Physical and photoelectrochemical characterizations of hematite α-Fe2O3: Application to photocatalytic oxygen evolution

The physical properties and photoelectrochemical characterization of α-Fe₂O₃, synthesized by co-precipitation, have been investigated in regard to solar energy conversion. The optical gap is found to be 1.94 eV and the transition is indirectly allowed. The chemical analysis reveals an oxygen deficiency and the oxide exhibits n-type conductivity, confirmed by a negative thermopower. The plot log σ vs 1/T shows linearity in the range (400-670 K) with the donor levels at 0.14 eV below the conduction band and a break at ∼590 K, attributed to the ionization of the donors. The conduction occurs by small polaron hopping through mixed valences Fe^2+/3+ with an electron mobility μ_400 K of 10⁻³ V cm² s⁻¹. α-Fe₂O₃ exhibits long term chemical stability in neutral solution and has been characterized photoelectrochemically to assess its activity as bias-free O₂-photoanode. The flat band potential V_fb (−0.45V_SCE) and the electron density N_D (1.63 × 10¹⁸ cm⁻³) were determined, respectively, by extrapolating the linear part to C⁻² = 0 and the slope of the Mott Schottky plot. At pH 6.5, the valence band (+1.35V_SCE) is suitably positioned with respect to the O₂/H₂O level (+0.62 V) and α-Fe₂O₃ has been evaluated for the chemical energy storage through the photocatalytic reaction: (, ΔG = 213.36 kJ mol⁻¹). The best photoactivity occurs in solution (0.025 M, pH 8) with an oxygen rate evolution of 7.8 cm³ (g catalyst)⁻¹ h⁻¹.     

Study of polymer electrolytes with grafted Au–γ-Fe2O3 nanoparticles

The work is aimed at enhancing the Li⁺ ion-conduction properties of polymer electrolytes (PE) for thin-film solid-state batteries. The research exploits novel ideas of structuring ionically conducting polymers or molecular polyether building blocks with grafted magnetic nanoparticles with the use of magnetic field, in order to enhance ionic conductivity along oriented helical PE chains. The experimental route being tested is based on the chemisorption of thiolated PEO on core–shell gold-coated maghemite. It was found that casting, under a gradient magnetic field (GMF), of concentrated PEs containing very small concentration – 0.5%(w/w) dithiol-connected Fe₂O₃/Fe₃O₄–Au nanoparticles results in enhancement of the total ionic conductivity by more than an order of magnitude.     

Photoelectrochemical water splitting at nanostructured α-Fe2O3 electrodes

In this study, nanostructured α-Fe₂O₃ thin films were deposited by simple electrodeposition for photoelectrochemical water splitting. Post-annealing temperature was found to have drastic effect on photoactivity of these films. SEM analysis illustrated that size of nanoparticles increases with annealing temperature. The current–potential characteristics showed that the water-splitting photocurrent strongly depends on post-annealing temperature. A maximum photocurrent density of 0.67 mA/cm² was observed at 1.23 V versus reversible hydrogen electrode (RHE) under standard illumination conditions (AM 1.5 G 100 mW/cm²), and the water-splitting current was over 1.0 mA/cm² before the dark current flow starts (at 1.55 V versus RHE). The electrode shows an onset potential as low as 0.8 V (versus RHE) for water photooxidation, which is one of the best results reported for hematite photoanodes. This high photoactivity of electrodes is attributed to the preferential growth of hematite nanostructures along the most conductive plane (001) and incorporation of Sn in film from the substrate at high annealing temperature. The best-performing electrode shows an incident photon conversion efficiency (IPCE) of 12% at 400 nm (in 1 M NaOH at 1.23 V versus RHE), which indicate the improved light-harvesting properties of these nanostructures.     

Preparation and photocatalytic H2-production on α-Fe2O3 prepared by sol-gel

In this work, the hematite α-Fe₂O₃ was synthesized by sol-gel method and characterized by X-ray diffraction and optical properties. The XRD patterns realized at different temperatures, show that pure hematite is obtained above 500 °C. The diffuse reflectance gives respectively direct and indirect optical transitions at 2.17 and 2.04 eV, in agreement with the red color. The capacitance measurement of α-Fe₂O₃ indicates p type behavior with a conduction band (?1.14 V vs. SCE), more cathodic than the H₂ evolution (～?0.8 V vs. SCE). The oxide was successfully tested for the hydrogen production under visible irradiation (29 mW cm^?2). α-Fe₂O₃ is photo-electrochemically stable in alkaline medium by hole consumption reactions involving X^2? (= SO₃^2? and S₂O₃^2?) as hole scavengers. The best photocatalytic activity for H₂ production was obtained on α-Fe₂O₃, calcined at 500 °C, in (Na₂S₂O₃ 0.025 M, pH ～ 13), with an average evolution rate of 0.015 cm³ h^?1 (mg catalyst)^?1 and a quantum efficiency of 0.26%. The system shows a tendency toward saturation, due to the competitive reduction of end products with the water reduction and the cathodic shift of the H₂ potential.     

Electrodeposited zirconium-doped α-Fe2O3 thin film for photoelectrochemical water splitting

Nanostructured hematite thin films were doped with zirconium successfully using electrodeposition method for their implementation as photoanode in photoelectrochemical (PEC) cell for hydrogen generation. XRD, Raman, XPS, SEM and UV-visible spectroscopy techniques were used to characterize the thin films. Highest photocurrent density of 2.1 mA/cm² at 0.6 V/SCE was observed for 2.0 at.% Zr⁴⁺ doped α-Fe₂O₃ sample with solar to hydrogen conversion efficiency of 1.43%. Flatband potential (−0.74 V/SCE) and donor density (2.6 × 10²¹ cm⁻³) were found to be maximum for the same sample. These results suggest substantial potential of hematite thin films with controlled doping of zirconium in PEC water splitting applications.     

Microwave-assisted low temperature fabrication of nanostructured α-Fe2O3 electrodes for solar-driven hydrogen generation

It is demonstrated for the first time that significant enhancement of photoelectrochemical performance could be achieved by using microwave-assisted annealing for the fabrication of α-Fe₂O₃ thin films. The process can also lead to significant energy savings (>60% when compared with conventional methods). Different types of Fe thin films were oxidized using both microwave and conventional heating techniques. The photoelectrochemical performance of electrodeposited, undoped and Si-doped iron oxide samples showed that microwave-annealing resulted in superior structural and performance enhancements. The photocurrent densities obtained from microwave annealed samples are among the highest values reported for α-Fe₂O₃ photoelectrodes fabricated at low temperatures and short times; the highest photocurrent density at 0.55 V vs. V_Ag/AgCl, before the dark current onset, was 450 μA cm⁻² for the Si-doped films annealed at 270 °C for 15 min using microwave irradiation (and 180 μA cm⁻² at 0.23 V vs. V_Ag/AgCl) while conventional annealing at the same temperature resulted in samples with negligible (3 μA cm⁻²) photoactivity. In contrast, a 450 °C/15 min conventional heat treatment only resulted in a film with 25% lower photocurrent density than that of the microwave annealed sample. The improved performance is attributed to the lower processing temperatures and rapidity of the microwave method that help to retain the nanostructure of the thin films whilst restricting the grain growth to a minimum. The lower processing temperature requirements of the microwave process can also open up the possibility of fabricating hematite thin films on conducting, flexible, plastic electronic substrates.     

Sn self-doped α-Fe2O3 nanobranch arrays supported on a transparent,conductive SnO2 trunk to improve photoelectrochemical water oxidation

We produced hierarchically branched Fe₂O₃ nanorods on a Sb:SnO₂ transparent conducting oxide (TCO) nanobelt structure as photoanodes for photoelectrochemical water splitting. Single-crystalline SnO₂ nanobelts (NBs) surrounded by Fe₂O₃ nanorods (NRs) were synthesized by thermal evaporation, then underwent chemical bath deposition and annealing. When Fe₂O₃ was crystallized by annealing, Sn was diffused from SnO₂ NBs and incorporated to Fe₂O₃ NRs, which was confirmed through Energy dispersive spectroscopy. Unlike previous high temperature sintering (∼800 °C), Sn doped hematite NRs were obtained at a low temperature (∼650 °C). This occurred since SnO₂ NBs directly connected to Fe₂O₃ NRs are an abundant source of Sn dopant. The 3D hematite NRs on SnO₂ NBs annealed at 650 °C produce a photocurrent density of 0.88 mA/cm² at 1.23 V vs. RHE, which is 3 times higher than that of hematite NRs on a fluorine doped tin oxide (FTO) glass substrate annealed at the same temperature. The enhanced photocurrent is attributed to the improved electrical conductivity of Fe₂O₃ NRs by Sn doping, the efficient electron transport pathway by TCO nanowire and the increased surface area by hierarchically branched structure.     

Effects of Y2O3-modification to Ni/γ-Al2O3 catalysts on autothermal reforming of methane with CO2 to syngas

The effects of Y₂O₃-modification to Ni/γ-Al₂O₃ catalysts on autothermal reforming of methane to syngas were investigated. It was found that the introduction of Y₂O₃ (5%, 8%, 10%) lead to significant improvement in catalytic activity and stability, and the H₂/CO ratio could be adjusted via controlling the O₂/CO₂ ratio of the feed gas. According to the characterization results of catalysts before and after reaction, it was found that the Y₂O₃·γ-Al₂O₃ supported Ni catalysts had higher NiO reducibility, smaller Ni particle size, higher Ni dispersion and stronger basicity than those of the Ni/γ-Al₂O₃ catalysts. The analysis of catalysts after reaction showed that the addition of Y₂O₃ inhibited the Ni sintering, changed the type of coke and decreased the amount of coke on the catalysts. All the experimental results indicated that the introduction of Y₂O₃ to Ni/γ-Al₂O₃ resulted in excellent catalytic performances in autothermal reforming of methane, and Y₂O₃ played important roles in preventing metal sintering and coke deposition via controlling NiO reducibility, Ni particle size and dispersion, and basicity of catalysts.     

CNTs@γ-Fe2O3@C composite electrode for high capacity lithium ion storage

Electrode materials with high specific capacity and cycle stability are the key factors that determine the overall performance of lithium ion batteries (LIBs) for new smart electronic device, and such materials with high performance are still challenging. Here, we report a composite material Carbon nanotube @ Iron oxide @ Carbon (γ-CNTs@γ-Fe₂O₃@C) with coaxial cable structure in hydrothermal method with the assistance of glucose. The as-prepared composite materials show superior electrochemical properties with good rate capability and excellent cycling performance, which show the great potential of CNTs@γ-Fe₂O₃@C for practical production and application in energy devices.     

Isothermal reduction of powdery 2CaO·Fe2O3 and CaO·Fe2O3 under H2 atmosphere

Injection of natural gas into the tuyere raceway of a blast furnace (BF) can effectively decrease the use of coke, as well as reduce CO₂ emission. Therefore, the reduction behaviour of sinters, which account for 60% of the raw materials charged into the BF process under H₂, is important for natural gas utilisation. This study used thermogravimetric analysis under H₂ atmosphere to investigate the reduction kinetics of dicalcium ferrite (2CaO·Fe₂O₃, C₂F) and calcium ferrite (CaO·Fe₂O₃, CF), which are the dominant components in fluxed sinters. Results indicated that CF reduction has a larger maximum reduction degree and a higher reaction constant than C₂F. The apparent activation energy of CF is also larger than that of C₂F, thereby illustrating that C₂F reduction proceeds more easily than CF. X–ray diffraction measurements indicated that C₂F is reduced to CaO and Fe in a single step, whereas CF is reduced with four steps in the following order: CaO·FeO·Fe₂O₃, CaO·3FeO·Fe₂O₃, C₂F and Fe. Sharp and ln–ln methods revealed that C₂F reduction is described by 2D Avrami–Erofeev (A–E) equation and that of CF is expressed by 2D A–E equation but tends slightly to 3D A–E equation in the late stage. A–E equations were verified to be consistent with the experimental reduction degree data of C₂F and CF. A kinetics model that links reduction routes to model functions was proposed to describe the powder reduction of C₂F and CF. Comparisons of the reduction behaviours of C₂F or CF by H₂ and CO implied that the reduction rate rises and activation energy declines during the reduction of samples by H₂.     

Preparation of nano-sized α-Al2O3 from oil shale ash

Oil shale ash (OSA), the residue of oil shale semi-coke roasting, was used as a raw material to synthesize nano-sized α-Al₂O₃. Ultrasonic oscillation pretreatment followed by azeotropic distillation was employed for reducing the particle size of α-Al₂O₃. The structural characterization at molecular and nanometer scales was performed using X-ray diffraction (XRD), transmission electron microscopy (TEM), respectively. The interaction between alumina and n-butanol was characterized by Fourier transform infrared spectroscopy (FT-IR). The results revealed that the crystalline phase of alumina nanoparticles was regular and the well dispersed alumina nanoparticles had a diameter of 50–80 nm. In addition, the significant factors including injection rate of carbon oxide (CO₂), ultrasonic oscillations, azeotropic distillation and surfactant were investigated with respect to their effects on the size of the alumina particles.     

Mechanochemical synthesis of NaBH4 starting from NaH–MgB2 reactive hydride composite system

The present investigation focuses on a new synthesis route of NaBH₄ starting from the 2NaH + MgB₂ system subjected to mechanochemical activation under reactive hydrogen atmosphere. The milling process was carried out under two different hydrogen pressures (1 and 120 bar) with two different rotation speeds (300 and 550 rpm). The reaction products were characterized by ex-situ solid state magic angle spinning (MAS) nuclear magnetic resonance (NMR), ex-situ X-ray powder diffraction (XRPD) and Infrared Spectroscopy (IR). From the results of these analyses, it can be concluded that milling in all the considered conditions led to the formation of NaBH₄ (cubic-Fm-3m). In particular, a reaction yield of 5 and 14 wt% is obtained after 20 h of milling at 120 bar of H₂ for the tests performed at 300 rpm and 550 rpm, respectively. The presence of MgH₂ is also detected among the final products on the as milled powders. The influence of the milling conditions and the evaluation of the parameters related the mechanochemical process are here discussed.     

All-solid-state lithium secondary batteries with oxide-coated LiCoO2 electrode and Li2S–P2S5 electrolyte

All-solid-state lithium secondary batteries using LiCoO₂ active materials coated with Li₂SiO₃ and SiO₂ oxide films and Li₂S–P₂S₅ solid electrolytes were fabricated and their electrochemical performance was investigated. The electrochemical performace of the all-solid-state cells at a high voltage region was highly improved by using oxide-coated LiCoO₂. The oxide coatings are effective in suppressing the formation of an interfacial resistance between LiCoO₂ and the solid electrolyte at a high cutoff voltage of 4.6 V (vs. Li). As a result, charge–discharge capacities and cycle performance at the cutoff voltage were improved. The cell with Li₂SiO₃-coated LiCoO₂ showed a large initial discharge capacity of 130 mAh g⁻¹ and a good capacity retention of 110 mAh g⁻¹ after 50th cycles at the cutoff voltage of 4.6 V (vs. Li).     

New three-dimensional electrode structure for the lithium battery: Nano-sized γ-Fe2O3 in a mesoporous carbon matrix

A new electrode structure based on a three-dimensional mesoporous matrix was developed. Nanoparticles of γ-iron oxide (Fe₂O₃) were introduced into the mesopores of a carbon matrix (mesoporous carbon, CMK-3) by oxidizing metallic iron, which was electroplated in the matrix. The resulting structure was found to have a high charge-discharge capacity when used as the positive electrode of a lithium battery. The iron oxide nanoparticles bonded tightly to the electrically conductive electrode framework, and showed a high activity for the electrochemical reaction: Fe₂O₃ + 6Li → 3Li₂O + 2Fe.     

Improved electrochemical hydrogen storage performance of Ti49Zr26Ni25 quasicrystal alloy by doping with mesoporous α-Fe2O3 particles

A Ti₄₉Zr₂₆Ni₂₅ quasicrystal alloy was prepared by mechanical alloying and subsequent annealing. Mesoporous α-Fe₂O₃ particles were obtained via a hydro-thermal procedure using chitosan as the template. Composites of Ti₄₉Zr₂₆Ni₂₅ mixed with different amounts of mesoporous α-Fe₂O₃ were synthesized to enhance the electrochemical properties of Ti₄₉Zr₂₆Ni₂₅. The structural characteristics of the alloy and composites were investigated using XRD, SEM, TEM and BET analysis. The electrochemical properties of the composite electrodes were tested using a three-electrode battery system at room temperature. The discharge capacities for the composites were higher than those for the Ti₄₉Zr₂₆Ni₂₅ alloy and reached a maximum (259.6 mAh/g) for 5% additive content of α-Fe₂O₃. Moreover, the composites showed enhanced high-rate dischargeability. The capacity decay rate and charge-transfer resistance decreased after α-Fe₂O₃ loading. The preferable performance of the composite alloys may be attributed to the doping of mesoporous α-Fe₂O₃, which may play a catalytic effect in the kinetics of the electrochemical reactions. The large surface area and mesoporous structure of α-Fe₂O₃ may also be advantageous for rapid transmission of hydrogen in the interior of the alloy, thus improving the discharge capacity of the alloy electrode.     

One step hydrothermal synthesis of novel Cu2S-MoO3 nanocomposite for lithium ion battery and photocatalytic applications

Novel Cu₂S-MoO₃ nanocomposite (NC) has been synthesized successfully by single step hydrothermal method. The crystal structure, morphology and optical properties of Cu₂S-MoO₃ NC were individualised by XRD, FTIR, SEM, TEM, UV–Visible spectroscopy. As synthesized Cu₂S-MoO₃ NC was used as anode material for lithium ion battery (LIB) and manifested first discharge capacity 1516 mAhg^?1 at C/4 current rate. Cu₂S-MoO₃ NC is also implemented for photocatalytic hydrogen generation. In addition to above applications, it is materialized for degradation of organic dye (methylene blue) and chromium reduction [Cr(VI) to Cr(III)] with peerless activity.     

Photocured PEO-based solid polymer electrolyte and its application to lithium–polymer batteries

A solid polymer electrolyte (SPE) based on polyethylene oxide (PEO) is prepared by photocuring of polyethylene glycol acrylates. The conductivity is greatly enhanced by adding low molecular weight poly(ethylene glycol) dimethylether (PEGDME). The maximum conducticity is 5.1×10⁻⁴ S cm⁻¹ at 30°C. These electrolytes display oxidation stability up to 4.5 V against a lithium reference electrode. Reversible electrochemical plating/stripping of lithium is observed on a stainless steel electrode. Li/SPE/LiMn₂O₄ as well as C(Li)/SPE/LiCoO₂ cells have been fabricated and tested to demonstrate the applicability of the resulting polymer electrolytes in lithium–polymer batteries.     

Plasma-reduced Ni/γ–Al2O3 and CeO2–Ni/γ–Al2O3 catalysts for improving dry reforming of propane

Pristine Ni/γ–Al₂O₃ and CeO₂–Ni/γ–Al₂O₃ catalysts were prepared by co-impregnation technique for dry reforming of propane. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) were used to examine the structure and morphology of the catalysts before and after the reforming reactions. The excellent interaction between catalyst active phases was observed in both CeO₂–Ni/γ–Al₂O₃ and Ni/γ–Al₂O₃ stabilized with polyethelene glycol (Ni/γ–Al₂O₃–PEG). Towards C₃H₈ and CO₂ conversion, the CeO₂–Ni/γ–Al₂O₃ and Ni/γ–Al₂O₃–PEG showed improved catalytic activity when compared to the pristine Ni/γ–Al₂O₃ catalyst. Interestingly, high H₂ concentration was achieved with the CeO₂–Ni/γ–Al₂O₃ and high CO concentration with the Ni/γ–Al₂O₃–PEG, which is due to the nanoconfinement of nickel particles within the support and favorable metal-support interaction as a result of plasma reduction. The CeO₂–Ni/γ–Al₂O₃ catalyst exhibited better stability for anti-sintering and coke resistance, thus exhibiting high reactivity and durability in the dry reforming.     

A comparative study of dry reforming of methane over nickel catalysts supported on perovskite-type LaAlO3 and commercial α-Al2O3

A systematic and comparative study was made to determine the influence of perovskite-type LaAlO₃ and commercial α-Al₂O₃ on the performance of nickel-based catalysts in dry reforming of methane (DRM). The perovskite-type LaAlO₃ was selected due to its characteristics of solid state semiconductor with oxygen vacancies and high structural stability. The catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), N₂ adsorption-desorption, temperature programmed reduction (TPR-H₂), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The catalyst performance was evaluated based on activity tests (600–800 °C) and short- and long-term stability (10 and 20 h) at 700 °C at a GHSV (Gas Hourly Space Velocity) of 18 and 72 L g^?1 h^?1. The TPR-H₂ profiles indicate that the oxygen vacancies on the perovskite surface exerted a strong effect on the reduction temperature and reducibility of the NiO nanoparticles, resulting in weak Ni⁰/support interaction. The results of the tests after 10 h under GHSV of 18 L g^?1 h^?1 indicate that the Ni/LaAlO₃ catalyst is 7.8 and 11.5% more stable than Ni/α-Al₂O₃ in the conversions of CH₄ and CO₂, respectively. The higher stability and activity of Ni/LaAlO₃ is directly ascribed to the presence of NiO (3.38 wt%) after activation, which promoted the formation of carbon nanotubes (CNT) and increased the dispersion of the metallic phase. Even under severe conditions of activation and reaction (high GHSV), as in the long-term test, the Ni/LaAlO₃ catalyst showed a 37.2% higher H₂ yield than the Ni/α-Al₂O₃. Analyses by TEM indicate that the Ni/α-Al₂O₃ catalyst exhibited deactivation problems associated with sintering effects. Thus, the presence of structural defects and surfaces rich in oxygen vacancies makes LaAlO₃ perovskite a potential support for application in methane catalytic reforming processes.     

Characterization and activity test of commercial Ni/Al2O3, Cu/ZnO/Al2O3 and prepared Ni–Cu/Al2O3 catalysts for hydrogen production from methane and methanol fuels

In this study, methane and methanol steam reforming reactions over commercial Ni/Al₂O₃, commercial Cu/ZnO/Al₂O₃ and prepared Ni–Cu/Al₂O₃ catalysts were investigated. Methane and methanol steam reforming reactions catalysts were characterized using various techniques. The results of characterization showed that Cu particles increase the active particle size of Ni (19.3 nm) in Ni–Cu/Al₂O₃ catalyst with respect to the commercial Ni/Al₂O₃ (17.9). On the other hand, Ni improves Cu dispersion in the same catalyst (1.74%) in comparison with commercial Cu/ZnO/Al₂O₃ (0.21%). A comprehensive comparison between these two fuels is established in terms of reaction conditions, fuel conversion, H₂ selectivity, CO₂ and CO selectivity. The prepared catalyst showed low selectivity for CO in both fuels and it was more selective to H₂, with H₂ selectivities of 99% in methane and 89% in methanol reforming reactions. A significant objective is to develop catalysts which can operate at lower temperatures and resist deactivation. Methanol steam reforming is carried out at a much lower temperature than methane steam reforming in prepared and commercial catalyst (275–325 °C). However, methane steam reforming can be carried out at a relatively low temperature on Ni–Cu catalyst (600–650 °C) and at higher temperature in commercial methane reforming catalyst (700–800 °C). Commercial Ni/Al₂O₃ catalyst resulted in high coke formation (28.3% loss in mass) compared to prepared Ni–Cu/Al₂O₃ (8.9%) and commercial Cu/ZnO/Al₂O₃ catalysts (3.5%).