Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Effect of precursors on the growth of carbon filaments onto clay surface

The successful growth of carbon filaments on two different precursors, i.e., the pristine sodium-montmorillonite (Na⁺MMT), which undergoes reflux at 100 °C (r-MMT), and the Na⁺MMT exchanged with Fe³⁺ ions (MMT(Fe)), was attained through chemical vapor deposition (CVD). The products obtained were characterized by X-ray diffraction, thermogravimetry, scanning electron microscopy, and transmission electron microscopy. Refluxing can make the Fe³⁺ ions in the octahedral layer of Na⁺MMT migrate to the interlayer and exchange with Na⁺ ions. Furthermore, through calcination at 500 °C, the Fe³⁺ ions migrate again to the surface of the clay layer and form iron oxides, which can serve as precursors for the deposition of carbon. Although r-MMT contained less iron than the MMT(Fe), the ultimate yield of carbon components grown was almost the same, indicating that the iron species in r-MMT possess higher catalytic activity. However, on the surface of r-MMT, CVD hardly generated carbon nanotubes with a clear hollow structure but that those with a carbon fiber structure instead.     

Mössbauer studies of mixed-valence spin-crossover iron complexes with a hexadentate tripod ligand

The spin-crossover behaviors of mixed-valence iron compounds [Fe^IIH₃L][Fe^IIIL](NO₃)₂ (1) and [Fe^IIH₃L^Me][Fe^IIIL^Me](NO₃)₂ (2) have been investigated by ⁵⁷Fe Mössbauer spectroscopy, where H₃L is a hexadentate N₆ tripod ligand containing three imidazole groups and H₃L^Me is its 2-methylimidazole derivative. Deconvolution analyses of the Mössbauer spectra revealed that a two-step SCO (LS Fe^II–LS Fe^III→HS Fe^II–LS Fe^III→HS Fe^II–HS Fe^III) proceeds in each compound on elevating the temperature. Compound 2 exhibited lower spin-transition temperatures than 1. “Frozen-in effect” was observed below 120 and 50 K for 1 and 2, respectively.     

Theoretical studies of the g factors and local structure for the rhombic Fe center in NaF

The anisotropic g factors and local structure for the rhombic Fe⁺ center in NaF are theoretically studied using the perturbation formulas of the g factors for a rhombically distorted octahedral 3d⁷ cluster. The impurity Fe⁺ is found not to occupy exactly the host Na⁺ site in NaF but to experience the off-center displacement of about 0.28 Å along [1 1 0] axis due to size mismatch substitution. The calculated g factors based on the above impurity displacement show reasonable agreement with the experimental data. The local structure of the Fe⁺ center is discussed.     

Low-temperature magnetic properties of the 2D molecular ferrimagnet N(n-C5H11)4 [FeIIFeIII(C2O4)3]

⁵⁷Fe Mössbauer and magnetometric studies of the molecular ferrimagnet N(n-C₅H₁₁)₄ [ Fe^IIFe^III(C₂O₄)₃] are indicative of a 2D magnetic character with strong uniaxial anisotropy in the basal plane of the crystal. It is established that the change in the sign of the net magnetization of this compound is related to a compensation between Fe^III and Fe^II sublattice magnetizations at T _comp=31.2 K. The form and parameters of the magnetic Hamiltonian describing the temperature dependence of the Fe^III sublattice and the net magnetizations are determined.     

Mössbauer study of fluorides: Ba2MFeF9 and NaBaFe2F9

The Mössbauer spectra of the compounds Ba₂NiFeF₉, Ba₂FeCrF₉ and NaBaFe₂F₉ have been studied as a function of temperature. Values of the Néel temperature are obtained and the effects of cationic inversion between the two sites of M^II and M^III in compounds Ni^IIFe^III and Fe^IICr^III are observed. In the latter compound, we observe broad lines at all temperatures and a smearing of the magnetic ordering temperature. However, the Fe^IIFe^III compound shows strict structural order. The two sites of Fe^III in NaBaFe₂F₉ have not been resolved.     

Core and valence level photoemission studies of iron oxide surfaces and the oxidation of iron

The core and valence level XPS spectra of Fe_xO (x ~ 0.90–0.95); Fe₂O₃ (α and γ); Fe₃O₄; and FeOOH have been studied under a variety of sample surface conditions. The oxides may be characterized by a combination of valence level differences and core-level effects (chemical shifts, multiplet splittings, and shake-up structure). Fe^II and Fe^III states are distinguishable, but octahedral and tetrahedral sites are not. The O 1 s BE cannot be used to distinghuish between the oxides since it has a nearly constant value. Fe 3d valence level structure spreads some 10 eV below E_F, much broader than suggested by previous UPS and photoelectron-spin-polarization (ESP) measurements for Fe_xO and Fe₃O₄. Fe surfaces (films, foils, (100) face) yield predominantly Fe^III species when exposed to high exposures of oxygen or air, though there is evidence for some Fe^II also. At low exposures the Fe^II/Fe^III ratio increases.     

Magnetism in some layer molecular magnets as revealed by Mössbauer spectroscopy

⁵⁷Fe Mössbauer spectroscopy was used to explore magnetic properties of two 2D molecular ferrimagnets. In NPn₄[Fe^IIFe^III(ox)₃] (Pn = n-C₅H₁₁, (ox) =(C₂O₄)^2?), the previously reported negative magnetization is shown here by external field studies to be due to a cross-over between Fe^III and Fe^II- magnetizations. The form and parameters of the magnetic Hamiltonian describing the temperature dependence of both the Fe^III hf-field and net magnetizations has been determined. In NBu₄[Mn^IIFe^III(ox)₃] (Bu = n-C₄H₉) soft XY-magnet the low temperature relaxation spectra are interpreted in terms of slowly varying classical magnetization-evolution at low temperature.     

Study on the ferromagnetic state in iron mixed-valence complexes, A[FeIIFeIII(dto)3] (A = (n-CnH2n + 1)4N; dto = C2S2O2) by means of Mössbauer spectroscopy

We have investigated the ferromagnetic states for (n-C_nH_2n?+?1)₄N[Fe^IIFe^III(dto)₃] (n = 3–6; dto = C₂O₂S₂) by means of ⁵⁷Fe Mössbauer spectroscopy. The major component of the spin configuration in the ferromagnetic states for n = 3 and 4 is the low-temperature phase (LTP) with the Fe^III (S = 5/2) and Fe^II (S = 0) states. The high-temperature phase (HTP) of n = 4 remains by more than 20%, which is consistent with two ferromagnetic transitions (T_C = 7 & 13 K). Moreover, it was revealed that the Mössbauer spectra in the ferromagnetic states for n = 5 and 6 correspond to the HTP consisting of the Fe^II (S = 2) and Fe^III (S = 1/2) states.     

Mössbauer study of Na0.82Co0.99Fe0.01O2

We studied by Mössbauer spectroscopy the Na_0.82CoO₂ compound using 1% ⁵⁷Fe as a local probe which substitutes for the Co ions. Mössbauer spectra at T=300 K revealed two sites which correspond to Fe³⁺ and Fe⁴⁺. The existence of two distinct values of the quadrupole splitting instead of a continuous distribution should be related with the charge ordering of Co⁺³, Co⁺⁴ ions and ion ordering of Na(1) and Na(2). Below T=10 K part of the spectrum area, corresponding to Fe⁴⁺ and all of Fe³⁺, displays broad magnetically split spectra arising either from short-range magnetic correlations or from slow electronic spin relaxation.     

Synthesis by Coprecipitation of Al-Substituted Hydroxysulphate Green Rust FeII 4FeIII (2−y)AlIII y (OH)12SO4,nH2O

Al-substituted hydroxysulphate green rust (Al-GR{SO₄}) were synthesised by the coprecipitation of Fe^II, Fe^III and Al^III cations. The Al-GR{SO₄} crystals (～50 nm) are significantly smaller than the hydroxysulphate green rust GR{SO₄} crystals (～500 nm). The Mössbauer spectrum of Al-GR{SO₄} was adjusted with two ferrous doublets D₁ and D₃ and one ferric doublet D₂. Doublet D₃ is attributed to Fe^II ions that have Al^III ions as a first neighbour.

     

Effects of impurity Na ions on the structural and magnetic properties of Ni-Zn-Cu ferrite powders: An improvement for chemical coprecipitation method

Ni-Zn-Cu ferrite powders with nominal composition Ni_0.4−xZn_0.6Cu_xFe₂O₄ (x=0.00-0.20) were prepared via chemical coprecipitation method. X-ray diffractometer, vibrating sample magnetometer, scanning electron microscopy, inductively coupled plasma-atomic emission spectrometry and energy dispersive spectrum were used to study the effects of impurity Na⁺ ions on the structural and magnetic properties. As a result, it was found that the impurity Na⁺ ions affect the crystalline structures and magnetic properties greatly. Moreover, the heterogeneous distribution of impurity Na⁺ ions and the formation of Na compounds retard the phase formation and the grain growth of specimens. Our study also reveals that for the chemical coprecipitation method, a second washing process introduced after drying can eliminate the impurity Na⁺ ions effectually and thus helps in the formation of single-phase structure and the growth of grains, which is very important for the improvement of magnetic properties and the preparation of ferrites via chemical coprecipitation method.     

Hybrid system of iron porphyrin on aminosilanized c-Si

Adsorption of iron porphyrin (Fe^IIITPPS₄) Fe(III)meso-tetra(4-sulfonatophenyl) porphine on aminosilanized surface of crystalline Si (c-Si) was investigated. Formation of nanometric structures of Fe^IIITPPS₄ on c-Si, the surface of which has been modified by various silanization procedures, was studied. Aqueous, ethanol and acetone solutions of 3-aminopropyltrietoxysilane (APTES) were prepared for deposition on c-Si by spinning or immersion techniques. Smooth homogeneous APTES films of thickness 100–500 nm were produced by multiple spin coating procedure. Thin APTES films of thickness 2.5 nm were fabricated by dipping technique followed by washing procedure. Hybrid system of Fe^IIITPPS₄/APTES/Si was prepared from a drop of Fe^IIITPPS₄ aqueous solution put on aminosilanized Si surface or by dipping the Si wafer in Fe^IIITPPS₄ aqueous solution. Nanostructures of size 50–250 nm were formed along with large rings of Ø50–100 μm which have been observed at chemisorption of highly concentrated (1 mM) Fe^IIITPPS₄ aqueous solution. Spectroscopic ellipsometry was used to characterize the APTES layer and to investigate the aggregation state of Fe^IIITPPS₄. The studies provided allowed one to presume that covalent bonds were formed between amino-groups of APTES and functional groups of sulfonic acid in porphyrin leading to immobilization of Fe^IIITPPS₄ on Si substrate.     

Anisotropic giant magnetoresistance originating from the π-d interaction in a molecule

We synthesized TPP[Fe^III(Pc)(CN)₂]₂, PTMA_x[Fe^III(Pc)(CN)₂]·y(MeCN), and PXX [Fe^III(Pc)(CN)₂], a new series of charge-transfer salts containing the axially-substituted phthalocyanine (Pc), [Fe^III(Pc)(CN)₂]⁻. In this molecular unit, the π conduction electron derived from the Pc-ring coexists with the d electron which is a potential source of a local magnetic moment. Therefore various phenomena associated with the interplay between local magnetic moments and conduction electrons are expected. We observed the giant negative magnetoresistance (GNMR) in all the three salts. The GNMR is highly anisotropic for the magnetic-field direction, and reflects the g-tensor anisotropy of the local magnetic moment in the [Fe^III(Pc)(CN)₂]⁻ unit. This indicates that the GNMR in these salts originates from the strong π-d interaction in the [Fe^III(Pc)(CN)₂]⁻ unit.     

Magnetic and Mössbauer spectra observed for mixed-metal magnets NBu4 {\bf Fe}^{\bf II}_{\bf n}MA II 1 − n [FeIII(OX)3] (MA=Mn, Fe)

Mixed-metal molecular-based magnets NBu₄ ${\rm Fe}^{\rm II}_{\rm n}$ M_A ^II _1???n[Fe^III(OX)₃] (M_A=Mn, Fe) were investigated by magnetic and Mössbauer measurements. The magnetic susceptibility of NBu₄ ${\rm Fe}^{\rm II}_{0.07}{\rm Mn}^{\rm II}_{0.93}$ [Fe^III(OX)₃] can be fitted to a Curie-Weiss law with a Weiss paramagnetic Curie temperature of θ?=??114.76 K. The negative Weiss constant indicates an intramolecular antiferromagnetic coupling interaction between the adjacent Fe(II) and Fe(III) ions through the oxalate bridge. In the complex NBu₄Fe^II[Fe^III(OX)₃], the Mössbauer results indicate that the Fe^II and Fe^III sublattices experience spontaneous magnetizations. The compound contains two different spin carriers; i.e. Fe^II(S = 2), Fe^III(S = 5/2). Two magnetic sublattices are defined. The appearance of nuclear Zeeman splittings suggests that long range magnetic ordering takes place below 50 K.     

Structural phase transitions evidenced by Mössbauer spectrometry in a ferric fluorophosphate: Na3Fe2(PO4)2F3

⁵⁷Fe Mössbauer spectrometry was carefully applied to Na₃Fe₂(PO₄)₂F₃, a fluorophosphate crystalline ferric compound. Two structural phase transitions involving very slight motions of Na⁺ cations were evidenced from the temperature dependence of the quadrupolar splitting, in agreement with those observed in isotypic compounds, either by diffraction technique or by calorimetric measurement. Consequently, it is important to emphasise the extremely high neighbouring sensitivity of ⁵⁷Fe Mössbauer spectrometry.     

Effect of FeCl3 and acetone on the structure of Na–montmorillonite studied by Mössbauer and XRD measurements

⁵⁷Fe Mössbauer spectroscopy, X-ray diffraction, X-ray fluorescence spectroscopy and infrared spectroscopy were used to study the effect of FeCl₃ and acetone on the structure of a Na–bentonite. XRD indicated the incorporation of Fe³⁺ ions into the interlayer space since the basal lattice spacing of montmorillonite increased to 1.6 from 1.24 nm after treatment with FeCl₃ dissolved in acetone. Interlayer Na⁺ ions could be exchanged to Fe³⁺. Magnetically split Mössbauer subspectra with internal magnetic fields 41 and 46 T at 74 K, were associated with two main Fe³⁺ microenvironments within the interlayer regions. The resultant Fe–montmorillonite was successfully applied as a catalyst in the preparation of 1,1-diacetates from aromatic aldehydes and acetic acid anhydride.     

Corelationship between local structure and water purifying ability of iron-containing waste glasses

A relationship between the structure and water purifying ability of waste glass prepared from household garbage and Fe₂O₃ was examined by ⁵⁷Fe-Mössbauer and induced coupled plasma (ICP) measurements. From the Debye temperature of waste glass, Fe^II proved to be loosely bound in the glass network as a network modifier. Dissolution amount of Fe^III into artificial drain can be controlled from 0.14 to 0.35 mg/l by changing the Fe₂O₃ content. It proved that chemical oxygen demand (COD) decreases in proportion to the content of Fe^III, indicating that iron causes decomposition of organic and phosphorus compounds.     

First-principles electronic-structure calculation on the spin distribution and the half-metallic properties of the mixed valence iron compound Ba2F2Fe1.5S3

The first principles within the full potential linearized augmented plane wave (FP-LAPW) method with the generalized gradient approximation (GGA) approach were applied to study the new mixed valence compound Ba₂F₂Fe_1.5S₃. The density of states, the electronic band structure and the spin magnetic moment are calculated. The calculations reveal that the compound has an antiferromagnetic interaction between the Fe^III and Fe^II ions arising from the bridging S atoms, which validate the experimental assumptions that there is a low-dimensional antiferromagnetic interaction in Ba₂F₂Fe_1.5S₃. The spin magnetic moment mainly comes from the Fe^III and Fe^II ions with smaller contribution from S anion. By analysis of the band structure, we find that the compound has half-metallic property.     

8-Hydroxyquinoline Functionalized Graphene Oxide: an Efficient Fluorescent Nanosensor for Zn<Superscript>2+</Superscript> in Aqueous Media

A nanosensor, based on 8-hydroxyquinoline functionalized graphene oxide, was developed for the fluorescence detection of Zn²⁺. It showed high selectivity and sensitivity for Zn²⁺ion in aqueous solution over other metal ions such as Li⁺, Na⁺, Ca²⁺, Mg²⁺, Al³⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Fe²⁺, Fe³⁺and Cr³⁺. Due to the linearity of the emission intensity toward Zn²⁺ concentration, fluorescent technique could be used for the detection of Zn²⁺ ion even at very low concentrations.