Processing and characterization of new passive and active oxysulfide glasses in the Ge-Ga-Sb-S-O system

New passive and active oxysulfide glasses have been prepared in the Ge-Ga-Sb-S-O system employing a two-step melting process which involves the processing of the chalcogenide glass (ChG) and its subsequent melting with amorphous GeO₂ or Sb₂O₃ powder. Optical characterization of the oxysulfide glasses has shown that the UV cut-off wavelength decreases with increasing oxygen content. Using Raman spectroscopy, correlations have been made between the formation of new Ge- and Sb-based oxysulfide structural units, the Sb content and the O/S ratio. We demonstrate the successful processing of active rare earth doped oxysulfide glasses by melting the chalcogenide glass with Er₂O₃ and Sb₂O₃ and also by melting the Er³⁺ doped chalcogenide glass with Sb₂O₃. Modification of the emission spectra at 1500 nm of Er³⁺ doped samples with the introduction of oxygen revealed that Er³⁺ most likely exists in dual O- and S-neighbor environments. Finally, the photo-response of these new glasses upon near-IR femtosecond laser irradiation has been investigated as a function of Sb content and O/S ratio and shows that the glasses are photo-sensitive to NIR fs laser light with the magnitude of the photo-sensitivity dependent on the glass’ Sb content and O/S ratio.     

Processing and characterization of new oxy-sulfo-telluride glasses in the Ge-Sb-Te-S-O system

New oxy-sulfo-telluride glasses have been prepared in the Ge-Sb-Te-S-O system employing a two-step melting process which involves the processing of a chalcogenide glass (ChG) and subsequent melting with TeO₂ or Sb₂O₃. The progressive incorporation of O at the expense of S was found to increase the density and the glass transition temperature and to decrease the molar volume of the investigated oxy-sulfo-telluride glasses. We also observed a shift of the vis-NIR cut-off wavelength to longer wavelength probably due to changes in Sb coordination within the glass matrix and overall matrix polarizability. Using Raman spectroscopy, correlations have been shown between the formation of Ge- and Sb-based oxysulfide structural units and the S/O ratio. Lastly, two glasses with similar composition (Ge₂₀Sb₆S₆₄Te₃O₇) processed by melting the Ge₂₃Sb₇S₇₀ glass with TeO₂ or the Ge₂₃Sb₂S₇₂Te₄ glass with Sb₂O₃ were found to have slightly different physical, thermal, optical and structural properties. These changes are thought to result mainly from the higher moisture content and sensitivity of the TeO₂ starting materials as compared to that of the Sb₂O₃.     

Spectroscopic Characterisation of Metallo-Cyclodextrins for Potential Chiral Separation of Amino Acids and L/D-DOPA

The derivatives 6-Deoxy-6-[1-(2-amino)ethylamino]-β-Cyclodextrin (CDEn), 6-Deoxy-6-[1-(3-amino)propylamino]-β-Cyclodextrin (CDPn) and 6-Deoxy-6-[1-(4-amino)butylamino]-β-Cyclodextrin (CDBn) were assessed with a view to demonstrating that increasing the chain length of the diaminoalkane moiety can affect the chiral selectivity of the metallo-complexes of these materials. It was shown that IR and Raman spectroscopies can be used to characterise these compounds. The results obtained from the electronic absorption spectra suggested the formation of CuCDAm binary complexes and that the derivatives CDEn and CDPn act as bidentate ligands while CDBn acts as a monodentate ligand due to its longer alkane chain. This study also showed that in the ternary complexes with DOPA there is further coordination of the metal ion to the amino nitrogen atom and the hydroxyl oxygen atom of the drug. On the basis of the results of the circular dichroic spectroscopic studies it was suggested that CuCDEn is the better enantioselective material for DOPA and it acts in a multi-site recognition manner, utilising the inclusion properties of the CD cavity in cooperation with the coordination properties of the metal ion.     

Genesis and activity of mo-based hydrotreating catalysts prepared by a sol-gel method

Molybdenum oxide-alumina catalysts used in hydrodesulfurization (HDS) with a wide range of Mo loadings (1–25% Mo) were prepared by the sol-gel process. Two different methods of adding the molybdenum oxide precursor to the support were used.In the first route, alumina is prepared by hydrolysis of aluminium tri sec-butylate in butanol and butanediol, and molybdenum is deposited by a classical dry impregnation with ammonium heptamolybdate (AHM). In the second route, the molybdenum oxospecies are dispersed in butanediol and added to the aluminium alkoxide before hydrolysis. The solids were calcined to obtain the oxide precursors which are then sulfided to give the active phase in hydrodesulfurization.The effect of preparation on the structural properties of alumina as well as on the state and dispersion of molybdenum in the dried, calcined and sulfided form was studied by various characterization techniques (XRD, XPS, Raman spectroscopy). Molybdenum appears to be present as well dispersed oxomolybdenum species in the oxide form even at high loadings. This good dispersion of molybdenum is preserved after sulfidation which induces the formation of MoS₂ crystallites whose morphology has been determined by HREM.The catalyst activities were evaluated in thiophene hydrodesulfurization and compared with that of catalysts prepared by dry impregnation of a commercial alumina. The observed performances are in agreement with the good dispersion of molybdenum at high loadings we were able to obtain owing to the sol-gel process.     

Solution preparation of the amorphous molybdenum oxysulfide MoOS2 and its use for catalysis

Acid condensation of aqueous MoO₂S₂²⁻ anion yields amorphous MoOS₂ oxysulfide. This compound possesses tubular morphology and when freshly precipitated is soluble in polar organics such as acetone and ethanol. The ensemble of characterizations (IR, UV-visible, EXAFS spectroscopy) suggests that it contains cyclic or short linear oligomers of neutral molybdenum (V) oxysulfide MoOS₂ core. Thermal decomposition of MoOS₂ under inert atmosphere leads to the formation of a mixture of MoO₂ and MoS₂ phases. Promotion of MoOS₂ with cobalt followed by sulfidation leads to highly active HDS catalysts.     

Sol-gel powder synthesis in the TiO2-TeO2-ZnO system: Structural characterization and properties

The present study deals with the gel formation tendency in the ternary TeO₂-TiO₂-ZnO system. Depending on the TiO₂ amount, the gelation occurred at different times and subsequently several gel formation regions have been determined. Homogeneous, transparent and monolithic gels were obtained using combination of organic and inorganic precursors during the synthesis. Using XRD analysis it was established that upon the heating composites were obtained which contain an amorphous phase and different crystalline phases: TiO₂ (anatase), TiO₂ (rutile), α-TeO₂ and ZnTeO₃, depending on composition. The IR results showed that the short range order of the amorphous phases which are part of the composite materials consist of TiO₆, ZnO₄ and TeO₄ structural units. Using UV–Vis spectroscopy it was established that the absorption edge of the gels varied from 330 nm to 364 mm and the increase in TiO₂ content caused a red shifting of the cut-off. The calculated Eg values are in the range 3.41–3.75 eV higher than that of pure TiO₂, TeO₂ and ZnO oxides. The XPS results showed that the Te atoms in the surface layers of the samples studied exist in several chemical states as Te²⁺, Te⁰, but Te⁶⁺ dominates. Octahedrally coordinated Ti⁴⁺ ions are observed in the gels and in the samples annealed at 200 °C but a small amount of tetrahedrally coordinated Ti⁴⁺ is also detected, which indicates the incomplete polymerization of TiO₆ units.     

Synthesis and electrochemical characteristics of oxysulfide spinel material for lithium secondary batteries

Oxysulfide spinel LiMn₂O_3.98S_0.02 powders with monodispersed, and highly homogeneous particles were synthesized by a sol-gel method using an aqueous solution of metal acetates and sulfide containing glycolic acid as a chelating agent. The oxysulfide spinel, LiMn₂O_3.98S_0.02 electrode initially delivers 80 mAh g⁻¹, steadily increases during cycling, and reaches 99 mAh g⁻¹ at the 20th cycle. The substitution of a small amount S for O in LiMn₂O₄ spinel helps to maintain structural integrity during cycling, which then overcomes the Jahn–Teller distortion in the spinel Mn phase in the 3 V region.     

Thermal,IR, Raman characteristics,Raman gain coefficient and bandwidths in quaternary glasses

Tellurite glasses with composition 75TeO₂–5WO₃–15Nb₂O₅–5M_xO_y in mol%, where M_xO_y = (Na₂O, Ag₂O, ZnO, MgO, CuO, NiO, TiO₂, MnO₂) have been prepared by using the conventional melt-quenching method. Thermal characteristic of prepared glasses were investigated by using DTA techniques. It was found that the glass with the composition 751TeO₂–5WO₃–15Nb₂O₅–5TiO₂ had high thermal stability (ΔT = 122 °C at heating rate 15 K/min). Raman gain coefficients and bandwidths of prepared glasses for Raman gain media were evaluated. The glass with composition 75TeO₂–5WO₃–15Nb₂O₅–5Na₂O had the maximum value of Raman gain coefficient (g = 4.43 × 10⁻¹² m/W) and it was 24 times as large as silica glass. The highest value of full width half maximum (FWHM ≈ 185 cm⁻¹) was observed in glass system 75TeO₂–5WO₃–15Nb₂O₅–5NiO. Finally, the structure of the glasses was investigated through deconvolution Raman and IR spectra.     

Spectroscopic characterization of lithium doped borate glasses

B₂O₃-xLi₂O₃ (x=0, 0.1, 0.5) glasses have been prepared by the Sol-Gel method. The evolution of the composition and the structure of the materials upon thermal treatments are analyzed. Raman spectroscopy measurements reveal that the structure transforms from crystalline to amorphous. After a thermal treatment at 400°C, the materials exhibit a strong luminescence band which disappears upon further heating. In the case of no dopant (x=0) heating at 1150°C results in a Raman spectrum which is almost identical to the one corresponding to bulk B₂O₃ glass obtained by melting and quenching.     

Crystal structure and electrical properties of the mixed valent titanium oxysulfide Sm2Ti2S2O4.5

A new phase Sm₂Ti₂S₂O_4.5 was synthesized and its crystal structure was solved by single-crystal X-ray diffraction. This compound crystallizes in the monoclinic system (C2/m) with lattice constants a=17.9987(11) Å, b=3.71607(14) Å, c=12.6172(8) Å and β=133.645(4)°. The structure is built up from double chains of Ti-centered octahedra between which Sm-polyhedra develop. In spite of very close formulations, the structure of Sm₂Ti₂S₂O_4.5 differs completely from that of the defect Ruddelsden-Popper phase Sm₂Ti₂S₂O₅ previously reported. The title compound presents a mixed valence for titanium with Ti(III) (d¹) and Ti(IV) (d⁰) located in different crystallographic sites. However, conductivity measurements show that this compound is non-metallic.     

Substitutional carbon defects in silicon: A quantum mechanical characterization through the infrared and Raman spectra

The infrared (IR) and Raman spectra of eight substitutional carbon defects in silicon are computed at the quantum mechanical level by using a periodic supercell approach based on hybrid functionals, an all electron Gaussian type basis set and the CRYSTAL code. The single substitutional C _s case and its combination with a vacancy (C _sV and C _sSiV) are considered first. The progressive saturation of the four bonds of a Si atom with C is then examined. The last set of defects consists of a chain of adjacent carbon atoms C, with i = 1–3. The simple substitutional case, C _s, is the common first member of the three sets. All these defects show important, very characteristic features in their IR spectrum. One or two C related peaks dominate the spectra: at 596 cm⁻¹ for C _s (and C _sSiV, the second neighbor vacancy is not shifting the C _s peak), at 705 and 716 cm⁻¹ for C _sV, at 537 cm⁻¹ for C and C (with additional peaks at 522, 655 and 689 for the latter only), at 607 and 624 cm⁻¹, 601 and 643 cm⁻¹, and 629 cm⁻¹ for SiC, SiC, and SiC, respectively. Comparison with experiment allows to attribute many observed peaks to one of the C substitutional defects. Observed peaks above 720 cm⁻¹ must be attributed to interstitial C or more complicated defects.     

A new organically templated gallium(III)-doped chromium(III) fluorophosphite, (C2H10N2)[Ga0.98Cr0.02(HPO3)F3] hydrothermal synthesis, crystal structure and spectroscopic properties

A new organically templated fluoro-phosphite gallium(III)-doped chromium(III) with formula (C₂H₁₀N₂)[Ga_0.98Cr_0.02(HPO₃)F₃] has been synthesized by using mild hydrothermal conditions under autogeneous pressure. The crystal structure has been solved from X-ray single-crystal data. The compound crystallizes in the P2₁2₁2₁ orthorhombic space group, with the unit-cell parameters a=12.9417(7) Å, b=9.4027(6) Å, c=6.3502(4) Å and Z=4. The final R factors were R1=0.022 (all data) and wR2=0.050. The crystal structure consists of [Ga_0.98Cr_0.02(HPO₃)F₃]²⁻ anionic chains extended along the c-axis, with the ethylenediammonium cations placed in the cavities of the structure delimited by three different chains. The IR and Raman spectra show the characteristic bands of the phosphite oxoanion. The diffuse reflectance spectroscopy allowed us to calculate the Dq and Racah parameters of the Cr(III) cations in octahedral environment. The values are Dq=1375 cm⁻¹, B=780 cm⁻¹ and C=3420 cm⁻¹. The polycrystalline ESR spectra performed at X and Q-bands show the signals belonging to the diluted Cr(III) cation in this phase. From the fit of the X-band ESR spectrum at 4.2 K, the calculated values of the axial (D) and rhombic (E) distortion parameters are 0.075 and 0.042 cm⁻¹, respectively, the components of the g-tensor being g_x=1.98, g_y=1.99 and g_z=1.90.     

Spectroscopic characterization of natural corals

The FTIR, micro-Raman, NMR, and XPS spectra of 25 different natural corals have been compared. Reflectance and transmission absorbance IR and Raman data have been used as rapid and efficient means of classification of natural corals containing aragonite (non-precious white species), calcite (red, pink, precious white species), and organic material (black protein polymer). The combination of reflectance IR and infrared microscopy could serve as a rapid, non-destructive method for distinguishing natural corals from artificial, fake jewels.     

Spectroscopic and potentiometric studies of the interaction of adenine with trivalent metal ions

Potentiometric titration was used to determine the potentiometric diagrams of complexes of adenine with Al³⁺, Cr³⁺, and Fe³⁺. IR and Raman spectra of solids show that the interaction of adenine with Cr³⁺ is not as strong as the other metals. Fe³⁺ binds to adenine at low and medium pH values at an Fe³⁺–adenine ratio of 6, while Al³⁺ binds to adenine at all pH values at an Al³⁺–adenine ratio of 8. The IR band associated with N-9–H is split into two components at high and low wavenumbers; IR band splitting has been observed for groups with a large dipole moment such as carbonyl and phosphate. To the best of our knowledge, this is the first time to see the splitting of IR bands involving a nitrogen. We also obtained potentiometric titration plots for adenine with Al³⁺, Cr³⁺, and Fe³⁺, independently, in various molar ratios which showed an interaction with adenine, consistent with the IR and Raman findings. Metal–adenine-hydroxo complexes were formed.     

Synthesis and characterization of new borate-vanadate mixed glasses

Summary It has been found that a series of M_xO_y-V₂O₅-B₂O₃glasses (M_xO_y=Li₂O, Na₂O, K₂O and MgO) containing 10 mol%<span style='font-size:12.0pt;font-family: Symbol;mso-bidi-font-family:Symbol'>a-Fe₂O₃exhibited glass-forming regions that shifted with the content of network modifier (NWM) compared to B₂O₃and V₂O₅glasses. The M?ssbauer spectra of a series of M_xO_y-V₂O₅-B₂O₃glasses showed increased quadrupole splitting (D) with increasing NWM content. This suggests that the coordination numbers of the V⁴⁺and V⁵⁺are fixed and that the formation number of non-bridging oxygens (NBO) is considered to increase with increasing NWM content, and with increasing formation number of NBO, the Fe³⁺ion site changes from VO₄to BO₄tetrahedra. Consequently, the quadrupole splitting increases with increasing NWM content.     

Compositional dependence of the nonlinear refractive index of new germanium-based chalcogenide glasses

In this paper, we report results of n₂ measurements of new chalcogenide glasses in the Ge-Sb-S-Se system using a modified Z-Scan technique. Measurements were made with picosecond pulses emitted by a 10 Hz Q-switched mode-locked Nd-YAG laser at 1064 nm under conditions suitable to characterize ultrafast nonlinearities. The nonlinear index increases up to 500 times the n₂ of fused silica with an increase in the Ge/Se ratio and a decrease with an increase of the Ge/Sb ratio. We confirmed, using Raman spectroscopy, that the nonlinear refractive index depends on the number of Ge-S(Se) and Sb-S(Se) bonds in the glass network. Sulfide glasses were shown to have a nonlinear FOM near or <1, at 1064 nm.     

Catalytic and physicochemical properties of crystalline pentasils in transformations of low-molecular-weight olefins and paraffins

The features of the catalytic action of pentasil type zeolites in transformations of low-molecular-weight olefins and paraffins are reviewed. Principal results describing the physicochemical properties of pentasils elucidated by IR spectroscopy, electron microscopy, XPS, and ESR are discussed. The mechanism of the formation of catalytically active sites on the surface of pentasils and the location of modifying elements in the zeolite frameworks are examined. The role of Lewis and Bronsted acid sites in promoting single pathways in the transformations of lower hydrocarbons is specified.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1018–1028, June, 1993.     

Spectroscopic characterization of crystalline AlF3 phases

A comprehensive spectroscopic characterization of all known crystalline AlF₃ phases (α-, β-, η-, κ-, θ-AlF₃) is presented for the first time in this study. Beside their X-ray diffraction powder patterns, which were already published in the literature, ²⁷Al and ¹⁹F MAS NMR, FT IR and XPS spectroscopic techniques were applied for all phases in a consistent manner. For all phases prepared the utilization of ²⁷Al satellite transition (SATRAS) NMR allowed to determine the quadrupolar parameters of the aluminium sites including their distributions.In addition, η-AlF₃ was isolated with high phase purity and characterized following a new preparation path different from those known so far in the literature.