Self-assembly of small ZnO nanoparticles toward flake-like single crystals

Flake-like single-crystalline ZnO nanocrystals with porous structure have been achieved, in which precursor of Zn₄CO₃(OH)₆·H₂O was first prepared by mild hydrothermal method with urea as the homogeneous precipitant and decomposed into small ZnO nanocrystals after being calcined at 400 °C, then the small ZnO nanocrystals self-assemble to form flake-like ZnO aggregates. The ZnO nanoflakes have lateral dimensions up to micrometer with the plane normal to [0 0 1] direction. The UV–vis absorption reveals that the ZnO nanoflakes have strong absorption in the UV region. The advantages of our method for the synthesis lie in the low temperature and mild reaction condition, which permit large-scale production at low cost.     

Synthesis and adsorption property of zinc rust of zinc hydroxynitrate

In order to clarify the formation condition of zinc rusts such as layered zinc hydroxynitrate (Zn₅(OH)₈(NO₃)₂·2H₂O: ZHN), ZnO particles were aged with aqueous Zn(NO₃)₂·6H₂O solution at 6–140 °C for 48 h. Further, adsorption of H₂O and CO₂ on ZHN was examined for simulating study of atmospheric corrosion of galvanized steel. The ZHN was formed at 6 °C and the ZnO completely disappeared, meaning the hydrolysis of ZnO particles in aqueous Zn(NO₃)₂·6H₂O solution to recrystallize as ZHN. Increasing the aging temperature improved the crystallinity of layered structure of ZHN, showing a maximum at 85 °C. The formed ZHN was hexagonal plate-like particles. The particle size was dependent of the crystallinity of layered structure of ZHN. The specific surface area of ZHN was decreased on elevating the aging temperature, showing a minimum at 85 °C. The adsorption of H₂O and CO₂ was enhanced on increasing the crystallinity of layered structure of ZHN, meaning that these molecules are adsorbed not only on particle surface but also in interlayer of ZHN. These facts infer that the preferred orientation of plate-like ZHN particles leads to the formation of compact rust layer on galvanized steel and to the enhancement of corrosion resistance.     

3D hierarchical Zn3(OH)2V2O7·2H2O and Zn3(VO4)2 microspheres: Synthesis,characterization and photoluminescence

Via a simple glycine-assisted hydrothermal route, large-scale 3D hierarchical Zn₃(OH)₂V₂O₇·2H₂O microspheres have been fabricated. Their purity, crystalline phase, morphologies and thermal stability were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Fourier transform IR (FTIR), scanning electron microscopy (SEM) and thermogravimetry-differential scanning calorimetry (TG-DSC). The SEM results indicate that the microspheres are self-assembled by numerous nanoflakes with mean thickness of 100 nm. Some factors influencing the morphologies of the Zn₃(OH)₂V₂O₇·2H₂O micro-/nanostructures have been systematically investigated, as well as quantity of glycine and the reaction time. The possible mechanism of the crystal growth and assembled procedure were also proposed. The as-prepared Zn₃(OH)₂V₂O₇·2H₂O can be transformed into Zn₃(VO₄)₂ with the similar morphologies by calcination in air at 600 °C. Furthermore, the photoluminescent properties of both Zn₃(OH)₂V₂O₇·2H₂O and Zn₃(VO₄)₂ were studied and exhibited different spectra.     

Morphological control of ZnO particles synthesized via a new and facile aqueous solution route

Zinc oxide with a diversity of well-defined morphologies was synthesized via a simple aqueous solution route by decomposing Zn_xO_y(OH)_z precursor at suitable reaction conditions. Flower-like ZnO composed of rods was obtained by treating Zn_xO_y(OH)_z precursor in the reaction solution at 90 °C for 6 h. The precipitate of layer-like Zn_xO_y(OH)_z precursor was decomposed by drying at 90 °C for 24 h in air, resulting in the formation of ZnO microtubes.     

Synthesis of hexagonal Zn3(OH)2V2O7·2H2O nanoplates by a hydrothermal approach: Magnetic and photocatalytic properties

Hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates have been successfully synthesized via a facile and template-free hydrothermal method. The nanocrystals have a hexagonal shape with 650–750 nm in diameter and 120–140 nm in thickness. The possible mechanism of forming such hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates may be due to its inherent anisotropic crystal structure. Magnetic hysteresis measurement indicates that the as-synthesized hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates have weak ferromagnetic property at room temperature. Compared to the floriated-like nanostructured Zn₃V₂O₇(OH)₂(H₂O)₂ synthesized by a hydrothermal route, the as-prepared hexagonal Zn₃(OH)₂V₂O₇·2H₂O nanoplates exhibited a significant increase in the methylene blue (MB) photodegradation rate under UV irradiation.     

Polymer-assisted synthesis of hydroxyapatite nanoparticle

Hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) nanoparticles were synthesized using calcining calcium dihydrogenphosphate (Ca(H₂PO₄)₂ · H₂O), calcium hydroxide (Ca(OH)₂), and polyethylene glycol (PEG) at 900 °C in an oxygen atmosphere. This one-step process yields HA nanoparticles with similar particle sizes (e.g., 50–80 nm) that are well-crystallized and non-aggregated. PEG is an important factor in controlling the particle size, crystal phase, and degree of aggregation in these HA particles. This conclusion is supported by results from a field-emission scanning electron microscope (FE-SEM), X-ray diffractometry (XRD), energy dispersive X-ray analysis (EDS), a high-resolution transmission electron microscope (HR-TEM), and dynamic light scattering (DLS).     

Synthesis of Co3(OH)2V2O7·1.7H2O nanosheets and its application in lithium ion batteries

Cobalt vanadium oxide hydroxide hydrate (Co₃(OH)₂V₂O₇·nH₂O) nanosheets are successfully synthesized by a simple hydrothermal method. The composition of Co₃(OH)₂V₂O₇·nH₂O is studied by thermal gravity (TG) analysis in N₂ atmosphere and subsequent X-ray powder diffraction (XRD) characterization of the sample obtained via annealing Co₃(OH)₂V₂O₇·nH₂O nanosheets in N₂ atmosphere at 800 °C for 6 h. The results indicate that there are 1.7 water molecules in a Co₃(OH)₂V₂O₇·nH₂O molecular formula. Electrochemical properties of Co₃(OH)₂V₂O₇·1.7H₂O nanosheets as negative electrode of lithium ion batteries are studied by conventional charge/discharge test, which show an initial capacity of 730 mAh g^?1 with steady plateau near 0.9 V at a current density of 0.05 mA cm^?2.     

Photocatalytic degradation of reactive brilliant blue X-BR in aqueous solution using quantum-sized ZnO

Quantum-sized ZnO was prepared using sol–gel method with zinc acetate dehydrate (Zn(CH₃COO)₂·2H₂O) and lithium hydroxide monohydrate (LiOH·H₂O) as raw material. The ZnO particles annealed at different temperature were characterized by means of X-ray diffraction (XRD), Infrared absorption spectroscopy (IR) and UV–vis spectroscopy. The degradation rate of reactive brilliant blue X-BR in aqueous solution was used to evaluate the photocatalytic performance of the quantum-sized ZnO. The experimental results indicated that the photocatalytic property of the ZnO was excellent. The photocatalytic efficiency of quantum-sized ZnO was significantly influenced by the calcining heat. When calcined at 300 °C, its size is 6.78 nm and the photocatalytic performance is the best. The degradation rate of reactive brilliant blue X-BR could exceed 90% in 15 min at 35 °C, when the concentration of the quantum-sized ZnO was 0.35 mg/L.     

Influence of porosity and relative humidity on consolidation of dolostone with calcium hydroxide nanoparticles: Effectiveness assessment with non-destructive techniques

Slaked lime (Ca(OH)₂) nanoparticles were exposed at 33% and 75% relative humidity (RH) to consolidate dolostone samples used in historical buildings. Non-destructive techniques (NDT) were applied to determine the chemical, morphological, physical and hydric properties of the stone samples, before and after 20 days treatment. Morphological and mineralogical characterisation of the nanoparticles was performed. 75% RH favors the consolidation process studied under Environmental Scanning Electron Microscopy (ESEM-EDS), spectrophotometry, capillarity, water absorption under vacuum, ultrasound velocity, Nuclear Magnetic Resonance (imaging and relaxometry) and Optical Surface Roughness analyses. At 75% RH the nanoparticles fill the pores and inter-crystalline dolomite grain contacts but do not favor calcite re-crystallization as it occurs at 33% RH. The ESEM, XRD and TEM analyses under 75% RH reveal the fast transformation of portlandite (Ca(OH)₂) into vaterite (CaCO₃), monohydrocalcite (CaCO₃ · H₂O) and calcite (CaCO₃), and eventually the physical and hydric properties of the stones significantly improve. New insights are provided for the assessment of consolidation effectiveness of porous carbonate stones with calcium hydroxide nanoparticles under optimum RH conditions combining several NDT.     

Analysis of growth parameters for hydrothermal synthesis of ZnO nanoparticles through a statistical experimental design method

Nanocrystalline ZnO particles were synthesized from an aqueous solution composed of zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and urea (H₂NCONH₂). A precipitating precursor, basic zinc carbonate (Zn₅(CO₃)₂(OH)₆), was first formed by hydrothermally treating the solution at 120 °C for 2–4 h. Nanocrystalline ZnO particles were then obtained by calcining the precursors at 350–650 °C for 0.5–2 h. The synthesis products were characterized using thermogravimetry–differential scanning calorimetry–mass spectrometry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. Based on the experimental results, a possible reaction mechanism for the ZnO formation was proposed. The effects of experimental parameters (namely, the hydrothermal treatment time, the calcination time, and the calcination temperature) on the characteristics of the resulting ZnO products (i.e., the crystalline size and the photoluminescence properties) were analyzed by the Taguchi method to attain the optimum synthesis conditions. By using the appropriate parameters derived from this method, we verified that the optimized synthesis provided a yield of ~70% and that the resulting ZnO particles possessed the characteristics of a ~25 nm crystalline size and a satisfactory photoluminescence property.     

Characterization of mechanical properties of epoxy resin reinforced with submicron-sized ZnO prepared via in situ synthesis method

In this paper, ZnO/epoxy composites with homogeneous dispersion were prepared via two simple steps: firstly, in situ preparation of zinc hydroxide (Zn(OH)₂)/epoxy from the reaction of aqueous zinc acetate (Zn(Ac)₂·2H₂O) and sodium hydroxide (NaOH) at 30 °C in the presence of high viscosity epoxy resin; secondly, thermal treatment of the as-prepared Zn(OH)₂/epoxy hybrid into ZnO/epoxy composites. Meanwhile, the structure, composition and mechanical properties of the resultant products were successfully investigated. From the result of characterization we found that the composite had the optimal mechanical property at ZnO fraction of 5 wt.%. Compared to pure epoxy resin, the improvement of ultimate tensile stress, elongation at break, tensile modulus and flexural strength achieved about 40.84%, 24.35%, 27.27% and 51.43%, respectively. The crack arresting mechanisms included particle matrix debonding, plastic void growth, in the composites with a stronger interface, significant plastic deformation of the matrix around the well bonded particles. At the same time, the possible reactive mechanism of the preparation of ZnO/epoxy composite was discussed in this paper.     

Synthesis of nanoparticle zinc phosphate dihydrate by solid state reaction at room temperature and its thermochemical study

Nanoparticle zinc phosphate dihydrate was prepared by solid-state reaction at ambient temperature from Na₃PO₄·12H₂O and ZnSO₄·7H₂O, and characterized by X-ray, Raman, FT-IR spectra and TEM. Thermochemical study was performed by a RD496-III microcalorimeter at 298.15 K. The results reveal that the obtained product is Zn₃(PO₄)₂·2H₂O with spherical shape and particle size is between 40–50 nm. The standard enthalpy value for above reaction is calculated as − 45.793 kJ·mol^− 1. The standard enthalpy of formation for zinc phosphate dihydrate is recommended as − 3788.607 kJ·mol^− 1.     

Basic zinc carbonate as a precursor in the solvothermal synthesis of nano-zinc oxide

ZnO nanoparticles were synthesized solvothermally in various diols (ethylene glycol, di(ethylene glycol), tetra(ethylene glycol), 1,2-propanediol, 1,4-butanediol), using basic zinc carbonate (2ZnCO₃·3Zn(OH)₂) as a precursor for the first time. Since ZnCO₃ was sparingly soluble in diols the transformation reaction proceeded at a low reaction rate. Ethylene glycol was found as the most suitable medium among five diols studied yielding the smallest ZnO particles (~ 55 nm) and short reaction time, t_r (2 h). Diols with shorter chain length produced smaller ZnO particles. p-Toluene sulfonic acid (p-TSA) acted as a catalyst and reduced t_r from 8 h to 2 h in concentration of 0.02 M. Optimum reaction conditions for the synthesis in ethylene glycol were 185 °C and 2 h. At higher p-TSA concentrations (0.04–0.08 M) the size of ZnO particles was reduced from 500–800 nm to 50–100 nm and crystallite size to 25–30 nm. Benzene sulfonic acid (BSA) and inorganic bases (LiOH, NaOH, and KOH) also showed catalytic activities. Raman and photoluminescence spectroscopies revealed high concentration of defects on ZnO surface causing the emission of visible light and giving this type of ZnO higher potential in various (opto)-electronic application in comparison to Zn(II) acetate based ZnO.     

Nanocrystalline LaFeO3 preparation and thermal process of precursor

Nanocrystalline LaFeO₃ was synthesized by calcining precursor La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O in air. XRD analysis showed that precursor dried at 80 °C was a mixture containing orthorhombic La₂(CO₃)₂(OH)₂ and amorphous Fe₂O₃?1.5H₂O. Orthorhombic LaFeO₃ with highly crystallization was obtained when La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O was calcined at 900 °C in air for 2 h. Magnetic characterization indicated that the calcined product at 900 °C behaved weak magnetic behavior at room temperature. The thermal process of La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O experienced five steps, which involves, at first, dehydration of 0.8 absorption water, then dehydration of 0.7 crystal water, decomposition of orthorhombic La₂(CO₃)₂(OH)₂ into orthorhombic LaCO₃OH, reaction of two LaCO₃OH into hexagonal La₂O₂CO₃ and crystallization of tetragonal Fe₂O₃, at last, reaction of hexagonal La₂O₂CO₃ with tetragonal Fe₂O₃ into orthorhombic LaFeO₃. In the DTG curve, four DTG peaks indicated the precursor experienced mass loss of four steps.     

Two 2-D 36 tessellated metal–organic frameworks constructed from trimetallic clusters and dicarboxylate ditopic links

Two metal–organic framework compounds, [Zn₃(1,4-BDC)₃(Py)₂]·2(1,4-dioxane) (MOF-CJ6) and [Cd₃(bpdc)₃(H₂O)₂] (MOF-CJ7), have been solvothermally synthesized and characterized by single crystal X-ray diffraction, X-ray powder diffraction, ICP, IR and photoluminescence spectroscopy analyses, respectively. MOF-CJ6 crystallizes in monoclinic, space group P2(1)/n (no. 14) with a = 14.6886(14) Å, b = 9.6194(6) Å, c = 15.9161(16) Å and β = 105.687(6)°. Its framework can be described as a 2-D 3⁶ tessellated net based on the assembly of trimeric Zn₃(CO₂)₆ clusters and 1,4-benzenedicarboxylates ditopic links. The 2-D nets can be further linked into a novel 3-D supramolecular hexagonal lattice (hex) network through π–π packing interaction. MOF-CJ7 crystallizes in trigonal, space group R-3 (no. 148) with a = 14.1129(8) Å, b = 14.1129(8) Å, c = 20.1168(13) Å and γ = 120°. MOF-CJ7 exhibits analogous framework topology with that of MOF-CJ6, consisting of trimeric Cd₃(CO₂)₆ clusters and 4,4′-biphenyldicarboxylate links.     

Application of carbonated apatite coating on a Ti substrate by aqueous spray method

The fabrication and characterization of a carbonate-containing apatite film deposited on a Ti plate via an aqueous spray method is described. The mist of the spray solution emitted from a perpendicularly oriented airbrush was made to strike a warmed Ti substrate. The thicknesses of the sprayed film and those heat-treated at 400 °C–700 °C under Ar gas flow were in the range 1.21–1.40 μm. The results of elemental analyses and Fourier transform infrared spectroscopy of the powders that were mechanically collected from the surface of the sprayed film suggest that the film was Ca₁₀(PO₄)6(CO₃) · 2CO₂ · 3H₂O. The presence of the carbonate ion and the lattice CO₂ molecule was confirmed via the aforementioned analyses; the finding was also consistent with the X-ray diffraction patterns of the films and the chemical identity of the sprayed and heat-treated films that were measured using X-ray photoelectron spectroscopy. The sprayed film comprises a characteristic network structure, which contains round particles within the networks, as was observed by field-emission scanning electron microscopy. A scratch test indicated that the shear stress of the sprayed film (21 MPa) significantly improved to 40 and > 133 MPa after heat-treatment at 600 °C and 700 °C, respectively, under Ar gas flow for 10 min.     

A new indium metal-organic 3D framework with 1,3,5-benzenetricarboxylate,MIL-96 (In), containing μ3-oxo-centered trinuclear units and a hexagonal 18-ring network

A new indium trimesate In₁₂O(OH)₁₂({OH}₄,{H₂O}₅)[btc]₆·≈31H₂O, called MIL-96, (btc = 1,3,5-benzenetricarboxylate or trimesate species) was hydrothermally synthesized under mild condition (210 °C, 5 h) in the presence of trimethyl 1,3,5-benzenetricarboxylate in water and characterized by single-crystal X-ray diffraction technique. The MIL-96 (In) structure exhibits a three-dimensional metal-organic framework containing isolated trinuclear μ₃-oxo-bridged indium clusters and infinite chains of InO₄(OH)₂ and InO₂(OH)₃(H₂O) octahedra generating a hexagonal network based on 18-membered ring. The two types of indium entities are connected to each other through the trimesate species which induce corrugated chains of indium octahedra, linked via μ₂-hydroxo bonds with the specific –cis–cis–trans– sequence. The 3D framework of MIL-96 reveals three kind of cavities (two of them have estimated ≈ 400 Å³ volumes), in which are encapsulated free water molecules. The latter species are removed upon heating at 150 °C.     

Nanocrystalline LaMnO3 preparation and kinetics of crystallization process

Precursor of nanocrystalline LaMnO₃ was synthesized by solid-state reaction at low heat using La(NO₃)₃·6H₂O, MnSO₄·H₂O, and Na₂CO₃·10H₂O as raw materials. XRD analysis showed that precursor was a mixture containing orthorhombic La₂(CO₃)₃·8H₂O and rhombohedral MnCO₃. When the precursor was calcined at 800 ^°C for 2 h, pure phase LaMnO₃ with rhombohedral structure was obtained. Magnetic characterization indicated that rhombohedral LaMnO₃ behaved weak magnetic properties. The thermal process of the precursor experienced four steps, which involved the dehydration of crystallization water at first, and then decomposition of manganese carbonate into MnO₂, and decomposition of La₂(CO₃)₃ and MnO₂ together into La₂O₂CO₃ and Mn₂O₃, and lastly reaction of monoclinic La₂O₂CO₃ with Mn₂O₃ and formation of rhombohedral LaMnO₃. Based on the Kissinger equation, the value of the activation energy associated with the formation of rhombohedral LaMnO₃ was determined to be 260 kJ mol^?1. The value of the Avrami exponent, n, was equal to 1.68, which suggested that crystallization process of LaMnO₃ was the random nucleation and growth of nuclei reaction.     

Preparation of rodlike t-ZrO2 nanoparticles by two-step calcination of 1,12-diaminododecane–zirconia mesostructured composites

Rodlike t-ZrO₂ nanoparticles with aspect ratio of 1.3–8.0 and large surface area (152 m²/g) have been produced by two-step calcination of 1,12-diaminododecane–hydrous zirconia mesostructured composites. The two-step calcination consists of first calcination at 300 °C for 24 h and then at 400 °C for another 24 h. The resulting t-ZrO₂ nanoparticles can be stored under ambient conditions for at least 2 months without discernible transformation to the monoclinic phase. Compared to one-step calcination at 400 °C, the two-step calcination increases the amount of hydrocarbon fragments (3.6 wt% versus 2.9 wt%) adsorbed onto the resulting t-ZrO₂ nanoparticles. This increase may account for the improved phase stability of the rodlike t-ZrO₂ nanoparticles.     

Optical properties of calcium chromate 1D-nanorods synthesized at low temperature from secondary resources

Calcium chromate 1D-nanorods have been synthesized from tannery waste solution. The solution was filtered to get rid of insoluble matters followed by addition of ammonia to precipitate calcium and chromium as hydroxide gel. The gel was heated within the temperature range 300–600 °C. At 300 °C amorphous phase of calcium chromate was formed. At 400 °C compounds of CaCrO₄, Cr₂O₃, CaCO₃ and minor amount of Mg₂CO₃(OH)₂(H₂O)₃ (Artinite) were detected. At 500 °C, CaCrO₄ compound was the major product together with traces of Cr₂O₃, CaCO₃ and MgO. At 600 °C, a crystalline compound of CaCrO₄ was formed. Nanorods of calcium chromate structured during heating associated with the crystal growth. Properties of heated products are evaluated with the help of XRD, TEM and FT-IR measurements. Optical properties of the obtained calcium chromate were estimated. A thermodynamic model of the involved reactions is suggested to explore the findings.