Advanced Photocatalytic Degradation of Cytarabine from Pharmaceutical Wastewaters.

The need to develop advanced wastewater treatment techniques and their use has become a priority, the main goal being the efficient removal of pollutants, especially those of organic origin. This study presents the photo-degradation of a pharmaceutical wastewater containing Kabi cytarabine, using ultraviolet (UV) radiation, and a synthesized catalyst, a composite based on bismuth and iron oxides (BFO). The size of the bandgap was determined by UV spectroscopy, having a value of 2.27 eV. The specific surface was determined using the BET method, having a value of 0.7 m2 g-1. The material studied for the photo-degradation of cytarabine presents a remarkable photo-degradation efficiency of 97.9% for an initial concentration 0f 10 mg/L cytarabine Kabi when 0.15 g of material was used, during 120 min of interaction with UV radiation at 3 cm from the irradiation source. The material withstands five photo-degradation cycles with good results. At the same time, through this study, it was possible to establish that pyrimidine derivatives could be able to combat infections caused by Escherichia coli and Candida parapsilosis.

Adsorption of Scandium Ions by Amberlite XAD7HP Polymeric Adsorbent Loaded with Tri-n-Octylphosphine Oxide.

In an actual economic context, the demand for scandium has grown due to its applications in top technologies. However, further development of new technologies will lead to an increase in the market for Sc related to such technologies. The present study aims to improve and upgrade existing technology in terms of efficient scandium recovery, proposing a new material with selective adsorptive properties for scandium recovery. To highlight the impregnation of Amberlite XAD7HP resin with tri-n-octylphosphine oxide extractant by the solvent-impregnated resin method, the obtained adsorbent material was characterized by physico-chemical techniques. Further, the specific surface of the adsorbent and the zero-point charge of the adsorbent surface have been determined. Different parameters, such as initial concentration, adsorbent amount, contact time, or temperature, have been studied. The initial pH effect was investigated when a maximum adsorption capacity of 31.84 mg g-1 was obtained at pH > 3, using 0.1 g of adsorbent and a contact time of 90 min and 298 K. An attempt was made to discuss and provide a clear representation of the studied adsorption process, proposing a specific mechanism for Sc(III) recovery from aqueous solutions through kinetic, thermodynamic, and equilibrium studies. Adsorption/desorption studies reveal that the prepared adsorbent material can be reused five times.

Arsenic Removal Using Unconventional Material with Iron Content: Batch Adsorption and Column Study.

The remediation of arsenic contamination in potable water is an important and urgent concern, necessitating immediate attention. With this objective in mind, the present study investigated arsenic removal from water using batch adsorption and fixed-bed column techniques. The material employed in this study was a waste product derived from the treatment of groundwater water for potable purposes, having a substantial iron composition. The material's properties were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier-transformed infrared spectroscopy (FT-IR). The point of zero charge (pHPZC) was measured, and the pore size and specific surface area were determined using the BET method. Under static conditions, kinetic, thermodynamic, and equilibrium studies were carried out to explore the influencing factors on the adsorption process, namely the pH, contact time, temperature, and initial arsenic concentration in the solution. It was found that the adsorption process is spontaneous, endothermic, and of a physical nature. In the batch adsorption studies, the maximum removal percentage was 80.4% after 90 min, and in a dynamic regime in the fixed-bed column, the efficiency was 99.99% at a sludge:sand = 1:1 ratio for 380 min for a volume of water with arsenic of ~3000 mL. The kinetics of the adsorption process conformed to a pseudo-second-order model. In terms of the equilibrium studies, the Sips model yielded the most accurate representation of the data, revealing a maximum equilibrium capacity of 70.1 mg As(V)/g sludge. For the dynamic regime, the experimental data were fitted using the Bohart-Adams, Thomas, and Clark models, in order to establish the mechanism of the process. Additionally, desorption studies were conducted, serving as an essential step in validating the practical applicability of the adsorption process, specifically in relation to the reutilization of the adsorbent material.

Selenite Removal from Aqueous Solution Using Silica-Iron Oxide Nanocomposite Adsorbents.

In recent years, during industrial development, the expanding discharge of harmful metallic ions from different industrial wastes (such as arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, or zinc) into different water bodies has caused serious concern, with one of the problematic elements being represented by selenium (Se) ions. Selenium represents an essential microelement for human life and plays a vital role in human metabolism. In the human body, this element acts as a powerful antioxidant, being able to reduce the risk of the development of some cancers. Selenium is distributed in the environment in the form of selenate (SeO42-) and selenite (SeO32-), which are the result of natural/anthropogenic activities. Experimental data proved that both forms present some toxicity. In this context, in the last decade, only several studies regarding selenium's removal from aqueous solutions have been conducted. Therefore, in the present study, we aim to use the sol-gel synthesis method to prepare a nanocomposite adsorbent material starting from sodium fluoride, silica, and iron oxide matrices (SiO2/Fe(acac)3/NaF), and to further test it for selenite adsorption. After preparation, the adsorbent material was characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism associated with the selenium adsorption process has been established based on kinetic, thermodynamic, and equilibrium studies. Pseudo second order is the kinetic model that best describes the obtained experimental data. Also, from the intraparticle diffusion study, it was observed that with increasing temperature the value of the diffusion constant, Kdiff, also increases. Sips isotherm was found to best describe the experimental data obtained, the maximum adsorption capacity being ~6.00 mg Se(IV) per g of adsorbent material. From a thermodynamic point of view, parameters such as ΔG0, ΔH0, and ΔS0 were evaluated, proving that the process studied is a physical one.

Nanomaterials Based on Collaboration with Multiple Partners: Zn3Nb2O8 Doped with Eu3+ and/or Amino Substituted Porphyrin Incorporated in Silica Matrices for the Discoloration of Methyl Red.

Designing appropriate materials destined for the removal of dyes from waste waters represents a great challenge for achieving a sustainable society. Three partnerships were set up to obtain novel adsorbents with tailored optoelectronic properties using silica matrices, Zn3Nb2O8 oxide doped with Eu3+, and a symmetrical amino-substituted porphyrin. The pseudo-binary oxide with the formula Zn3Nb2O8 was obtained by the solid-state method. The doping of Zn3Nb2O8 with Eu3+ ions was intended in order to amplify the optical properties of the mixed oxide that are highly influenced by the coordination environment of Eu3+ ions, as confirmed by density functional theory (DFT) calculations. The first proposed silica material, based solely on tetraethyl orthosilicate (TEOS) with high specific surface areas of 518-726 m2/g, offered better performance as an adsorbent than the second one, which also contained 3-aminopropyltrimethoxysilane (APTMOS). The contribution of amino-substituted porphyrin incorporated into silica matrices resides both in providing anchoring groups for the methyl red dye and in increasing the optical properties of the whole nanomaterial. Two different types of methyl red adsorption mechanisms can be reported: one based on surface absorbance and one based on the dye entering the pores of the adsorbents due to their open groove shape network.

Adsorbent Material Based on Carbon Black and Bismuth with Tunable Properties for Gold Recovery.

Adsorption recovery of precious metals on a variety of solid substrates has steadily gained increased attention in recent years. Special attention was paid to the studies on the characterization of the adsorptive properties of materials with a high affinity for gold depending on the nature of the pendant groups present in the structure of the material. The aim of the present work was to synthesize and characterize a new material by using the sol-gel synthesis method (designated as BCb/CB). In this case, synthesis involved the following precursors: bismuth carbonate (III), carbon black, and IGEPAL surfactant (octylphenoxypolyethoxyethanol). Immobilization of the heterojunction as bismuth oxide over a flexible support such as carbon black (CB) can prevent their elution in solution and make it versatile for its use in a system. In this work, a new adsorbent material based on bismuth carbonate supported over carbon black (BCb/CB) was developed and used further for gold recovery from aqueous solutions. The required material was characterized physically/chemically by scanning electron microscopy (SEM); energy dispersive X-ray spectrometry (EDX); X-ray diffraction (XRD); thermal analysis (DTG/DTA); atomic force microscopy (AFM). The Brunauer-Emmett-Teller (BET) method was used to determine the specific surface area indicating a value of approximately 40 m2/g, higher than the surface of CB precursor (36 m2/g). The adsorptive properties and the adsorption mechanism of the materials were highlighted in order to recover Au(III). For this, static adsorption studies were carried out. The parameters that influence the adsorption process were studied, namely: the pH, the contact time, the temperature, and the initial concentration of the gold ions in the used solution. In order to establish the mechanism of the adsorption process, kinetic, thermodynamic, and equilibrium studies were carried out. Experimental data proved that the gold recovery can be conducted with maximum performance at pH 3, at room temperature. Thermodynamic studies proved that the gold adsorption on BCb/CB material is a spontaneous and endothermal process. The results indicate a total adsorption capacity of 13.1 mg Au(III)/g material. By using this material in real solutions, a recovery efficiency of 90.5% was obtained, concomitant with a higher selectivity (around 95%).

Vanadium (V) Adsorption from Aqueous Solutions Using Xerogel on the Basis of Silica and Iron Oxide Matrix.

Vanadium is considered a strategic metal with wide applications in various industries due to its unique chemical and physical properties. On the basis of these considerations, the recovery of vanadium (V) is mandatory because of the lack of raw materials. Various methods are used to recover vanadium (V) from used aqueous solutions. This study develops a clean and effective process for the recovery of vanadium (V) by using the adsorption method. At the same time, this study synthesizes a material starting from silica matrices and iron oxides, which is used as an adsorbent material. To show the phase composition, the obtained material is characterized by X-ray diffraction showing that the material is present in the amorphous phase, with a crystal size of 20 nm. However, the morphological texture of the material is determined by the N2 adsorption-desorption method, proving that the adsorbent material has a high surface area of 305 m2/g with a total pore volume of 1.55 cm3/g. To determine the efficiency of the SiO2FexOy material for the recovery of vanadium through the adsorption process, the role of specific parameters, such as the L-to-V ratio, pH, contact time, temperature, and initial vanadium concentration, must be evaluated. The adsorption process mechanism was established through kinetic, thermodynamic, and equilibrium studies. In our case, the process is physical, endothermic, spontaneous, and takes place at the interface of SiO2FexOy with V2O5. Following equilibrium studies, the maximum adsorption capacity of the SiO2FexOy material was 58.8 mg (V)/g of material.

Indium Recovery by Adsorption on MgFe2O4 Adsorbents.

Indium and its compounds have many industrial applications and are widely used in the manufacture of liquid crystal displays, semiconductors, low temperature soldering, and infrared photodetectors. Indium does not have its own minerals in the Earth's crust, and most commonly, indium is associated with the ores of zinc, lead, copper and tin. Therefore, it must be recovered as a by-product from other metallurgical processes or from secondary raw materials. The aim of this study is to investigate the adsorption properties for recovering indium from aqueous solutions using iron-magnesium composite (MgFe2O4). In addition, the results show that the material offers very efficient desorption in 15% HCl solution, being used for 10 adsorption-desorption cycle test. These results provide a simple and effective process for recovering indium. Present study was focuses on the synthesis and characterization of the material by physico-chemical methods such as: X-ray diffraction, FT-IR spectroscopy, followed by the adsorption tests. The XRD indicates that the MgFe2O4 phase was obtained, and the crystallite size was about 8 nm. New prepared adsorbent materials have a point of zero charge of 9.2. Studies have been performed to determine the influence of pH, initial indium solution concentration, material/solution contact time and temperature on the adsorption capacity of the material. Adsorption mechanism was established by kinetic, thermodynamic and equilibrium studies. At equilibrium a maximum adsorption capacity of 46.4 mg/g has been obtained. From kinetic and thermodynamic studies was proved that the studied adsorption process is homogeneous, spontaneous, endothermic and temperature dependent. Based on Weber and Morris model, we can conclude that the In (III) ions takes place at the MgFe2O4/In (III) solution-material interface.

Antimicrobial Perspectives of Active SiO2FexOy/ZnO Composites.

The antibacterial activity of zinc oxide particles has received significant interest worldwide, especially through the implementation of technology to synthesize particles in the nanometer range. This study aimed to determine the antimicrobial efficacy of silica-based iron oxide matrix (SiO2FexOy) synthesized with various amounts of ZnO (SiO2FexOyZnO) against various pathogens. It is observed that, with the addition of ZnO to the system, the average size of the porosity of the material increases, showing increasingly effective antibacterial properties. Zinc-iron-silica oxide matrix composites were synthesized using the sol-gel method. The synthesized materials were investigated physicochemically to highlight their structural properties, through scanning electron microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), and Fourier-transform infrared spectroscopy (FT-IR). At the same time, surface area, pore size and total pore volume were determined for materials synthesized using the Brunauer-Emmett-Teller (BET) method. Although the material with 0.0001 g ZnO (600 m2/g) has the highest specific surface area, the best antimicrobial activity was obtained for the material with 1.0 g ZnO, when the average pore volume is the largest (~8 nm) for a specific surface of 306 m2/g. This indicates that the main role in the antibacterial effect has reactive oxygen species (ROS) generated by the ZnO that are located in the pores of the composite materials. The point of zero charge (pHpZc) is a very important parameter for the characterization of materials that indicate the acid-base behaviour. The pHpZc value varies between 4.9 and 6.3 and is influenced by the amount of ZnO with which the iron-silica oxide matrix is doped. From the antimicrobial studies carried out, it was found that for S. aureus the total antibacterial effect was obtained at the amount of 1.0 g ZnO. For Gram-negative bacteria, a total antibacterial effect was observed in S. flexneri (for the material with 0.1 g ZnO), followed by E. coli (for 1.0 g ZnO). For P. aeruginosa, the maximum inhibition rate obtained for the material with 1.0 g ZnO was approximately 49%.

Ordered Mesoporous Silica Prepared in Different Solvent Conditions: Application for Cu(II) and Pb(II) Adsorption.

In this work, the synthesis of ordered mesoporous silica of MCM-41 type was investigated aimed at improving its morphology by varying the synthesis conditions in a one-pot process, employing different temperatures and solvent conditions. 2-methoxyethanol was used as co-solvent to ethanol. The co-solvent ratio and the synthesis temperature were varied. The pore morphology of the materials was characterized by nitrogen porosimetry and small angle neutron scattering (SANS), and the particle morphology by transmission electron microscopy (TEM) and ultra-small angle neutron scattering (USANS). The thermal behavior was investigated by simultaneous thermogravimetry-differential scanning calorimetry (TG-DSC) measurements. The SANS and N2 sorption results demonstrated that a well-ordered mesoporous structure was obtained at all conditions in the synthesis at room temperature. Addition of methoxyethanol led to an increase of the pore wall thickness. Simultaneously, an increase of methoxyethanol content led to lowering of the mean particle size from 300 to 230 nm, according to the ultra-small angle scattering data. The ordered porosity and high specific surfaces make these materials suitable for applications such as adsorbents in environmental remediation. Batch adsorption measurements of metal ion removal from aqueous solutions of Cu(II) and Pb(II) showed that the materials exhibit dominantly monolayer surface adsorption characteristics. The adsorption capacities were 9.7 mg/g for Cu(II) and 18.8 mg/g for Pb(II) at pH 5, making these materials competitive in performance to various composite materials.

Highly Efficient Recovery of Ruthenium from Aqueous Solutions by Adsorption Using Dibenzo-30-Crown-10 Doped Chitosan.

Ruthenium, as an industrial by-product or from natural sources, represents an important economical resource due to its specific applications. A complex problem is represented by ruthenium separation during reprocessing operations, therefore, different materials and methods have been proposed. The present study aims to develop a new material with good adsorbent properties able to be used for ruthenium recovery by adsorption from aqueous solutions. Absorbent material was obtained using chitosan (Ch) surface modification with dibenzo-30-crown-10 ether (DB30C10). Chitosan represents a well-known biopolymer with applicability in different adsorptive processes due to the presence of hydroxyl-, carboxyl-, and nitrogen-containing groups in the structure. Additionally, crown ethers are macromolecules with a good complexation capacity for metallic ions. It is expected that the adsorptive efficiency of newly prepared material will be superior to that of the individual components. New synthesized material was characterized using scanning electron microscopy coupled with energy dispersive X-ray (SEM-EDX), Fourier transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller surface area analysis (BET), and determination of point of zero charge (pZc). Results obtained from the performed kinetic, thermodynamic, and equilibrium studies confirmed the good adsorptive capacity of the prepared material, Ch-DB30C10, obtaining a maximum adsorption capacity of 52 mg Ru(III) per gram. This adsorption capacity was obtained using a solution with an initial concentration of 275 mg L-1, at pH 2, and 298 K. Ru(III) adsorption kinetics were studied by modeling the obtained experimental data with pseudo-first order and pseudo-second order models. Desorption studies established that the optimum eluent was represented by the 5M HNO3 solution. Based on the performed studies, a mechanism for recovery of ruthenium by adsorption was proposed.

Molybdate Recovery by Adsorption onto Silica Matrix and Iron Oxide Based Composites.

Aggressive industrial development over the last century involved different heavy metals being used, including high quantities of molybdenum, which need to be treated before discharge in industrial waters. Molybdenum's market price and industrial applicability make its recovery a big challenge. In the present study the possibility to recover molybdenum ions from aqueous solutions by adsorption on a composite material based on silica matrix and iron oxides-SiO2FexOy-was evaluated. Tests were performed in order to determine the influence of adsorbent material dose, initial solution pH, contact time and temperature over adsorption capacity of synthesized adsorbent material. For better understanding of the adsorption process, the obtained experimental data were modelled using Langmuir, Freundlich and Sips adsorption isotherms. Based on the obtained data, it can proved that the Sips isotherm was describing with better orderliness the studied process, obtaining a maximum adsorption capacity of 10.95 mg MoO42- for each gram of material. By modelling the studied adsorption process, it was proven that the pseudo-second order model is accurately describing the adsorption process. By fitting experimental data with Weber-Morris model, it was proven that MoO42- adsorption is a complex process, occurring in two different steps, one controlled by diffusion and the second one controlled by mass transfer. Further, studies were performed in order to determine the optimum pH value needed to obtain maximum adsorption capacity, but also to determine which are the adsorbed species. From pH and desorption studies, it was proven that molybdate adsorption is a physical process. In order to establish the adsorption mechanism, the thermodynamic parameters (ΔG0, ΔH0 and ΔS0) were determined.

Comparison of Structure and Adsorption Properties of Mesoporous Silica Functionalized with Aminopropyl Groups by the Co-Condensation and the Post Grafting Methods.

The adsorptive potential has been evaluated for the aminopropyl functionalized mesoporous silica materials obtained by co-condensation and post grafting methods. Nitrogen sorption, small angle neutron and X-ray scattering (SANS and SAXS) demonstrated high surface area and well-ordered hexagonal pore structure suitable for applications as adsorbents of metals from waste waters. A comparison of Cr(VI) adsorption properties of the materials prepared by different functionalization methods has been performed. The obtained results demonstrated the adsorption capacity due to the affinity of the chromium ions to the amino groups, and showed that co-condensation of tetraethoxysilane (TEOS) and 3-aminopropyl triethoxysilane (APTES) resulted in higher metal sorption capacity of the materials compared to post-synthesis grafting of aminopropyl groups onto the mesoporous silica particles.

Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal.

Multifunctional hybrid materials with applications in gas sensing or dye removal from wastewaters were obtained by incorporation into silica matrices of either Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (PtTAOPP) or platinum nanoparticles (PtNPs) alone or accompanied by 5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (TAOPP). The tetraethylorthosilicate (TEOS)-based silica matrices were obtained by using the sol-gel method performed in two step acid-base catalysis. Optical, structural and morphological properties of the hybrid materials were determined and compared by UV-vis, fluorescence and FT-IR spectroscopy techniques, by atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) and by Brunauer-Emmett-Teller (BET) analysis. PtTAOPP-silica hybrid was the most efficient material both for CO2 adsorption (0.025 mol/g) and for methylene blue adsorption (7.26 mg/g) from wastewaters. These results were expected due to both the ink-bottle mesopores having large necks that exist in this hybrid material and to the presence of the porphyrin moiety that facilitates chemical interactions with either CO2 gas or the dye molecule. Kinetic studies concerning the mechanism of dye adsorption demonstrated a second order kinetic model, thus it might be attributed to both physical and chemical processes.