NaGeP: A Zintl Phase Featuring [PGe-GeP] Dimers as Building Blocks.

Recently, ternary lithium phosphidotetrelates have attracted interest particularly due to their high ionic conductivities, while corresponding sodium and heavier alkali metal compounds have been less investigated. Hence, we report the synthesis and characterization of the novel ternary sodium phosphidogermanate NaGeP, which is readily accessible via ball milling of the elements and subsequent annealing. According to single crystal X-ray structure determination, NaGeP crystallizes in the monoclinic space group 2/ (no.

Direct Band Gap Semiconductors with Two- and Three-Dimensional Triel-Phosphide Frameworks (Triel=Al, Ga, In).

Recently, several ternary phosphidotrielates and -tetrelates have been investigated with respect to their very good ionic conductivity, while less focus was pointed towards their electronic structures. Here, we report on a novel series of compounds, in which several members possess direct band gaps. We investigated the known compounds LiAlP, LiGaP, LiInP, and NaInP and describe the synthesis and the crystal structure of novel NaInP.

Li SnP - a Member of the Series Li Sn P for x=0 Comprising the Fast Lithium-Ion Conductors Li SnP (x=0.5) and Li SnP (x=1).

The targeted search for suitable solid-state ionic conductors requires a certain understanding of the conduction mechanism and the correlation of the structures and the resulting properties of the material. Thus, the investigation of various ionic conductors with respect to their structural composition is crucial for the design of next-generation materials as demanded. We report here on Li SnP which completes with x=0 the series Li Sn P of the fast lithium-ion conductors α- and β-Li SnP (x=0.

Supertetrahedral polyanionic network in the first lithium phosphidoindate LiInP - structural similarity to LiSiP and LiGeP and dissimilarity to LiAlP and LiGaP.

Phosphide-based materials have been investigated as promising candidates for solid electrolytes, among which the recently reported LiAlP displays an ionic conductivity of 3 mS cm. While the phases Li-Al-P and Li-Ga-P have already been investigated, no ternary indium-based phosphide has been reported up to now. Here, we describe the synthesis and characterization of the first lithium phosphidoindate LiInP, which is easily accessible ball milling of the elements and subsequent annealing.

NaTaP: A Ternary Sodium Phosphidotantalate Containing [TaP] Tetrahedra.

While lithium phosphides have been investigated intensively, very little is known about the corresponding sodium-based phosphides. Here, we report on the first ternary Na-Ta-P compound NaTaP, which is easily accessible via ball milling of the elements and subsequent annealing. The single crystal X-ray structure determination [monoclinic symmetry; space group 2/; and lattice parameters = 11.

Synthesis, Structure, Solid-State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li AlP and Li GaP.

The lithium phosphidoaluminate Li AlP represents a promising new compound with a high lithium ion mobility. This triggered the search for new members in the family of lithium phosphidotrielates, and the novel compounds Li AlP and Li GaP , obtained directly from the elements via ball milling and subsequent annealing, are reported here. It was unexpectedly found through band structure calculations that Li AlP and Li GaP are direct band gap semiconductors with band gaps of 3.

Fast Lithium Ion Conduction in Lithium Phosphidoaluminates.

Solid electrolyte materials are crucial for the development of high-energy-density all-solid-state batteries (ASSB) using a nonflammable electrolyte. In order to retain a low lithium-ion transfer resistance, fast lithium ion conducting solid electrolytes are required. We report on the novel superionic conductor Li AlP which is easily synthesised from the elements via ball-milling and subsequent annealing at moderate temperatures and which is characterized by single-crystal and powder X-ray diffraction.

Fast Ionic Conductivity in the Most Lithium-Rich Phosphidosilicate LiSiP.

Solid electrolytes with superionic conductivity are required as a main component for all-solid-state batteries. Here we present a novel solid electrolyte with three-dimensional conducting pathways based on "lithium-rich" phosphidosilicates with ionic conductivity of σ > 10 S cm at room temperature and activation energy of 30-32 kJ mol expanding the recently introduced family of lithium phosphidotetrelates. Aiming toward higher lithium ion conductivities, systematic investigations of lithium phosphidosilicates gave access to the so far lithium-richest compound within this class of materials.

Charged Si Clusters in Neat Solids and the Detection of [H Si ] in Solution: A Combined NMR, Raman, Mass Spectrometric, and Quantum Chemical Investigation.

Polyanionic silicon clusters are provided by the Zintl phases K Si , comprising [Si ] units, and K Si , consisting of [Si ] and [Si ] clusters. A combination of solid-state MAS-NMR, solution NMR, and Raman spectroscopy, electrospray ionization mass spectrometry, and quantum-chemical investigations was used to investigate four- and nine-atomic silicon Zintl clusters in neat solids and solution. The results were compared to Si isotope-enriched samples.

Synthesis and Characterization of the Lithium-Rich Phosphidosilicates LiSiP and LiSiP.

The lithium phosphidosilicates LiSiP and LiSiP are obtained by high-temperature reactions of the elements or including binary Li-P precursors. LiSiP (P2/n, Z = 2, a = 7.2051(4) Å, b = 6.

A combined metal-halide/metal flux synthetic route towards type-I clathrates: crystal structures and thermoelectric properties of A8Al8Si38 (A = K, Rb, and Cs).

Single-phase samples of the compounds K8Al8Si38 (1), Rb8Al8Si38 (2), and Cs7.9Al7.9Si38.

Advanced surface functionalization of periodic mesoporous silica: Kinetic control by trisilazane reagents.

The surface reactions of mesoporous silica MCM-41 with a series of new trisilylamines (trisilazanes) (SiHMe2)2NSiMe2R and (SiMe2Vin)2NSiMe2R (R = indenyl, norpinanyl, chloropropyl, 3-(N-morpholin)propyl; Vin = vinyl), disilylalkylamine (SiHMe2)iPrNSiMe2(CH2)3Cl, and monosilyldialkylamines Me2NSiMe2R (R = indenyl, chloropropyl, 3-(N-morpholin)propyl) were investigated. 1H, 13C, and 29Si MAS NMR spectroscopy, nitrogen adsorption/desorption, infrared spectroscopy, and model reactions with calix[4]arene as a mimic for an oxo surface were used to clarify the chemical nature of surface-bonded silyl groups. The trisilylamines exhibited a comparatively slow surface reaction, which allowed for the adjustment of the amount of silylated and nonreacted SiOH groups and led to a stoichiometric distribution of surface functionalities.

Heterogenization of an organorhenium(VII) oxide on a modified mesoporous molecular sieve.

A novel route to heterogenize an organorhenium(VII) oxide, derived from the well examined methyltrioxorhenium(VII) (MTO), on the surface of an iodosilane-modified MCM-41 is applied. The successful grafting of the -CH(2)-ReO3 moiety on the surface was evidenced by 1H CP MAS NMR, IR spectroscopy, TG-MS, and elemental analysis. XRD and TEM analyses confirm the retaining of long-range ordering throughout the grafting process.