imiazolium hexafluorophosphate [BMIm]PF₆, was coated onto halloysite nanotubes (HNTs) in tetrahydrofuran–water mixture. The IL layers on the HNTs were confirmed by thermogravimetric analysis, diffuse reflectance infrared Fourier transform spectroscopy, determination of contact angle, and porosity analysis. The interaction between IL and HNTs, proposed to be hydrogen bonding, was verified by various spectral results such as Raman spectroscopy, nuclear magnetic resonance and X-ray photoelectron spectroscopy. Because of their interaction, the crystallization behavior of IL in the presence of HNTs was found to be changed, as indicated by the results of differential scanning calorimetry. The IL-coated HNTs (m-HNTs) were used as reinforcement for styrene–butadiene rubber. Compared with the compounds with uncoated HNTs, the uncured compounds with m-HNTs showed faster curing, and the resulting vulcanizates showed substantially higher tensile strength and much lower hardness. The unique changes in the compounds are correlated to the changes in filler dispersion and interaction between IL and HNTs.     

Formation of nanoparticles containing zinc in Si(001) by ion-beam implantation and subsequent annealing

The formation of nanoparticles containing zinc in Si(001) substrates by the implantation of ⁶⁴Zn⁺ ions and subsequent annealing in dry oxygen at 800 and 1000°C for 1 h is studied. The structure of the samples is studied by high-resolution transmission electron microscopy, X-ray diffraction, and photoluminescence spectroscopy. 20-nm zinc nanoparticles located at a depth of about 50 nm are revealed in the as-implanted sample. 10–20-nm pores are observed in the surface layer. Annealing leads to oxidation of the Zn nanoparticles to the Zn₂SiO₄ state. It is shown that the oxidation of Zn nanoparticles begins on their surface and at an annealing temperature of 800°C results in the formation of nanoparticles with the “соre–shell” structure. The X-ray diffraction technique shows simultaneously two Zn and Zn₂SiO₄ phases. ZnO nanoparticles are not formed under the given implantation and annealing conditions.     

Preparation and optical properties of ZnO@PPEGMA nanoparticles

The poly(poly(ethylene glycol) methyl ether monomethacrylate) (PPEGMA) grafted zinc oxide (ZnO) nanoparticles were successfully prepared via the surface-initiated atom transfer radical polymerizations (ATRP) from the surfaces functionalized ZnO nanoparticles. The 2-bromoisobutyrate (BIB) was immobilized onto the surface of the ZnO nanoparticles through the reaction between 2-bromoisobutyryl bromide (BIBB) and the hydroxyl groups on nanoparticles, serving as the initiator to induce the ATRP of poly(ethylene glycol) monomethacrylate (PEGMA). Well-defined polymer chains were grown from the surfaces to yield hybrid nanoparticles comprised of ZnO cores and PPEGMA polymer shells having multifunctional end groups. The structure and morphology of the nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optical properties of the nanoparticles were investigated by UV-vis absorption spectroscopy and photoluminescence spectroscopy (PL). The results showed that the dispersion and near-band edge (NBE) emission of ZnO nanoparticles could be improved by the grafted PPEGMA polymer segments.     

A facile method to prepare monodispersed ZnO–Ag core-shell microspheres

Monodispersed and core-shell structured ZnO–Ag microspheres were realized by coating the Ag nanoparticles onto the surface of ZnO microspheres via a novel solution method. The obtained materials were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible (UV–Vis) absorption measurement. It was shown that face-center-cubic Ag nanoparticles with the mean size of 20 nm were successfully grown on the surface of ZnO microspheres. The absorption band of ZnO–Ag core-shell microspheres showed a large redshift comparing to pure Ag nanoparticles, indicating the strong interfacial interaction between ZnO and Ag. The effects of Ag coating thickness on the structure, morphology and optical absorption of ZnO–Ag core-shell microspheres were investigated. The discussion on the growth process of ZnO–Ag core-shell microspheres revealed the important role of Sn²⁺. This approach was simple, mild and readily scaled up, affording a simple method for the synthesis of size-tunable inorganic-metal core-shell nanostructures.     

Study on the structure and luminescence properties of the coordinated ZnO crystallites

The coordinated ZnO nanoparticles and crystallites have been produced by focused pulsed laser ablation of ZnO target submerged in the ethanol solution of 8-hydroxyquinoline. The structure of the nanoparticles was characterized by high-resolution transmission electron microscopy (HRTEM). The ZnO crystallites properties were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis coupled to differential scanning calorimetry (TG/DSC), X-ray photoelectron spectroscopy (XPS) and luminescence spectrometry. The results show the surface Zn²⁺ ions of the ZnO nanoparticles are coordinated by the 8-hydroxyquinoline. The crystal class and the space group of the coordinated ZnO crystallites are triclinic and P-1(2), respectively. The lattice parameters are refined to a=1.1904 nm, b=1.2135 nm, c=0.8586 nm, α=108.28^°,β=100.27^° and γ=85.50^°, respectively. The coordinated ZnO crystallites have better thermo stability than bis(8-hydroxyquinoline)zinc and can emit yellow-green light under UV and visible radiations.     

Au cluster growth on ZnO thin films by pulsed laser deposition

Nanostructures formed by Au nanoparticles on ZnO thin film surface are of interest for applications which include medical implants, gas-sensors, and catalytic systems. A frequency tripled Nd:YAG laser (λ = 355 nm, τ_FWHM ∼ 10 ns) was used for the successive irradiation of the Zn and Au targets. The ZnO films were synthesized in 20 Pa oxygen pressure while the subsequent Au coverage was grown in vacuum. The obtained structures surface morphology, crystalline quality, and chemical composition depth profile were investigated by acoustic (dynamic) mode atomic force microscopy, X-ray diffraction, and wavelength dispersive X-ray spectroscopy. The surface is characterized by a granular morphology, with average grain diameters of a few tens of nanometers. The surface roughness decreases with the increase of the number of laser pulses applied for the irradiation of the Au target. The Au coverage reveals a predominant (1 1 1) texture, whereas the underlying ZnO films are c-axis oriented. A linear dependence was established between the thickness of the Au coverage and the number of laser pulses applied for the irradiation of the Au target.     

Aqueous synthesis and enhanced photocatalytic activity of ZnO/Fe2O3 heterostructures

We report a facile synthesis of ZnO/Fe₂O₃ heterostructures based on the hydrolysis of FeCl₃ in the presence of ZnO nanoparticles. The material structure, composition, and its optical properties have been examined by means of transmission electron microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and diffuse reflectance UV–visible spectroscopy. Results obtained show that 2.9 nm-sized Fe₂O₃ nanoparticles produced assemble with ZnO to form ZnO/Fe₂O₃ heterostructures. We have evaluated the photodegradation performances of ZnO/Fe₂O₃ materials using salicylic acid under UV-light. ZnO/Fe₂O₃ heterostructures exhibited enhanced photocatalytic capabilities than commercial ZnO due to the effective electron/hole separation at the interfaces of ZnO/Fe₂O₃ allowing the enhanced hydroxyl and superoxide radicals production from the heterostructure.     

ZnO nanoparticle creating in a SiO2/Si structure using the Zn ion implantation with subsequent heat treatment

The distribution profiles of the dopant in the surface layer of a SiO₂/Si structure implanted with Zn and O ions are studied via Rutherford backscattering spectroscopy for He²⁺ ions using the channeling technique. The redistribution of implanted impurities in the Si surface layer during the formation process of zinc oxide (ZnO) nanoparticles is analyzed. The effect of the annealing temperature on the formation process and growth of ZnO nanoparticles is studied. The sample-surface morphology is examined via atomic force microscopy. The optical absorption and photoluminescence of the implanted layers are studied.     

Poly(hydroethyl acrylate) grafted from ZnO nanoparticles via surface-initiated atom transfer radical polymerization

Poly(hydroethyl acrylate) (PHEA) was grafted from ZnO nanoparticles via the copper-mediated surface-initiated atom transfer radical polymerization (SI-ATRP) technique with the bromo-acetamide modified ZnO nanoparticles (BrA-ZnO) as macroinitiators with the catalysts of 1,10-phenanthroline and Cu(I)Br in water. Graft reaction was first order kinetic with respect to the polymerizing time in the low monomer conversion stage, this being typical for ATRP. A percentage of grafting (PG%) of 62.4% was achieved in 12 h, calculated from the elemental analysis results. The product, poly(hydroethyl acrylate) grafted ZnO nanoparticles (PHEA-ZnO) were also characterized with Fourier transform infrared spectroscopy (FT-IR), UV–vis spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).     

Photocatalytic activity of ZnO nanoparticles prepared via submerged arc discharge method

ZnO nanostructures were synthesized through arc discharge of zinc electrodes in deionized (DI) water. X-ray diffraction (XRD) analysis of the prepared nanostructures indicates formation of crystalline ZnO of hexagonal lattice structures. Transmission electron microscopy (TEM) images illustrate rod-like as well as semi spherical ZnO nanoparticles with 15–20 nm diameter range, which were formed during the discharge process with 5 A arc current. The average particle size was found to increase with the increasing arc current. X-ray photoelectron spectroscopy (XPS) analysis confirms formation of ZnO at the surface of the nanoparticles. Surface area of the sample prepared at 5 A arc current, measured by BET analysis, was 34 m²/g. Photodegradation of Rhodamine B (Rh. B) shows that the prepared samples at lower currents have a higher photocatalytic activity due to larger surface area and smaller particle size.     

Fabrication and characterization chitosan/functionalized zinc oxide bionanocomposites and study of their antibacterial activity

This study deals with preparation and evaluation of properties of chitosan/zinc oxide bionanocomposites (CT/ZnO BNCs) with different amounts of modified zinc oxide nanoparticles (ZnO NPs) through ultrasonic irradiation technique. Due to the high surface energy and tendency for agglomeration, the surface ZnO NPs was modified by a coupling agent as 3-aminopropyltriethoxysilane (APS) to form APS–ZnO nanoparticles. Fourier transform infrared (FTIR) spectroscopy confirmed that APS was successfully grafted onto the ZnO nanoparticles surface. Thermogravimetric analysis (TGA) revealed a surface coverage of the coupling molecule of 2.6 wt%. The resulting bionanocomposites were characterized by FTIR spectra, X-ray diffraction patterns, and TGA. The antibacterial activity of bionanocomposite films was tested against gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) and gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). The results of CT/ZnO BNCs revealed that the thermal and antibacterial properties obviously improved the presence of ZnO NPs in comparison with the pure CT and that this increase is higher when the NP content increases. Further, it was observed that antibacterial activity of the resulting hybrid biofilms showed somewhat higher for gram-positive bacteria compared to gram-negative bacteria.     

Tailoring Cu2−xTe quantum-dot-decorated ZnO nanoparticles for potential solar cell applications

Cu_2−xTe QDs on ZnO nanoparticles were synthesized using a successive ionic layer absorption and reaction technique (SILAR) at room temperature. The as-synthesized QDs which were distributively deposited on ZnO nanoparticles surface were characterized by field emission scanning electron microscope (FE-SEM), X-ray diffraction and high-resolution transmittance microscope (HR-TEM). It revealed that the average diameter of the QDs was ∼2 nm. The synthesized Cu_2−xTe QDs were solely orthorhombic Cu_1.44Te phase. The growth mechanism was supposed that it based on ions deposition. The energy gap of as-synthesized Cu_2−xTe QDs was determined ∼1.1 eV and the smallest energy gap of 0.76 eV was obtained, equal to that of bulk material. Raman spectroscopy and FTIR were also used to study the Cu_2−xTe QDs on ZnO nanoparticles. These characteristics suggest a promising implication for a potential broadband sensitizer of QDSCs.     

Effect of monocationic ionic liquids as electrolyte additives on the electrochemical and thermal properties of Li-ion batteries

The conventional electrolyte system has been compared with the ionic liquid (IL) additive containing electrolyte system at room temperature as well as elevated temperature. In this work, two types of monocationic ILs such as 1-butyl-3-methylpyrrolidinium hexafluorophosphate (Pyr IL) and 1-ethyl-3-methylimidazolium hexafluorophosphate (IMI IL) are added as an additive at two different weight ratios in 1.15 M LiPF₆ (EC/EMC = 3/7 v/v) electrolyte solution, the structural, electrochemical and thermal characteristics of LiNi_0.80Co_0.15Al_0.05O₂ (NCA)/carbon full-cell in different electrolyte formulations have been reconnoitered. X-ray diffraction (XRD) studies have proved that IL as an electrolyte additive does not alter the structural stability of cathode materials after cycling. Under room temperature, Pyr IL additives at 1 wt% and 3 wt% deliver better cycleability than others, with the retention ratios of 93.62% and 92.8%, respectively. At elevated temperature, only 1 wt% Pyr IL additive is giving stable capacity retention ratio of 80.74%. Ionic conductivity and self-extinguishing time (SET) values are increasing with respect to the amount of additive added to the electrolyte. Thermal studies reveal that 3 wt% Pyr IL is favorable regarding the safety of the battery as it shows shifting of peak to higher temperature of 272.10 °C. Among the IL additives evaluated in this study, addition of 1 wt% Pyr IL is the most desirable additive for achieving the best cycling performance as well as thermal behavior of Li-ion batteries.     

Influence of high-pressure hydrogen treatment on structural and electrical properties of ZnO thin films

ZnO thin films were treated by high-pressure hydrogen (H₂). Scanning electron microscope (SEM) images show that the surface morphology of ZnO films has been changed significantly by H₂ treatment. X-ray diffraction patterns show that the Zn(OH)₂ phases formed after H₂ treatment. The X-ray photoelectron spectroscopy results indicate that H atoms were doped into the surface of ZnO by forming H-O-Zn bond. The phenomenon shows that it is easy to form O-H bond in ZnO rather than H interstitial atom under high-pressure hydrogen circumstance.