HEAVY METALS REMOVAL FROM AQUEOUS SOLUTIONS USING TiO2, MgO,AND Al2O3 NANOPARTICLES

This study investigated the removal of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ from aqueous solutions using nanoparticle sorbents (TiO₂, MgO, and Al₂O₃) with a range of experimental approaches. The maximum uptake values (sum of four metals) with multiple component solutions were 594.9, 114.6, and 49.4 mg g^?1, for MgO, Al₂O₃, and TiO₂, respectively. The sorption equilibrium isotherms were described using the Freundlich and Langmuir models. The best interpretation for experiment data was given by the Freundlich model for Cd²⁺, Cu²⁺, and Ni²⁺ in single- and multiple-component solutions. A first-order kinetic model adequately described the experimental data using MgO, Al₂O₃, and TiO₂. SEM-EDX both before and after metal sorption and soil solution saturation indices (SI) in MgO nanoparticles indicated that the main sorption mechanism for heavy metals was attributable to adsorption and precipitation, whereas heavy metal sorption by TiO₂ and Al₂O₃ adsorbents was due to adsorption. These nanoparticles may potentially be used as efficient sorbents for heavy metal removal from aqueous solutions. MgO nanoparticles were the most promising sorbents because of their high metal uptake.     

Comparison of Ethylene Glycol Steam Reforming Over Pt and NiPt Catalysts on Various Supports

Steam reforming of ethylene glycol (EG) was studied on Pt and NiPt catalysts supported on γ-Al₂O₃, TiO₂, and carbon. On all supports bimetallic NiPt catalysts show higher activity for H₂ production than the corresponding Pt catalysts as predicted from model surface science studies. The kinetic trends are similar for all catalysts (Pt and NiPt) with the H₂ production rate being zero-order and fractional order with respect to water and ethylene glycol, respectively. Slight differences in selectivity to minor products are observed depending both on active metal and support. On γ-Al₂O₃, NiPt shows higher H₂ and less alkane formation than Pt. TiO₂ supported catalysts show increased water-gas shift activity but also increased selectivity to alkane precursors. NiPt/C is identified as an active and selective catalyst for EG reforming.     

Bimagnetic hard/soft and soft/hard ferrite nanocomposites: Structural,magnetic and hyperthermia properties

Recent studies show that the chemical composition and shape of magnetic nanoparticles (NPs) play an important role in their properties. In particular, the bimagnetic NPs display useful and in many cases, more interesting properties than single-phase NPs. In this work, we prepared Fe₃O₄ and CoFe₂O₄ cube-like NPs and bimagnetic hard/soft (CoFe₂O₄/Fe₃O₄) and soft/hard (Fe₃O₄/CoFe₂O₄) nanocomposites (core/coating) using a facile and eco-friendly co-precipitation method that allows the synthesis of the cube-like NPs at temperatures near room temperature. The phase purity and the crystallinity of the NPs with a spinel structure were confirmed by the X-ray diffraction and infrared spectra techniques. Transmission electron microscopy (TEM) images revealed that the NPs have a cubic-like shape with an average dimension of 20 nm. Energy dispersive X-ray analysis, Mössbauer spectroscopy and SQUID magnetic measurements indicated the co-existence of Fe₃O₄ and CoFe₂O₄ phases in nanocomposites. In addition, the hysteresis loops exhibited a single-phase behavior in the nanocomposites that indicates there is a good exchange-coupling interaction between the hard and soft magnetic phases. The CoFe₂O₄/Fe₃O₄ nanocomposites presented a larger saturation magnetization than the CoFe₂O₄ NPs that is effective for their use in magnetic hyperthermia. Finally, we studied the hyperthermia properties of samples in an alternating magnetic field with a frequency of 276 kHz and field amplitude of 13.9 kA/m. Our results showed that magnetic hyperthermia efficiency simultaneously depends on the composition of samples along with magnetic anisotropy and saturation magnetization.     

Magnesium ferrite nanoparticles as a magnetic sorbent for the removal of Mn2+, Co2+, Ni2+ and Cu2+ from aqueous solution

The aim of this research was to prepare magnesium ferrite (MgFe₂O₄) magnetic nanoparticles and to investigate their sorption characteristics towards Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ ions in aqueous solution. MgFe₂O₄ was synthesized by glycine-nitrate combustion method and was characterized by low crystallinity with crystallite size of 8.2?nm, particle aggregates of 13–25?nm, BET surface area of 14?m²/g and pore size of 8.0?nm. Sorption properties of MgFe₂O₄ towards Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ ions were studied using one-component model solutions and found to be dependent on metal ions concentration, contact time, pH and conditions of regeneration experiment. The highest sorption capacity of MgFe₂O₄ was detected towards Co²⁺ (2.30?mmol?g¹) and Mn²⁺ (1.56?mmol?g^?1) and the lowest towards Ni²⁺ (0.89?mmol?g^?1) and Cu²⁺ (0.46?mmol?g^?1). It was observed that sorption equilibrium occurs very quickly within 20–60?min. The pH_zpc of sorbent was calculated to be 6.58. At studied pH interval (3.0–7.0) the sorption capacity of MgFe₂O₄ was not significantly affected. Regeneration study showed that the metal loaded sorbent could be regenerated by aqueous solution of 10^?3 M MgCl₂ at pH 6.0 within 120?min of contact time. Regeneration test suggested that MgFe₂O₄ magnetic sorbent can be efficiently used at least for four adsorption-desorption cycles. The high sorption properties and kinetics of toxic metal ion sorption indicates good prospects of developed sorbent in practice for wastewater treatment.     

Preparation of Al2O3-coated expanded graphite with enhanced hydrophilicity and oxidation resistance

Expanded graphite (EG), as a new kind of functional carbon-based material, is a vital supporting material and heat transfer enhancer for preparing highly conductive form-stable composite phase change materials (PCMs). However, the hydrophobic nature of EG makes it difficult to incorporate with inorganic PCMs. In this work, we intended to solve this drawback and a modified EG named Al₂O₃-coated EG which was characterized by enhanced hydrophilicity was developed via a heterogeneous nucleation technique and subsequent heat treatment. Experiments found that the Al₂O₃ layer on the surface of EG was uniform and essentially amorphous, and was well-bonded to EG via chemical interactions between oxygen atoms from Al₂O₃ and carbon atoms from EG. The hydrophilicity and oxidation resistance of Al₂O₃-coated EG could be enhanced by increasing the amount of Al₂O₃. Most importantly, compared with EG, the water contact angle of Al₂O₃-coated EG dropped from 90.7° to 33.9° when only 4.4?wt% Al₂O₃ was used, indicating that the hydrophilicity of EG could be greatly enhanced by low cost. Moreover, molecular dynamics (MD) simulation of the hydrophilicity of EG and Al₂O₃-coated EG proved that the preparation of Al₂O₃-coated EG was an efficient and feasible method to improve the hydrophilicity of EG.     

Effects of Sorbents on the Partitioning and Speciation of Cu During Municipal Solid Waste Incineration

Oxides of silicon, aluminium and calcium are normally dominant minerals during municipal solid waste (MSW) combustion. In flue gas, SiO₂, Al₂O₃ and CaO all act as sorbents capturing heavy metals (and semi-volatile organics). To further understand the effect of sorbents during MSW combustion, the effects of SiO₂, Al₂O₃ and CaO on Cu partitioning were experimentally investigated by the combustion of synthetic MSW in a tubular furnace and their effects on Cu speciation were studied by thermodynamic equilibrium calculations using ChemKin software. The experiments show that CaO has the highest Cu sorption efficiency at 900 °C, followed by Al₂O₃ and SiO₂. Thermodynamic equilibrium calculations show that for Cu the addition of SiO₂ and Al₂O₃ reduces the amount of liquid CuCl, which is more volatile. However, the addition of CaO has little influence on chemical sorption of Cu, indicating that the sorption of CaO is resulted from physical sorption.     

Solid phase extraction and removal of 2,4-dichlorophenol from aqueous samples using magnetic graphene nanocomposite

A magnetic graphene nanocomposite (Fe₃O₄-GNC) was prepared and used for the solid phase extraction (SPE) and removal of 2,4-dichlorophenol from aqueous solutions. The physicochemical properties were investigated using SEM, EDX, FTIR, and TGA. Different factors affecting sorption capacity were studied systematically. Results for kinetics studies revealed that 2,4-dichlorophenol sorption followed pseudo-second-order kinetics and the q_e value (987.45 mg/g) was in close agreement with experimental value (1000 mg/g). Thermodynamic study showed that the sorption is endothermic (?Hº = +56.116 kJ/mol) and spontaneous. The desorption studies were carried out for the reusability and extraction of 2,4-dichlorophenol from aqueous samples and 94% recoveries were obtained. The method was found feasible for the removal and preconcentration of trace analysis of 2,4-dichlorophenol in environmental water samples.     

Effect of low activation rare-earth oxides on sintering of β-SiC

The feasibility of sintering β-SiC at 1850 ℃ with using low-activation rare-earth oxides as sintering additives was studied. Thermodynamic calculation suggested that all five rare-earth oxides (Y₂O₃, Sc₂O₃, CeO₂, La₂O₃, and Pr₆O₁₁) were suitable sintering additives. Comprehensive microstructure characterization further revealed that Pr₆O₁₁ was the most effective sintering additive as it suffered the least influence from the content effect. A mechanism based on liquid phase sintering was proposed based on microstructure observations. The radiation stability of sintered SiC was investigated as well. The intergranular phases (rare-earth oxides and silicates) and SiC grains remained after being irradiated to 17 dpa at 750 ℃.     

Hybrid hematite/calcium ferrite fibers by solution blow spinning: Microstructural,optical and magnetic characterization

Iron oxide and Ca-doped ferrite fibers were successfully prepared via Solution Blow Spinning (SBS). Fibers with several calcium contents (nFe/nCa = 3.0, 5.2, and 20.0 atomic ratio) were prepared after dissolving polyvinylpyrrolidone and Fe and Ca nitrates in an acidic aqueous solution, followed by SBS spinning and calcination at 800 °C. The morphological, structural, optical, vibrational, and magnetic properties of the fibers were evaluated by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–Vis diffuse reflectance spectroscopy (DRS), Mössbauer spectroscopy, and magnetometry. The Rietveld refinement revealed Ca-doped fibers consisting of a mixture of Fe₂O₃, CaFe₂O₄, and Ca_3.6Fe_14.4O_25.2 crystalline phases. The Mössbauer spectra at 300 K showed a sextet belonging to the hematite phase and two doublets belonging to the calcium-related phases. Measurements at low temperatures showed a transition at 181.6 K attributed to Ca ferrite. The hematite fibers showed a saturation magnetization (Ms ~ 0.75 emu/g) relatively higher than the bulk α-Fe₂O₃ (Ms = 0.3 emu/g). The saturation magnetization increased from 3.6 to 6.4 emu/g with increasing Ca content.     

IR spectroscopy investigations of acidic character of carbonaceous films oxidized with HNO3 solution

Sorption of bases on carbonaceous films from liquid (NaHCO₃, Na₂CO₃ and NaOH solutions) and gaseous phases (NH₃) was studied using IR spectroscopy. Parallel to the IR spectroscopy the exchange of H⁺ ions for Na⁺ ions was determined by alkalimetry as well and NH₃ sorption isotherms were measured. The IR spectra indicate that chemisorption of NH₃ leads to the formation of amide structures and ammonium salts of carboxylic acids. The surface acidic centers on the films oxidized with HNO₃ solution are centres of Bronsted type.     

Structural and optical study of Fe3+-doped Al2O3 nanocrystals prepared by new sol gel precursors

Pure and Fe-doped Al₂O₃ nanoparticles (NPs) were synthesized with different iron doping percentage of 1, 3, and 5 mol% employing sol gel technique with AlCl₃, FeCl₃ as well as ethylene glycol (EG) and Polyvinylpyrrolidone (PVP) stabilizers as precursors. The XRD results indicated that the hexagonal structure of Fe/Al₂O₃ nanocomposite with alpha phase was formed by the substitution of Fe³⁺ ions in the alumina network. The sizes of the NPs obtained for the pure samples and doped samples at percentage dopant of 5% were 35 and 28 nm, respectively. The results of FTIR optical analysis showed the vibrational bond at the wavelength of 448 cm⁻¹, indicating the Al-O band in the sample. The UV-DRS analysis showed that the energy band gap for the pure NPs was 4 eV, but with increase in iron dopant up to 5%, it decreased to 3.42 eV. In addition, the results of photoluminescence (PL) analysis demonstrated that with increase in doping percentage, the PL intensity diminished. VSM magnetic analysis showed that with increase in iron dopant, the ferromagnetic state emerged in the NPs at saturation magnetism of 0.136 emu/g. Finally, photocatalytic experimental results demonstrated that 5% Fe-doped Al₂O₃ NPs effectively degrade MB approximately 53%.     

Tetrahydrofuran polymerization initiated by heteropolyacid in the presence of ethylene oxide: Reaction behavior of water and glycol

The reaction behavior of water and low molecular weight glycol in tetrahydrofuran polymerization initiated by H₃PW₁₂O₄₀ in the presence of ethylene oxide has been studied. A lot of water was used in the hydrolysis reaction of ethylene oxide at the early stage of the polymerization and transformed into ethylene glycol (EG), which was consumed subsequently through a chain transfer reaction. EG was more reactive both than 1,4‐butylene glycol and hexamethylene glycol toward propagating species, and the reaction rate constants at 0°C were determined by GC to be 0.142, 8.83 × 10⁻², and 5.53 × 10⁻² L · mol⁻¹s⁻¹, respectively. The molecular weight of the product can be predicted by an equation based upon conversion of polymerization and the concentrations of molecular weight controller and H₃PW₁₂O₄₀. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1821–1826, 1999     

Melting Relations of CaO-Manganese Oxide and MgO-Manganese Oxide Mixtures in Air

Melting relations in the systems CaO-manganese oxide and MgO-manganese oxide in air have been determined at temperatures up to 1705°C. In the system CaO-manganese oxide four crystalline phases have stable existence in equilibrium with liquids: lime (approximate composition CaO-MnO), spinel (approximate composition Mn₃O₄-CaMn₂O₄), and two ternary solid solution phases in which Ca/Mn ratios as well as oxygen contents vary over considerable ranges. One of these ternary solid solution phases may for the sake of simplicity be represented approximately by the formula CaMnO₃ and the other by the formula CaMn₂O₄. Three isobaric invariant situations exist, with temperatures and phase assemblages as follows: At 1588°± 10°C the two crystalline phases lime and CaMnO₃ coexist in equilibrium with liquid (40 wt% CaO, 60 wt% manganese oxide) in a peritectic situation. Another peritectic at 1455°± 5°C is characterized by the equilibrium coexistence of CaMnO₃, CaMn₂O₄, and liquid (25 wt% CaO, 75 wt% manganese oxide). A eutectic situation exists at 1439°± 5°C with CaMn₂O₄, spinel, and liquid (18 wt% CaO, 82 wt% manganese oxide) present together in equilibrium. In the system MgO-manganese oxide in air periclase-manganosite solid solution (approximate composition MgO-MnO) and spinel (approximate composition Mn₃O₄-MgMn₂O₄) are the only crystalline phases present in equilibrium with liquids. Liquidus and solidus temperatures increase with increasing MgO content. A peritectic situation exists at 1587°± 10°C, with the two crystalline phases coexisting in equilibrium with liquid (1 wt% MgO, 99 wt% manganese oxide).     

Water sorption on composites “LiBr in a porous carbon”

Water sorption equilibrium of LiBr confined to pores of a mesoporous synthetic carbon Sibunit and a macroporous expanded graphite (samples SWS-2C and SWS-2EG, respectively) was studied. Isobars of water sorption on these composites are measured at vapor pressure 6–81 mbar and temperature 30–145 °C. The type of sorption equilibrium for the two composites appears to be quite different. The isobars for SWS-2EG have a plateau corresponding to one molecule of H₂O adsorbed by one molecule of LiBr, which indicates the formation of crystalline hydrate LiBr·H₂O inside pores with a monovariant type of equilibrium. At lower temperatures, the equilibrium becomes divariant that is typical for LiBr–water solutions. On the contrary, the water sorption equilibrium for SWS-2C is divariant over the whole temperature and pressure range which means that no crystalline hydrates are formed inside Sibunit pores. In our opinion, this distinction results from differences in a pore structure of the host carbons. The composite sorption capacity can reach 0.6–1.1 g H₂O per 1 g of the dry sorbent at relative humidity 70%. The advanced sorption capacity makes the sorbents promising for gas drying, thermal storage of energy and other applications.     

Thermo-magnetic properties of Fe2O3-doped lithium zinc silicate glass-ceramics for magnetic applications

The crystallization behaviour and thermo-magnetic characteristics of glass-ceramic based on the 15Li₂O–20ZnO–10CaO–55SiO₂ system doped with varied Fe₂O₃ additions (0.0125, 0.025, and 0.05 mol) are described in this work. In some cases, Al₂O₃ was also added to the iron-containing sample. Glasses were successfully prepared by melt-quenching technique and converted into glass-ceramics by controlled heat-treatment, using DTA, SEM, XRD, and VSM techniques. The density, thermal expansion coefficients (TCE), and magnetic characteristics of the glass-ceramic were examined. XRD results confirmed characteristic peaks for various phases like quartz, Li₂ZnSiO₄, wollastonite, Li₂Si₂O₅, ZnFe₂O₄, and β-spodumene. By doping Fe₂O₃ and Al₂O₃ with lowering annealing temperature, the particle size was reduce, resulting in glass-ceramics with a more uniform and dense microstructure. The density of glass-ceramics rises from 2.74 g/cm³ to 3.45 g/cm³, whereas the TCE values in average 14–78 × 10⁻⁷/°C with temperature range of 25–500 °C. The doped glass-ceramics have superior magnetic properties with saturation magnetization (0.143–0.548 emu/g), the coercivity force (65.116–86.359 G), and remanence magnetization (0.074–0.436 emu/g). Under an alternating magnetic field, the presence of the Zn-ferrite phase in the glass-ceramics improves their magnetic properties and increases their heat-generating capability. Certain features of the doped glass-ceramics control the extensive variety of possibilities for their usage in various magnetic applications particularly for cancer hyperthermia treatment.     

The effect of Al content on the wettability between liquid iron and MgOAl2O3 binary substrate

In the present study, the wettability between liquid iron with two different Al contents and MgOAl₂O₃ binary substrates was studied in reducing atmosphere. The contact angles between liquid iron with 18?ppm Al and MgO, MgO·Al₂O₃, Al₂O₃ were 133.5°, 113.7°, 126.9° respectively. With the variation of the substrate composition, the contact angles for the intermediate binary phases of the three components (MgO, MgO·Al₂O₃, Al₂O₃) obeyed the Cassie theory. In the experiment using iron with 370?ppm Al, all the contact angles were higher than that using low Al-containing iron. The surface of the iron drop was covered with an oxide layer, which mainly consisted of many small particles. With the variation of the substrate gradually from MgO to Al₂O₃, the composition of the oxide layer changed from MgO·Al₂O₃ to CaOAl₂O₃. The formation of the oxide layer prevented the spreading of liquid iron, leading to the increase of the contact angle.     

A study on the wetting behavior of liquid iron on forsterite,mullite, spinel and quasi-corundum substrates

Wetting characteristics of liquid iron on magnesia, alumina and silica mixture substrates were studied by sessile drop experiments. Chromium-free forsterite, mullite, spinel and quasi-corundum phases were selected as alternative refractories in MgO-Al₂O₃-SiO₂. Morphological changes of molten electrolytic iron on the oxide substrates were investigated via apparent contact angle measurements. The results showed that the wetting behavior was significantly influenced by FeO compounds that were formed via oxidation of the liquid iron. Morphologies of the reacted layer were studied by Scanning Electron Microscope (SEM)/EDX analysis. The ternary phases FeO-MgO-SiO₂ and FeO-Al₂O₃-SiO₂ improved the wetting of liquid iron on the forsterite and mullite substrates by providing liquid phases at solid (refractory)–liquid (iron) interfaces. However, corrosion by liquid iron was significantly inhibited at spinel phase which did not feature FeO based compounds at the interface. Quasi-corundum (10MgO-25SiO₂-65Al₂O₃) showed a much enhanced resistance to liquid iron compared to forsterite or mullite refractories.     

Experimental phase equilibria study and thermodynamic modelling of the PbO-“FeO”-SiO2-ZnO,PbO-“FeO”-SiO2-Al2O3 and PbO-“FeO”-SiO2-MgO systems in equilibrium with metallic Pb and Fe

Phase equilibria of the PbO-“FeO”-SiO₂-ZnO, PbO-“FeO”-SiO₂-Al₂O₃ and PbO-“FeO”-SiO₂-MgO slags with liquid Pb metal, solid or liquid Fe metal and solid oxides (cristobalite and tridymite SiO₂, willemite (Zn,Fe)₂SiO₄, wustite (Fe,Al)O_1+x, spinel (Fe,Al)₃O₄, olivine Fe₂SiO₄, corundum (Al,Fe)₂O₃, mullite Al₆Si₂O₁₃ and pyroxene (Mg,Fe)SiO₃) were investigated at 1125–1670 °C. These conditions correspond to the minimum solubility of PbO in slag in presence of Pb and Fe metals at reducing conditions and represent the limit of lead smelting and slag cleaning process. High-temperature equilibration on silica, corundum or iron foil substrates, followed by quenching and direct measurement of Pb, Fe, Si, Zn, Al and Mg concentrations in the liquid and solid phases with the electron probe X-ray microanalysis (EPMA) was used. Present data can be used to improve the thermodynamic models for all phases in this system.     

Microstructural and electromagnetic study of low temperature fired nano crystalline MgCuZn ferrite with Bi2O3 addition

The present study investigates electromagnetic properties, as well as microstructural and thermal stability, of low temperature fired MgCuZn ferrite with the addition of various amounts of Bi₂O₃. To achieve better performance at low sintering temperature, ceramic specimens were fabricated using nano-sized precursor powders through the nitrate-citrate auto-combustion method. X-ray diffraction study shows the formation of single phase spinel structure without any impurity phases. Compared with the additive-free sample, the addition of Bi₂O₃ increases the density of all specimens. Scanning electron microscopy micrographs of samples indicate that Bi₂O₃ content significantly affects densification through grain growth promotion. Excessive amounts of Bi₂O₃, however, lead to abnormal grain growth. Moreover, the sample with 0.25 wt% Bi₂O₃ shows the highest density and grain shape uniformity as well as the lowest porosity. Dynamic magnetic properties were studied in a frequency range of 1–90 MHz, using an impedance analyzer. Results reveal that the sample with a low amount of additive (0.25 wt%) has the highest saturation magnetization, initial permeability (at 1 MHz), and quality factor, whereas it's Curie temperature slightly decreases. With the further increase of Bi₂O₃ content, however, the initial permeability and saturation magnetization of samples deteriorate gradually.     

On the Efficacy of Ru/Al2O3 Catalyst for Steam Reforming of Ethylene Glycol

This work describes hydrogen (H₂) production via steam reforming of ethylene glycol (EG) over a supported ruthenium catalyst. EG is chosen as a model compound for the alcohols contained in the aqueous phase of bio-oil. Using a fixed-bed reactor, experimental runs are carried out over Ru/Al₂O₃ at various temperatures (350–500°C), ratios of the mass of the catalyst (W) to the molar flow rate (F_O) of EG at the inlet (W/F_O = 0.37 ? 2.38 g h/mol), and feed concentrations (22.3–53.4 wt.% EG in water). The role of Ru in conversion of EG, production of H₂, and product distribution of the carbonaceous species is studied. Reaction pathways previously described in the literature are used to elucidate our results.