Evaluation of SnO2 for sunlight photocatalytic decontamination of water.

The broad bandgap tin (IV) oxide (SnO2) is the least investigated semiconductor material for photocatalytic water decontamination in sunlight exposure. A detailed study covering the synthesis, characterization and the evaluation of photocatalytic activity of SnO2, in the natural sunlight exposure, is presented. The structural characterization by XRD revealed the formation of phase pure tetragonal SnO2 with the average crystallite size of ∼41.5 nm whereas minor Sn2+ states in the material were identified by XPS analysis. As explored by diffuse reflectance (DR) and photoluminescence (PL) spectroscopy, the material exhibited a distinct absorption edge at ∼3.4 eV. The morphological and microstructure analysis of the synthesized SnO2 was carried out by FESEM and HRTEM. The electrochemical impedance spectroscopy (EIS) and chronopotentiometry (CP) predicted the better charge transport and retention ability of the material under illumination whereas the Mott-Schottky extrapolation prophesied the n-type behavior with the flat-band potential of -0.60 V. The photocatalytic activity of SnO2 was assessed in the exposure of complete spectrum natural sunlight for the removal of 2,4,6-trichlorophenol. The HPLC and TOC analysis monitored the progress of degradation and mineralization whereas the released chloride ions were evaluated by ion chromatography. The effect of the transition metal ions (Fe3+, Cu2+, Ni2+, and Zn2+) as electron capture agents and H2O2 as ROS generator was explored during the degradation process. The utility of the material for the simultaneous removal of chlorophenols in the mixture was also investigated. The SnO2 exhibited sustained activity in the repeated use. Based on experimental evidence congregated, the mechanism of the removal process and the efficacy of SnO2 for sunlight photocatalytic decontamination of water was established.

Photocatalytic removal of imidacloprid containing frequently applied insecticide in agriculture industry using Co3O4 modified MoO3 composites.

Water pollution caused by the frequent utilization of pesticides in the agriculture industry is one of the major environmental concerns that require proper attention. In this context, the photocatalytic removal of pesticides from contaminated water in the presence of metallic oxide photocatalysts is quite in approach. In the present study, Orthorhombic MoO3 has been modified with varying amount of cobalt oxide through wet impregnation for the removal of imidacloprid and imidacloprid-containing commercially available insecticide. The solid-state absorption response and band gap evaluation of synthesized composites revealed a significant extension of absorption cross-section and absorption edge in the visible region of the light spectrum than pristine MoO3. The indirect band gap energy varied from ∼2.88 eV (MoO3) to ∼2.15 eV (10% Co3O4-MoO3). The role of Co3O4 in minimizing the photo-excitons' recombination in MoO3 was studied using photoluminescence spectroscopy. The orthorhombic shape of MoO3 was confirmed through X-ray diffraction analysis and scanning electron microscopy. Moreover, the presence of distinct absorption edges and diffraction peaks corresponding to Co3O4 and MoO3 in absorption spectra and XRD patterns, respectively verified the composite nature of 10% Co3O4-MoO3. The photocatalytic study under natural sunlight irradiation showed higher photocatalytic removal (∼98%) of imidacloprid with relatively higher rate by 10% Co3O4-MoO3 composite among all contestants. Furthermore, the photocatalytic removal (∼93%) of commercially applied insecticide, i.e., Greeda was also explored.

Transition metal doped CeO2 for photocatalytic removal of 2-chlorophenol in the exposure of indoor white light and antifungal activity.

Besides natural sunlight and expensive artificial lights, economical indoor white light can play a significant role in activating a catalyst for photocatalytic removal of organic toxins from contaminated water. In the current effort, CeO2 has been modified with Ni, Cu, and Fe through doping methodology to study the removal of 2-chlorophenol (2-CP) in the illumination of 70 W indoor LED white light. The absence of additional diffractions due to the dopants and few changes such as reduction in peaks' height, minor peak shift at 2θ (28.525°) and peaks' broadening in XRD patterns of modified CeO2 verifies the successful doping of CeO2. The solid-state absorption spectra revealed higher absorbance of Cu-doped CeO2 whereas a lower absorption response was observed for Ni-doped CeO2. An interesting observation regarding the lowering of indirect bandgap energy of Fe-doped CeO2 (∼2.7 eV) and an increase in Ni-doped CeO2 (∼3.0 eV) in comparison to pristine CeO2 (∼2.9 eV) was noticed. The process of e -- h + recombination in the synthesized photocatalysts was also investigated through photoluminescence spectroscopy. The photocatalytic studies revealed the greater photocatalytic activity of Fe-doped CeO2 with a higher rate (∼3.9 × 10-3 min-1) among all other materials. Moreover, kinetic studies also revealed the validation of the Langmuir-Hinshelwood kinetic model (R2 = 0.9839) while removing 2-CP in the exposure of indoor light with a Fe-doped CeO2 photocatalyst. The XPS analysis revealed the existence of Fe3+, Cu2+ and Ni2+ core levels in doped CeO2. Using the agar well-diffusion method, the antifungal activity was assessed against the fungus M. fructicola and F. oxysporum. Compared to CeO2, Ni-doped CeO2, and Cu-doped CeO2 nanoparticles, the Fe-doped CeO2 nanoparticles have outstanding antifungal properties.

The efficacy of Co3O4 loaded WO3 sheets for the enhanced photocatalytic removal of 2,4,6-trichlorophenol in natural sunlight exposure.

Owing to the promising photocatalytic performance, the sheet-like WO3 was modified by depositing nanostructured Co3O4 at the surface. The appearance of the varying dual absorption edges in the optical analysis exposed the composite nature of the synthesized materials. The structural analysis revealed the deposition of Co3O4 particles at the surface without altering the lattice of WO3 however, during the processing the cracking of disc was also evidenced. The FESEM and HRTEM analysis corroborated the uniform surface dispersion of Co3O4 nanoparticles. The co-existence of 2+ and 3+ oxidation states of Co in the deposited Co3O4 was examined by XPS analysis. The efficient trapping of excitons by Co3O4 surface entities was witnessed in the emission measurements whereas the same was authenticated by the photo-electrochemical chronopotentiometry. The Co3O4 loaded sheets exhibited substantially enhanced activity for the removal of 2,4,6-trichlorophenol as compared to pure WO3 in the complete spectrum and visible region of natural sunlight exposure. The progress of the degradation process was monitored by HPLC whereas the degradation products were identified by GC-MS. The measurement and identification of the ion released during the photocatalytic process facilitated the estimation of the probable route and role of reactive oxygen species involved in the removal process. Although, the careful analysis of the findings from the analytical tools revealed the major involvement of hydroxyl radicals however, the role of superoxide anions was also exposed. An alternative mechanism of the generation of the superoxide radical involving the 2+ and 3+ oxidation states of Co was also proposed. The effect of the pH and the added concentration of H2O2 on the ease of removal process was also investigated.

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).

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.