Photocatalytic reduction of levulinic acid using thermally modified niobic acid

After the discovery that commercial niobic acid (H0) is able to reduce the levulinic acid in value added molecules, H0 was thermally treated at 200 °C, 400 °C, and 600 °C, generating the niobium oxides H1, H2 and H3 and the photocatalytic improvement towards reduction was investigated. Although the higher temperatures significantly decreased the specific surface area, it was important to remove surface hydroxyl groups and create the T and TT-Nb2O5 phase mixture in H3 which were responsible for its best performance (36.4% of conversion and almost 99% of selectivity for reduced products). To further improve the H3 photoactivity, an identical synthesis was performed in H2 flow to produce oxygen vacancies in the structure of the new photocatalyst (H3OV). This simple modification method increased ∼7% of products yield, which is the best photocatalytic result obtained for pure niobium oxides so far, and proved that it is possible to significantly increase photocatalytic performance without laborious modifications. The electronic and structural differences between H3 and H3OV were investigated by XRD Rietveld refinement, EPR, HR-TEM, DRS and SAED analyses

Nanocrystalline transition-metal gallium oxide spinels from acetylacetonate precursors via solvothermal synthesis

The synthesis of mixed-metal spinels based on substituted γ-Ga2O3 is reported using metal acetylacetonate precursors in solvothermal reactions with alcohols as solvents at 240 °C. New oxides of Cr, Mn and Fe have been produced, all of which are formed as nanocrystalline powders, as seen by high-resolution transmission electron microscopy (HR-TEM). The first chromium-gallium mixed oxide is thus formed, with composition 0.33Ga1.87Cr0.8O4 ( = vacant site). X-ray absorption near-edge spectroscopy (XANES) at the chromium K-edge shows the presence of solely octahedral Cr3+, which in turn implies a mixture of tetrahedral and octahedral Ga3+, and the material is stable on annealing to at least 850 °C. An analogous manganese material with average chemical composition close to MnGa2O4 is shown to contain octahedral Mn2+, along with some Mn3+, but a different inversion factor to materials reported by conventional solid-state synthesis in the literature, which are known to have a significant proportion of tetrahedral Mn2+. In the case of iron, higher amounts of the transition metal can be included to give an Fe:Ga ratio of 1:1. Elemental mapping using energy dispersive X-ray spectroscopy on the TEM, however, reveals inhomogeneity in the distribution of the two metals. This is consistent with variable temperature 57Fe Mössbauer spectroscopy that shows the presence of Fe2+ and Fe3+ in more than one phase in the sample. Variable temperature magnetisation and electron paramagnetic resonance (EPR) indicate the presence of superparamagnetism at room temperature in the iron-gallium oxides. View Full-Tex

Electron paramagnetic resonance signature of point defects in neutron-irradiated hexagonal boron nitride

© 2018 American Physical Society. Hexagonal boron nitride (h-BN) is an attractive van der Waals material for studying fluorescent defects due to its large band gap. In this work, we demonstrate enhanced pink color due to neutron irradiation and perform electron paramagnetic resonance (EPR) measurements. The point defects are tentatively assigned to doubly occupied nitrogen vacancies with (S=1) and a zero-field splitting (D=1.2GHz). These defects are associated with a broad visible optical absorption band and a near-infrared photoluminescence band centered at ∼490 and 820 nm, respectively. The EPR signal intensities are strongly affected by thermal treatments in the temperature range between 600 °C and 800 °C, where also the irradiation-induced pink color is lost. Our results are important for understanding of point defects in h-BN and their deployment for quantum and integrated photonic applications

Initialization and read-out of intrinsic spin defects in a van der Waals crystal at room temperature

Optically addressable spins in wide-bandgap semiconductors are a promising platform for exploring quantum phenomena. While colour centres in three-dimensional crystals such as diamond and silicon carbide were studied in detail, they were not observed experimentally in two-dimensional (2D) materials. Here, we report spin-dependent processes in the 2D material hexagonal boron nitride (hBN). We identify fluorescence lines associated with a particular defect, the negatively charged boron vacancy ([Formula: see text]), showing a triplet (S = 1) ground state and zero-field splitting of ~3.5 GHz. We establish that this centre exhibits optically detected magnetic resonance at room temperature and demonstrate its spin polarization under optical pumping, which leads to optically induced population inversion of the spin ground state-a prerequisite for coherent spin-manipulation schemes. Our results constitute a step forward in establishing 2D hBN as a prime platform for scalable quantum technologies, with potential for spin-based quantum information and sensing applications

OCORRÊNCIA, CONTEXTO MINERALÓGICO E QUÍMICA MINERAL DA BRAZILIANITA E SEUS DEPÓSITOS EM MINAS GERAIS

A brazilianita é um fosfato gemológico relativamente raro, amarelo a amarelo-esverdeado, descrito em 1945 em amostras coletadas no Pegmatito Córrego Frio (Divino das Laranjeiras, MG), onde vários depósitos similares foram depois reportados. No mesmo Estado, existe ainda outro pegmatito mineralizado, em Itinga. Tais pegmatitos, ora estudados, originam-se de granitogêneses relacionadas ao Orógeno Araçuaí, constituindo em geral corpos tabulares de pequeno porte, além de pouco diferenciados. Análises químicas com microssonda eletrônica no mineral revelaram valores muito homogêneos para os diversos pegmatitos estudados, semelhantes aos da descrição original; Análises sobre feldspatos associados mostraram que os pegmatitos hospedeiros são pobres em B (não turmaliníferos), Cs, Rb e Zr, mas ricos em F. Um deles, o Pegmatito Telírio, apresenta uma anomalia em Li em relação aos demais. A cor amarela do mineral, estudada por EPR e absorção óptica, deve-se a uma banda de absorção no UV próximo, e sua intensidade está relacionada com um centro O1- fixo, do tipo buraco. Diferentes tipos de centros de elétrons são responsáveis pela ampla faixa de estabilidade térmica da cor do mineral; o componente esverdeado é causado por uma extensa banda de absorção na região vermelha do espectro. Nos depósitos estudados, a brazilianita constitui um produto secundário de alteração da montebrasita, em estágio hidrotermal precoce (350-250°C)

Structural and magnetic characterization of colloidal CdMnS

This paper reports on the synthesis (chemical co-precipitation reaction) and characterization (X-ray diffraction, magnetization, and electron paramagnetic resonance) of nanosized Cd1-xMnxS particles with manganese concentration up to x = 0.73. Though the literature reports that nanosized (bulk) CdS can incorporate as much as 30% (50%) of manganese ion within its crystal structure we found manganese segregation at the nanoparticle surface at doping levels as low as 14%. We found that both XRD and magnetization data support the presence of the Mn3O4 phase (observed spin-glass transition around 43 K) at the high manganese doping levels whereas the EPR data strongly suggest preferential incorporation of manganese at the nanoparticle's surface, even at low manganese doping levels. Analyses of the experimental data strongly suggest the preparation of well-defined core/shell (Cd1-xMnxS/Mn3O4) structures at higher levels of manganese doping.CNPQ [503533/2003-3]CNP

Optical phonon features of triclinic montebrasite : dispersion analysis and non-polar Raman modes.

Polarized infrared and Raman spectra of triclinic LiAl(PO4)(OH) [montebrasite] single crystal were recorded for appropriate optical configurations. Dispersion analysis was applied on the infrared reflectivity spectra taken at low incidence angle (11 ) to determine the oscillator parameters and the dipole directions of the polar phonons. In particular, all the 27 polar phonons, predicted by group theory for triclinic P1 structure,were determined. The obtained dielectric tensor parameters have been checked by comparison between predicted and measured infrared spectra at higher incidence angle (34 ). The azimuth and co-elevation angles obtained from the dispersion analysis showed that the response of several polar phonons is close to that of an orthorhombic system. Polarized Raman spectra obtained in several scattering geometries allowed us to obtain well-defined 24 non-polar modes, also in perfect agreement with group theory. The selection rule between Raman and infrared phonons was respected, confirming the centrosymmetric structure and ruling out any relevant influence of defects. The relatively narrow phonon bands are compatible with a highly ordered structure with fully occupied atomic sites