Hydrothermal synthesis of Litchi-like SrTiO3 with the help of ethylene glycol

Templated by TiO₂ microspheres , litchi-like SrTiO₃ crystals with a narrow size distribution and monodispersity were synthesized through the combination of regulating the ethylene glycol concentration during the hydrothermal process and the post heat treatment. The results show that when the volume ratio of water and ethylene glycol reached 10:70, microsized SrCO₃ was firstly formed under the hydrothermal process, and then the litchi-like SrTiO₃ powder was obtained after the postheat treatment at 700°C for 4 hours, which shows a large specific surface area of 37.41 m²/g. It is found that the concentration of ethylene glycol aqueous solution plays an important role on the morphology of the SrTiO₃ crystals, and the slightly higher viscosity and proper amount of OH hydroxyl groups facilitate the formation of the micrometer spherical hierarchical surface.     

沉淀法制备氧化锌粉体

以碳酸钠和硫酸锌为原料,采用沉淀法制备前驱体碱式碳酸锌,前驱体经过热分解得到氧化锌粉体。采用热重分析（TG-DTG-DTA）、X射线衍射（XRD）、红外光谱（IR）和扫描电镜（SEM）等方法对前驱体和产品氧化锌进行表征。结果表明：制备的前驱体为碱式碳酸锌Zn4（OH）6CO3;以水、乙二醇为溶剂及聚乙二醇（PEG）为分散剂,均可制备出较为纯净的氧化锌;乙二醇为溶剂和PEG为分散剂,改善了氧化锌的形貌和分散性,避免了氧化锌团聚。     

Sol−gel-based hydrothermal method for the synthesis of 3D flower-like ZnO microstructures composed of nanosheets for photocatalytic applications

Self-assembled 3D flower-like ZnO microstructures composed of nanosheets have been prepared on a large scale through a sol−gel-assisted hydrothermal method using Zn(NO₃)₂·6H₂O, citric acid, and NaOH as raw materials. The product has been characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The optical properties of the product have been examined by room temperature photoluminescence (PL) measurements. A possible growth mechanism of the 3D flower-like ZnO is proposed based on the results of experiments carried out for different hydrothermal treatment times. Experiments at different hydrothermal treatment temperatures have also been carried out to investigate their effect on the final morphology of the ZnO. The photocatalytic activities of the as-prepared ZnO have been evaluated by photodegradation of Reactive Blue 14 (KGL) under ultraviolet (UV) irradiation. The experimental results demonstrated that self-assembled 3D flower-like ZnO composed of nanosheets could be obtained over a relatively broad temperature range (90−150 °C) after 17 h of hydrothermal treatment. All of the products showed good photocatalytic performance, with the degree of degradation of KGL exceeding 82% after 120 min. In particular, the sample prepared at 120 °C for 17 h exhibited superior photocatalytic activity to other ZnO samples and commercial ZnO, and it almost completely degraded a KGL solution within 40 min. The relationship between photocatalytic activity and the structure, surface defects, and surface areas of the samples is also discussed.     

Supercritical hydrothermal synthesis of nano-ZnO: Effects of key parameters and reaction mechanism

In this paper, ZnO particles with the particle size as low as 23 nm were successfully prepared by supercritical hydrothermal synthesis technique. The particle size of nano-ZnO decreased with the increase of temperature and pressure. Nano-ZnO particles in ZnSO₄ system were spherical with smaller particle size. The discrepancy in nano-ZnO produced by different precursor of Zn(NO₃)₂, Zn(CH₃COO)₂ or ZnSO₄ is attributed to the anion effects and supersaturation. The particles in the KOH system (29 nm) were smaller than those in the NaOH system (44 nm). For precursor concentration, intermediate Zn(OH)₂ was generated at lower concentration, while Zn₄SO₄(OH)₆·4H₂O was produced at higher concentration. For alkali concentration, as the gradual increase of KOH concentration, Zn(OH)₂ began to decrease and gradually transformed into Zn(OH)₃^– and [Zn(OH)₄]²⁻. When the KOH concentration reached a certain value, [Zn(OH)₄]²⁻ occupied the dominance in the mixed solution.     

Electrochemical performances of Bi based compound film-coated ZnO as anodic materials of Ni–Zn secondary batteries

Microstructures and electrochemical performances of Bi based compound film-coated ZnO are investigated and compared with those of Ni film-coated ZnO and Bi nanocompound-modified ZnO in order to illuminate the coating effect of Bi based compound film. Bi based compound film is composed of nanoparticles (1–2 nm in diameter) of Bi₆(NO₃)₄(OH)₂O₆, BiO and Bi₂O₃, containing lots of micropores. In comparison with Bi nanocompound-modified ZnO and Ni film-coated ZnO, Bi based compound film-coated ZnO shows higher discharge capacity and more stable cycling performance. The highest average discharge capacity is as high as 535 mAh g⁻¹, and the discharge capacity does not obviously decrease during the cycling tests. Cyclic voltammograms indicates that Bi based compound film can limit transfer of H₂O, OH⁻, and enhance electrochemical activity of ZnO. The improvement of cycling performance is due to: (1) the coating film structure avoids the direct contact between ZnO/Zn with the electrolyte, and suppresses the dissolution of ZnO/Zn; (2) the micropores in the film is beneficial to adequate diffusion of H₂O, OH⁻ and zincates ions, leading to high discharge capacity and good cycling performance; (3) the light weight of the film also has a contribution to high specific discharge capacity.     

Controllable preparation of ZnO porous flower through a membrane dispersion reactor and their photocatalytic properties

Three dimensional (3D) flower-like basic zinc carbonate constructed by multilayered nanoplates were rapidly prepared at room temperature through the direct precipitation method coupled with membrane dispersion technology, and porous ZnO with similar structures could be obtained after calcining the precursor. The structural properties of the products before and after the calcining process were characterized by SEM, TEM and XRD. The supersaturation of the reaction system due to the membrane dispersion played an important role in the formation of uniform Zn₅(CO₃)₂(OH)₆ precursors. A plausible mechanism was proposed for the formation of the flower-like ZnO assembled by nanoplates composed of nanoparticles. The obtained ZnO microspheres showed excellent photocatalytic properties, which could be attributed to the open structure and remarkable amount of porous nanoplates.     

Continuous synthesis of surface-modified zinc oxide nanoparticles in supercritical methanol

Continuous synthesis of surface-modified zinc oxide (ZnO) nanoparticles was examined using surface modifiers (oleic acid and decanoic acid) in supercritical methanol at 400 °C, 30 MPa and a residence time of ∼40 s. Wide angle X-ray diffraction (WAXD) analysis revealed that the surface-modified nanoparticles retained ZnO crystalline structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the surface modifiers changed drastically the size and morphology of the ZnO nanoparticles. When the molar ratio of oleic acid to Zn precursor ratio was 30, 10 nm size particles with low degree of aggregation were produced. The surface-modified ZnO nanoparticles had higher BET surface areas (29-36 m²/g) compared to unmodified ZnO particles synthesized in supercritical water (0.7 m²/g). Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA) indicated that aliphatic, carboxylate and hydroxyl groups were chemically attached on the surface of ZnO nanoparticles. Long-term (80 days) dispersion test using ultraviolet transmittance showed that the surface-modified ZnO particles had enhanced dispersion stability in ethylene glycol.     

Preparation of ZnO/Eu mixed films by electrochemical precipitation

The electrochemical preparation of europium doped zinc oxide and europium oxide/hydroxide as thin films is investigated. First, a thermodynamic study of the Eu-Cl-H₂O system has been carried out at 25 and 70 °C in order to predict the electrochemical behaviour of Eu(III) dissolved in aqueous solution containing chloride ions. A comparison of the Eu-Cl-H₂O and Zn-Cl-H₂O systems indicates the possible coprecipitation of ZnO and Eu(OH)₃ from deposition solutions containing well-adjusted Eu(III)/Zn(II) concentrations ratio. The thermodynamic predictions have been confirmed experimentally by the electrochemical co-deposition of ZnO/Eu thin films on conducting electrode substrates at −1.4 V versus MSE. The presence of europium in the film is detected for Eu(III)/Zn(II) concentration ratio at (0.6 mM/5 mM) which is lower than the predicted value. Increasing Eu(III) concentration leads to the rapid appearance of two phases: dispersed zinc oxide nanorods and, at the bottom of the rods, a covering layer containing Eu(OH)₃ and zinc. The density of ZnO rods decreases and the rod size increases with increasing Eu(III) concentration in the bath. Above 1 mM EuCl₃, a dramatic fall in the current density is observed with the formation of a less conducting ZnO/Eu mixed deposit.     

The crystallization behavior of calcium carbonate in ethanol/water solution containing mixed nonionic/anionic surfactants

Crystallization of CaCO₃ was performed in an ethanol/water solution containing Pluronic F127 (EO₉₇PO₆₈EO₉₇) and sodium dodecyl sulfate (SDS). The effects of the ethanol/water volume ratio, concentration of surfactants, and aging temperature (30-90 °C) on the morphology and polymorphs of CaCO₃ were investigated using scanning electron microscopy (SEM) and powder X-ray diffraction (XRD). The presence of both F127 and SDS in solution favored the vaterite phase of CaCO₃. A binary calcite-vaterite mixture and a ternary calcite-vaterite-aragonite mixture were produced at low (< 60 °C) and high temperatures, respectively. Spherical, plate-like, flower-like, and rod-like crystals were obtained at different ethanol/water volume ratios. Controllable synthesis of nearly pure flower-like vaterite and rod-like aragonite can be realized by adjusting the ethanol/water volume ratio. The formation mechanism of flower-like CaCO₃ crystals is discussed.     

Hydrothermal Synthesis of Copper Hydroxyphosphate Hierarchical Architectures

Copper hydroxyphosphate, Cu₂(OH)PO₄, with six hierarchical architectures was successfully synthesized through a hydrothermal route. The resulting hierarchical superstructures were characterized using powder X‐ray diffraction and scanning electron microscopy. In this hydrothermal process, the morphology of copper hydroxyphosphate changed drastically with the addition of different amounts of alcohol (ethanol, n‐propanol, or ethylene glycol) as solvent. A possible mechanism for the formation of these copper hydroxyphosphate hierarchical superstructures is proposed. This approach provides a facile strategy to synthesize copper hydroxyphosphate crystals with unique morphologies and complex architectures. This binary reaction medium (alcohol and water) could provide an alternative and versatile strategy for controlling inorganic microcrystals by manipulating the supersaturation of the growing solution.     

Zinc oxide obtained by the solvothermal method with high sensitivity and selectivity to nitrogen dioxide

The effect of heat treatment using [Zn(H₂O)(O₂C₅H₇)₂] precursor ethylene glycol solution (synthesis temperature 125–185 °C, holding time 2–6 h) on the characteristics of the obtained nanocrystalline zinc oxide powder was studied. Under all synthesis conditions crystalline ZnO was formed with a wurtzite structure and an average crystallite size of 8–37 nm. The thermal behaviour and microstructure of the nanostructured ZnO powder were studied. The sensory properties of the obtained films in terms of the detection of hydrogen, methane, carbon monoxide and nitrogen dioxide were studied. The high sensitivity and selectivity of a thick ZnO film (synthesis temperature 145°С, holding time 6 h) when detecting NO₂ was established. It was found, that humidity had almost no effect on response value for NO₂ detection.     

One-step synthesis of magnetically-functionalized reduced graphite sheets and their use in hydrogels

Graphene/Fe₃O₄ hybrids were prepared using a one-step solvothermal method in ethylene glycol using graphite oxide as the graphene precursor and FeCl₃·6H₂O as the Fe₃O₄ precursor. The Fe₃O₄ nanoparticles, with a diameter of 100–200 nm, were densely and randomly deposited on the graphene sheets. The electrical conductivity of the hybrid reached 1.011 × 102 S m⁻¹ and the saturation magnetization reached 83.6 emu g⁻¹. The as-prepared magnetically-functionalized graphene hybrid was used for the functionalization of hydrogels for the first time.     

Hydrothermal growth of ZnO nanostructures from nano-ZnO seeded in P(MMA-co-BA) matrix

Nano-ZnO synthesized by hydrothermal reaction were embedded in poly(methyl methacrylate-co-butyl acrylate) matrix (P(MMA-co-BA)) to produce the nano-ZnO/P(MMA-co-BA) nanocomposites via in-situ polymerization at 85 °C. The nano-ZnO/P(MMA-co-BA) nanocomposites were hydrothermal treated in the mixture solution of Zn(NO₃)₂·6H₂O and NH₄OH at 90 °C under various pH (i.e.7, 8, 9 and 10) and treatment time (i.e. 4, 6, 8, 10, 12 and 24 hrs). The nano-ZnO could act as seeding particles for hydrothermal growth of ZnO nanostructures on the surfaces of nanocomposites. The higher pH of basic solutions used in the hydrothermal treatment, the higher amount of Zn(OH)₄²⁻nuclei would be created, leading to a modification of the ZnO morphology from nano-nuclei to nanorods, nanorods bushes (flower-like nanostructure) and nanofibers with nanospine. The increase of hydrothermal treatment time resulted in the increases of amount and length of multidirectional grown ZnO nanorods. Data of the contact angle measurement exhibited the increase of hydrophobicity of the nano-ZnO/P(MMA-co-BA) nanocomposites after hydrothermal growth of ZnO nanostructures. The nanocomposites treated at pH = 10 for 24 hrs shows the highest hydrophobicity with the contact angle of 121˚. In addition, the thermal stability of the nano-ZnO/P(MMA-co-BA) could be improved by the formation of hydrothermal grown ZnO nanostructure on the nanocomposite surface.     

Facile synthesis of nanorods of tetragonal barium titanate using ethylene glycol

Tetragonal barium titanate (BaTiO₃) nanorods were synthesized from hydroxide precursor by a hydrothermal/solvothermal method with 10 vol% ethylene glycol as solvent. The hydroxide precursor slurry was prepared by the addition of 10 M NaOH to a mixed solution of BaCl₂ and TiCl₄. When the above aqueous slurry was heated with water only at 200 °C, cubic BaTiO₃ nanocrystals formed, whereas tetragonal BaTiO₃ nanorods were obtained when heated with 10 vol% ethylene glycol. The crystallization of cubic BaTiO₃ via dissolution–reprecipitation of precursor could be suppressed by the addition of ethylene glycol, resulting in the formation of tetragonal BaTiO₃ under hydrothermal treatment at 200 °C.     

Synthesis, characterisation and aqueous behaviour of a one-ended perfluorocarbon-modified poly(ethylene glycol)

Establishing structure-properties relationships for an associative polymer requires a precise knowledge of its structure. In previous works, we studied water-soluble telechelic perfluorocarbon (C₈F₁₇) derivatives of poly(ethylene glycol)s. They exhibit stronger hydrophobic intermolecular associations than the corresponding hydrocarbon derivatives (C₈H₁₇). We now report the synthesis and study of one-ended perfluorocarbon derivative of poly(ethylene glycol). The composition and structure of this polymer were elucidated before analysing its behaviour in aqueous solution by viscosimetry and ¹⁹F NMR. The synthesis procedure allows us to reach total grafting. This polymer presents a micellar behaviour above 2×10⁻⁴ g/ml and an associative behaviour above 10⁻³ g/ml.     

One-step solution synthesis and formation mechanism of flower-like ZnO and its structural and optical characterization

The regular hierarchical flower-like ZnO nanostructures assembled by nanosheets were successfully synthesized by one-step solution route with citrate assistance at room temperature. It was demonstrated that the concentration of citrate and the molar ratio of Zn²⁺/OH⁻ had strong effect on the formation of nanosheets and self-assembly flower-like nanostructures. A reasonable formation mechanism of the flower-like nanostructures was proposed. According to UV–vis spectrum, the flower-like ZnO nanostructures exhibited strong light absorption, and the value of band gap of the obtained ZnO was estimated to be 3.26 eV. Moreover, the room-temperature photoluminescence (PL) spectrum of the sample presented only a near-band edge emission at 382 nm.     

Synthesis and Characterization of ZnO Nanorods and Nanodisks from Zinc Chloride Aqueous Solution

ZnO nanorods and nanodisks were synthesized by solution process using zinc chloride as starting material. The morphology of ZnO crystal changed greatly depending on the concentrations of Zn²⁺ ion and ethylene glycohol (EG) additive in the solution. The effect of thermal treatment on the morphology was investigated. Photocatalytic activities of plate-like Zn₅(OH)₈Cl₂ · H₂O and rod-like ZnO were characterized. About 18% of 1 ppm NO could be continuously removed by ZnO particles under UV light irradiation.     

Al-doped Ni-rich cathode powders prepared from the precursor powders with fine size and spherical shape

LiNi_0.8Co_0.15Al_0.05O₂ cathode powders with fine size and spherical shape were prepared by solid-state reaction method using the Ni-Co-Al-O precursor powders with fine size and spherical shape. The Ni-Co-Al-O precursor powders with fine size and filled inner structure were prepared by spray pyrolysis from the spray solution with drying control chemical additive (DCCA), citric acid and ethylene glycol. The one LiNi_0.8Co_0.15Al_0.05O₂ cathode powder with fine size and spherical shape was formed from the one precursor powder with spherical shape and filled morphology. The mean size of the spherical shape LiNi_0.8Co_0.15Al_0.05O₂ cathode powders was 1.1 μm. The initial discharge capacity of the LiNi_0.8Co_0.15Al_0.05O₂ cathode powders prepared from the spray solution with citric acid, ethylene glycol and DCCA was 200 mAh g⁻¹. The cycle properties of the cathode powders prepared from the spray solution with and without additives were compared.     

Synthesis, structure and photoelectrochemical performance of micro/nano-textured ZnO/eosin Y electrodes

Micro/nano-textured ZnO thick films were synthesized through deposition and pyrolysis of layered hydroxide zinc acetate (LHZA), Zn₅(OH)₈(CH₃COO)₂·2H₂O. LHZA films having a unique, rose-like morphology were initially deposited on conducting glass sheets in a chemical bath composed of methanol and zinc acetate dihydrate at 60 °C under neutral conditions. Pyrolysis of the LHZA films resulted in formation of ZnO without destroying the original morphology. Pyrolysis temperatures were found to greatly influence grain sizes and specific surface areas of the ZnO films. Photoelectrochemical performance of the films as ZnO/eosin Y electrodes was investigated in dye-sensitized solar cells using an I⁻/I₃⁻ redox electrolyte solution. The cell using the ZnO film pyrolyzed at 150 °C exhibited overall light to electricity conversion efficiencies of 2.0 and 3.3% under an AM-1.5 illumination at 100 and 10 mW cm⁻², respectively. While microscale pores in the electrodes facilitated mass transfer of fluid electrolytes in the depth direction, nanoscale pores contributed to an increase in the amount of adsorbed dye. The maximum incident photon-to-current conversion efficiency (IPCE) of the electrode reached 84.9% at a wavelength of 530 nm.     

PEG-based hydrogel membrane coatings

As a first step towards preparing fouling-resistant coatings for water purification membranes, three series of copolymer hydrogel networks were synthesized using poly(ethylene glycol) diacrylate (PEGDA) as the crosslinker and acrylic acid (AA), 2-hydroxyethyl acrylate (HEA), or poly(ethylene glycol) acrylate (PEGA) as comonomers. Copolymers containing varying amounts of PEGDA with each of these comonomers were prepared. Glass transition temperatures obeyed the Fox equation. Crosslink density strongly influenced water uptake and water permeability for materials of constant chemical composition. For example, the volume fraction of water sorbed by a 100 mol% PEGDA hydrogel was 0.61. However, introducing comonomers into the network reduced hydrogel crosslink density, and in hydrogels having the same ethylene oxide content, water sorption increased as crosslink density decreased. The highest water volume fraction observed was 0.72, obtained in a copolymer containing 80 mol% PEGA and 20 mol% PEGDA. Water permeability increased systematically with increasing water sorption, and water permeability coefficients ranged from 10 to 26 L μm/(m² h bar). NaCl partition coefficients ranged from 0.36 to 0.53 (g NaCl/cm³ hydrogel)/(g NaCl/cm³ solution). NaCl diffusion coefficients varied little with polymer composition; in this regard, diffusion coefficient values ranged from 4.3 × 10⁻⁶ to 7.4 × 10⁻⁶ cm²/s. Based on contact angle measurements using n-decane in water, oil exhibited a low affinity for the surfaces of these polymers, suggesting that coatings prepared from such materials might improve the fouling resistance of membranes towards oily wastewater.