Synthesis of ternary and quaternary graphite intercalation compounds containing alkali metal cations and diamines

A series of ternary graphite intercalation compounds (GICs) of alkali metal cations (M = Li, Na, K) and diamines [EN (ethylenediamine), 12DAP (1,2-diaminopropane), and DMEDA (N,N-dimethylethylenediamine)] are reported. These include stage 1 and 2 M-EN-GIC (M = Li, d(i) = 0.68-0.84 nm; M = Na, d(i) = 0.68 nm), stage 2 Li-12DAP-GIC (d(i) = 0.83 nm), and stage 1 and 2 Li-DMEDA-GIC (d(i) = 0.91 nm), where d(i) is the gallery height. For M = Li, a perpendicular-to-parallel transition of EN is observed upon evacuation, whereas for M = Na, the EN remains in parallel orientation. Li-12DAP-GIC and Li-DMEDA-GIC contain chelated Li(+) and do not show the perpendicular-to-parallel transition. We also report the quaternary compounds of mixed cations (Li,Na)-12DAP-GIC and mixed amines Na-(EN,12DAP)-GIC, with d(i) values in both cases between those of the ternary end members. (Li,Na)-12DAP-GIC is a solid solution with lattice dimensions dependent on composition, whereas for Na-(EN,12DAP)-GIC, the lattice dimension does not vary with amine content.     

Ternary graphite intercalation compounds associating an alkali metal and an electronegative element or radical

Ternary graphite intercalation compounds associating an alkali metal and an electronegative element are described. The synthesis is more often realized in molten alkali metal media containing the associate electronegative element or radical in the adequate concentration. The intercalated sheets are systematically polylayered. The arrangement along c-axis and the in-plane structures are described. The physical properties of the compounds are precised.     

Intermediate phases during alkali metal intercalation in HfNCl

The mechanism of the chemical and electrochemical alkali metal intercalation reactions in β-HfNCl has been investigated through electrochemical potential spectroscopy (EPS), in-situ powder X-ray diffraction during electrochemical intercalation and room temperature chemical intercalation experiments. EPS experiments in lithium cells reveal the presence of a plateau, at 1.8 V vs. Li⁺/Li⁰ accounting for ca. 0.14 mol Li, that indicates the formation of a new intermediate phase, and then a gradual decrease of potential with composition that extends up to very high lithium contents (ca. 1.1 per formula), consistent with the formation of a solid solution. Sodium electrochemical intercalation experiments showed a relatively similar behaviour with a plateau at 1.4 V vs. Na⁺/Na⁰, corresponding to ca. 1.7 V vs. Li⁺/Li⁰. In-situ monitored powder X-ray diffraction electrochemical intercalation experiments showed that the electrolyte solvent (ethylene carbonate/dimethyl carbonate, EC/DMC or propylene carbonate, PC) co-intercalated with the alkaline atom. This leads to a large expansion of the interlayer spacing that reaches a value of 21.06 Å in the lithium co-intercalated phase with EC/DMC, Li_x(EC/DMC)_yHfNCl, and 22.01 Å in the sodium co-intercalated phase with PC, Na_x(PC)_yHfNCl. Chemical intercalation using naphthyl-sodium solutions in tetrahydrofuran (THF) leads to solvent-free, multiple-phase samples showing in different proportions the pristine and the superconducting stage 2 and stage 1 phases. The composition of the intercalated samples depends on the pristine sample, the concentration of the naphthyl-sodium solution, the ratio Na:HfNCl and the reaction time. Pristine samples exhibiting low lithium intercalation degree upon electrochemical reduction gave the second stage as the major phase when treated with short reaction times or using low Na:HfNCl ratios, coexisting either with the host or with the first stage phase, whereas stage 1 is obtained as the major phase from pristine samples showing high electrochemical capacities. The staging behaviour and the multiphase nature of these samples account for the wide superconducting transitions and the different critical temperatures observed in these superconductors.     

Facile preparation of graphite intercalation compounds in alkali solution

Graphite intercalation compounds are often prepared by flake graphite, oxidants, inorganic acids, organic acids and intercalated ions which are usually hydrogen protons between the graphene planes. They are also known as the acid-treated graphite intercalation compounds. In this work, alkaline graphite intercalation compounds were prepared by flake graphite, K₂Cr₂O₇, concentrated H₂SO₄ and NaOH, and the morphology and structure were characterized by Electron microscopy and X-ray techniques. The results display that the combination of neutralisation heat and oxidation capability produced by K₂Cr₂O₇ can break the bonds to produce the spaces between the graphene planes and hydroxyl ions also intercalate into the graphene planes to form alkaline graphite intercalation compounds in alkali solution. The morphology and structure of alkaline graphite intercalation compounds are analogous to the ones of the acid-treated graphite intercalation compounds, but the intercalated ions and the expansion volume are different. The results show that the method is an innovation.     

In-situ TEM investigation of MoS_2 upon alkali metal intercalation

Phase transition in two dimensional molybdenum disulfide (MoS_2) can be induced by several methods and has been investigated for decades. Alkali metal insertion of MoS_2 had been proved an effective method to cause phase transition early in 1970s, and has been gaining renewed interest recently, due to the possible application of MoS_2 in energy storage. The alkali metal intercalation of MoS_2 has been studied by various techniques, among which in-situ transmission electron microscopy (TEM) provides unique capability of real time resolving the structural evolution of the materials at high spatial resolutions. Here by in-situ TEM technique we investigated the structural evolution of MoS_2 upon lithium and sodium intercalation, along with transformation of the nanosheet and variation of the electron diffraction patterns. The intercalation process is accompanied by emergence of superstructures, which exist in several forms. The ion intercalation results in phase transition of MoS_2 from 2H to 1T, and the driving mechanism of the phase transition are discussed. The work provides a more comprehensive understanding of ion intercalation induced phase transition of MoS_2.     

Effect of sorbed molecules on the resistivity of alkali metal-graphite intercalation compounds

Alkali metal-graphite intercalation compounds with the composition of MC₂₄ (M=K, Rb, Cs) were prepared by heating a mixture of MC₈ (saturated compound) and graphite sheet (Grafoil) at 350-450 °C. The resistivity perpendicular to the layer planes (ρ_c) of the resulting compounds was determined by the two-terminal method. The anisotropy factor of the resistivity, (ρ_c/ρ_a), of KC₂₄ prepared from Grafoil was ∼130, being about 1/6-1/10 in magnitude compared with that of KC₂₄ prepared from highly oriented pyrolytic graphite. The resistivity change during sorption of hydrogen (at 90 K), ethylene (at 194 K) and acetylene (at 194 K) was determined. The resistivity of MC₂₄ increased with increase of the sorbed amount of H₂. The magnitude of the increase was in the order KC₂₄>RbC₂₄>CsC₂₄. This resistivity increase was considered to be due to the expansion along c-direction which reduces the charge-transfer interaction between the carbon layers and potassium ions, resulting in the decrease of the density of the conduction electron. The resistivity of MC₂₄ increased extensively during sorption of C₂H₄ and C₂H₂. It was discussed in connection with the in-plane structural transition and chemical interaction between alkali metal ions and sorbed molecules.     

Modeling the electronic structure of graphite intercalation compounds with lithium by metal complexes with polybenzene systems

The electronic structure of intercalation compounds obtained by inclusion of an alkali metal in graphite is considered using molecular complexes C₆H₆Li₂, (C₆H₆)₂Li, and (C₆H₆)₃Li₂ in the lowest energy states as examples. Modeling the electron distributions of the intercalates requires inclusion of metal d-orbitals in the basis set of AOs and rejection of purely ionic models. It was found that exclusion of the lithium d-AO from the basis set significantly increases the ionic character of the distributions. Moscow State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 3, pp. 450–457, May–June, 1996.     

Graphite fluoride intercalation compounds for manufacturing composites with metal nanoparticles

The feasibility of using graphite fluoride intercalation compounds (GFICs) containing metal compounds for manufacturing metal nanoparticles in a graphite or graphite fluoride matrix is shown using the hydrogen reduction of a dicarbon fluoride matrix intercalated with a chloroform solution of palladium acetylacetonate Pd(AA)₂. The composite manufactured with a GFIC containing about 10.5 wt % Pd(AA)₂ at 80°C is Pd-fluorographite; at 450°C, Pd-graphite is manufactured. The palladium particle size in the composites is about 20–30 nm; the palladium concentration is about 5 and 9 wt %, respectively.     

Preparation of complexes from trimethylgallium and alkali metal hydrides

Conclusions Monohydride complexes of type MGa(CH₃)₃H are formed when trimethylgallium is reacted with alkali metal hydrides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 126–127, January, 1973.     

The heat capacities of selected inorganic alkali metal compounds

The heat capacities of selected inorganic binary and ternary alkali metal compounds are determined using differential scanning calorimetry (DSC). As part of an ongoing research program at Battelle Memorial Institute since 1983, the heat capacities of cesium and rubidium chalcogenides, aluminates, silicates and uranates in the temperature range 310 to 800 K have been added to the series of compounds. The measured data is to be combined with the standard enthalpies of formation and low temperature heat capacities to obtain reliable thermodynamic data on the alkali metal compounds to high temperatures.     

A method for controlled stoichiometry intercalation of alkali metals in layered metal dichalcogenide crystals

Crystals ofLi_yTiS₂ (0 < y < 1) and2HA_yTaX₂ (A =Li, Na, K; 0 < y < 1; X =S, Se) have been prepared by equilibration of the unintercalated crystals with a source powder of the desired alkali ion stoichiometry via the alkali vapor pressure of the compounds at 400–650°C. Crystals of 1 cm² area were intercalated. The final stoichiometry of the crystals is in good agreement with that expected from the source.     

Synthesis and structure of alkali metal zirconium vanadate phosphates

Mixed vanadate phosphates in the systems MZr₂(VO₄) _x (PO₄)_{3 ? x} , where M is an alkali metal, were synthesized and studied by X-ray diffraction, electron probe microanalysis, and IR spectroscopy. Substitutional solid solutions with the structure of the mineral kosnarite (NZP) are formed at the compositions 0 ≤ x ≤ 0.2 for M = Li; 0 ≤ x ≤ 0.4 for M = Na; 0 ≤ x ≤ 0.5 for M = K; 0 ≤ x ≤ 0.3 for M = Rb; and 0 ≤ x ≤ 0.2 for M = Cs. Apart from the high-temperature NZP modification, lithium vanadate phosphates LiZr₂(VO₄) _x (PO₄)_{3 ? x} with 0 ≤ x ≤ 0.8 synthesized at temperatures not exceeding 840°C crystallize in the scandium tungstate type structure. The crystal structures of LiZr₂(VO₄)_0.8(PO₄)_2.2 (space group P2₁/n, a = 8.8447(6) Å, b = 8.9876(7) Å, c = 12.3976(7) Å, β = 90.821(4)○, V = 985.4(1) ų, Z = 4) and NaZr₂(VO₄)_0.4(PO₄)_2.6 (space group $R\bar 3c$ = 8.8182(3) Å, c = 22.7814(6) Å, V = 1534.14(1) ų, Z = 6) were refined by the Rietvield method. The framework of the vanadate phosphate structure is composed of tetrahedra (that are statistically occupied by vanadium and phosphorus atoms) and ZrO₆ octahedra. The alkali metal atoms occupy extra-framework sites.     

Synthesis, structure and properties of intercalation compounds containing perfluoroalkyl groups

Synthesis, structure and properties of various layered materials containing perfluoroalkyl groups in their interlayer space were summarized. They were obtained by ion exchange method for layered materials with ion exchange capacity and by silylation technique for those possessing acidic hydroxyl groups. The orientation of perfluoroalkyl groups greatly changed depending on their contents in the layered materials. The nature of the interlayer space of them changed from hydrophilic to hydrophobic and they were well dispersed in appropriate organic solvents. Some of them formed so called nanosheet solution and film samples were prepared from it. Organic molecules were introduced into the intercalation compounds by co-adsorption or exfoliation-restacking methods. The empty space surrounded by perfluoroalky chains where organic molecules are included showed unique properties. The weak interaction between perfluoroalkyl chains and included organic molecules lead the easy diffusion of them in the interlayer space, which caused the aggregation of them or affected the distribution of isomers obtained by photochemical reaction. The low vibrational C-F bonding in perfluoroalky groups reduced radiational quenching, accordingly enhanced the fluorescence from included organic dyes.     

Crystal structure transformations in ammonium and alkali metal perchlorates

A comparative study of the polymorphic transformations in ammonium and the alkali metal perchlorates has been made using differential thermal analysis. Certain correlations have been attempted between the observed trends in the transformation temperatures and available crystallographic and thermodynamic data. The transformation in the case of sodium perchlorate shows pronounced second-order effects. Considerable hysteresis is observed in the transformations in ammonium, potassium, rubidium and caesium perchlorates. Doping of ammonium perchlorate with ammonium phosphate is seen to result in an upward shift in the transformation temperature and an increase in the thermal hysteresis. Prior mechanical and thermal treatment is also seen to result in a broadening of the hysteresis loops in the case of ammonium and potassium perchlorates. The results are explained in terms of contrapolarization effects and the production of strain in the material as a result of prior treatment.     

The thermodynamic properties of alkali metal compounds at high temperatures

A research program has been in progress to obtain reliable thermodynamic data on various binary and ternary alkali metal compounds in the temperature range of 300 to 1500 K. To date, heat capacity measurements have been made on cesium and rubidium chromates, dichromates, zirconates, molybdates, dimolybdates, and halides in the temperature range of 300 to 800K. In addition, measurements are planned or are currently in progress on cesium and rubidium chalcogenides, aluminates, uranates, silicates, and several other lithium, sodium, and potassium compounds. The status of the research program is discussed.     

Polynuclear coordination compounds of alkali metal ions with organic chromophores

The crystal structures of sodium 4‐({4‐[N,N‐bis(2‐hydroxy­ethyl)­amino]­phenyl}diazenyl)­benzoate 3.5‐hydrate, Na⁺·C₁₇H₁₈N₃O₄^?·3.5H₂O, (I), and potassium 4‐({4‐[N,N‐bis(2‐hydroxy­ethyl)­amino]­phenyl}diazenyl)­benzoate dihydrate, K⁺·C₁₇H₁₈N₃O₄^?·2H₂O, (II), are described. The results indicate an octahedral coordination around sodium in (I) and a trigonal prismatic coordination around potassium in (II). In both cases, coordination around the metal cation is achieved through O atoms of the water mol­ecules and hydroxy groups of the chromophore. The organic conjugated part of the chromophore is approximately planar in (I), while a dihedral angle of 30.7 (2)° between the planes of the phenyl rings is observed in (II).     

Molecular structure and microbiological activity of alkali metal 3,4-dihydroxyphenylacetates

The changes in physical, chemical and biological properties of chemical compounds decide about their biological activity. In this paper the molecular structure of alkali metal 3,4-dihydroxyphenylacetates is studied in comparison to 3,4-dihydroxyphenylacetic acid (3,4-DHPAA) using FT-IR, FT-Raman and UV–Vis spectroscopy as well as density functional theory (DFT) calculations. The B3LYP/6-311++G⁷ method is used to calculate optimized geometrical structures of studied compounds, atomic charges (Mulliken, APT, NBO), dipole moments, energies as well as the wavenumbers and intensities of the bands in vibrational spectra. Theoretical parameters are compared to the experimental data. The relationship between spectroscopic parameters of studied compounds and their biological activity is analyzed. Antioxidant activity is studied using FRAP and DPPH methods. IC₅₀ parameter is also calculated. Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli and Klebsiella oxytoca are used in microbiological analysis of 3,4-DHPAA as well as its sodium and potassium salts.     

Synthesis and crystal structure of new alkali metal hydrogen tellurates

New alkali metal hydrogen tellurates have been synthesized, and their structures have been determined by X-ray crystallography. Hydrogen tellurates I–VI contain centrosymmetric binuclear anions [Te₂O₁₀H_4+x ]^(4?x)?, where x=0, 1, 2. Hydrogen tellurates II and VI contain, in addition to the binuclear anion, mononuclear species [TeO₆H₄]^2? and Te(OH)₆, respectively. The CNs of alkali metals vary from 8 to 12. In all structures, the hydrogen atoms (of both the hydroxy groups and water molecules) are involved in hydrogen bonding.