Martina Tribus

A Synthesis and Crystal Chemical Study of the Fast Ion Conductor Li7–3xGaxLa3 Zr2O12 with x = 0.08 to 0.84

Fast-conducting phase-pure cubic Ga-bearing Li7La3Zr2O12 was obtained using solid-state synthesis methods with 0.08 to 0.52 Ga3+ pfu in the garnet. An upper limit of 0.72 Ga3+ pfu in garnet was obtained, but the synthesis was accompanied by small amounts of La2Zr2O12 and LiGaO3. The synthetic products were characterized by X-ray powder diffraction, electron microprobe and SEM analyses, ICP-OES measurements, and 71Ga MAS NMR spectroscopy. The unit-cell parameter, a0, of the various garnets does not vary significantly as a function of Ga3+ content, with a value of about 12.984(4) Å. Full chemical analyses for the solid solutions were obtained giving: Li7.08Ga0.06La2.93Zr2.02O12, Li6.50Ga0.15La2.96Zr2.05O12, Li6.48Ga0.23La2.93Zr2.04O12, Li5.93Ga0.36La2.94Zr2.01O12, Li5.38Ga0.53La2.96Zr1.99O12, Li4.82Ga0.60La2.96Zr2.00O12, and Li4.53Ga0.72La2.94Zr1.98O12. The NMR spectra are interpreted as indicating that Ga3+ mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet.

Nanoindentation, High-Temperature Behavior, and Crystallographic/Spectroscopic Characterization of the High-Refractive-Index Materials TiTa2O7 and TiNb2O7.

Colorless single crystals, as well as polycrystalline samples of TiTa2O7 and TiNb2O7, were grown directly from the melt and prepared by solid-state reactions, respectively, at various temperatures between 1598 K and 1983 K. The chemical composition of the crystals was confirmed by wavelength-dispersive X-ray spectroscopy, and the crystal structures were determined using single-crystal X-ray diffraction. Structural investigations of the isostructural compounds resulted in the following basic crystallographic data: monoclinic symmetry, space group I2/m (No. 12), a = 17.6624(12) Å, b = 3.8012(3) Å, c = 11.8290(9) Å, β = 95.135(7)°, V = 790.99(10) Å(3) for TiTa2O7 and a = 17.6719(13) Å, b = 3.8006(2) Å, c = 11.8924(9) Å, β = 95.295(7)°, V = 795.33(10) Å(3), respectively, for TiNb2O7, Z = 6. Rietveld refinement analyses of the powder X-ray diffraction patterns and Raman spectroscopy were carried out to complement the structural investigations. In addition, in situ high-temperature powder X-ray diffraction experiments over the temperature range of 323-1323 K enabled the study of the thermal expansion tensors of TiTa2O7 and TiNb2O7. To determine the hardness (H), and elastic moduli (E) of the chemical compounds, nanoindentation experiments have been performed with a Berkovich diamond indenter tip. Analyses of the load-displacement curves resulted in a hardness of H = 9.0 ± 0.5 GPa and a reduced elastic modulus of Er = 170 ± 7 GPa for TiTa2O7. TiNb2O7 showed a slightly lower hardness of H = 8.7 ± 0.3 GPa and a reduced elastic modulus of Er = 159 ± 4 GPa. Spectroscopic ellipsometry of the polished specimens was employed for the determination of the optical constants n and k. TiNb2O7 as well as TiTa2O7 exhibit a very high average refractive index of nD = 2.37 and nD = 2.29, respectively, at λ = 589 nm, similar to that of diamond (nD = 2.42).

Development of magnetic ytterbium oxide core–shell particles for selectively trapping phosphopeptides

Protein phosphorylation is one of the most important post-translational modifications and plays a key role in a large number of cellular processes. The progress in studying protein phosphorylation is largely based on the development of novel, selective and sensitive sample preparation tools for mass spectrometry. Here we report for the first time magnetic core–shell particles based on ytterbium for the selective enrichment of phosphopeptides from complex samples including human saliva. The newly fabricated Fe3O4@SiO2@Yb2O3 particles exhibit two unique features, which are specificity and response to a magnetic field. Thus, phosphopeptides are easily enriched on magnetic core–shell particles. In a further step, particles are simply removed from the sample matrix by applying a magnetic field. Electrostatic interactions, stable bidentate ligand chemistry and the high coordination number of ytterbium provide high selectivity, which was demonstrated for a spiked protein standard with a 10 000 fold background. The limit of detection was found to be in the femtomolar range for the applied mass spectrometer. Furthermore, magnetic Fe3O4@SiO2@Yb2O3 particles were compared to classical phosphopeptide enrichment by titanium oxide and revealed higher recoveries for the core–shell particles. The synthesized core–shell particles also allow the enrichment of multiply phosphorylated peptides.

Monoclinic structure and nonstoichiometry of 'KAlSiO4-O1'.

Crystals of KAlSiO4-O1 (potassium aluminium silicate) were synthesized using a flux method and analysed utilizing single-crystal X-ray diffraction and electron microprobe analysis. Both methods confirm that the crystals are nonstoichiometric according to K(1-x)Al(1-x)Si(1+x)O4 with x = 0.04 (1). KAlSiO4-O1 is closely related to the stuffed derivatives of tridymite, although the topology of the Si/Al-ordered framework is different. Six-membered rings of UUDDUD and UUUDDD (U = up and D = down; ratio 2:1) configurations are present in layers parallel to the ab plane. In contrast, the framework of tridymite exhibits UDUDUD rings. The crystals are affected by inversion, pseudo-orthorhombic and pseudo-hexagonal twinning.

Verbeekite, the Long-Unknown Crystal Structure of Monoclinic PdSe2

Verbeekite, a monoclinic polymorph of PdSe2, was reported for the first time in 2002 by Roberts et al. The mineral has been discovered in the Musonoi Cu-Co-Mn-U mine, Democratic Republic of Congo, and was named after Dr. Théodore Verbeek, the first geoscientist who studied the palladium mineralization there (1955-1967). Until today, the crystal structure of this very rare mineral has been unknown. By syntheses via multianvil high-pressure/high-temperature methods at 11.5 GPa and 1300 °C, synthetic verbeekite could be obtained in a high degree of purity and comparatively good crystal quality, which made it possible to determine the full crystal structure for PdSe2 verbeekite from single-crystal X-ray diffractometer data: I2/a, a = 671.0(2) pm, b = 415.42(8) pm, c = 891.4(2) pm, β = 92.42(3)°, V = 248.24(4) Å3, R1 = 0.0368, wR2 = 0.0907 (all data). In contrast to layered PdS2-type PdSe2, verbeekite exhibits a novel crystal structure type of dichalcogenides of the platinum-group metals with (Se2)2- dimer anions connecting the layers. The possibility of different arrangements of the characteristic (Se2)2- dumbbells is the reason for the various polymorphs of the dichalcogenides, with now five known PdSe2 representatives.

Single-crystal structure of pyrite-type HP-Pd0.84(1)Se2 prepared by high-pressure/ high-temperature synthesis

Abstract At ambient conditions, PdSe2 dichalcogenides crystallize in the layered PdS2-type structure. If pressure is applied, the coordination number of palladium atoms increases and the three-dimensional pyrite-type structure with octahedral (PdSe6)4− coordination geometry is observed. For the first time, single crystals of a pyrite-type PdSe2 modification could be obtained and characterized, which were grown by multianvil high-pressure/high-temperature synthesis at 7.5 GPa and 1023 K. The crystals show the expected pyrite-type space group Pa3̅ (no. 205) and refinement results of a=613.26(3) pm, R1=0.0233, and wR2=0.0247 (all data) were received for HP-Pd0.84(1)Se2. The single-crystal data revealed significant defect formation on the palladium site with 16% vacancies, which is in line with the orthorhombic PdX2-type high-pressure polymorphs HP-Pd0.94(1)S2 and HP-Pd0.88(1)Se2. The tendency of vacancy formation on the palladium site could also be verified by EDX measurements.

Synthesis, Crystal Structure, and Compressibilities of Mn3−x Ir5B2+x (0≤x≤0.5) and Mn2IrB2

Abstract The new ternary transition metal borides Mn3‐xIr5B2+x (0≤x≤0.5) and Mn2IrB2 were synthesized from the elements under high temperature and high‐pressure/high‐temperature conditions. Both phases can be synthesized as powder samples in a radio‐frequency furnace in argon atmosphere. High‐pressure/high‐temperature conditions were used to grow single‐crystals. The phases represent the first ternary compounds within the system Mn–Ir–B. Mn3−xIr5B2+x (0≤x≤0.5) crystallizes in the Ti3Co5B2 structure type (P4/mbm; no. 127) with parameters a=9.332(1), c=2.896(2) Å, and Z=2. Mn2IrB2 crystallizes in the β‐Cr2IrB2 crystal structure type (Cmcm; no. 63) with parameters a=3.135(3), b=9.859(5), c=13.220(3) Å, and Z=8. The compositions of both compounds were confirmed by EDX measurements and the compressibility was determined experimentally for Mn3−xIr5B2+x and by DFT calculations for Mn2IrB2.

Synthesis and characterization of the alkali borate-nitrates Na3–x Kx[B6O10]NO3 (x=0.5, 0.6, 0.7)

Abstract Three novel mixed alkali borate-nitrates Na3−x Kx[B6O10]NO3 (x=0.5, 0.6, 0.7) were synthesized hydrothermally; their crystal structures were determined through Rietveld analyses, and supported through EDX as well as vibrational spectroscopy. The phases represent solid solutions of the alkali borate-nitrate Na3(NO3)[B6O10], which was reported in 2002 as a “New type of boron-oxygen framework in the Na3(NO3)[B6O10] crystal structure” (O. V. Yakubovich, I. V. Perevoznikova, O. V. Dimitrova, V. S. Urusov, Dokl. Phys. 2002, 47, 791). Only two of the three crystallographically independent Na+ positions in the new structures are partially substituted by K+; a pure potassium borate-nitrate was not formed until now. The cell parameters of the novel phases vary from a=1261.72(5)–1267.12(5), b=1004.19(5)–1007.96(4), c=770.55(3)–774.38(3) pm, and V=0.97630(6)–0.98905(6) nm3 in the orthorhombic space group Pnma (no. 62), in alignment with increasing K+ content.

Synthesis and characterization of the novel rare earth orthophosphates Y0.5Er0.5PO4 and Y0.5Yb0.5PO4

Abstract The new mixed rare earth (RE) orthophosphates Y0.5Er0.5PO4 and Y0.5Yb0.5PO4 were synthesized by a classical solid state reaction in an electrical furnace at 1200 °C. As starting materials, the corresponding rare earth oxides and diammonium hydrogen phosphate were used. The powder diffraction analyses revealed that the new compounds Y0.5Er0.5PO4 and Y0.5Yb0.5PO4 crystallize in a zircon-type structure being isostructural with the rare earth orthophosphate YPO4. Y0.5Er0.5PO4 and Y0.5Yb0.5PO4 crystallize in the tetragonal space group I41/amd (no. 141) with four formula units in the unit cell. The structural parameters based on Rietveld refinements are a = 687.27(2), c = 601.50(2) pm, V = 0.28412(1) nm3, Rp= 0.0143, and Rwp = 0.0186 (all data) for Y0.5Er0.5PO4 and a = 684.61(2), c = 599.31(2) pm, V = 0.28089(2) nm3, Rp = 0.0242, and Rwp = 0.0313 (all data) for Y0.5Yb0.5PO4. Furthermore, the structure of Y0.5Er0.5PO4 was refined from single-crystal X-ray diffraction data: a = 687.78(5), c = 601.85(4) pm, V = 0.28470(5) nm3, R1= 0.0165, and wR2 = 0.0385 (all data). In both compounds, the rare earth metal ions are eightfold coordinated by oxygen atoms, forming two unique interlocking tetrahedra with two individual RE–O distances. The tetrahedral phosphate groups [PO4]3– are slightly distorted in both compounds. The individual rare earth ions share a common position (Wyckoff site 4a). The presence of two rare earth ions in the structures of the new orthophosphates Y0.5Er0.5PO4 and Y0.5Yb0.5PO4 was additionally confirmed by single-crystal EDX spectroscopy revealing a ratio of 1:1.

Mechanical Properties, Quantum Mechanical Calculations, and Crystallographic/Spectroscopic Characterization of GaNbO4, Ga(Ta,Nb)O4, and GaTaO4

Single crystals as well as polycrystalline samples of GaNbO4, Ga(Ta,Nb)O4, and GaTaO4 were grown from the melt and by solid-state reactions, respectively, at various temperatures between 1698 and 1983 K. The chemical composition of the crystals was confirmed by wavelength-dispersive electron microprobe analysis, and the crystal structures were determined by single-crystal X-ray diffraction. In addition, a high-P-T synthesis of GaNbO4 was performed at a pressure of 2 GPa and a temperature of 1273 K. Raman spectroscopy of all compounds as well as Rietveld refinement analysis of the powder X-ray diffraction pattern of GaNbO4 were carried out to complement the structural investigations. Density functional theory (DFT) calculations enabled the assignment of the Raman bands to specific vibrational modes within the structure of GaNbO4. To determine the hardness (H) and elastic moduli (E) of the compounds, nanoindentation experiments have been performed with a Berkovich diamond indenter tip. Analyses of the load-displacement curves resulted in a high hardness of H = 11.9 ± 0.6 GPa and a reduced elastic modulus of Er = 202 ± 9 GPa for GaTaO4. GaNbO4 showed a lower hardness of H = 9.6 ± 0.5 GPa and a reduced elastic modulus of Er = 168 ± 5 GPa. Spectroscopic ellipsometry of the polished GaTa0.5Nb0.5O4 ceramic sample was employed for the determination of the optical constants n and k. GaTa0.5Nb0.5O4 exhibits a high average refractive index of nD = 2.20, at λ = 589 nm. Furthermore, in situ high-temperature powder X-ray diffraction experiments enabled the study of the thermal expansion tensors of GaTaO4 and GaNbO4, as well as the ability to relate them with structural features.