Polypyrrole- and Polyaniline-Coated Cotton Fabrics as Efficient Adsorbents for the Pharmaceutical Water Contaminants Diclofenac and Salicylic Acid.

The emerging pharmaceutical contaminants diclofenac (DCF) and salicylic acid (SA) pose potential hazards to humans and living organisms due to their persistence in water environments. In this work, the conductive polymers polypyrrole (PPY) and polyaniline (PANI) were successfully coated on cotton fabrics, as confirmed by FTIR and SEM measurements. The coated fabrics efficiently removed DCF at pH 5.3 and SA at pH 4, with removal efficiencies that exceeded 90% and 70%, respectively. Adsorption was rapid for most of the tested contaminant-fabric systems and reached equilibrium within 20-30 min. The best adsorption performance for both contaminants was shown on the PPY-coated fabrics, which yielded adsorption capacities of about 65 and 21 mg/g for DCF and SA, respectively. This could be explained by molecular modeling simulations, which mostly estimated higher total cohesive energy densities for adsorption on the PPY-coated fabrics than on the PANI-coated ones. The adsorption mechanism involved both coulombic electrostatic attractions and non-coulombic van der Waals and π-π stacking. The fabrics could be reused for three adsorption-desorption cycles. Immobilization of the conductive polymers on cotton fabrics provides a facile method for their handling and collection during adsorption and regeneration cycles while maintaining their multi-functionality in adsorbing different contaminants.

Novel ultra-sensitive and highly selective cyanine sensors based on solvent-free microwave synthesis for the detection of trace hypochlorite ions in drinking water.

The adoption of chlorine in drinking water disinfection with the determination of residual chlorine in the form of hypochlorite ion (ClO-) is in widespread demand. Several sensors including colorimetric, fluorometric, and electrochemical methods are currently in use, but detection limits and ease of application remain a challenge. In this work, two new cyanine derivatives-based ClO- sensors, that were prepared by solvent-free microwave synthesis, are reported. The two sensors are highly sensitive and selective to ClO-, exhibiting a noticeable color change visible to the naked eye. Additionally, the sensors can detect ClO- without interference from other potential water pollutants, with low detection limits of 7.43 ppb and 0.917 ppb based on absorption performance. When using fluorometric methods, the sensors' detection limits are pushed down to 0.025 ppb and 0.598 ppb for sensors I and II, respectively. The sensors can be loaded with paper strips for field and domestic detection of ClO- in tap water treatment installations. Using the quartz crystal microbalance (QCM) technique, these sensors showed strong detection sensitivity to ClO-, with detection limits of 0.256 ppm and 0.09 ppm for sensors I and II, respectively. Quantum chemical studies using density functional theory (DFT) calculations, natural bond orbital (NBO) analysis, molecular electrostatic potential (MESP), and time-dependent density functional theory (TD-DFT) supported the findings. The sensing mechanism is rationalized in terms of radical cation formation upon ClO- oxidation of cyanine sensors I and II.

Green synthesis of carbon quantum dots toward highly sensitive detection of formaldehyde vapors using QCM sensor.

In the present study, an eco-friendly method for the preparation of carbon quantum dots (CQDs) is demonstrated using hydrothermal treatment of laurel leaves. The optical and structural characteristics of the prepared CQDs are investigated using transmission electron microscopy (TEM), X-ray photoelectron (XPS), fluorescent and UV-visible spectroscopies, Fourier transform infrared (FTIR), and X-ray diffraction (XRD). The quartz crystal microbalance (QCM) sensor designed and modified with CQDs is capable of detecting formaldehyde vapors in the presence of other interfering chemical-vapor analytes. The changes in the frequency of the QCM sensor are linearly correlated with the injected formaldehyde concentrations. The sensing properties of formaldehyde, including sensitivity and reversibility, are investigated. Detection of formaldehyde in the presence of humidity is carefully discussed for home or workplace room environment use. The adsorption kinetics of various VOCs vapors are also calculated and discussed.

Novel aspartic-based bio-MOF adsorbent for effective anionic dye decontamination from polluted water.

In this study, a cost-effective powdered Zn l-aspartic acid bio-metal organic framework (Zn l-Asp bio-MOF) was reported as an efficient adsorbent for Direct Red 81 (DR-81) as an anionic organic dye. The prepared bio-MOF was characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), field emission transmission electron microscopy (FETEM), surface area analysis (BET), and thermal gravimetrical analysis (TGA). The resulting bio-MOF has a large surface area (180.43 m2 g-1) and large mesopore volume (0.144 cm3 g-1), as well as good chemical inertness and mechanical stability. The optimum dosage from the Zn l-Asp bio-MOF was 1.0 g L-1 at pH = 7 for 95.3% adsorption of 10 ppm DR-81 after 45 min. Thermodynamic analysis results demonstrated that the decontamination processes were done with spontaneous, thermodynamically, and exothermic nature onto the fabricated bio-MOF. Kinetic parameters were well-fitted with pseudo-second-order kinetics, and the adsorption process was described by the Freundlich isotherm. The adsorption data proved that Zn l-Asp bio-MOF is an effective adsorbent for DR-81 from aqueous solutions with high stability and recycling ability for eight cycles, as well as the easy regeneration of the sorbent.

Novel eco-friendly electrospun nanomagnetic zinc oxide hybridized PVA/alginate/chitosan nanofibers for enhanced phenol decontamination.

In the current study, poly(vinyl alcohol)/alginate/chitosan (PVA/Alg/CS) composite nanofiber was immobilized with six different ratios of nanomagnetic zinc oxide (M-ZnO) (0 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, and 1 wt%) via the electrospinning technique. The various fabricated composite (M-6) nanofibers were characterized using Fourier transform infrared (FTIR), X-ray diffractometer (XRD), vibrating sample magnetometer (VSM), scanning electron microscope (SEM), atomic force microscope (AFM), thermogravimetric analysis (TGA), mechanical testing machine, and optical contact angle measurement. The fabricated composite nanofibers were applied for the adsorption of phenol from aqueous solutions. The 1.0 wt% M-ZnO/PVA/Alg/CS composite nanofibers were selected as the best phenol adsorbent with removal percentage of 84.22%. The influence of different processing parameter such as contact time, composite nanofiber dosage, pH, initial pollutant concentration, and temperature were examined. Increasing nanofiber dosage and the solution temperature was found to enhance the phenol adsorption onto the prepared nanocomposites. The maximum percentage of phenol removal was achieved at 84.22% after 90 min. Meanwhile, the maximum monolayer adsorption capacity (at pH = 5.0) was estimated to be 10.03 mg g-1 at 25 °C. Kinetic, isotherm, and thermodynamic studies were designated to proof the endothermic, spontaneous, and thermodynamically nature of the phenol adsorption process. These outcomes indicate the effectiveness of the fabricated M-ZnO/PVA/Alg/CS nanofibers as adsorbent materials for phenol from aqueous solutions.

Physical Expansion of Layered Graphene Oxide Nanosheets by Chemical Vapor Deposition of Metal-Organic Frameworks and their Thermal Conversion into Nitrogen-Doped Porous Carbons for Supercapacitor Applications.

Graphene oxide (GO) nanosheets show good electrical conductivity and corrosion resistance in electrochemical devices. However, strong van der Waals attraction between adjacent nanosheets causes GO materials to collapse, reducing the exposed surfaces and limiting electron/ion transport in porous electrodes. GO nanosheets mixed with Zn5 (OH)8 (NO3 )2 ⋅2 H2 O (ZnON) nanoplates create a layered composite structure. Exposing the resultant GO/ZnON to 2-methylimidazole vapor leads to the conversion of ZnON into the zeolitic imidazolate framework ZIF-8. The transformation of ZnON into ZIF-8 leads to a huge physical expansion of the interlayer space between the GO sheets. Annealing the material at high temperature caused the ZIF-8 to be converted into highly porous nitrogen-doped carbon, but the GO nanosheets maintained a large separation and high surface area. The morphology and porous structure of the post-annealing carbon material was sensitive to the initial ratio of ZnON to GO. The optimized sample exhibited several favorable features, including a large surface area, high degree of graphitization, and a high amount of nitrogen doping. Using chemical vapor deposition of metal-organic frameworks to physically expand nanomaterials is a novel method to increase the surface area and porosity of materials. It enabled the synthesis of nanoporous carbon electrodes with high capacitance, good rate capability, and long cyclic stability in supercapacitor devices.

Rational design of a polypyrrole-based competent bifunctional magnetic nanocatalyst.

The combination of conducting polymers with semiconductors for the fabrication of organic/inorganic hybrid nanocatalysts is one of the most promising research areas for many applications. In this work, the synthesized nanocomposite combines several advantages such as the photoresponse shift from the UV region toward visible light by narrowing the band gap of the semiconductor, magnetic separation ability and dual applications including the catalytic reduction of p-nitrophenol (PNP) and the photocatalytic degradation of methylene blue (MB) dye. In addition to the core magnetite nanoparticles (NPs), the synthesized nanocomposite contains polypyrrole (PPY) and TiO2 shells that are decorated with silver metal NPs to prevent electron-hole recombination and to enhance the catalytic performance. Indeed, the catalytic PNP reduction experiments reveal that the synthesized nanocomposite exhibits significantly high catalytic activity with a rate constant of 0.1169 min-1. Moreover, the photocatalytic experiments show that the synthesized nanophotocatalyst has a boosting effect toward MB dye degradation under normal daytime visible light irradiation with a rate constant of 6.38 × 10-2 min-1. The synergetic effect between silver NPs, PPY and TiO2 is thought to play a fundamental role in enhancing the photocatalytic activity.

Acid green crystal-based in situ synthesis of polyaniline hollow nanotubes for the adsorption of anionic and cationic dyes.

In this article, acid green (AG) dye played a dual pivotal role. The first role is as a structure-guiding agent and a soft template for the acid-free synthesis of polyaniline hollow nanotubes (PANI-HNTs) while the second role is as a target dye to be removed as a model of anionic dyes, alongside methylene blue (MB) as a model of cationic dyes. After characterization using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms (BET), and UV-visible absorption spectroscopy techniques, the prepared PANI-HNTs were exploited for the adsorption of basic MB dye and acidic AG dye from aqueous media. To optimize the adsorption process, the effects of different variables, such as adsorbent dose, contact time and pH, were studied. Due to the structural differences between the MB and AG dyes, the obtained data revealed that the best pH for the medium for optimal adsorption was 9.0 and 3.0, respectively. The rapid sorption dynamics were found to proceed in a second-order kinetic model and the equilibrium data for the adsorption of MB and AG dyes were fitted well to the Langmuir isotherm. The maximum monolayer capacity, q max, for MB and AG was calculated from the Langmuir model and equalled 69.4 and 57.8 mg g-1, respectively. A thermodynamic study revealed that the adsorption of MB by PANI-HNTs was a feasible, spontaneous, and exothermic process. Investigation of the substrate regeneration revealed that PANI-HNTs can be reused for dye adsorption several times. Therefore, the synthesized PANI-NTs are highly efficient for the dual removal of basic and acidic dyes. TEM images showed that PANI-HNTs were formed with an external and internal diameter of 50-60 nm and 5-10 nm, respectively.

Novel Magnetic Zinc Oxide Nanotubes for Phenol Adsorption: Mechanism Modeling.

Considering the great impact of a material's surface area on adsorption processes, hollow nanotube magnetic zinc oxide with a favorable surface area of 78.39 m²/g was fabricated with the assistance of microwave technology in the presence of poly vinyl alcohol (PVA) as a stabilizing agent followed by sonic precipitation of magnetite nano-particles. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) micrographs identified the nanotubes' morphology in the synthesized material with an average aspect ratio of 3. X-ray diffraction (XRD) analysis verified the combination of magnetite material with the hexagonal wurtzite structure of ZnO in the prepared material. The immobilization of magnetite nanoparticles on to ZnO was confirmed using vibrating sample magnetometry (VSM). The sorption affinity of the synthesized magnetic ZnO nanotube for phenolic compounds from aqueous solutions was examined as a function of various processing factors. The degree of acidity of the phenolic solution has great influence on the phenol sorption process on to magnetic ZnO. The calculated value of ΔH° designated the endothermic nature of the phenol uptake process on to the magnetic ZnO nanotubes. Mathematical modeling indicated a combination of physical and chemical adsorption mechanisms of phenolic compounds on to the fabricated magnetic ZnO nanotubes. The kinetic process correlated better with the second-order rate model compared to the first-order rate model. This result indicates the predominance of the chemical adsorption process of phenol on to magnetic ZnO nanotubes.

Synthesis of Fe3O4@poly(methylmethacrylate-co-divinylbenzene) magnetic porous microspheres and their application in the separation of phenol from aqueous solutions.

A simple strategy to fabricate magnetic porous microspheres of Fe(3)O(4)@poly(methylmethacrylate-co-divinylbenzene) was demonstrated. The magnetic microspheres, consisting of polymer-coated iron oxide nanoparticles, were synthesized by the modified suspension polymerization of methacrylate and divinylbenzene in the presence of a magnetic fluid. The morphology and the properties of the magnetic porous microspheres were examined by scanning electron microscopy, transmission electron microscopy, superconducting quantum interference device, Fourier transform infrared spectroscopy, thermogravimetry, and X-ray powder diffraction. The pore size distribution and the specific surface area of the microspheres were measured by nitrogen sorption and mercury porosimetry technique. As predicted from the previous knowledge, the magnetic porous microspheres possessed a high specific surface area using n-hexane as a porogen. It was further found that the amounts of divinylbenzene and methacrylate, the ratio of porogens, and the dosage of ferrofluids affect the specific surface area of the microspheres. Furthermore, the microspheres were applied to remove phenol from aqueous solutions. The results showed that the microspheres had a high adsorption capacity for phenol and a high separation efficiency due to their porous structure, polar groups, and superparamagnetic characteristic.