Nd-Doped ZnO Nanostructures with Enhanced Photocatalytic Performance for Environmental Protection.

Neodymium (Nd)-doped ZnO nanostructures with different amounts of Nd were obtained by the electrospinning-calcination method. X-ray diffraction measurements indicated that the prepared nanostructures have a wurtzite structure without undesirable impurities. Nd doping changes the mean crystallite size as well the lattice strain, as proved by Williamson-Hall plots. The ZnO-based nanostructures were tested as photocatalysts for methylene blue (MB) dye and ciprofloxacin (CIP) drug pollutant degradations under visible light irradiation. Corroborating the obtained results, it was found that the reaction rate constant increased almost linearly with the mean crystallite size (from 2.235 × 10-2 to 3.482 × 10-2 min-1) with a variation in the mean crystallite size from 24.2 to 42.1 nm. Furthermore, the best catalyst sample (0.1% Nd-doped ZnO) was used to optimize the photodegradation process of ciprofloxacin, taking into account the pollutant concentration as well as the catalyst dose. The removal efficiency after 120 min was about 100%, with the rate constant of k = 5.291·10-2 min-1 (CIP) and k = 4.780·10-2 min-1 (MB) for the established optimal conditions. Considering the value of the rate constant, the half-life of the reaction (τ1/2 = ln2/k) was evaluated to be about τ1/2 =13 min for CIP and 14.5 min corresponding to MB. Several catalytic cycles were successfully performed without any loss of photocatalytic activity using these nanostructures, demonstrating that the obtained nanostructures have good stability in the leaching processes.

Adsorption of Brilliant Green Dye onto a Mercerized Biosorbent: Kinetic, Thermodynamic, and Molecular Docking Studies.

This study reports the valorization of pistachio shell agricultural waste, aiming to develop an eco-friendly and cost-effective biosorbent for cationic brilliant green (BG) dye adsorption from aqueous media. Pistachio shells were mercerized in an alkaline environment, resulting in the treated adsorbent (PSNaOH). The morphological and structural features of the adsorbent were analyzed using scanning electron microscopy, Fourier transform infrared spectroscopy, and polarized light microscopy. The pseudo-first-order (PFO) kinetic model best described the adsorption kinetics of the BG cationic dye onto PSNaOH biosorbents. In turn, the equilibrium data were best fitted to the Sips isotherm model. The maximum adsorption capacity decreased with temperature (from 52.42 mg/g at 300 K to 46.42 mg/g at 330 K). The isotherm parameters indicated improved affinity between the biosorbent surface and BG molecules at lower temperatures (300 K). The thermodynamic parameters estimated on the basis of the two approaches indicated a spontaneous (ΔG < 0) and exothermic (ΔH < 0) adsorption process. The design of experiments (DoE) and the response surface methodology (RSM) were employed to establish optimal conditions (sorbent dose (SD) = 4.0 g/L and initial concentration (C0) = 10.1 mg/L), yielding removal efficiency of 98.78%. Molecular docking simulations were performed to disclose the intermolecular interactions between the BG dye and lignocellulose-based adsorbent.

Tuning of Sm3+ and Er3+-doped TiO2 nanofibers for enhancement of the photocatalytic performance: Optimization of the photodegradation conditions.

Titanium dioxide (TiO2)-based nanofibers doped with samarium (Sm3+) and erbium (Er3+) at doping levels tuned in the range of 0.05-1.0% were prepared by the electrospinning-calcination method. The produced materials were well characterized by X-ray diffraction, SEM, EDX, and UV-vis diffuse reflectance spectroscopy. These one-dimensional nanostructures showed a crystalline structure with values of fiber diameters values between 60 and 100 nm. The best catalyst sample of this study was formulated as TiO2:Sm (0.1%) and sintered at 600 °C. And, it was employed to intensify the photocatalytic process under visible-light irradiation. Likewise, the chemometric approach was applied to optimize the process. The results revealed that the rate constant for the photo-degradation of a cationic organic pollutant was significantly improved (k = 3.496 × 10-1 min-1). In terms of the reaction half-life, the intensification and optimization of the process led to a decrease in the half-life of the reaction from 68 to 2 min. And, these are outstanding findings for the photo-degradation process under visible-light irradiation. In addition, the total organic carbon (TOC) removal efficiencies were found to be 69.95% and 72.30% for the mineralization of MB and CIP, respectively, after a 360 min reaction time, which are significant results. Moreover, this material demonstrated remarkable photocatalytic activity for the degradation of ciprofloxacin (CIP) with a 99.6% removal efficiency and a rate constant of 4.292 × 10-1 min-1. Finally, the stability and reusability of this catalyst were demonstrated during five repetitive cycles of the CIP photodegradation.

Cobalt Ferrite Particles Produced by Sol-Gel Autocombustion and Embedded in Polysilane: An Innovative Route to Magnetically-Induced Fluorescence Composites.

Fluorescence detection is currently one of the commonly used techniques worldwide. Through this work, the preparation and optical properties of an interesting composite material are discussed. It is shown that encapsulating cobalt spinel ferrite (CoFe2O4), obtained by the sol-gel autocombustion method, into poly[diphenyl-co-methyl(H)]silane matrix leads to fluoromagnetic particles (PSCo) with intriguing optical properties. Transmission electron microscopy, combined with energy-dispersive X-ray analysis, showed 500 nm large spherical structures containing a core (around 400 nm in diameter) composed of magnetic ferrite particles, surrounded by a thin layer of semiconductive fluorescent polymer. The as-obtained material exhibited ferrimagnetic properties. The FTIR spectrum confirmed that the Si-H functionality of the polysilane was preserved. UV spectroscopy combined with molecular modeling studies indicated that the magnetic core had a strong influence on the intramolecular electron transitions characteristic of the σ-conjugated polysilane. Further analysis by steady-state fluorescence spectroscopy revealed that the internal magnetic field strongly enhances the polysilane emission. This property will be further investigated in the future in order to develop new detection devices.

Oxidized Biomass and Its Usage as Adsorbent for Removal of Heavy Metal Ions from Aqueous Solutions.

Nowadays, very coarse wool fibers are considered waste biomass and are discarded at random or burned. Therefore, it is of actual interest to valorize coarse wool fibers as utile products. In this sense, we report herein an environmentally-friendly process for the preparation of a new material based on oxidized wool fibers and designed for efficient adsorption of heavy metals from wastewater. The morphology and the structure of the obtained product were characterized by scanning electron microscopy (SEM) coupled with an X-ray energy-dispersive module (EDX) and by Fourier-transform infrared spectroscopy (FTIR). Likewise, the performances of the oxidized wool fibers for the adsorption of heavy metal cations (Cu2+, Cd2+, Pb2+) from aqueous solutions were tested. The adsorption kinetics data were analyzed by applying the pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models. The equilibrium of the adsorption process was investigated by using the Freundlich and Langmuir isotherm models. According to the Langmuir isotherms registered at 300 K, the maximum adsorption capacities of the oxidized wool were found to increase from Cu2+ (9.41 mg/g) and Cd2+ (10.42 mg/g) to Pb2+ (30.71 mg/g). Consequently, the removal efficiency of metal ions was found to vary in the range of 96.8-99.7%. The thermodynamic parameters (e.g., enthalpy, entropy, and Gibbs free energy) were calculated and discussed.

Novel rare earth (RE-La, Er, Sm) metal doped ZnO photocatalysts for degradation of Congo-Red dye: Synthesis, characterization and kinetic studies.

Synthesis and characterization of novel ZnO:RE nanostructured materials doped with 1% rare-earth elements (RE = La, Er, Sm) and their testing for photocatalytic applications were reported. The materials were obtained via electrospining, followed by calcination at 700 °C. The samples were characterized in terms of surface morphology (SEM, TEM), crystalline structure (XRD) and band gap energies. TEM results showed the formation of a unidimensional structure (ZnO) with an average fiber diameter of 600 nm and a morphology consisting of interconnected nanoparticles having dimensions in the range 25-134 nm (ZnO doped with RE). Optical properties were explored by using UV-VIS reflectance spectra and the band gap values were determined with the Kubelka-Munk function (KM) by plotting [F(R∞)hν]2vs. hʋ. The photocatalytic activity was assessed by studying the degradation of a water-soluble anionic dye (Congo-Red) under UV-light irradiation. The data related to photodegradation kinetics were reasonably fitted to the pseudo-first-order kinetic model. Results revealed that the values of the rate constants ranged from 10-3 to 10-2 min-1, depending on the material type and initial dye concentration. In addition, Langmuir-Hinshelwood (LH) model was utilized to explain the kinetics of photodegradation reactions of CR in the presence of (ZnO:Sm) sample. The LH approach suggested that both adsorption and photocatalysis phenomena prevailed in the process of dye removal. Optimal conditions of experiments were determined empirically by employing the gradient method. Thus, a maximal value of color removal efficiency (95.8%) was observed experimentally for the initial dye concentration of 10.7 mg/L and 0.236 g/L catalyst dosage (ZnO:Sm). Furthermore, a successful recovery of the spent catalyst was accomplished by thermal activation.

Polyethylene Terephthalate (PET) Recycled by Catalytic Glycolysis: A Bridge toward Circular Economy Principles.

Plastic pollution has escalated into a critical global issue, with production soaring from 2 million metric tons in 1950 to 400.3 million metric tons in 2022. The packaging industry alone accounts for nearly 44% of this production, predominantly utilizing polyethylene terephthalate (PET). Alarmingly, over 90% of the approximately 1 million PET bottles sold every minute end up in landfills or oceans, where they can persist for centuries. This highlights the urgent need for sustainable management and recycling solutions to mitigate the environmental impact of PET waste. To better understand PET's behavior and promote its management within a circular economy, we examined its chemical and physical properties, current strategies in the circular economy, and the most effective recycling methods available today. Advancing PET management within a circular economy framework by closing industrial loops has demonstrated benefits such as reduced landfill waste, minimized energy consumption, and conserved raw resources. To this end, we identified and examined various strategies based on R-imperatives (ranging from 3R to 10R), focusing on the latest approaches aimed at significantly reducing PET waste by 2040. Additionally, a comparison of PET recycling methods (including primary, secondary, tertiary, and quaternary recycling, along with the concepts of "zero-order" and biological recycling techniques) was envisaged. Particular attention was paid to the heterogeneous catalytic glycolysis, which stands out for its rapid reaction time (20-60 min), high monomer yields (>90%), ease of catalyst recovery and reuse, lower costs, and enhanced durability. Accordingly, the use of highly efficient oxide-based catalysts for PET glycolytic degradation is underscored as a promising solution for large-scale industrial applications.

Dynamic Adsorption of a Cationic Dye onto Wool Fibers as Column-Filling Media: Response Surface Optimization and Fixed-Bed Adsorption Modeling.

This study reports a simple and low-cost method for water purification using recyclable natural fibers (coarse wool fibers) as column-filling media for adsorption in the dynamic mode. As an instance of a dissolved organic pollutant, a cationic dye (basic blue 9, BB9) was assayed. According to the Langmuir isotherm (recorded at 300 K), the calculated maximum adsorption capacity of the fibrous material was found to be 24.86 mg/g for the retention of BB9. Response surface methodology (RSM) was employed for the design of experiments and the model-based optimization of the adsorption process performed in the dynamic regime (fixed-bed column). The optimal conditions provided by RSM indicated an adsorbent column height of H = 13.5 cm and a feed flow rate of Fv = 3 mL/min; these operating parameters ensured a color removal efficiency of 92.56% after 240 min of contact time. The recorded breakthrough curve under the optimal conditions was further interpolated using five quantitative mathematical models (Adams-Bohart, Thomas, Yoon-Nelson, Yan, and Clark) to assess the dynamic behaviors in the fixed-bed column. The best goodness-of-fit was achieved for the Thomas and Yoon-Nelson models. Thus, the coarse wool fibers used in a fixed bed demonstrated a relevant efficiency in the removal of cationic organic pollutants from contaminated water.

Application of Surface-Modified Nanoclay in a Hybrid Adsorption-Ultrafiltration Process for Enhanced Nitrite Ions Removal: Chemometric Approach vs. Machine Learning.

Herein, we report the results of a study on combining adsorption and ultrafiltration in a single-stage process to remove nitrite ions from contaminated water. As adsorbent, a surface-modified nanoclay was employed (i.e., Nanomer® I.28E, containing 25-30 wt. % trimethyl stearyl ammonium). Ultrafiltration experiments were conducted using porous polymeric membranes (Ultracel® 10 kDa). The hybrid process of adsorption-ultrafiltration was modeled and optimized using three computational tools: (1) response surface methodology (RSM), (2) artificial neural network (ANN), and (3) support vector machine (SVM). The optimal conditions provided by machine learning (SVM) were found to be the best, revealing a rejection efficiency of 86.3% and an initial flux of permeate of 185 LMH for a moderate dose of the nanoclay (0.674% w/v). Likewise, a new and more retentive membrane (based on PVDF-HFP copolymer and halloysite (HS) inorganic nanotubes) was produced by the phase-inversion method, characterized by SEM, EDX, AFM, and FTIR techniques, and then tested under optimal conditions. This new composite membrane (PVDF-HFP/HS) with a thickness of 112 µm and a porosity of 75.32% unveiled an enhanced rejection efficiency (95.0%) and a lower initial flux of permeate (28 LMH). Moreover, molecular docking simulations disclosed the intermolecular interactions between nitrite ions and the functional moiety of the organonanoclay.

Magnetic Ionotropic Hydrogels Based on Carboxymethyl Cellulose for Aqueous Pollution Mitigation.

In this work, stabilized ionotropic hydrogels were designed using sodium carboxymethyl cellulose (CMC) and assessed as inexpensive sorbents for hazardous chemicals (e.g., Methylene Blue, MB) from contaminated wastewaters. In order to increase the adsorption capacity of the hydrogelated matrix and facilitate its magnetic separation from aqueous solutions, sodium dodecyl sulfate (SDS) and manganese ferrite (MnFe2O4) were introduced into the polymer framework. The morphological, structural, elemental, and magnetic properties of the adsorbents (in the form of beads) were assessed using scanning electron microscopy (SEM), energy-dispersive X-ray analysis, Fourier-transform infrared spectroscopy (FTIR), and a vibrating-sample magnetometer (VSM). The magnetic beads with the best adsorption performance were subjected to kinetic and isotherm studies. The PFO model best describes the adsorption kinetics. A homogeneous monolayer adsorption system was predicted by the Langmuir isotherm model, registering a maximum adsorption capacity of 234 mg/g at 300 K. The calculated thermodynamic parameter values indicated that the investigated adsorption processes were both spontaneous (ΔG < 0) and exothermic (ΔH < 0). The used sorbent can be recovered after immersion in acetone (93% desorption efficiency) and re-used for MB adsorption. In addition, the molecular docking simulations disclosed aspects of the mechanism of intermolecular interaction between CMC and MB by detailing the contributions of the van der Waals (physical) and Coulomb (electrostatic) forces.

Thermal and Viscoelastic Responses of Selected Lignocellulosic Wastes: Similarities and Differences.

Woody lignocellulosic biomasses comprise the non-edible parts of fruit trees. In recent years, the exploitation of this biomass has been widening in order to mitigate environmental issues. At the same time, this waste could be transformed into a value-added product (active carbon by pyrolysis, isolation of nanocellulose, oils or proteins). For either valorization path, a complete thermo-mechanical characterization is required. A detailed thermo-mechanical study (TGA, DSC, DMA) was performed on two types of lignocellulosic wastes, with and without kernels: on one side, the walnut shells (WS) and the pistachio shells (PsS) and, in the second category, the apricot seeds (AS), the date seeds (DS), and the plum seeds (PS). The results of the sample-controlled thermal analyses (HiRes TGA) evidenced a better resolution of the degradation steps of WS. Kinetic studies conducted also by conventional TGA (Flynn-Wall-Ozawa) and modulated TGA (MTGA) allowed us to make comparative reasonings concerning the degradation of the investigated biomasses. The DMA results revealed the effect of water traces and oil kernels on relaxation and supported the atypical DSC endotherm emphasized in the freezing temperature domain.

Green Synthesis of Advanced Carbon Materials Used as Precursors for Adsorbents Applied in Wastewater Treatment.

Huge amounts of vegetable waste, mainly resulting from the food industry, need large areas for storage, as they could cause hazardous environmental impact, leading to soil and water pollution or to CO2 emissions during accidental incineration. This work was aimed at recycling certain lignocellulosic waste (walnut shells, kernels of peach, apricot, and olive) to design advanced carbon material precursors (ACMP) to be used for obtaining nano-powders with high applicative potential in pollution abatement. Both waste and ACMP were characterized using proximate and elemental analysis, and by optical microscopy. Complex characterization of raw materials by FTIR, TGA-DTG, and SEM analysis were carried out. The ACMP were synthetized at 600-700 °C by innovative microwave heating technology which offers the advantages of lower energy consumption using 3.3 kW equipment at laboratory level. The ACMP ash < 3% and increased carbon content of 87% enabled the development of an extended pore network depending on degassing conditions during heating. TEM analysis revealed a well-developed porous structure of the synthesized ACMP carbonaceous materials. Due to the presence of oxygen functional groups, ACMPs exhibit adsorption properties highlighted by an iodine index of max. 500 mg/g and surface area BET of 300 m2/g, which make them attractive for removal of environmental pollutants such as dyes having molecule sizes below 2 nm and ions with pore dimensions below 1 nm, widely used industrially and found in underground waters (NO3-) or waste waters (SO42-).

Ultrasonic-Assisted Rapid Preparation of Sulfonated Polyether Ether Ketone (PEEK) and Its Testing in Adsorption of Cationic Species from Aqueous Solutions.

Herein, we report a new approach for the sulfonation of polyether ether ketone (PEEK) following a shorter path of reaction undertaken at 60 °C under ultrasonication. The application of this method enabled the reduction of the reaction time from several hours to less than one hour, achieving a relevant sulfonation degree. The sulfonated-PEEK (SPEEK) was characterized by advanced chemical and physical instrumental methods. According to 1H-NMR analysis, the degree of sulfonation of the polymer was equal to 70.3%. Advanced microscopy (SEM) showed that the fabricated SPEEK beads (2-4 mm) were porous inside with a log-normal distribution of pore sizes within the range 1.13-151.44 µm. As an application, the SPEEK polymer was tested for the adsorption of a cationic organic pollutant (Methylene blue, MB) from aqueous solutions. The equilibrium studies (isotherms) disclosed maximum adsorption capacities of 217 mg/g, 119 mg/g, and 68 mg/g at temperatures of 323 K, 313 K, and 300 K, respectively. The thermodynamic calculations indicated an endothermic effect (ΔHad = +11.81 kJ/mol) of the investigated adsorption process. The maximum removal efficiency of 99.14% was established by process optimization using the design of experiments strategy and data-driven modeling. Additionally, molecular docking simulations were performed to disclose the mechanism of interaction at the molecular level between the adsorbent (SPEEK) and pollutant.

Evaluation of Physically and/or Chemically Modified Chitosan Hydrogels for Proficient Release of Insoluble Nystatin in Simulated Fluids.

To avoid fungal spreading in the bloodstream and internal organs, many research efforts concentrate on finding appropriate candidiasis treatment from the initial stage. This paper proposes chitosan-based physically or chemically cross-linked hydrogels aimed to provide sustained release of micronized nystatin (NYSm) antifungal drug, known for its large activity spectrum. Nystatin was demonstrated itself to provide hydrodynamic/mechanic stability to the chitosan hydrogel through hydrophobic interactions and H-bonds. For chemical cross-linking of the succinylated chitosan, a non-toxic diepoxy-functionalized siloxane compound was used. The chemical structure and composition of the hydrogels, also their morphology, were evidenced by infrared spectroscopy (FTIR), by energy dispersive X-ray (EDX) analysis and by scanning electron microscopy (SEM), respectively. The hydrogels presented mechanical properties which mimic those of the soft tissues (elastic moduli < 1 MPa), necessary to ensure matrix accommodation and bioadhesion. Maximum swelling capacities were reached by the hydrogels with higher succinic anhydride content at both pH 7.4 (429%) and pH 4.2 (471%), while higher amounts of nystatin released in the simulative immersion media (57% in acidic pH and 51% in pH 7.4) occurred from the physical cross-linked hydrogel. The release mechanism by non-swellable matrix diffusion and the susceptibility of three Candida strains make all the hydrogel formulations effective for NYSm local delivery and for combating fungal infections.

Amphiphilic Chitosan Porous Membranes as Potential Therapeutic Systems with Analgesic Effect for Burn Care.

Eliminating or at least lessening the pain is a crucial aspect of burns management, as pain can negatively affect mental health and quality of life, and it can also induce a delay on wound healing. In this context, new amphiphilic chitosan 3D porous membranes were developed and investigated as burns therapeutic systems with analgesic effect for delivery of lidocaine as local anesthetic. The highly porous morphology of the membranes and the structural modifications were evidenced by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis and infrared spectroscopy (FTIR). Improved compression mechanical properties, long-term hydrolytic degradation (28 days) evaluation and high swelling capacities (ranging from 8 to 22.6 g/g) indicate an increased capacity of the prepared membranes to absorb physiological fluids (burns exudate). Lidocaine in vitro release efficiency was favored by the decreased content of cross-linking agent (reaching maximum value of 95.24%) and the kinetic data modeling, indicating that lidocaine release occurs by quasi-Fickian diffusion. In addition to the in vitro evaluation of analgesic effect, lidocaine-loaded chitosan membranes were successfully investigated and proved antibacterial activity against most common pathogens in burns infections: Staphylococcus aureus and Methicillin-resistant Staphylococcus aureus.

Valorization of ß-Chitin Extraction Byproduct from Cuttlefish Bone and Its Application in Food Wastewater Treatment.

The nontoxicity, worldwide availability and low production cost of cuttlefish bone products qualify them an excellent biocoagulant to treat food industry wastewater. In this study, cuttlefish bone liquid waste from the deproteinization step was used as a biocoagulant to treat food industry wastewater. This work concerns a waste that has never before been investigated. The objectives of this work were: the recovery of waste resulting from cuttlefish bone deproteinization, the replacementof chemical coagulants with natural ones to preserve the environment, and the enhancement ofthe value of fishery byproducts. A quantitative characterization of the industrial effluents of a Moroccan food processing plant was performed. The physicochemical properties of the raw cuttlefish bone powder and the deproteinization liquid extract were determined using specific analysis techniques: SEM/EDX, FTIR, XRD and 1H-NMR. The protein content of the deproteinization liquid was determined by OPA fluorescent assay. The zeta potential of the liquid extract was also determined. The obtained analytical results showed that the deproteinization liquid waste contained an adequate amount of soluble chitin fractions that could be used in food wastewater treatment. The effects of the coagulant dose and pH on the food industrial effluents were studied to confirm the effectiveness of the deproteinization liquid extract. Under optimal conditions, the coagulant showed satisfactory results. Process optimization was performed using the Box-Behnken design and response surface methodology. Thus, the optimal removal efficiencies predicted using this model for turbidity (99.68%), BOD5 (97.76%), and COD (82.92%) were obtained at a dosage of 8 mL biocoagulant in 0.5 L of food processing wastewater at an alkaline pH of 11.

Investigation of a biosystem based on Arthrospira platensis for air revitalisation in spacecrafts: Performance evaluation through response surface methodology.

Arthrospira platensis is featured as a promising microalgae candidate for the development of the biosystems for air revitalisation in spacecrafts and life support in space. An enhanced configuration of a sparged type photobioreactor (PBR), containing 5 L of A. platensis culture, which was equipped with an external LED lighting tube around the reactor, was used in this study. The PBR was operated under dynamic conditions (0.5 L/min) with synthetic air containing CO2 (400, 900, 1400 ppm) and other gas traces (NO2 1 ppm, SO2 2.5 ppm, acetic acid vapours 1 ppm), at various light intensities (1.5, 2.5, 3.5 klux), according to an experimental design. The removal of gas traces (NO2, SO2 and acetic acid vapours) was below the detection limit (e.g. above 90% removal efficiency), while the removal of CO2 ranged between 69% and 85%, depending on the initial CO2 concentration and the light intensity. Thus, the system is able to roughly decrease the contaminant concentration from 1 ppm to below 0.1 ppm for NO2, 2.5 ppm to below 0.1 ppm for SO2, 1 ppm to below 1 ppb for acetic acid vapours and from 1400 ppm to 370 or from 400 ppm to 60 ppm for CO2. The system performance was thus subject to mathematical modelling and optimization in terms of CO2 removal efficiency and CO2 elimination capacity, which were also corroborated with the power consumption for illumination.

Development of Porous Titania Structure with Improved Photocatalytic Activity: Response Surface Modeling and Multi-Objective Optimization.

Porous titania was successfully synthesized by an ultrasound-assisted sol-gel route. The synthesis process was empirically modeled and optimized using the response surface methodology (RSM). Input variables adopted for optimization dealt with the weight ratio of precursors (r) and the sonication time (t), representing the used factors in the synthesis procedure. With regard to application, the synthesized TiO2 samples were tested for the photodegradation of two water-soluble organic pollutants under UV-Vis irradiation. Optimal conditions for the efficient pollutants' photodegradation were found to involve a precursors ratio of 3 and a sonication time of 60 min. Thus, the M5 sample prepared under the founded optimal conditions yielded the maximal removal efficiencies of 98.4% and 46.3% for the photodegradation of CR dye and 2,4-D herbicide, respectively. In addition, the photodegradation kinetics revealed the pseudo first-order rate constants, showing the photodegradation of CR (k1 = 8.86 × 10-2 min-1) by M5 sample is about 1.3-fold faster than the photodegradation of 2,4-D pesticide (k2 = 6.84 × 10-2 min-1).

Chitosan-Sulfated Titania Composite Membranes with Potential Applications in Fuel Cell: Influence of Cross-Linker Nature.

Chitosan-sulfated titania composite membranes were prepared, characterized, and evaluated for potential application as polymer electrolyte membranes. To improve the chemical stability, the membranes were cross-linked using sulfuric acid, pentasodium triphosphate, and epoxy-terminated polydimethylsiloxane. Differences in membranes' structure, thickness, morphology, mechanical, and thermal properties prior and after cross-linking reactions were evaluated. Membranes' water uptake capacities and their chemical stability in Fenton reagent were also studied. As proved by dielectric spectroscopy, the conductivity strongly depends on cross-linker nature and on hydration state of membranes. The most encouraging results were obtained for the chitosan-sulfated titania membrane cross-linked with sulfuric acid. This hydrated membrane attained values of proton conductivity of 1.1 × 10-3 S/cm and 6.2 × 10-3 S/cm, as determined at 60 °C by dielectric spectroscopy and the four-probes method, respectively.

Chitosan-based magnetic adsorbent for removal of water-soluble anionic dye: Artificial neural network modeling and molecular docking insights.

Herein, we report a new composite magnetic-adsorbent made of doped spinel ferrite (15%) dispersed throughout a matrix of chitosan (CS) cross-linked with glutaraldehyde (GA). The composite material was well characterized by using instrumental methods of physical-chemical analysis (SEM, EDX, FTIR and VSM). The produced adsorbent was applied for the removal of Acid Orange 7 (AO7) dye from aqueous solutions. Aspects of adsorption kinetics, isotherms and thermodynamics were detailed. According to the Dubinin-Radushkevich (D-R) isotherm, the mean free energy of adsorption ranged from 14.37 to 16.59 (kJ/mol), suggesting ion-exchange dominating phenomena. In addition, we developed an artificial neural network (ANN) model to explore extensively the effects of factors on the adsorption performance. The coupling of ANN model with a genetic algorithm provided optimal conditions of adsorption. A maximal color removal efficiency of 98.01% was observed experimentally under optimal conditions (pH 2.51, sorbent dosage 3.88 g/L, initial dye concentration 25.3 mg/L, contact time 204 min). To unveil interaction mechanism, we employed molecular docking simulations. Computational outcomes suggested the formation of hydrophobic contacts and hydrogen bonds between AO7 dye molecule and CS-GA receptor. Molecular docking results agreed with the D-R isotherm findings, highlighting that electrostatic forces were greater than Van-der-Waals interactions.