A mechanothermal approach for the synthesis of Fe3O4 nanoparticles as dopant on mesoporous TiO2 for electrochemical determination of catechol.

The subject of water contamination and how it gets defiled to the society and humans is confabulating from the past decades. Phenolic compounds widely exist in the water sources and it is emergent to determine the toxicity in natural and drinking water, because it is hazardous to the humans. Among these compounds, catechol has sought a strong concern because of its rapid occurrence in nature and its potential toxicity to humans. The present work aims to develop an effective electrochemical sensing of catechol using mesoporous structure of Fe3O4-TiO2 decorated on glassy carbon (GC) electrode. The creation of pure TiO2 using the sol-gel technique was the first step in the synthesis protocol for binary nanocomposite, which was then followed by the loading of Fe3O4 nanoparticles on the surface of TiO2 using the thermal decomposition method. The resultant Fe3O4-TiO2 based nanocomposite exhibited mesoporous structure and the cavities were occupied with highly active magnetite nanoparticles (Fe3O4) with high specific surface area (90.63 m2/g). When compared to pure TiO2, catechol showed a more prominent electrochemical response for Fe3O4-TiO2, with a significant increase in anodic peak current at a lower oxidation potential (0.387 V) with a detection limit of 45 µM. Therefore, the prepared magnetite binary nanocomposite can serve as an efficient electroactive material for sensing of catechol, which could also act as a promising electrocatalyst for various electrocatalytic applications.

Using functionalized asphaltenes as effective adsorbents for the removal of chromium and lead metal ions from aqueous solution.

For the first time, functionalized asphaltene has been designed, synthesized, and used for the removal of heavy metals from the water. Asphaltene was separated from the crude oil with the addition of n-alkanes. Asphaltene having a complex chemical structure including multilayered and clustered aromatic fused rings bearing aliphatic chains. Asphaltene also contains heteroatoms like N, S, and O atoms along with Ni and V as prominent trace metals. On functionalization of asphaltene with nitric acid, the aliphatic chains and some of the naphthenic rings broke down and developed -COOH, -CO, C-O, and other oxygen functional groups which are playing key roles as surface-active agents in the removal of the heavy metals via chemisorption. The study was conducted using different parameters such as dose, time, pH, and concentration. The adsorption efficiency for this material at pH 4 is excellent for the removal of chromium and lead. The Langmuir, Freundlich and Temkin adsorption isotherm models as well as Lagergren pseudo second-order kinetic model were investigated. The positive enthalpies ΔHs confirm that the adsorption process is endothermic and the negative free energies ΔGs confirm the spontaneity of the process. The good efficiency of the adsorption implies the efficacy in the removal of the heavy metal ions, as well as the good efficiency in desorption, which implies the excellent recovery of the adsorbent. The effective reusability of this adsorbent makes it applicable for industrial water treatment from contaminants.

An Ionic-Liquid-Imprinted Nanocomposite Adsorbent: Simulation, Kinetics and Thermodynamic Studies of Triclosan Endocrine Disturbing Water Contaminant Removal.

The presence of triclosan in water is toxic to human beings, hazardous to the environment and creates side effects and problems because this is an endocrine-disturbing water pollutant. Therefore, there is a great need for the separation of this notorious water pollutant at an effective, economic and eco-friendly level. The interface sorption was achieved on synthesized ionic liquid-based nanocomposites. An N-methyl butyl imidazolium bromide ionic liquid copper oxide nanocomposite was prepared using green methods and characterized by using proper spectroscopic methods. The nanocomposite was used to remove triclosan in water with the best conditions of time 30 min, concentration 100 µg/L, pH 8.0, dose 1.0 g/L and temperature 25 °C, with 90.2 µg/g removal capacity. The results obeyed Langmuir, Temkin and D-Rs isotherms with a first-order kinetic and liquid-film-diffusion kinetic model. The positive entropy value was 0.47 kJ/mol K, while the negative value of enthalpy was -0.11 kJ/mol. The negative values of free energy were -53.18, -74.17 and -76.14 kJ/mol at 20, 25 and 30 °C. These values confirmed exothermic and spontaneous sorption of triclosan. The combined effects of 3D parameters were also discussed. The supramolecular model was developed by simulation and chemical studies and suggested electrovalent bonding between triclosan and N-methyl butyl imidazolium bromide ionic liquid. Finally, this method is assumed as valuable for the elimination of triclosan in water.

Recent progress in green and biopolymer based photocatalysts for the abatement of aquatic pollutants.

Enormous research studies on the abatement of anthropogenic aquatic pollutants including organic dyes, pesticides, cosmetics, antibiotics and inorganic species by using varieties of semiconductor photocatalysts have been reported in recent decades. Besides, many of these photocatalysts suffer in real applications owing to their high production cost and low stability. In many cases, the photocatalysts themselves are being considered as secondary pollutants. To eliminate these drawbacks, the green synthesized photocatalysts and the use of biopolymers as photocatalyst supports are considered in recent years. In this context, recent developments in green synthesized metals, metal oxides, other metal compounds, and carbon based photocatalysts in water purification are critically reviewed. Furthermore, the pivotal role of biopolymers including chitin, chitosan, cellulose, natural gum, hydroxyapatite, alginate in photocatalytic removal of aquatic pollutants is comprehensively reviewed. The presence of functional groups, electron trapping ability, biocompatibility, natural occurrence, and low production cost are the major reasons for using biopolymers in photocatalysis. Finally, the summary and conclusion are presented along with existing challenges in this research area.

Development of Bio-Composites with Enhanced Antioxidant Activity Based on Poly(lactic acid) with Thymol, Carvacrol, Limonene, or Cinnamaldehyde for Active Food Packaging.

The new trend in food packaging films is to use biodegradable or bio-based polymers, such as poly(lactic acid), PLA with additives such as thymol, carvacrol, limonene or cinnamaldehyde coming from natural resources (i.e., thyme, oregano, citrus fruits and cinnamon) in order to extent foodstuff shelf-life and improve consumers' safety. Single, triple and quadruple blends of these active compounds in PLA were prepared and studied using the solvent-casting technique. The successful incorporation of the active ingredients into the polymer matrix was verified by FTIR spectroscopy. XRD and DSC data revealed that the crystallinity of PLA was not significantly affected. However, the Tg of the polymer decreased, verifying the plasticization effect of all additives. Multicomponent mixtures resulted in more intense plasticization. Cinnamaldehyde was found to play a catalytic role in the thermal degradation of PLA shifting curves to slightly lower temperatures. Release of thymol or carvacrol from the composites takes place at low rates at temperatures below 100 °C. A combined diffusion-model was found to simulate the experimental release profiles very well. Higher antioxidant activity was noticed when carvacrol was added, followed by thymol and then cinnamaldehyde and limonene. From the triple-component composites, higher antioxidant activity measured in the materials with thymol, carvacrol and cinnamaldehyde.

Highly efficient porous sorbent derived from asphalt for the solid-phase extraction of polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are generated primarily during the incomplete combustion of organic matter and are ubiquitous environmental pollutants. For the first time, in this study, a mesoporous carbon derived from asphalt with high surface area (2300 m²g-1 with an average of 1.2 cm³ g-1) was utilized as a sorbent for the solid-phase extraction (SPE) of several PAHs in tap water samples. The factors influencing the extraction capability of the new material were investigated and the optimum conditions were determined to be as follows: Sample volume - 200 mL, no adjustment of sample pH, and sorbent amount - 50 mg. Under the most favorable SPE conditions, with gas chromatography-mass spectrometric analysis, the method exhibited a linear range of 0.5-50 µgL-1 with limits of detection between 0.004 and 0.026 µgL-1. The recoveries obtained from spiked tap water samples spiked at 1 µgL-1 and 5 µgL-1, were in the range 86.7-98.2% with relative standard deviations of <9%. The method was also applied to tap water samples collected from the local environment. The concentrations of PAHs detected ranged between 0.13 and 48 µgL-1. The reusability of the sorbent was tested with five consecutive SPE extraction, and no carryover of analytes was observed.

Household solid fuel burning emission characterization and activity levels in India.

Emission factors (EFs) of PM2.5, carbon fractions, major ionic (K+, Ca2+, NH4+, SO42-, NO3- and Cl-) and elemental (Al, Cr, Cu and Fe) species from combustion of commonly used household solid fuel were determined in 10 different states in India during cooking practices. The study involved sampling during actual household cooking involving use of a variety of fuels including coal balls (CB), fuel wood (FW), dung cakes (DC), crop residues (CR), mixed fuels (MF: dung cakes + fuel woods). Species-wise highest EFs (g·kg-1) were: 34.16 ±â€¯10.1 for PM2.5 (CB), 14.18 ±â€¯5.8 for OC (CB), 2.33 ±â€¯1.4 for EC (DC), 1.03 ±â€¯0.2 for K+ (CR), 2.21 ±â€¯0.6 NH4+ (DC), 0.61 ±â€¯0.2 for NO3- (CB), 0.59 ±â€¯0.1 for SO42- (CB), 0.69 ±â€¯0.1 for Cl- (CR) among the fuels. Higher OC EFs for CB could be attributed to higher moisture content (>13%) in coal-powder that is used to handmade coal balls. It is observed that, in general, OC3 and EC1 were the dominant thermally evolved carbon mass fractions. The study averaged MCE values were in the range 0.93-0.98, which could be attributed to higher variability in flaming and smoldering episodes during the combustion of selected fuels. Sum of ionic EFs for emissions from DC, CR and MF were found to be higher than those observed for FW and CB. The K+/EC and Cl-/EC (~1) ratios could be better indicators of CR fuels to differentiate it from FW, whereas NH4+/EC (~1) is suitable to indicate DC. Average annual emission estimates of PM2.5 (2.00 ±â€¯0.53 Tg·yr-1), OC (0.86 ±â€¯0.23 Tg·yr-1) and EC (0.11 ±â€¯0.02 Tg·yr-1) for tested fuels are evaluated to be contributing 27, 15 and 4% of total PM2.5, OC and EC, respectively, toward annual emission budget from different anthropogenic activities in India.

Conversion of hazardous plastic wastes into useful chemical products.

Azoisobutylnitrile (AIBN) initiator was used in the treatment of most widely used domestic plastics in lieu of catalysts. The pyrolysis of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), poly-ethylene terephthalate (PET) and polystyrene (PS) plastics with azoisobutylnitrile was carried out individually under nitrogen atmosphere. A series of single (plastic/AIBN) and binary (mixed plastics/AIBN) reactions were carried out in a 25-cm(3) micro-autoclave reactor. The optimum conditions selected for this study were: 5% AIBN by weight of total plastics, 60 min, 650 psi and 420 degrees C. It was found that HDPE, LDPE, PP underwent to a maximum cracking and produced highest amounts of liquid and gaseous products. Pyrolysis of PET and PS plastics with AIBN afforded comparatively significant amount of insoluble organic materials. In other reactions, fixed ratios of mixed plastics were pyrolyzed with AIBN that afforded excellent yields of liquid hydrocarbons. This result shows a very significant increase in the liquid portions of the products on using AIBN in the pyrolysis of plastics. The use of AIBN in the pyrolysis of plastics is seems to be feasible and an environmental friendly alternative to catalytic process for maximizing the liquid fuels or chemical feed stocks in higher amounts.