Computationally Driven Discovery of a Family of Layered LiNiB Polymorphs

Two novel lithium nickel boride polymorphs, RT‐LiNiB and HT‐LiNiB, with layered crystal structures are reported. This family of compounds was theoretically predicted by using the adaptive genetic algorithm (AGA) and subsequently synthesized by a hydride route with LiH as the lithium source. Unique among the known ternary transition‐metal borides, the LiNiB structures feature Li layers alternating with nearly planar [NiB] layers composed of Ni hexagonal rings with a B–B pair at the center. A comprehensive study using a combination of single crystal/synchrotron powder X‐ray diffraction, solid‐state ⁷Li and ¹¹B NMR spectroscopy, scanning transmission electron microscopy, quantum‐chemical calculations, and magnetism has shed light on the intrinsic features of these polymorphic compounds. The unique layered structures of LiNiB compounds make them ultimate precursors for exfoliation studies, thus paving a way toward two‐dimensional transition‐metal borides, MBenes.     

Temperature behavior of the protonic conductor K4LiH3(SO4)4

The results of the X-ray structural study for the K₄LiH₃(SO₄)₄ single crystal are presented at a wide temperature range. The thermal expansion of the crystal using the X-ray dilatometry and the capacitance dilatometry from 8 to 500 K was carried out. The crystal structures data collection, solution and refinement at 125, 295, 443 and 480 K were performed. The K₄LiH₃(SO₄)₄ crystal has tetragonal symmetry with the P4₁ space group (Z=4) at room temperature as well as at the considered temperature range. The existence of a low-temperature, para-ferroelastic phase transition at about 120 K is excluded. The layered structure of the crystal reflects a cleavage plane parallel to (001) and an anisotropy of the protonic conductivity. The superionic high-temperature phase transition at T_S=425 K is isostructural. Nevertheless, taking into account an increase of the SO₄ tetrahedra libration above T_S, a mechanism of the Grotthus type could be applied for the proton transport explanation.     

Why pressure induces an abrupt structural rearrangement in PdTe2 but not in PtTe2

High-pressure X-ray diffraction measurements were carried out for polymeric CdI₂-type compounds MTe₂ (M=Pt, Pd) to investigate if they undergo a structural phase transition under pressure as does IrTe₂. Up to 27 GPa at room temperature PtTe₂ does not undergo any structural phase transition. In contrast, however, an abrupt change in the inter-atomic distances occurs in PdTe₂ above 15.7 GPa at room temperature, and above 5 GPa at 300 °C, but the volume vs. pressure curve exhibits no discontinuity. To account for the differences between the isostructural compounds PtTe₂, PdTe₂ and IrTe₂, their electronic structures and bonding were analyzed on the basis of first principles electronic band structure calculations.     

Ion Segregation and Electrostatic Imbalance in Metal Hydrides

Crystal chemical indices of ion segregation and electrostatic imbalance after Beck help to rationalize inorganic crystal structures and sometimes even to predict them. Metal hydrides, from hydrido‐aluminates and ‐gallates, to complex transition metal hydrides, ternary ionic magnesium hydrides and mixed anionic hydrides, were investigated using these tools. Beck's ion segregation and electrostatic imbalance indices are found to work well in explaining crystal structures of most metal hydrides, although the electronegativity differences between cations and hydride anions are often much smaller in ionic metal hydrides, as compared to metal fluorides and oxides. This includes complex transition metal hydrides, despite the fact that formal oxidation states do not describe the actual charges properly. Rare cases of violations can be explained by the chemical bonding situation, e.g. the presence of weak metal–metal bonds in Li₃RhH₄.     

Ternary equiatomic transition metal silicides and germanides

The phases TiRhSi, TiPdSi, MnRhSi, ZrFeGe, ZrRhGe, ZrPdGe, and NbRhGe crystallize with the TiNiSi (ordered anti-PbCl₂) structure. ZrRuSi possesses the Fe₂P structure, while TiRuSi has the closely related TiFeSi structure. Cell parameters for these phases and a refinement of the structure of ZrRuSi from X-ray powder data are reported. Relationships among the observed structural types as well as the “filled” NiAs (Ni₂In) type are pointed out. The crystal chemistry of ternary equiatomic phases of two transition metals and silicon or germanium is discussed, emphasizing differences in metal-metal bonding.     

Mn5Si3-type host-interstitial boron rare-earth metal silicide compounds RE5Si3: Crystal structures, physical properties and theoretical considerations

A series of binary rare-earth metal silicides RE₅Si₃ and ternary boron-interstitial phases RE₅Si₃B_x (RE=Gd, Dy, Ho, Lu, and Y) adopting the Mn₅Si₃-type structure, have been prepared from the elemental components by arc melting. Boron “stuffed” phases were subsequently heated at 1750 K within a high-frequency furnace. Crystal structures were determined for both binary and ternary series of compounds from single-crystal X-ray data: hexagonal symmetry, space group P6₃/mcm, Z=2. Boron insertion in the host binary silicides results in a very small decrease of the unit cell parameters with respect to those of the binaries. According to X-ray data, partial or nearly full boron occupancy of the interstitial octahedral sites in the range 0.6-1 is found. The magnetic properties of these compounds were characterized by the onset of magnetic ordering below 100 K. Boron insertion induces a modification of the transition temperature and θ_p values in most of the antiferromagnetic binary silicides, with the exception of the ternary phase Er₅Si₃B_x which was found to undergo a ferromagnetic transition at 14 K. The electrical resistivities for all binary silicides and ternary boron-interstitial phases resemble the temperature dependence of metals, with characteristic changes of slope in the resistivity curves due to the reduced electron scattering in the magnetically ordered states. Zintl-Klemm concept would predict a limiting composition RE₅Si₃B_0.6 for a valence compound and should then preclude the stoichiometric formula RE₅Si₃B. Density functional theory calculations carried out on some RE₅Si₃Z_x systems for different interstitial heteroatoms Z and different x contents from 0 to 1 give some support to this statement.     

Effects of Feed Composition of Coke Oven Gas on a Layered Bed H2 PSA Process

The effects of feed composition on the adsorption dynamics and the optimal process design were studied from the experimental and simulated results in the H₂ layered bed PSA with activated carbon and zeolite 5A. The breakthrough results using the base composition (56.4 vol% H₂; 26.6 vol% CH₄; 8.4 vol% CO; 5.5 vol% N₂; and 3.1 vol% CO₂) in various layered beds were compared with those using the higher nitrogen composition and the no nitrogen composition. In the breakthrough dynamics, the propagation velocity of wave front of each component was closely related to the slope of isotherm estimated at its concentration in the feed. Breakthrough behavior at each layered bed in the higher nitrogen composition showed similar trends as that in the base composition. However, the no nitrogen composition showed different breakthrough behavior from the other groups. In this feed composition, it was observed that the order of CO and CH₄ breakthrough times was reversed with a change in the carbon-to-zeolite ratio. Based on the adsorption dynamics and breakthrough behavior of each feed composition group in various layered beds, the effect of feed composition on a seven-step two-bed PSA process for the H₂ recovery from coke oven gas was investigated numerically to develop a well-designed H₂ PSA process under various operating conditions. As expected from the breakthrough results, the trends of the PSA performance in the higher nitrogen composition were similar to those in the base composition except for the slight decrease in the optimal carbon-to-zeolite ratio. However, in case of the no nitrogen composition, high purity product was obtained from the activated carbon-rich layered bed PSA because the adsorption capacity of the activated carbon for impurities was superior to that of zeolite. As a result, the optimum carbon-to-zeolite ratio at each operating condition was slightly changed depending on the propagation velocity of each component on each layer.     

Synthesis and red luminescence of Pr-doped CaTiO3 nanophosphor from polymer precursor

Uniform and sphere-like nanoparticles of crystalline Pr³⁺-doped CaTiO₃ have been prepared from complex polymer precursor at 600°C, in which, metal atoms are previously dispersed by citric acid in ethylene glycol solvent. The decomposition process of the precursor, crystallization, and particle sizes of CaTiO₃ have been investigated by using thermal analysis, powder X-ray diffraction and transmission electron microscopy. Diffuse reflectance spectra, photoluminescence and decay curve indicate that a strong red emission located at the nearly NTCS “ideal red” site is deduced from the energy transfer from the band gap absorption to doping Pr³⁺ ions. The thermoluminescence curves exhibit that a potential long phosphorescent material based on Pr³⁺-doped CaTiO₃ will be explored in future.     

Structural observations on La2(Ni,Co)O4±δ phases determined from in situ neutron powder diffraction

In situ neutron powder diffraction data have been analysed for a number of compositions in the solid solution series La₂Ni_1−xCo_xO_4±δ over the temperature range 150-650 °C. High-quality Rietveld refinements indicate no major structural transitions have occurred in any of the compositions, although close examination of the Ni/CoO bond distances highlight changes in the coordination environment with increasing temperature. Further, the changes in the coordination can be correlated to changes in both the oxide ion and electronic conductivity indicating a direct link between transport properties, bonding and transition metal valence state in these Co containing layered perovskites.     

Highly Dispersed and Stable Supported Metal Catalysts Prepared by Solid Phase Crystallization Method

Starting from the precursors containing active metal species in the crystal structure, highly dispersed supported metal catalysts have been prepared by the calcination-reduction treatment. This method is named as solid phase crystallization (spc) method and was compared with the conventional impregnation (imp) method. As the precursors, both perovskite-type and hydrotalcite-type oxides have been utilized for preparing various supported metal catalysts, which were successfully applied for the reforming of CH₄ and the decomposition of methanol. Especially spc-Ni/Mg–Al catalyst prepared from the hydrotalcite-type precursors showed high activity as well as high sustainability for the hydrogen production from methane.     

Structural change of layered perovskite La2Ti2O7 at high pressures

The perovskite-related layered structure of La₂Ti₂O₇ has been studied at pressures up to 30 GPa using synchrotron radiation powder X-ray diffraction (XRD) and Raman scattering. The XRD results indicate a pronounced anisotropy for the compressibility of the monoclinic unit cell. The ratio of the relative compressibilities along the [100], [010] and [001] directions is ∼1:3:5. The greatest compressibility is along the [001] direction, perpendicular to the interlayer. A pressure-induced phase transition occurs at 16.7 GPa. Both Raman and XRD measurements reveal that the pressure-induced phase transition is reversible. The high-pressure phase has a close structural relation to the low-pressure monoclinic phase and the phase transition may be due to the tilting of TiO₆ octahedra at high pressures.     

Improving CO2 selectivity in polymerized room-temperature ionic liquid gas separation membranes through incorporation of polar substituents

Solid, polymer membranes fabricated from room-temperature ionic liquid monomers containing oligo(ethylene glycol) or nitrile-terminated alkyl substituents tethered to imidazolium cations were found to exhibit ideal CO₂/N₂ and CO₂/CH₄ separation factors significantly greater than those with comparable length n-alkyl substituents, with similar CO₂ permeability. Polymers containing these functional groups exhibited CO₂/N₂ gas separation performance exceeding the “upper bound” of a “Robeson Plot”.     

Controlled synthesis of monodispersed AgGaS2 3D nanoflowers and the shape evolution from nanoflowers to colloids

Monodispersed AgGaS₂ three-dimensional (3D) nanoflowers have been successfully synthesized in a “soft-chemical” system with the mixture of 1-octyl alcohol and cyclohexane as reaction medium and oleylamine as surfactant. The crystal phase, morphology and chemical composition of the as-prepared products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution TEM (HTEM), respectively. Results reveal that the as-synthesized AgGaS₂ nanoflowers are in tetragonal structure with 3D flower-like shape. Controlled experiments demonstrated that the shape transformation of AgGaS₂ nanocrystals from 3D nanoflowers (50 nm) to nanoparticles (10-20 nm) could be readily realized by tuning the reaction parameters, e.g., the ratio of octanol to cyclohexane, the length of carbon chain of fatty alcohol, the concentration of oleylamine, etc. The UV-vis and PL spectra of the obtained AgGaS₂ nanoflowers and colloids were researched. In addition, the photoelectron energy conversion (SPV) of AgGaS₂ nanoflowers was further researched by the surface photovoltage spectra.     

The use of high-energy shock wave treatment as pre-activation of sintering high-entropy solid solutions of transition metal borides and carbides

Synthesis of solid solutions of transition metal borides (NbB₂, TaB₂, HfB₂ and ZrB₂) and carbides (NbC, TaC, HfC, ZrC and VC) was carried out via sintering the individual components without applying pressure. To activate the interaction of the components, the initial powders were processed by high-energy shock wave treatment (HESWT). HESWT enables the formation of homogeneous solid solution for a mixture of carbides; however, this method did not give the desired results for a mixture of transition metal borides, likely due to the higher strength of borides crystal lattice in comparison with carbides.     

A general solution-chemistry route to the synthesis LiMPO4 (M=Mn, Fe, and Co) nanocrystals with [010] orientation for lithium ion batteries

A general and efficient solvothermal strategy has been developed for the preparation of lithium transition metal phosphate microstructures (LiMnPO₄, LiFePO₄, and LiCoPO₄), employing ethanol as the solvent, LiI as the Li source, metal salts as the M sources, H₃PO₄ as the phosphorus source, and poly(vinyl pyrrolidone) (PVP) as the carbon source and template. This route features low cost, environmental benign, and one-step process for the cathode material production of Li-ion batteries without any complicated experimental setups and sophisticated operations. The as-synthesized LiMPO₄ microstructures exhibit unique, well-shaped and favorable structures, which are self-assembled from microplates or microrods. The b axis is the preferred crystal growth orientation of the products, resulting in a shorter lithium ion diffusion path. The LiFePO₄ microstructures show an excellent cycling stability without capacity fading up to 50 cycles when they are used as a cathode material in lithium-ion batteries.     

V2O5-TiO2复合半导体光催化材料结构及光响应性能研究

采用溶胶凝胶法制备了V₂O₅-TiO₂复合半导体材料，通过Raman、XRD及UV-Vis DRS等实验方法研究了V₂O₅与TiO₂复合对材料表面组成、晶体结构以及光响应性能的影响。结果表明：钒加入后优先与TiO₂作用形成较为稳定的金红石型TiVO₄晶相，其中V⁴⁺是促进TiO₂发生相变的关键；随着钒加入量的增加，V₂O₅由表面高分散状态逐渐聚集形成晶相，并释放部分Ti⁴⁺使之形成锐钛矿型TiO₂晶相，使得体相中金红石型TiO₂的含量有所下降；复合后形成的TiVO₄晶相显著提高了材料对可见光的吸收率，并使其吸光域红移至460 nm左右。     

Ge2H2 a π-ligand in organometallic chemistry

η² π-Complexes of Ge₂H₂ with the organometallic fragments V(PH₃)₂(I)(CO)₂, Cr(CO)₄, Co(PH₃)₂(Cl) and M(PH₃)₂ (M = Ni, Pd, Pt) have been studied at the B3LYP level using the SBKJC relativistic effective core potentials and their associated basis sets on metals and iodine, and the 6-31G(d) basis set on all other elements. The transition metal fragments of V, Cr, Co, Ni, Pd and Pt were chosen based on known alkyne compounds. All the complexes are local minima for both the HGeGeH and GeGeH₂ isomers of the Ge₂H₂ ligand. The complexes containing GeGeH₂ isomer as a ligand are lower in energy than those with the HGeGeH ligand (except in the V complex in which the difference is only 1.0 kcal/mol). There is a net charge transfer from ligand to metal in complexes V-Co and from metal to ligand in late transition metal complexes (Ni-Pt).     

Topological complexity of potential surfaces and application to C2H2 molecule

Summary In this work, we search for the simplest complete surfaces of systems with three and four atoms, i.e. the minimal sets of critical points with their index, which are topologically consistent in the whole configuration space. Then we show the smallest change in the A₂B₂ system by requiring at least one stable acetylene configuration and one stable vinylidene configuration, like on the C₂H₂ surface. Finally, we give complete sets of minima, saddle points and maxima obtained for C₂H₂ with analytical potentials proposed in the literature and with a semi-empirical method at the CAS-CI level.     

Synthesis, structure and physical properties of the new Zintl phases Eu11Zn6Sb12 and Eu11Cd6Sb12

Reported are the syntheses, crystal structure determinations from single-crystal X-ray diffraction, and magnetic properties of two new ternary compounds, Eu₁₁Cd₆Sb₁₂ and Eu₁₁Zn₆Sb₁₂. Both crystallize with the complex Sr₁₁Cd₆Sb₁₂ structure type—monoclinic, space group C2/m (no. 12), Z=2, with unit cell parameters a=31.979(4) Å, b=4.5981(5) Å, c=12.3499(14) Å, β=109.675(1)° for Eu₁₁Zn₆Sb₁₂, and a=32.507(2) Å, b=4.7294(3) Å, c=12.4158(8) Å, β=109.972(1)° for Eu₁₁Cd₆Sb₁₂. Their crystal structures are best described as made up of polyanionic and ribbons of corner-shared ZnSb₄ and CdSb₄ tetrahedra and Eu²⁺ cations. A notable characteristic of these structures is the presence of Sb-Sb interactions, which exist between two tetrahedra from adjacent layers, giving rise to unique channels. Detailed structure analyses shows that similar bonding arrangements are seen in much simpler structure types, such as Ca₃AlAs₃ and Ca₅Ga₂As₆ and the structure can be rationalized as their intergrowth. Temperature-dependent magnetization measurements indicate that Eu₁₁Cd₆Sb₁₂ orders anti-ferromagnetically below 7.5 K, while Eu₁₁Zn₆Sb₁₂ does not order down to 5 K. Resistivity measurements confirm that Eu₁₁Cd₆Sb₁₂ is poorly metallic, as expected for a Zintl phase.     

Synthesis and crystal structure of the Sr2MnGa(O,F)6 oxyfluorides

The fluorine-containing derivatives of Sr₂MnGaO_5.5 were prepared by treatment with XeF₂ at temperatures ranging from 300°C to 600°C. The compounds crystallize in a tetragonal unit cell with a_t≈a_p, c_t≈2a_p (a_p—the parameter of the perovskite subcell). An increase in fluorine content is accompanied by a reduction of the Mn oxidation state due to a partial replacement of oxygen by fluorine. The crystal structure of Sr₂MnGaO_4.78F_1.22 was determined by electron diffraction and X-ray powder diffraction (a=3.85559(2) Å, c=7.78289(6) Å, S.G. P4/mmm, R_I=0.012, R_P=0.019). The structure consists of alternating (MnO₂), (SrO) and (GaO_0.78F_1.22) layers. The Ga atoms are situated in slightly elongated octahedra, the MnO₆ octahedra are characterized by two short apical Mn-O distances of 1.876(8) Å and four long equatorial ones of 1.9278(1) Å. This is interpreted as an “apically compressed” type of Jahn-Teller distortion, in contrast to the “apically elongated” one in the Sr₂MnGaO_5+δ brownmillerites with different oxygen content. Possible structural reasons for the reversed Jahn-Teller effect are discussed.