Starch-coated magnetic iron oxide nanoparticles have been synthesized by a simple, fast, and cost-effective co-precipitation method with cornstarch as a stabilizing agent. The structural and magnetic ...characteristics of the synthesized material have been studied by transmission electron microscopy, Mössbauer spectroscopy, and vibrating sample magnetometry. The nature of bonds between ferrihydrite nanoparticles and a starch shell has been examined by Fourier transform infrared spectroscopy. The data on the magnetic response of the prepared composite particles have been obtained by magnetic measurements. The determined magnetic characteristics make the synthesized material a good candidate for use in magnetic separation. Starch-coated magnetic iron oxide nanoparticles have been tested as an affinity sorbent for one-step purification of several recombinant proteins (cardiac troponin I, survivin, and melanoma inhibitory activity protein) bearing the maltose-binding protein as an auxiliary fragment. It has been shown that, due to the highly specific binding of this fragment to the starch shell, the target fusion protein is selectively immobilized on magnetic nanoparticles and eluted with the maltose solution. The excellent efficiency of column-free purification, high binding capacity of the sorbent (100-500 µg of a recombinant protein per milligram of starch-coated magnetic iron oxide nanoparticles), and reusability of the obtained material have been demonstrated.
We report here a simple hydrothermal synthesis of 100-200 nm flakes of tochilinite (Fe
1−
x
S)·
n
(Mg,Fe)(OH)
2
constructed by interchanging atomic sulfide and hydroxide sheets as a representative of ...a new platform of multifunctional two-dimensional materials. The reliable formation of tochilinites was ensured by an excess of sodium sulfide, with the assembly of the metal sulfide and hydroxide sheets driven by their opposite electric charges. X-ray photoelectron spectroscopy found that the hydroxide layers involved Fe
3+
cations from 10 to 40% of total iron tuned by addition of Al and Li entering the layers; the Fe
1−
x
S sheets comprised comparable amounts of high-spin Fe
3+
and Fe
2+
centers, and minor S-S bonding. The room-temperature Mössbauer spectra fitted with several doublets (chemical shift of 0.35-0.4 mm s
−1
and varying quadrupole splitting) transformed to three six-line patterns (hyperfine fields of ∼290, 350 and 480 kOe) due to magnetic ordering at 4.2 K, albeit the paramagnetic behavior observed in SQUID experiments. A series of UV-vis absorption maxima were explained in terms of both the high-index all-dielectric Mie resonance, in line with the permittivity measurement data, and the ligand-metal charge transfer resembling that in Fe-S clusters in proteins. Prospective properties and applications of the materials are discussed.
We report the reliable synthesis of 2D iron sulfide-magnesium hydroxide nanoflakes. The sulfide and hydroxide sheets assemble
via
opposite electric charges. Comparable amounts of high-spin Fe
3+
and Fe
2+
centers occur in the sulfide layers.
Electronic and magnetic states of Fe ions in Co2FeBO5 Knyazev, Yurii V; Kazak, Natalia V; Zhandun, Vyacheslav S ...
Dalton transactions : an international journal of inorganic chemistry,
07/2021, Letnik:
50, Številka:
28
Journal Article
Recenzirano
Odprti dostop
The ludwigite Co2FeBO5 has been studied experimentally using 57Fe Mössbauer spectroscopy and theoretically using DFT + GGA calculations. The room-temperature Mössbauer spectra are composed of four ...quadrupole doublets corresponding to the high-spin Fe3+ ions in octahedral oxygen coordination. All components undergo splitting below 117 K due to the magnetic hyperfine fields. The DFT + GGA calculations performed for three models of Fe ion distributions have revealed that the ground state corresponds to the “Fe4(HS)” model with the high-spin Fe3+ ions located at the M4 site and the high-spin Co2+ ions located at the M1, M2, and M3 sites. A ferrimagnetic ground state, with the Co and Fe magnetic moments being nearly parallel to the b-axis and a total magnetic moment of circa 1.1μB f.u.−1, was found. The other Fe distributions cause an increase in the local octahedral distortions and transformation of the spin state. The calculated quadrupole splitting values are in good agreement with the experimental values obtained by Mössbauer spectroscopy.
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•Oxidative coupling of methane was investigated over ferrospheres possessing more than 76wt% Fe2O3 isolated from fly ashes.•The quantity of Fe-containing phases, the state, and ...distribution of iron within the crystallographic sites were determined.•The catalytic active site of the OCM reaction was established.
Ferrospheres with the Fe2O3 content in the range from 76 to 97wt% were applied as catalysts for the oxidative coupling of methane (OCM). To identify their phase composition and distribution of iron sites, the ferrospheres were characterized by X-ray powder diffraction and Mössbauer spectroscopy before and after the OCM reaction. Magnetite-based ferrite spinel, hematite and aluminosilicate glasses were established to be the main phases. The ferrospinel of all ferrospheres partially oxidized to hematite after the OCM reaction. It was established that the yield of C2-hydrocarbons sharply increased at the ferrospheres with Fe2O3 content higher than 89wt% The spinel phase of these ferrospheres includes Fevv3+(B) sites with a Ca2+ tetrahedral cation and an octahedral cation vacancy among the nearest neighbors. A linear correlation between the yield of C2-hydrocarbons (ethane and ethylene) and the content of such sites was established, thus indicating that their electrophilic oxygen species participate in selective CH4 conversion to C2H6.
We introduce here a multifunctional material composed of alternating atomic sulfide sheets close to the composition of CuFeS
2
and Mg-based hydroxide ones (valleriite), which are assembled due to ...their electric charges of opposite sign. Valleriite particles 50-200 nm in lateral size and 10-20 nm in thickness were synthesized
via
a simple hydrothermal pathway using various concentrations of precursors and dopants, and examined with XRD, TEM, EDS, X-ray photoelectron spectroscopy, reflection electron energy loss spectroscopy (REELS), Mössbauer, Raman and UV-vis-NIR spectroscopies, and magnetization, dynamic light scattering, and zeta potential measurements. The electronic, magnetic and optical characteristics are found to be critically dependent on the charge (electron density) at the narrow-gap sulfide layers containing Cu
+
and Fe
3+
cations, and can be tuned
via
the composition of the hydroxide part. Particularly, substitution of Mg
2+
with Al
3+
increases the negative charge of the hydroxide layers and reduces the content of Fe
3+
-OH centers (10-45% of total iron); the effects of Cr and Co dopants entering both layers are more complicated. Mössbauer doublets of paramagnetic Fe
3+
detected at room temperature transform into several Zeeman sextets at 4.2 K; the hyperfine fields up to 500 kOe and complex magnetic behavior, but not pure paramagnetism or antiferromagnetism, were observed for valleriites with the higher positive charge of the sulfide sheets, probably due to the depopulation of the minority-spin 3d states of S-bonded Fe
3+
ions. Aqueous colloids of valleriite show optical absorption at 500-750 nm, which, along with the peaks at the same energies in REELS, may arise due to quasi-static dielectric resonance involving the vacant Fe 3d band and being dependent on the composition of both layers too. These and other findings call attention to valleriites as a new rich family of 2D materials for a variety of potential applications.
We propose a simple hydrothermal synthesis of nanoflakes composed of alternating sulfide and hydroxide quasi-monolayers and their aqueous colloids, as a prospective family of novel multifunctional 2D materials.
Characterization of magnetic particulate matter (PM) in coal fly ashes is critical to assessing the health risks associated with industrial coal combustion and for future applications of fine ...fractions that will minimize solid waste pollution. In this study, magnetic narrow fractions of fine ferrospheres related to environmentally hazardous PM2.5, PM2.5–10, and PM10 were for the first time separated from fly ash produced during combustion of Ekibastuz coal. It was determined that the average diameter of globules in narrow fractions is 1, 2, 3, and 7 μm. The major components of chemical composition are Fe2O3 (57–60) wt %, SiO2 (25–28 wt %), and Al2O3 (10–12 wt %). The phase composition is represented by crystalline phases, including ferrospinel, α-Fe2O3, ε-Fe2O3, mullite, and quartz, as well as the amorphous glass phase. Mössbauer spectroscopy and magnetic measurements confirmed the formation of nanoscale particles of ε-Fe2O3. Stabilization of the ε-Fe2O3 metastable phase, with quite ideal distribution of iron cations, occurs in the glass matrix due to the rapid cooling of fine globules during their formation from mineral components of coal.
Biogenic ferrihydrite nanoparticles were synthesized as a result of the cultivation of
microorganisms. The distribution of nanoparticles in the body of laboratory animals and the physical properties ...of the nanoparticles were studied. The synthesized ferrihydrite nanoparticles are superparamagnetic at room temperature, and the characteristic blocking temperature is 23-25 K. The uncompensated moment of ferrihydrite particles was determined to be approximately 200 Bohr magnetons. In vitro testing of different concentrations of ferrihydrite nanoparticles for the functional activity of neutrophilic granulocytes by the chemiluminescence method showed an increase in the release of primary oxygen radicals by blood phagocytes when exposed to a minimum concentration and a decrease in secondary radicals when exposed to a maximum concentration. In vivo testing of ferrihydrite nanoparticles on Wister rats showed that a suspension of ferrihydrite nanoparticles has chronic toxicity, since it causes morphological changes in organs, mainly in the spleen, which are characterized by the accumulation of hemosiderin nanoparticles (stained blue according to Perls). Ferrihydrite can also directly or indirectly stimulate the proliferation and intracellular regeneration of hepatocytes. The partial detection of Perls-positive cells in the liver and kidneys can be explained by the rapid elimination from organs and the high dispersion of the nanomaterial. Thus, it is necessary to carry out studies of these processes at the systemic level, since the introduction of nanoparticles into the body is characterized by adaptive-proliferative processes, accompanied by the development of cell dystrophy and tension of the phagocytic system.
Valleriite, (Cu,Fe)S2·n(Mg,Al,Fe)(OH)2, and related layered minerals are of interest due to their unusual two-dimensional structure, formation mechanisms, physical and chemical properties, and ...potential involvement into mineral processing and materials science applications. Here, we have studied Kingash Cu-Ni ore samples containing 10-25% of valleriite in association with serpentines (lizardite and chrysotile) and magnetite using scanning electron microscopy and electron microprobe analysis, Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal analysis and zeta potential measurement. The data are compared with those for Al-doped valleriite synthesized via a hydrothermal route. It was found that the Kingash valleriite contains excessive iron relative to CuFeS2 stoichiometry, which mainly occurs, leaving aside magnetite, as Fe3+-OH species in hydroxide layers of valleriite and minor Fe centers in serpentines. Thermal dehydroxylation of hydroxide layers of valleriites occurs near 500°C in inert atmosphere; in air, sulfide sheets oxidize with an exothermal peak at 447°C, and sulfur oxides don't volatilize but react with hydroxide groups of valleriite rather than serpentines. Zeta potential measurements of coarse ore particles using the flow potential technique suggested that the surface of valleriite is negatively charged in a wide pH range while the positive values at low pHs for fine particles are inflicted by serpentine. The findings demonstrate close resemblance of the natural and synthetic Al-doped valleriites, and the key role of valleriite, despite its moderate content, for the interfacial characteristics of the valleriite-bearing ores.
The Mössbauer spectroscopy method was used to study the ligand microstructure of natural arsenopyrite (31 specimens) from the ores of the major gold deposits of the Yenisei Ridge (Eastern Siberia, ...Russia). Arsenopyrite and native gold are paragenetic minerals in the ore; meanwhile, arsenopyrite is frequently a gold carrier. We detected iron positions with variable distribution of sulfur and arsenic anions at the vertexes of the coordination octahedron {6S}, {5S1As}, {4S2As}, {3S3As}, {2S4As}, {1S5As}, {6As} in the mineral structure. Iron atoms with reduced local symmetry in tetrahedral cavities, as well as iron in the high-spin condition with a high local symmetry of the first coordination sphere, were identified. The configuration {3S3As} typical for the stoichiometric arsenopyrite is the most occupied. The occupation degree of other configurations is not subordinated to the statistic distribution and varies within a wide range. The presence of configurations {6S}, {3S3As}, {6As} and their variable occupation degree indicate that natural arsenopyrites are solid pyrite {6S}, arsenopyrite {3S3As}, and loellingite {6As} solutions, with the thermodynamic preference to the formation of configurations in the arsenopyrite–pyrite–loellingite order. It is assumed that in the variations as part of the coordination octahedron, the iron output to the tetrahedral positions and the presence of high-spin Fe cations depend on the physical and chemical conditions of the mineral formation. It was identified that the increased gold concentrations are typical for arsenopyrites with an elevated content of sulfur or arsenic and correlate with the increase of the occupation degree of configurations {5S1As}, {4S2As}, {1S5As}, reduction of the share of {3S3As}, and the amount of iron in tetrahedral cavities.
Valleriite is of interest as a mineral source of basic and precious metals and as an unusual material composed of two-dimensional (2D) Fe-Cu sulfide and magnesium hydroxide layers, whose ...characteristics are still very poorly understood. Here, the mineral samples of two types with about 50% of valleriites from Noril'sk ore provenance, Russia, were examined using Cu K- and Fe K-edge X-ray absorption fine structure (XAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS),
Fe Mössbauer spectroscopy, and magnetic measurements. The Cu K X-ray absorption near-edge structures (XANES) spectra resemble those of chalcopyrite, however, with a higher electron density at Cu
centers and essentially differ from those of bornite Cu
FeS
; the Fe K-edge was less informative because of accompanying oxidized Fe-containing phases. The post-edge XANES and extended XAFS (EXAFS) analysis reveal differences in the bond lengths, e.g., additional metal-metal distances in valleriites as compared with chalcopyrite. The XPS spectra confirmed the Cu
and Fe
state in the sulfide sheets and suggest that they are in electron equilibrium with (Mg, Al) hydroxide layers. Mössbauer spectra measured at room temperature comprise central doublets of paramagnetic Fe
, which decreased at 78 K and almost disappeared at 4.2 K, producing a series of hyperfine Zeeman sextets due to internal magnetic fields arising in valleriites. Magnetic measurements do not reveal antiferromagnetic transitions known for bornite. The specific structure and properties of valleriite are discussed in particular as a platform for composites of the 2D transition metal sulfide and hydroxide (mono)layers stacked by the electrical charges, promising for a variety of applications.
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