α-Fe2 O3 Research Articles

Enhanced Solar Water Splitting by Swift Charge Separation in Au/FeOOH Sandwiched Single-Crystalline Fe2 O3 Nanoflake Photoelectrodes.

In this work, single crystalline α-Fe2 O3 nanoflakes (NFs) are formed in a highly dense array by Au seeding of a Fe substrate by a thermal oxidation technique. The NFs are conformally decorated with a thin FeOOH cocatalyst layer. Photoelectrochemical (PEC) measurements show that this photoanode, incorporating α-Fe2 O3 /FeOOH NFs rooted on the Au/Fe structure, exhibits significantly enhanced PEC water oxidation performance compared to the plain α-Fe2 O3 nanostructure on the Fe substrate. The α-Fe2 O3 /FeOOH NFs on Au/Fe photoanode yields a photocurrent density of 3.1 mA cm-2 at 1.5 VRHE , and a remarkably low onset potential of 0.5-0.6 VRHE in 1 m KOH under AM 1.5G (100 mW cm-2 ) simulated sunlight illumination. The enhancement in PEC performance can be attributed to a synergistic effect of the FeOOH top decoration and the Au underlayer, whereby FeOOH facilitates hole transfer at the interface of electrode/electrolyte and the Au layer provides a sink for the electron transport to the back contact. This results in a drastically improved charge-separation efficiency in the single crystalline α-Fe2 O3 NF photoanode.

Photocatalytic and Antibacterial Performance of α-Fe2 O3 Nanostructures

Photocatalytic and Antibacterial Performance of α-Fe₂ O₃ Nanostructures

Localized Synthesis of Iron Oxide Nanowires and Fabrication of High Performance Nanosensors Based on a Single Fe2 O3 Nanowire.

A composed morphology of iron oxide microstructures covered with very thin nanowires (NWs) with diameter of 15-50 nm has been presented. By oxidizing metallic Fe microparticles at 255 °C for 12 and 24 h, dense iron oxide NW networks bridging prepatterned Au/Cr pads are obtained. X-ray photoelectron spectroscopy studies reveal formation of α-Fe2 O3 and Fe3 O4 on the surface and it is confirmed by detailed high-resolution transmission electron microscopy and selected area electron diffraction (SAED) investigations that NWs are single phase α-Fe2 O3 and some domains of single phase Fe3 O4 . Localized synthesis of such nano- and microparticles directly on sensor platform/structure at 255 °C for 24 h and reoxidation at 650 °C for 0.2-2 h, yield in highly performance and reliable detection of acetone vapor with fast response and recovery times. First nanosensors on a single α-Fe2 O3 nanowire are fabricated and studied showing excellent performances and an increase in acetone response by decrease of their diameter was developed. The facile technological approach enables this nanomaterial as candidate for a range of applications in the field of nanoelectronics such as nanosensors and biomedicine devices, especially for breath analysis in the treatment of diabetes patients.

Red and yellow ochres from the archaeological site Pedra do Cantagalo I, in Piripiri, Piauí, Brazil

The archaeological site Pedra do Cantagalo I is a sandstone shelter displaying rupestrian inscriptions. It is located in the rural area of the municipality of Piripiri, in the northern region of the Piaui state, Brazil. The site was found as being originally decorated with more than 1,900 prehistoric rupestrian paintings, along with engravings, lithics, ceramic fragments and mineral pigments forming reddish and yellowish ochres. Materials of these ochres, collected from recent excavations in this archaeological site, were analyzed by energy dispersive X-ray fluorescence (EDXRF); backscattering and transmission 57Fe-Mossbauer spectroscopy at 298 K and 25 K and powder X-ray diffraction (XRD), in an effort to assess the chemical and mineralogical characteristics of these sources of pigments that composed the ancient paint materials of the site. The iron contents (expressed as Fe 2O3) for the reddish ochres were found to range from ∼60 to ∼68 mass%; for the yellowish ochres the corresponding content was ∼34 mass%, as determined by EDXRF. From the Mossbauer spectra for these red ochre samples, hematite (αFe 2O3) or a mixture of hematite and goethite (αFeOOH) were identified. Actually, the spectra at room temperature for the yellow ochres are rather complex, as it is usual for most soil clay materials. At least part of the intense central doublet was assumed to be from superparamagnetic iron oxides in very small particles. The Mossbauer patterns at 25 K allowed confirming this assumption, as the superparamagnetic relaxation effects were virtually suppressed; the spectral contributions due to goethite could be thus more easily separated.

Crystalline-selected synthesis of ferrous oxalate dihydrate from spent pickle liquor

Ferrous oxalate dihydrate with different crystalline structures, polymorphs and sizes have been synthesized through a facile precipitation reaction from spent pickling liquors (SPL) by controlling synthesis conditions. The β-FeC2 O4 · 2H2 O in orthorhombic phase can be formed at room temperature, whereas α-FeC2 O4 · 2H2 O with a monoclinic unit cell can be obtained after aging at 80 °C. With the increasing aging temperature, the morphology of samples can be tailored from flower-like to prismatic-like and the particle-sizes are decreased. Innovatively, thermal decomposition behaviors of products have been investigated in details by X-ray diffraction pattern (XRD) and thermal gravimetric-differential scanning calorimetry (TG-DSC). The results show that both FeC2 O4 · 2H2 O samples can be transformed to α-Fe2 O3 in air atmosphere and Fe3 O4 in argon atmosphere at T ≧ 400 °C. In air atmosphere, there are two sharp exothermic peaks for β-FeC2 O4 · 2H2 O (250 °C) and α-FeC2 O4 · 2H2 O (239.5 °C) correspond to the decomposition reactions. In argon atmosphere, the decomposition end temperatures are 500 °C and 430 °C for β-FeC2O4 · 2H2O and α-FeC2O4 · 2H2O, respectively. This indicates that β-FeC2O4 · 2H2O has higher thermal stability in comparison with α-FeC2O4 · 2H2O.

Batteries: Highly Stable Cycling of Amorphous Li2 CO3 -Coated α-Fe2 O3 Nanocrystallines Prepared via a New Mechanochemical Strategy for Li-Ion Batteries (Adv. Funct. Mater. 3/2017)

Batteries: Highly Stable Cycling of Amorphous Li₂ CO₃ -Coated α-Fe₂ O₃ Nanocrystallines Prepared via a New Mechanochemical Strategy for Li-Ion Batteries (Adv. Funct. Mater. 3/2017)

Constructing Hierarchical Tectorum-like α-Fe2 O3 /PPy Nanoarrays on Carbon Cloth for Solid-State Asymmetric Supercapacitors.

The design of complex heterostructured electrode materials that deliver superior electrochemical performances to their individual counterparts has stimulated intensive research on configuring supercapacitors with high energy and power densities. Herein we fabricate hierarchical tectorum-like α-Fe2 O3 /polypyrrole (PPy) nanoarrays (T-Fe2 O3 /PPy NAs). The 3D, and interconnected T-Fe2 O3 /PPy NAs are successfully grown on conductive carbon cloth through an easy self-sacrificing template and in situ vapor-phase polymerization route under mild conditions. The electrode made of the T-Fe2 O3 /PPy NAs exhibits a high areal capacitance of 382.4 mF cm-2 at a current density of 0.5 mA cm-2 and excellent reversibility. The solid-state asymmetric supercapacitor consisting of T-Fe2 O3 /PPy NAs and MnO2 electrodes achieves a high energy density of 0.22 mWh cm-3 at a power density of 165.6 mW cm-3 .

Cooperative Catalytic Effect of ZrO2 and α-Fe2 O3 Nanoparticles on BiVO4 Photoanodes for Enhanced Photoelectrochemical Water Splitting.

Photoelectrochemical water splitting with metal oxide semiconductors offers a cost-competitive alternative for the generation of solar fuels. Most of the materials studied so far suffer from poor charge-transfer kinetics at the semiconductor/liquid interface, making compulsory the use of catalytic layers to overcome the large overpotentials required for the water oxidation reaction. Herein, we report a very soft electrolytic synthesis deposition method, which allows remarkably enhanced water oxidation kinetics of BiVO4 photoanodes by the sequential addition of Zr and Fe precursors. Upon a heat treatment cycle, these precursors are converted into monoclinic ZrO2 and α-Fe2 O3 nanoparticles, which mainly act as catalysts, leading to a five-fold increase of the water oxidation photocurrent of BiVO4 . This method provides a versatile platform that is easy to apply to different semiconductor materials, fully reproducible, and facile to scale-up on large area conductive substrates with attractive implications for technological deployment.

Human Urine‐Fueled Light‐Driven NADH Regeneration for Redox Biocatalysis

Human urine is considered as an alternative source of hydrogen and electricity owing to its abundance and high energy density. Here we show the utility of human urine as a chemical fuel for driving redox biocatalysis in a photoelectrochemical cell. Ni(OH)2 -modified α-Fe2 O3 is selected as a photoanode for the oxidation of urea in human urine and black silicon (bSi) is used as a photocathode material for nicotinamide cofactor (NADH: hydrogenated nicotinamide adenine dinucleotide) regeneration. The electrons extracted from human urine are used for the regeneration of NADH, an essential hydride mediator that is required for numerous redox biocatalytic reactions. The catalytic reactions at both the photoanode and the photocathode were significantly enhanced by light energy that lowered the overpotential and generated high currents in the full cell system.

Two-Dimensional Hollow TiO2 Nanoplates with Enhanced Photocatalytic Activity.

Two-dimensional anatase TiO2 hollow nanoplates were firstly synthesized through a facile synthesis route by using α-Fe2 O3 nanoplates as removable templates. Two-dimensional hollow TiO2 nanoplates with different ratios of anatase and rutile phases were obtained by adjusting the calcining temperature. The average diameters were around 600 nm, and the shell thickness was approximately 30 nm. The photocatalytic performance of TiO2 was investigated by decomposing rhodamine B under simulated sunlight. Among the TiO2 samples, the anatase TiO2 hollow nanoplates manifested a significant enhancement in the photocatalytic performances. The excellent catalytic performance can be attributed to the unique structure of the two-dimensional anatase TiO2 hollow nanoplates, including a large surface area and increased dye-photocatalyst contact areas as well as more active sites for photodegradation.

Origin of the Ability of α-Fe2 O3 Mesopores to Activate C-H Bonds in Methane.

Methane is a most abundant and inexpensive hydrocarbon feedstock for the production of chemicals and fuels. However, it is extremely difficult to directly convert methane to higher hydrocarbons because the C-H bonds in methane are the most stable C-H bonds of all hydrocarbons. The activation of the C-H bonds in methane by using an efficient and mild route remains a daunting challenge. Here, we show that the inner surface structures of the pore walls in mesoporous α-Fe2 O3 possess excellent catalytic performance for methane activation and convert C-H bonds into the C-O bonds in an O2 atmosphere at 140 °C. We found that such unusual structures are mainly comprised of turbostratic ribbons and K crystal faces and have higher catalytic activity than the (110) plane. These results are without precedent in the history of catalysis chemistry and will provide a new pathway for designing and preparing highly efficient catalytic materials.

Built-In Potential in Fe2O3-Cr2O3 Superlattices for Improved Photoexcited Carrier Separation.

Hematite (α-Fe2 O3) is engineered to improve photoexcited electron-hole pair separation by synthesizing Fe2O3-Cr2O3 superlattices (SLs) with precise atomic control. The different surface terminations exhibited by Fe2O3 and Cr2O3 determine the hetero-junction interface structure and result in controllable, noncommutative band offset values. This controllable band alignment is harnessed to generate a built-in potential as large as 0.8 eV in Fe2 O3-Cr2O3 SLs.

Fe K-Edge X-ray Absorption Fine Structure Determination of γ-Al2 O3 -Supported Iron-Oxide Species.

The structure of FeOx species supported on γ-Al2 O3 was investigated by using Fe K-edge X-ray absorption fine structure (XAFS) and X-ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al2 O3 and co-gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α-Fe2 O3 particles at an Fe loading of above 10 wt %, whereas the formation of iron-oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K-edge XAFS was characterized by a clear pre-edge peak, which indicated that the FeO coordination structure deviates from central symmetry and that the degree of FeOFe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K-edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron-oxide monomer on the γ-Al2 O3 surface.

Activation of Ultrathin Films of Hematite for Photoelectrochemical Water Splitting via H2 Treatment.

Thermal treatment of ultrathin films of hematite (α-Fe2 O3 ) under an atmosphere of 5 % H2 in Ar is presented as a means of activating α-Fe2 O3 towards the photoelectrochemical splitting of water. Spin-coated films annealed in air exhibited no photoactivity, whereas films treated in hydrogen exhibited a photocurrent response. X-ray photoelectron spectroscopy and UV/Vis absorption spectroscopy results showed that the H2 -treated films contain oxygen vacancies, which suggests improved charge transport. However, Tafel slopes, scan-rate dependent measurements, and kinetic analyses performed by using H2 O2 as a hole scavenger suggested that surface modification may also contribute to their induced photoactivity. Electrochemical impedance spectroscopy results revealed the buildup of a surface trap capacitance at the point of photocurrent onset for the hydrogen-treated films under illumination. A decrease in charge trapping resistance was also observed, which suggests improved transport of charges away from the surface.

Template-Assisted Synthesis of Metal Oxide Hollow Spheres Utilizing Glucose Derived-Carbonaceous Spheres As Sacrificial Templates

A series of metal oxides hollow spheres (Cr2 O3 , α-Fe2 O3 , Co3 O4 , NiO and ZnO) have been fabricated using the glucose derived-carbonaceous spheres as sacrificial templates and the metal chlorides as precursors for the metal oxides in a sacrificial templating process. Heating of an aqueous solution of the metal chloride and glucose in an autoclave at 180 oC affords - as indicated by transmission electron microscopy (TEM) - a nanospherical composite consisting of a metal precursor shell sheathing a carbonaceous core. Consequently, hollow crystalline oxides spheres are obtained by removal of the carbonaceous cores through calcination in air. Correlations between the particle size and the various synthesis conditions such as glucose concentration, the molar concentration ratio between glucose and metal chloride, temperature, reaction time and the addition of acetic acid as a catalyst are uncovered. The obtained metal oxides hollow spheres were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray powder diffraction (XRD), infrared spectroscopy (IR), and nitrogen adsorption/desorption isotherms (BET).

Rapid and up-scalable fabrication of free-standing metal oxide nanosheets for high-performance lithium storage.

Free-standing α-Fe2 O3 nanosheets, SnO2 mesoporous nanosheets and sandwich-like polyaniline (PAN)/SnO2 /PAN nanosheets are fabricated at very mild conditions (room temperature or 60 °C) via a galvanic replacement method for the first time. These nanosheets show excellent high-rate capability and long-term durability as anodes for lithium-ion batteries.

Halide-Ion-Assisted Synthesis of Different α-Fe2 O3 Hollow Structures and Their Lithium-Ion Storage Properties.

Various α-Fe2 O3 hollow structures, such as wormlike shapes, ellipsoids, and quasicubes, were synthesized successfully by a halide-ion-assisted solvothermal method. The self-assembly assisted by selective absorption of halide ions and Ostwald ripening speeded up by acidic etching commonly determine the final unique structures. The electrochemical performance of the α-Fe2 O3 with different structures in reversible lithium-ion storage was investigated, and showed that the hollow Fe2 O3 quasicubes exhibit the best cycling performance with a charge capacity of 401.6 mAh g-1 after 100 cycles at 0.2 C. The superior cycling stability and high specific capacity can be ascribed to the higher specific surface area, lower charge-transfer resistance, and adequate alleviation of volume variation.

Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C-C bond formation and alcohol oxidation.

The trivalent metal cations Al(3+) , Cr(3+) , and Fe(3+) were each introduced, together with Sc(3+) , into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2 O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel-Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2 O3 nanoparticles were also active Lewis acid species, although less active than Sc(3+) in trimer sites. The incorporation of Fe(3+) into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc(3+) and Fe(3+) . A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.

The Role of Surface States in the Oxygen Evolution Reaction on Hematite

Hematite (α-Fe2 O3 ) is an extensively investigated semiconductor for photoelectrochemical (PEC) water splitting. The nature and role of surface states on the oxygen evolution reaction (OER) remain however elusive. First-principles calculations were used to investigate surface states on hematite under photoelectrochemical conditions. The density of states for two relevant hematite terminations was calculated, and in both cases the presence and the role of surface states was rationalized. Calculations also predicted a Nerstian dependence on the OER onset potential on pH, which was to a very good extent confirmed by PEC measurements on hematite model photoanodes. Impedance spectroscopy characterization confirmed that the OER takes place via the same surface states irrespective of pH. These results provide a framework for a deeper understanding of the OER when it takes place via surface states.

Oxygen‐Deficient Hematite Nanorods as High‐Performance and Novel Negative Electrodes for Flexible Asymmetric Supercapacitors

Oxygen-deficient α-Fe2 O3 nanorods with outstanding capacitive performance are developed and demonstrated as novel negative electrodes for flexible asymmetric supercapacitors. The asymmetric-supercapacitor device based on the oxygen-deficient α-Fe2 O3 nanorod negative electrode and a MnO2 positive electrode achieves a maximum energy density of 0.41 mW·h/cm(3) ; it is also capable of charging a mobile phone and powering a light-emitting diode indicator.