Catalytic fabrication of graphene, carbon spheres, and carbon nanotubes from plastic waste.

In this study, we reported sustainable and economical upcycling methods for utilizing plastics such as polyethylene terephthalate (PET) and polypropylene (PP) compiled from the garbage of a residential area as cheap precursors for the production of high-value carbon materials such as graphene (G), carbon spheres (CS), and carbon nanotubes (CNTs) using different thermal treatment techniques. Graphene, carbon spheres, and carbon nanotubes were successfully synthesized from PET, PP, and PET, respectively via catalytic pyrolysis. XRD and FTIR analyses were conducted on the three materials, confirming the formation of carbon and their graphitic structure. TEM images displayed uniform and consistent morphological structures of the fabricated materials. EDX data confirmed that the prepared carbon-based materials only contained carbon and oxygen without any significant contaminations. XPS results revealed significant peaks in the C 1s spectra associated with sp2 and sp3 hybridized carbon for the three materials. BET spectra showed that the prepared CNTs (54.872 m2 g-1) have the highest surface area followed by carbon spheres (54.807 m2 g-1). The thermal stability of graphene surpassed both carbon spheres and carbon nanotubes which is mainly attributed to the stronger inter-molecular bonds of graphene. Based on the characterization of the prepared materials, these materials are promising to be utilized in environmental remediation applications due to their high carbon content, low cost, and high surface area.

Optical Properties of Cationic Perylenediimide Nanowires in Aqueous Medium: Experimental and Computational Studies.

Cationic perylenediimide derivative, namely N,N'-di(2-(trimethylammoniumiodide)ethylene) perylenediimide (TAIPDI), has been synthesized and characterized in an aqueous medium by using dynamic light scattering (DLS), X-ray diffraction (XRD), fourier-transform infrared (FTIR), scanning electron microscope (SEM), and high-resolution transmission electron microscopy (HRTEM) techniques. The optical absorption and fluorescence spectra of TAIPDI revealed the formation of aggregated TAIPDI nanowires in water, but not in organic solvents. In order to control the aggregation behavior, the optical properties of TAIPDI have been examined in different aqueous media, namely cetyltrimethylammonium bromide (CTAB), and sodium dodecyl sulfate (SDS). Furthermore, the utilization of the examined TAIPDI for constructing supramolecular donor-acceptor dyad has been achieved by combining the electron accepting TAIPDI with the electron donating 4,4'-bis (2-sulfostyryl)-biphenyl disodium salt (BSSBP). The formed supramolecular dyad TAIPDI-BSSBP through the ionic and electrostatic π-π interactions have been well examined by various spectroscopic techniques, e.g., steady-state absorption and fluorescence, cyclic voltammetry, and time-correlated single-photon counting (TCSPC), and first principle computational chemistry methods. Experimental results suggested the occurring of intra-supramolecular electron transfer from BSSBP to TAIPDI with rate constant and efficiency of 4.76 × 109 s-1 and 0.95, respectively. The ease of construction, absorption in the UV-Visible region, and fast electron transfer process render the supramolecular TAIPDI-BSSBP complex as a donor-acceptor material for optoelectronic devices.

Surface-decorated porphyrinic zirconium-based metal-organic frameworks (MOFs) using post-synthetic self-assembly for photodegradation of methyl orange dye.

We report herein the surface decoration of a water-soluble free-base porphyrin, namely, 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin-tetra(p-toluenesulfonate) (H2TMPyP), over three different zirconium-based metal-organic frameworks of different linker structure and functionality; namely UiO66, UiO66-NH2, and MIP-202, via self-assembly. The synthesized MOFs along with the resulting complexes have been characterized via spectroscopic and analytical techniques (XRD, FT-IR, TEM, N2 adsorption/desorption, and laser scanning confocal microscopy). The self-assembly of H2TMPyP with the examined three MOFs was observed by using the steady-state absorption and fluorescence, as well as the fluorescence lifetime studies. It was evident that the highest complex interaction was recorded between porphyrin and UiO-66-NH2 compared with the lowest interactions between porphyrin and MIP-202. This is in good agreement with the high surface area and pore volume of UiO-66 (1100 m2 g-1 and 0.68 cm3 g-1) and compared to that of MIP-202 (94 m2 g-1 and 0.26 cm3 g-1). The photocatalytic activities of the three porphyrin entities immobilized zirconium-based MOFs were compared toward methyl orange dye degradation from aqueous solution under visible light irradiation (λex = 430 nm). The photocatalytic studies render the fabrication of the self-assembled H2TMPyP@UiO-66-NH2 composite as a promising material for dye degradation from polluted wastewater.

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.

Assessment of antimicrobial, cytotoxicity, and antiviral impact of a green zinc oxide/activated carbon nanocomposite.

This work deals with the synthesis of zinc oxide nanoparticles/activated carbon (ZnO NPs/AC) nanocomposites with different weight ratios (3:1, 1:1, and 1:3), where the antimicrobial, antiviral, and cytotoxicity impact of the formulated nanocomposites were evaluated versus the crude ZnO and AC samples. The formula (3:1; designated Z3C1) exhibited the utmost bactericidal effect against Gram positive group, unicellular and filamentous fungi. Regarding Gram negative group, the sample (Z3C1) was remarkably effective against Klebsiella pneumonia, unlike the case of Escherichia coli. Moreover, the whole samples showed negligible cytotoxicity against the human WI38 cell line, where the most brutality (4%) was exerted by 1000 µg/mL of the formula (Z1C3). Whilst, the formula (Z3C1) exerted the apical inhibition impact against Herpes simplex (HSV1) virus. Consequently, the synthesized (Z3C1) nanocomposite was sorted out to be fully characterized via different physicochemical techniques including FTIR, XRD, SEM, TEM, Zeta potential, TGA, and BET. XRD indicated a predominance of the crystalline pattern of ZnO NPs over the amorphous AC, while the FTIR chart confirmed an immense combination between the ZnO NPs and AC. SEM, TEM, and size distribution images illustrated that the fabricated ZnO NPs/AC was in the nanoscale size swung from 30 to 70 nm. The distinctive surface area of composite material, recording 66.27 m2/g, clearly disclosed its bioactivity toward different bacterial, fungal, and virus species.

Fe Nanoparticle Size Control of the Fe-MOF-Derived Catalyst Using a Solvothermal Method: Effect on FTS Activity and Olefin Production.

The design of a highly active Fe-supported catalyst with the optimum particle and pore size, dispersion, loading, and stability is essential for obtaining the desired product selectivity. This study employed a solvothermal method to prepare two Fe-MIL-88B metal-organic framework (MOF)-derived catalysts using triethylamine (TEA) or NaOH as deprotonation catalysts. The catalysts were analyzed using X-ray diffraction, N2-physisorption, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, H2 temperature-programed reduction, and thermogravimetric analysis and were evaluated for the Fischer-Tropsch synthesis performance. It was evident that the catalyst preparation in the presence of TEA produces a higher MOF yield and smaller crystal size than those produced using NaOH. The pyrolysis of MOFs yielded catalysts with different Fe particle sizes of 6 and 35 nm for the preparation in the presence of TEA and NaOH, respectively. Also, both types of catalysts exhibited a high Fe loading (50%) and good stability after 100 h reaction time. The smaller particle size TEA catalyst showed higher activity and higher olefin yield, with 94% CO conversion and a higher olefin yield of 24% at a lower reaction temperature of 280 °C and 20 bar at H2/CO = 1. Moreover, the smaller particle size TEA catalyst exhibited higher Fe time yield and CH4 selectivity but with lower chain growth probability (α) and C5+ selectivity.

Methyl Orange Biodegradation by Immobilized Consortium Microspheres: Experimental Design Approach, Toxicity Study and Bioaugmentation Potential.

Methyl orange (MO) is categorized among the recalcitrant and refractory xenobiotics, representing a significant burden in the ecosystem. To clean-up the surrounding environment, advances in microbial degradation have been made. The main objective of this study was to investigate the extent to which an autochthonous consortium immobilized in alginate beads can promote an efficient biodegradation of MO. By employing response surface methodology (RSM), a parametric model explained the interaction of immobilized consortium (Raoultella planticola, Ochrobactrum thiophenivorans, Bacillus flexus and Staphylococcus xylosus) to assimilate 200 mg/L of MO in the presence of 40 g/L of NaCl within 120 h. Physicochemical analysis, including UV-Vis spectroscopy and FTIR, and monitoring of the degrading enzymes (azoreductase, DCIP reductase, NADH reductase, laccase, LiP, MnP, nitrate reductase and tyrosinase) were used to evaluate MO degradation. In addition, the toxicity of MO-degradation products was investigated by means of phytotoxicity and cytotoxicity. Chlorella vulgaris retained its photosynthetic performance (>78%), as shown by the contents of chlorophyll-a, chlorophyll-b and carotenoids. The viability of normal lung and kidney cell lines was recorded to be 90.63% and 99.23%, respectively, upon exposure to MO-metabolic outcomes. These results reflect the non-toxicity of treated samples, implying their utilization in ferti-irrigation applications and industrial cooling systems. Moreover, the immobilized consortium was employed in the bioremediation of MO from artificially contaminated agricultural and industrial effluents, in augmented and non-augmented systems. Bacterial consortium remediated MO by 155 and 128.5 mg/L in augmented systems of agricultural and industrial effluents, respectively, within 144 h, revealing its mutual synergistic interaction with both indigenous microbiotas despite differences in their chemical, physical and microbial contents. These promising results encourage the application of immobilized consortium in bioaugmentation studies using different resources.

Bio-Zirconium Metal-Organic Framework Regenerable Bio-Beads for the Effective Removal of Organophosphates from Polluted Water.

Organophosphate-based pesticides, such as diazinon, are among the most toxic organic contaminants to human and environment. Effective removal of diazinon from contaminated water sources is critical. Zirconium Metal-organic frameworks (Zr-MOFs) are promising candidates for the removal of organic contaminants from wastewater. Herein, we report the adequacy of a bio based Zr-MOF named MIP-202 for the removal of diazinon from water. On the other hand, the use of these materials in powder form is not workable, the development of scalable and economical processes and integrative of these materials onto beads is paramount for industrial processes. Hence, it was reported a scalable, bio aqueous solution-based preparation strategy for Bio Zr-MOF beads production. The composite material exposed identical reactivity under the same ambient parameters compared to powdered material in an aqueous solution. These results signify a critical procedure to an integrated strategy for organophosphates removal using bio-based MOFs, which demonstrates high potential for manufacturing applications such as continued removal of organophosphates from wastewater supplies.

Photocatalytic Degradation of Malachite Green Dye from Aqueous Solution Using Environmentally Compatible Ag/ZnO Polymeric Nanofibers.

An efficient, environmentally compatible and highly porous, silver surface-modified photocatalytic zinc oxide/cellulose acetate/ polypyrrole ZnO/CA/Ppy hybrid nanofibers matrix was fabricated using an electrospinning technique. Electrospinning parameters such as solution flow rate, applied voltage and the distance between needles to collector were optimized. The optimum homogenous and uniform ZnO/CA/Ppy polymeric composite nanofiber was fabricated through the dispersion of 0.05% wt ZnO into the dissolved hybrid polymeric solution with an average nanofiber diameter ranged between 125 and 170 nm. The fabricated ZnO-polymeric nanofiber was further surface-immobilized with silver nanoparticles to enhance its photocatalytic activity through the reduction of the nanofiber bandgap. A comparative study between ZnO polymeric nanofiber before and after silver immobilization was investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and thermal gravimetric analysis (TGA). The photocatalytic degradation efficiency of the two different prepared nanofibers before and after nanosilver immobilization for malachite green (MG) dye was compared against various experimental parameters. The optimum degradation efficiency of nanosilver surface-modified ZnO-polymeric nanofibers was recorded as 93.5% for malachite green dye after 1 h compared with 63% for ZnO-polymeric nanofibers.

Biocompatible MIP-202 Zr-MOF tunable sorbent for cost-effective decontamination of anionic and cationic pollutants from waste solutions.

This reported work aims to fabricate an eco-friendly Zr bio-based MOF and assessment its adsorption efficiency towards the cationic and anionic dye pollutants including methylene blue (MB) and direct red 81 (DR-81), respectively. Also, its adsorption tendency for the highly toxic heavy metal of hexavalent chromium (Cr(VI)) was compared with dyes. The adsorption performance of bio-MOF showed that the maximum monolayer adsorption capacities were recorded as 79.799 mg/g for MB, 36.071 mg/g for DR-81, and 19.012 mg/g for Cr(VI). Meanwhile, the optimum dosage of as-synthesized MIP-202 bio-MOF was 0.5, 1, and 2 g L-1 for MB, DR-81, and Cr(VI), respectively. Thermodynamic analysis demonstrated the spontaneous, thermodynamically, and endothermic nature of the decontamination processes onto the fabricated Zr bio-based MOF. The adsorption data were fitted by Langmuir isotherm model compared with Freundlich and Temkin models for all studied water pollutants. Pseudo-second-order kinetic model was a fit model for description of the adsorption kinetics of the different cationic and anionic pollutants onto Zr bio-based MOF. These outcomes indicated that Zr bio-based MOF has potential application for adsorption of different types of industrial water pollutants including cationic and anionic dyes and heavy metals.

Impact of synthesized metal oxide nanomaterials on seedlings production of three Solanaceae crops.

Prospective involvement of metal oxide nanomaterials as a prominent agriculture practice for improving existing crop production directed the present investigation for synthesizing of ZnO and TiO2 nanomaterials as an attempt to enhance the transplants production of some Solanaceae crops. The morphological characterizations of the prepared nanomaterials indicated that the hydrothermal synthesized ZnO was produced in nanorod structure with an average aspect ratio of 7. However, SEM and TEM micrographs of microwave prepared TiO2 evident that it has a nanoparticle structure with an average diameter of 43 nm. The BET results confirmed the high specific areas of the two prepared metal oxide nanomaterials. The two synthesized metal oxide nanomaterials were coated in gel and mixed with the seeds of eggplant, pepper and tomato crops at four concentrations 0, 50, 100 and 150 mg/L, whilst the control seeds were germinated in distilled water without gel-coating. The results pointed to the outstanding effect of TiO2 and ZnO nanoparticles on germination characters and seedlings growth. The maximum transplants lengths, fresh and dry weight were recorded at the level 100 mg/L whatever the crop plant used. Hastening germination operation of nanomaterials-gel coated seedlings compared to control plants may be ascribed to the reduction of mean germination time and coefficient variation of the germination process besides increasing the mean germination rate and the synchrony of germination traits. Overall, better performance of growing transplants has been accredited for nanoparticles-gel coated seedlings more than the control treatments which could be efficient for the safer production of transplants in an innovative way.

Electrospun cellulose acetate nanofiber incorporated with hydroxyapatite for removal of heavy metals.

Due to the negative impact of the heavy metal ions in water, the rejection of these toxic materials is one of the urgent requests for wastewater treatment. This work aims to facile fabrication and characterization of new organic/inorganic hybrid nanofiber membrane composites for removal of Fe (III) and Pb (II) ions using a batch technique. The manufacturing of pure cellulose acetate nanofibers (CA NFs) and its impregnated with hydroxyapatite (CA/HAp) nanocomposite fibers is explored by an electrospinning process. A production process of uniform and bead-free nanofiber is developed by adjusting various electrospinning conditions. The experiments prove that the slight changes in operating parameters may result in significant variations in the fiber morphology. The influence of various adsorption conditions and its effect on the removal efficiency is investigated. High separation efficiency of about 99.7 and 95.46% within 35 and 40 min. for adsorption Pb (II) and Fe (III) ions using hybrid nanofiber composite, respectively are obtained. The adsorption process was found to obey a pseudo-second-order and Freundlich models. The adsorption mechanism on the CA/HAp composite can be established via ion exchange and surface complexation.

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.

Applying Taguchi design and large-scale strategy for mycosynthesis of nano-silver from endophytic Trichoderma harzianum SYA.F4 and its application against phytopathogens.

Development of reliable and low-cost requirement for large-scale eco-friendly biogenic synthesis of metallic nanoparticles is an important step for industrial applications of bionanotechnology. In the present study, the mycosynthesis of spherical nano-Ag (12.7 ± 0.8 nm) from extracellular filtrate of local endophytic T. harzianum SYA.F4 strain which have interested mixed bioactive metabolites (alkaloids, flavonoids, tannins, phenols, nitrate reductase (320 nmol/hr/ml), carbohydrate (25 µg/µl) and total protein concentration (2.5 g/l) was reported. Industrial mycosynthesis of nano-Ag can be induced with different characters depending on the fungal cultivation and physical conditions. Taguchi design was applied to improve the physicochemical conditions for nano-Ag production, and the optimum conditions which increased its mass weight 3 times larger than a basal condition were as follows: AgNO3 (0.01 M), diluted reductant (10 v/v, pH 5) and incubated at 30 °C, 200 rpm for 24 hr. Kinetic conversion rates in submerged batch cultivation in 7 L stirred tank bioreactor on using semi-defined cultivation medium was as follows: the maximum biomass production (Xmax) and maximum nano-Ag mass weight (Pmax) calculated (60.5 g/l and 78.4 g/l respectively). The best nano-Ag concentration that formed large inhibition zones was 100 µg/ml which showed against A.alternate (43 mm) followed by Helminthosporium sp. (35 mm), Botrytis sp. (32 mm) and P. arenaria (28 mm).

Adsorption Profile of Basic Dye onto Novel Fabricated Carboxylated Functionalized Co-Polymer Nanofibers.

Acrylonitrile-Styrene co-polymer was prepared by solution polymerization and fabricated into nanofibers using the electrospinning technique. The nanofiber polarization was enhanced through its surface functionalization with carboxylic acid groups by simple chemical modification. The carboxylic groups' presence was dedicated using the FT-IR technique. SEM showed that the nanofiber attains a uniform and porous structure. The equilibrium and kinetic behaviors of basic violet 14 dye sorption onto the nanofibers were examined. Both Langmuir and Temkin models are capable of expressing the dye sorption process at equilibrium. The intraparticle diffusion and Boyd kinetic models specified that the intraparticle diffusion step was the main decolorization rate controlling the process.

Characterization and flocculation properties of a carbohydrate bioflocculant from a newly isolated Bacillus velezensis 40B.

In this study, a bioflocculant with a high flocculation activity (> 98%) produced by strain 40B, which was isolated from a brackish water was investigated By 16S rDNA sequence analysis, strain 40B was identified as Bacillus velezensis. Chemical analysis of the bioflocculant 40B indicated that it contained 2% protein and 98% carbohydrates. FTIR analysis showed the presence of carboxyl, hydroxyl and amino groups, which were preferred for the flocculation process. The optimal concentration for the flocculation activity was 3.5 mg (-1). This polysaccharide could also flocculate kaolin suspension over a wide range of pH (1-10) and temperature (5-85 degrees C) in the presence of CaCl2. The stability of the bioflocculant 40B under various conditions suggests its possible use in the industries and environmental applications. However, no previous report exists on the isolation and characterization of a bioflocculant from the Bacillus velezensis.