High surface area alumina-supported nickel (II) oxide aerogels using epoxide addition method

Nickel (II) oxide aerogels with an amorphous alumina support were synthesized by the expoxide addition method. The monoliths were obtained by adding propylene oxide to an alcoholic solution of hydrated metal nitrate salts. The wet gels were dried by supercritical extraction to produce porous monolithic aerogels. The as-synthesized aerogels were amorphous containing aluminum and nickel hydroxides. Annealing of the as-synthesized aerogels at 400 °C yields crystalline nickel oxide materials which retain the high surface areas (>160 m²/g) and porosities of the original aerogels. The resultant aerogel materials were characterized using powder X-ray diffraction, thermo-gravimetric analysis, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray analysis, and nitrogen adsorption/desorption analysis.     

Characterization of the microstructures of copper-based aerogels on the sol–gel process

In this thesis, we will elaborate on the sol–gel process during the preparation of monolithic copper-based aerogel. The microstructure of the copper-based aerogel appears to be various due to the different amounts of raw materials, such as polyacrylic acid, propene oxide, deionized water (H₂O) and copper(II) chloride (CuCl₂) in the sol–gel process. The proper molar ratios between these reactants play a crucial factor in mediating the morphology of the aerogel. The aerogels are characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy and Brunauer–Emmett–Teller methods. The combined results indicate that the copper-based aerogel shows a typical three-dimensional porous structure with a large surface areas about 568 m²/g, and the skeleton structure of the aerogel is composed of a large number of primary particles with the size about a few nanometers.     

Carbonization and graphitization of pitch applied for anode materials of high power lithium ion batteries

The artificial graphite materials were prepared by carbonizing coal tar pitch using two methods, namely, one- and two-step processes, and all sintered samples were graphitized at 2800 °C. Effects of different heat treatments on the performance of the samples were characterized by scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction, Brunauer–Emmett–Teller, electrochemical impedance spectroscopy (EIS), particle size analysis, polarized light microscopy, and charge–discharge measurements. All samples show a typical graphite crystalline structure; moreover, the degree of graphitization (g factor) and crystallite size along the c-axis (L _c ) were calculated from (002) peak. The polarized light microscopy indicates that the coke with carbonization at 700 °C has an obvious wide domain (D) optical structure, while that with two-step sintering at 400 and 700 °C has a mixed optical structures of wide D, flow domains, and mosaics. TEM analysis revealed a number of irregular graphene layer images which are caused by the defects of graphite. EIS shows that the sample carbonized by two-step has a larger diffusion coefficient than the sample carbonized at 700 °C by one step. Higher carbonization temperature leads to better cycle performance as the temperature increasing from 500 to 700 °C in the one-step route. Specifically, the charge (Li⁺ extraction) capacity at the 50th cycle increases from 318 mA?h?g^?1 to 357 mA?h?g^?1. The results show that the rate performance of the artificial graphite is improved with the addition of the presintering at 400 °C.     

Improved electrochemical performance of nano-crystalline Li2FeSiO4/C cathode material prepared by the optimization of sintering temperature

Li₂FeSiO₄/C cathode materials have been prepared using the conventional solid-state method by varying the sintering temperature (650 °C, 700 °C and 750 °C), and the structure and electrochemical performance of Li₂FeSiO₄/C materials are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, respectively. The results show that Li₂FeSiO₄ nano-crystals with a diameter of about 6–8 nm are inbedded in the amorphous carbon, and the Li₂FeSiO₄/C material obtained at 700 °C exhibits an initial discharge capacity of 195 mA?h g^?1 at 1/16 C in the potential range of 1.5–4.8 V. The excellent electrochemical performance of Li₂FeSiO₄/C attributes to the improvement of conductivity and reduction of impurity by the optimization of the sintering temperature.     

Synthesis of tin oxide nanoparticles by sol–gel process: effect of solvents on the optical properties

Tin oxide (SnO₂) nanoparticles were synthesized by the reaction of SnCl₄·5H₂O in methanol, ethanol and water via sol–gel method. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared, Scanning electron microscopy and Transmission electron microscopy. The optical properties of the as-prepared samples were investigated. The XRD analysis showed well crystallized tetragonal SnO₂ can be obtained and the crystal sizes were 3.9, 4.5 and 5 nm for the sample calcined at 400 °C for 2 h. It was found that solvents played important roles in the particle size effect of nanocrystalline SnO₂.     

Structural and particle size evolution of sol–gel-derived nanocrystalline hydroxyapatite

An easy alkoxide-based sol–gel method based on Ca(NO₃)₂·4H₂O and triethyl phosphate [PO(OC₂H₅)₃; TEP] as Ca and P precursors have been developed to synthesize nano-hydroxyapatite (HA). The structural evolution of the samples was studied using X-ray diffraction (XRD), thermal behavior, infrared analysis, and elemental analysis via scanning electron microscopy. It is noticeable that raising of the firing temperature resulted in increasing the HA content as the dominant phase at 600 and 700 °C. The phase transformation from amorphous to crystalline HA occurred at the low temperature of 400 °C, while at higher temperatures other Ca–P compounds as secondary phases transformed to HA. The crystallite size distributions and micro-strain of the HA samples produced were characterized by XRD methods with the aid of Scherrer and Williamson–Hall equations. The results of transmission electron microscopy as a complementary and reliable technique are in good agreement with those obtained from XRD. The results indicate that increasing the firing temperature caused permanent growth of mean crystallite size and a decrease in micro-strain.     

Preparation and characterization of a nitrogen-doped mesoporous carbon aerogel and its polymer precursor

Nitrogen-containing carbon aerogel was prepared from resorcinol–melamine–formaldehyde (R–M–F) polymer gel precursor. The polymer gel was supercritically dried with CO₂, and the carbonization of the resulting polymer aerogel under nitrogen atmosphere at 900 °C yielded the carbon aerogel. The polymer and carbon aerogels were characterized with TG/DTA–MS, low-temperature nitrogen adsorption/desorption (??196 °C), FTIR, Raman, powder XRD and SEM–EDX techniques. The thermal decomposition of the polymer aerogel had two major steps. The first step was at 150 °C, where the unreacted monomers and the residual solvent were released, and the second one at 300 °C, where the species belonging to the polymer network decomposition could be detected. The pyrolytic conversion of the polymer aerogel was successful, as 0.89 at.% nitrogen was retained in the carbon matrix. The nitrogen-doped carbon aerogel was amorphous and possessed a hierarchical porous structure. It had a significant specific surface area (890 m² g^?1) and pore volume (4.7 cm³ g^?1). TG/DTA–MS measurement revealed that during storage in ambient conditions surface functional groups formed, which were released upon annealing.     

ZnO/MgO nanocomposites generated from alcoholic solutions

A process was proposed for the synthesis of ZnO/MgO nanocomposites from alcoholic solutions by means or the consecutive precipitation of coprecipitation of alcoholic solutions of zinc acetate and magnesium with an alkali solution followed by annealing in the range 400–500°C. X-ray powder diffraction showed crystalline ZnO and MgO phases in the resulting composite. Zinc oxide particle sizes in the composite with magnesium oxide were determined by transmission electron microscopy and from X-ray diffraction peak broadening. The zinc oxide nanoparticle size was weakly affected by the molar ratio of zinc to magnesium and the concentration of the precipitated component. The ZnO exciton peak in cathodoluminescence spectra for nanocomposites synthesized at low temperatures (400 and 500°C) shifted toward the UV. At ≥600°C or higher, Mg_{1 ? x} Zn _x O solid solution was generated, as evidenced by X-ray diffraction and cathodoluminescence data.     

Facile preparation of ZrCO composite aerogel with high specific surface area and low thermal conductivity

A novel ZrCO composite aerogel is synthesized using zirconium oxychloride and resorcinol–formaldehyde (RF) as precursors through the sol–gel route and carbothermal reduction process. The effects of different Zr/R molar ratios and calcination temperatures on the physical chemistry properties of ZrCO aerogels are investigated. The ZrCO composite aerogel consists of the C/ZrO₂/ZrC ternary aerogel. The results show that with the increase of R/Zr molar ratios, the specific surface area and bulk density increase with calcination temperature up to 1300?°C, but decrease at even temperature (1500?°C). The specific surface area is as high as 637.4?m²/g for ZrCO composite aerogel (R:Zr?=?2:1), which was higher than ever reported. As the heat-treatment temperature increases to 1500?°C, the ZrC crystalline phase occurs and the t-ZrO₂ phase still appears within the composite. The thermal conductivity of the carbon fiber mat-reinforced composite aerogel is as low as 0.057?W/m/K at room temperature (25?°C).

Open image in new window

     

The synthesis and characterization of zinc ferrite aerogels prepared by epoxide addition

Over the past decade sol–gel methods have become increasingly popular alternatives to the solid state synthesis of metal oxides. In many cases sol–gel synthesis is preferred due to desirable physical properties such as high surface area, high porosity, and small crystallite size. Monolithic zinc ferrite aerogels were produced by the epoxide addition sol–gel method. It was observed that addition of propylene oxide to 2-propanol solution of either the hydrated metal nitrate salts or the hydrated metal chloride salts resulted in the formation of stable red–brown gels. Aerogels were characterized using powder X-ray diffraction, high resolution scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption/desorption analysis. The metal salt used in the synthesis was found to significantly influence the properties of the aerogel. All aerogels synthesized exhibited low densities and high surface areas (>340 m²/g). Annealing of the aerogel at relatively low temperatures (below 450 °C) yielded a highly crystalline porous material which is composed of nanometer sized particles.     

Structure and electric conductivity of vapor deposition polymerization products of cyanoacetylene

Cyanoacetylene can be polymerized from the vapor state onto an inactive surface of substrate at a temperature as low as 200°C. The polymerization first occurs by way of the carbon–carbon triple bond. The reaction product obtained at 1000°C contains nitrogen at a concentration as high as 13.7%. At least some of this nitrogen is in naphtiridine ring or rings similar to it. The product obtained at 400°C is amorphous, while the product obtained at 1000°C has at least partly graphite-like crystalline structures with an apparent crystallite size (L_c) of about 17 Å. The electric conductivities of the products obtained at 400, 700, and 1000°C are 7.7 × 10^?2, 91, and 1600 S/cm, respectively. These values are extremely high compared to the pyrolized PAN treated at the same temperature. Electric conductivity of the product obtained at 400°C is well explained by the variable range hopping model in 3-dimensional amorphous materials. With the products obtained at the higher temperatures, conductivity cannot be accounted for by the hopping model. This is probably due to the development of graphite-like structure.     

The effect of heat-treatment on the physico-chemical properties of silica aerogel prepared by sub-critical drying technique

Synthesis of transparent and crack-free monoliths of silica aerogel by sub-critical drying technique is reported in the present article. Silane ageing with 50% tetraethylorthosilicate:ethanol followed by solvent exchange using ethanol was adopted. The effect of heat-treatment on the textural and physical characteristics of silica aerogel was evaluated. The chosen composition resulted in a high surface area silica aerogel of 1,000 m² g⁻¹ and a pore volume of 1.4 cm³ g⁻¹ at room temperature. The aerogel heat-treated at 900 °C possessed a surface area of 450 m² g⁻¹ with a pore volume of 0.4 cm³ g⁻¹. The decrease in surface area and pore volume was associated with the sintering process. The present technique seems advantageous in preserving the high surface area of the material at high temperatures. The XRD studies showed that the amorphous nature of aerogel matrix was retained till 1,400 °C, beyond which it crystallized to phase pure crystoballite.     

Study of crystallization process of soda lead silicate glasses by thermal and spectroscopic methods

The crystallization process of some glasses in the ternary Na₂O–SiO₂–PbO system with good chemical stability that can be used for waste inertization was studied using X-ray diffraction (XRD), infrared spectroscopy (FT-IR), differential thermal analysis (DTA) and scanning electron microscopy. The parent glasses were characterized by XRD and FT-IR, and their vitreous state was determined. DTA measurements evidenced glass transition (T _g) and crystallization temperatures (T _c). The thermal treatments were conducted at vitreous transition temperature (400 °C) and at highest effect of crystallization (650 °C). XRD evidenced the lead and sodium silicate crystalline phases in samples treated at 650 °C for 12 h. Micrometer crystallites dispersed in the glass matrices have affected the transparence of glasses and made them opaque after treatment at 650 °C. The influence of oxide quantities in compositions on the crystallization tendency was revealed. A PbO higher content than that of SiO₂ as well as lower Na₂O content decreased the tendency of crystallization.     

Beiträge zur Chemie der selteneren Elemente. LXVII*)1). Infrarotabsorptionsspektren von amorphem und kristallinem ScPO42

The IR spectra (400–4000 cm^?1) of hydrated and amorphous scandium phosphate and crystalline ScPO₄ were recorded on samples prehented at 20–1100°C. The course of dehydration and crystallisation of amorphous scandium phosphate was recorded. The PO₄^3?-ion in amorphous anhydrous phosphate shows C_3v symmetry, while in the anhydrous crystalline product V_d site-symmetry occurs. Anhydrous crystalline ScPO₄ spectrum belongs to the xeno-time-type group. The latter represents one from two groups of spectra of anhydrous rare earth phosphates.     

Thermal behavior of the composite xerogels of zirconium oxyhydroxide and silicic acid

Gels were prepared via sol?Cgel method by addition of zirconium oxychloride solution into sodium metasilicate (SZ) and sodium metasilicate solution into zirconium oxychloride (ZS) at varying final pH. Si/Zr molar ratio equaled 1/1. Synthesized gels were dried with calcium chloride until they reached a constant mass. SEM and nitrogen adsorption analysis have shown that SZ gels have surface area 175?C200?m^2?g^?1, consist of 20?C30?nm grains. ZS samples have surface area about 1?m^2?g^?1, consist of grains smaller than 10?nm. Thermal and X-ray phase analysis have shown that transition of amorphous ZrO₂ to crystalline form shifts from 430 to 850?C870?°C for SZ gels. Unlike zirconia gels phase transitions that proceed in order: ??amorphous (430?°C)??tetragonal (800?°C)??monoclinic (1,000?°C) phases??, the monoclinic phase in ZS gels appears immediately after transition from amorphous to crystalline state; the tetragonal phase in SZ samples is stable until 1,000?°C.     

Structural investigation of sol–gel derived SiO2–GeO2 noncrystalline and nanocomposite materials

Noncrystalline and nanocomposite materials of (1?x)SiO₂·xGeO₂ system, with Si:Ge ratio from 8:1 to 2:1 (x?=?0.111; 0.142; 0.2; 0.333), initially obtained by sol?Cgel method, were characterized by thermal analyses, X-ray diffraction, nuclear magnetic resonance and Raman spectroscopy. According to DTA and XRD results, the noncrystalline state of the as-prepared samples is stable up to 1,000?°C and only after 30?min heat treatment at 1,200?°C the samples become partial crystalline, due to development of cristobalite and quartz nanocrystals. Solid-state ²⁹Si MAS-NMR was employed in order to characterize the local structure around silicon as a function of composition and thermal history of the samples. The NMR data indicate the presence of Q², Q³ and Q⁴ units in all samples. The fraction of the highly interconnected SiO₄ tetrahedra increases both with germanium content and with annealing temperature. The Raman spectroscopy results evidence structural changes related to silicon- and germanium-oxygen units but also to their interconnection, that depend on Si:Ge ratio and annealing temperature.     

Influence of different templates on the morphology of mesoporous aluminas

Mesoporous alumina has many environmental applications as catalysts support and adsorption or separation material. We studied the synthesis conditions for the mesoporous alumina formation from aluminum isopropoxide in the presence of anionic (lauric and stearic acid), cationic (cetyltrimethylammonium bromide, CTAB) and non-ionic (triblock poly(ethylene oxide)-poly(propylene oxide)-polyethyleneoxide, P123) templates. The X-ray diffraction data show that the alumina mesophases obtained at 550°C in the presence of fatty acids or P123 have amorphous walls, whereas the samples prepared at 500°C by using CTAB, in alkaline medium are crystalline with a γ-alumina structure. The solvothermal treatment caused the alumina mesophase with crystalline walls to be obtained at 550°C. The samples were investigated by nitrogen adsorption-desorption isotherms and scanning electron microscopy. The obtained alumina mesophases have specific surface areas in the range of 300–450 m² g⁻¹, narrow pore size distribution, and different morphology depending on the template used in the synthesis.      

The effect of calcination on morphology of phosphate coating and microstructure of sintered iron phosphated powder

Carbonyl iron powder was coated with phosphate layer using phosphating precipitation method. The phosphated powder was dried at 60 °C for 2 h in air and heat treated by calcination at 400 and 800 °C for 3 h in air. Cylindrical specimens density of ~6.5 g.cm^?3 based on iron phosphated powder calcined at 400 °C were sintered at 820, 900, 1110 °C in N₂ + 10%H₂ atmosphere and 1240 °C in vacuum for 30 min. The morphology and phase composition of the phosphate coating and sintered compacts were studied by scanning electron microscopy, atomic force microscopy (AFM) and X‐ray diffraction (XRD) analysis. Gelatinous morphology of dried phosphate coating (thickness of ~100 nm) containing nanoparticles of iron oxyhydroxides and hydrated iron phosphate was observed. From XRD, diffractogram indicated the presence of goethite α‐FeOOH, lepidocrocite γ‐FeOOH and ludlamite Fe₃(PO₄)₂.4H₂O. The calcined phosphate coating (thickness of ~ 400 nm) contained non‐homogeneous consistency of α‐Fe₂O₃ layer on iron particles, an inter‐layer of amorphous FePO₄ and Fe₃O₄ top layer. The transformation to crystalline FePO₄ structure occurred during calcination at 800 °C with the presence of α‐Fe₂O₃ forming a light top zone (rough morphology). The microstructure of compacts sintered in solid state at temperatures up to 900 °C has retained composite network character. A fundamental change in microstructure due to the liquid phase sintering occurred after sintering at temperatures of 1100 and 1240 °C. It was confirmed that the microstructure complex consists of spheroidized α‐Fe and α‐Fe₂O₃ phases surrounded by solidified liquid phase consisting various phosphate compounds. Copyright © 2013 John Wiley & Sons, Ltd.     

High surface area sol–gel alumina–titania nanocatalyst

Alumina–titania mixed oxide nanocatalysts with molar ratios = 1:0.5, 1:1, 1:2, 1:5 have been synthesized by adopting a hybrid sol–gel route using boehmite sol as the precursor for alumina and titanium isopropoxide as the precursor for titania. The thermal properties, XRD phase analysis, specific surface area, adsorption isotherms and pore size details along with temperature programmed desorption of ammonia are presented. A specific surface area as high as 291 m²/g is observed for 1:5 Al₂O₃/TiO₂ composition calcined at 400 °C, but the same composition when calcined at 1,000 °C, resulted in a surface area of 4 m²/g, while 1:0.5 composition shows a specific surface area of 41 m²/g at 1,000 °C. Temperature programmed desorption (of ammonia) results show more acidic nature for the titania rich mixed oxide compositions. Transmission electron microscopy of low and high titania content samples calcined at 400 °C, shows homogeneous distribution of phases in the nano range. In the mixed oxide, the particle size ranges between 10–20 nm depending on titania content. The detailed porosity data analysis contributes very much in designing alumina–titania mixed oxide nanocatalysts.     

Spectroscopic studies of 1,4-dibromobutyne-2

Infrared spectra of 1,4-dibromobutyne-2 have been recorded over the 4000-200 cm^?1 region in the vapour, liquid, amorphous and crystalline states Raman spectra were extended to ca. 20 cm^?1 in the same states of aggregation, except for the non-recorded vapour phase spectrum. The temperature was varied between ?190 and 160 °C, and the pressure up to 10 kbar.A high proportion of the molecules exhibited free, internal rotation in the vapour and liquid phases, but to a smaller extent in the amorphous state at ?190 °C. For those molecules not being excited beyond the potential barrier, an unsymmetric conformation was preferred, whereas in the crystalline state the molecules possessed the anti conformation (C_2h) both at low temperature and at high pressure at ambient temperature.A vibrational analysis based upon force field calculations was carried out and the mean amplitudes of vibration computed. The data have been related to preliminary results from dipole moment and electron diffraction investigations.