Highly active reduced graphene oxide supported Ni nanoparticles for C-S coupling reactions.

Air-stable Ni nanoparticles (with particle size ∼ 11 nm) supported on reduced graphene oxide [Ni(0)@RGO] was prepared by a simple and easy procedure. We previously described the Kumada-Corriu C-C cross-coupling reaction between iodo-arenes and Grignard reagents with Ni(0)RGO as a stable and efficient catalyst. This Ni(0)RGO catalyst gave an excellent yield (92%) and good recyclability (up to the 5th cycle). This communication confirms that the catalyst shows superior efficacy for the C-S coupling reaction, similar to that for the Kumada-Corriu C-C cross-coupling reaction. A catalytic experiment with the Ni(0)@RGO recycled material was also performed. HRTEM study of the reused material after the C-S coupling reaction confirmed the retention of the original (fresh) catalyst structure. It is reusable up to the 7th cycle without any activity loss.

In Situ Synthesis of ß-Na1.5Y1.5F6: Er3+ Crystals in Oxyfluoride Silicate Glass for Temperature Sensors and Their Spectral Conversion and Optical Thermometry Analysis.

Transparent oxyfluoride glass-ceramics (GCs) with embedded ß-Na1.5Y1.5F6 crystals doped with Er3+ ions were fabricated by a melt-quenching method with subsequent heat-treatment. The structural characterizations and spectroscopic techniques were performed to verify the precipitation of ß-Na1.5Y1.5F6 crystals and partition of the Er3+ dopant into the crystals. Bright green up-conversion (UC) emission was achieved in Er3+-doped glass-ceramic (Er-GC). Furthermore, the temperature-dependent visible UC behavior based on thermally coupled energy levels (TCLs) and non-thermally coupled energy levels (NTCLs) was also examined in the temperature range 298 k to 823 K with maximum relative sensitivity (Sr) of 1.1% K-1 at 298 K for TCLs in Er-G and Er-GC samples.

Non-Linear Optical Properties of Er3+-Yb3+-Doped NaGdF4 Nanostructured Glass-Ceramics.

Transparent oxyfluoride glass-ceramics containing NaGdF4 nanocrystals were prepared by melt-quenching and doped with Er3+ (0.5 mol%) and different amounts of Yb3+ (0-2 mol%). The selected dopant concentration the crystallization thermal treatments were chosen to obtain the most efficient visible up-conversion emissions, together with near infrared emissions. The crystal size increased with dopant content and treatment time. NaGdF4 NCs with a size ranging 9-30 nm were obtained after heat treatments at Tg + 20-80 °C as confirmed by X-ray diffraction and high-resolution transmission electron microscopy. Energy dispersive X-ray analysis shows the incorporation of rare earth ions into the NaGdF4 nanocrystals. Near-infrared emission spectra, together with the up-conversion emissions were measured. The optical characterization of the glass-ceramics clearly shows that Er3+ and Yb3+ ions are incorporated in the crystalline phase. Moreover, visible up-conversion emissions could be tuned by controlling the nanocrystals size through appropriated heat treatment, making possible a correlation between structural and optical properties.

Transparent Sol-Gel Oxyfluoride Glass-Ceramics with High Crystalline Fraction and Study of RE Incorporation.

Transparent oxyfluoride glass-ceramic films and self-supported layers with composition 80SiO2-20LaF3 doped with Er3+ have been successfully synthesized by sol-gel process for the first time. Crack-free films and self-supported layer with a maximum thickness up to 1.4 µm were obtained after heat treatment at the low temperature of 550 °C for 1 min, resulting in a LaF3 crystal fraction of 18 wt%, as confirmed by quantitative Rietveld refinement. This is the highest value reported up to now for transparent oxyfluoride glass-ceramics prepared by sol-gel. This work provides a new synthesis strategy and opens the way to a wide range of potential applications of oxyfluoride glass-ceramics. The characterization by a wide range of techniques revealed the homogeneous precipitation of LaF3 nanocrystals into the glass matrix. X-ray absorption spectroscopy and electron paramagnetic resonance confirmed that the Er3+ ions are preferentially embedded in the low phonon-energy LaF3 nanocrystals. Moreover, photoluminescence (PL) measurements confirmed the incorporation of dopants in the LaF3 nanocrystals. The effective concentration of rare-earth ions in the LaF3 nanocrystals is also estimated by X-ray absorption spectroscopy.

Tunable upconversion emission in NaLuF4-glass-ceramic fibers doped with Er3+ and Yb3.

Novel glass-ceramic optical fibers containing NaLuF4 nanocrystals doped with 0.5ErF3 and 2YbF3 (mol%) have been prepared by the rod-in-tube method and controlled crystallization. NaLuF4 nanocrystals with a size around 20 nm are obtained after heat treatment at 600 °C. Intense upconverted green and red emissions due to (2H11/2, 4S3/2) → 4I15/2 and 4F9/2 → 4I15/2 transitions, respectively, together with a blue emission due to 2H9/2 → 4I15/2 transition have been observed under excitation at 980 nm. The intensity of the green and red upconversion bands shows a nearly linear dependence on the excitation power which can be explained by saturation effects in the intermediate energy states and proves that a sensitized energy transfer upconversion process is responsible for the population of the emitting levels of Er3+ ions. The upconversion emission color changes from yellow to green by increasing the excitation power density which allows to manipulate the color output of the Er3+ emission in the glass-ceramic fibers. The tunable emission color is easily detected with the naked eye. This interesting characteristic makes these glass-ceramic fibers promising materials for photonic applications.

Transparent Glass-Ceramics Produced by Sol-Gel: A Suitable Alternative for Photonic Materials.

Transparent glass-ceramics have shown interesting optical properties for several photonic applications. In particular, compositions based on oxide glass matrices with fluoride crystals embedded inside, known as oxyfluoride glass-ceramics, have gained increasing interest in the last few decades. Melt-quenching is still the most used method to prepare these materials but sol-gel has been indicated as a suitable alternative. Many papers have been published since the end of the 1990s, when these materials were prepared by sol-gel for the first time, thus a review of the achievements obtained so far is necessary. In the first part of this paper, a review of transparent sol-gel glass-ceramics is made focusing mainly on oxyfluoride compositions. Many interesting optical results have been obtained but very little innovation of synthesis and processing is found with respect to pioneering papers published 20 years ago. In the second part we describe the improvements in synthesis and processing obtained by the authors during the last five years. The main achievements are the preparation of oxyfluoride glass-ceramics with a much higher fluoride crystal fraction, at least double that reported up to now, and the first synthesis of NaGdF4 glass-ceramics. Moreover, a new SiO2 precursor was introduced in the synthesis, allowing for a reduction in the treatment temperature and favoring hydroxyl group removal. Interesting optical properties demonstrated the incorporation of dopant ions in the fluoride crystals, thus obtaining crystal-like spectra along with higher efficiencies with respect to xerogels, and hence demonstrating that these materials are a suitable alternative for photonic applications.

Theory of the kinetics of luminescence and its temperature dependence for Ag nanoclusters dispersed in a glass host.

We have measured and fitted the kinetics of luminescence of Ag nanoclusters homogeneously dispersed within the bulk of an oxyfluoride glass, with various sample temperatures. The balance equations for the populations of the excited singlet and triplet states of the Ag nanoclusters are proposed and used in this fitting while taking into account inter-system crossing between the singlet and triplet states and their wavelength dependent spontaneous decay to the ground singlet state. The involved energy barriers and rate constants and spontaneous emission cross-sections for the excited singlet and triplet states are evaluated.