Deciphering the Polymorphism of CaSi2: The Influence of Heat and Composition.

The Zintl phase CaSi2 is a layered compound with stacking variants known as 1P, 3R, and 6R. We extend the series by the 21R polytype formed by rapid cooling of the melt. The crystal structure of 21R-CaSi2 (space group R3̅m) was derived from HRTEM images, and the atomic positions were optimized by using the FPLO code (a = 3.868 Å, c = 107.276 Å). We explore polytype transformations by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), electron backscattering diffraction (EBSD), and thermal analysis. While 6R-CaSi2 is thermodynamically stable at ambient conditions, nanosized impurities of silicon stabilize 3R-CaSi2 as a bulk phase.

Structural Complexity in the Apparently Simple Crystal Structure of Be2 Ru.

The structural features of the hexagonal layered crystal structure of Be2 Ru (a=5.7508(3) Å, c=3.0044(2) Å, space group P 6 ‾ ${\bar{6}}$ 2m) were investigated by single crystal X-ray diffraction and transmission electron microscopy (TEM). The residual electron density and high-resolution TEM images show that the real structure can be described as an intergrowth of the main hexagonal matrix of the Fe2 P type with minor orthorhombic inclusions of its stacking variants. Such atomic arrangement is stabilized by the charge transfer from Be to Ru and by a system of polar three- and four-atomic bonds involving both components. The calculated electronic density of states (DOS) of Be2 Ru revealed, contrarily to typical intermetallic compounds, a pseudo gap (dip) in the vicinity of the Fermi level. The temperature dependence of the electrical resistivity of Be2 Ru shows metal behaviour in agreement with the non-zero DOS at the Fermi level.

Nitridochromate(IV): LiSr2[CrN3].

The quaternary nitridochromate(IV) LiSr2[CrN3] crystallizes in a new structure type with the non-centrosymmetric space group P21 (no. 4) with a = 5.5685(7) Å, b = 5.3828(8) Å, c = 7.5381(1) Å, and ß = 92.291(8)°. Predominant structural features of the compound are slightly nonplanar trigonal units [CrN3]5-, which are connected by three-fold coordinated lithium to form slabs in the (001) plane. Shorter Cr-N bond lengths in comparison with reported nitridochromates(III), as well as diamagnetic behavior and vibrational spectroscopy data indicate Cr(IV), which is in a good agreement with the charge balance. According to electronic structure calculations, the compound is a semiconductor with a band gap of 1.19 eV.

Na2Ga7: A Zintl-Wade Phase Related to "α-Tetragonal Boron".

Na2Ga7 crystallizes with the orthorhombic space group Pnma (no. 62; a = 14.8580(6) Å, b = 8.6766(6) Å, and c = 11.6105(5) Å; Z = 8) and constitutes a filled variant of the Li2B12Si2 structure type. The crystal structure consists of a network of icosahedral Ga12 units with 12 exohedral bonds and four-bonded Ga atoms in which the Na atoms occupy the channels and cavities. The atomic arrangement is consistent with the Zintl [(4b)Ga]- and Wade [(12b)Ga12]2- electron counting approach. The compound forms peritectically from Na7Ga13 and the melt at 501 °C and does not show a homogeneity range. The band structure calculations predict semiconducting behavior consistent with the electron balance [Na+]4[(Ga12)2-][Ga-]2. Magnetic susceptibility measurements show that Na2Ga7 is diamagnetic.

Al-Pt intermetallic compounds: HAXPES study.

Intermetallic compounds in the Al-Pt system were systematically studied via hard X-ray photoelectron spectroscopy, focusing on the positions of Pt 4f and Al 2s core levels and valence band features. On one hand, with increasing Al content, the Pt 4f core levels shift towards higher binding energies (BE), revealing the influence of the atomic interactions (chemical bonding) on the electronic state of Pt. On the other hand, the charge transfer from Al to Pt increases with increasing Al content in Al-Pt compounds. These two facts cannot be combined using the standard "chemical shift" approach. Computational analysis reveals that higher negative effective charges of Pt atoms are accompanied by reduced occupancy of Pt 5d orbitals, leading to the limited availability of these electrons for the screening of the 4f core hole and this in turn explains the experimentally observed shift of 4f core levels to higher BE.

The Reduced Nitridogermanates(III) Ca6 [Ge2 N6 ] and Sr6 [Ge2 N6 ] with Ge-Ge Bonds.

The first nitridogermanates(III) Ca6 [Ge2 N6 ] and Sr6 [Ge2 N6 ] were synthesized from sodium flux and structurally characterized by powder and single crystal X-ray diffraction, respectively. They crystallize isostructurally to each other and homeotypic to Ca6 [Cr2 N6 ]H in space group R 3 ‾ . They feature unprecedented, mutually isolated, ethane-like [GeIII 2 N6 ]12- anions in a staggered conformation. The compounds are semiconductors according to resistivity measurements and electronic structure calculations, yielding band gaps of 1.1 eV for Ca6 [Ge2 N6 ] and 0.2 eV for Sr6 [Ge2 N6 ].

In-Cage Interactions in the Clathrate Superconductor Sr8 Si46.

The clathrate I superconductor Sr8 Si46 is obtained under high-pressure high-temperature conditions, at 5 GPa and temperatures in the range of 1273 to 1373 K. At ambient pressure, the compound decomposes upon heating at T=796(5) K into Si and SrSi2 . The crystal structure of the clathrate is isotypic to that of Na8 Si46 . Chemical bonding analysis reveals conventional covalent bonding within the silicon network as well as additional multi-atomic interactions between Sr and Si within the framework cages. Physical measurements indicate a bulk BCS type II superconducting state below Tc =3.8(3) K.

Crystal Structure and Physical Properties of the Cage Compound Hf2B2-2δIr5+δ.

Hf2B2-2δIr5+δ crystallizes with a new type of structure: space group Pbam, a = 5.6300(3) Å, b = 11.2599(5) Å, and c = 3.8328(2) Å. Nearly 5% of the boron pairs are randomly replaced by single iridium atoms (Ir5+δB2-2δ). From an analysis of the chemical bonding, the crystal structure can be understood as a three-dimensional framework stabilized by covalent two-atom B-B and Ir-Ir as well as three-atom Ir-Ir-B and Ir-Ir-Ir interactions. The hafnium atoms center 14-atom cavities and transfer a significant amount of charge to the polyanionic boron-iridium framework. This refractory boride displays moderate hardness and is a Pauli paramagnet with metallic electrical resistivity, Seebeck coefficient, and thermal conductivity. The metallic character of this system is also confirmed by electronic structure calculations revealing 5.8 states eV-1 fu-1 at the Fermi level. Zr2B2-2δIr5+δ is found to be isotypic with Hf2B2-2δIr5+δ, and both form a continuous solid solution.

Al2 Pt for Oxygen Evolution in Water Splitting: A Strategy for Creating Multifunctionality in Electrocatalysis.

The production of hydrogen via water electrolysis is feasible only if effective and stable catalysts for the oxygen evolution reaction (OER) are available. Intermetallic compounds with well-defined crystal and electronic structures as well as particular chemical bonding features are suggested here to act as precursors for new composite materials with attractive catalytic properties. Al2 Pt combines a characteristic inorganic crystal structure (anti-fluorite type) and a strongly polar chemical bonding with the advantage of elemental platinum in terms of stability against dissolution under OER conditions. We describe here the unforeseen performance of a surface nanocomposite architecture resulting from the self-organized transformation of the bulk intermetallic precursor Al2 Pt in OER.

Cluster Formation in the Superconducting Complex Intermetallic Compound Be21Pt5.

Materials with the crystal structure of γ-brass type (Cu5Zn8 type) are typical representatives of intermetallic compounds. From the electronic point of view, they are often interpreted using the valence electron concentration approach of Hume-Rothery, developed previously for transition metals. The γ-brass-type phases of the main-group elements are rather rare. The intermetallic compound Be21Pt5, a new member of this family, was synthesized, and its crystal structure, chemical bonding, and physical properties were characterized. Be21Pt5 crystallizes in the cubic space group F4̅3m with lattice parameter a = 15.90417(3) Å and 416 atoms per unit cell. From the crystallographic point of view, the binary substance represents a special family of intermetallic compounds called complex metallic alloys (CMA). The crystal structure was solved by a combination of synchrotron and neutron powder diffraction data. Besides the large difference in the scattering power of the components, the structure solution was hampered by the systematic presence of very weak reflections mimicking wrong symmetry. The structural motif of Be21Pt5 is described as a 2 × 2 × 2 superstructure of the γ-brass structure (Cu5Zn8 type) or 6 × 6 × 6 superstructure of the simple bcc structural pattern with distinct distribution of defects. The main building elements of the crystal structure are four types of nested polyhedral units (clusters) with the compositions Be22Pt4 and Be20Pt6. Each cluster contains four shells (4 + 4 + 6 + 12 atoms). Clusters with different compositions reveal various occupation of the shells by platinum and beryllium. Polyhedral nested units with the same composition differ by the distance of the shell atoms to the cluster center. Analysis of chemical bonding was made applying the electron localizability approach, a quantum chemical technique operating in real space that is proven to be especially efficient for intermetallic compounds. Evaluations of the calculated electron density and electron localizability indicator (ELI-D) revealed multicenter bonding, being in accordance with the low valence electron count per atom in Be21Pt5. A new type of atomic interactions in intermetallic compounds, cluster bonds involving 8 or even 14 atoms, is found in the clusters with shorter distances between the shell atoms and the cluster centers. In the remaining clusters, four- and five-center bonds characterize the atomic interactions. Multicluster interactions within the polyhedral nested units and three-center polar intercluster bonds result in a three-dimensional framework resembling the structural pattern of NaCl. Be21Pt5 is a diamagnetic metal and one of rather rare CMA compounds revealing superconductivity (Tc = 2.06 K).

Ca-Ag compounds in ethylene epoxidation reaction.

The ethylene epoxidation is a challenging catalytic process, and development of active and selective catalyst requires profound understanding of its chemical behaviour under reaction conditions. The systematic study on intermetallic compounds in the Ca-Ag system under ethylene epoxidation conditions clearly shows that the character of the oxidation processes on the surface originates from the atomic interactions in the pristine compound. The Ag-rich compounds Ca2Ag7 and CaAg2 undergo oxidation towards fcc Ag and a complex Ca-based support, whereas equiatomic CaAg and the Ca-rich compounds Ca5Ag3 and Ca3Ag in bulk remain stable under harsh ethylene epoxidation conditions. For the latter presence of water vapour in the gas stream leads to noticeable corrosion. Combining the experimental results with the chemical bonding analysis and first-principles calculations, the relationships among the chemical nature of the compounds, their reactivity and catalytic performance towards epoxidation of ethylene are investigated.

Interplay of Atomic Interactions in the Intermetallic Semiconductor Be5 Pt.

Semiconducting substances form one of the most important families of functional materials. However, semiconductors containing only metals are very rare. The chemical mechanisms behind their ground-state properties are only partially understood. Our investigations have rather unexpectedly revealed the semiconducting behaviour (band gap of 190 meV) for the intermetallic compound Be5 Pt formed at a very low valence-electron count. Quantum-chemical analysis shows strong charge transfer from Be to Pt and reveals a three-dimensional entity of vertex-condensed empty Be4 tetrahedrons with multi-atomic cluster bonds interpenetrated by the framework of Pt-filled vertex-condensed Be4 tetrahedrons with two-atomic polar Be-Pt bonds. The combination of strong Coulomb interactions with relativistic effects results in a band gap.

Anisotropic Reactivity of CaAg under Ethylene Epoxidation Conditions.

The chemical behavior of CaAg as catalyst for ethylene epoxidation was studied using a combination of experimental (X-ray powder diffraction, scanning electron microscopy, thermal analysis and infrared spectroscopy), and quantum chemical techniques as well as real-space chemical bonding analysis. Under oxidative ethylene epoxidation conditions, the CaAg (010) surface possesses an outstanding stability during long-term experiments. It is caused by the formation of an ordered, stable and dense CaO passivation layer with a small amount of embedded Ag atoms. On this way, the (010) surface constitutes a kinetic barrier for further incorporation of oxygen into the subsurface region and thereby prevents  further oxidative decomposition of CaAg. The calculated adsorption energies of the reaction species show strong adsorption of the reaction products that may explain the observed low conversion of ethylene toward ethylene oxide using CaAg as catalyst.

CO Adsorption on GaPd-Unravelling the Chemical Bonding in Real Space.

The electron localizability indicator-an efficient quantum chemical tool for analysis of chemical bonding-is applied to unveil the chemical bonding behind the CO adsorption on the (1‾ 1‾ 1‾ ) surface of the highly selective semi-hydrogenation catalyst GaPd. Refining the commonly applied Blyholder model, the obtained results are in excellent agreement with previous experimental and theoretical findings. The clean GaPd(1‾ 1‾ 1‾ ) surface presents unshielded negatively charged Pd centers and positively charged Ga species partially shielded by dangling bonds. The CO molecule adsorbs on-top of the Pd centers perperdicular to the surface, while no CO-Ga interaction is observed. The chemical bonding analysis results in deep understanding, thus enabling a cost efficient route to innovative materials by reverse engineering.

On the twinning in ZnPd.

The intermetallic compound ZnPd has demonstrated excellent catalytic properties in methanol steam reforming. While it is known that defects and microstructures influence the catalytic properties, little is known about the defects occurring in ZnPd. Due to recent advances in synthetic methods, coarse-grained ZnPd samples are accessible. This enables the detection and investigation of twinning in ZnPd by studying the twinned regions from the macroscopic scale by polarised light and electron backscattering diffraction (EBSD) down to the atomic scale by high-resolution transmission electron microscopy (HR-TEM). Twinning occurs in {101} and is coupled with a change in the c/a ratio in the vicinity of the twin boundary. Quantum chemical calculations result in only very small energy differences between the ideal and the twinned structure, explaining the experimentally observed thermal stability of the latter. The chemical bonding was investigated by the electron localizability indicator (ELI) and compared to the one in the ideal structure. The results confirm twinning along the {101} plane and demonstrate the high stability of the twin boundaries after formation.

Interpenetration of a 3D Icosahedral M@Ni12 (M=Al, Ga) Framework with Porphyrin-Reminiscent Boron Layers in MNi9 B8.

Two ternary borides MNi9 B8 (M=Al, Ga) were synthesized by thermal treatment of mixtures of the elements. Single-crystal X-ray diffraction data reveal AlNi9 B8 and GaNi9 B8 crystallizing in a new type of structure within the space group Cmcm and the lattice parameters a=7.0896(3) Å, b=8.1181(3) Å, c=10.6497(4) Šand a=7.0897(5) Å, b=8.1579(4) Å, c=10.6648(7) Å, respectively. The boron atoms build up two-dimensional layers, which consist of puckered [B16 ] rings with two tailing B atoms, whereas the M atoms reside in distorted vertices-condensed [Ni12 ] icosahedra, which form a three-dimensional framework interpenetrated by boron porphyrin-reminiscent layers. An unusual local arrangement resembling a giant metallo-porphyrin entity is formed by the [B16 ] rings, which, due to their large annular size of approximately 8 Å, chelate four of the twelve icosahedral Ni atoms. An analysis of the chemical bonding by means of the electron localizability approach reveals strong covalent B-B interactions and weak Ni-Ni interactions. Multi-center dative B-Ni interaction occurs between the Al-Ni framework and the boron layers. In agreement with the chemical bonding analysis and band structure calculations, AlNi9 B8 is a Pauli-paramagnetic metal.

ThPt2: A New Representative of Close Packed Tetragonal Structures.

ThPt2 crystallizes with unique type of structure (space group I4/mmm, a = 4.1565(1) Å, c = 14.3663(7) Å, Pearson symbol tI12), which belongs to the group of the close packed tetragonal structures. An analysis of the chemical bonding by the electron localizability approach reveals the formation of two-dimensional layered platinum anionic substructures interlinked by strongly polar bonds to Th. Measurements of magnetic susceptibility, electrical resistivity, and specific heat show ThPt2 to be diamagnetic with metallic type of electrical conductivity in good agreement with the calculated electronic structure (N(EF) = 0.9 states eV(-1) f.u.(-1)).

Ordering by cation replacement in the system Na2-xLixGa7.

Samples of the pseudo-binary system Na2-xLixGa7 (x ≤ 1) were synthesized from the elements at 300 °C in sealed Ta ampoules or by the reaction of Na2Ga7 with LiCl. The peritectic formation temperature decreases with increasing Li content from 501(2) °C (x = 0) to 489(2) °C (x = 1). The boundary compositions Na2Ga7 and Na1Li1Ga7 crystallize with different structure types related by a group-subgroup relation. While the Na-rich compositions (x ≤ 0.5) represent a substitutional solid solution (space group Pnma), the Li-rich compositions feature an unconventional replacement mechanism in which Li atoms occupying interstitial positions induce vancancies at the Na positions (space group Cmce). The crystal structure of Na1Li1Ga7 (a = 8.562(1) Å, b = 14.822(2) Å, c = 11.454(2) Å; Z = 8) was determined from X-ray single-crystal diffraction data, and reveals an anionic framework comprising 12-bonded Ga12 icosahedra and 4-bonded Ga atoms, with alkali-metal atoms occupying channels and cavities. The arrangement of cations makes NaLiGa7 a new structure type within the MgB12Si2 structure family. Band structure calculations for the composition NaLiGa7 predict semiconducting behavior consistent with the balance [Na+]2[Li+]2[(Ga12)2-][Ga-]2, considering closo Wade clusters [(12b)Ga12]2- and Zintl anions [(4b)Ga]-. Susceptibility measurements indicate temperature-independent diamagnetic behavior.

Nitridochromate(IV) fluoride - LiCa8[CrN3]2N2F.

LiCa8[CrIVN3]2N2F (Pnnm (#58), a = 17.5230(13) Å, b = 7.3379(5) Å, c = 4.9433(4) Å) is an example of a multinary nitridochromate fluoride, that provides additional information on almost elusive tetravalent nitridochromates. Shorter Cr-N bond lengths compared to those in the previously reported nitridochromates(III), as well as diamagnetic behavior and vibrational spectroscopy data suggest Cr(IV), which is in good agreement with the charge balance and crystal structure refinement. According to band structure calculations, LiCa8[CrIVN3]2N2F is a semiconductor with a band gap of 1.1 eV. The compound features trigonal planar [CrN3]5- units of Cs symmetry, and lithium, calcium, nitrogen and fluorine atoms arranged in a fragment of the rock salt type structure.

Al-Pt compounds catalyzing the oxygen evolution reaction.

Al-Pt compounds have been systematically studied as electrocatalysts for the oxygen evolution reaction (OER). Considering the harsh oxidative conditions of the OER, all Al-Pt compounds undergo modifications during electrochemical experiments. However, the degree of changes strongly depends on the composition and crystal structure of a compound. In contrast to Al-rich compounds (Al4Pt and Al21Pt8), which reveal strong leaching of aluminum, changes in other compounds (Al2Pt, Al3Pt2, rt-AlPt, Al3Pt5, and rt-AlPt3) take place only on the surface or in the near-surface region. Furthermore, surface modification leads to a change in the electronic structure of Pt, giving rise to the in situ formation of catalytically more active surfaces, which are composed of intermetallic compounds, Pt-rich AlxPt1-x phases and Pt oxides. Forming a compromise between sufficient OER activity and stability, Al2Pt and Al3Pt2 can be considered as precursors for OER electrocatalysts.