Lukas Perfler

Hydrogen Surface Reactions and Adsorption Studied on Y2O3, YSZ, and ZrO2.

The surface reactivity of Y2O3, YSZ, and ZrO2 polycrystalline powder samples toward H2 has been comparatively studied by a pool of complementary experimental techniques, comprising volumetric methods (temperature-programmed volumetric adsorption/oxidation and thermal desorption spectrometry), spectroscopic techniques (in situ electric impedance and in situ Fourier-transform infrared spectroscopy), and eventually structural characterization methods (X-ray diffraction and scanning electron microscopy). Reduction has been observed on all three oxides to most likely follow a surface or near-surface-limited mechanism involving removal of surface OH-groups and associated formation of water without formation of a significant number of anionic oxygen vacancies. Partly reversible adsorption of H2 was proven on the basis of molecular H2 desorption. Dictated by the specific hydrophilicity of the oxide, readsorption of water eventually takes place. The inference of this surface-restricted mechanism is further corroborated by the fact that no bulk structural and/or morphological changes were observed upon reduction even at the highest reduction temperatures (1173 K). We anticipate relevant implications for the use of especially YSZ in fuel cell research, since in particular the chemical state and structure of the surface under typical reducing high-temperature conditions affects the operation of the entire cell.

Methane Decomposition and Carbon Growth on Y2O3, Yttria-Stabilized Zirconia, and ZrO2

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents.

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).

High-Pressure Synthesis and Characterization of the Actinide Borate Phosphate U2(BO4)(PO4)

A new actinide borate phosphate, U2[BO4][PO4], was synthesized in a Walker-type multianvil apparatus at 12.5 GPa and 1000 °C. The crystal structure was determined from single-crystal X-ray diffraction data collected at room temperature. U2[BO4][PO4] crystallizes in the monoclinic space group P21/c with four formula units per unit cell and the lattice parameters a = 854.6(2), b = 775.3(2), c = 816.3(2) pm, and β = 102.52(3)°. The structure consists of double layers of linked uranium–oxygen polyhedra parallel to [100]. The borate tetrahedra are located between the uranium–oxygen layers inside the double layer. The phosphate groups link the double layers.

High-Pressure Synthesis and Characterization of New Actinide Borates, AnB4O8 (An=Th, U)

New actinide borates ThB4O8 and UB4O8 were synthesized under high-pressure, high-temperature conditions (5.5 GPa/1100 °C for thorium borate, 10.5 GPa/1100 °C for the isotypic uranium borate) in a Walker-type multianvil apparatus from their corresponding actinide oxide and boron oxide. The crystal structure was determined on basis of single-crystal X-ray diffraction data that were collected at room temperature. Both compounds crystallized in the monoclinic space group C2/c (Z=4). Lattice parameters for ThB4O8: a=1611.3(3), b=419.86(8), c=730.6(2) pm; β=114.70(3)°; V=449.0(2) Å3; R1=0.0255, wR2=0.0653 (all data). Lattice parameters for UB4O8: a=1589.7(3), b=422.14(8), c=723.4(2) pm; β=114.13(3)°; V=443.1(2) Å3; R1=0.0227, wR2=0.0372 (all data). The new AnB4O8 (An=Th, U) structure type is constructed from corner-sharing BO4 tetrahedra, which form layers in the bc plane. One of the four independent oxygen atoms is threefold-coordinated. The actinide cations are located between the boron–oxygen layers. In addition to Raman spectroscopic investigations, DFT calculations were performed to support the assignment of the vibrational bands.

High-pressure syntheses and crystal structures of orthorhombic DyGaO3 and trigonal GaBO3

Abstract Orthorhombic dysprosium orthogallate DyGaO3 and trigonal gallium orthoborate GaBO3 were synthesized in a Walker-type multianvil apparatus under high-pressure/high-temperature conditions of 8.5 GPa/1350 °C and 8 GPa/700 °C, respectively. Both crystal structures could be determined by single-crystal X-ray diffraction data collected at room temperature. The orthorhombic dysprosium orthogallate crystallizes in the space group Pnma (Z = 4) with the parameters a = 552.6(2), b = 754.5(2), c = 527.7(2) pm, V = 0.22002(8) nm3, R1 = 0.0309, and wR2 = 0.0662 (all data) and the trigonal compound GaBO3 in the space group R3̅c (Z = 6) with the parameters a = 457.10(6), c = 1419.2(3) pm, V = 0.25681(7) nm3, R1 = 0.0147, and wR2 = 0.0356 (all data).

Structural, spectroscopic and computational studies on the monoclinic polymorph (form I) of potassium hydrogen disilicate (KHSi2O5)

Abstract Hydrothermal treatment of quartz with 2 M K2CO3 solutions at 623 K and 1 kbar resulted in the formation of single crystals of the monoclinic polymorph of potassium hydrogen disilicate (KHSi2O5 or KSi2O4(OH)). Basic crystallographic data of this so-called phase I at room conditions are as follows: space group C2/m, a = 14.5895(10) Å, b = 8.2992(3) Å, c = 9.6866(7) Å, b = 122.756(10)°, V = 986.36(10) Å3, Z = 8. The structure was determined by direct methods and refined to a residual of R(|F|) = 0.0224 for 892 independent observed reflections with I > 2σ(I). The compound belongs to the group of chain silicates. It is based on crankshaft-like vierer double-chains running parallel to [010]. The H atoms are associated with silanol groups. Hydrogen bonding between neighbouring double-chains results in the formation of ~5 Å wide slabs. The three crystallographically independent K cations with six to eight O ligands provide linkage (1) between the chains of a single slab or (2) between adjacent slabs. Structural investigations have been supplemented by micro-Raman spectroscopy. The interpretation of the spectroscopic data including the allocation of the bands to certain vibrational species has been aided by DFT calculations.

Structural, Spectroscopic, and Computational Studies on Tl4Si5O12: A Microporous Thallium Silicate

Single crystals of the previously unknown thallium silicate Tl4Si5O12 have been prepared from hydrothermal crystallization of a glassy starting material at 500 °C and 1 kbar. Structure analysis resulted in the following basic crystallographic data: monoclinic symmetry, space group C2/c, a = 9.2059(5) Å, b = 11.5796(6) Å, c = 13.0963(7) Å, β = 94.534(5)°. From a structural point of view the compound can be classified as an interrupted framework silicate with Q(3)- and Q(4)-units in the ratio 2:1. Within the framework 4-, 6-, and 12-membered rings can be distinguished. The framework density of 14.4 T-atoms/1000 Å(3) is comparable with the values observed in zeolitic materials like Linde type A, for example. The thallium cations show a pronounced one-sided coordination each occupying the apex of a distorted trigonal TlO3 pyramid. Obviously, this reflects the presence of a stereochemically active 6s(2) lone pair electron. The porous structure contains channels running along [110] and [-1 1 0], respectively, where the Tl(+) cations are located for charge compensation. Structural investigations have been completed by Raman spectroscopy. The interpretation of the spectroscopic data and the allocation of the bands to certain vibrational species have been aided by DFT calculations, which were also employed to study the electronic structure of the compound.

High-Pressure Synthesis and Crystal Structure of Ce4B14O27.

Ce4B14O27 was synthesized under conditions of 2.6 GPa and 750 °C in a Walker-type multianvil apparatus. The crystal structure was determined on the basis of single-crystal X-ray diffraction data, collected at room temperature, revealing that Ce4B14O27 is isotypic to La4B14O27. Ce4B14O27 crystallizes monoclinically with four formula units in the space group C2/c (No. 15) and the lattice parameters a = 1117.8(2), b = 640.9(2), c = 2531.7(5) pm, and β = 100.2(1)°. The three-dimensional boron-oxygen framework consists of [BO4]5– tetrahedra and trigonal-planar [BO3]3– groups. The structure contains two crystallographically different cerium ions. Furthermore, Raman spectroscopy was performed on single crystals of Ce4B14O27.

Synthesis and Characterization of the Manganese Borate α-MnB2O4

The high-pressure manganese borate α-MnB2O4 was synthesized under high-pressure/hightemperature conditions of 6.5 GPa and 1100 ◦C in a modified Walker-type multianvil apparatus. The monoclinic compound is isotypic to α-FeB2O4, CaAl2O4-II, CaGa2O4, andβ -SrGa2O4 crystallizing with eight formula units in the space group P21/c (Z = 8) with the lattice parameters a = 712.1(2), b = 747.1(2), c = 878.8(2) pm, β = 94.1(1)◦, V = 0.466(1) nm3, R1 = 0.0326, and wR2 = 0.0652 (all data). The compound is built up from layers of “sechser” rings of corner-sharing BO4 tetrahedra that are interconnected to a three-dimensional network. The manganese ions are coordinated by seven oxygen atoms and situated in channels along the a axis. Graphical Abstract Synthesis and Characterization of the Manganese Borate α-MnB2O4