Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 32
Filtrar
Mais filtros








Base de dados
Intervalo de ano de publicação
1.
Front Chem ; 11: 1251774, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37744059

RESUMO

Hydrogenation reactions at gigapascal pressures can yield hydrogen-rich materials with properties relating to superconductivity, ion conductivity, and hydrogen storage. Here, we investigated the ternary Na-Si-H system by computational structure prediction and in situ synchrotron diffraction studies of reaction mixtures NaH-Si-H2 at 5-10 GPa. Structure prediction indicated the existence of various hypervalent hydridosilicate phases with compositions NamSiH(4+m) (m = 1-3) at comparatively low pressures, 0-20 GPa. These ternary Na-Si-H phases share, as a common structural feature, octahedral SiH6 2- complexes which are condensed into chains for m = 1 and occur as isolated species for m = 2, 3. In situ studies demonstrated the formation of the double salt Na3[SiH6]H (Na3SiH7, m = 3) containing both octahedral SiH6 2- moieties and hydridic H-. Upon formation at elevated temperatures (>500°C), Na3SiH7 attains a tetragonal structure (P4/mbm, Z = 2) which, during cooling, transforms to an orthorhombic polymorph (Pbam, Z = 4). Upon decompression, Pbam-Na3SiH7 was retained to approx. 4.5 GPa, below which a further transition into a yet unknown polymorph occurred. Na3SiH7 is a new representative of yet elusive hydridosilicate compounds. Its double salt nature and polymorphism are strongly reminiscent of fluorosilicates and germanates.

2.
Inorg Chem ; 62(21): 8093-8100, 2023 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-37188333

RESUMO

K2SiH6, crystallizing in the cubic K2PtCl6 structure type (Fm3̅m), features unusual hypervalent SiH62- complexes. Here, the formation of K2SiH6 at high pressures is revisited by in situ synchrotron diffraction experiments, considering KSiH3 as a precursor. At the investigated pressures, 8 and 13 GPa, K2SiH6 adopts the trigonal (NH4)2SiF6 structure type (P3̅m1) upon formation. The trigonal polymorph is stable up to 725 °C at 13 GPa. At room temperature, the transition into an ambient pressure recoverable cubic form occurs below 6.7 GPa. Theory suggests the existence of an additional, hexagonal, variant in the pressure interval 3-5 GPa. According to density functional theory band structure calculations, K2SiH6 is a semiconductor with a band gap around 2 eV. Nonbonding H-dominated states are situated below and Si-H anti-bonding states are located above the Fermi level. Enthalpically feasible and dynamically stable metallic variants of K2SiH6 may be obtained when substituting Si partially by Al or P, thus inducing p- and n-type metallicity, respectively. Yet, electron-phonon coupling appears weak, and calculated superconducting transition temperatures are <1 K.

3.
Chemistry ; 29(17): e202203932, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36718944

RESUMO

The reduction of metal oxides with hydrogen is widely used for the production of fine chemicals and metals both on the laboratory and industry scale. In situ methods can help to elucidate reaction pathways and to gain control over such synthesis reactions. In this study, the reduction of WO3 and V2 O5 with hydrogen was investigated by in situ X-ray powder diffraction with regard to intermediates and the influence of heating rates and hydrogen flow rates. Mixtures of V4 O9 , V6 O13 and VO2 in two modifications were identified as intermediates on the way to phase-pure V2 O3 . None of the intermediates occurs in a single phase and therefore cannot be prepared this way. In contrast, the intermediates of the WO3 reduction, H0.23 WO3 and W10 O29 , appear consecutively and can be isolated. For both reactions, the heating and flow rates have little influence on the formation of intermediates.

4.
J Chem Phys ; 157(21): 214503, 2022 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-36511554

RESUMO

Neutron diffraction with magnesium isotope substitution, high energy x-ray diffraction, and 29Si, 27Al, and 25Mg solid-state nuclear magnetic resonance (NMR) spectroscopy were used to measure the structure of glassy diopside (CaMgSi2O6), enstatite (MgSiO3), and four (MgO)x(Al2O3)y(SiO2)1-x-y glasses, with x = 0.375 or 0.25 along the 50 mol. % silica tie-line (1 - x - y = 0.5) or with x = 0.3 or 0.2 along the 60 mol. % silica tie-line (1 - x - y = 0.6). The bound coherent neutron scattering length of the isotope 25Mg was remeasured, and the value of 3.720(12) fm was obtained from a Rietveld refinement of the powder diffraction patterns measured for crystalline 25MgO. The diffraction results for the glasses show a broad asymmetric distribution of Mg-O nearest-neighbors with a coordination number of 4.40(4) and 4.46(4) for the diopside and enstatite glasses, respectively. As magnesia is replaced by alumina along a tie-line with 50 or 60 mol. % silica, the Mg-O coordination number increases with the weighted bond distance as less Mg2+ ions adopt a network-modifying role and more of these ions adopt a predominantly charge-compensating role. 25Mg magic angle spinning (MAS) NMR results could not resolve the different coordination environments of Mg2+ under the employed field strength (14.1 T) and spinning rate (20 kHz). The results emphasize the power of neutron diffraction with isotope substitution to provide unambiguous site-specific information on the coordination environment of magnesium in disordered materials.

5.
Chem Commun (Camb) ; 58(93): 12971-12974, 2022 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-36326033

RESUMO

Substituting 2 O2- ⇒ N3- + H- in LiLa2HO3 yields dark-brown heteroanionic hydrides, which were synthesized by solid-state reactions from Li3N, LaH3 (and La2O3). They crystallize in the K2NiF4 type structure with mixed H/N sites in LiLa2N1.5H2.5 and with mixed N/O sites in LiLa2N0.84(6)H1.56(3)O1.16(6). The latter is a semiconductor with small band gap and partly covalent Li-H interaction.

6.
Inorg Chem ; 61(26): 10126-10132, 2022 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-35708297

RESUMO

During the production of molybdenum, the first reduction step of molybdenum trioxide to molybdenum dioxide is crucial in directing important product properties like particle size and oxygen content. In this study, the influence of heating rate, hydrogen flow, and potassium content on the reduction of MoO3 has been investigated via in situ X-ray powder diffraction. For low heating rates, a molybdenum bronze HxMoO3 could be confirmed as an intermediate, while γ-Mo4O11 can only be observed at high heating rates. Molybdenum formation at temperatures as low as 873 K can be controlled via hydrogen flow. The potassium content of reactants has a direct influence on the amount of Mo4O11 formed during the reaction as well as rates of Mo4O11 and MoO2 formation.

7.
J Appl Crystallogr ; 55(Pt 1): 67-73, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-35145356

RESUMO

In situ neutron diffraction is an important characterization technique for the investigation of many functional materials, e.g. for hydrogen uptake and release in hydrogen storage materials. A new sapphire single-crystal gas-pressure cell for elastic neutron scattering has been developed and evaluated; it allows conditions of 298 K and 9.5 MPa hydrogen pressure and 1110 K at ambient pressure. The pressure vessel consists of a sapphire single-crystal tube of 35 mm radius and a sapphire single-crystal crucible as sample holder. Heating is realized by two 100 W diode lasers. It is optimized for the D20 diffractometer, ILL, Grenoble, France, and requires the use of a radial oscillating collimator. Its advantages over earlier sapphire single-crystal gas-pressure cells are higher maximum temperatures and lower background at low and high diffraction angles. The deuterium uptake in palladium was followed in situ for validation, proving the potential of the type-III gas-pressure cell for in situ neutron diffraction on solid-gas reactions.

8.
Inorg Chem ; 60(23): 17775-17782, 2021 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-34792346

RESUMO

Mixed anionic hydrides of the rare earths are a fascinating class of compounds as potential functional materials, especially in luminescence, as photochromic thin films and for ion conduction. For exploratory studies, the effectiveness of various synthesis methods must be investigated, which is done here for metathesis reactions. The reaction of Sm2O3 with PTFE yields SmOF (P21/c, a = 5.60133(19) Å, b = 5.65567(19) Å, c = 5.6282(2) Å, ß = 90.169(5)°, V = 178.295(11) Å3, and Z = 4) in a new, probably metastable, polymorph of the baddeleyite-type structure. Metathesis reactions of SmOF with LiH, NaH, or CaH2 led to a samarium hydride oxide fluoride, SmHxOF1-x; i.e., incomplete H/F exchange occurs. X-ray diffraction and neutron diffraction on a compound with x = 0.78 obtained via NaH reveal hydride, oxide, and fluoride ions to be partially ordered. SmH0.78OF0.22 (Ia3̅, a = 10.947(2) Å, V = 1311.7(4) Å3, Z = 32) crystallizes in an anti-Li3AlN2-type structure with distorted cubic anion coordination for samarium atoms (site symmetry 3̅ and 2) and distorted tetrahedral arrangement of samarium atoms around the anions (site symmetry 1 and 3). It is a fully structurally characterized hydride oxide fluoride and shows a rare crystal chemical feature─the occupation of a crystallographic site by three different anions (0.188 H + 0.667 O + 0.145 F). Interatomic distances between samarium and hydrogen and samarium and the mixed hydrogen/oxygen/fluorine site range from 2.45 to 2.48 Å and 2.29 to 2.42 Å, respectively, and are similar to those in samarium hydride, samarium oxide, and samarium fluoride. Fluoride extraction by reaction with alkali and alkaline earth hydrides has thus proven to be a useful synthesis route to hydride oxides and also hydride oxide halogenides, which might be further exploited in exploratory research on heteroanionic metal hydrides.

9.
J Appl Crystallogr ; 54(Pt 3): 839-846, 2021 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-34188615

RESUMO

A sapphire single-crystal gas-pressure cell without external support allowing unobstructed optical access by neutrons has been developed and optimized for elastic in situ neutron powder diffraction using hydrogen (deuterium) gas at the high-intensity two-axis diffractometer D20 at the Institut Laue-Langevin (Grenoble, France). Given a proper orientation of the single-crystal sample holder with respect to the detector, parasitic reflections from the sample holder can be avoided and the background can be kept low. Hydrogen (deuterium) gas pressures of up to 16.0 MPa at 298 K and 8.0 MPa at 655 K were tested successfully for a wall thickness of 3 mm. Heating was achieved by a two-sided laser heating system. The typical time resolution of in situ investigations of the reaction pathway of hydrogen (deuterium) uptake or release is on the order of 1 min. Detailed descriptions of all parts of the sapphire single-crystal gas-pressure cell are given, including materials information, technical drawings and instructions for use.

10.
Inorg Chem ; 60(6): 3972-3979, 2021 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-33656854

RESUMO

The substitution of hydrogen for oxygen atoms in metal oxides provides opportunities for influencing the solid-state properties. Such hydride oxides (or oxyhydrides) are potential functional materials and scarce. Here, we present the synthesis and characterization of holmium hydride oxide with the stoichiometric composition HoHO. It was prepared by the reaction of Ho2O3 with either HoH3 or CaH2 as a powder of light-yellow color in sunlight and pink color in artificial light (Alexandrite effect), which is commonly observed for ionic Ho(III) compounds. HoHO crystallizes with an ordered fluorite superstructure (F4̅3m, a = 5.27550(13) Å, half-Heusler LiAlSi type), as evidenced by powder X-ray and neutron powder diffraction on both hydride and deuteride and supported by quantum-mechanical calculations. HoHO is the first representative with considerable ionic bonding for this structure type. The thermal stability and inertness toward air are remarkably high for a hydride because it reacts only above 540 K to form Ho2O3. At 294(1) K and 25(3)% relative humidity, HoHO is stable for at least 3 months. HoHO is paramagnetic with µeff(Ho3+) = 10.41(2) µB without any sign of magnetic ordering down to 2 K.

11.
Dalton Trans ; 49(42): 15081-15094, 2020 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-33107529

RESUMO

Two new mixed nickel-gallium chalcogenides, Ni9.39Ga2S2 and Ni5.80GaTe2, and a new mixed nickel-indium telluride, Ni5.78InTe2, have been synthesized by a high-temperature ampoule route with the addition of iodine, and characterized from single-crystal or powder diffraction data. They belong to the relatively uncommon Ni7-xMQ2/Ni10-xM2Q2 type of structures (M = Ge, Sn, Sb, In), and are built from p-block metal-centered nickel cuboctahedra, alternating along the c axis with defective Cu2Sb-type nickel-chalcogen ones. Both tellurium-containing compounds show a small degree of orthorhombic distortion with respect to the idealized tetragonal structure, only detectable in the powder diffraction data. No phase transition to the tetragonal structure was detected for Ni5.80GaTe2 by the in situ powder diffraction measurements from room temperature to 550 °C. DFT calculations show close relationships of electronic structures of these ternary compounds to their parent intermetallics, Ni3M (M = Ga, In). Metallic conductivity and paramagnetic properties are predicted for all three with the latter confirmed by magnetic measurements. The bonding patterns, investigated via the ELF topological analysis, show multi-centered nickel - p-block metal bonds in the AuCu3-type fragments and pairwise covalent interactions in the nickel-chalcogen fragments. Both Ni7-xMTe2 compounds showed no structural or compositional changes upon high-temperature mid-pressure hydrogenation.

12.
Inorg Chem ; 58(21): 14635-14641, 2019 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-31626539

RESUMO

Metal hydride oxides are an emerging field in solid-state research. While some lanthanide hydride oxides (LnHO) were known, YHO has only been found in thin films so far. Yttrium hydride oxide, YHO, can be synthesized as bulk samples by a reaction of Y2O3 with hydrides (YH3, CaH2), by a reaction of YH3 with CaO, or by a metathesis of YOF with LiH or NaH. X-ray and neutron powder diffraction reveal an anti-LiMgN type structure for YHO (Pnma, a = 7.5367(3) Å, b = 3.7578(2) Å, and c = 5.3249(3) Å) and YDO (Pnma, a = 7.5309(3) Å, b = 3.75349(13) Å, and c = 5.3192(2) Å); in other words, a distorted fluorite type with ordered hydride and oxide anions was observed. Bond lengths (average 2.267 Å (Y-O), 2.352 Å (Y-H), 2.363 Å (Y-D), >2.4 Å (H-H and D-D), >2.6 Å (H-O and D-O), and >2.8 Å (O-O)) and quantum-mechanical calculations on density functional theory level (band gap 2.8 eV) suggest yttrium hydride oxide to be a semiconductor and to have considerable ionic bonding character. Nonetheless, YHO exhibits a surprising stability in air. An in situ X-ray diffraction experiment shows that decomposition of YHO to Y2O3 starts at only above 500 K and is still not complete after 14 h of heating to a final temperature of 1000 K. YHO hydrolyzes in water very slowly. The inertness of YHO in air is very beneficial for its potential use as a functional material.

13.
Adv Sci (Weinh) ; 6(16): 1802126, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31453049

RESUMO

Research on lithium compounds has attracted much attention nowadays. However, to elucidate the precise structure of lithium compounds is a challenge, especially when considering the small ions that may be transferred between the interstitial voids. Here, the discovery of reduced local symmetry (symmetry breaking) in small domains of Li2SrSiO4 is reported by employing Eu3+ as a spectroscopic probe, for which X-ray, neutron, and electron diffraction have confirmed the average long-range structure with the space group P3121. However, luminescence shows a lower local symmetry, as confirmed by the extended X-ray absorption fine structure. By considering the reduced symmetry of the local structure, this work opens the door to a new class of understanding of the properties of materials.

14.
Phys Chem Chem Phys ; 21(20): 10594-10602, 2019 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-31074753

RESUMO

The Zintl phase deuterides CaSiD4/3, SrSiD5/3, BaSiD2, SrGeD4/3, BaGeD5/3 and BaSnD4/3 were investigated by nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations to reliably determine element-deuterium bond lengths. These compounds show deuterium bound to the polyanion and deuteride ions in tetrahedral cationic voids. With 2H-NMR experiments we characterised the individual signals of the two distinct crystal sites. Quadrupolar coupling constants (CQ) of the anion-binding site were determined as 58 to 78 kHz (Si compounds), 51 to 61 kHz (Ge compounds) and 38 kHz (Sn compound). These values agree well with the quadrupole couplings derived from DFT using optimized structural models. We further calculated the general element-deuterium distance dependency of CQ using DFT methods that allow an accurate determination of bond lengths via the 2H quadrupole interaction. The thus determined bond lengths are evaluated as d(Si-D) = 1.53-1.59 Å, d(Ge-D) = 1.61-1.65 Å and d(Sn-D) = 1.86 Å. Chemical shifts of the anion-binding site range from 0.3 to 1.3 ppm. The isotropic chemical shifts of the tetrahedral sites are 5.1 ppm (CaSiD4/3), 7.0 to 10.0 ppm (Sr compounds) and 10.7 to 11.6 ppm (Ba compounds).

15.
Inorg Chem ; 57(19): 11851-11854, 2018 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-30203971

RESUMO

LiSr2SiO4H is synthesized by solid-state reaction of LiH and α-Sr2SiO4. It crystallizes in space group P21/ m ( a = 658.63(4) pm, b = 542.36(3) pm, c = 695.01(4) pm, ß = 112.5637(9)°) as proven by X-ray and neutron diffraction, is isotypic to LiSr2SiO4F, and exhibits isolated SiO4 tetrahedra. Hydride anions are located in Li2Sr4 octahedra, which share faces to form columns, with H-H distances of 271.18(2) pm. NMR, IR, and Raman spectroscopy, density measurements, elemental analysis, and theoretical calculations confirm these results. Despite its hydridic nature, it is stable in air up to 550 K. When doped with europium, it emits bright yellow-green light with an intensity maximum at 560 nm for LiSr1.98Eu0.02SiO4H. Even after treatment in water for several hours, the solid shows luminescence. The broad emission peak is attributed to the allowed 4f65d → 4f7 transition of divalent europium. LiSr2SiO4H is the first silicate hydride, a class of compounds that might have potential as host for luminescent materials.

16.
Inorg Chem ; 57(17): 10925-10934, 2018 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-30124045

RESUMO

The hydrogenation properties of the cubic Laves phase CaRh2 and the formation of the perovskite CaRhH3 were studied by in situ thermal analysis (differential scanning calorimetry), sorption experiments, and in situ neutron powder diffraction. Three Laves phase hydrides are formed successively at room temperature and hydrogen gas pressures up to 5 MPa. Cubic α-CaRh2H0.05 is a stuffed cubic Laves phase with statistically distributed hydrogen atoms in tetrahedral [Ca2Rh2] voids (ZrCr2H3.08 type, Fd3̅ m, a = 7.5308(12) Å). Orthorhombic ß-CaRh2D3.93(5) (own structure type, Pnma, a = 6.0028(3) Å, b = 5.6065(3) Å, c = 8.1589(5) Å) and γ-CaRh2D3.20(10) (ß-CaRh2H3.9 type, Pnma, a = 5.9601(10) Å, b = 5.4912(2) Å, c = 8.0730(11) Å) are low-symmetry variants thereof with hydrogen occupying distorted tetrahedral [Ca2Rh2] and trigonal bipyramidal [Ca3Rh2] voids. Hydrogen sorption experiments show the hydrogenation to take place already at 0.1 MPa and to yield ß-CaRh2H3.8(2). At 560 K and 5 MPa hydrogen pressure the Laves phase hydride decomposes kinetically controlled to nanocrystalline rhodium and CaRhD2.93(2) (CaTiO3 type, Pm3̅ m, a = 3.6512(2) Å). The hydrogenation of CaRh2 provides a synthesis route to otherwise not accessible perovskite-type CaRhH3.

17.
Inorg Chem ; 57(4): 1702-1704, 2018 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-29373788

RESUMO

The crystal and magnetic structure of SmCo5 is determined by neutron powder diffraction between 5 K and the Curie temperature. In order to overcome the enormous neutron absorption of samarium, a 154Sm isotopically enriched sample was used. The ordered magnetic moments of both crystallographically distinct cobalt atoms are not significantly different over the whole temperature range. They decrease from 2.2 µB at 5 K to about 0.6 µB at 1029 K. Samarium's ordered magnetic moment decreases from 1.0 µB at 5 K, runs through a minimum of 0.2 µB around 650 K, and becomes larger than cobalt's ordered magnetic moment above 950 K. No sign or orientation change of the samarium and cobalt ordered magnetic moments is found between the Curie temperature and 5 K. SmCo5 is thus a ferromagnet and does not switch to a ferrimagnetic state as discussed in the literature.

18.
Inorg Chem ; 56(24): 15006-15014, 2017 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-29166003

RESUMO

The hydrogenation properties of Laves phases LnMg2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb) were investigated by thermal analysis, X-ray, synchrotron, and neutron powder diffraction. At 14.0 MPa hydrogen gas pressure and 393 K, PrMg2 and NdMg2 take up hydrogen and form the colorless, ternary hydrides PrMg2H7 (P41212, a = 632.386(6) pm, c = 945.722(11) pm) and NdMg2H7 (P41212, a = 630.354(9) pm, c = 943.018(16) pm). The crystal structures were refined by the Rietveld method from neutron powder diffraction data on the deuterides (PrMg2D7, P41212, a = 630.56(2) pm, c = 943.27(3) pm; NdMg2D7, P41212, a = 628.15(2) pm, c = 940.32(3) pm) and shown to be isotypic to LaMg2D7. The LaMg2D7 type of hydrides decompose at 695 K (La), 684 K (Ce), 684 K (Pr), 672 K (Nd), and 639 K (Sm) to lanthanide hydrides and magnesium. The Laves phase EuMg2 forms a hydride EuMg2Hx of black color. Its crystal structure (P212121, a = 664.887(4) pm, b = 1136.993(7) pm, c = 1069.887(7) pm) is closely related to the hexagonal Laves phase (MgZn2 type) of the hydrogen-free parent intermetallic. GdMg2 and TbMg2 form hydrides GdMg2Hx with orthorhombic unit cells (a = 1282.7(4) pm, b = 572.5(2) pm, c = 881.7(2) pm) and TbMg2Hx (a = 617.8(3) pm, b = 1045.8(8) pm, c = 997.1(5) pm), presumably also with a distorted MgZn2 type of structure. CeMg2H7 and NdMg2H7 are paramagnetic with effective magnetic moments of 2.49(1) µB and 3.62(1) µB, respectively, in good agreement with the calculated magnetic moments of the free trivalent rare-earth cations (µcalc(Ce3+) = 2.54 µB; µcalc(Nd3+) = 3.62 µB).

19.
Angew Chem Int Ed Engl ; 56(40): 12344-12347, 2017 09 25.
Artigo em Inglês | MEDLINE | ID: mdl-28727236

RESUMO

The hydrogenation of Zintl phases enables the formation of new structural entities with main-group-element-hydrogen bonds in the solid state. The hydrogenation of SrSi, BaSi, and BaGe yields the hydrides SrSiH5/3-x, BaSiH5/3-x and BaGeH5/3-x . The crystal structures show a sixfold superstructure compared to the parent Zintl phase and were solved by a combination of X-ray, neutron, and electron diffraction and the aid of DFT calculations. Layers of connected HSr4 (HBa4 ) tetrahedra containing hydride ions alternate with layers of infinite single- and double-chain polyanions, in which hydrogen atoms are covalently bound to silicon and germanium. The idealized formulae AeTtH5/3 (Ae=alkaline earth, Tt=tetrel) can be rationalized with the Zintl-Klemm concept according to (Ae2+ )3 (TtH- )(Tt2 H2- )(H- )3 , where all Tt atoms are three-binding. The non-stoichiometry (SrSiH5/3-x , x=0.17(2); BaGeH5/3-x , x=0.10(3)) can be explained by additional π-bonding of the Tt chains.

20.
Inorg Chem ; 56(3): 1072-1079, 2017 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-28098993

RESUMO

Hydrides (deuterides) of the CrB-type Zintl phases AeTt (Ae = alkaline earth; Tt = tetrel) show interesting bonding properties with novel polyanions. In SrGeD4/3-x (γ phase), three zigzag chains of Ge atoms are condensed and terminated by covalently bound D atoms. A combination of in situ techniques (thermal analysis and synchrotron and neutron powder diffraction) revealed the existence of two further hydride (deuteride) phases with lower H (D) content (called α and ß phases). Both are structurally related to the parent Zintl phase SrGe and to the ZrNiH structure type containing variable amounts of H (D) in Sr4 tetrahedra. For α-SrGeDy, the highest D content y = 0.29 was found at 575(2) K under 5.0(1) MPa of D2 pressure, and ß-SrGeDy shows a homogeneity range of 0.47 < y < 0.63. Upon decomposition of SrGeD4/3-x (γ-SrGeDy), tetrahedral Sr4 voids stay filled, while the Ge-bound D4 site loses D. When reaching the lower D content limit, SrGeD4/3-x (γ phase) with 0.10 < x < 0.17, decomposes to the ß phase. All three hydrides (deuterides) of SrGe show variable H (D) content.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA