Green Synthesis of Er-Doped ZnO Nanoparticles: An Investigation on the Methylene Blue, Eosin, and Ibuprofen Removal by Photodegradation.

We present a study on the green synthesis of undoped and Er-doped ZnO compounds using Mangifera indica gum (MI). A set of tests were conducted to assess the structure of the material. The tests included X-ray diffraction, Raman, and Fourier-transform infrared spectroscopy. Optical properties were studied using diffuse reflectance and photoluminescence. Morphological and textural investigations were done using SEM images and N2 adsorption/desorption. Furthermore, photocatalytic tests were performed with methylene blue (MB), yellow eosin (EY), and the pharmaceutical drug ibuprofen (IBU) under UV irradiation. The study demonstrated that replacing the stabilizing agent with Mangifera indica gum is an effective method for obtaining ZnO nanoparticles. Additionally, the energy gap of the nanoparticles exhibits a slight reduction in value. Photoluminescence studies showed the presence of zinc vacancies and other defects in both samples. In the photocatalytic test, the sample containing Er3+ exhibited a degradation of 99.7% for methylene blue, 81.2% for yellow eosin, and 52.3% for ibuprofen over 120 min. In the presence of methyl alcohol, the degradation of MB and EY dyes is 16.7% and 55.7%, respectively. This suggests that hydroxyl radicals are responsible for the direct degradation of both dyes. In addition, after the second reuse, the degradation rate for MB was 94.08%, and for EY, it was 82.35%. For the third reuse, the degradation rate for MB was 97.15%, and for EY, it was 17%. These results indicate the significant potential of the new semiconductor in environmental remediation applications from an ecological synthesis.

Organic-Inorganic Hybrid Pigments Based on Bentonite: Strategies to Stabilize the Quinoidal Base Form of Anthocyanin.

Anthocyanins are one of the natural pigments that humanity has employed the most and can substitute synthetic food dyes, which are considered toxic. They are responsible for most purple, blue, and red pigment nuances in tubers, fruits, and flowers. However, they have some limitations in light, pH, oxygen, and temperature conditions. Combining biomolecules and inorganic materials such as clay minerals can help to reverse these limitations. The present work aims to produce materials obtained using cetyltrimethylammonium bromide in bentonite clay for incorporation and photostabilization of anthocyanin dye. Characterizations showed that the organic molecules were intercalated between the clay mineral layers, and the dye was successfully incorporated at a different pH. Visible light-driven photostability tests were performed with 200 h of irradiation, confirming that the organic-inorganic matrices were efficient enough to stabilize the quinoidal base form of anthocyanin. The pigment prepared at pH 10 was three-fold more stable than pH 4, showing that the increase in the synthesis pH promotes more stable colors, probably due to the stronger intermolecular interaction obtained under these conditions. Therefore, organobentonite hybrids allow to stabilize the fragile color coming from the quinoidal base form of anthocyanin dyes.

Facile Synthesis of Ni-Doped ZnO Nanoparticles Using Cashew Gum: Investigation of the Structural, Optical, and Photocatalytic Properties.

This work adopted a green synthesis route using cashew tree gum as a mediating agent to obtain Ni-doped ZnO nanoparticles through the sol-gel method. Structural analysis confirmed the formation of the hexagonal wurtzite phase and distortions in the crystal lattice due to the inclusion of Ni cations, which increased the average crystallite size from 61.9 nm to 81.6 nm. These distortions resulted in the growth of point defects in the structure, which influenced the samples' optical properties, causing slight reductions in the band gaps and significant increases in the Urbach energy. The fitting of the photoluminescence spectra confirmed an increase in the concentration of zinc vacancy defects (VZn) and monovacancies (Vo) as Zn cations were replaced by Ni cations in the ZnO structure. The percentage of VZn defects for the pure compound was 11%, increasing to 40% and 47% for the samples doped with 1% and 3% of Ni cations, respectively. In contrast, the highest percentage of VO defects is recorded for the material with the lowest Ni ions concentration, comprising about 60%. The influence of dopant concentration was also reflected in the photocatalytic performance. Among the samples tested, the Zn0.99Ni0.01O compound presented the best result in MB degradation, reaching an efficiency of 98.4%. Thus, the recovered material underwent reuse tests, revealing an efficiency of 98.2% in dye degradation, confirming the stability of the photocatalyst. Furthermore, the use of different inhibitors indicated that •OH radicals are the main ones involved in removing the pollutant. This work is valuable because it presents an ecological synthesis using cashew gum, a natural polysaccharide that has been little explored in the literature.

Efficient photocatalytic degradation of diclofenac drug using the Zn1-x-yPrxAlyO photocatalyst under UV light irradiation.

Herein, we report the efficient photocatalytic degradation of the diclofenac drug using the Zn1-x-yPrxAlyO photocatalyst [x, y] = (0.00, 0.00), (0.03, 0.01), (0.03,0.03) under UV light irradiation. The analysis of the structure reveals that the Pr3+ and Al3+ cations insertion into the ZnO lattice leads to a decrease in the lattice constant (a and c), Zn-O bond length, strain lattice, and crystallite size. These alterations are linked to the high degree of atomic disorder triggered by the dopants, which produce stress and strain in the ZnO structure. The Raman measurements confirmed the structural phase and showed changes in the position and intensity of the E2High mode, associated with oxygen vibrations and material crystallinity. The presence of the dopants reduces the concentration of VZn and VO++ type defects while increasing the levels of VO, VO+, and Oi defects, as observed from the fitting of the Photoluminescence spectra. Furthermore, it was noted that de Pr3+ and Al3+ cations insertion into ZnO increases the optical band gap, which is associated with the Moss-Burstein effect. The micrograph images show that dopants transform the morphology from quasi-spherical particles to irregular cluster structures. The textural analysis indicated that an increase in the concentration of Al3+ in the ZnO lattice led to a higher surface area, likely enhancing photocatalytic activity. The sample containing 3% Pr3+ and 3% Al3+ showed the highest photocatalytic activity and degraded up to 71.42% of diclofenac. In addition, experiments with scavengers revealed that hydroxyl radicals are the main species involved in the drug's photodegradation mechanism. Finally, the Zn1-x-yPrxAlyO compound is highly recyclable and stable.

Clays as Vehicles for Drug Photostability.

Clay minerals are often used due to their high adsorption capacity, which has sparked interest in their biological applications to stabilize drugs and pharmaceutical products. This research aims to summarize information about the stability of drugs, cosmetics, dermocosmetics, and pharmaceutical compounds incorporated in the structure of different clay minerals. The databases used to search the articles were Web of Science, Scopus, PubMed, and Science Direct. Photostabilization of these compounds is reviewed and its importance demonstrated. For biological applications, the increase in solubility and bioavailability of clay minerals has proven useful for them as drug carriers. While their natural abundance, low toxicity, and accessible cost have contributed to classical applications of clay minerals, a wide range of interesting new applications may be facilitated, mainly through incorporating different organic molecules. The search for new functional materials is promising to challenge research on clay minerals in biological or biotechnological approaches.

Montmorillonite with essential oils as antimicrobial agents, packaging, repellents, and insecticides: an overview.

Essential oils (EOs) are complex natural mixtures of secondary plant metabolites that function as biocides and therapeutic agents. They are extensively used in bactericidal, virucidal, fungicidal, antiparasitic, insecticidal, pharmaceutical, and cosmetic products. However, certain characteristics, such as the volatility of EOs, hinder their widespread use. To mitigate this limitation, several studies have investigated combinations of EOs with natural materials, including clay minerals. Clay minerals are abundant in nature, biocompatible, and non-toxic to the environment and humans. Clay minerals such as montmorillonite possess available sites where EO molecules can interact. The combination of EOs with clay minerals produces new materials for various applications including antibacterial, antifungal, insecticidal/repellent, and active packaging materials. Therefore, this review focuses on the immobilization of several types of EOs in raw and modified montmorillonites. The applications of the described systems were evaluated and demonstrated the synergism of the properties of the isolated components as a function of different EOs incorporated in the silicate matrix.

Au@Ag bimetallic nanoparticles deposited on palygorskite in the presence of TiO2 for enhanced photodegradation activity through synergistic effect.

Herbicides are hazardous organic pollutants that contribute to the risk of environmental contamination. The aim of this work was to investigate the synergistic effect of silver (Ag) and gold (Au) bimetallic nanoparticles deposited on palygorskite (PAL) in the presence of TiO2 for photodegradation of bentazone (BTZ) herbicide under UV light. Ag and Au@Ag nanoparticles exhibited an average size below 75 nm and surface charge values less than - 30 mV. UV-Vis spectroscopy indicates the formation of core@shell bimetallic nanoparticles. XRD results showed the interactions between the NPs and the palygorskite structure. SEM images clearly illustrate the presence of small spherical particles distributed in the clay fibers. The control of the size and distribution of the nanoparticles played an important role in the properties of the composites. The degradation of the herbicide BTZ showed that nanoparticles, clay, and only TiO2 did not produce satisfactory results; however, when Ag-Pal and Au@Ag-Pal were in the presence of the TiO2, the degradation was efficient. The best photodegradative system was Au@Ag-Pal+TiO2, which was maintained after the third cycle. The bentazone photodegradation using Au@Ag-PAL+TiO2 exhibited toxicity against Artemia salina. Therefore, Au@Ag-PAL+TiO2 photocatalyst showed that the synergy of bimetallic nanoparticles deposited on clay for enhanced photodegradation activity of bentazone herbicide.

Monitoring diclofenac adsorption by organophilic alkylpyridinium bentonites.

Organoclays have been applied as efficient adsorbents for pharmaceutical pollutants from aqueous solution. In this work, dodecylpyridinium chloride (C12pyCl) and hexadecylpyridinium chloride (C16pyCl) cationic surfactants were used for the preparation of organobentonites destined for diclofenac sodium (DFNa) adsorption, an anionic drug widely detected in wastewater. The organofunctionalization of the clay samples was performed under microwave irradiation at 50 °C for 5 min with surfactant amounts of 100% and 200% in relation to the cation exchange capacity (CEC) of the pristine bentonite. The amount of incorporated ammonium salts based on CHN elemental analysis was higher for all samples prepared with 200% of the CEC. The basal spacings of the organoclays ranged from 1.54 to 2.13 nm, indicating the entrance of organic cations into the interlayer spacing of the clay samples, and the spacing depended on the size of the alkyl organic chain. The hydrophobic character of the organobentonites was verified by thermogravimetry and infrared spectroscopy (FTIR). The adsorption isotherms showed that the drug capacity adsorption was influenced by the amount of surfactant incorporated into the bentonite, the packing density and the arrangement of the surfactants in the interlayer spacing. Zeta potential measurements of the organobentonites and FTIR analysis after drug adsorption suggested that electrostatic and nonelectrostatic interactions contributed to the mechanism of adsorption.

Eco-friendly synthesis and photocatalytic application of flowers-like ZnO structures using Arabic and Karaya Gums.

Flowers-like ZnO structures were synthesized using Arabic Gum (AGZnO) or Karaya Gum (KGZnO). The AGZnO and KGZnO were characterized by X-ray diffractometry, Fourier Transformed Infrared, Scanning Electron Microscopy, Photoluminescence, nitrogen adsorption/desorption and diffuse reflectance techniques. The materials were tested in the discoloration of Methylene Blue (MB) dye under visible light and scavenger studies were also performed. The toxicity of the MB irradiated was investigated in bioassays with Artemia salina. The structural characterization demonstrated the formation of hexagonal ZnO. All samples presented flower-like morphology with presence of mesopores identified by BET method. The optical properties indicated band gap of 2.99 (AGZnO) and 2.76 eV (KGZnO), and emission in violet, blue and green emissions also were observed. The KGZnO demonstrated better photocatalytic performance than the AGZnO, and scavenger studies indicated that OH radicals are the main species involved in the degradation of the pollutant model. The photodiscoloration of MB solution did not demonstrate toxicity. Therefore, KGZnO is a promising material for photocatalysis application.

A novel green approach based on ZnO nanoparticles and polysaccharides for photocatalytic performance.

Novel green photocatalysts based on ZnO in the presence of arabic gum (AGZ) or karaya gum (KGZ) were synthesized by a sol-gel method for photocatalytic performance. The materials were characterized by XRD, FTIR spectroscopy, SEM, nitrogen adsorption/desorption, and PL and diffuse reflectance spectroscopy. Photocatalytic test was performed using methylene blue (MB) dye as the target pollutant under visible light. The reuse of photocatalysts and Artemia saline bioassays were investigated. The ZnO nanoparticles showed a hexagonal structure and the values of the band gaps were 2.95 (AGZ) and 2.98 eV (KGZ). The PL results demonstrated emission bands at 440, 473 or 478 and 549 nm. The textural properties indicated the presence of typically mesoporous materials. The MB discoloration efficiency was 81.5% and 91.0% for AGZ and KGZ, respectively. The photocatalytic activity of AGZ and KGZ was maintained after the third run. The ˙OH radicals are the main species involved in the MB discoloration. The MB discoloration from the photocatalysts showed no toxicity; therefore, they are considered to be promising materials for the degradation of the dye in the photocatalytic process.

Going through the wine fining: Intimate dialogue between organics and clays.

Wine chemistry inspires and challenges with its complexity and intriguing composition. In this context, the composites based on the use of a model protein, a polyphenol of interest and montmorillonite in a model hydroalcoholic solution have been studied. A set of experimental characterization techniques highlighted the interactions between the organic and the inorganic parts in the composite. The amount of the organic part was determined by ultraviolet-visible (UV-VIS) and thermal analysis. X-ray diffraction (XRD) and transmission electronic microscopy (TEM) informed about the stacking/exfoliation of the layers in the composites. Vibrational and nuclear magnetic resonance spectroscopies methods stressed on the formation of a complex between the protein and the polyphenol before adsorption on the clay mineral. The mobility/rigidity of the organic parts were determined by fluorescence time resolved spectroscopy. Changes in the secondary structure of the protein occured upon complexation with polyphenol on clay mineral due to strong interactions. Although not representating faithfully enological conditions, these results highlight the range and nature of mechanisms possibly involved in wine fining.