Highly dispersed Mn2O3 microspheres: Facile solvothermal synthesis and their application as Li-ion battery anodes

Nanostructured transition metal oxides are promising alternative anodes for lithium ion batteries. Li-ion storage performance is expected to improve if high packing density energy particles are available. Herein, Mn₂O₃ microspheres with a ca. 18 μm diameter and a tapped density of 1.33 g/cm³ were synthesized by a facile solvothermal–thermal coversion route. Spherical MnCO₃ precursors were obtained through solvothermal treatment and they decomposed and converted into Mn₂O₃ microspheres at an annealing temperature of 700 °C. The Mn₂O₃ microspheres consisted of Mn₂O₃ nanoparticles with an average 40 nm diameter. These porous Mn₂O₃ microspheres allow good electrolyte penetration and provide an ion buffer reservoir to ensure a constant electrolyte supply. The Mn₂O₃ microspheres have reversible capacities of 590 and 320 mAh/g at 50 and 400 mA/g, respectively. We thus report an efficient route for the fabrication of energy particles for advanced energy storage.     

Preparation of 3D micro/nanostructured CeO2: Influence of organic/inorganic acids

CeO₂ is an important porous material with a wide range of applications in the abatement of volatile organic compounds (VOCs). In this paper, we prepared a series of novel three-dimensional (3D) micro/nanostructured CeO₂ materials via a solvothermal method. Organic acid-assisted synthesis and inorganic acid post-treatment were used to adjust the CeO₂ microstructures. The size of the 3D micro/nanostructures could be controlled in the range from 180 nm to 1.5 μm and the surface morphology changed from rough to smooth with the use of different organic acids. The CeO₂ synthesized with acetic acid featured a hierarchical porosity and showed good performance for toluene catalytic combustion: a T₅₀ of 187 °C and a T₉₀ of 195 °C. Moreover, the crystallite size, textural properties, and surface chemical states could be tuned by inorganic acid modification. After treatment with HNO₃, the modified CeO₂ materials exhibited improved catalytic activity, with a T₅₀ of ∼175 °C and a T₉₀ of ∼187 °C. We concluded that the toluene combustion activity is related to the porosity and the amount of surface active oxygen of the CeO₂. Both these features can be tuned by the co-work of organic and inorganic acids.     

Fabrication of magnetic nanosized γ-FeNi-coated ceramic core–shell microspheres by heterogeneous precipitation and thermal reduction

Precursors with NiCO₃·2Ni(OH)₂·2H₂O- and Fe₂O₃·nH₂O-coated alumina, graphite and cenosphere were synthesized by precipitation using ferrous sulfate, nickel sulfate, ammonium bicarbonate, alumina, graphite and cenosphere as the main starting materials. Magnetic γ-FeNi-coated alumina, graphite and cenosphere core–shell structural microspheres were subsequently prepared by thermal reduction of the as-prepared precursors at 600 °C for 2 h. Precipitation parameters, e.g. concentration of ceramic micropowders (10 g/L), sulfate solution (0.2 mol/L), rate of adding reactants (3 mL/min) and pH value were optimized by a trial-and-error method. Powders of the precursors and the resulting coating of γ-FeNi with grain size below 40 nm on alumina, graphite and cenosphere microspheres were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The magnetic properties of the nanosize γ-FeNi-coated alumina, graphite and cenosphere microspheres were measured by vibrating sample magnetometer (VSM). The results show that the core–shell structural γ-FeNi-coated ceramic microspheres exhibited higher coercivity than pure γ-FeNi powders, indicating that these materials can be used for high-performance functional materials and devices.     

Synthesis of mesoporous γ-AlOOH@Fe3O4 magnetic nanomicrospheres

Mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres were synthesized using superparamagnetic Fe₃O₄ nanoparticles as the core and aluminum isopropoxide (AIP) as the aluminum source. The obtained magnetic nanomicrospheres were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N₂ adsorption–desorption and vibrating sample magnetometry (VSM). The effects of preparation parameters such as hydrolysis time of AIP, concentration of AIP and coating layer number on microspheres were investigated. The results indicated that the mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres consisted of a mesoporous γ-AlOOH shell and a Fe₃O₄ magnetic core. The diameter of γ-AlOOH@Fe₃O₄ nanomicrospheres was about 200 nm, the thickness of mesoporous γ-AlOOH shell was about 5 nm and the average pore size was 3.8 nm. The thickness of the mesoporous γ-AlOOH shell could be controlled via layer-by-layer coating times. The formation mechanism of the mesoporous γ-AlOOH shell involved a “chemisorption–hydrolysis” process.     

Microwave-assisted polyol synthesis of LiMnPO4/C and its use as a cathode material in lithium-ion batteries

We synthesized LiMnPO₄/C with an ordered olivine structure by using a microwave-assisted polyol process in 2:15 (v/v) water–diethylene glycol mixed solvents at 130 °C for 30 min. We also studied how three surfactants—hexadecyltrimethylammonium bromide, polyvinylpyrrolidone k30 (PVPk30), and polyvinylpyrrolidone k90 (PVPk90)—affected the structure, morphology, and performance of the prepared samples, characterizing them by using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, charge/discharge tests, and electrochemical impedance spectroscopy. All the samples prepared with or without surfactant had orthorhombic structures with the Pnmb space group. Surfactant molecules may have acted as crystal-face inhibitors to adjust the oriented growth, morphology, and particle size of LiMnPO₄. The microwave effects could accelerate the reaction and nucleation rates of LiMnPO₄ at a lower reaction temperature. The LiMnPO₄/C sample prepared with PVPk30 exhibited a flaky structure coated with a carbon layer (∼2 nm thick), and it delivered a discharge capacity of 126 mAh/g with a capacity retention ratio of ∼99.9% after 50 cycles at 1C. Even at 5C, this sample still had a high discharge capacity of 110 mAh/g, demonstrating good rate performance and cycle performance. The improved performance of LiMnPO₄ likely came from its nanoflake structure and the thin carbon layer coating its LiMnPO₄ particles. Compared with the conventional polyol method, the microwave-assisted polyol method had a much lower reaction time.     

Advanced microemulsion synthesis and characterization of wollastonite (CaSiO3)/polystyrene one-dimensional nanorods with core–shell structures

In this work, one-dimensional core–shell nanorods (CSNRs; 185–250 nm wide and 1–1.5 μm long) consisting of triethoxyvinylsilane-modified wollastonite (CaSiO₃) nanorods (MWNRs) as a core and polystyrene as a shell with uniform size were successfully synthesized using an advanced microemulsion technique. The effect of varying the surfactant cetyltrimethylammonium bromide (producing CSNRs_CTAB) or sodium dodecyl sulphate (producing CSNRs_SDS) upon the size and morphology of the CSNRs was investigated by field-emission scanning electron microscopy (FE-SEM). X-ray diffractometry and Fourier transform infrared spectrophotometer revealed the existence of a strong interaction between the MWNRs and polystyrene, which implies that the polymer chains were successfully grafted onto the surface of the MWNRs. The CSNRs were blended with polypropylene by melt processing, and the effect of the CSNRs upon the morphological properties of the polypropylene matrix was investigated by FE-SEM and atomic force microscopy. It was observed that the polystyrene chains that grafted onto the CaSiO₃ nanorods interfered with the aggregation of CaSiO₃ nanorods in the polypropylene matrix and thus improved the compatibility of the CaSiO₃ nanorods with the polypropylene matrix. Furthermore, the compatibility of CaSiO₃ nanorods with polypropylene of CSNR_SDS/polypropylene was superior to that of CSNR_CTAB/polypropylene.     

A novel method for fast and continuous preparation of superfine titanium dioxide nanoparticles in microfluidic system

Previously we had developed a microfluidic system that can be easily fabricated by bending a stainless-steel tube into large circular loops. In this study, a fast and continuous preparation method for superfine TiO₂ nanoparticles (TiO₂-NPs) was developed for the aforementioned microfluidic system. The proposed method can yield anatase TiO₂ in 3.5 min, in contrast to the traditional hydrothermal reaction method, which requires hours or even days. Different reaction conditions, such as reaction temperature (120–200 °C), urea concentration (20–100 g/L), and tube length (5–20 m) were investigated. X-ray diffraction and Brunauer–Emmett–Teller analysis indicate that the as-prepared TiO₂-NPs have crystalline sizes of 4.1–5.8 nm and specific surface areas of 250.7–330.7 m²/g. Transmission electron microscopy images show that these TiO₂-NPs have an even diameter of approximately 5 nm. Moreover, because of their small crystalline sizes and large specific surface areas, most of these as-prepared TiO₂-NPs exhibit considerably better absorption and photocatalytic performance with methylene blue than commercial P5 TiO₂ does.     

Influence of temperature on a carbon–fibre epoxy composite subjected to static and fatigue loading under mode-I delamination

In this paper, interlaminar crack initiation and propagation under mode-I with static and fatigue loading of a composite material are experimentally assessed for different test temperatures. The material under study is made of a 3501-6 epoxy matrix reinforced with AS4 unidirectional carbon fibres, with a symmetric laminate configuration [0°]_16/S. In the experimental programme, DCB specimens were tested under static and fatigue loading. Based on the results obtained from static tests, fatigue tests were programmed to analyse the mode-I fatigue behaviour, so the necessary number of cycles was calculated for initiation and propagation of the crack at the different temperatures. G–N curves were determined under fatigue loading, N being the number of cycles at which delamination begins for a given energy release rate. G_ICmax–a, a–N and da/dN–a curves were also determined for different G_cr rates (90%, 85%, 75%, etc.) and different test temperatures: 90 °C, 50 °C, 20 °C, 0 °C, ?30 °C and ?60 °C.     

Hydrothermal synthesis of ultrathin hexagonal nickel hydroxide nanosheets

Nickel hydroxide, Ni(OH)₂ is widely used in electrodes of nickel-based alkaline secondary batteries. Ultrathin hexagonal Ni(OH)₂ nanosheets of space group P-3m1 were hydrothermally prepared at 200 °C for 10 h. Their diameter and thickness were 200–300 and 3–5 nm, respectively. Their formation was attributed to the oriented assembly of growing particles, which was assisted by surfactant molecules. The specific surface area of the Ni(OH)₂ nanosheets was 8.66 m²/g. Their magnetization curve exhibited linear paramagnetic behavior across the entire measurement region.     

Capuli cherry-mediated green synthesis of silver nanoparticles under white solar and blue LED light

In this article, the Capuli (Prunus serotina Ehrh. var. Capuli) cherry extract was used for the synthesis of silver nanoparticles (AgNPs) in the presence of white/visible solar and blue light-emitting diode (LED) light. For the characterization of the extract and the AgNPs, Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy were employed, along with hydrodynamic particle size analysis, transmission electron microscopy and X-ray diffraction. The Ag nanospheres obtained using white light were 40–100 nm in diameter and exhibited an absorption peak at λ_max = 445 nm, whereas those obtained using blue LED light were 20–80 nm in diameter with an absorption peak at λ_max = 425 nm. Thermal analysis revealed that the content of biomolecules surrounding the AgNPs was about 55–65%, and it was also found that blue LED light AgNPs (56.28%, 0.05 mM) had a higher antioxidant efficacy than the white solar light AgNPs (33.42%, 0.05 mM) against 1,1-diphenyl-2-picrylhydrazyl. The results indicate that obtaining AgNPs using a blue LED light may prove to be a simple, cost-effective and easily reproducible method for creating future nanopharmaceuticals.     

Influence of disodium hydrogen phosphate dodecahydrate on hydrothermal formation of hemihydrate calcium sulfate whiskers

The influence of Na₂HPO₄·12H₂O on the hydrothermal formation of hemihydrate calcium sulfate (CaSO₄·0.5H₂O) whiskers from dihydrate calcium sulfate (CaSO₄·2H₂O) at 135 °C was investigated. Experimental results indicate that the addition of phosphorus accelerates the hydrothermal conversion of CaSO₄·2H₂O to CaSO₄·0.5H₂O via the formation of Ca₃(PO₄)₂ and produces CaSO₄·0.5H₂O whiskers with thinner diameters and shorter lengths. Compared with the blank experiment without Na₂HPO₄·12H₂O, the existence of minor amounts (8.65 × 10⁻⁴–4.36 × 10⁻³ mol/L) of Na₂HPO₄·12H₂O led to a decrease in the diameter of CaSO₄·0.5H₂O whiskers from 1.0–10.0 to 0.5–2.0 μm and lengths from 70–300 to 50–200 μm.     

Mesoporous composite of LiFePO4 and carbon microspheres as positive-electrode materials for lithium-ion batteries

Mesoporous LiFePO₄/C microspheres consisting of LiFePO₄ nanoparticles are successfully fabricated by an eco-friendly hydrothermal approach combined with high-temperature calcinations using cost-effective LiOH and Fe³⁺ salts as raw materials. In this strategy, pure mesoporous LiFePO₄ microspheres, which are composed of LiFePO₄ nanoparticles, were uniformly coated with carbon (∼1.5 nm). Benefiting from this unique architecture, these mesoporous LiFePO₄/C microspheres can be closely packed, having high tap density. The initial discharge capacity of LiFePO₄/C microspheres as positive-electrode materials for lithium-ion batteries could reach 165.3 mAh/g at 0.1 C rate, which is notably close to the theoretical capacity of LiFePO₄ due to the large BET surface area, which provides for a large electrochemically available surface for the active material and electrolyte. The material also exhibits high rate capability (∼100 mAh/g at 8 C) and good cycling stability (capacity retention of 92.2% after 400 cycles at 8 C rate).     

Sol-gel synthesis and characterization of hydroxyapatite nanorods

In the present study hydroxyapatite （HA） nano-hexagonal rods with 70-90 nm diameter and 400-500 nm length are synthesized using a simple sol-gel route with calcium nitrate and potassium dihydrogenphosphate as calcium and phosphorus precursors respectively. Deionized water was used as a diluting media for HA sol preparation and ammonia was used to adjust the pH = 9. After aging, the HA gel was dried at 60 ℃ and calcined at different temperatures ranging from 300 to 700 ℃. The dried and calcined powders were characterized for phase composition using X-ray diffractrometry, elemental dispersive X-ray and Fourier transform infrared spectroscopy. Rietveld analysis showed the calcined HA powders of high purity with a hexagonal unit cell structure. Calcination yielded HA nanopowders of increased particle size and crystallinity with increase in temperature. The particle size and morphology was studied using transmission electron microscopy. The aspect ratio （length to diameter ratio） of HA nanorods was measured to be between 6 and 7.     

Hydrothermal preparation of nanocrystalline ZnO2

A green hydrothermal method was proposed for the synthesis of nanocrystalline ZnO₂, using Zn₅(CO₃)₂(OH)₆ powder and 6 vol% H₂O₂ aqueous solution as the starting materials. Characterization results from X-ray diffraction, Raman, high resolution transmission electron microscopy and selected area electron diffraction revealed that the products synthesized at 80–120 °C for 6–18 h were pure cubic phase ZnO₂ nanocrystals. Room temperature photoluminescence spectra of the as-synthesized ZnO₂ nanocrystals displayed a wide and strong emission band in the visible region of about 525–570 nm upon laser excitation at 325 nm, which may have originated from their surface state and other crystal defects.     

Fabrication of nano-sized Ca(OH)2 with excellent adsorption ability for N2O4

Uniform nano-sized calcium hydroxide (Ca(OH)₂) monocrystal powder was synthesized from calcium oxide in a surfactant solution via a digestion method by decreasing the surface tension of the reaction system to control the growth of crystalline Ca(OH)₂. The Ca(OH)₂ monocrystal powder samples were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), and Fourier transform-infrared spectroscopy (FT-IR). The NO_x adsorption ability of the samples was evaluated, and the influence of various types and concentrations of surfactants on powder agglomeration and then the specific surface area in the precipitation process were studied. The specific surface area of the samples was found as high as 58 m²/g and 92 m²/g and the particle size, 300–400 nm and 200–300 nm in the presence of 10 wt% PEG600 and 0.086 mL/L SDS at a reaction time of 5 h, respectively. The product has an exceptionally strong adsorption ability for NO_x, which makes it a highly promising adsorbent for emission control and air purification.     

Influences of ions and temperature on performance of carbon nano-particulates in supercapacitors with neutral aqueous electrolytes

A commercial product of carbon nano-particles, Cabot MONACH 1300 pigment black (CMPB), was studied for basic structural information and electrochemical performance in neutral aqueous electrolytes, aiming at applications in supercapacitors. As confirmed by SEM and HRTEM, the CMPB had a hierarchical structure, containing basic 10 nm nano-spheres which combined into ca. 50 nm agglomerates which further aggregated into larger particles of micrometres. The capacitance of this commercial material was found to increase with decreasing the size of hydrous cation (Li⁺ → Na⁺ → K⁺), instead of the cation crystal radius (K⁺ → Na⁺ → Li⁺) when coupled with the same anion (Cl⁻). In electrolytes with the same cation concentration (K⁺), changing the anion from the larger dianion (SO₄²⁻) to the smaller monoanion (Cl⁻) also increased the capacitance at high potential scan rates (>50 mV/s). Increasing electrolyte concentration produced expected effect, including raising the electrode capacitance, but lowering the equivalent series resistance (ESR), charge transfer resistance (CTR), and the diffusion resistance. At higher temperatures, the CMPB exhibited slightly higher capacitance, which does not agree with the Gouy–Chapman theory on electric double layer (EDL). A hypothesis is proposed to account for the capacitance increase with temperature as a result of the CMPB opening up some micro-pores for more ions to access in response to the temperature increase.     

Influence of single rectangular groove on the flow past a circular cylinder

In the present study, flow control mechanism of single groove on a circular cylinder surface is presented experimentally using Particle image velocimetry (PIV). A square shaped groove is patterned longitudinally on the surface of the cylinder with a diameter of 50 mm. The flow characteristics are studied as a function of angular position of the groove from the forward stagnation point of the cylinder within 0° ≤ θ ≤ 150°. In the current work, instantaneous and time-averaged flow data such as vorticity, ω streamline, Ψ streamwise, u/U_o and transverse, v/U_o velocity components, turbulent kinetic energy, TKE and RMS of streamwise, u_rms and transverse, v_rms velocity components are utilized in order to present the results of quantitative analyses. Furthermore, Strouhal numbers are calculated using Karman vortex shedding frequency, f_k obtained from single point spectral analysis. It is concluded that a critical angular position of the groove, θ = 80° is observed. The flow separation is controlled within 0° ≤ θ < 80°. At θ = 80°, the flow separation starts to occur in the upstream direction. The instability within the shear layer is also induced on grooved side of the cylinder with frequencies different than Karman vortex shedding frequency, f_k.     

Catalytic oxidation of benzene over Ce–Mn oxides synthesized by flame spray pyrolysis

Flame spray pyrolysis (FSP) was utilized to synthesize Ce–Mn oxides in one step for catalytic oxidation of benzene. Cerium acetate and manganese acetate were used as precursors. The materials synthesized were characterized using X-ray diffraction (XRD), N₂ adsorption, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Raman spectroscopy, and H₂-temperature programmed reduction (H₂-TPR) and their benzene catalytic oxidation behavior was evaluated. Mn ions were evidenced in multiple chemical states. Crystalline Ce–Mn oxides consist of particles with size <40 nm and specific surface areas (SSA) of 20–50 m²/g. Raman spectrums and H₂-TPR results indicated the interaction between cerium and manganese oxides. Flame-made 12.5%-Ce–Mn oxide exhibited excellent catalytic activity at relatively low temperatures (T₉₅ about 260 °C) compared to other Ce–Mn oxides with different cerium-to-manganese ratios. Redox mechanism and strong interaction conform to structure analysis that Ce–Mn strong interaction formed during the high temperature flame process and the results were used to explain catalytic oxidation of benzene.     

Experimental study of lean flammability limits of methane/hydrogen/air mixtures in tubes of different diameters

Lean limit flames in methane/hydrogen/air mixtures propagating in tubes of internal diameters (ID) of 6.0, 8.9, 12.3, 18.4, 25.2, 35.0, and 50.2 mm have been experimentally studied. The flames propagated upward from the open bottom end of the tube to the closed upper end. The content of hydrogen in the fuel gas has been varied in the range 0–40 mol%. Lean flammability limits have been determined; flame shapes recorded and the visible speed of flame propagation measured. Most of the observed limit flames in tubes with diameters in the range of 8.9–18.4 mm had enclosed shape, and could be characterized as distorted or spherical flame balls. The tendency was observed for mixtures with higher hydrogen content to form smaller size, more uniform flame balls in a wider range of tube diameters. At hydrogen content of 20% or more in the fuel gas, limit flames in largest diameters (35.0 mm and 50.2 mm ID) tubes had small, compared to the tube diameter, size and were “lens”-shaped. “Regular” open-front lean limit flames were observed only for the smallest diameters (6.0 mm and 8.9 mm) and largest diameters (35.0 and 50.2 mm ID), and only for methane/air and (90% CH₄ + 10% H₂)/air mixtures, except for 6 mm ID tube in which all limit flames had open front. In all experiments, except for the lean limit flames in methane/air and (90% CH₄ + 10% H₂)/air mixtures in the 8.9 mm ID tube, and all limit flames in 6.0 mm ID tube, visible flame speeds very weakly depended on the hydrogen content in the fuel gas and were close to- or below the theoretical estimate of the speed of a rising hot bubble. This observation suggests that the buoyancy is the major factor which determines the visible flame speed for studied limit flames, except that last mentioned. A decrease of the lean flammability limit value with decreasing the tube diameter was observed for methane/air and (90% CH₄ + 10% H₂)/air mixtures for tubes having internal diameters in the range of 18.4–50.2 mm. This effect has been attributed to the stronger combined effect of the preferential diffusion and flame stretch in narrower tubes for flames which resemble rising bubble.     

Gas–liquid pressure drop in vertical internally wavy 90° bend

Experiments of air water two-phase flow pressure drop in vertical internally wavy 90° bend have been carried out. The tested bends are flexible and made of stainless steel with inner diameter of 50 mm and various curvature radiuses of 200, 300, 400 and 500 mm. The experiments were performed under the following conditions of two-phase parameters; mass flux from 350 to 750 kg/m² s. Gas quality from 1% to 50% and system pressure from 4 to 7.5 bar. The results demonstrate that the effect of the above-mentioned parameters is very significant at high ranges of mass flow quality. Due to the increasing of two-phase flow resistance, energy dissipations, friction losses and interaction of the two-phases in the vertical internally wavy 90° bend the total pressure drops are perceptible about 2–5 times grater than that in smooth bends. Based on the mass and energy balance as well as the presented experimental results, new empirical correlation has been developed to calculate the two-phase pressure drop and hence the two-phase friction factor of the tested bends. The correlation includes the relevant primary parameter, fit the data well, and is sufficiency accurate for engineering purposes.