The effect of transition metals on the structure of h-BN intercalation compounds

In this study, hexagonal boron nitride (h-BN) were synthesized by the modified O’Connor method in the presence of various metal nitrates [M(NO₃)_x, M=Cr, Mn, Fe, Co, Ni, Cu, Zn, and Ag]. The composites were analyzed by FTIR, XRF, XRD, and SEM techniques. XRD results indicated a change in the interlayer spacing due to the intercalation of Cr, Mn, Fe and Ag. SEM analyses illustrated the grain growth upon metal intercalation even at a temperature of 1320 K.     

Preparation and structure of alkali metal intercalation compounds

The preparation methods of intercalation compounds fall into four main groups: use of alkali metal solutions in liquid ammonia, organometallic reagents, electrochemical methods, and solid state processes. Each of these will be briefly described and a general comparison of the advantages and disadvantages will be made. Structural problems concern the positions occupied by the guest ions and their mobility from one site to one another in the host structure. The resulting ionic conductivity of the intercalation compounds depends on factors such as the ratio between available and occupied sites in the van der Waals gap, the ionicity of the bonds in the host structure, the site geometry, and the nature of the alkali metal.     

Role of crystal chemical factors in the formation of the magnetic structure of inorganic compounds

The role of crystal chemical factors in the development of conditions for the formation of the magnetic structure of inorganic compounds is shown. A crystal chemical method is proposed to quantitatively estimate the strength of magnetic interactions and to determine magnetic moment orientation based on the structural data. By the example of determining the magnetic structures of two known antiferromagnetics Cs2CuCl4 and Sr2CuO3 the correspondence between the results obtained by this method and the experiment is shown. It is found that the search for new materials with the sought magnetic structure can be made using the data on the crystal structure of compounds. New Tl2Cu(CO3)2, BaCu2(AsO4)2, BaV2P2O10, VOSe2O5, KCu(CO3)F, and A(VO)(XO4) (A = Li, Na, NH4, K; X = P and As) magnets containing low-dimensional fragments are found. Magnetic interactions are analyzed; based on the structural data, the sign and strength of magnetic interactions is calculated both inside the low-dimensional fragments and between them; geometrical frustrations are studied in all compounds found.     

Li intercalation and anion/cation substitution of transition metal chalcogenides: Effects on crystal structure,microstructure, magnetic properties and Li+ ion mobility

We investigated experimentally the effect of Li intercalation on the structural, microstructural and magnetic properties as well as on the Li ion diffusivity of the complex chalcogenides Cr_5?yTi_ySe₈. In addition, the effect of anion substitution in TiS_2?zSe_z on the Li diffusion parameters was studied by ⁷Li nuclear magnetic resonance (NMR) spin-lattice relaxation measurements.For Cr_5?yTi_ySe₈ the Li⁺ insertion is accompanied by an irreversible phase transition from monoclinic to trigonal symmetry which is electronically driven. The maximal Li content in the host material depends on the Ti content and decreases with increasing y in Cr_5?yTi_ySe₈. The intercalated materials can be deintercalated and the minimal Li content in the residual compound increases with Ti abundance. The intercalation process is accompanied by drastic changes of the microstructure. Electrochemical discharge curves depend significantly on the Ti. According to the results of XANES investigations performed on Cr₄TiSe₈, Ti is first reduced during Li uptake and Cr atoms accept electrons at later stages of the intercalation reaction. In-situ energy dispersive X-ray diffraction experiments show that the Li intercalation at room temperature proceeds via two different mechanisms while intercalation at 60 °C is faster and is dominated by one mechanism. ⁷Li MAS NMR measurements revealed a variety of transition metal environments around the Li sites corresponding to the Cr/Ti disorder. The NMR studies also indicate fast Li dynamics. The magnetism of the educts is dominated by strong antiferromagnetic exchange interactions in the high temperature region and by spin-glass behavior in the low temperature range. Intercalation of Li weakens the antiferromagnetic exchange and for fully intercalated materials ferromagnetic exchange is observed. The interpretation of the experimental results is supported by accompanying band structure calculations.In layer-structured Li_xTiS_2?zSe_z (x ≈ 0.7) the Li diffusivity was investigated by various NMR techniques and compared with results obtained for the pure end members Li_xTiS₂ and Li_xTiSe₂. In particular, anion substitution clearly influences the slopes of the low-T flanks of the diffusion induced NMR relaxation-rate peaks. The corresponding activation barriers characterizing local hopping processes are reduced in the mixed samples with 0 < z < 2 and can be explained by a domain model. DFT calculations yield very small hopping barriers along S-rich and Se-rich domain boundaries while the barriers for Li migration inside the domains are rather high. It is therefore assumed that Li migrates along the domain boundaries.     

Influence of the crystallinity on the Li+ intercalation process in Nb2O5 films

Nb₂O₅ thin films were prepared by the Pechini method. The effect of the film crystallinity on the electrochemical and electrochromic properties was investigated. A relationship between the crystalline structure and the Li⁺ intercalation/extraction process, stability and kinetics was observed. A significant decrease in the electrochemical response was observed as a function of the number of cycles for films treated at 400 and 450 °C. However, as the calcination temperature increases this effect disappears. XRD studies shown that at 400 °C, the material is amorphous, evolving to orthorhombic phase. The transmittance variation as well as the coloration efficiency increases as the temperature is increased. In the initial cycles the intercalation charge is higher for the amorphous oxide than for the orthorhombic phase. However, the variation in the optical density is small. On the other hand, the charge of the orthorhombic phase oxide does not change. These results suggest that there are two different processes associated with Li⁺ intercalation, but only one of them leads to the coloration process.     

On the importance of surface structure in electrochemistry: the well-defined Au (111) single crystal electrode surface

The electrochemical nucleation of cadmium onto vitreous carbon and onto tin oxide electrodes in studied using potentiostatic methods. The influence of supporting electrolyte is investigated and in every case new and interesting features arise. The deposition of cadmium on tin oxide is of particular interest and evidently occurs via an initial process of 2D nucleation followed, at higher overpotentials, by 3D nucleation.     

钼簇合物的簇解反应和两个多钼酸盐化合物的晶体结构

含μ-Cl桥的三核钼簇阴离子[Mo~3(μ~3-O)(μ-Cl)~3(μ-OAc)~3Cl~3]^-在Fe^3^+作用下发生簇解反应, 形成钼同多酸盐[FeCl(DMF)~5][Mo~6O~1~9]。在合成[Mo~3(μ~3-S)(μ-S~2)~3(dtp)~3Cl]簇合物的反应中如果有CuI存在, 则形成钼磷杂多酸盐(Et~4N)~4[PMo~1~2O~4~0](DMF)~2。本文报道这两个多钼酸盐化合物的晶体结构, 并讨论有关的簇解反应。     

The lithium intercalation compound Li2CoSiO4 and its behaviour as a positive electrode for lithium batteries

The electrochemical behaviour of 3 polymorphs of the lithium intercalation compound Li2CoSiO4, betaI, betaII and gamma0, as positive electrodes in rechargeable lithium batteries is investigated for the first time.     

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.     

Electro-optical performance of inorganic monolithic electrochromic device with a pulsed DC sputtered Li x Mg y N ion conductor

Journal of Solid State Electrochemistry - Lithium magnesium nitride (Li x Mg y N) thin films were deposited by pulsed DC reactive magnetron sputtering from a LiMg alloy target in the mixture gas of...     

The adsorption of monomers (metal complexes with Schiff bases) and the structure and properties of polymeric films formed on the surface of graphite

The adsorption of nickel(II) and copper(II) complexes with the N,N′-ethylenebis(salicylideneimine) ligand on carbonaceous materials and at the air-solution boundary was studied. A correlation was observed between adsorption parameters and the structure of polymeric films formed as a result of the electrode oxidation of these compounds (monomers).     

Topology of the structure of metal sublattices in inorganic compounds

The Voronoi-Dirichlet polyhedron (VDP) method is used to study the topology of atomic metal sublattices in the structures of 350 inorganic compounds. For the sample under consideration, it is confirmed that the rule of twelve and fourteen neighbors is valid. It is found for 26 compounds that the environment of metal atoms in the cationic framework possesses noncrystallographic features. The advantages of using the VDP method for determination of coordination numbers of atoms are shown on several examples. The local and global homogeneity of the structures of the compounds is discussed. Samara State University. Translated fromZhurnal Struktumoi Khimii, Vol. 37, No. 1, pp. 116–122, January–February, 1996. Translated by L. Smolina     

Effects of chemical structure and composition of the polymer matrix on the morphology and electro-optical performance of polymer-dispersed liquid crystal films

Polymer-dispersed liquid crystal (PDLC) systems on the basis of nematic liquid crystal E7 and amphiphilic binary copolymers of acrylic acid (AA) with such acrylates as 2-ethylhexyl acrylate (EHA), n-butyl acrylate (BA), and methyl acrylate (MA) are investigated. It is shown that the liquid crystal (LC) drops in the copolymer EHA–AA have submicrometre sizes, and their dependence on the composition of the photo-curable monomer mixture is described by a parabolic curve. The highly oriented domain structure in the same system is first revealed when electric field is applied. The threshold voltage for all systems begins to increase with some critical composition of a monomer mixture in which the longer the hydrocarbonic radical in an acrylate molecule, the higher the content of AA. The PDLC system based on the BA–AA copolymer with 30 wt% LC exhibits the least value of the driving voltage, 1 V μm^–1, and the lowest memory effect.     

The impedance of the Li+/Li electrode in SOCl2

Impedance measurements have been made on a lithium electrode in SOCl₂ containing 1.8 M LiAlCl₄. Impedance loci were recorded over a range of frequencies at a series of potentials.The results confirm the existence of a film on the Li electrode which grows continuously with time. Kinetic data for the Li⁺/Li ion exchange were estimated by arranging for measurements to be made as rapidly as possible and after a practical minimum time of electrode/electrolyte contact. The exchage current density for the lithium electrode was estimated under our best conditions to be 0.48 mA/cm² and α for the Li⁺ couple ≈ 0.59.     

Adsorption of bisulfate on the Ru(0001) single crystal electrode surface

Adsorption of anions from sulfuric acid solutions has been studied on Ru(0001) single crystal and polycrystalline surfaces by electrochemical techniques and in-situ Fourier transform infrared spectroscopy. Infrared spectroscopy shows that bisulfate is the anion adsorbed on the Ru(0001) surface. The bisulfate adsorption is detected at the H₂ evolution potential and extends into the potential region where the Ru surface is oxidized. A method for extracting unipolar bands from bipolar bands has been presented. The tuning rate of adsorbed bisulfate in the double layer potential region of Ru(0001) was found to be significantly smaller than those observed for other platinum metals. This has been ascribed to a small change in bisulfate coverage on Ru(0001) in this potential range. Bisulfate vibration frequencies are higher on this surface than at any face-centered cubic metal with the (111) orientation. Oxidation of the Ru(0001) surface is limited to one electron per Ru atom, distinctly different from the high degree of oxidation seen in polycrystalline surfaces. For oxidized polycrystalline Ru, only solution phase sulfates and bisulfates are observed in the IR spectra.     

无机离子交换剂Mg1.5Mn0.5Ti0.75O4对Li 的交换选择性实验

利用共沉淀,固相反应热结晶法,合成具有尖晶石型的复合金属氧化物Mg1.5Mn0.5Ti0.75O4。具有尖晶石型结构的物质,可以插入大量的替代离子并且改变自身锂和氧的化学计量数,与此同时,还保持了结构的稳定。这种特性能够使得它们被用于离子交换研究,用来满足提取锂的需求。通过检测该复合氧化物的饱和交换能力值,分配系数值等,从而确定出该物质具体特性。实验表明,经过酸化的Mg1.5Mn0.5Ti0.75O4,其Mg2 的抽出比率能够达到72%,Mn4 和Ti4 的溶解比率低于8.2%。实验分析得出,Li 能够从无机离子交换剂Mg1.5Mn0.5Ti0.75O4中抽出以及插入,主要是归因于离子交换机理。被酸化的样品对Li 有一个10.6mmol?g-1的离子交换能力,并且对Li 还具有记忆性的离子筛性能。     

嵌入电极反应循环伏安曲线的理论研究

嵌入电极反应的循环伏安图一般具有氧化峰和还原峰间距很大的特点,并且往往要求采用非常低的电位扫描速度。本研究基于嵌入电极反应的热力学方程和电荷传递动力学方程,对其循环伏安曲线进行了理论处理,讨论了嵌入电极反应热力学参数b,动力学参数D和k,电位扫描速度u,及电极和溶液电阻对循环伏安曲线的影响,解释了实验得到的嵌入电极反应循环伏安曲线的特殊性。