Studies on Synthesis and Characterization of Fe3O4@SiO2@Ru Hybrid Magnetic Composites for Reusable Photocatalytic Application

Degradation of dye pollutants by the photocatalytic process has been regarded as the most efficient green method for removal organic dyes from contaminated water. The current research work describes the synthesis of Fe3O4@SiO2@Ru hybrid magnetic composites (HMCs) and their photocatalytic degradation of two azo dye pollutants, methyl orange (MO) and methyl red (MR), under irradiation of visible light. The synthesis of Fe3O4@SiO2@Ru HMCs involves three stages, including synthesis of Fe3O4 magnetic microspheres (MMSs), followed by silica (SiO2) coating to get Fe3O4@SiO2 MMSs, and then incorporation of presynthesized Ru nanoparticles (~3 nm) onto the surface of Fe3O4@SiO2 HMCs. The synthesized HMCs were characterized by XRD, FTIR, TEM, EDS, XPS, BET analysis, UV-DRS, PL spectroscopy, and VSM to study the physical and chemical properties. Furthermore, the narrow band gap energy of the HMC photocatalyst is a significant parameter that provides high photocatalytic properties due to the high light adsorption. The photocatalytic activity of synthesized Fe3O4@SiO2@Ru HMCs was assessed by researching their ability to degrade the aqueous solution of MO and MR dyes under visible radiation, and the influence of various functional parameters on photocatalytic degradation has also been studied. The results indicate that the photocatalytic degradation of MO and MR dyes is more than 90%, and acid media favors better degradation. The probable mechanism of photodegradation of azo dyes by Fe3O4@SiO2@Ru HMC catalysts has been proposed. Furthermore, due to the strong ferromagnetic Fe3O4 core, HMCs were easily separated from the solution after the photocatalytic degradation process for reuse. Also, the photocatalytic activity after six cycles of use is greater than 90%, suggesting the stability of the synthesized Fe3O4@SiO2@Ru HMCs.

Efficient near-infrared quantum cutting by cooperative energy transfer in Bi3TeBO9:Nd3+ phosphors

An efficient near-infrared quantum cutting process by cooperative down-conversion of active Bi3+ and Nd3+ ions was demonstrated in Bi3TeBO9:Nd3+ phosphors. In particular, the near-infrared emission of Nd3+ ions enhanced by Bi3+ ions of a series of novel Bi3TeBO9:Nd3+ microcrystalline powders doped with Nd3+ ions in various concentrations was investigated. In order to investigate the luminescent properties of BTBO:Nd3+ powders, the excitation and emission spectra and the fluorescence decay time were measured and analyzed. In particular, the emission of Bi3TeBO9:Nd3+ at 890 and 1064 nm was excited at 327 nm (via energy transfer from Bi3+ ions) and at 586.4 nm (directly by Nd3+ ions). The highest intensity emission bands in near-infrared were detected in the spectra of Bi3TeBO9:Nd3+ doped with 5.0 and 0.5 at.% of Nd3+ ions upon excitation in ultraviolet and visible spectral range, respectively. The fluorescence decay lifetime monitored at 1064 nm for Bi3TeBO9:Nd3+ powders shows the single- or double-exponential character depending on the concentrations of Nd3+ ions. The possible mechanisms of energy relaxation after excitation Bi3TeBO9:Nd3+ powders in ultraviolet or visible spectral range were discussed. The investigated Bi3TeBO9:Nd3+ phosphors efficiently concentrate the ultraviolet/visible radiation in the near-infrared spectral range and can be potentially used as effective spectral converters. Graphical abstract

A Multiwavelength Approach for the Study of Contemporary Painting Materials by Means of Fluorescence Imaging Techniques: An Integration to Spectroscopic Methods

Imaging methods based on visible luminescence induced by ultraviolet (UV) radiation are well consolidated in the investigation of ancient works of art, to map varnishes, retouches, and possibly some pigments. As far as contemporary art is involved, the wide range of synthetic materials, especially pigments, introduced from 1850 onwards, makes the possible application of the technique particularly challenging. Among the colouring substances used by artists in the 19th and 20th centuries, only cadmium-based pigments received attention due to their typical near-infrared luminescence. Nevertheless, the fluorescence emission exhibited by several synthetic pigments upon visible excitation was recently demonstrated and confirmed using UV radiation in the present work. The subsequent possibility of individuating such materials in paintings by ultraviolet fluorescence (UVF) images was explored on mock-up painting samples of a wide series of pigments dispersed in oil or acrylic binder. Visible and infrared luminescence images obtained by irradiating with visible radiation (VIVF and VIL) were also collected. It was thus evidenced the possible advantage of the choice of a different excitation wavelength in discriminating between the contributions of pigment and binder. Finally, a recent oil painting on panel was also examined as case study.

In vitro Assessment of Solar Filters for Erythropoietic Protoporphyria in the Action Spectrum of Protoporphyrin IX

Introduction: Subjects with erythropoietic protoporphyria rely on broad-spectrum sunscreens with high sun protection factor, which is not informative on efficacy in the absorption spectrum of protoporphyrin IX, spanning visible radiation and peaking around 408 nm. Photoactivation of protoporphyrin IX is responsible for painful skin photosensitivity in erythropoietic protoporphyria.The authors assessed the protective efficacy of six sunscreens in vitro in the absorption spectrum of protoporphyrin IX.Method: Transmittance measurements were performed in the 300–850 nm wavelengths on samples of six photoprotective products applied to polymethyl methacrylate plates. Porphyrin protection factor was calculated in the 300–700 nm region to provide a measurement for the efficacy of each product based on the action spectrum of protoporphyrin IX.Results: Product A showed the highest porphyrin protection factor among tested products with a median value of 4.22. Product A is a sunscreen containing organic filters, titanium dioxide and synthetic iron oxides, pigmentary grade active ingredients that absorb visible radiation. Other products showed inefficient protection in the visible, with transmittance between 75 and 95% at 500 nm. The low porphyrin protection factor of inorganic filter product B was attributed to particle micronization, as declared by the manufacturer.Conclusion: Adding porphyrin protection factor to sunscreen labeling could help patients with erythropoietic protoporphyria and other photosensitivity disorders identify products tailored on their specific needs. The development of sunscreens providing protection from visible radiation and excellent cosmetical tolerability could improve the lifestyle of patients with erythropoietic protoporphyria.

Au/CeO2 Photocatalyst for the Selective Oxidation of Aromatic Alcohols in Water under UV, Visible and Solar Irradiation

Au nanoparticles supported on CeO2 have been prepared and investigated as photocatalysts for the photocatalytic selective oxidation of benzyl alcohol and 4-methoxybenzyl alcohol to the correspondent benzaldehydes, in aqueous suspensions and room conditions under UV, visible and natural solar light irradiation. Au nanoparticles have been supported by impregnation (1 and 3 wt.%) on two types of CeO2 (i.e., a commercial one and a home prepared oxide obtained in the presence of NaOH as precipitation agent). The Au impregnated samples showed strong visible radiation absorption at 565–570 nm associated to localized surface plasmon resonance (LSPR). The bare CeO2 samples are activated by UV light and resulted virtually inactive under visible irradiation, whereas the presence of Au improved both the conversion of the alcohols and the selectivity of the reaction towards the aldehyde, giving rise to good results, particularly under visible and natural solar light irradiation. The activity of the materials increased by increasing the Au content.

Understanding the physicochemical properties of Zn–Fe LDH nanostructure as sorbent material for removing of anionic and cationic dyes mixture

In our work, the removal of cationic and anionic dyes from water was estimated both experimentally and computationally. We check the selectivity of the adsorbent, Zn–Fe layered double hydroxide (LDH) toward three dyes. The physical and chemical properties of the synthesis adsorbent before and after the adsorption process were investigated using X-ray photoelectron spectroscopy, energy dispersive X-ray, X-ray diffraction, FT-IR, HRTEM, and FESEM analysis, particle size, zeta potential, optical and electric properties were estimated. The effect of pH on the adsorption process was estimated. The chemical stability was investigated at pH 4. Monte Carlo simulations were achieved to understand the mechanism of the adsorption process and calculate the adsorption energies. Single dye adsorption tests revealed that Zn–Fe LDH effectively takes up anionic methyl orange (MO) more than the cationic dyes methylene blue (MB) and malachite green (MG). From MO/MB/MG mixture experiments, LDH selectively adsorbed in the following order: MO > MB > MG. The adsorption capacity of a single dye solution was 230.68, 133.29, and 57.34 mg/g for MO, MB, and MG, respectively; for the ternary solution, the adsorption capacity was 217.97, 93.122, and 49.57 mg/g for MO, MB, and MG, respectively. Zn–Fe LDH was also used as a photocatalyst, giving 92.2% and 84.7% degradation at concentrations of 10 and 20 mg/L, respectively. For visible radiation, the Zn–Fe LDH showed no activity.

Ag-TiO2 Nanocomposites: visible or solar light driven plasmonic photocatalysis?

Background: The demand for photocatalytic processes assisted by solar radiation has stimulated the upgrading of established systems, as the semiconductor modification with noble metals. Objective: the synthesis, characterization, and photocatalytic activity evaluation of the Ag-TiO2, against sulfamethoxazole molecule, and investigate the significance of the plasmonic phenomenon in Visible (450 - 1000nm) and UV-Vis (315-800 nm) radiation. Methods: Different nanocomposites Ag/TiO2 ratios were synthesized by the deposition of Ag nanoparticles on the TiO2 surface by in-situ photoreduction, and then calcinated at 400°C for 2 hr. The chemical-physical properties of the materials were examined by UV-Vis Diffuse Reflectance (UV-Vis DRS) Scanning Electronic Microscopy (SEM), Transmission Electronic Microscopy (TEM), X-Ray Energy Dispersive Spectroscopy (EDS). The experiments were conducted in a cooled photochemical reactor irradiated by halogen lamp (250W). The degradation of Sulfamethoxazole was monitored by HPLC-DAD. Results: Although the prepared photocatalysts show an intense plasmonic band centered at 500 nm, no photocatalytic activity was observed in the process assisted by artificial visible radiation ( ≥ 450 nm). In processes assisted by artificial UV-Vis radiation, the photolysis rate of the model compound (sulfamethoxazole) was higher than the photocatalytic rate, and in the absence of UV radiation, all the reactions were inhibited. The positive effect of the presence of silver nanoparticles onto the TiO2 surface was only evidenced in studies involving solar radiation. Conclusion: The results suggest the need for a balance between UV and Vis radiation to activate the nanocomposite and perform the sulfamethoxazole degradation.

Ultra-portable, smartphone-based spectrometer for heavy metal concentration measurement in drinking water samples

Heavy metals are very toxic and hazardous for human health. Onsite screening of heavy metal contaminated samples along with location-based automation data collection is a tedious job. Traditionally high-end equipment’s such as gas chromatography mass spectrometer (GC–MS) and atomic absorption spectrometers have been used to measure the concentration of different heavy metals in water samples but most of them are costly, bulky, and time consuming, and requires expert human intervention. This manuscript reports an ultra-portable, rapid, cost-effective, and easy-to-use solution for onsite heavy metal concentration measurement in drinking water samples. Presented solution combines off-the-shelf available chemical kits for heavy metal detection and developed spectrometer-based readout for concentration prediction, quality judgment, and automatic data collection. Two chemical kits for copper and iron detection have been imported form Merck and have been used for overall training and testing. The developed spectrometer has capability to work with smartphone-based android app and also can work in standalone mode. The developed spectrometer uses white light-emitting diode as a source and commercially imported spectral sensor (AS7262) for visible radiation reception. A low-power sub-GHZ-based wireless embedded platform has been developed and interfaced with source and detector. A power management module also has been designed to monitor the battery status and also to generate low battery indication. Overall modules has been packaged in custom designed enclosure to avoid external light interference. The developed system has been trained using standard buffer samples with known heavy metal concentrations and further tested for water samples collected from institute colony and nearby villages. The obtained results have been validated with commercially imported system from HANNA instruments, and it has been observed that developed system has shown excellent accuracy to predict heavy metal concentration (tested for Fe and Cu) in water samples.