Structure, Photoluminescence Emissions, and Photocatalytic Activity of Ag2SeO3: A Joint Experimental and Theoretical Investigation.

In this paper, we report the synthesis of silver selenite (Ag2SeO3) by different methods [sonochemistry, ultrasonic probe, coprecipitation, and microwave-assisted hydrothermal methods]. These microcrystals presented a structural long-range order as confirmed by X-ray diffraction (XRD) and Rietveld refinements and a structural short-range order as confirmed by Fourier transform infrared (FTIR) and Raman spectroscopies. X-ray photoelectron spectroscopy (XPS) provided information about the surface of the samples indicating that they were pure. The microcrystals presented different morphologies and sizes due to the synthesis method as observed by field emission scanning electron microscopy (FE-SEM). The optical properties of these microcrystals were evaluated by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) measurements. Thermal analysis confirmed the temperature stability of the as-synthetized samples. Further trapping experiments prove that the holes and hydroxyl radicals, to a minor extent, are responsible for the photocatalytic reactions. The experimental results are sustained by first-principles calculations, at the density functional theory (DFT) level, to decipher the structural parameters, electronic properties of the bulk, and surfaces of Ag2SeO3. By matching the experimental FE-SEM images and theoretical morphologies, we are capable of finding a correlation between the morphology and photocatalytic activity, along with photodegradation of the Rhodamine B dye under UV light, based on the different numbers of unsaturated superficial Ag and Se cations (local coordination, i.e., clusters) of each surface.

α-Ag2-2xZnxWO4 (0 ≤ x ≤ 0.25) Solid Solutions: Structure, Morphology, and Optical Properties.

A theoretical study was elaborated to support the experimental results of the Zn-doped α-Ag2WO4. Theses α-Ag2-2xZnxWO4 (0 ≤ x ≤ 0.25) solid solutions were obtained by coprecipitation method. X-ray diffraction data indicated that all α-Ag2-2xZnxWO4 (0 ≤ x ≤ 0.25) microcrystals presented an orthorhombic structure. The experimental values of the micro-Raman frequencies were in reasonable agreement with both previously reported and calculated results. Microscopy images showed that the replacement of Ag+ by Zn2+ promoted a reduction in the average crystal size and modifications in the morphology, from rod-like with hexagonal shape to roll-like with a curved surface. A theoretical methodology based on the surfaces calculations and Wulff constructions was applied to study the particle shapes transformations and the surface energy variations in α-Ag2-2xZnxWO4 (0 ≤ x ≤ 0.25) system. The decrease in the band gap value (from 3.18 to 3.08 eV) and the red shift in photoluminescence with the Zn2+ addition were associated with intermediary energy levels between the valence and conduction bands. First-principles calculations with density functional theory associated with B3LYP hybrid functional were conducted. The calculated band structures revealed an indirect band gap for the α-Ag2-2xZnxWO4 models. The electronic properties of α-Ag2WO4 and α-Ag2-2xZnxWO4 microcrystals were linked to distortion effects and oxygen vacancies (VOx) present in the clusters, respectively. Finally, photoluminescence properties of α-Ag2WO4 and α-Ag2-2xZnxWO4 microcrystals were explained by means of distortional effects and oxygen vacancies (VOx) in [AgOy] (y = 2, 4, 6, and 7) and [WO6] clusters, respectively, causing a red shift. Calculations revealed that the substitution for Ag+ with Zn2+ occurred randomly in the α-Ag2WO4 lattice, and it was more favorable on the Ag4 site, where the local coordination of Ag+ cations was four.

Towards a relationship between photoluminescence emissions and photocatalytic activity of Ag2SeO4: combining experimental data and theoretical insights.

A systematic theoretical and experimental study was carried out to find a relationship between photoluminescence emissions and photocatalytic activity of Ag2SeO4 obtained by different synthesis methods (sonochemistry, ultrasonic probe, coprecipitation and microwave assisted hydrothermal synthesis). Experimental characterization techniques (XRD with Rietveld refinement, Raman, FTIR, UV-vis, XPS and photoluminescence spectroscopy) were used to elucidate its structural order at short, medium, and long ranges. Morphological analysis performed by FE-SEM showed distinct morphologies due to the different methods of synthesis. Based on density functional theory (DFT) calculations, it was possible to study in detail the Ag2SeO4 surface properties, including its surface energy, geometry, and electronic structure for the (100), (010), (001), (101), (011), (110), (111), (021), (012) and (121) surfaces. The equilibrium morphology of Ag2SeO4 was predicted as a truncated octahedron with exposed (111), (001), (010) and (011) surfaces. Photoluminescence emissions showed a band covering the visible spectrum, and the Ag2SeO4 obtained by the coprecipitation method presented the most intense band with a maximum in the red region. Photocatalytic results confirmed that Ag2SeO4 synthesized by the sonochemistry method is the best photocatalyst for rhodamine B degradation under UV light irradiation.

Femtosecond-laser-irradiation-induced structural organization and crystallinity of Bi2WO6.

Controlling the structural organization and crystallinity of functional oxides is key to enhancing their performance in technological applications. In this work, we report a strong enhancement of the structural organization and crystallinity of Bi2WO6 samples synthetized by a microwave-assisted hydrothermal method after exposing them to femtosecond laser irradiation. X-ray diffraction, UV-vis and Raman spectroscopies, photoluminescence emissions, energy dispersive spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy were employed to characterize the as-synthetized samples. To complement and rationalize the experimental results, first-principles calculations were employed to study the effects of femtosecond laser irradiation. Structural and electronic effects induced by femtosecond laser irradiation enhance the long-range crystallinity while decreasing the free carrier density, as it takes place in the amorphous and liquid states. These effects can be considered a clear cut case of surface-enhanced Raman scattering.

Structural and photoluminescence properties of Eu(3+) doped α-Ag2WO4 synthesized by the green coprecipitation methodology.

Europium doped silver tungstates α-Ag2-3xEuxWO4 (x = 0, 0.0025, 0.005, 0.0075 and 0.01 mol) were synthesized by the coprecipitation method at 90 °C for 30 minutes. These crystals were structurally characterized by means of X-ray diffraction (XRD), Rietveld refinement, and micro-Raman (MR) and Fourier transformed infrared (FT-IR) spectroscopies. Field emission scanning electron microscopy (FE-SEM) images were employed to observe the shape of the crystals. The optical properties were investigated by ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) measurements. The XRD pattern indicated structural organization at a long range for all undoped and Eu-doped samples, while MR and FT-IR revealed that the presence of the Eu(3+) ions favors the structural organization at a short range. The Rietveld refinement showed that all the crystals are monophasic with an orthorhombic structure and the Pn2[combining macron]n space group. The refined lattice parameters and atomic positions were employed to model the WO6 and AgOn (n = 2, 4, 6 and 7) polyhedra in the unit cell. FE-SEM analysis revealed nanorod-like microcrystals with growth of metallic silver on the surface. Further, the UV-vis absorption spectra indicated the existence of intermediary energy levels within the band gap. PL spectra showed a broad band related to the [WO6] group and characteristic narrow peaks due to the f-f transitions of Eu(3+) as a result of efficient energy transfer from the matrix. Also, the emission line shape transitions from (5)D0 to (7)FJ (J = 0-4) levels of the Eu(3+) were noticed. Among the samples, the most intense photoluminescence results were observed for the α-Ag2-3xEuxWO4 (x = 0.0075) sample. Lifetime decays support that the Eu(3+) ions occupy at least two crystallographic sites. CIE coordinates confirmed the colors of the emission spectra which classify this material as a potential phosphor in the visible range.