Large-scale synthesis of hierarchical MnO2 for benzene catalytic oxidation

Hierarchical sea-urchin-shaped manganese oxide microspheres were synthesized via a facile method based on the reaction between KMnO₄ and MnSO₄ in HNO₃ solution at 50 °C. The average diameter of the microspheres is ∼850 nm. The microspheres consist of a core of diameter of ∼800 nm and nanorods of width ∼50 nm. The nanorods exist at the edge of the core. The Brunauer–Emmett–Teller surface area of the sea-urchin-shaped microspheres is 259.4 m²/g. A possible formation mechanism of the hierarchical sea-urchin-shaped microspheres is proposed. The temperature for 90% conversion of benzene (T_90%) on the hierarchical urchin-shaped MnO₂ microspheres is about 218 °C.     

Solid-state synthesis of Li[Li0.2Mn0.56Ni0.16Co0.08]O2 cathode materials for lithium-ion batteries

Layered Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials were synthesized via a solid-state reaction for Li-ion batteries, in which lithium hydroxide monohydrate, manganese dioxide, nickel monoxide, and cobalt monoxide were employed as metal precursors. To uncover the relationship between the structure and electrochemical properties of the materials, synthesis conditions such as calcination temperature and time as well as quenching methods were investigated. For the synthesized Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ materials, the metal components were found to be in the form of Mn⁴⁺, Ni²⁺, and Co³⁺, and their molar ratio was in good agreement with stoichiometric ratio of 0.56:0.16:0.08. Among them, the one synthesized at 800 °C for 12 h and subsequently quenched in air showed the best electrochemical performances, which had an initial discharge specific capacity and coulombic efficiency of 265.6 mAh/g and 84.0%, respectively, and when cycled at 0.5, 1, and 2 C, the corresponding discharge specific capacities were 237.3, 212.6, and 178.6 mAh/g, respectively. After recovered to 0.1 C rate, the discharge specific capacity became 259.5 mAh/g and the capacity loss was only 2.3% of the initial value at 0.1 C. This work suggests that the solid-state synthesis route is easy for preparing high performance Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials for Li-ion batteries.     

Effects of multi-dopants (Zn and Ho) in stabilizing spinel structure for cathode materials in lithium rechargeable batteries—Novel chelated sol–gel synthesis

Multi-doped spinels, namely LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ (x = 0.10–0.18; y = 0.02–0.10), for use as cathode materials for lithium-ion rechargeable batteries were synthesized via sol–gel method, using lauric acid as the chelating agent, to obtain micron-sized particles. The physical properties of the synthesized samples were investigated using differential thermal analysis, Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, energy-dispersive X-ray analysis, and electrochemical methods. XRD showed that LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ have high degrees of crystallinity and good phase purities. The SEM images of LiMn₂O₄ showed an ice-cube morphology with particles of size 1 μm. Charge–discharge studies showed that undoped LiMn₂O₄ delivered the discharge capacity of 124 mA h/g with coulombic efficiency of 95% during the first cycle, whereas doped spinels delivered discharge capacities of 125, 120, and 127 mA h/g in the first cycle with coulombic efficiencies of 96%, 91%, and 91%, respectively.     

Synthesis of layered cathode materials Li[CoxNiyMn1−x−y]O2 from layered double hydroxide precursors

Cathode materials Li[Co_xNi_yMn_1?x?y]O₂ for lithium secondary batteries have been prepared by a new route using layered double hydroxides (LDHs) as a precursor. The resulting layered phase with the α-NaFeO₂ structure crystallizes in the rhombohedral system, with space group R-3m having an interlayer spacing close to 0.47 nm. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation states of Co, Ni and Mn. The effects of varying the Co/Ni/Mn ratio on both the structure and electrochemical properties of Li[Co_xNi_yMn_1?x?y]O₂ have been investigated by X-ray diffraction and electrochemical tests. The products demonstrated a rather stable cycling behavior, with a reversible capacity of 118 mAh/g for the layered material with Co/Ni/Mn = 1/1/1.     

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.     

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).     

Magnetic and electrochemical behavior of rhombohedral α-Fe2O3 nanoparticles with (1 0 4) dominant facets

Uniform rhombohedral α-Fe₂O₃ nanoparticles, ～60 nm in size, were synthesized via a triphenylphosphine-assisted hydrothermal method. Scanning electron micrograph (SEM) and transmission electron micrograph (TEM) analyses showed that the as-synthesized rhombohedral nanoparticles were enclosed by six (1 0 4) planes. The concentration of triphenylphosphine played an important role in morphological evolution of the α-Fe₂O₃ nanoparticles. The as-prepared rhombohedral nanoparticles possessed remanent magnetization M_r of 2.6 × 10^?3 emu/g and coercivity H_C of 2.05 Oe, both lower than those of other α-Fe₂O₃ particles with similar size, indicating their potential applications as superparamagnetic precursor materials. Furthermore, these rhombohedral α-Fe₂O₃ nanoparticles exhibited good sensor capability toward H₂O₂ with a linear response in the concentration range of 2–20 mM.     

Microwave-hydrothermal preparation of a graphene/hierarchy structure MnO2 composite for a supercapacitor

Graphene/hierarchy structure manganese dioxide (GN/MnO₂) composites were synthesized using a simple microwave-hydrothermal method. The properties of the prepared composites were analyzed using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) measurements. The electrochemical performances of the composites were analyzed using cyclic voltammetry, electrochemical impedance spectrometry (EIS), and chronopotentiometry. The results showed that GN/MnO₂ (10 wt% graphene) displayed a specific capacitance of 244 F/g at a current density of 100 mA/g. An excellent cyclic stability was obtained with a capacity retention of approximately 94.3% after 500 cycles in a 1 mol/L Li₂SO₄ solution. The improved electrochemical performance is attributed to the hierarchy structure of the manganese dioxide, which can enlarge the interface between the active materials and the electrolyte. The preparation route provides a new approach for hierarchy structure graphene composites; this work could be readily extended to the preparation of other graphene-based composites with different structures for use in energy storage 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.     

Tribological and tribochemical properties of magnetite nanoflakes as additives in oil lubricants

This detailed the tribological and tribochemical properties of magnetite (Fe₃O₄) nanoflakes used as additives in ^#40 base oil in a four-ball tribo-tester. The average friction coefficient of the friction pair for lubricant containing the Fe₃O₄ nanoflakes of 1.5 wt% as a lubricant additive in the base oil is decreased by 18.06% compared to that of solely base oil. The chemical composition of base oil with the Fe₃O₄ nanoflake additives did not change during the 48-h friction assessment. The decreased saturation magnetization and increased coercivity of magnetite nanoflakes occurred due to the distortion of the basal planes and the presence of hematite (α-Fe₂O₃) generated by the tribochemical reactions during the friction process. The multi-layer low-shear-stress tribochemical lubrication films on the surface of the friction pair could form because the nanoflake particles arrange and adhere onto the surface of the friction pair in an orderly manner, and the tribochemical reactions of the friction pair in the presence of the nanoflakes occur as Fe → FeO → Fe₃O₄ → γ-FeOOH → γ-Fe₂O₃ → α-Fe₂O₃. The formation of the films can improve the tribological properties.     

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.     

Synthesis and phase evolution of LiNb0.6Ti0.5O3 powder via a sol–gel method

A simple sol–gel route was demonstrated for the synthesis of LiNb_0.6Ti_0.5O₃ (M-phase) powder, using cheap and manageable starting materials at a relatively low temperature. The phase transitions in both chemical and solid-state processes were studied by X-ray diffraction (XRD) in detail. The results showed that in the sol–gel process the anatase TiO₂ phase first appeared at 400 °C and then LiNbO₃ solid solution (LiNbO₃ ss) emerged at 500 °C. When calcined to 600 °C, the M-phase started to appear along with the decrease of TiO₂ and LiNbO₃ ss. Single M-phase could be formed at 700 °C, which is 300 °C lower than that by the traditional solid-state method. A plausible evolution mechanism of the as-synthesized powder in calcination was proposed. The produced powder has potential applications in microelectronics systems.     

Observation and analysis of near-surface atmospheric aerosol optical properties in urban Beijing

Year-round measurements of the mass concentration and optical properties of fine aerosols (PM_2.5) from June 2009 to May 2010 at an urban site in Beijing were analyzed. The annual mean values of the PM_2.5 mass concentration, absorption coefficient (Ab), scattering coefficient (Sc) and single scattering albedo (SSA) at 525 nm were 67 ± 66 μg/m³, 64 ± 62 Mm⁻¹, 360 ± 405 Mm⁻¹ and 0.82 ± 0.09, respectively. The bulk mass absorption efficiency and scattering efficiency of the PM_2.5 at 525 nm were 0.78 m²/g and 5.55 m²/g, respectively. The Ab and Sc showed a similar diurnal variation with a maximum at night and a minimum in the afternoon, whereas SSA displayed an opposite diurnal pattern. Significant increases in the Ab and Sc were observed in pollution episodes caused by the accumulation of pollutants from both local and regional sources under unfavorable weather conditions. Aerosol loadings in dust events increased by several times in the spring, which had limited effects on the Ab and Sc due to the low absorption and scattering efficiency of dust particles. The frequency of haze days was the highest in autumn because of the high aerosol absorption and scattering under unfavorable weather conditions. The daily PM_2.5 concentration should be controlled to a level lower than 64 μg/m³ to prevent the occurrence of haze days according to its exponentially decreased relationship with visibility.     

Open-pore LiFePO4/C microspheres with high volumetric energy density for lithium ion batteries

LiFePO₄/C microspheres with different surface morphologies and porosities were prepared from different carbon sources. The effects of the surface morphology and pore structure of the microspheres on their electrochemical properties and electrode density were investigated. The electrochemical performance and electrode density depended on the morphology and pore structure of the LiFePO₄/C microspheres. Open-pore LiFePO₄/C microspheres with rough surfaces exhibited good adhesion with current collectors and a high electrode density (2.6 g/cm³). They also exhibited high performance in a half cell and full battery with a high volumetric energy density.     

Chemical characteristics of PM2.5 during dust storms and air pollution events in Chengdu,China

Daily fine particulate (PM_2.5) samples were collected in Chengdu from April 2009 to February 2010 to investigate their chemical profiles during dust storms (DSs) and several types of pollution events, including haze (HDs), biomass burning (BBs), and fireworks displays (FDs). The highest PM_2.5 mass concentrations were found during DSs (283.3 μg/m³), followed by FDs (212.7 μg/m³), HDs (187.3 μg/m³), and BBs (130.1 μg/m³). The concentrations of most elements were elevated during DSs and pollution events, except for BBs. Secondary inorganic ions (NO₃^?, SO₄^2?, and NH₄⁺) were enriched during HDs, while PM_2.5 from BBs showed high K⁺ but low SO₄^2?. FDs caused increases in K⁺ and enrichment in SO₄^2?. Ca²⁺ was abundant in DS samples. Ion-balance calculations indicated that PM_2.5 from HDs and FDs was more acidic than on normal days, but DS and BB particles were alkaline. The highest organic carbon (OC) concentration was 26.1 μg/m³ during FDs, followed by BBs (23.6 μg/m³), HDs (19.6 μg/m³), and DSs (18.8 μg/m³). In contrast, elemental carbon (EC) concentration was more abundant during HDs (10.6 μg/m³) and FDs (9.5 μg/m³) than during BBs (6.2 μg/m³) and DSs (6.0 μg/m³). The highest OC/EC ratios were obtained during BBs, with the lowest during HDs. SO₄^2?/K⁺ and TCA/SO₄^2? ratios proved to be effective indicators for differentiating pollution events. Mass balance showed that organic matter, SO₄^2?, and NO₃^? were the dominant chemical components during pollution events, while soil dust was dominant during DSs.     

Preparation of nano-sized Al2O3–2SiO2 powder by sol–gel plus azeotropic distillation method

Nano-sized amorphous Al₂O₃–2SiO₂ powder was prepared by a sol–gel method coupled with azeotropic distillation. The structure of the powder was investigated by DTS, BET, TEM, FT-IR, TG-DTA and XRD, showing that n-butanol azeotropic distillation could effectively remove water from the aluminosilicate gels and prevent the formation of hard agglomerates in the drying process. The average particle diameter of the powder was about 70 nm. The largest BET specific surface area of the powder was 669 m²/g. To examine the alkali-activation reactivity of the powder, alkali-activation tests were performed with the powder reacting with sodium silicate solution. The synthetic powder was found to be highly reactive.     

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.     

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.     

Effects of cerium incorporation on the catalytic oxidation of benzene over flame-made perovskite La1−xCexMnO3 catalysts

Perovskite-type La_1−xCe_xMnO₃ (x = 0–10%) catalysts were prepared by flame spray pyrolysis and their activities during the catalytic oxidation of benzene were examined over the temperature range of 100–450 °C. The structural properties and reducibility of these materials were also characterized by X-ray diffraction (XRD), N₂ adsorption/desorption, H₂ temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS). The incorporation of Ce was found to improve the benzene oxidation activity, and the perovskite in which x was 0.1 exhibited the highest activity. Phase composition and surface elemental analyses indicated that non-stoichiometric compounds were present. The incorporation of Ce had a negligible effect on the specific surface area of the perovskites and hence this factor has little impact on the catalytic activity. Introduction of Ce⁴⁺ resulted in modification of the chemical states of both B-site ions and oxygen species and facilitated the reducibility of the perovskite. The surface Mn⁴⁺/Mn³⁺ ratio was increased as a result of Ce⁴⁺ substitution, while a decrease in the surface-adsorbed O/lattice O (O_ads/O_latt) ratio was observed. The relationship between the surface elemental ratios and catalytic activity was established to allow a better understanding of the process by which benzene is oxidized over perovskites.