The syntheses of amorphous Fe(2)O(3) nanoparticles of varying size and morphology, their magnetic properties, crystallization mechanism, and applications are reviewed herein. The synthetic routes are classified according to the nature of the sample (powders, nanocomposites, films, coated particles). The contributions of various experimental techniques to the characterization of an amorphous Fe(2)O(3) phase are considered in this review, including some key experimental markers, allowing its distinction from nanocrystalline "X-ray amorphous" polymorphs (maghemite, hematite). We discuss the thermally induced crystallization mechanisms depending on transformation temperature, atmosphere, and the size of the amorphous particles that predetermine the structure of the primarily formed crystalline polymorph. The controversial description of the magnetic behavior, including an interpretation of the low-temperature and in-field Mössbauer spectra, is analyzed.
Hematite, α-Fe2O3, is considered as one of the most promising materials for sustainable hydrogen production via photoelectrochemical water splitting with a theoretical solar-to-hydrogen efficiency of 17%. However, the poor electrical conductivity of hematite is a substantial limitation reducing its efficiency in real experimental conditions. Despite of computing models suggesting that the electrical conductivity is extremely anisotropic, revealing up to 4 orders of magnitude higher electron transport with conduction along the (110) hematite crystal plane, synthetic approaches allowing the sole growth in that direction have not been reported yet. Here, we present a strategy for controlling the crystal orientation of very thin hematite films by adjusting energy of ion flux during advanced pulsed reactive magnetron sputtering technique. The texture and effect of the deposition mode on the film properties were monitored by XRD, conversion electron Mössbauer spectroscopy, XPS, SEM, AFM, PEC water splitting, IPCE, transient photocurrent measurements, and Mott-Schottky analysis. The precise control of the synthetic conditions allowed to fabricate hematite photoanodes exhibiting fully textured structures along (110) and (104) crystal planes with huge differences in photocurrents of 0.65 and 0.02 mA cm(-2) (both at 1.55 V versus RHE), respectively. The photocurrent registered for fully textured (110) film is among record values reported for thin planar films. Moreover, the developed fine-tuning of crystal orientation having a huge impact on the photoefficiency would induce further improvement of thin hematite films mainly if cation doping will be combined with the controllable texture.
The thermally induced decomposition of Prussian Blue, Fe 4 [Fe(CN) 6 ] 3 (PB), was studied in air at 250 and 350 °C. Amorphous Fe 2 O 3 nanoparticles, cubic bixbyite β-and cubic spinel γ-Fe 2 O 3 (maghemite) polymorphs, have been identified as the products of the decomposition under different reaction conditions. 57 Fe Mo ¨ssbauer spectroscopy, XRD, AFM, TEM, quasielastic light scattering method (QELS) of particle size analysis, BET surface area, and magnetization measurements were used to understand the influence of the PB particle size and oxidation conditions on the decomposition mechanism at 250 and 350 °C. At a minimum decomposition temperature of 250 °C, amorphous Fe 2 O 3 nanoparticles were formed with the size ranging from 1 to 4 nm and large surface area of 400-200 m 2 /g in dependence on the PB particle size. Such small amorphous Fe 2 O 3 nanoparticles were obtained by the solid-state route for the first time. At 350 °C, cubic β-Fe 2 O 3 and γ-Fe 2 O 3 polymorphs were identified and their contents were found to be strongly dependent on the initial PB particle size and oxidation-diffusion conditions. Generally, the higher relative content of γ-Fe 2 O 3 was obtained for larger PB particles and in air-limited conditions.
There are several green methods available to synthesize iron-based nanoparticles using different bio-based reducing agents. Although their useful properties in degradation of organic dyes, chlorinated organics, or arsenic have been described earlier, their characterization has been ambiguous, and further research is needed in this area. Synthesis and characterization details on iron-based nanoparticles produced by green tea extract are described in detail; characterization was carried out by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and UV−vis spectrometry followed by ecotoxicological assay. XRD and TEM analyses revealed that iron forms amorphous nanosized particles with size depending on reaction time. Moreover, low-temperature Mossbauer spectroscopy confirmed progressive reduction of Fe 3+ to Fe 2+ during the reaction. Finally, the iron(II,III) nanoparticles prepared by green tea extract (GT−Fe nanoparticles) were found to have negative ecotoxicological impacts on important aquatic organisms such as cyanobacterium (Synechococcus nidulans), alga (Pseudokirchneriella subcapitata), and even invertebrate organisms (Daphnia magna). The EC 50 values are 6.1 ± 0.5 (72 h), 7.4 ± 1.6 (72 h), and 21.9 ± 4.3 (24 h) mg of Fe per L, respectively.
Iron(III) oxide shows a polymorphism, characteristic of existence of phases with the same chemical composition but distinct crystal structures and, hence, physical properties. Four crystalline phases of iron(III) oxide have previously been identified: α-Fe2O3 (hematite), β-Fe2O3, γ-Fe2O3 (maghemite), and ε-Fe2O3. All four iron(III) oxide phases easily undergo various phase transformations in response to heating or pressure treatment, usually forming hexagonal α-Fe2O3, which is the most thermodynamically stable Fe2O3 polymorph under ambient conditions. Here, from synchrotron X-ray diffraction experiments, we report the formation of a new iron(III) oxide polymorph that we have termed ζ-Fe2O3 and which evolved during pressure treatment of cubic β-Fe2O3 ( space group) at pressures above 30 GPa. Importantly, ζ-Fe2O3 is maintained after pressure release and represents the first monoclinic Fe2O3 polymorph (I2/a space group) that is stable at atmospheric pressure and room temperature. ζ-Fe2O3 behaves as an antiferromagnet with a Néel transition temperature of ~69 K. The complex mechanism of pressure-induced transformation of β-Fe2O3, involving also the formation of Rh2O3-II-type Fe2O3 and post-perovskite-Fe2O3 structure, is suggested and discussed with respect to a bimodal size distribution of precursor nanoparticles.
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