Eu(III) and Am(III) adsorption on aluminum (hydr)oxide minerals: surface complexation modeling.

Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals-corundum (α-Al2O3), γ-alumina (γ-Al2O3) and gibbsite (γ-Al(OH)3)-and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al2O3) and γ-alumina (γ-Al2O3) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weak sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals.

Chitosan/Gamma-Alumina/Fe3O4@5-FU Nanostructures as Promising Nanocarriers: Physiochemical Characterization and Toxicity Activity.

Today, cancer treatment is an important issue in the medical world due to the challenges and side effects of ongoing treatment procedures. Current methods can be replaced with targeted nano-drug delivery systems to overcome such side effects. In the present work, an intelligent nano-system consisting of Chitosan (Ch)/Gamma alumina (γAl)/Fe3O4 and 5-Fluorouracil (5-FU) was synthesized and designed for the first time in order to influence the Michigan Cancer Foundation-7 (MCF-7) cell line in the treatment of breast cancer. Physico-chemical characterization of the nanocarriers was carried out using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), vibrating sample magnetometry (VSM), dynamic light scattering (DLS), and scanning electron microscopy (SEM). SEM analysis revealed smooth and homogeneous spherical nanoparticles. The high stability of the nanoparticles and their narrow size distribution was confirmed by DLS. The results of the loading study demonstrated that these nano-systems cause controlled, stable, and pH-sensitive release in cancerous environments with an inactive targeting mechanism. Finally, the results of MTT and flow cytometry tests indicated that this nano-system increased the rate of apoptosis induction on cancerous masses and could be an effective alternative to current treatments.

Monitoring the ecotoxicity of γ-Al2O3 and Ni/γ-Al2O3 nanomaterials by means of a battery of bioassays.

The increasing application of nanoparticles (NPs) to a variety of new technologies has become a matter of concern due to the potential toxicity of these materials. Many questions about the fate of NPs in the environment and the subsequent impact on ecosystems need to be answered. The aim of this work was to evaluate the ecotoxicity of two alumina-based nanoceramics, γ-Al2O3 (NC) and Ni/ γ-Al2O3 (NiNC) by means of three different standardized tests: Biochemical Oxygen Demand (BOD5), bioassay with luminescent bacteria (Vibrio fischeri; Microtox), and bioassay on amphibian larvae (Rhinella arenarum) (AMPHITOX). BOD5 values of a very biodegradable mixture (glucose/glutamic acid) decreased with the addition of NiNC(43.8%) and NC (31.6%) with respect to control samples (52.9%). Microtox test results indicated that NiNC presents higher toxicity than NC, with EC50s values of 16.1% and 29.9% respectively; a reduced toxicity was observed, however, in presence of organic matter, thus obtaining EC50s of 37.8% and 19.4%. The results of AMPHITOX test showed a significant increase in the toxicity of both substances over time, the NiNC toxicity being greater than that of NC. The values of 96h-LC50 and 504h-LC50 determined for NiNC were 1.58 and 0.83mg/L, respectively, and 14.5 and 10.5mg/L for NC samples. Amphibian larvae exhibited collapsed cavities, edema, axial flexures, and behavioral alterations as hyperkinesia and reduced movements. These results evidence the vulnerability of wildlife to xenobiotics and the need to develop specific standardized ecotoxicity tests in order to help environmental sustainability and natural species conservation.

Biomedical behaviors of CuO/γ-alumina/chitosan nanocomposites: Scolicidal and apoptotic effects on hydatid cysts protoscolices.

Hydatid cysts caused by Echinococcus granulosus are a serious health problem that requires effective treatment. This study aimed to evaluate the scolicidal and apoptotic effects of copper oxide (CuO) and gamma alumina (γ-Al2O3) with or without chitosan (Chit), using Rosmarinus officinalis extract and chemical methods on protoscolices (PSCs) in vitro. The nanomaterials (NMs) were characterized by FTIR, EDS, DLS, XRD, FESEM, PDI, and zeta potential (ZP). Scolicidal and apoptotic effects of NMs were tested against PSCs at different concentrations and exposure times. The CuO NPs showed the highest scolicidal effect (33.26 %) among all NMs at 1.6 mg/mL and 60 min, followed by phytosynthesized CuO/γ-Al2O3 NC (23.41 %). The chitosan-modified CuO/γ-Al2O3 NC and the chemically synthesized CuO/γ-Al2O3 NC had less effect. The CuO NPs and the phytosynthesized CuO/γ-Al2O3 NC also significantly increased the expression of the caspase-3 gene in the PSCs at 0.4 mg/mL, indicating the induction of apoptosis. In conclusion, this study suggests that the phytosynthesized CuO/γ-Al2O3 NC and the CuO NPs could be potential candidates for treating echinococcosis by killing the PSCs through apoptosis. Further studies are needed to verify the in vivo efficacy and toxicity of these NMs and to optimize their delivery and targeting systems.

Preliminary performance study of synthetic Alumina nanoparticles for retention of cobalt and cesium cations.

In the present study, a facile nano-sized gamma alumina was synthesized and then examined for immobilization of cobalt and cesium ions individually from aqueous solutions. The comprehensive analysis of functional groups, phase composition, surface morphology and sorption characteristics of the synthesized nano-sized ϒ alumina was executed. It was deduced that acquired material was low-crystalline with a high elimination efficacy towards the concerned cations under slightly alkali and acidic conditions. Time-transient elimination scrutiny was executed and cobalt elimination rate was found relatively faster than cesium cations. Equilibrium sorption examinations confirmed that the sorption is proceeding via two diverse sites on the scavenger surface. Cobalt and cesium elimination is a spontaneous endothermic reaction of increased chaos. The attained results proved the high proficiency of the synthesized scavenger in the cations immobilization.

Nanoporous Metatitanic acid on γ-Al2O3 aerogel for higher CO2 adsorption capacity and lower energy consumption.

Carbon dioxide capture has become an important issue in reducing atmospheric heat these days. In this study, adsorption of carbon dioxide by aerogel Gamma Alumina-Metatitanic Acid has been investigated and optimized. Morphological and structural analyses such as BET, FESEM, FT-IR, and XRD have also been conducted. In addition, Response surface methodology has been applied in order to achieve the optimal conditions, using a five-level Central composite design. The highest amount of adsorption, 12.874 (mmol/g), was recorded at a temperature of 20 (°C), pressure of 7 (bar), and 25 (%wt) of Metatitanic Acid. This was approximately 11.46% and 4.84% higher than those of mesoporous MgO and 4Azeolite, respectively. Regeneration of the adsorbent was also studied at different temperatures and process durations. Metatitanic acid, as a catalyst, reduces the temperature and regeneration time of the adsorbent by creating active sites and surface hydroxyl groups. It also lowers the required activation energy and enhances the thermal conductivity of the composite material. The optimal result was achieved at a temperature of 100 (°C) and a duration of 30 (min). Finally, isothermal and thermodynamic experiments were conducted to establish the most accurate predictive model and conditions, including Enthalpy, Entropy, and Gibbs free energy. The results indicate that the Freundlich model aligned well with the laboratory findings. Additionally, the negative values of Enthalpy, Entropy, and Gibbs free energy suggested that the adsorption process was physical, exothermic, and spontaneous.

Novel chitosan/γ-alumina/carbon quantum dot hydrogel nanocarrier for targeted drug delivery.

Curcumin (CUR) is among the most natural and effective antitumor drugs for cancer treatment. These drugs have low solubility and short half-lives that reduce their effectiveness in drug release systems. Herein, a hydrogel nanocarrier containing chitosan (CS), alumina (γ-Al2O3), and carbon quantum dots (CQDs) was prepared by the water-in-oil-in-water (W/O/W) double nanoemulsion method. DLS revealed a nanocarrier size of 227 nm, with a zeta potential of -37.8 mV, which corroborates its stability. FE-SEM showed its quasi-spherical shape, FT-IR and XRD confirmed the presence of all the components in the nanocomposite and gave information about the intermolecular interactions between them and the crystalline nature of the nanocarrier, respectively. The drug loading (48 %) and entrapment efficiency (86 %) were higher than those reported previously for other CUR nanocarriers. The drug release profile revealed a controlled and stable release, and a pH-sensitive behavior, with faster CUR release in an acid environment. The breast cancer cell line was examined by cytotoxicity and cell apoptosis analyses. The results showed that the slow release over time and the programmed cell death were due to interactions between CUR and the nanocarrier. Considering the results obtained herein, CS/γAl2O3/CQDs/CUR can be considered as a promising new nanosystem for tumor treatment.

Inductively Coupled Nonthermal Plasma Synthesis of Size-Controlled γ-Al2O3 Nanocrystals.

Gamma alumina (γ-Al2O3) is widely used as a catalyst and catalytic support due to its high specific surface area and porosity. However, synthesis of γ-Al2O3 nanocrystals is often a complicated process requiring high temperatures or additional post-synthetic steps. Here, we report a single-step synthesis of size-controlled and monodisperse, facetted γ-Al2O3 nanocrystals in an inductively coupled nonthermal plasma reactor using trimethylaluminum and oxygen as precursors. Under optimized conditions, we observed phase-pure, cuboctahedral γ-Al2O3 nanocrystals with defined surface facets. Nuclear magnetic resonance studies revealed that nanocrystal surfaces are populated with AlO6, AlO5 and AlO4 units with clusters of hydroxyl groups. Nanocrystal size tuning was achieved by varying the total reactor pressure yielding particles as small as 3.5 nm, below the predicted thermodynamic stability limit for γ-Al2O3.

Integration of Li4Ti5O12 Crystalline Films on Silicon Toward High-Rate Performance Lithionic Devices.

The growth of crystalline Li-based oxide thin films on silicon substrates is essential for the integration of next-generation solid-state lithionic and electronic devices including on-chip microbatteries, memristors, and sensors. However, growing crystalline oxides directly on silicon typically requires high temperatures and oxygen partial pressures, which leads to the formation of undesired chemical species at the interface compromising the crystal quality of the films. In this work, we employ a 2 nm gamma-alumina (γ-Al2O3) buffer layer on Si substrates in order to grow crystalline thin films of Li4Ti5O12 (LTO), a well-known active material for lithium-ion batteries. The ultrathin γ-Al2O3 layer enables the formation of a stable heterostructure with sharp interfaces and drastically improves the LTO crystallographic and electrochemical properties. Long-term galvanostatic cycling of 50 nm LTO films in liquid-based half-cells demonstrates a high capacity retention of 91% after 5000 cycles at 100 C. Rate capability tests showcase a specific charge of 56 mA h g-1 at an exceptional C-rate of 5000 C (15 mA cm-2). Moreover, with sub-millisecond current pulse tests, the reported thin-film heterostructure exhibits rapid Li-ion (de)intercalation, which could lead to fast switching timescales in resistive memory devices and electrochemical transistors.

Impact of an effective Prandtl number model on the flow of nanofluids past an oblique stagnation point on a convective surface.

The stretched surface's convective heat transfer capability can be improved by using nanoparticles. There is a significant role of the Prandtl number in determining the thermal and momentum stretching layer surfaces. It is proposed in this study that an effective Prandtl number model be used to explore the two-dimensional oblique stagnation point flow of γ A l 2 O 3 - H 2 O and γ A l 2 O 3 - C 2 H 6 O 2 nanofluids moving over a convective stretching surface. The fluid in question is subjected to a thorough investigation. It is necessary to apply non-linear ordinary differential equations in order to connect the controlling partial differential equations with the boundary conditions. To solve these equations, an efficient and reliable numerical technique is used. Shooting Method with Runge Kutta-IV in Mathematica software. Visual representations of normal and tangential velocity and temperature as well as streamlines as a function of many physical parameters are shown. The results show that as the volume fraction of nanoparticles increases, the fluid flow f ( y ) , h ( y ) and velocity f ' ( y ) , h ' ( y ) all increase, whereas the flow f ( y ) and velocity f ' ( y ) both increase against the stretching ratio parameter, while the flow h ( y ) and velocity h ' ( y ) both decrease. When the volume percentage of nanoparticles and the Biot number are both increased, the temperature rises. However, when the stretching ratio parameter is increased, the temperature falls. Physical attributes like the local skin friction coefficient and the heat flow may be characterized in many ways. A nanofluid comprised of γ A l 2 O 3 - C 2 H 6 O 2 outperformed a γ A l 2 O 3 - H 2 O nanofluid in terms of heat transfer rate. The source of zero skin friction may be observed to move to the left or right depending on the balance of obliqueness and straining motion at point x s . The computed numerical results of the current research correspond well with those accessible in the literature for the limiting scenario.

Alumina supported copper oxide nanoparticles (CuO/Al2O3) as high-performance electrocatalysts for hydrazine oxidation reaction.

Direct hydrazine liquid fuel cell (DHFC) is perceived as effectual energy generating mean owing to high conversion efficiency and energy density. However, the development of well-designed, cost effective and high performance electrocatalysts is the paramount to establish DHFCs as efficient energy generating technology. Herein, gamma alumina supported copper oxide nanocatalysts (CuO/Al2O3) are synthesized via impregnation method and investigated for their electrocatalytic potential towards hydrazine oxidation reaction. CuO with different weight percentages i.e., 4%, 8%, 12%, 16% and 20% are impregnated on gamma alumina support. X-ray diffraction analysis revealed the cubic crystal structure and nanosized particles of the prepared metal oxides. Transmission electron microscopy also referred to the cubic morphology and nanoparticle formation. Electrochemical oxidation potential of the CuO/Al2O3 nanoparticles is explored via cyclic voltammetry as the analytical tool. Optimization of conditions and electrocatalytic studies shown that 16% CuO/Al2O3 presented the best electronic properties towards N2H2 oxidation reaction. BET analysis ascertained the high surface area (131.2546 m2 g1) and large pore diameter (0.279605 cm³ g-1) for 16% CuO/Al2O3. Nanoparticle formation, high porosity and enlarged surface area of the proposed catalysts resulted in significant oxidation current output (600 µA), high current density (8.2 mA cm-2) and low charge transfer resistance (3.7 kΩ). Electrooxidation of hydrazine on such an affordable and novel electrocatalyst opens a gateway to further explore the metal oxide impregnated alumina materials for different electrochemical applications.

Catalytic conversion of enzymatic hydrolysis lignin into cycloalkanes over a gamma-alumina supported nickel molybdenum alloy catalyst.

The efficient depolymerization and hydrodeoxygenation of enzymatic hydrolysis lignin are achieved in cyclohexane solvents over a gamma-alumina supported nickel molybdenum alloy catalyst in a single step. Under initial 3 MPa hydrogen at 320 °C, the highest overall cycloalkane yield of 104.4 mg/g enzymatic hydrolysis lignin with 44.4 wt% selectivity of ethyl-cyclohexane was obtained. The reaction atmosphere and temperature have significant effects on enzymatic hydrolysis lignin conversion, product type and distribution. The conversion of enzymatic hydrolysis lignin was also investigated over different nickel and molybdenum-based catalysts, and the gamma-alumina supported nickel molybdenum alloy catalyst exhibited the highest activity among those catalysts. To reveal the reaction pathways of alkylphenol hydrodeoxygenation, 4-ethylphenol was tested as a model compound. Complete conversion of 4-ethylphenol into cycloalkanes was achieved. A two-step mechanism of 4-ethylphenol dihydroxylation - hydrogenation is proposed, in which the benzene ring saturation is deemed as the rate-determining step.

Production of Gamma Alumina Using Plasma-Treated Aluminum and Water Reaction Byproducts.

High purity hydrogen and solid-state byproducts are produced using a proposed plasma-activated aluminum and water reactions approach. These byproducts could be transformed into pure gamma Al2O3 powder material, while hydrogen can be used for electricity generation. Various chemical methods can be used for the synthesis of gamma alumina, but most could result in high levels of remaining impurities. Boehmite is a cost-effective starting material for the production of high-purity Al2O3. Herein, we present a novel method for the synthesis of boehmite and its transformation into high-specific-surface-area γ-alumina. Specifically, this method implicates the direct reaction between distilled water and plasma-treated aluminum powder. The results show the structural and morphological changes of the byproduct of the aluminum/water reaction to boehmite and γ-Al2O3 after a simple heating procedure (at 280 and 500 °C respectively). The high-purity hydrogen produced during the aluminum/water reaction can be used for the high-efficiency and environmentally friendly production of electrical energy.

Synthesis of Silica Membranes by Chemical Vapor Deposition Using a Dimethyldimethoxysilane Precursor.

Silica-based membranes prepared by chemical vapor deposition of tetraethylorthosilicate (TEOS) on γ-alumina overlayers are known to be effective for hydrogen separation and are attractive for membrane reactor applications for hydrogen-producing reactions. In this study, the synthesis of the membranes was improved by simplifying the deposition of the intermediate γ-alumina layers and by using the precursor, dimethyldimethoxysilane (DMDMOS). In the placement of the γ-alumina layers, earlier work in our laboratory employed four to five dipping-calcining cycles of boehmite sol precursors to produce high H2 selectivities, but this took considerable time. In the present study, only two cycles were needed, even for a macro-porous support, through the use of finer boehmite precursor particle sizes. Using the simplified fabrication process, silica-alumina composite membranes with H2 permeance > 10-7 mol m-2 s-1 Pa-1 and H2/N2 selectivity >100 were successfully synthesized. In addition, the use of the silica precursor, DMDMOS, further improved the H2 permeance without compromising the H2/N2 selectivity. Pure DMDMOS membranes proved to be unstable against hydrothermal conditions, but the addition of aluminum tri-sec-butoxide (ATSB) improved the stability just like for conventional TEOS membranes.

Spectrophotometrical analysis for fabrication of pH-independent nano-sized γ-alumina by dealumination of kaolin and precipitation in the presence of surfactant composites.

The challenge with γ-Al2O3 is its pH-dependent removal efficiency and relatively low adsorption capacity in recovery of wastewaters contaminated by cationic dyes. Therefore; the objective of present investigation was to fabricate a pH-independent nano-sized alumina powder by dealumination of kaolin for uptake of dye. The dealumination of meta-kaolin was carried out by nitric acid solution and the amorphous aluminum hydroxide was precipitated with ammonia in the presence of combined surfactants containing cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG) and polyoxyethylene octyl phenyl ether (TX100). The nano-sized gamma alumina particles were fabricated after calcination at 800 °C and then were analyzed based on spectrophotometrical method. The rod-like nano-particles with average width of 5 nm and length of 20 nm were synthesized by precipitation in the presence of admixed surfactant, CTAB-TX100, which improves the removal efficiency due to efficient modification in the interaction of particles. TX100 also showed a significant affinity for increasing the specific surface area because of ability to prevent the particle aggregation which provides a potential for synthesis of alumina adsorbent without foaming, normally observed in the presence of CTAB. Both of mentioned powders indicated relatively pH-independent removal efficiency with higher adsorption capacity. Moreover, adsorption isotherm parameters were determined to verify the improvement of removal efficiency. The presented fabrication technique eventually overcame the pH-dependent recovery problem which is feasible for the development of adsorbents because the starting material is abundant, very low energy is needed, no hazardous waste is generated and applicable in the acidic environments.

Tuning Acid-Base Properties Using Mg-Al Oxide Atomic Layer Deposition.

Atomic layer deposition (ALD) was used to coat γ-Al2O3 particles with oxide films of varying Mg/Al atomic ratios, which resulted in systematic variation of the acid and base site areal densities. Variation of Mg/Al also affected morphological features such as crystalline phase, pore size distribution, and base site proximity. Areal base site density increased with increasing Mg content, while acid site density went through a maximum with a similar number of Mg and Al atoms in the coating. This behavior leads to nonlinearity in the relationship between Mg/Al and acid/base site ratio. The physical and chemical properties were elucidated using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 physisorption, and CO2 and NH3 temperature-programmed desorption (TPD). Fluorescence emission spectroscopy of samples grafted with 1-pyrenebutyric acid (PBA) was used for analysis of base site proximity. The degree of base site clustering was correlated to acid site density. Catalytic activity in the self-condensation of acetone was dependent on sample base site density and independent of acid site density.