Iqbal M.I. Ismail

XPS study of lithium surface after contact with lithium-salt doped polymer electrolytes

Abstract X-ray photoelectron spectroscopy (XPS) is used to probe the surface layer and element composition of Li-metal electrodes before and after contact with polymer electrolytes containing LiN(SO 2 CF 3 ) 2 (LiTFSI) or LiBF 4 . Native film on as-received metallic lithium was composed of Li 2 CO 3 /LiOH in the outer layer and Li 2 O in the inner layer. LiF was formed during lithium contact with electrolyte due to reaction between the native film and impurities in the electrolyte. The polymer electrolyte containing LiTFSI yielded a very thin film with limited porosity in the inner layers, which was reflected in the limited amplitude dependence of complex impedance spectra. LiBF 4 mixed with polymer resulted in a thicker film with high porosity, as was postulated from the greater influence of the amplitude of the oscillation level.

Morphology controlled bulk synthesis of disc-shaped WO3 powder and evaluation of its photocatalytic activity for the degradation of phenols

The surfactant assisted synthesis of disc-shaped WO3 powder and its photocatalytic performance in sunlight exposure is reported. UV-vis DRS, XRD and FESEM characterized the synthesized WO3. The synthesized powder exhibited a bandgap of ∼2.55eV with cubic lattice and high crystallinity. The photocatalytic activity of the synthesized WO3 was examined for the degradation of phenol, resorcinol, 2-chlorophenol and 2-nitrophenol in complete spectrum and visible segment of sunlight. The highly efficient degradation/mineralization of 2-chloro and 2-nitrophenol compared to that of phenol and resorcinol, under identical experimental conditions, suggested the regulatory role of substituents attached to the aromatic ring in degradation/mineralization process. The time-scale HPLC degradation profiles, identification of intermediates by GC-MS and removal of organic carbon during the course of reaction were utilized to approximate the possible route of degradation/mineralization of phenolic substrates. The measurement of the anions released during the photocatalytic process was used to identify the nature of the major oxidants (O2(•-), OH(•)) and the possible interaction sites. A significant decrease in the photocatalytic activity of synthesized WO3, ∼50%, was observed in visible portion of sunlight however, a sustained activity was observed in the repeated exposures.

Synthesis, Characterization, and Sunlight Mediated Photocatalytic Activity of CuO Coated ZnO for the Removal of Nitrophenols

CuO@ZnO core-shell catalysts, coated by varying the CuO layer density ranging from 0.5% to 10%, were synthesized with the aim to enhance the photocatalytic activity of ZnO in sunlight and control its photocorrosion. Initially, the Cu(2+) ions were impregnated on presynthesized ZnO by wet impregnation and finally converted to CuO layers by calcination. The optical and structural characterization of the synthesized powders was performed by DRS, PL, Raman spectroscopy, and XRD analysis, respectively. The homogeneity of the coated layers was explored by FESEM. The photocatalytic activity of CuO coated ZnO was investigated for the degradation of mononitrophenols (2-, 3-, and 4-nitrophenol) and dinitrophenols (2,4-, 2,5-, and 2,6-dinitrophenol) in the exposure of the complete spectrum and visible region (420-800 nm) of sunlight. The effect of the increasing density coated layers of CuO on photocatalytic activity was evaluated for the degradation of 4-NP. Compared to pristine ZnO, a substantial increase in the degradation/mineralization ability was observable for the catalysts coated with 0.5% and 1% CuO, whereas a detrimental effect was noticed for higher coating density. Prior to photocatalytic studies, as evaluated by cyclic voltammetry (CV), compared to pure ZnO, a significant suppression of photocorrosion was noticed, under illumination, for catalysts coated with lower CuO coating. The progress of the photocatalytic degradation process was monitored by HPLC while the mineralization ability of the synthesized catalysts was estimated by TOC. The estimation of the released ions and their further interaction with the excited states and the reactive oxygen was monitored by ion chromatography (IC).

Synthesis and characterization of ZnO-TiO2 nanocomposites and their application as photocatalysts

Nanocomposite ZnO-TiO2 powders of varying ZnO/TiO2 molar ratios have been prepared from their salt/compound by heating at 600°C and 900°C and characterized using scanning electron microscope and X-ray diffraction techniques. The nanosized powders can decolorize/degrade brilliant golden yellow (BGY), an azo dye extensively used in textile industries, in water under solar irradiation. The effects of various parameters such as photocatalyst loading, molar ratio of ZnO/TiO2, pH of the solution, initial dye concentration, and irradiation time on the photodecolorization have been investigated. ZnO-TiO2 nanocomposite (6 g/L) in the molar ratio of 1:1 or 3:1, prepared at 900°C, can efficiently decolorize about 98% of 20 mg/L BGY at pH of about 7 by 2-h illumination in sunlight. The initial dye decolorization follows pseudo-first-order kinetics. Finally, trial experiments were done using real textile wastewater to find out the effectiveness of the photocatalysts to a more complex system.

Bacteria and fungi can contribute to nutrients bioavailability and aggregate formation in degraded soils

Intensive agricultural practices and cultivation of exhaustive crops has deteriorated soil fertility and its quality in agroecosystems. According to an estimate, such practices will convert 30% of the total world cultivated soil into degraded land by 2020. Soil structure and fertility loss are one of the main causes of soil degradation. They are also considered as a major threat to crop production and food security for future generations. Implementing safe and environmental friendly technology would be viable solution for achieving sustainable restoration of degraded soils. Bacterial and fungal inocula have a potential to reinstate the fertility of degraded land through various processes. These microorganisms increase the nutrient bioavailability through nitrogen fixation and mobilization of key nutrients (phosphorus, potassium and iron) to the crop plants while remediate soil structure by improving its aggregation and stability. Success rate of such inocula under field conditions depends on their antagonistic or synergistic interaction with indigenous microbes or their inoculation with organic fertilizers. Co-inoculation of bacteria and fungi with or without organic fertilizer are more beneficial for reinstating the soil fertility and organic matter content than single inoculum. Such factors are of great importance when considering bacteria and fungi inocula for restoration of degraded soils. The overview of presented mechanisms and interactions will help agriculturists in planning sustainable management strategy for reinstating the fertility of degraded soil and assist them in reducing the negative impact of artificial fertilizers on our environment.

Enhanced photocatalytic activity of V2O5–ZnO composites for the mineralization of nitrophenols

In an effort to enhance the photocatalytic activity of ZnO in natural sunlight, V2O5-ZnO nanocomposites were synthesized by co-precipitation technique. The characterization of the synthesized powders by FESEM, XRD and UV-visible diffuse reflectance spectroscopy (DRS) revealed that the both V2O5 and ZnO retain their individual identity in the composites but the increasing concentration of V2O5 affect the particle size of ZnO. As estimated by photoluminescence spectroscopy, in comparison to pure ZnO, the presence of V2O5 significantly suppressed the charge carriers recombination process. The photocatalytic activity of the synthesized powders was evaluated for the degradation/mineralization of three potential nitrophenol pollutants (2-nitrophenol, 4-nitrophenol, and 2,4-dinitrophenol). The synthesized composites showed significantly higher activity for both degradation and mineralization of nitrophenols compared to pure ZnO. The progress of the degradation process was evaluated by HPLC while mineralization was monitored by TOC analysis. The degradation/mineralization route was estimated by identifying the intermediates using GC-MS. The correlation of the experimental data revealed that the position of NO2 group in 2- and 4-nitrophenol significantly affect the rate of degradation. The identification of hydroxyl group containing intermediates in the degradation of 4-NP confirmed the formation and vital role of hydroxyl radicals in degradation process. The rapid mineralization of nitrophenol substrates pointed out superoxide anions as major contributors in degradation and mineralization process. The assessment of the release of relevant ions (NO2(-), NO3(-), ONOO(-) and NH4(+)) during the degradation process assisted in identifying the plausible interaction sites.

Evaluation of sunlight induced structural changes and their effect on the photocatalytic activity of V2O5 for the degradation of phenols

Despite knowing the fact that vanadium pentoxide is slightly soluble in aqueous medium, its photocatalytic activity was evaluated for the degradation of phenol and its derivatives (2-hydroxyphenol, 2-chlorophenol, 2-aminophenol and 2-nitrophenol) in natural sunlight exposure. The prime objective of the study was to differentiate between the homogeneous and heterogeneous photocatalysis incurred by dissolved and undissolved V2O5 in natural sunlight exposure. V2O5 was synthesized by chemical precipitation procedure using Triton X-100 as morphology mediator and characterized by DRS, PLS, Raman, FESEM and XRD. A lower solubility of ∼ 5% per 100ml of water at 23 °C was observed after calcination at 600 °C. The study revealed no contribution of the dissolved V2O5 in the photocatalytic process. In sunlight exposure, V2O5 powder exhibited substantial activity for the degradation, however, a low mineralization of phenolic substrates was observed. The initial low activity of V2O5 followed by a sharp increase both in degradation and mineralization in complete spectrum sunlight exposure, was further investigated that revealed the decrease in the bandgap and the reduction in the particle size with the interaction of UV photons (<420 nm) as this effect was not observable in the exposure of visible region of sunlight. The role of the chemically different substituents attached to an aromatic ring at 2-positions and the secondary interaction of released ions during the degradation process with the reactive oxygen species (ROS) was also explored.

The suitability of Ce3+-modified ZnO photocatalyst for the mineralization of monochlorophenol isomers in sunlight exposure

The photocatalytic activity of Ce3+-modified hexagonal ZnO for the degradation/mineralization of monochlorophenol isomers (2-chlorophenol, 3-chlorophenol and 4-chlorophenol), in natural sunlight exposure, is reported. Compared to bare ZnO, the modified catalysts showed superior activity for the mineralization of MCP isomers. The identification of the intermediates disclosed that the mode of degradation of chlorophenol substrates also varies with increased Ce3+ loading. Increased mineralization was discovered with increasing concentration of Ce3+ at the surface of ZnO. The correlation of the results obtained by various analytical tools revealed that the photocatalytic removal of MCP isomers initially proceeds with the cleavage of the aromatic ring, the release of chloride ions and the formation of oxygenated intermediates. Finally, the intermediates are oxidized further by the oxidizing species to mineralization. The efficacy of the synthesized catalysts was tested for the mixture of chlorophenol isomers. Based on the intermediates formed, the major contribution of superoxide anion radicals was evidenced in the removal process. The Ce3+ impregnation protected the surface of ZnO against photocorrosion.

Enhanced photocatalytic hydrogen generation of mesoporous rutile TiO2 single crystal with wholly exposed {111} facets

Abstract The development of semiconductor photocatalysts with highly reactive facets exposed has great potential to improve their photocatalytic reactivity. We report the synthesis of mesoporous rutile TiO 2 single crystals with tunable ratios of {110} and {111} facets through the seeded-template hydrothermal method. With increasing the amount of morphology controlling agent NaF, the facet ratio of {111} to {110} increases, and eventually the mesoporous rutile TiO 2 single crystals with wholly exposed {111} reactive facets are obtained. The resultant faceted mesoporous single crystals exhibit a superior photocatalytic performance of hydrogen evolution to mesoporous single crystals with a large percentage of thermodynamically stable {110} facets, as well as the solid rutile single crystals.

The suitability of ZnO film-coated glassy carbon electrode for the sensitive detection of 4-nitrophenol in aqueous medium

The performance of a ZnO nanoparticle-based electrochemical sensor, fabricated by different treatments of ZnO on glassy carbon electrode, was evaluated for the determination of 4-nitrophenol (4-NP) in aqueous medium. The sensing performance of ZnO film-coated GCE (ZnO/F/GCE) was compared with a variety of electrodes, which included GCEs modified with ZnO powder, RGO (reduced graphene oxide), and RGO-Nafion® composite. Among the fabricated electrodes, the ZnO film-coated electrode, prepared by dispersing the well-sonicated chloroform suspension of ZnO on the GCE, showed excellent response toward the sensitive detection of 4-NP in aqueous medium, and a significant enhancement in the reduction peak current predicted the suitability of the developed sensor. Square wave voltammetry (SWV) detection mode was applied for the determination of 4-NP. The reproducibility and accuracy of ZnO/F/GCE were evaluated in the linear concentration ranges of 0.035 μM to 1.4 μM and 2.1 μM to 6.3 μM. Appreciably low SWV detection limits of 0.008 μM and 0.02 μM were estimated. Minimal influence was observed from the interfering species, added into the sample solution, on the determination of 4-NP. The performance of the developed electrode was initially optimized for 4-NP samples prepared in-house and finally tested against two real samples collected from municipality wastewater. The recovery of the ZnO/F/GCE varied from 96.8% to 105.7%.