Showing papers on "Hematite published in 2013"

Single-crystalline, wormlike hematite photoanodes for efficient solar water splitting

Abstract: A hematite photoanode showing a stable, record-breaking performance of 4.32 mA/cm2 photoelectrochemical water oxidation current at 1.23 V vs. RHE under simulated 1-sun (100 mW/cm2) irradiation is reported. This photocurrent corresponds to ca. 34% of the maximum theoretical limit expected for hematite with a band gap of 2.1 V. The photoanode produced stoichiometric hydrogen and oxygen gases in amounts close to the expected values from the photocurrent. The hematitle has a unique single-crystalline “wormlike” morphology produced by in-situ two-step annealing at 550°C and 800°C of β-FeOOH nanorods grown directly on a transparent conducting oxide glass via an all-solution method. In addition, it is modified by platinum doping to improve the charge transfer characteristics of hematite and an oxygen-evolving co-catalyst on the surface.

Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes

Abstract: Hematite is currently considered one of the most promising materials for the conversion and storage of solar energy via the photoelectrolysis of water. Whilst there has been extensive research and much progress in the development of hematite structures with enhanced photoelectrochemical (PEC) activity, relatively limited information has been available until recently concerning the dynamics of photogenerated charge carriers in hematite and their impact upon the efficiency of water photoelectrolysis. In this perspective we present an overview of our recent studies of the dynamics of photoinduced charge carrier processes in hematite, derived primarily from transient absorption spectroscopy of nanostructured photoanodes. The relationship between PEC activity and transient measurements are discussed in terms of a phenomenological model which rationalizes the observations and in particular the impact of external potential bias on the relative rates of charge carrier trapping, recombination and interfacial transfer in hematite photoanodes for water oxidation.

Atomic layer deposition of a submonolayer catalyst for the enhanced photoelectrochemical performance of water oxidation with hematite.

Abstract: Hematite photoanodes were coated with an ultrathin cobalt oxide layer by atomic layer deposition (ALD). The optimal coating—1 ALD cycle, which amounts to <1 monolayer of Co(OH)2/Co3O4—resulted in significantly enhanced photoelectrochemical water oxidation performance. A stable, 100–200 mV cathodic shift in the photocurrent onset potential was observed that is correlated to an order of magnitude reduction in the resistance to charge transfer at the Fe2O3/H2O interface. Furthermore, the optical transparency of the ultrathin Co(OH)2/Co3O4 coating establishes it as a particularly advantageous treatment for nanostructured water oxidation photoanodes. The photocurrent of catalyst-coated nanostructured inverse opal scaffold hematite photoanodes reached 0.81 and 2.1 mA/cm2 at 1.23 and 1.53 V, respectively.

Photocatalytic Water Oxidation by Hematite/Reduced Graphene Oxide Composites

Abstract: The photocatalytic water oxidation activity of hematite (α-Fe2O3) has been greatly enhanced by incorporating hematite nanoparticles on the reduced graphene oxide (rGO) nanosheets. Photoelectrochemical measurement results show that coupling the hematite nanoparticles with the rGO greatly increases the photocurrent and reduces the charge recombination rate. Transient absorption spectroscopy and time-domain terahertz spectroscopy have provided the direct evidence that the photogenerated electrons have transferred as the mobile carriers from α-Fe2O3 to rGO, which enhances the charge separation and suppresses the charge recombination. This work has provided new insight into the mechanism of photocatalysis enhancement by reduced graphene oxide, which has implications in the design of semiconductor/graphene heterojunction photocatalysts.

“In rust we trust”. Hematite – the prospective inorganic backbone for artificial photosynthesis

Abstract: The search for affordable high performance electrode materials in photoelectrochemical hydrogen production by solar water splitting is an ongoing quest. Hematite is a photoanode material with an electronic band gap suitable for efficient absorption of visible light in a photoelectrochemical cell (PEC). Although its poor electronic structure makes hematite a controversial candidate for PEC, it remains promising because it is an earth abundant, chemically stable and low cost material – necessary prerequisites for PEC to become a competitive cost-efficient solar fuel economy. In addition to reviewing some recent PEC research on hematite and its relevant physical and chemical characteristics, we show how hematite obtained by a low cost synthesis can be refined by hydrothermal treatment and further functionalized by coating with phycocyanin, a light harvesting protein known for photosynthesis in blue-green algae.

Facile post-growth doping of nanostructured hematite photoanodes for enhanced photoelectrochemical water oxidation

Abstract: We report a facile approach to perform post-growth doping of hematite (α-Fe2O3) nanostructures by depositing titanium (Ti) precursor solution and subsequent annealing in air. Using hematite nanowire photoanodes on fluorine doped tin oxide (FTO) glass substrates as a model system, the doping conditions were carefully optimized and highly photoactive hematite photoanodes were prepared at a more practically acceptable temperature of 650–700 °C than the ≥800 °C commonly used in previous works. A combination of microstructural characterization, elemental analysis, photoelectrochemical (PEC) measurements, and electrochemical impedance spectroscopy (EIS) analysis were employed to confirm the distribution of Ti atoms in hematite nanostructures and the role of Ti dopants in enhancing the photocurrent of hematite photoanodes. It was found that the Ti-treatment increases the donor concentration of hematite by about 10 fold and facilitates majority carrier transport and collection, which may account for the performance enhancement. Moreover, EIS measurements under illumination and Mott–Schottky analysis clearly showed that Ti dopants interact with the surface trap states of hematite, suggesting that surface passivation may also contribute to the improved PEC performance. This facile post-growth doping method can be applied to other hematite nanostructures such as electrochemically deposited hematite films and expanded to other dopants such as zirconium (Zr).

Naturally occurring iron oxide nanoparticles: morphology, surface chemistry and environmental stability

Abstract: The widespread nanostructures of iron oxides and oxyhydroxides are important reagents in many biogeochemical processes in many parts of our planet and ecosystem. Their functions in various aspects are closely related to their shapes, sizes, and thermodynamic surroundings, and there is much that we can learn from these natural relationships. This review covers these subjects of several phases (ferrihydrite, goethite, hematite, magnetite, maghemite, lepidocrocite, akaganeite and schwertmannite) commonly found in water, soils and sediments. Due to surface passivation by ubiquitous water in aquatic and most terrestrial environments, the difference in formation energies of bulk phases can decrease substantially or change signs at the nanoscale because of the disproportionate surface effects. Phase transformations and the relative abundance are sensitive to changes in environmental conditions. Each of these phases (except maghemite) displays characteristic morphologies, while maghemite appears frequently to inherit the precursor's morphology. We will see how an understanding of naturally occurring iron oxide nanostructures can provide useful insight for the production of synthetic iron oxide nanoparticles in technological settings.

Highly photoactive Ti-doped α-Fe2O3 thin film electrodes: resurrection of the dead layer

Abstract: Uniform thin films of hematite and Ti-doped hematite (α-Fe2O3) were deposited on transparent conductive substrates using atomic layer deposition (ALD). ALD's epitaxial growth mechanism allowed the control of the morphology and thickness of the hematite films as well as the concentration and distribution of Ti atoms. The photoelectrochemical performances of Ti-doped and undoped hematite electrodes were examined and compared under water oxidation conditions. The incorporation of Ti atoms into hematite electrodes was found to dramatically enhance the water oxidation performance, with much greater enhancement found for the thinnest films. An optimum concentration ∼3 atomic% of Ti atoms was also determined. A series of electrochemical, photoelectrochemical and impedance spectroscopy measurements were employed to elucidate the cause of the improved photoactivity of the Ti-doped hematite thin films. This performance enhancement was a combination of improved bulk properties (hole collection length) and surface properties (water oxidation efficiency). The improvement in both bulk and surface properties is attributed to the resurrection of a dead layer by the Ti dopant atoms.

Characteristics of Phosphate Adsorption-Desorption Onto Ferrihydrite: Comparison With Well-Crystalline Fe (Hydr)Oxides

Abstract: The adsorption-desorption behavior of phosphate on ferrihydrite, goethite, and hematite and underlying mechanisms were comparatively investigated with batch kinetics, solution equilibrium, and mineral characterization. The phosphate adsorption kinetics for all Fe (hydr)oxides are described b

CeO2-modified Fe2O3 for CO2 utilization via chemical looping

Abstract: Both pure and mixed CeO2–Fe2O3 were prepared for CO2 reduction to CO by chemical looping. The crystallographic structure of the investigated materials was monitored in situ during H2 reduction and CO2 oxidation. A solid solution of iron in ceria was identified. Up to 70 wt % CeO2, a distinct Fe2O3 hematite phase occurred next to the solid solution. At higher CeO2 content, no diffraction patterns corresponding to iron oxide phases were present, but upon H2 temperature programmed reduction, a metal iron phase appeared. The Fe2O3 phase at lower CeO2 content, during H2 temperature programmed reduction, completely reduced at 700 °C while the solid solution was only partially reduced. For all investigated samples, CO2 reoxidized iron in one-step to Fe3O4 from 500 °C during temperature programmed oxidation. Adding CeO2 to Fe2O3 was beneficial for the materials activity and stability. Isothermal redox cycles were performed without significant loss of CO2 conversion. The highest CO yield was obtained for 20 wt % C...

A novel strategy for surface treatment on hematite photoanode for efficient water oxidation

Abstract: In this paper, we report a novel strategy for surface treatment of hematite nanorods for efficient photo-driven water oxidation. This is the first report describing the growth of Sn treated hematite from α-FeOOH nanorod arrays in one step without substantially altering morphologies. With this treatment the photocurrent density increased from 1.24 for pristine hematite nanorods to 2.25 mA cm−2 at 1.23 V vs. RHE (i.e. 81% improvement). The increase in photocurrent density was also accompanied by improved incident-photon-to-current efficiencies and oxygen evolution. The photocurrent improvement is mainly attributed to a reduced electron–hole recombination at the hematite–electrolyte interface through the formation of FexSn1−xO4 layer at the hematite nanorod surface as shown by XPS, HRTEM, EDAX line scan analyses and PEC measurements.

A hematite-bearing layer in Gale Crater, Mars: Mapping and implications for past aqueous conditions

Abstract: Oversampled Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) visible and near-infrared hyperspectral data over Mount Sharp in Gale Crater, Mars, were used to generate spatially sharpened maps of the location of red crystalline hematite within the uppermost stratum of an ∼6.5-km-long ridge on the mound’s northern flank. Finely layered strata underlie the ridge to the north and have dips consistent with the nearby Mount Sharp sedimentary sequence. Fe-Mg smectites are exposed in a valley to the south of the ridge. Emplacement of the hematite is hypothesized to result either from exposure of anoxic Fe^(2+)-rich groundwater to an oxidizing environment, leading to precipitation of hematite or its precursors, or from in-place weathering of precursor silicate materials under oxidizing conditions. These hypotheses and implications for habitability will be testable with in situ measurements by the Mars rover Curiosity when it reaches Mount Sharp.

Facile synthesis of carbon-coated hematite nanostructures for solar water splitting

Abstract: Carbon-coated hematite nanostructures for solar water splitting were prepared by a simple pyrolysis of ferrocene which showed a remarkable photocurrent of 2.1 mA cm−2 at 1.23 V vs. RHE, compared to a value of 0.5 mA cm−2 for hematite without the carbon layer. The carbon layer is a few nm thick covering the surface of hematite nanostructures. X-Ray photoelectron spectroscopy and X-ray absorption spectroscopy revealed that the electronic structure of hematite was significantly modified with the existence of oxygen vacancy, which was responsible for the remarkable photocurrent. The carbon layer plays an important role for the appearance of oxygen vacancy. The simple and cheap method could be scaled up easily which may pave the way for the practical application for efficient solar water splitting.

Factors Affecting Zeta Potential of Iron Oxides

Abstract: This review examines the factors that affect the isoelectric point (IEP) and the magnitude of the Zeta potential for hematite. It addresses the various values that have been reported in the literature, with natural hematite typically having a more acidic IEP than does high-purity synthetic hematite. The key finding is that the IEP for natural hematite is very similar to that for silica. This is consistent with a coating of silica slimes forming on natural hematite, causing the hematite surfaces to behave as if they were silica surfaces. Adsorption of chemical reagents on the hematite surfaces causes changes in the magnitude of the Zeta potential, generally without changing the IEP.

The Composition and Depositional Environments of Mesoarchean Iron Formations of the West Rand Group of the Witwatersrand Supergroup, South Africa

Abstract: This paper documents the sedimentological setting, mineralogy, and geochemistry of several iron formation units interbedded with siliciclastic strata of the Mesoarchean Witwatersrand Supergroup, well known for its world-class conglomerate-hosted Au-U deposits. Four major iron formation beds, with associated magnetic mudstones, are present in two distinctly different lithostratigraphic associations, namely shale- and diamictiteassociated iron formation. The shale association is represented by the Water Tower and Contorted Bed iron formations in the Parktown Formation of the Hospital Hill Subgroup in the lower part of the succession and the diamictite association by the Promise and Silverfield iron formations in the overlying Government Subgroup. The iron formation units have been subjected to lower greenschist facies metamorphism. Oxide (magnetite and limited hematite), carbonate, and silicate facies iron formations are recognized. The iron formations typically overlie major transgressive flooding surfaces in the succession and, in turn, form the base of progradational coarsening-upward increments of sedimentation comprising magnetic mudstone, nonmagnetic shale, and interbedded siltstone-quartzite. The upward transition from iron formation into magnetic mudstone is accompanied by a change in mineralogical composition from hematite-magnetite iron formation at the base in the most distal setting through magnetite-siderite- and siderite-facies iron formation in the transition zone to magnetic mudstone. The siderite with associated ankerite displays highly depleted δ13C values, suggesting crystallization via iron respiration in presence of organic carbon. The iron formations display positive postArchean Australian shale-normalized Eu and Y anomalies with depletion in light rare-earth elements relative to heavy rare-earth elements, indicating precipitation from marine water with a high-temperature hydrothermal component. Integration of sedimentological, petrographic, and geochemical results indicates that the shale-associated iron formation was deposited during the peak of transgression, when reduced iron-rich hydrothermal waters entered the Witwatersrand Basin over a limited vertical extent due to neutral buoyancy, with the top of the plume occurring below the photic zone. It is suggested that chemolithoautotrophic iron-oxidizing bacteria, which would have been able to exploit the difference in chemistry between the iron-enriched plume water and ambient ocean water to fuel metabolic activity in the presence of limited free molecular oxygen, were responsible for precipitation of initial ferric iron oxyhydroxides. The vertical facies associations in the iron formations most likely developed in response to the limited vertical extent of the hydrothermal plume, with (from distal to proximal) hematite preserved where the base of the plume was not in contact with the basin floor, magnetite where the plume water was in contact with bottom sediment, iron-rich carbonates where organic carbon input was high, iron-rich alumosilicates where siliciclastic input became significant in more proximal settings, and iron-poor sediment above the top of the plume. Diamictite-associated iron formations in the Witwatersrand are inferred to have been deposited in a fashion similar to the shale-associated iron formations, with the exception that major transgressions and hydrothermal plume invasion were preceded by glacial ice cover. The climate warming and increased volcanic activity required could have been related to increased tectonic activity inferred for the Witwatersrand Supergroup during deposition of the glacially associated iron formations.

Surface potentials of (001), (012), (113) hematite (α-Fe2O3) crystal faces in aqueous solution.

Abstract: Hematite (α-Fe2O3) is an important candidate electrode for energy system technologies such as photoelectrochemical water splitting. Conversion efficiency issues with this material are presently being addressed through nanostructuring, doping, and surface modification. However, key electrochemical properties of hematite/electrolyte interfaces remain poorly understood at a fundamental level, in particular those of crystallographically well-defined hematite faces likely present as interfacial components at the grain scale. We report a combined measurement and theory study that isolates and evaluates the equilibrium surface potentials of three nearly defect-free single crystal faces of hematite, titrated from pH 3 to 11.25. We link measured surface potentials with atomic-scale surface topology, namely the ratio and distributions of surface protonation–deprotonation site types expected from the bulk structure. The data reveal face-specific points of zero potential (PZP) relatable to points of zero net charge (PZC) that lie within a small pH window (8.35–8.85). Over the entire pH range the surface potentials show strong non-Nernstian charging at pH extremes separated by a wide central plateau in agreement with surface complexation modeling predictions, but with important face-specific distinctions. We introduce a new surface complexation model based on fitting the entire data set that depends primarily only on the proton affinities of two site types and the two associated electrical double layer capacitances. The data and model show that magnitudes of surface potential biases at the pH extremes are on the order of 100 mV, similar to the activation energy for electron hopping mobility. An energy band diagram for hematite crystallites with specific face expression and pH effects is proposed that could provide a baseline for understanding water splitting performance enhancement effects from nanostructuring, and guide morphology targets and pH for systematic improvements in efficiency.

Enhanced Hematite Water Electrolysis Using a 3D Antimony-Doped Tin Oxide Electrode

Abstract: We present herein an example of nanocrystalline antimony-doped tin oxide (nc-ATO) disordered macroporous “inverse opal” 3D electrodes as efficient charge-collecting support structures for the electrolysis of water using a hematite surface catalyst. The 3D macroporous structures were created via templating of polystyrene spheres, followed by infiltration of the desired precursor solution and annealing at high temperature. Using cyclic voltammetry and electrochemical impedance spectroscopy, it was determined that the use of this 3D transparent conducting oxide with a hematite surface catalyst allowed for a 7-fold increase in active surface area for water splitting with respect to its 2D planar counterpart. This ratio of surface areas was evaluated based on the presence of oxidized trap states on the hematite surface, as determined from the equivalent circuit analysis of the Nyquist plots. Furthermore, the presence of nc-ATO 2D and 3D “underlayer” structures with hematite deposited on top resulted in decreas...

Designed synthesis of hematite-based nanosorbents for dye removal

Abstract: We report the design and synthesis of two hematite (α-Fe2O3)-based nanomaterials based on effective hydrothermal conversion of chemically metastable K1.33Mn8O16 nanowires (KWs) in Fe(NO3)3 aqueous solution. Insights are gained into the functions of sodium dodecyl benzene sulfonate (SDBS) and the mechanisms for generating large quantities of α-Fe2O3 hollow structures (FHSs) and K1.33Mn8O16@α-Fe2O3 heterostructured nanowires (KFHWs) in solution phase. The controllable growth dynamics allows convenient control over the morphology and production of the hematite-based nanostructures. Adsorption experiments indicate that the resulting hematite-based materials are powerful nanosorbents for swift removal of Congo red from wastewater at room temperature. The adsorption kinetics and adsorption isotherm are also investigated and the findings indicate that the as-prepared KFHW and FHS hold great potential as environmentally friendly filter materials for water purification and organic waste removal.

Iron Sulfide (FeS) Nanotubes Using Sulfurization of Hematite Nanowires

Abstract: We report the phase transformation of hematite (α-Fe2O3) single crystal nanowires to crystalline FeS nanotubes using sulfurization with H2S gas at relatively low temperatures. Characterization indicates that phase pure hexagonal FeS nanotubes were formed. Time-series sulfurization experiments suggest epitaxial growth of FeS as a shell layer on hematite. This is the first report of hollow, crystalline FeS nanotubes with NiAs structure and also on the Kirkendall effect in solid–gas reactions with nanowires involving sulfurization.

The Function of Ca(OH)2 and Na2CO3 as Additive on the Reduction of High-Phosphorus Oolitic Hematite-coal Mixed Pellets

Abstract: A process with coal-based direct reduction followed by magnetic separation is presented for recovering metallic iron from high-phosphorus oolitic hematite in this study. Ca(OH)2 and Na2CO3 were used as additives in the reduction roasting. A Direct Reduction Iron (DRI) with 93.28 mass% Fe, and 0.07 mass% P can be obtained at a recovery percentage of 92.30 mass% under optimal conditions. The mechanisms of Ca(OH)2 and Na2CO3 were investigated by XRD and SEM with EDS. It showed that fluorapatite was reduced to P smelt into metallic iron without additives while the hematite was reduced. The addition of Ca(OH)2 can not only inhibit the reduction of fluorapatite but also promote the reduction of hematite. Na2CO3 can promote the separation of iron from slag, meanwhile it may also inhibit the reduction of fluorapatite at the presence of 15 mass% Ca(OH)2. Under optimal conditions, phosphorus remained as fluorapatite in the slag and can be removed by grinding and magnetic separation.