Modified hydrothermal synthesis of SnOy-SiO2 for lithium-ion battery anodes

A modified hydrothermal method was developed to synthesize tin oxide doped with highly dispersed silicon oxide. The microstructure, morphology and electrochemical performance of the mixtures were analyzed by X-ray diffraction (XRD), infra-red (IR), scanning electron microscopy (SEM) and electrochemical methods. The average size of the particles is about 30 nm. Silicon oxide as matrix should be able to support the anode changes accompanied by the formation of lithium-tin alloys, thus an improvement of the cycleability of the Li-ion battery would be expected. The electrochemical results showed that addition of silicon oxide reduces the irreversible capacity during the first discharge/charge cycle. The material delivers a charge capacity of more than 750 mAh g⁻¹. The capacity loss per-cycle is about 0.9% after cycling 20 times. The electrochemical performance indicates that silicon oxide is an appropriate matrix and these composites are good anode candidates for application in lithium-ion batteries.     

Pulse-mode electrochemical reduction of carbon dioxide using copper and copper oxide electrodes for selective ethylene formation

Although the electrochemical reduction of CO₂ at a copper electrode produces hydrocarbons, the activity for the conversion of CO₂ is significantly reduced after several tens of minutes by the deposition of poisoning species on the electrode. In order to solve the poisoning species problem, the electrochemical reduction of CO₂ was carried out using a copper electrode in the pulse electrolysis mode by anodic as well as cathodic polarization. The anodic polarization intervals suppressed the deposition of the poisoning species on the electrode, and the amount of two hydrocarbons produced, CH₄ and C₂H₆, decreased only slightly even after one hour. By choosing the appropriate anodic potential and time duration the selectivity for C₂H₆ formation was significantly enhanced. The enhancement was found to be due to the copper oxide formed on the copper electrode. The selectivity was further improved when the electrochemical reduction was carried out using a copper oxide electrode. The highest efficiency of about 28% was obtained at −3.15 V.     

Effect of substrate surface treatment on the hydrothermal synthesis of zinc oxide nanostructures

In this investigation, ZnO nanostructures were coated via hydrothermal process on glass substrate surfaces, which were treated by acidic and alkaline solutions. Furthermore, the ZnO structure was doped by different amounts of Al⁺³ ions to investigate the microstructural variation. Characteristics of the samples by XRD and SEM analyses confirmed the formation of different morphologies and various crystal sizes for the nanostructured ZnO on the substrates including nanoflower, nanorod, and nanopanel morphologies. Furthermore, XRD results showed that the Zn²⁺ concentration was a crucial factor in changing the grain size. EDS analysis confirmed the uniform distribution of Al dopant, while the FTIR spectra revealed the presence of Al–O and Zn–O stretching bonds in the coatings. The results confirmed that the sample, which was etched by fused NaOH had a uniform and compacted structure. Moreover, it was evident the proposed treatment and synthesis process was successful in the formation of uniform nanostructured ZnO film on the glass substrate without the requirement for seed layer deposition.     

Arsenic adsorption using copper (II) oxide nanoparticles

Arsenic poisoning is a major problem in today's life. To reduce its concentration in drinking water, different metal based compounds were explored as arsenic adsorbents. In the present study, copper (II) oxide nanoparticles were prepared by thermal refluxing technique and used as an adsorbent for arsenic removal from water. Characterization of the adsorbent using TEM, BET, XRD and FTIR implied that the prepared adsorbent was in nano size and had excellent adsorption behavior with surface area of 52.11 m²/g. Systematic adsorption experiments were carried out with different process parameters such as contact time, adsorbent mass, pH, temperature and stirring speed and found that copper (II) oxide had very good efficiency towards arsenic adsorption. Thermodynamic parameters and adsorption kinetics were studied in detailed to know the nature and mechanism of adsorption. Results showed that the adsorption process followed pseudo second order kinetic and endothermic behavior. Adsorption equilibrium was studied with Langmuir and Freundlich isotherm models. The adsorption process followed Langmuir isotherm with an adsorption capacity of 1086.2 μg/g. A regeneration study was proposed in order to reuse the adsorbent for better economy of the process. Finally, a process design calculation is reported to know the amount of adsorbent required for efficient removal of arsenic from aqueous medium.     

Synthesis and characterization of a novel 3D copper(I) coordination polymer with a ligand generated in situ

Hydrothermal reaction of CuCl₂ · 2H₂O, NaN₃ with 1,4-dicyanobenzene in water/ethanol yielded a novel Cu(I)-tetrazolate, {Cu(cptz)}_n, (1) (Hcptz is 5-(4-cyanophenyl)-tetrazole). The cptz ligand in the complex was generated in situ through the [2 + 3] cycloaddition reaction involving one of the two cyano-groups of the precursor 1,4-dicyanobenzene. The structure characterization shows that 1 possesses a 3D 4-connected SrAl₂ topological network. Additionally, complex 1 exhibits strong yellow fluorescence at room temperature in the solid state.     

Hydrothermal synthesis of flower-like Zn2SnO4 composites and their performance as anode materials for lithium-ion batteries

Flower-like Zn₂SnO₄ composites had been prepared through a green hydrothermal synthesis. The structural, morphological and electrochemical properties were investigated by means of XRD, BET, SEM, TEM, and electrochemical measurement. The results show that the as-prepared sample is in high purity phase and of good crystallinity; meanwhile it has a particular 3-D structure and large surface area. Electrochemical measurement suggests that flower-like Zn₂SnO₄ composites exhibit better cycling properties and lower initial irreversible capacities than the solid Zn₂SnO₄ cubes. The first discharge and charge capacities of the material are 1750 mA h g⁻¹ and 880 mA h g⁻¹ respectively. A higher reversible capacity of 501 mA h g⁻¹ was obtained after 50 cycles at a current density of 300 mA g⁻¹. The higher reversible capacity and good stability can be related to the special nanostructural features of the material. Such Zn₂SnO₄ structures synthesized by the simple and cheap method are expected to have potential application in energy storage.     

The electrochemical synthesis of poly(aniline-co-o-anisidine) on copper and their corrosion performances

The copolymer films PANI-co-POA and poly(aniline-co-o-anisidine) were carried out on copper (Cu) electrode, by applying two different scan rates (20 and 50 mV s⁻¹) and using two different thicknesses at high scan rate. Synthesizes were achieved under cyclic voltammetric conditions from 0.075 M aniline and 0.075 M o-anisidine containing sodium oxalate solutions. The synthesized copolymer films were strongly adherent and homogeneous in both cases. AC impedance spectroscopy (EIS), anodic polarization plots and open circuit potential–time curves were used to evaluate the corrosion performance of copolymer coated and uncoated electrodes in 3.5% NaCl. It was shown that the copolymer film coated at low scan rate exhibited a better property initially when compared with the copolymer film produced at high scan rate. However, it could not resist the attack of corrosion products, in longer time and meanwhile its barrier property significantly diminished. It was found that the thin copolymer film produced at high scan rate by its catalysing effect led to the formation of highly protective copper oxides on the surface whereby providing a better protection for long exposure times. It also emerged that the corrosion resistances of thin copolymer film produced at high scan rate and copolymer film synthesized at low scan rate were almost same and relatively higher for much longer periods when compared with the one observed for bare copper electrode.     

MnO anchored reduced graphene oxide nanocomposite for high energy applications of Li-ion batteries: The insight of charge-discharge process

In the present work, a new class of anode material for high energy applications of Li-ion battery is prepared by easy and large-scale producible process. Herein, the nanocomposite of MnO and reduced graphene oxide (rGO) is prepared by anchoring MnO nanoparticles into 3D matrix of rGO hydrogel followed by annealing process. The composite which has homogeneous distribution of MnO particles on conducting rGO layers demonstrated superior electrochemical performance such as high reversible capacity, stable cycle life and better rate capability. It has shown initial discharge capacity of 2358 mAh g⁻¹ and retained 570 mAh g⁻¹ after 100 cycles as compared to pristine MnO which shown initial discharge capacity of 820 mAh g⁻¹ and retained only 45 mAh g⁻¹ after 100 cycles. The retained capacity of new MnO/rGO anode is much higher than the theoretical capacity of conventional graphite anode. Moreover, the MnO/rGO nanocomposite shows six times higher Li⁺ ion diffusion of 4.18 × 10⁻¹² cm² s⁻¹ as compared to 6.84 × 10⁻¹³ cm² s⁻¹ of MnO. In addition, the study provides insight of charge-discharge process, which conducted in initial, discharge and charge states of pristine MnO and MnO/rGO composite using ex-situ X-ray diffraction and X-ray photon spectroscopy techniques.     

Hydrothermal synthesis of vanadium oxide nanotubes from V2O5 gels

Vanadium oxide nanotubes (VO_x-NT) have been synthesized in high yield by adding hexadecylamine to V₂O₅·nH₂O gels, followed by a hydrothermal treatment (150–180 °C, 2–7 days). Scanning electron microscopy (SEM) and X-ray diffraction analysis have been performed to optimize the temperature and reaction time required for formation of VO_x-NT and the morphology of the nanotubes investigated by transmission electron microscopy (TEM).     

Kinetics of the dissolution of copper(ii) oxide in acidified ascorbic acid solution

The zero order kinetics of the dissolution of CuO in ascorbic acid solution, acidified with HCl, was followed by measuring the absorbance of the coloured solution formed at 750 nm. From the variation of the logarithm of the rate constant with the reciprocal of the absolute temperature, an activation energy of 36 kJ mol^-1 was calculated. The infrared spectrum of a solid isolated from the reaction mixture was compared with the spectrum of ascorbic acid. A tentative mechanism of the reaction is suggested.     

Simple synthesis of surface-modified hierarchical copper oxide spheres with needle-like morphology as anode for lithium ion batteries

Hierarchical, nanostructured copper oxide spheres were synthesized in a stirred solution of cupric acetate and ammonium hydroxide. Cetyltrimethylammonium bromide (CTAB) was used as a surfactant to modify the surface morphology of CuO spheres. Ordered nano-needle arrays can be formed on the surface of the CuO spheres (instead of disordered nano-leaves) in the presence of CTAB. Each CuO sphere is about 2 μm in diameter and possesses a large number of nano-needles that are about 20-40 nm in width and more than 300 nm in length. The needle-like hierarchical structure can greatly increase the contact area between CuO and electrolyte, which provides more sites for Li⁺ accommodation, shortens the diffusion length of Li⁺ and enhances the reactivity of electrode reaction, especially at high rates. After 50 cycles, the reversible capacity of the prepared needle-like CuO can sustain 62.4% and 56.4% of the 2nd cycle at a rate of 0.1C and 1C, respectively.     

原子吸收光谱法测定橡胶配合剂氧化锌中氧化铜含量（以铜计）的不确定度评定

采用空气-乙炔火焰原子吸收光谱法测定橡胶配合剂氧化锌中的氧化铜（以铜计）含量。阐述了测量不确定度的主要来源: 样品质量m,定容体积V以及铜的测定浓度c。进行了不确定度的评定,给出了合成不确定度。原子吸收光谱法测定橡胶配合剂氧化锌中氧化铜含量不确定度结果表示为：（0.001±0.00014）%,k=2。     

Structural,optical, morphological and electrochemical properties of ZnO and graphene oxide blended ZnO nanocomposites

A simple cost-effective co-precipitation method was adopted to prepare ZnO nanoparticles from a metal organic framework. The synthesized ZnO nanoparticles were blended with graphene oxide (GO) to prepare the ZnO-GO nanocomposite. The physicochemical properties of ZnO nanoparticles and ZnO-GO nanocomposite were analyzed via various techniques. The structural behavior of ZnO and ZnO-GO nanocomposite was studied by XRD and FT-IR analysis. The XRD profile confirms the hexagonal structure with an average crystallite size of 19.4 nm for ZnO and 16.2 nm for ZnO-GO nanocomposites. The functional groups and the vibration modes of the samples were examined through FT-IR. It confirms the metallic presence in the ZnO and ZnO-GO samples in the wavenumber range of 400–600 cm^?1. The optical properties of ZnO and ZnO-GO were studied via UV–vis spectra. The surface morphology of the samples was recorded through FESEM, and the elemental presence in the samples was examined by EDX. It confirms that the prepared samples are spherical in shape with uniform size distributions. Cyclic voltammetry has been used to study the redox behavior of electroactive ZnO and ZnO-GO composites.     

Effect of microwave sintering on the properties of copper oxide doped Y-TZP ceramics

The effect of various amounts of copper oxide (CuO) up to 1?wt% on the densification behaviour and mechanical properties of 3?mol% yttria-tetragonal zirconia polycrystal (Y-TZP) were studied by using microwave (MW) sintering method. The MW sintering was performed at temperatures between 1100?°C and 1400?°C, with a heating rate of 30?°C/min. and holding time of 5?min. The beneficial effect of MW in enhancing densification was also compared for the undoped and 0.2?wt% CuO-doped Y-TZP when subjected to conventional sintering (CS) method. The results showed that significant enhancement in the relative density and Vickers hardness were observed for the undoped Y-TZP when MW-sintered between 1100?°C and 1250?°C. It was revealed that the 0.2?wt% CuO-doped Y-TZP and MW sintered at 1250–1300?°C could attain ≥?99.8% of theoretical density, Vickers hardness of about 14.4?GPa, fracture toughness of 7.8 MPam^1/2 and exhibited fine equiaxed tetragonal grain size of below 0.25?µm. In contrast, the addition of 1?wt% CuO was detrimental and the samples exhibited about 50% monoclinic phase upon sintering coupled with poor bulk density and mechanical properties. The study also revealed that the addition of 0.2?wt% CuO and subjected to conventional sintering produced similar densification as that obtained for microwave sintering, thus indicating that the dopant played a more significant role than the sintering method.     

Synthesis of poly(aniline-co-o-anisidine)-intercalated graphite oxide composite by delamination/reassembling method

Aniline/o-anisidine copolymer (P(An-co-oAs))-intercalated GO composite was synthesized by the delamination/reassembling method in N-methyl-2-pyrrolidone (NMP) solvent, and was characterized by FTIR, XRD, DSC, SEM, TGA, conductivity and cyclic voltammetry. XRD and FTIR spectra indicate that the P(An-co-oAs) exists as a monolayer of outstretched chains in the gallery of GO due to the hydrogen bonds between -NH, N- and -OCH₃ groups of P(An-co-oAs) and the oxygen functional groups of the GO layers. The results of thermal analysis show that no de-intercalation of P(An-co-oAs) from GO occurred during heating. Its electrical conductivity has reached 1.9 × 10⁻² S/cm, which is by 3 orders of magnitude higher than that of GO. The intercalation of P(An-co-oAs) also has a pronounced effect on the stabilization of electrochemical response in relation to the GO matrix and P(An-co-oAs).     

Green synthesis and characterisation of nanocrystalline NiO-GDC powders with low activation energy for solid oxide fuel cells

This work reports the preparation of nanocrystalline Ni-Gd_0.1Ce_0.9O_1.95 (NiO-GDC) anode powders using a novel single-step co-precipitation synthesis method (carboxylate route) based on ammonium tartrate as a low-cost green precipitant. The thermogravimetric analysis (TGA) of the synthesised powder showed the complete calcination/crystallisation of the resultant precipitates to take place at 500 °C. The prepared NiO-GDC powder was coated on a GDC electrolyte disc and co-sintered at 1300 °C. A mixture of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ and GDC was used as the cathode material and subsequently coated onto the anode-electrolyte bilayer, resulting in the fabrication of a NiO-GDC|GDC|La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ-GDC cell. The crystallite size of both NiO and CeO₂ phases were estimated using the X-ray powder diffraction (XRD) profiles and were calculated to be ~14 nm. Applied H₂ temperature-programmed reduction (H₂-TPR) analysis indicated a synergetic effect among different anode composites' constituents, where an intense interaction between the dispersed NiO nanocrystalline particles and the GDC crystallite phase had weakened the metal-oxygen bonds in the synthesised anode composites, resulting in a strikingly high catalytic activity at temperatures as low as 300 °C. The electrochemical impedance spectroscopy (EIS) and the electrochemical performance of the fabricated cells were measured over a broad range of operating temperatures (500–750 °C) and H₂/Ar-ratios of the anode fuel (e.g. 100%–15%). Quantitative analysis from the EIS data and the application of the distribution of relaxation times (DRT) method allowed for the estimation of the activation energies of the anodic high and intermediate frequency processes that were 0.45 eV and 0.76 eV, respectively. This is the first report of a NiO-GDC synthesis, where a considerable improvement in activation energy is observed at the low-temperature region. Such low activation energies were later associated with the adsorption/desorption process of water molecules at the surface of NiO-GDC composite, indicating a high activity towards hydrogen oxidation.     

Preparation of Ag/reduced graphene oxide reinforced copper matrix composites through spark plasma sintering: An investigation of microstructure and mechanical properties

The reduced graphene oxide (rGO) decorated with Ag nanoparticles was synthesized by the chemical reduction of graphene oxide in an aqueous solution containing AgNO₃, in the presence of hydrazine hydrate as a reducing agent. The reduction of graphene oxide was confirmed by FT-IR and raman spectroscopy analyses. The x-ray diffraction pattern and UV–visible investigations demonstrated the formation of Ag particles on the surface of rGO sheets. After successful decoration, the Ag/rGO nano-composite was used as the reinforcement in the copper matrix composite. Cu–Ag/rGO composites with different percentages of Ag/rGO (0.4, 0.8, 1.6 and 3.2 vol%.) were prepared by mechanical milling and spark plasma sintering (SPS). The effects of the Ag/rGO content on the consolidation process, micro-hardness, bending strength and also, fracture surface of the prepared samples were then investigated. The three-point bending strength of the sintered samples was increased from 285 to 472 MPa by the addition 0.8 vol%. of Ag/rGO, as compared to the pure Cu. Moreover, increasing the reinforcement content to the 3.2 vol%. Ag/rGO led to decreasing the bending strength to 433 MPa. The highest micro-hardness (81 Hv) was obtained for the composite sample containing the 1.6 vol%. Ag/rGO. By increasing Ag/r-GO as the reinforcement (3.2 vol%.), the Vickers hardness was decreased to 69 Hv. Also, investigation of the fracture surface morphology showed transformation of fracture mechanism from plastic changes to brittle ones by raising the Ag/rGO content volume from 0.8 to 1.6 vol %.     

Designing zinc oxide nanostructures (nanoworms,nanoflowers, nanowalls,and nanorods) by pulsed laser ablation technique for gas-sensing application

In this study, pulsed laser ablation technique, also known as pulsed laser deposition (PLD), is used to design and grow zinc oxide (ZnO) nanostructures (nanoworms, nanowalls, and nanorods) by template/seeding approach for gas-sensing applications. Conventionally, ZnO nanostructures used for gas-sensing have been usually prepared via chemical route, where the 3D/2D nanostructures are chemically synthesized and subsequently plated on an appropriate substrate. However, using pulsed laser ablation technique, the ZnO nanostructures are structurally designed and grown directly on a substrate using a two-step temperature-pressure seeding approach. This approach has been optimized to design various ZnO nanostructures by understanding the effect of substrate temperature in the 300-750°C range under O₂ gas pressure from 10-mTorr to 10 Torr. Using a thin ZnO seed layer as template that is deposited first at substrate temperature of ~300°C at background oxygen pressure of 10 mTorr on Si(100), ZnO nanostructures, such as nanoworms, nanowalls, and nanorods (with secondary flower-like growth) were grown at substrate temperatures and oxygen background pressures of (550°C and 2 Torr), (550°C and 0.5 Torr), and (650°C and 2 Torr), respectively. The morphology and the optical properties of ZnO nanostructures were examined by Scanning Electron Microscope (SEM-EDX), X-ray Diffraction (XRD), and photoluminescence (PL). The PLD-grown ZnO nanostructures are single-crystals and are highly oriented in the c-axis. The vapor-solid (VS) model is proposed to be responsible for the growth of ZnO nanostructures by PLD process. Furthermore, the ZnO nanowall structure is a very promising nanostructure due to its very high surface-to-volume ratio. Although ZnO nanowalls have been grown by other methods for sensor application, to this date, only a very few ZnO nanowalls have been grown by PLD for this purpose. In this regard, ZnO nanowall structures are deposited by PLD on an Al₂O₃ test sensor and assessed for their responses to CO and ethanol gases at 50 ppm, where good responses were observed at 350 and 400°C, respectively. The PLD-grown ZnO nanostructures are very excellent materials for potential applications such as in dye-sensitized solar cells, perovskite solar cells and biological and gas sensors.     

Hydrothermal synthesis and crystal structure of a novel cyanide-bridged double helical copper(I) coordination polymer [Cu3(CN)3(phen)]n

Hydrothermal reaction of CuCN, K₃[Fe(CN)₆] and 1,10-phenanthroline affords a novel cyanide-bridged copper(I) coordination polymer [Cu₃(CN)₃(phen)]_n (1). The complex displays an interesting one-dimensional neutral double helical framework with (phen)Cu–CN– side-arms as interchain bridges. The double helical chains are close packed in a parallel fashion, and the phen ligands stack in an interpenetrating mode, which leads to π–π interactions between parallel phen planes. The thermal stability and fluorescent property have also been investigated.