The Co-Entrapment of a Homogeneous Catalyst and an Ionic Liquid by a Sol-gel Method: Recyclable Ionogel Hydrogenation Catalysts

Molecular hydrogenation catalysts have been co-entrapped with the ionic liquid [Bmim]NTf(2) inside a silica matrix by a sot-gel method. These catalytic ionogels have been compared to simple catalyst-doped glasses, the parent homogeneous catalysts, commercial heterogeneous catalysts, and Rh-doped mesoporous silica. The most active ionogel has been characterised by transmission electron microscopy, X-ray photoelectron spectroscopy, and solid state NMR before and after catalysis. The ionogel catalysts were found to be remarkably active, recyclable and resistant to chemical change.

Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Vidros e vitrocerâmicas em sistemas oxifluoretos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Verres et vitrocéramiques à base de chalco: halogénures dopés par des ions de terres rares pour la luminescence dans le visible

Pós-graduação em Química - IQ

Growth kinetics of CdS in germanium oxide glassy matrix

In the present work we revisit the size data of CdS microcrystals previously collected in the glassy matrix of Germanium oxide. The CdS clusters analyzed using electron microscopy images have shown a wurtzite structure. The mean average radius, dispersion and volume evaluated from the histograms showed good agreement for t(1/3), t(2/3) and t laws, respectively. We observed that the amount of microcrystals remains constant throughout the heat treatment process, as well as that the radii distribution has a lower limit and increases with heat treatment. The distribution of radii follows a distribution similar to the Lifshitz-Slyozov-Wagner distribution limited in the origin. Discussions led to the conclusion that the growth of CdS is a process that occurs after the fluctuating nucleation and coalescence phases. We then analyze the growth process, assuming that the evaporation is overcome by the precipitation rate, stabilizing all clusters with respect to dissolution back into the matrix. The problem was simplified neglecting anisotropy and the assuming a spherical shape for clusters and particles. The low interface tension was described in terms of an empirical potential barrier in the surface of the cluster. The growth dynamics developed considering that the number of clusters remains constant, and that the minimum size of these clusters grow with time, as the first order approximation showed a good agreement with the flaw. (C) 2012 Elsevier B.V. All rights reserved.

Semiconductor saturable absorber mirror passively Q-switched 2.97 μm fluoride fiber laser

A diode-cladding-pumped mid-infrared passively Q-switched Ho3+-doped fluoride fiber laser using a reverse designed broad band semiconductor saturable mirror (SESAM) was demonstrated. Nonlinear reflectivity of the SESAM was measured using an in-house Yb3+-doped mode-locked fiber laser at 1062 nm. Stable pulse train was produced at a slope efficient of 12.1% with respect to the launched pump power. Maximum pulse energy of 6.65 μ J with a pulse width of 1.68 μ s and signal-to-noise ratio (SNR) of ∼50 dB was achieved at a repetition rate of 47.6 kHz and center wavelength of 2.971 μ m. To the best of our knowledge, this is the first 3 μ m region SESAM-based Q-switched fiber laser with the highest average power and pulse energy, as well as the longest wavelength from mid-infrared passively Q-switched fluoride fiber lasers. © 2014 Astro Ltd.

Semiconductor saturable absorber mirror passively Q-switched 2.97 μm fluoride fiber laser

A diode-cladding-pumped mid-infrared passively Q-switched Ho 3+-doped fluoride fiber laser using a reverse designed broad band semiconductor saturable mirror (SESAM) was demonstrated. Nonlinear reflectivity of the SESAM was measured using an in-house Yb3+-doped mode-locked fiber laser at 1062 nm. Stable pulse train was produced at a slope efficient of 12.1% with respect to the launched pump power. Maximum pulse energy of 6.65 μJ with a pulse width of 1.68 μs and signal to noise ratio (SNR) of ~50 dB was achieved at a repetition rate of 47.6 kHz and center wavelength of 2.971 μm. To the best of our knowledge, this is the first 3 μm region SESAM based Q-switched fiber laser with the highest average power and pulse energy, as well as the longest wavelength from mid-infrared passively Q-switched fluoride fiber lasers. © 2014 SPIE.

Strong visible up-conversion emission in Tb3+, Tm3+ and Tb3+-Tm3+ co-doped tellurite glasses sensitized by Yb3+

Up-conversion luminescence characteristics under 975 nm excitation have been investigated with Tb3+/Tm3+/Yb3+ triply doped tellurite glasses. Here, green (547 nm: D-5(4) --> F-7(4)) and red (660 nm: D-5(4) --> F-7(2)) up-conversion (UC) luminescence originating from Tb3+ is observed strongly, because of the quadratic dependences of emission intensities on the excitation power. Especially, the UC luminescence was intensified violently with the energy transfer from the Tm3+ ions involves in the Tb3+ excitation. To the Tb3+/Tm3+/Yb3+ triply doped glass system, a novel up-conversion mechanism is proposed as follows: the energy of (3)G(4) level (Tm3+) was transferred to D-5(4) (Tb3+) and the 477-nm UC luminescence of Tm3+ was nearly quenched. (C) 2006 Elsevier B.V. All rights reserved.

Upconversion emissions in Yb3+-Tm3+-doped tellurite glasses excited at 976 nm

Intense Tm3+ blue upconversion emission has been observed in Tm3+-Yb3+ codoped oxyfluoride tellurite glass under excitation with a diode laser at 976 nm. Three emission bands centered at 475, 650 and 796 nm corresponding to the transitions (1)G(4) -> H-3(6), (1)G(4) -> H-3(4) and F-3(4) -> H-3(6), respectively, simultaneously occur. The dependence of upconversion intensities on Tm3+ ions concentration and excitation power are investigated. For fixed Yb2O3 concentrations of 5.0 mol%, the maximum upconversion intensity was obtained with Tm2O3 concentration of about 0.1 mol%. The blue upconversion luminescence lifetimes of the Tm3+ transitions (1)G(4) -> H-3(6) are measured. The results are evaluated by the possible upconversion mechanisms.

Intense frequency upconversion fluorescence of Er3+/Yb3+ co-doped lithium-strontium-lead-bismuth glasses

Infrared-to-visible upconversion fluorescence of Er(3+)/Yb(3+) co-doped lithium-strontium-lead-bismuth (LSPB) glasses for developing potential upconversion lasers has been studied under 975-nm excitation. Based on the results of energy transfer efficiency and upconversion spectra, the optimal Yb(3+)-Er(3+) concentration ratio is found to be 5:1. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions 2H_(11/2)-->4I_(15/2), 4S_(3/2)-->4I_(15/2), and 4F_(9/2)-->4I_(15/2), respectively, were observed. The quadratic dependence of the 525-, 546-, and 657-nm emissions on excitation power indicates that a two-photon absorption process occurs under 975-nm excitation. The high-populated 4I_(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. The intense upconversion luminescence of Er(3+)/Yb(3+) co-doped LSPB glasses may be a potentially useful material for developing upconversion optical devices.

Upconversion luminescence and mechanisms in Yb3+-sensitized Tm3+-doped oxyhalide tellurite glasses

Effect of Yb2O3 content on upconversion luminescence and mechanisms in Yb3+-sensitized Tm3+-doped oxyhalide tellurite glasses were investigated under 980 nm excitation. Intense blue and relatively weak red upconversion emission centered at 476 and 649nm corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4) of Tm3+, respectively, are simultaneously observed at room temperature. The results show that upconversion blue and red emission intensities of Tm3+ first increase, reach its maximum at Yb2O3% = 3 mol%, and then decrease with increasing Yb2O3 content. The effect of Yb2O3 content on upconversion intensity is discussed, and possible effect mechanisms are evaluated. The investigated results were conducing to increase upconversion luminescence efficiency of Tm3+. (c) 2005 Elsevier B.V. All rights reserved.

Effect of lithium-sodium mixed-alkali on phase transformation kinetics in Er3+/Yb3+ co-doped aluminophosphate glasses

Er3+ doped aluminophosphate glasses with various Na2O/Li2O ratios were prepared at 1250 degrees C using a silica crucible to study mixed alkali effect (MAE). The effect of relative alkali content on glass transition temperature, crystallization temperature and thermal stability were investigated using differential scanning calorimetry (DSC). In addition, apparent activation energies for crystallization, E, were determined employing the Kissinger equation. The effect of Al2O3 content on the magnitude of MAE was also discussed. No mixed-alkali effect is observed on crystallization temperature. (c) 2006 Elsevier B.V. All rights reserved.

Tb3+/Yb3+ heavily-doped tellurite glasses with efficient green light emission

Without introducing concentration quenching phenomenon, a few wt% of Tb3+ and Yb3+ ions were doped into a group of easily-fiberized tellurite glasses characterized by loose polyhedron structures and rich interstitial positions. Intense green upconversion emission from Tb3+ ions centered at 539 nm due to transition 5D4→7F5 was observed by direct excitation of Yb3+ ions with a laser diode at 976 nm. Optimizing the concentration ratio of Tb3+/Yb3+, a tellurite glass with composition of 80TeO2-10ZnO-10Na2O (mol%)+1.0wt% Tb2O3+3.0wt% Yb2O3 was found to present the highest green light intensity and therefore is especially suitable for efficient green fiber laser development.