Coexistence of Tellurium Cations and Anions in Phosphonium-Based Ionic Liquids.

Elemental tellurium readily dissolves in ionic liquids (ILs) based on tetraalkylphosphonium cations even at temperatures below 100 °C. In the case of ILs with acetate, decanoate, or dicyanamide anions, dark red to purple colored solutions form. A study combining NMR, UV-Vis and Raman spectroscopy revealed the formation of tellurium anions (Ten )2- with chain lengths up to at least n=5, which are in dynamic equilibrium with each other. Since external influences could be excluded and no evidence of an ionic liquid reaction was found, disproportionation of the tellurium is the only possible dissolution mechanism. Although the spectroscopic detection of tellurium cations in these solutions is difficult, the coexistence of tellurium cations, such as (Te4 )2+ and (Te6 )4+ , and tellurium anions could be proven by cyclic voltammetry and electrodeposition experiments. DFT calculations indicate that electrostatic interactions with the ions of the ILs are sufficient to stabilize both types of tellurium ions in solution.

One-pot synthesis of brewer's spent grain-supported superabsorbent polymer for highly efficient uranium adsorption from wastewater.

High-efficient and fast adsorption of uranium is important to reduce the hazards caused by the uranium contamination of water environment due to the increased human activities. Herein, brewer's spent grain (BSG)-supported superabsorbent polymers (SAP) with different cross-linking densities are prepared as cheap and eco-friendly adsorbents for the first time via one-pot swelling and graft polymerization. A 7 wt% NaOH solution is used to swell BSG before grafting and subsequently neutralize the acrylic acid to control the reaction rate without producing alkaline wastewater. Compared with the traditional methods, swelling improves the grafting density and the utilization of raw materials due to the increased disorder degree of the BSG fibers. This results in the grafting of abundant carboxyl and amide groups onto the BSG backbone, forming a strongly hydrophilic polymer network of the BSG-SAP. Compared with the reference polymers without BSG, BSG-SAP presents higher adsorption capacity and enhanced reusability. The highly cross-linked BSG-SAP (BSG-SAP-H) shows an outstanding adsorption capacity of U(VI) (1465 mg/g at pH0 = 4.6), a fast adsorption rate (81% of equilibrium adsorption capacity in 15 min), and a high selectivity in the presence of competing ions. Adsorption mechanism studies reveal the involvement of amide groups, a bidentate binding structure between UO22+ and the carboxyl groups, and a cation exchange between Na+ and UO22+. More importantly, the adsorption capacity of BSG-SAP-H reaches 254.4 mg/g in the fixed-bed column experiment at a low initial concentration (c0(U) = 30 mg/L) and keeps 80% of the adsorption capacity after four cycles, indicating a great potential for uranium removal from wastewater. This work shows a suitable approach to explore the untreated biomass to prepare SAP with enhanced adsorption performance via a general and low-cost strategy.

Potassium Ion Conductivity in the Cubic Labyrinth of a Piezoelectric, Antiferromagnetic Oxoferrate(III) Tellurate(VI).

Orange-colored crystals of the oxoferrate tellurate K12+6x Fe6 Te4-x O27 [x=0.222(4)] were synthesized in a potassium hydroxide hydroflux with a molar water-base ratio n(H2 O)/n(KOH) of 1.5 starting from Fe(NO3 )3 ⋅ 9H2 O, TeO2 and H2 O2 at about 200 °C. By using (NH4 )2 TeO4 instead of TeO2 , a fine powder consisting of microcrystalline spheres of K12+6x Fe6 Te4-x O27 was obtained. K12+6x Fe6 Te4-x O27 crystallizes in the acentric cubic space group I 4 ‾ 3d. [FeIII O5 ] pyramids share their apical atoms in [Fe2 O9 ] groups and two of their edges with [TeVI O6 ] octahedra to form an open framework that consists of two loosely connected, but not interpenetrating, chiral networks. The flexibility of the hinged oxometalate network manifests in a piezoelectric response similar to that of LiNbO3 .The potassium cations are mobile in channels that run along the <111> directions and cross in cavities acting as nodes. The ion conductivity of cold-pressed pellets of ball-milled K12+6x Fe6 Te4-x O27 is 2.3×10-4 S ⋅ cm-1 at room temperature. Magnetization measurements and neutron diffraction indicate antiferromagnetic coupling in the [Fe2 O9 ] groups.

Freestanding Nanolayers of a Wide-Gap Topological Insulator through Liquid-Phase Exfoliation.

The layered salt Bi14 Rh3 I9 is a weak three-dimensional (3D) topological insulator (TI), that is, a stack of two-dimensional (2D) TIs. It has a wide non-trivial band gap of 210 meV, which is generated by strong spin-orbit coupling, and possesses protected electronic edge-states. In the structure, charged layers of ∞ 2 [ (Bi4 Rh)3 I]2+ honeycombs and ∞ 1 [ Bi2 I8 ]2- chains alternate. The non-trivial topology of Bi14 Rh3 I9 is an inherent property of the 2D intermetallic fragment. Here, the exfoliation of Bi14 Rh3 I9 was performed using two different chemical approaches: (a) through a reaction with n-butyllithium and poly(vinylpyrrolidone), (b) through a reaction with betaine in dimethylformamide at 55 °C. The former yielded few-layer sheets of the new compound Bi12 Rh3 I, while the latter led to crystalline sheets of Bi14 Rh3 I9 with a thickness down to 5 nm and edge-lengths up to several ten microns. X-ray diffraction and electron microscopy proved that the structure of Bi14 Rh3 I9 remained intact. Thus, it was assumed that the particles are still TIs. Dispersions of these flakes now allow for next steps towards the envisioned applications in nanoelectronics, such as the study of quantum coherence in deposited films, the combination with superconducting particles or films for the generation of Majorana fermions, or studies on their behavior under the influence of magnetic or electric fields or in contact with various materials occurring in devices. The method presented generally allows to exfoliate layers with high specific charges and thus the use of layered starting materials beyond van der Waals crystals.

Structural Variations and Bonding Analysis of the Rare-Earth Metal Tellurides RETe1.875±Î´ (RE = Ce, Pr, Sm, Gd; 0.004 ≤ δ ≤ 0.025).

Crystals of RETe1.875±Î´ (RE = Ce, Pr, Sm, Gd; 0.004 ≤ δ ≤ 0.025) were grown using alkali halide flux and chemical transport reactions. The crystal structures are described in space group Amm2 (no. 38), with lattice parameters of a = 13.3729(5) Å, b = 17.7918(5) Å, c = 18.1561(4) Å for CeTe1.87(1) (T = 100 K), a = 13.271(2) Å, b = 17.747(3) Å, c = 18.160(3) Å for PrTe1.85(1) (T = 100 K), a = 13.1251(6) Å, b = 17.4269(8) Å, c = 17.8808(8) Å for SmTe1.87(1) (T = 100 K), and a = 13.1762(4) Å, b = 17.4995(5) Å, c = 17.9591(5) Å for GdTe1.88(1) (T = 296 K). The structures contain alternating stacks of puckered [RETe] slabs and planar [Te] layers. The latter are composed of small anionic entities, such as Te2- and Te22-, along with a large anionic eight-membered Te ring, as supported by electron localizability indicator-based bond analysis for an ordered model of GdTe1.875. Slightly different patterns for individual compounds indicate a considerable structural flexibility. Temperature-dependent resistance measurements confirm semiconducting behavior for PrTe1.875±Î´ and GdTe1.875±Î´ (magnetic data evidence RE3+ and an antiferromagnetic transition at TN = 4 K for CeTe1.875±Î´ and TN = 11 K for GdTe1.875±Î´), whereas PrTe1.875±Î´ and SmTe1.875±Î´ show no long-range order down to 2 K.

Inorganic Synthesis Based on Reactions of Ionic Liquids and Deep Eutectic Solvents.

Ionic liquids and deep eutectic solvents are of growing interest as solvents for the resource-efficient synthesis of inorganic materials. This Review covers chemical reactions of various deep eutectic solvents and types of ionic liquids, including metal-containing ionic liquids, [BF4 ]- - or [PF6 ]- -based ionic liquids, basic ionic liquids, and chalcogen-containing ionic liquids. Cases in which cations, anions, or both are incorporated into the final products are also included. The purpose of this Review is to raise caution about the chemical reactivity of ionic liquids and deep eutectic solvents and to establish a guide for their proper use.

The Weak 3D Topological Insulator Bi12 Rh3 Sn3 I9.

Topological insulators (TIs) gained high interest due to their protected electronic surface states that allow dissipation-free electron and information transport. In consequence, TIs are recommended as materials for spintronics and quantum computing. Yet, the number of well-characterized TIs is rather limited. To contribute to this field of research, we focused on new bismuth-based subiodides and recently succeeded in synthesizing a new compound Bi12 Rh3 Sn3 I9 , which is structurally closely related to Bi14 Rh3 I9 - a stable, layered material. In fact, Bi14 Rh3 I9 is the first experimentally supported weak 3D TI. Both structures are composed of well-defined intermetallic layers of ∞ 2 [(Bi4 Rh)3 I]2+ with topologically protected electronic edge-states. The fundamental difference between Bi14 Rh3 I9 and Bi12 Rh3 Sn3 I9 lies in the composition and the arrangement of the anionic spacer. While the intermetallic 2D TI layers in Bi14 Rh3 I9 are isolated by ∞ 1 [Bi2 I8 ]2- chains, the isoelectronic substitution of bismuth(III) with tin(II) leads to ∞ 2 [Sn3 I8 ]2- layers as anionic spacers. First transport experiments support the 2D character of this material class and revealed metallic conductivity.

Synthesis of (Li2Fe1-yMny)SO Antiperovskites with Comprehensive Investigations of (Li2Fe0.5Mn0.5)SO as Cathode in Li-ion Batteries.

A series of solid solutions (Li2Fe1-yMny)SO with a cubic antiperovskite structure was successfully synthesized. The composition (Li2Fe0.5Mn0.5)SO was intensively studied as a cathode in Li-ion batteries showing a reversible specific capacity of 120 mA h g-1 and almost a 100% Coulombic efficiency after 50 cycles at 0.1C meaning extraction/insertion of 1 Li per formula unit during 10 h. Operando X-ray absorption spectroscopy confirmed the redox activity of both Fe2+ and Mn2+ cations during battery charge and discharge, while operando synchrotron X-ray diffraction studies revealed a reversible formation of a second isostructural phase upon Li-removal and insertion at least for the first several cycles. In comparison to (Li2Fe)SO, the presence of Mn stabilizes the crystal structure of (Li2Fe0.5Mn0.5)SO during battery operation, although post mortem TEM studies confirmed a gradual amorphization after 50 cycles. A lower specific capacity of (Li2Fe0.5Mn0.5)SO in comparison to (Li2Fe)SO is probably caused by slower kinetics, especially in the two-phase region, as confirmed by Li-diffusion coefficient measurements.

Detuning the Honeycomb of the α-RuCl3 Kitaev Lattice: A Case of Cr3+ Dopant.

Fine-tuning chemistry by doping with transition metals enables new perspectives for exploring Kitaev physics on a two-dimensional (2D) honeycomb lattice of α-RuCl3, which is promising in the field of quantum information protection and quantum computation. The key parameters to vary by doping are both Heisenberg and Kitaev components of the nearest-neighbor exchange interaction between the Jeff = 1/2 Ru3+ spins, depending strongly on the peculiarities of the crystal structure. Here, we present crystal growth by chemical vapor transport and structure elucidation of a solid solution series Ru1- xCr xCl3 (0 ≤ x ≤ 1), with Cr3+ ions coupled to the Ru3+ Kitaev host. The Cr3+ substitution preserves the honeycomb type lattice of α-RuCl3 and creates mixed occupancy of Ru/Cr sites without cationic order within the layers as confirmed by single-crystal X-ray diffraction and transmission electron microscopy investigations. In contrast to high-quality single crystals of α-RuCl3 with ABAB-stacked layers, the ternary compounds demonstrate a significant stacking disorder along the c-axis direction as evidenced by X-ray diffraction and high resolution scanning transmission electron microscopy (HR-STEM). Raman spectra of substituted samples are in line with the symmetry conservation of the parent lattice upon chromium doping. At the same time, our magnetic susceptibility data indicate that the Kitaev physics of α-RuCl3 is increasingly suppressed by the dominant spin-only driven magnetism of Cr3+ ( S = 3/2) in Ru1- xCr xCl3.

Unusual Phonon Heat Transport in α-RuCl_{3}: Strong Spin-Phonon Scattering and Field-Induced Spin Gap.

The honeycomb Kitaev-Heisenberg model is a source of a quantum spin liquid with Majorana fermions and gauge flux excitations as fractional quasiparticles. Here we unveil the highly unusual low-temperature heat conductivity κ of α-RuCl_{3}, a prime candidate for realizing such physics: beyond a magnetic field of B_{c}≈7.5 T, κ increases by about one order of magnitude, both for in-plane as well as out-of-plane transport. This clarifies the unusual magnetic field dependence unambiguously to be the result of severe scattering of phonons off putative Kitaev-Heisenberg excitations in combination with a drastic field-induced change of the magnetic excitation spectrum. In particular, an unexpected, large energy gap arises, which increases linearly with the magnetic field, reaching remarkable ℏω_{0}/k_{B}≈50 K at 18 T.

On Jeff =0 Ground State Iridates(V): Tracking Residual Paramagnetism in New Bi2 NaIrO6.

Open-shell transition metal oxides are capable of developing a rich diversity of electronic phases. The specific features evolving crucially depend on an intricate interplay of various local and long-range electronic interactions. Recently, the 5d transition elements have come into sharp focus because for these elements spin-orbit coupling (SOC) and onsite Coulomb repulsion (U) are on a comparable energy scale. For Ir4+ the t2g level associated to an octahedral crystal field (CF) is split by SOC, giving rise to a Jeff = 1 / 2 spin state and rendering respective oxides like Sr2 IrO4 as Mott insulators. Transferring this scenario to iridium(V) oxides would lead to a diamagnetic ground state, Jeff =0. However, reported experimental results do not lend unambiguous support for such an electronic state. Theoretical explanations for the breakdown of the J=0 magnetic state suffer from conspicuous discrepancies. In an attempt to empirically contribute to resolving the puzzle, Bi2 NaIrO6 was synthesized in high purity by precipitation from homogeneous solution; it represents an iridium(V) oxide where long range band structure effects and magnetic superexchange are minimized, and the t2g degeneracy is lifted geometrically. We managed to reduce the strength of paramagnetic response, lending support to a Jeff =0 ground state of Bi2 NaIrO6 , exhibiting van Vleck type behavior.

Understanding the Chemical Reactivity of Phosphonium-Based Ionic Liquids with Tellurium.

The chemical reactivity of phosphonium based ionic liquids (ILs) towards tellurium at temperatures above 220 °C was systematically investigated by a series of dissolution experiments, tracking the solute tellurium species by nuclear magnetic resonance, and characterizing the reaction products by X-ray diffraction and scanning electron microscopy. The initial step is the thermal elimination of an alkyl group of the phosphonium cation of the ILs, most probably via an SN 2 mechanism. The addition of tellurium follows to form trialkylphosphane tellurides as evidenced by 31 P and 125 Te NMR spectroscopic experiments. The trialkylphosphane tellurides can serve as a tellurium reservoir for the formation of metal tellurides, like Bi2 Te3 and Ag2 Te. It was observed that trihexyltetradecylphosphonium chloride ([P6 6 6 14 ]Cl) shows a very weak reactivity that is reflected by a low solubility of tellurium, while trihexyltetradecylphosphonium dicyanamide/decanoate ([P6 6 6 14 ][N(CN)2 ]/[P6 6 6 14 ][decanoate]) and tetrabutylphosphonium decanoate ([P4 4 4 4 ][decanoate]) dissolve tellurium to a much higher extent. We attribute these observations to the different Lewis basicity of the anions of the ILs as main influencing factor.

The Intermetalloid Cluster Cation (CuBi8 )3.

The reaction of Bi, BiCl3 , and CuCl in the ionic liquid [BMIm]Cl⋅4 AlCl3 (BMIm=1-n-butyl-3-methylimidazolium) at 180 °C yielded air-sensitive shiny black crystals of (CuBi8 )[AlCl4 ]2 [Al2 Cl7 ] and (CuBi8 )[AlCl4 ]3 . For both compounds X-ray diffraction on single crystals revealed monoclinic structures that contain the intermetalloid cluster (CuBi8 )3+ . It is the first pure bismuth cluster with a 3d metal and the first with a metal that does not form binary intermetallics with bismuth under ambient pressure. The cluster can be interpreted either as a copper(I) cation, η4 -coordinated by a square-antiprismatic Bi82+ polycation (Bi-Cu 267 pm), or as a nine-atomic intermetalloid nido-cluster with 22 skeletal electrons and the C4v symmetry. One of the chloride ions of a tetrahedral [AlCl4 ]- group coordinates the copper atom (Cu-Cl 228 pm) and thereby completes its 18 electron count. DFT-based calculations, followed by real-space bonding analysis, revealed a multicenter bonding situation between copper and bismuth atoms with about seven shared electrons.

Spontaneous Substitutions at Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: Grotthuss Diffusion of Anions?

PX3 compounds (X=Cl, Br, I) in imidazolium halide ionic liquids combine with the anion Z (Z=Cl, Br, I) of the solvent to form [PX3 Z]- complex anions. These anions have a sawhorse shape in which the lone pair of the phosphorus atom fills the third equatorial position of the pseudotrigonal bipyramid. Theoretical results show that this association remains incomplete due to strong hydrogen bonding with the cations of the ionic liquid, which competes with the phosphorus trihalide for interaction with the Z- anion. Temperature-dependent 31 P NMR experiments indicated that the P-Z binding is weaker at higher temperature. Both theory and experiment evidence dynamic exchange of the halide anions at the phosphorus atom, together with continuous switching of the ligands at the phosphorus atom between equatorial and axial positions. Detailed knowledge of the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic-liquid mixtures.

Synthesis of a Cu-Filled Rh17S15 Framework: Microwave Polyol Process Versus High-Temperature Route.

Metal-rich, mixed copper-rhodium sulfide Cu3-δRh34S30 that represents a new Cu-filled variant of the Rh17S15 structure has been synthesized and structurally characterized. Copper content in the [CuRh8] cubic cluster was found to vary notably dependent on the chosen synthetic route. Full site occupancy was achieved only in nanoscaled Cu3Rh34S30 obtained by a rapid, microwave-assisted reaction of CuCl, Rh2(CH3CO2)4 and thiosemicarbazide at 300 °C in just 30 min; whereas merely Cu-deficient Cu3-δRh34S30 (2.0 ≥ δ ≥ 0.9) compositions were realized via conventional high-temperature ceramic synthesis from the elements at 950 °C. Although Cu3-δRh34S30 is metallic just like Rh17S15, the slightly enhanced metal content has a dramatic effect on the electronic properties. Whereas the Rh17S15 host undergoes a superconducting transition at 5.4 K, no signs of the latter were found for the Cu-derivatives at least down to 1.8 K. This finding is corroborated by the strongly reduced density of states at the Fermi level of the ternary sulfide and the disruption of long-range Rh-Rh interactions in favor of Cu-Rh interactions as revealed by quantum-chemical calculations.

Resource-Efficient High-Yield Ionothermal Synthesis of Microcrystalline Cu3-xP.

Polycrystalline Cu3-xP was successfully synthesized in different ionic liquids comprising imidazolium and phosphonium cations. The reaction of elemental copper and red phosphorus in trihexyltetradecylphosphonium chloride at 200 °C led to single-phase Cu3-xP (x = 0.05) within 24 h with a quantitative yield (99%). Liquid-state nuclear magnetic resonance spectroscopy of the ionic liquids revealed degeneration of the imidazolium cations under the synthesis conditions, while phosphonium cations remain stable. The solid products were characterized with X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and elemental analysis. A reinvestigation of the electronic transport properties of Cu2.95(4)P showed metallic behavior for the bulk material. The formation of CuP2 during the synthesis of phosphorus-rich Cu3-xP (x ≥ 0.1) was observed.

Downscaling Effect on the Superconductivity of Pd3Bi2X2 (X = S or Se) Nanoparticles Prepared by Microwave-Assisted Polyol Synthesis.

Pd3Bi2S2 and Pd3Bi2Se2 have been successfully prepared in the form of nanoparticles with diameters of ∼50 nm by microwave-assisted modified polyol synthesis at low temperatures. The composition and morphology of the samples have been studied by means of powder X-ray diffraction as well as electron microscopy methods, including X-ray intensity mapping on the nanoscale. Superconducting properties of the as-prepared samples have been characterized by electrical resistivity measurements down to low temperatures (∼0.2 K). Deviations from the bulk metallic behavior originating from the submicrometer nature of the samples were registered for both phases. A significant critical-field enhancement up to 1.4 T, i.e., 4 times higher than the value of the bulk material, has been revealed for Pd3Bi2Se2. At the same time, the critical temperature is suppressed to 0.7 K from the bulk value of ∼1 K. A superconducting transition at 0.4 K has been observed in nanocrystalline Pd3Bi2S2. Here, a zero-temperature upper critical field of ∼0.5 T has been estimated. Further, spark plasma-sintered Pd3Bi2S2 and Pd3Bi2Se2 samples have been investigated. Their superconducting properties are found to lie between those of the bulk and nanosized samples.

Na2Fe2Se2O: a double anti-perovskite with prevalence of anionic redox activity in Na-ion batteries.

Na2Fe2Se2O with the I4/mmm space group was studied in sodium-ion batteries, delivering a reversible specific capacity of more than 140 mA h g-1. Operando XRD and XAS studies disclosed bifunctional redox behaviour with the prevalence of anionic electrochemical activity and a likely partial decomposition of the material, which, however, does not influence the electrochemical behaviour of the system.

Electron spin resonance study on the 4fhoneycomb quantum magnet YbCl3.

The local magnetic properties of Yb3+in the layered honeycomb material YbCl3were investigated by electron spin resonance on single crystals. For in-plane and out-of-plane field orientations theg-factor shows a clear anisotropy (g∥=2.97(8)andg⊥=1.53(4)), whereas the low temperature exchange coupling and the spin relaxation display a rather isotropic character. At elevated temperatures the contribution of the first excited crystal field level (21±2meV) dominates the spin relaxation.

In situ Investigations of the Formation Mechanism of Metastable γ-BiPd Nanoparticles in Polyol Reductions.

Synthesizing intermetallic phases containing noble metals often poses a challenge as the melting points of noble metals often exceed the boiling point of bismuth (1560 °C). Reactions in the solid state generally circumvent this issue but are extremely time consuming. A convenient method to overcome these obstacles is the co-reduction of metal salts in polyols, which can be performed within hours at moderate temperatures and even allows access to metastable phases. However, little attention has been paid to the formation mechanisms of intermetallic particles in polyol reductions. Identifying crucial reaction parameters and finding patterns are key factors to enable targeted syntheses and product design. Here, we chose metastable γ-BiPd as an example to investigate the formation mechanism from mixtures of metal salts in ethylene glycol and to determine critical factors for phase formation. The reaction was also monitored by in situ X-ray diffraction using synchrotron radiation. Products, intermediates and solutions were characterized by (in situ) X-ray diffraction, electron microscopy, and UV-Vis spectroscopy. In the first step of the reaction, elemental palladium precipitates. Increasing temperature induces the reduction of bismuth cations and the subsequent rapid incorporation of bismuth into the palladium cores, yielding the γ-BiPd phase.