The effect of intercalation by 3d elements on the structure and physical properties of titanium diselenide MxTiSe2 (M=Cr, Fe, Co)

The dependences of the structural parameters and the electrical and magnetic properties of titanium diselenide, intercalated by chromium, iron, and cobalt on the intercalant concentration and temperature were studied experimentally. The possibility of the involvement of d electrons in the formation of interlayer covalent bonds in relation to the 3d-shell filling of intercalated ion is discussed.     

Electrical and Magnetic Properties of Hafnium Disulfide Intercalated with Iron Atoms

Simultaneous study of the dependences of the structural parameters, electrical, and magnetic properties of hafnium disulfide intercalated iron atoms in the dependence on the intercalate concentration and temperature has been performed for the first time. The temperature dependences of the electrical resistance are shown to exhibit the activation character with the activation energies characteristic of impurity conduction. The effective magnetic moments of iron ions in Fe _x HfS₂ is found to be significantly lesser than the values of free iron ions and to decrease as the iron content increases. The character of the temperature dependences of the effective magnetic moments and negative values of the paramagnetic Curie temperatures indicate possible interactions of the antiferromagnetic type between intercalated atoms. However, the dependences of the magnetization on field for Fe_0.33HfS₂ and Fe_0.5HfS₂ obtained at T = 2 K demonstrate the hysteresis phenomenon characteristic of the ferromagnetic state. The results are discussed assuming the existence of hybridization 3d electron states of intercalated iron atoms with the electronic states of HfS₂ matrices and the competition of various exchange interaction.     

Mössbauer study of the kinetics of simulated corrosion process of iron in chlorinated aqueous solution around room temperature: The hyperfine structure of ferrous hydroxides and Green Rust I

The hyperfine structure of the two ferrous hydroxides, Fe(OH)₂, [2Fe(OH)₂, FeOCl] and Green Rust I obtained during the oxidation of iron in chlorinated aqueous medium is determined. The structure of GRI is proposed. The kinetics of oxidation and the role of the chlorine concentration is thoroughly discussed.     

Spin excitations in a K0.84Fe1.99Se2 superconductor as studied by Mssbauer spectroscopy

Mssbauer spectroscopy was used to probe the site-specific information of a K 0.84 Fe 1.99 Se 2 superconductor. A spin excitation gap,△ E ≈ 5.5 meV, is observed by analyzing the temperature dependence of the hyperfine magnetic field (HMF) at the iron site within the spin wave theory. Using the simple model suggested in the literature, the temperature dependence of the HMF is well reproduced, suggesting that, below room temperature, the alkali metal intercalated iron–selenide superconductors can be regarded as ferromagnetically coupled spin blocks that interact with each other antiferromagnetically to form the observed checkerboard-like magnetic structure.     

Iron Oxychloride/Bovine Serum Albumin Nanosheets as Chemodynamic Therapy Agents

Iron oxychloride (FeOCl) is known for reactive oxygen species (ROS) generation through Fenton chemistry. The activity of FeOCl is preserved in the slightly acidic pH value of the tumor microenvironment (pH 6.5−6.9). Such property can be advantageous in biobased systems, where ROS generation can be modulated in slightly acidic conditions, which is characteristic of the solid tumor microenvironment. In the present study, BSA-stabilized FeOCl nanosheets (NSs) are synthesized and characterized by transmission electron microscope, Fourier transform infrared spectroscopy, zeta potential analysis, dynamic light scattering, and UV–vis spectroscopy. The morphology of the nanoparticles is flake-like, and their hydrodynamic diameter is around 200 nm. MTT, apoptosis assay, and trypan blue staining evaluate the toxicity of FeOCl NSs toward the 4T1 cell line. It is found that the toxicity of the NSs is higher in physiological conditions of solid tumors (pH 6.5, H₂O₂ 100 × 10⁻⁶ m ) than in the conditions of healthy organs (pH 7.4). Specifically, cancer cells are in their late apoptotic stage by more than eight times higher at pH 6.5 than pH 7.4. The toxicity results are in agreement with the in vitro catalytic assay of the NSs. Therefore, the FeOCl NSs can be the building blocks for constructing chemodynamic therapy agents.     

In situ Mössbauer spectroscopic study of iron III chloride intercalated in graphite under reaction conditions

In situ⁵⁷Mössbauer spectroscopy has been used to study the process of reduction and Fischer-Tropsch reactions on FeCl₃ intercalated in graphite layers. It is found that on flowing H₂ on graphite intercalated by FeCl₃ at 400° C, FeCl₃ converts to FeCl₂ and partly to small particles of α-Fe. The Mössbauer spectra of the reduced sample are superposition of a sextuplet and two quadrupole doublets indicative of metallic iron and two species of FeCl₂. However, at room temperature and at 400° C for a short period of reduction the magnetic hyperfine splittings (ca. 295 kOe and 262 kOe respectively) are smaller than the corresponding parameters for bulk metallic iron. The differences have been attributed to the interaction between the monolayers of iron atoms and the carbon nets of the graphite support. When the reduction was carried out for a longer period, α-Fe was formed. When a sample reduced for a short period of time is heated at 400°C in the presence of the synthesis gas, part of the iron particles sinter, and α-iron is observed. On heating the above sample once again at 400°C in the presence of the synthesis gas, the remaining small particles of iron are totally converted to the bulk phase (α-Fe). Experimental observations indicate that α-Fe and FeCl₂ are present on the surface as well as inbetween the intercalated graphite layers.     

Intercalation of Iron Atoms under Graphene Formed on Silicon Carbide

The intercalation of iron under a graphene monolayer grown on 4H-SiC(0001) is studied. The experiments have been carried out in situ under conditions of ultrahigh vacuum by low-energy electron diffraction, high-energy-resolution photoelectron spectroscopy using synchrotron radiation, and near carbon K-edge X-ray absorption spectroscopy. The deposited iron film thicknesses have been varied within 0.1–2 nm and the sample temperatures from room temperature to 700°C. It is shown that the intercalation process begins at temperatures higher than ~350°C. In this case, it is found that intercalated iron atoms are localized not only between graphene and a buffer layer coating SiC, but also under the buffer layer itself. The optimal conditions of the intercalation are realized in the range 400–500°C, because, at higher temperatures, the system becomes unstable due to the chemical interaction of the intercalated iron with silicon carbide. The inertness of the intercalated films to action of oxygen is demonstrated.

     

Influence of the chalcogen substitution on the character of magnetic ordering in Fe<Subscript>0.5</Subscript>TiS<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> intercalated compounds

The crystal structure and magnetic properties of layered Fe_0.5TiS_{2 − x} Se _x (0 ≤ x ≤ 2) compounds intercalated by iron atoms have been investigated. It has been shown that the substitution of selenium for sulfur is accompanied by an increase in the unit cell volume, a transition from the ferromagnetic to antiferromagnetic behavior, and a nonmonotonic variation in the paramagnetic Curie temperature. The intercalated iron atoms are characterized by lower values of the effective moment (3.4–4.0μ_B) as compared to the predicted value (4.89μB) for the Fe²⁺ ion at g = 2. The results obtained have been discussed under the assumption that there are the hybridization of 3d electronic states of intercalated Fe atoms with the electronic states of the TiS_{2 − x} Se _x host compounds and the competition of exchange interactions of different types.     

Spin excitations in a K0.84Fe1.99Se2 superconductor as studied by Mössbauer spectroscopy

Mössbauer spectroscopy was used to probe the site-specific information of a K_0.84Fe_1.99Se₂ superconductor. A spin excitation gap, ΔE ≈5.5 meV, is observed by analyzing the temperature dependence of the hyperfine magnetic field (HMF) at the iron site within the spin wave theory. Using the simple model suggested in the literature, the temperature dependence of the HMF is well reproduced, suggesting that, below room temperature, the alkali metal intercalated iron-selenide superconductors can be regarded as ferromagnetically coupled spin blocks that interact with each other antiferromagnetically to form the observed checkerboard-like magnetic structure.     

Hyperfine interactions in the anisotropic layer compound FeOCl from57Fe Mössbauer studies

The anisotropic layer compound FeOCl has been synthesized by two different techniques to give, respectively, a large single crystal blade-like product (SC) and a polycrystalline powder product (PC), each of which was examined by temperature dependent⁵⁷Fe Mössbauer spectroscopy over the range 4.2≤T≤300 K. In particular, the onset of magnetic ordering on sample cooling (near 90 K) has been studied in detail, in the light of the 2-dimensional ordering of the paramagnetic ion spins in the crystallographica, c plane. The high temperature (～300 K) and low temperature (～4.2 K) Mössbauer parameters for the SC and PC material are identical within experimental error. The persistence in the spectra of the paramagnetic doublet due to h.s. Fe(III) below the magnetic ordering temperature in the PC material is shown to be consistent with the superparamagnetism of small particles in those samples.     

“111”型铁基超导材料研究进展

“111”型铁基超导体系包含LiFeAs,NaFeAs和LiFeP三个组员.这三个组员的晶体结构简单,具有非极性解离面等特点,在铁基超导物理机理研究中发挥着独特的作用.本文简要介绍“111”型铁基超导体的研究进展.     

Mössbauer study of iron oxide modified montmorillonite

Montmorillonite particles were modified by iron oxides using the precipitation process with the aim to monitor the differences in the structural and magnetic properties of intercalated and adsorbed Fe³⁺. The Mössbauer spectra recorded at 5 K in zero and 6 T external fields, IR spectra and TG curves measured in zero and 32 mT fields identified the ferrihydrite pillars in an interlayer space of the montmorillonite structure and γ-Fe₂O₃ nanoparticles adsorbed on the mineral surface. The temperature dependent Mössbauer spectra (25–300 K) reflect the superparamagnetic behaviour of maghemite nanoparticles and ferrihydrite pillars with the blocking temperatures of about 80 and 25 K, respectively.     

Highly hydrated poly(allylamine)/silica magnetic resin

The creation of multifunctional nanomaterials by combining organic and inorganic components is a growing trend in nanoscience. The unique size-dependent properties of magnetic nanoparticles (MNPs) make them amenable to numerous applications such as carriers of expensive biological catalysts, in magnetically assisted chemical separation of heavy metals and radionuclides from contaminated water sources. The separation of minor actinides from high-level radionuclide waste requires a sorbent stable in acidic pH, with ease of surface functionalization, and a high capacity for binding the molecules of interest. For the described experiments, the MNPs with 50 nm average size were used (size distribution from 20 to 100 nm and an iron content of 80–90 w/w%). The MNPs that have been double coated with an initial silica coating for protection against iron solubilization and oxidation in nitric acid solution (pH 1) and a second silica/polymer composite coating incorporating partially imbedded poly(allylamine) (PA). The final product is magnetic, highly swelling, containing >95% water, with >0.5 mmol amines g^?1 available for functionalization. The amine groups of the magnetic resin were functionalized with the chelating molecules diethylenetriaminepentaacetic acid (DTPA) and N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) for separation of minor actinides from used nuclear fuel.     

Strain induced changes in the magnetic phase diagram of metamagnetic heteroepitaxial EuSe/PbSe(1-x)Tex multilayers

Multilayers of strained metamagnetic EuSe intercalated with nonmagnetic PbSe1-xTex were grown by molecular beam epitaxy under conditions optimized by electron diffraction. From detailed structural and magnetic characterization using anomalous synchrotron x-ray diffraction and magnetization measurements, the phase transition temperatures and the magnetic phase diagrams of strained EuSe as a function of the in-plane lattice constant are determined. In this way, it is demonstrated that the magnetic properties of the samples can be significantly changed by applying biaxial strain on EuSe in superlattice structures.     

Common crystalline and magnetic structure of superconducting A2Fe4Se5 (A=K,Rb,Cs,Tl) single crystals measured using neutron diffraction

Single-crystal neutron diffraction studies on superconductors A(2)Fe(4)Se(5), where A=Rb, Cs, (Tl, Rb), and (Tl, K) (T(c) ～ 30 K), uncover the same Fe vacancy ordered crystal structure and the same block antiferromagnetic order as in K(2)Fe(4)Se(5). The Fe order-disorder transition occurs at T(S)=500-578 K, and the antiferromagnetic transition at T(N) = 471-559 K with an ordered magnetic moment ～3.3μ(B)/Fe at 10 K. Thus, all recently discovered A intercalated iron selenide superconductors share the common crystalline and magnetic structure, which are very different from previous families of Fe-based superconductors, and constitute a distinct new 245 family.     

Synthesis,characterization, and in vitro biological evaluation of highly stable diversely functionalized superparamagnetic iron oxide nanoparticles

In this article, we report the design and synthesis of a series of well-dispersed superparamagnetic iron oxide nanoparticles (SPIONs) using chitosan as a surface modifying agent to develop a potential T ₂ contrast probe for magnetic resonance imaging (MRI). The amine, carboxyl, hydroxyl, and thiol functionalities were introduced on chitosan-coated magnetic probe via simple reactions with small reactive organic molecules to afford a series of biofunctionalized nanoparticles. Physico-chemical characterizations of these functionalized nanoparticles were performed by TEM, XRD, DLS, FTIR, and VSM. The colloidal stability of these functionalized iron oxide nanoparticles was investigated in presence of phosphate buffer saline, high salt concentrations and different cell media for 1 week. MRI analysis of human cervical carcinoma (HeLa) cell lines treated with nanoparticles elucidated that the amine-functionalized nanoparticles exhibited higher amount of signal darkening and lower T ₂ relaxation in comparison to the others. The cellular internalization efficacy of these functionalized SPIONs was also investigated with HeLa cancer cell line by magnetically activated cell sorting (MACS) and fluorescence microscopy and results established selectively higher internalization efficacy of amine-functionalized nanoparticles to cancer cells. These positive attributes demonstrated that these nanoconjugates can be used as a promising platform for further in vitro and in vivo biological evaluations.     

Magnetic Properties and Nature of Magnetic State of Intercalated CrxMoSe2 Compounds

Physics of the Solid State - This is a pioneering work on the synthesis of molybdenum diselenides intercalated by chromium atoms. Their magnetic properties are studied at various intercalant...     

Transformation of the magnetic structure of FeBO<Subscript>3</Subscript> under high pressures

The transformation of magnetic structure under hydrostatic and quasi-hydrostatic pressures up to 4 GPa was studied for iron borate FeBO₃ by the neutron diffraction method. Under quasi-hydrostatic conditions, the orientation of iron magnetic moments changes at pressures P≥1.4 GPa. Under hydrostatic conditions, no changes in the magnetic structure of iron borate were observed up to 2.1 GPa. This behavior is caused by the influence of the inhomogeneity (in magnitude and direction) of elastic stresses on the configuration of magnetic sublattices.     

Modification of the electronic structure of graphene by intercalation of iron and silicon atoms

The ab initio calculations of the electronic structure of low-dimensional graphene–iron–nickel and graphene–silicon–iron systems were carried out using the density functional theory. For the graphene–Fe–Ni(111) system, band structures for different spin projections and total densities of valence electrons are determined. The energy position of the Dirac cone caused by the p _z states of graphene depends weakly on the number of iron layers intercalated into the interlayer gap between nickel and graphene. For the graphene–Si–Fe(111) system, the most advantageous positions of silicon atoms on iron are determined. The intercalation of silicon under graphene leads to a sharp decrease in the interaction of carbon atoms with the substrate and largely restores the electronic properties of free graphene.

     

Specific features of the structure,magnetic properties,and heat capacity of intercalated compounds Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiSe<Subscript>2</Subscript>

Structural features, magnetic properties, and heat capacity of Cr _x TiSe₂ intercalated compounds with a layered structure have been studied experimentally for 0 ≤ x ≤ 0.5. It is shown that, at high chromium concentrations (x > 0.25), the magnetic properties of the compounds are strongly affected by the degree of ordering and distribution pattern of the intercalated atoms. Depending on the cooling rate of samples of the same composition (x = 0.5), an antiferromagnetic or a cluster-glass-type state can be obtained. Heat capacity measurements have revealed a nonmonotonic variation in the lattice rigidity with increasing concentration of intercalated atoms.