Fabrication of samarium doped MOF-808 as an efficient photocatalyst for the removal of the drug cefaclor from water.

MOFs are emerging photocatalysts designed by tuning organic ligands and metal centers for optimal efficiency. In this study, a samarium decorated MOF-808(Ce) metal organic framework was fabricated by facile hydrothermal synthesis. The synthesized samarium decorated MOF-808(Ce) was characterized by using analytical techniques such as SEM, EDX, XRD and TGA to study its morphological, thermal and structural properties. SEM images showed that MOF-808(Ce) comprised of truncated octahedrons. The morphology of the material was changed upon Sm incorporation. Sm/MOF-808(Ce) exhibited better UV-vis light absorption properties than MOF-808(Ce) as evidenced by its slightly higher band gap value. This material was exploited for the degradation of the drug cefaclor from water. Cefaclor removal followed double a first order in parallel model (DFOP). Under UV light, 97.7% of the cefaclor was removed in only 20 minutes and after 60 minutes this removal efficiency was increased to 99.25%. These features exhibited that samarium decorated MOF has immense potential for the photocatalytic degradation of cefaclor as it generates e- and h+ to enhance the photocatalytic efficiency and it is a promising candidate to treat wastewater without formation of harmful byproducts.

Fabrication and characterization of g-C3N4 supported Cu-single atom catalysts for the photocatalytic degradation of dyes.

Methylene blue and Congo red are widely used organic dyes in biomedical laboratories and textile industries. The abundant use of these dyes has led to their emission in wastewaters, which causes major health hazards to exposed populations. Therefore, it is necessary to properly treat the dye effluents before being discharged into the water bodies. The present study presents Cu-g-C3N4 as an efficient and cost-effective catalyst for the photocatalytic degradation of these dyes. The single-atom catalyst was prepared by a simple co-precipitation method and the composition, structure, morphologies, and electronic state were determined by FT-IR SEM, XRD, XPS, PL, and TGA analyses. The photocatalytic activity of the catalyst was studied by optimizing various parameters i.e. concentration of dye, time, catalyst dose, and pH under UV irradiation and dark conditions. The results evidenced that Cu-g-C3N4 is an excellent catalyst as it achieved 100% degradation of the methylene blue and Congo red dyes in only 5 and 30 minutes respectively. The kinetics of photocatalytic degradation revealed that the half-life of methylene blue and Congo red was reduced significantly. The stability of the catalyst was determined by using it for five consecutive cycles and the results proved that Cu-g-C3N4 is a highly stable catalyst. Thus, Cu-g-C3N4 proved itself to be a highly active, stable, and cost-effective catalyst for the degradation of dyes with minimum resources. This material is also believed to have great potential to degrade other environmental pollutants too.

Photocatalytic degradation of imidacloprid using Ag2O/CuO composites.

Imidacloprid is one of the most commonly used neonicotinoid pesticides that has been identified as a neurotoxin for various non-target organisms. It binds to the central nervous system of organisms, causing paralysis and eventually death. Thus, it is imperative to treat waterwaters contaminated with imidacloprid using an efficient and cost effective method. The present study presents Ag2O/CuO composites as excellent catalysts for the photocatalytic degradation of imidacloprid. The Ag2O/CuO composites were prepared in different compositions by adopting the co-precipitation method and used as a catalyst for the degradation of imidacloprid. The degradation process was monitored using UV-vis spectroscopy. The composition, structure, and morphologies of the composites were determined by FT-IR, XRD, TGA, and SEM analyses. The effect of different parameters i.e time, concentration of pesticide, concentration of catalyst, pH, and temperature on the degradation was studied under UV irradiation and dark conditions. The results of the study evidenced the 92.3% degradation of imidacloprid in only 180 minutes, which was 19.25 hours under natural conditions. The degradation followed first-order kinetics, with the half life of the pesticide being 3.7 hours. Thus, the Ag2O/CuO composite was an excellent cost-effective catalyst. The non-toxic nature of the material adds further benefits to its use. The stability of the catalyst and its reusability for consecutive cycles make it more cost effective. The use of this material may help to ensure an immidacloprid free environment with minimal use of resources. Moreover, the potential of this material to degrade other environmental pollutants may also be explored.

Development of highly permselective Mixed Matrix Membranes comprising of polyimide and Ln-MOF for CO2 capture.

Mixed Matrix Membranes (MMMs) with hybrid organic-inorganic characteristics offer a strong alternative to traditional polymer-based membranes to reduce the trade-off between gas permeability and selectivity. This work incorporated lanthanum-Metal Organic Frameworks in the Matrimid to fabricate MMMs. To understand the effects of nano-filler on membranes' morphology, porosity, thermal stability, and chemical composition, MMMs were fabricated with three different loadings of nano-filler, i.e., 10, 20 and 30 wt%. The selectivity and permeability of CH4, CO2, and N2 gases through MMMs were investigated at 10 bar pressure and temperatures ranging from 25 to 55 °C. All MMMs exhibited enhanced CO2 permeation with increased nano-filler loading because the porous nano-filler provided additional channels and fractional free volume in the polymer matrix. The 30 wt% loaded membrane showed a 183% increase in permeability of CO2 than neat membrane. With increasing nano-filler loading, the selectivity of MMMs increased from 34.1 to 48.45 for CO2/N2 and from 36.2 to 54.67 for CO2/CH4, confirming the absence of membrane defects, improved filler/polymer interface, and excellent dispersion of nano-filler in the polymer matrix. The results proved that these membranes could be further used for gas separation industrial applications.

Photocatalytic degradation of imidacloprid by Ag-ZnO composite.

The present study focused on exploring the potential of Ag-ZnO composites for complete mineralization of imidacloprid with the aim to sustain the pollutant free safe water supply. The composites were prepared by hydrothermal method and characterized by Scanning electron microscope (SEM), Energy dispersive X-ray crystallography (EDX), X-ray diffraction (XRD) and band gap measurements. These composites were used to study the UV irradiated degradation of imidacloprid while optimizing the process parameters such as time of UV irradiation, pH of medium, pesticide concentration and composite loading. The results of the study revealed an increase in photodegradation of imidacloprid by Ag-ZnO composites than pure ZnO. Temperature and catalyst loading had a positive effect on degradation efficiency, while an inverse relation was observed between pesticide concentration and degradation. Moreover, no harmful degradation products of imidacloprid were observed in GC-MS analyses that confirmed its complete mineralization.

Reductive transformation of profenofos with nanoscale Fe/Ni particles.

Profenofos is an abundantly used organophosphate pesticide in agriculture but its excessive use may lead to hazardous effects on environment. Thus, the present study focused on the reductive transformation of this pesticide in the presence of Fe/Ni bimetallic nanoparticles by optimizing the process parameters such as stirring time, nanoparticles dose, pH, and initial pesticide concentration. The results of reductive transformation were compared with photodegradation studies. It was found that with the increase in UV irradiation time, the percent degradation was increased. After 660 min, a 78% photodegradation of 100 µM solution of pesticide was observed. On increasing the initial pesticide concentration to 200 µM, the maximum degradation was achieved in 570 min, but here, only 73% degradation was observed. The rates of photodegradation observed with 100 to 400 µM solutions were 1.4 × 10-3, 1.5 × 10-3, 1.5 × 10-3, and 5 × 10-4 min-1 respectively.In case of reductive transformation carried out in the presence of Fe/Ni bimetallic nanoparticles, the degradation was observed to be increased from 78 to 93.9% in only 180 min. A further increase in pesticide concentration led to a decrease in degradation. Under these conditions, the rate of reaction was found to be 1.09 × 10-2 min-1. A 93% degradation of profenofos was further increased to 98% when the quantity of nanoparticles was increased twice; hence, a significant reduction in time of irradiation was observed. Reductive transformation of pesticide thus provided an efficient and cheaper method for reducing the burden of profenofos from the environment.

Photodegradation of bifenthrin and deltamethrin-effect of copper amendment and solvent system.

The photodegradation of bifenthrin and deltamethrin was studied in the presence of Cu salts and two different solvents, methanol and acetonitrile. Results of the study showed that in the absence of any metal salt, the two pesticides degraded more rapidly in acetonitrile than in methanol. After 24 h of UV irradiation, 70% of deltamethrin had degraded in acetonitrile, while only 41% bifenthrin degraded in this solvent. In methanol, bifenthrin degraded at a much enhanced rate than in acetonitrile while the rate of degradation of deltamethrin was comparable to that in acetonitrile. The photodegradation was further enhanced by the addition of copper to the solution of bifenthrin and deltamethrin in acetonitrile. The rate of photodegradation of deltamethrin increased from 2.4 × 10-2 to 3.5 × 10-2 h-1 in acetonitrile and 2.5 × 10-2 to 3.4 × 10-2 h-1 in methanol after the addition of copper. Similarly, the rate of photodegradation of bifenthrin was increased from 5.0 × 10-3 to 9.0 × 10-3 h-1 in acetonitrile and 7.0 × 10-3to 9.05 × 10-3 h-1 in methanol with the addition of copper. Thus, copper has the potential to enhance the photodegradation of bifenthrin and deltamethrin in both the solvents.

Distribution of Heavy Metals in the Soils Associated with the Commonly Used Pesticides in Cotton Fields.

Agricultural soils contain both heavy metals and pesticides originating from various agricultural practices. It is quite important to study the relationships between these two classes of compounds. To accomplish this, 52 soil samples were collected from cotton fields and analyzed for their metal contents (Ni, Cu, Co, Pb, Cr, and Cd) and levels of most commonly used pesticides (imidacloprid, acetamiprid, and emamectin). FAAS was used for metal estimation and the pesticides were determined by HPLC equipped with UV detector. The results of the study revealed slightly enhanced levels of Ni and Cd in these samples while the rest of the metals were present within tolerable range. Acetamiprid residues in soil were strongly positively correlated with Cu and negatively correlated with Cr. Similarly, imidacloprid in soil was negatively correlated with Ni. Thus it was evidenced that Cu stabilizes acetamiprid while Cr and Ni facilitate the degradation of acetamiprid and imidacloprid in the soil.

Design and fabrication of branched polyamine functionalized mesoporous silica: an efficient absorbent for water remediation.

A novel branched polyamine (polyethyleneimine, PEI) functionalized mesoporous silica (MS) adsorbent is developed via a facile "grafting-to" approach. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectroscopy verified the effective surface functionalization of MS with monolayer and polymer. The transmission electron microscopy (TEM) was employed to reveal the morphology of the fabricated materials. The adsorption behavior of the polyamine functionalized mesoporous silica (MS-PEI) is assessed against anionic dyes. The adsorbent characteristics of MS-PEI are compared with a monolayer platform comprising of 3-aminopropyltriethoxy silane (APTES) functionalized mesoporous silica (MS-APTES). The adsorption behavior of the MS-PEI and MS-APTES toward anionic dyes is further evaluated by studying the effect of adsorbent dosage, pH, contact time, and temperature. Langmuir and Freundlich isotherm models are employed to understand the adsorption mechanism. The obtained kinetic data support a pseudo-second-order adsorption behavior for both monolayer and polymer functionalized MS. The associated thermodynamic parameters (ΔG°, ΔH°, and ΔS°) reveal that the process of adsorption with MS-PEI is more spontaneous and energetically favored as compared to the adsorption with MS-APTES. Taken together, the novel adsorbent system derived from a combination of MS and branched polymer (MS-PEI) shows the higher absorption efficiency and capacity toward the anionic dyes than the monolayer based adsorbent (MS-APTES).

Speciative distribution and bioavailability of metals in agricultural soils receiving industrial wastewater.

In order to assess the metal pollution status of agricultural lands of Mandi Bahauuddin receiving industrial wastewater, 35 top soil samples were investigated for the determination of selected metal levels, i.e., Fe, Cu, Cd, Cr, Ca, Ni, and Pb by flame atomic absorption spectroscopy under optimum analytical conditions. The distribution of these metals in different operationally defined chemical fractions was also determined by using the sequential extraction technique. The highest mean total concentration was found for Fe while the least one was observed for Pb. All the studied metals were found to be present at levels much enhanced than national and international standards. Moreover, most of the metals were distributed principally in residual fraction with the exception of Ni which was found to be associated mainly with oxidizable fraction. The significant correlations were observed between Fe-Mn oxide-bound and residual fractions and exchangeable and oxidizable fractions for most of the metals. The highest mobility was exhibited by Ni that evidenced its enhanced bioavailability in the soil. The multivariate statistical analyses in terms of principal component analysis (PCA) and cluster analysis (CA) revealed multiple sources for various geochemical fractions of different metals. CA also revealed that the nonresidual fractions of most of the metals were very closely associated while PCA presented a distinctive behavior of Ca in the soil. It was therefore suggested that in order to avoid the metal contamination arising from industrial wastewater, appropriate remediation strategies must be adopted.