Synthesis of Smart Core-shell Nanocomposites with Enhanced Photocatalytic Efficacy

ABSTRACT

This current research represents practical synthetic protocol for novel core-shell nanocomposites (CSNCs) containing titania. TiO₂/poly(anthranilic acid, m-aminobenzoic acid, and o-phenylenediamine) (TiO₂/PANA-m-ABA-o-PDA) CSNCs were fabricated applying 2:2:1 molar ratio of the appropriate monomers and varied loads of TiO₂ via polycondensation. The fabrication of the TiO₂/PANA-m-ABA- o-PDA CSNCs was affirmed using various characterizations. The bond between TiO₂ and PANA-m-ABA-o-PDA was detected in the FTIR spectra. The CSNC’s features are having core-shell structures with sizes 12–27 nm. Under irradiation, the CSNCs exhibit intensive photocatalysis efficacy toward methylene blue degradation. Acceptable explanations of the photocatalytic efficiency consequences were substantiated. The zeta potential of a particle (ζ), the polydispersity index (PDI), and y-intercept were anticipated via dynamic light scattering (DLS) of the terpolymer colloidal system. The procedure manipulates a facile, new, beneficial as well as cheap synthetic technique to fabricate innovative CSNC as a new potential formulation.     

Simplistic transesterification approach for the synthesis of benzyl salicylate over honeycomb monoliths coated with modified forms of zirconia as catalysts: Kinetics

The catalysts such as Al₂O₃/ZrO₂ with 2–10?wt% of Al₂O₃ were coated on honeycomb monoliths by dip-and-dry technique. These catalysts were also prepared in their powder form. All the catalysts (honeycomb and powder form) were characterized for their surface acidity, crystallinity, functionality, elemental analysis, and morphology. The catalytic activity of all the catalysts was performed in the transesterification of methyl salicylate with benzyl alcohol to synthesize benzyl salicylate. Reaction conditions like reaction time, reaction temperature, and the molar ratio of the reactants were varied to obtain the highest yield of benzyl salicylate. The 6% Al₂O₃/ZrO₂ coated on honeycomb exhibited the highest conversion of methyl salicylate at 383?K in 60?min. Kinetic studies were conducted to determine the energy of activation and temperature coefficient. The rate constants in the case of 6AZ (HCM) was found to be 5.0?×?10^?3?min^?1 (373?K); 6.4?×?10^?3?min^?1 (383?K) and 2.2?×?10^?3?min^?1 (373?K); 3.2?×?10^?3?min^?1 (383?K) in the case of 6AZ (PF) catalyst, while the energy of activation (E_a) values were found to be 35.12 and 39.93 kJ mol^?1 for 6AZ (HCM) and 6AZ (PF), respectively. The reactant preadsorption study discloses that the transesterification follows the Eley–Rideal mechanism. Reactivation and recyclability of the catalysts were also examined and the results clearly indicate that Al₂O₃/ZrO₂ coated on the honeycomb is efficient and green catalytic system.     

In situ synthesis,mechanical and cyclic oxidation properties of Ti3AlC2/Al2O3 composites

ABSTRACT

Ti₃AlC₂/Al₂O₃ composite materials were successfully fabricated from TiO₂/TiC/Ti/Al powders by the in situ reactive hot pressed technique. The microstructure, mechanical and oxidation properties of the composites were investigated in the paper. Vickers hardness increased with the Al₂O₃ content. The relative density of Ti₃AlC₂/Al₂O₃ composites exhibits a declining tendency with Al₂O₃ content especially exceeds 10 vol.?%. The Ti₃AlC₂/Al₂O₃ composites show excellent electrical conductivity. The flexural strength and fracture toughness of Ti₃AlC₂/10 vol. % Al₂O₃ are 461 ± 20?MPa and 6.2?±?0.2?MPa m^1/2, respectively. The cyclic oxidation behaviour of resistance of Ti₃AlC₂/10 vol. % Al₂O₃ composites at 800–1000°C generally obeys a parabolic law. The oxide scale of sample consists of a mass of α-Al₂O₃ and TiO₂, forming a dense and adhesive protect layer. The result indicates that the Al₂O₃ can greatly improve the oxidation resistance of Ti₃AlC₂.     

PREPARATION AND THERMAL EXPANSION OF FE2-xYxW3O12 POWDER BY CITRATE SOL-GEL PROCESS

Fe_2-xY_xW₃O₁₂ powder has been synthesized by the citrate sol-gel process. A model was proposed to calculate the concentration of species in a citric solution. The calculated results could provide valuable information for determining the optimal molar ratio of cation to citric acid and pH value of solution for Fe_2-xY_xW₃O₁₂ preparation. The predicted parameters derived from this model are in good agreement with the experimental results. The prepared gel and the Fe_2-xY_xW₃O₁₂ powder were characterized by X-ray diffraction (XRD) and differential thermal analysis-thermogravimetry (DTA-TG). The results show that it is very difficult to obtain pure Fe₂W₃O₁₂ powder by the citrate sol-gel process in the temperature range 500°–1000°C, however, Y₂W₃O₁₂ can easily be prepared even at 500°C. Y₂W₃O₁₂ annealed at 1000°C for 10 h is favorable for absorbing moisture in air to form Y₂W₃O₁₂·3.3H₂O. The thermal expansion coefficients of Y₂W₃O₁₂·3.3H₂O are: α_a = ? 8.01 × 10^?6°C^?1, α_b = ? 2.51 × 10^?7°C^?1, and α_c = ? 5.55 × 10^?6°C^?1 in 473–1173 K.     

Self-propagating high-temperature synthesis,phase composition and aqueous durability of Nd–Al bearing zirconolite-rich composites as nuclear waste form

ABSTRACT

In this study, the zirconolite-rich composite was rapidly synthesised from self-propagating high-temperature synthesis plus quick pressing using MoO₃ as the oxidant and Ti as the reductant. As a surrogate of trivalent actinides, Nd was introduced to substitute the Ca site of zirconolite and Al was employed as the charge compensator to replace the Ti site (nominally Ca_1?xNd_xZrTi_2?xAl_xO₇). The phase composition and Nd occupancy were analysed after Nd₂O₃ addition. Nd-bearing zirconolite was produced as the major ceramic phase. Nd mostly substitutes the Ca sites of zirconolite, which results in waste loading higher than 8.6?wt-% Nd. The aqueous durability of Nd–Al codoped sample (with 15?at.-% Nd substitutes the Ca site of zirconolite) was evaluated at 90°C as well. The 42 days normalised leaching rates of Mo, Ca and Nd were measured to be 3.70, 1.90?×?10^?2 and 3.46?×?10^?4?g?m^?2?d^?1.     

Preparation and characterisation of closed-pore Al2O3-MgAl2O4 refractory aggregate utilising superplasticity

ABSTRACT

A novel high closed porosity Al₂O₃-MgAl₂O₄ refractory aggregate has been successfully fabricated by utilising superplasticity with Al₂O₃ and MgO as raw materials, SiC as high temperature pore-forming agent. The effects of the addition amounts of MgO and SiC on porosity, sintering behaviours, phase composition, pore size distribution and microstructure of the refractory aggregate have been investigated. The formation mechanism of the closed pore in the refractory aggregate has been discussed. The results showed that the MgO can improve the superplastic deformation ability of Al₂O₃-based ceramic at high temperature. With the content of MgO and SiC increased, the closed porosity and the pore size increased. The oxidation of SiC improved the sinterability of materials at the initial stage of sintering, and then the released gases due to the further oxidation of SiC promoted the formation of closed pores by motivating the superplastic deformation ability of Al₂O₃-based materials.     

Two-step pulsed electric current sintering of transparent Al2O3 ceramics

Abstract

Fully densified Al₂O₃ ceramics with fine grain size were obtained by pulsed electric current sintering through a two-step heating profile (referred to as TS-PECS). Highly transparent Al₂O₃ polycrystals with fine grain size (400 nm) were successfully fabricated by the TS-PECS process, namely, sintering at 1000°C for 1 h and followed at 1200°C for 20 min under uniaxial pressure of 100 MPa. Effects of the first step temperature and heating rate were discussed for bulk density, grain size and transparency. The temperature in the first step strongly affects densification and grain growth of Al₂O₃. On the other hand, heating rate, even of 100 K min^?1, in TS-PECS does not give significant influences on densification and grain growth of Al₂O₃. Inline transmittance at 640 nm in wavelength normalised to 1 mm in thickness is increased by decreasing heating rate even in TS-PECS.     

Synthesis and application of nanocomposite Fe3O4@SiO2@CTAB–SiO2 as a novel adsorbent for removal of cyclophosphamide from water samples

ABSTRACT

We present a way of synthesizing nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ by employing simple sol–gel technique with selective etching for extreme selectivity adsorption of cyclophosphamide (CP). The transmission electron microscopy (TEM); scanning electron microscopy (SEM); X-ray diffraction (XRD); Fourier transform infrared (FT-IR); vibrating sample magnetometer (VSM); pH_PZC; and Brunauer, Emmett and Teller (BET) techniques were used for nanocomposite characterization. These nanoparticles have an S_BET of 157.8 m² g^?1 and a high saturation magnetization of 67.5 emu g^?1. First, the adsorption system was examined as a function of contact time under various initial CP contents, ionic strength, initial solution pH, adsorbent dose and temperature in batch test. The optimum dose, pH and contact time were obtained to be 0.01 g, 7.0 and 30 min, respectively. Ultimately, experimental isotherm and kinetics data of adsorption of CP onto nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ were fitted to classical models. Additionally, it was found that the maximum adsorption process capacity of CP on adsorbent was 342.8 mg g^?1.     

Hydrogen Production by Steam Reforming of Commercially Available LPG in UAE

Steam reforming of commercially available LPG using Ru/Al₂O₃ and Ni/Al₂O₃ catalysts has been studied at temperatures between 573 and 773 K. Ru/Al₂O₃ catalyst showed higher rates of reaction and lower activation energies of the three main components of LPG, compared with Ni/Al₂O₃. However, Ni/Al₂O₃ catalyst showed a better H₂:CH₄ selectivity. The activation energy of n-butane was the lowest over Ru/Al₂O₃, whereas over Ni/Al₂O₃, propane had the lowest activation energy. The activation energy of i-butane was always the highest over both catalysts, which suggests that both catalysts performed better with unbranched molecules. A slight increase in activation energy was observed, when each component of the LPG mixture was studied separately as a pure gas, compared with being mixed in LPG. At a constant temperature of 773 K, hydrogen production yield and H₂:CH₄ selectivity were determined using Ru/Al₂O₃ at different steam:carbon (S:C) ratios and LPG flow rates. It was found that the yield and selectivity increased with the increase in S:C ratio and the decrease in the flow rate. The highest yield of 0.64 was achieved using S:C ratio of 6.5 and a LPG flow rate of 50 mL min^?1. The work provides valuable information on steam reforming of pure components of LPG, compared with when they are in the mixture. The comparison is done using conventional steam reforming catalyst, Ni/Al₂O₃, and compared with Ru/Al₂O₃. The observed trends and variations in reaction rates, in pure and mixed gases, indicated that the mechanism of steam reforming of a hydrocarbon mixture depends on its composition.     

Effects of Synthesis Temperature and Support Material on CO2 and CH4 Permeation through SAPO-34 Membranes

In this research, continuous SAPO-34 membranes were synthesized via secondary growth method onto both α-Al₂O₃ and mullite supports at three levels of synthesis temperature: 185, 195, and 220°C for 24 h. The synthesized membranes were characterized using XRD and SEM analysis and single gas permeation experiments. It was found out that support material and synthesis temperature both have significant effects on the membrane performance. At higher synthesis temperature, SAPO-34 crystals grown over the mullite support become more uniform and smaller in size but those grown on the α-Al₂O₃ support become larger. Effect of synthesis temperature on single gas permeation properties of the synthesized SAPO-34 membranes was also studied. For the mullite supported membranes, the CH₄ and CO₂ permeances decrease as synthesis temperature increases; but in the case of the alumina supported membranes, by increasing synthesis temperature, CH₄ and CO₂ permeances first decrease up to 195°C and then increase up to 220°C. Even in equal membrane thicknesses, the mullite supported membrane shows lower gas permenaces. Increasing synthesis temperature decreases CO₂/CH₄ ideal selectivity for the α-Al₂O₃ supported membranes, while increases for the mullite supported membranes. Under optimum synthesis conditions, at room temperature and 2 bar feed pressure, the CO₂ permeance through the α-Al₂O₃ and the mullite supported SAPO-34 membranes are 8.2 × 10^?7 and 8.5 × 10^?8 (mol/m² · s · Pa), respectively, and CO₂/CH₄ ideal selectivities are 51 and 61, respectively.     

Synthesis of High Surface Area MgAl2O4 Nanopowder as Adsorbent for Leather Dye Removal

Abstract

MgAl₂O₄ nanopowder has been prepared by alkoxides hydrolysis with further calcination at temperature of 700°C. The adsorption of a leather dye, Direct Black 38, onto this material was investigated. The sample was characterized by X-ray-diffraction (XRD), N₂ adsorption–desorption isotherm and Fourier transform infrared spectroscopy. The results showed that sample present a pure phase, and the average nanocrystal size of 8 nm, the BET surface area is about 206.5 m² · g^?1 and total pore volume is about 1.44 cm³ · g^?1. Adsorption kinetics data were modeled by film and pore diffusion model. The experimental isotherm was described by the Langmuir model. MgAl₂O₄ nanopowder presented a great removal efficiency of leather dye by adsorption process, with a maximum adsorption capacity of 833 mg of dye per gram of adsorbent.     

The effect of solvent water content on the dielectric properties of Al2O3 films grown by atmospheric pressure mist-CVD

Aluminum oxide (Al₂O₃) dielectric layers were grown by a mist-chemical vapor deposition (mist-CVD) process at 300 °C, using solvent mixtures containing acetone and water. As the acetone to water ratio was varied from 9:1 to 7:3, the leakage current of Al₂O₃ at an electric field of 7 MV/cm² decreased from 9.0 × 10^?7 to 4.4 × 10^?10 A/cm², and the dielectric constant increased from 6.03 to 6.85 with improved hysteresis during capacitance-voltage measurements. Consequently, the most robust Al₂O₃ films were obtained at an acetone to water ratio of 7:3, with a dielectric constant (κ) close to the ideal value 7.0, and a breakdown field of approximately 9 MV/cm. Thin film transistors (TFTs) incorporating In-Sn-Zn-O (ITZO) as the semiconductor were fabricated with the Al₂O₃ (7:3) dielectric onto p⁺⁺-Si substrates. The devices exhibit high electrical performance, with a high field effect mobility of 42.7 cm²V^?1s^?1, and a small subthreshold swing (S.S.) value of 0.44 V/decade.     

Photoluminescence properties of Eu3+-doped stalk-like Al2O3 via a hydrothermal route followed by heat treatment

ABSTRACT

Uniform Al₂O₃:Eu³⁺ samples were successfully fabricated via a hydrothermal method and subsequent thermal decomposition of Eu³⁺-doped precursors. The sample characterisations were carried out by means of X-ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence spectra. XRD results revealed Eu³⁺-doped samples were a pure γ-Al₂O₃ phase after being calcined at 1173?K. SEM results showed that these Eu³⁺-doped Al₂O₃ samples were stalk-like, with an average length of 1.5?μm. Upon excitation at 394?nm, the orange–red emission bands, having wavelengths longer than 580?nm, were to be from ⁵D₀→⁷F_J (J?=?1, 2) transitions. The asymmetry ratio of (⁵D₀→⁷F₂)/(⁵D₀→⁷F₁) intensity is about 0.54, 2.76, 3.29, 2.86, 3.36, 3.13 for Eu³⁺ concentrations of 0.1, 0.4, 0.7, 1.0, 1.5 and 2.0?mol-%, respectively. The optimal doping concentration of Eu³⁺ ions in Al₂O₃ is 1.5?mol-%. According to Dexter's theory, the critical distance between Eu³⁺ ions for energy transfer was determined to be 14?Å.     

Combined XPS and TPR study of sulfur removal from a Pt/BaO/Al2O3 NO x storage reduction catalyst

Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts (1 wt% Pt, 10 wt%BaO) were sulfated under conditions simulating a real NSR catalyst operation. Comparative TPR and XPS studies of sulfur removal from Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts indicate that the sulfur removal from Al₂O₃ surface precedes reductive decomposition of BaSO₄ (250–400 °C). Barium sulfate decomposition started with further increase in desulfation temperature at the point of surface atomic ratio Ba:S = 1 (~450^o). Simultaneously, an intensive formation of sulfide species on the catalyst surface was observed. Thermodynamic analysis of the desulfation process allows us to hypothesize that barium sulfide formation may hinder sulfur removal under reducing conditions.     

Preparation of Al2O3–SiC composite powder from kyanite tailings via carbothermal reduction process

ABSTRACT

Al₂O₃–SiC composite powders were prepared from kyanite tailings mixed with 20% excess carbon coke via carbothermal reduction (CR) reaction. The optimised synthesis condition for synthesising Al₂O₃–SiC composite powders was at 1600°C for 6?h. The equilibrium relationship curves of the condensed phases were presented and the temperature dependence of the phase composition was also studied. The results show that irregular Al₂O₃ and SiC grains first formed at 1500°C, and the elements C, O, Al, and Si randomly distributed in the each crystal particles. The amount of Al₂O₃–SiC composites increased with the increasing synthesis temperature and reaction time. Finally, Al₂O₃–SiC composite bulk materials were further prepared by pressureless sintering using the synthesised Al₂O₃–SiC composite powders as raw materials, and their mechanical properties were investigated in detail. All these results indicate that the CR method can offer a niche application for the development of kyanite tailings.     

Effect of alumina on the structure and properties of polyimide matrix films

To improve the properties of polyimide (PI), different mass fractions of alumina (Al₂O₃) nanoparticles, unmodified or modified by KH550, were incorporated into PI matrix to form PI/Al₂O₃ hybrid films by in situ polymerisation. The effects of Al₂O₃ additives on the structure, dielectric and mechanical properties of the films were studied. Fourier transform infrared spectroscopy confirmed the successful preparation of PI/Al₂O₃ hybrid films, and the microstructures of the samples showed a more uniform dispersion of the modified Al₂O₃ nanoparticles than the unmodified ones in the matrix. The dielectric constant of the films increased with increasing filler content, and the maximum electrical breakdown strength of 311 MV m^?1 was obtained with a filler content of 8.0 wt-% modified Al₂O₃ in the matrix. Both unmodified and modified Al₂O₃-reinforced PI hybrids demonstrated improved mechanical properties compared with the PI matrix. Moreover, the properties of films with Al₂O₃ modified by KH550 were better.     

Efficiency and Mechanism of Ciprofloxacin Hydrochloride Degradation in Wastewater by Fe3o4/Na2S2O8

ABSTRACT

The nanosized Fe₃O₄ catalyst was synthesized via a modified reverse coprecipitation method and characterized by means of a scanning electron microscope (SEM) and an X-ray diffraction (XRD) analysis instrument. The degradation efficiency and reaction rate of Fe₃O₄ in activating sodium persulfate used to degrade ciprofloxacin were determined from the catalyst dosage, oxidant concentration, and initial pH. The results showed that under the optimum conditions of a catalyst dosage of 2.0 g·L^?1, a sodium persulfate concentration of 1.0 g·L^?1, and an initial pH of 7, the degradation rate of ciprofloxacin was 93.73%, the removal rate of total organic carbon was 78%, and the first-order reaction constant was 0.06907 min^?1 within 40 min. It was also demonstrated that the reactive oxygen species in the Fe₃O₄/sodium persulfate catalytic system were mainly composed of SO₄^– and supplemented by OH· and HO₂· using probe compounds such as ethanol, tertiary butanol, and benzoquinone.     

Preparation and characterization of gel polymer electrolyte based on PVA-K2CO3

ABSTRACT

In this study, electrolyte materials were synthesized by mixing a highly conducting salt (K₂CO₃) with the poly(vinyl alcohol) (PVA) in different proportions (from 10 to 50 wt.%). The synthesized electrolyte was characterized using Fourier transform infrared (FTIR) spectroscopy, field-emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV) for their functional groups, morphology, thermal stability, glass transition temperature (T_g ), ionic conductivity, and potential window, respectively. Characterization results show that the complex formation between PVA and K₂CO₃ salt has been established by FTIR spectroscopic study, which indicates the detailed interaction between PVA and the salts in PVA-K₂CO₃ composites while the amorphous nature of the electrolyte after incorporation of the salts has been confirmed by FESEM analysis. Similarly, TGA and DSC analysis revealed that both decomposition temperature and T_g of the synthesized electrolytes decrease with the addition of K₂CO₃ due to the strong plasticizing effect of the salt. The results confirm that the electrolytes have sufficient thermal stability for supercapacitor operation, as well as an amorphous phase to effectively deliver high ionic conductivity. The highest ionic conductivity of 4.53 × 10^?3 S cm^?1 at 373 K and potential window of 2.7 V was exhibited by PK30 (30 wt.% K₂CO₃), which can be considered as high value for solid-state electrolytes which are superior to those electrolytes from PVA salts earlier reported. The results similarly show that the prepared electrolyte is temperature-dependent as conductivity increase with increase in temperature. Based on these properties, it can be imply that the PVA-K₂CO₃ gel polymer electrolyte (GPE) could be a promising electrolyte candidate for EDLC applications. The results indicate that the PVA-K₂CO₃ as a new electrolyte material has great potential in practical applications of portable energy-storage devices.     

Sintering mechanism and dielectric properties of LiTaO3 matrix composites with the addition of Al2O3 particles

Highly densified Al₂O₃/LiTaO₃ (ALT) ceramic composites were fabricated by hot-pressing in a nitrogen atmosphere. The addition of Al₂O₃ particles could significantly improve the densification of LiTaO₃. Sintering mechanism of the LiTaO₃ ceramic incorporated with Al₂O₃ particles is proposed. Dielectric constant of 5 vol.% Al₂O₃/LiTaO₃ (5ALT) composite ceramic was slightly increased in the range from 30 kHz to 10⁶ Hz, but the dielectric loss was lowered in the whole range from 10³ Hz to 10⁶ Hz. Piezoelectric constant (d₃₃) of the 5ALT ceramic composite is about 50% of that of LiTaO₃ single crystal.     

Homogeneous precipitation synthesis and thermoelectric properties of Ca2Co2O5 ceramics

Abstract

Homogeneous precipitation method was applied to synthesise Ca₂Co₂O₅ powders using calcium nitrate, cobalt nitrate and urea as raw materials. Uniform plate-like Ca₂Co₂O₅ powders with an average grain size of 1 μm can be obtained by calcining the precursor for 8 h at 1073 K in the air. The Ca₂Co₂O₅ ceramics were gained after sintering for 4 h at 1083 K using uniaxial pressure moulding and then sintering technique. The thermoelectric properties of ceramic samples were measured from 303 to 973 K, and the result shows that the electrical conductivity, Seebeck coefficient, thermal conductivity and figure of merit of the sample are 2236·85 S m^?1, 175·95 μV K^?1, 1·01 W m^?1 K^?1 and 0·69 at 973 K respectively.