Sulfur enriched slow-release coated urea produced from inverse vulcanized copolymer.

Slow-release fertilizers are developed to enhance the nutrient use efficiency (NUE), by coating urea with less water soluble or hydrophobic material. Diverse range of materials have been utilized to coat urea, however, their inherit non-biodegradability, hydrophilicity, crystallinity, and high synthesis cost limits their scalability. Herein, we reported the preparation of a novel slow-release sulfur enriched urea fertilizers using sustainable hydrophobic, biodegradable, crosslinked copolymer made from sulfur and rubber seed oil (Poly(S-RSO)) through the use of dip coating method. Scanning electron microscopy (SEM) was employed to study the fertilizers morphology and estimate the coating film thickness. A nitrogen release test was carried out in distilled water, which revealed that the coated fertilizers with a coating thickness of 165 µm, 254 µm and 264 µm released only 65 % of its total nutrient content after 2, 19 and 43 days of incubation, respectively: hence, showing an excellent slow-release property. In soil, fertilizer with 264 µm coating thickness released only 17 % nitrogen after 20 days of incubation, in line with the European standard (EN 13266, 2001). The release kinetic data best fits the Ritger-Peppas model with a R2 value of 0.99 and the n value of 0.65 indicated the release was mainly due to diffusion. Submerged cultivation (SmC) demonstrated the potential of poly(S-RSO) to enhance sulfur oxidation; it was observed that the copolymer oxidation was 50 % greater than that of elemental sulfur. A comparison between the newly developed fertilizers and existing coated fertilizers was also presented. On the whole, the results demonstrated outstanding slow-release characteristics and improved sulfur oxidation.

Ionic Liquid and Tween-80 Mixture as an Effective Dispersant for Oil Spills: Toxicity, Biodegradability, and Optimization.

Chemical dispersants are used extensively for oil spill remediation. Most of these dispersants are composed of a mixture of surfactants and organic solvents, which raises concerns about aquatic toxicity and environmental impact. In this study, the toxicity and biodegradability of an oil spill dispersant composed of the surface-active ionic liquid 1-butyl-3-methylimidazolium lauroyl sarcosinate [Bmim][Lausar] and Tween-80 were investigated. In addition, important environmental factors including salinity, temperature, and wave-mixing energy were optimized to obtain maximum dispersion effectiveness. The acute toxicity against zebrafish (Danio rerio) showed that the developed dispersant was practically non-toxic with a median lethal dose of more than 100 mg L-1 after 96 h. The dispersant also demonstrated outstanding biodegradability of 66% after 28 days. A model was developed using a response surface methodology that efficiently (R 2 = 0.992) related the salinity, temperature, and wave-mixing energy of seawater to dispersion effectiveness. The system was then optimized, and a high dispersion effectiveness of 89.70% was obtained with an experimental error of less than 2%. Our findings suggest that the surface-active ionic liquid and Tween-80 mixture could be a viable alternative to toxic chemical dispersants for oil spill remediation.

Crosslinked chitosan/poly(vinyl alcohol) nanofibers functionalized by ionic liquid for heavy metal ions removal.

Nanostructure adsorbents namely nanofibers have been demonstrated to have a high adsorption rate and are efficient to treat wastewater. Herein, chitosan/poly(vinyl alcohol) (PVA) blend nanofiber membranes prepared by electrospinning method were crosslinked using glutaraldehyde and functionalized with 1-allyl-3-methylimidazolium chloride to be used as a potential bio-sorbent for heavy metal ions removal. The chitosan was first hydrolyzed before electrospinning with PVA, followed by crosslinking and further functionalized by ionic liquid to overcome the limitation of chitosan which has low adsorption capacity and unsuitable physical properties for the adsorption process. The morphology and the chemical bond formed were investigated by using field emission scanning electron microscopy with energy dispersive x-ray spectroscopy (FESEM-EDX) and Fourier transform infrared (FTIR) showing that the hydrolyzed chitosan/PVA nanofiber membranes were successfully crosslinked and functionalized. The synthesized adsorbent was evaluated in pure heavy metal ions solutions namely Pb(II), Mn(II), and Cu(II) and shown best performance for Pb(II) ions. The highest adsorption capacity recorded for Pb(II) ions was 166.34 mg/g and are well fitted to the Freundlich isotherm model and pseudo-second-order kinetic model to describe the adsorption equilibrium and kinetic rate of the Pb(II) uptake, respectively. The synthesized adsorbent clearly shows a great capability to remove Pb(II) ions.

Effects of nitrogen/bismuth-doping on the photocatalyst composite of carbon dots/titanium dioxide nanoparticles (CDs/TNP) for enhanced visible light-driven removal of diclofenac.

The present work demonstrates the coupling of titanium dioxide, TiO2 nanoparticles (TNP) with N-doped, Bi-doped, and N-Bi co-doped rice husk-derived carbon dots (CDs) via a facile dispersion method, forming respective photocatalyst composites of CDs/TNP, N-CDs/TNP, Bi-CDs/TNP and N-Bi-CDs/TNP. Characterization analyzes verified the successful incorporation of respective CDs samples into TNP, forming photocatalyst composite with narrowed band gap and quenched photoluminescence intensity. Photocatalytic activity of TNP and the respective composites was investigated for photodegradation of diclofenac (DCF) under both simulated sunlight and natural sunlight irradiation. The as-prepared N-Bi-CDs/TNP composite showed the best photocatalytic performance among all composites, able to completely degrade 5 ppm of DCF within 60 min and 180 min under both types of visible light irradiation, respectively. The N-Bi-CDs/TNP composite also showed a TOC removal efficiency up to 87.63%. N-Bi-CDs, worked as photosensitizer and electron reservoir, contributed to the outstanding photocatalytic activity of N-Bi-CDs/TNP, whereby the recombination was prolonged and light absorption was shifted towards the visible light region. Furthermore, the composite of N-Bi-CDs/TNP also demonstrated good stability and reusability over repeated degradation cycles. The photodegradation of DCF resulted into several intermediates, which were identified from LC-MS analysis. The present work could provide an insight on the application of heteroatoms doped and co-doped carbon dots in semiconductor oxide as high performance photocatalysts.

Elucidation of the Roles of Ionic Liquid in CO2 Electrochemical Reduction to Value-Added Chemicals and Fuels.

The electrochemical reduction of carbon dioxide (CO2ER) is amongst one the most promising technologies to reduce greenhouse gas emissions since carbon dioxide (CO2) can be converted to value-added products. Moreover, the possibility of using a renewable source of energy makes this process environmentally compelling. CO2ER in ionic liquids (ILs) has recently attracted attention due to its unique properties in reducing overpotential and raising faradaic efficiency. The current literature on CO2ER mainly reports on the effect of structures, physical and chemical interactions, acidity, and the electrode-electrolyte interface region on the reaction mechanism. However, in this work, new insights are presented for the CO2ER reaction mechanism that are based on the molecular interactions of the ILs and their physicochemical properties. This new insight will open possibilities for the utilization of new types of ionic liquids. Additionally, the roles of anions, cations, and the electrodes in the CO2ER reactions are also reviewed.

Rapid esterification of fatty acid using dicationic acidic ionic liquid catalyst via ultrasonic-assisted method.

Biodiesel production via esterification/transesterification reactions can be catalyzed by homogenous or heterogeneous catalysts. Development of heterogeneous catalysts for biodiesel production is highly advantageous due to the ease of product purification and of catalyst recyclability. In this current work, a novel acidic [DABCODBS][CF3SO3]2 dicationic ionic liquid (DIL) was used as heterogeneous catalyst to produce biodiesel using oleic acid as model oil. The esterification was conducted under ultrasonic irradiation (20 kHz) using a 14 mm ultrasonic horn transducer operated at various duty cycles. It was observed that the duty cycle, amplitude, methanol to oil molar ratio, catalyst amount and reaction temperature were the major factors that greatly impact the necessary reaction time to lead to a high yield of biodiesel. The reaction conditions were optimized with the aid of Response Surface Methodology (RSM) designed according to the Quadratic model of the Box Behnken method. The optimum conditions were found to be at catalyst amount of 0.64 mol%, methanol to oil ratio of 14.3:1, temperature of 59 °C, reaction time of 83 min and amplitude of 60% in continuous mode. The results showed that the oleic acid was successfully converted into esters with conversion value of 93.20% together with significant reduction of reaction time from 7 h (using mechanical stirring) to 83 min (using ultrasonication). The results also showed that the acidic DIL catalyst we designed purposely was efficient to catalyze the ultrasonic-assisted esterification yielding high conversion of oleic acid to methyl oleate on short times. The DIL was also recycled and reused for at least five times without significant reduction in performance. Overall, the procedureoffersadvantages including short reaction time, good yield, operational simplicity and environmentally benign characteristics.

Electrodeposited ZnO nanowires as photoelectrodes in solid-state organic dye-sensitized solar cells.

A new approach for developing solid-state dye-sensitised solar cells (DSSCs) on glass/ITO and plastic substrates (PEN/ITO) is presented in this manuscript. A two step electrodeposition technique has been employed to realize the ZnO photoelectrodes. First a ZnO thin film is deposited on the ITO substrate and subsequently on this buffer layer 650 nm long ZnO nanowires are grown. The different nanostructured electrodes are crystallized and show a transparency close to 80% in the visible spectral range. The electrodes are then sensitized with a new purely organic dye, whose synthesis is presented here, which reveals a wide absorption spectrum and a high molar extinction coefficient. Finally, the sensitized electrodes were employed for the fabrication of liquid and solid-state DSSCs, using, respectively, a liquid iodine/iodide electrolyte and the spiro-OMeTAD hole transporter. These devices represent the first solid-state DSSCs fabricated using electrodeposited zinc oxide nanowires. Their power conversion efficiency is still limited, respectively, 0.18% and 0.03% under standard AM 1.5G sunlight (100 mW cm(-2)), nevertheless, these results prove the interest in this low-temperature deposition method for the realization of nanostructured electrodes on rigid and flexible substrates, and open up new perspectives for the development of solid state DSSCs on plastic substrates.