Structural Chemistry of Silicates

Liebau, F.

doi:10.1007/978-3-642-50076-3

Cited by 1,175 publications

(837 citation statements)

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“…Such modulations are usually due to a displacive phase transition of the lattice involving rotations of SiO 4 tetrahedra without substantial internal distortions of the tetrahedra themselves [9,10,11]. BaCuSi 2 O 6 can be thought of as a 'vierer' single ring cyclosilicate [12], in which isolated Si 4 O 12 rings (composed of 4 corner sharing SiO 4 tetrahedra) are linked by CuO 4 groups in the ab-plane, and separated by Ba cations between successive layers. It is likely that SiO 4 tetrahedra in this compound rotate and twist as a unit with respect to each other causing a lattice modulation involving both Ba and/or Cu atoms.…”

Section: Discussionmentioning

confidence: 99%

Low-temperature structural phase transition and incommensurate lattice modulation in the spin-gap compoundBaCuSi2O6

et al. 2006

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Results of high resolution x-ray diffraction experiments are presented for single crystals of the spin gap compound BaCuSi2O6 in the temperature range from 16 to 300 K. The data show clear evidence of a transition from the room temperature tetragonal phase into an incommensurately modulated orthorhombic structure below ∼100 K. This lattice modulation is characterized by a resolution limited wave vector qIC =(0,∼0.13,0) and its 2 nd and 3 rd harmonics. The phase transition is first order and exhibits considerable hysteresis. This observation implies that the spin Hamiltonian representing the system is more complex than originally thought.

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Section: Discussionmentioning

confidence: 99%

Low-temperature structural phase transition and incommensurate lattice modulation in the spin-gap compoundBaCuSi2O6

et al. 2006

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“…4]. Such a hexagonal prism slab, which is similar to double layer structures found in sheet silicates [12], has been proposed as a model for hydrophobic silica surfaces [29]. It was previously considered as a possible model for the silica film on Mo(112), but discarded because of disagreement with the experimental results [3].…”

Section: Prl 105 146104 (2010) P H Y S I C a L R E V I E W L E T T Ementioning

confidence: 99%

“…The experimental results, obtained by photoelectron and vibrational spectroscopies and high-resolution scanning probe microscopy, are complemented by density functional theory calculations which together provide compelling evidence for the formation of a double-layer sheet silicate, with a SiO 2 stoichiometric composition, weakly bound to a metal support. The results open new perspectives for employing a ''surface science'' approach to understand the reactivity of silicate surfaces consisting of hydrophobic Si-O-Si bonds, such as those of microporous all-silica zeolites [12]. Also, these films can be used as model supports for catalytically active metal and oxide clusters [4,13].…”

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confidence: 95%

Growth and Structure of Crystalline Silica Sheet on Ru(0001)

et al. 2010

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Thin SiO 2 films were grown on a Ru(0001) single crystal and studied by photoelectron spectroscopy, infrared spectroscopy and scanning probe microscopy. The experimental results in combination with density functional theory calculations provide compelling evidence for the formation of crystalline, double-layer sheet silica weakly bound to a metal substrate. DOI: 10.1103/PhysRevLett.105.146104 PACS numbers: 68.35.Àp, 68.47.Gh, 68.55.Àa Silicon dioxide (SiO 2 ) plays a key role in many modern technologies and applications that range from insulating layers in integrated circuits to supports for metal and oxide clusters in catalysts. For better understanding of structureproperty relationships on silica-based materials, particularly of reduced dimensions, thin silica films grown on metal single crystal substrates are suggested as suitable model systems that allow the facile application of many ''surface science'' techniques. It has recently been shown that crystalline silica films and nanowires can be grown on Mo(112) [1][2][3][4][5]. The ultrathin film consists of a monolayer honeycomblike network of corner-sharing [SiO 4 ] tetrahedra, thus resulting in a SiO 2:5 stoichiometry of the film. The Si atoms in these films can be partly substituted by Al in the course of preparing metal supported aluminosilicate films [6], which is the first step towards experimental modeling of catalytic centers in zeolitelike materials. However, attempts to grow thicker silica films on the Mo substrates resulted in amorphous structures [7][8][9], most likely due to the formation of strong Si-O-Mo bonds at the interface that govern the growth mode [9]. Recently, the preparation of crystalline silica films on other supports such as Pd(100) [10] and Ni(111) [11] has been reported. However, the atomic structure of the films, film surface termination, and the nature of the silica-metal interface were not determined.In this Letter, we report on the preparation and the atomic structure of well-defined silica films on Ru(0001). The experimental results, obtained by photoelectron and vibrational spectroscopies and high-resolution scanning probe microscopy, are complemented by density functional theory calculations which together provide compelling evidence for the formation of a double-layer sheet silicate, with a SiO 2 stoichiometric composition, weakly bound to a metal support. The results open new perspectives for employing a ''surface science'' approach to understand the reactivity of silicate surfaces consisting of hydrophobic Si-O-Si bonds, such as those of microporous all-silica zeolites [12]. Also, these films can be used as model supports for catalytically active metal and oxide clusters [4,13].The experiments were performed in an ultrahigh vacuum chamber equipped with low energy electron diffraction (LEED) and Auger electron spectroscopy, x-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRAS), and scanning tunneling microscopy (STM). Atomically resolved atomic force microscopy (AFM) and STM image...

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“…[22,24] Li 7 PN 4 (620 8C, ambient pressure) is the lithium nitridophosphate with the lowest P/N atomicr atio and consists of non-condensed [PN 4 ] 7À tetrahedra. [23] Non-condensed [P 3 N 9 ] 12À dreier-rings, [25,26] which are isoelectronic with [Si 3 O 9 ] 6À ,a re observed in Li 12 P 3 N 9 (790 8C, ambient pressure). [22] At 820 8Ca nd 6GPa,t hese non-condensed [P 3 N 9 ] 12À dreier-rings polymerize to infinite zweierchains of corner-sharing PN 4 tetrahedra (Li 4 PN 3 ).…”

Section: Introductionmentioning

confidence: 99%

Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br

Bertschler

Dietrich

Leichtweiß

et al. 2017

Chemistry A European J

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b-Li 10 P 4 N 10 and Li 13 P 4 N 10 X 3 with X = Cl, Br have been synthesized from mixtures of P 3 N 5 ,L i 3 N, LiX,L iPN 2 ,a nd Li 7 PN 4 at temperatures below 850 8C. b-Li 10 P 4 N 10 is the lowtemperature polymorph of a-Li 10 P 4 N 10 and crystallizes in the trigonal space group R3. It is made up of non-condensed [P 4 N 10 ] 10À T2 supertetrahedra, whicha re arrangedi ns phalerite-analogous packing. Li 13 P 4 N 10 X 3 (X = Cl, Br) crystallizes in the cubic space group Fm " 3m.B oth isomorphic compounds comprise adamantane-type [P 4 N 10 ] 10À ,L i + ions, and halides, which form octahedra. These octahedra build up af ace-centered cubic packing,w hose tetrahedral voids are occupied by the [P 4 N 10 ] 10À ions. The crystal structures have been elucidated from X-ray powder diffraction data and corroborated by EDX measurements, solid-state NMR, and FTIR spectroscopy.F urthermore,w eh ave examined the phase transition between a-a nd b-Li 10 P 4 N 10 .T oc onfirm the ionic character, the migration pathways of the Li + ions have been evaluated and the ion conductivity and its temperature dependence have been determined by impedance spectroscopy.X PS measurementsh aveb een carriedo ut to analyze the stability with respect to Li metal.

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Structural Chemistry of Silicates

Cited by 1,175 publications

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Low-temperature structural phase transition and incommensurate lattice modulation in the spin-gap compoundBaCuSi2O6

Low-temperature structural phase transition and incommensurate lattice modulation in the spin-gap compoundBaCuSi2O6

Growth and Structure of Crystalline Silica Sheet on Ru(0001)

Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br

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Structural Chemistry of Silicates

Cited by 1,175 publications

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Low-temperature structural phase transition and incommensurate lattice modulation in the spin-gap compoundBaCuSi2O6

Low-temperature structural phase transition and incommensurate lattice modulation in the spin-gap compoundBaCuSi2O6

Growth and Structure of Crystalline Silica Sheet on Ru(0001)

Li+ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li10P4N10 and Li13P4N10X3 with X=Cl, Br

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Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br