Highly Conformal Deposition of an Ultrathin FeOOH Layer on a Hematite Nanostructure for Efficient Solar Water Splitting

An ultrathin (ca. 2 nm) amorphous FeOOH overlayer was deposited conformally on a hematite nanostructure by a simple solution‐based precipitation method, to generate an oxygen evolution cocatalyst for efficient solar water splitting. This uniform and highly conformal coating of the ultrathin metal oxyhydroxide is rare and is distinguished from the layers prepared by other conventional methods. With the FeOOH overlayer as the cocatalyst, the water oxidation photocurrent of hematite increased by a factor of approximately two and the onset potential shifted in the cathodic direction by 0.12 V under 1 sun illumination. The enhanced performance was attributed to the improved water oxidation kinetics and the passivation of the surface states of the hematite.     

不同晶化度γ-FeOOH的合成及其液相转化研究

进行了空气氧化Fe(OH)2悬浮液, EDTA作用下可见光诱导, 不同温度(14～20 ℃)制备不同晶化度γ-FeOOH的研究, 进行了其沸腾回流液相转化历程的探讨. 结果表明: 随温度的升高, γ-FeOOH的晶化程度变差; 而γ-FeOOH的晶化程度越差, 在液相沸腾回流时就越易转化成α-Fe2O3, 反之则易转化为α-FeOOH. 在pH近中性, 微量Fe(II)存在条件下低晶态的γ-FeOOH可以快速转化为均匀球形的α-Fe2O3.     

Dynamic measurements of adsorption of hydrolyzed polyacrylamide (HPAM) onto hematite

The adsorption measurements of hydrolyzed polyacrylamide (HPAM) onto hematite suspension are carried out to study the dynamics of the polymer adsorption onto the suspension particles and to investigate the mode of the polymer adsorption. The polymer is found to show much affinity for the adsorption because of the opposite charges possessed by the polymeric flocculant and the suspension particles. Various adsorption parameters such as adsorption coefficient, the rate constants for the adsorption and desorption, are evaluated with the help of a recently proposed kinetic scheme. It is found that the extent of adsorption and the adsorption rate are adequately affected by increasing the pH of the suspension while, unexpectedly, the adsorption is found to show only a marginal increase on addition of Na₂SO₄. Both the amount of the adsorbed polymer and the adsorption rate are also found to increase with the degree of hydrolysis of the polyelectrolyte.     

Aluminium-doped catalysts for the high temperature shift reaction

The replacement of chromium by aluminium in high temperature shift catalysts was investigated. It was found that aluminium-doped hematite is a convenient candidate as an environmental friendly catalyst.     

Influence of Amines on Formation and Texture of Uniform Hematite Particles

The structure and properties of hematite particles obtained by hydrolysis of ferric chloride solution doped with various kinds of amines were examined by TEM, XRD, TG-DTA, N₂and H₂O adsorption, and zeta potential measurements. The shape of precipitates was concentration dependent; they changed from large spheres (diameter: ca. 820 nm) to cubes (edge length: ca. 400 nm) via double-spheres (long axis length: ca. 600 nm) with increasing monoamine concentrations. This effect was enhanced by increasing their pK_avalues. Much pronounced effects of di- and triamines on the particle formation were observed; cubic and double-spherical particles were obtained at a much lower concentration of di- and triamines and small spherical (diameter: ca. 100 nm) and diamond-like (long axis length: ca. 100 nm) particles were further produced at higher concentration. It was suggested that the acceleration of the rate of phase transformation from β-FeOOH to hematite induced by amines plays an important role for producing fairly uniform hematite particles with different shape and size. The hematite particles produced with amines contained small amounts of OH⁻ions in the lattice but were confirmed to be nearly single crystal.     

Precipitation phenomena in FeCl3-NaH2PO2 aqueous solutions at 245°C

Precipitation phenomena in aqueous solutions containing FeCl₃ and NaH₂PO₂ in varying concentrations have been studied at 245 °C. The composition and the morphology of the resulting particles depended strongly on the concentration ratios of the reacting ions. In the presence of small amounts of NaH₂PO₂ only hematite formed of different particle shapes. An increased addition of hypophosphite ions had two effects: first, anions of phosphorus were incorporated in the solids and, second, ferric ions were reduced to ferrous ions giving a variety of products.Supported by the Electric Power Research Institute, Contract RP-966-2.On leave from Yokohama City University, Japan.     

Quasi-2D Monte Carlo simulations of the regime change in the aggregates of magnetic cubic particles on a material surface

We have investigated the aggregate structure of a suspension composed of magnetic particles with a cubic geometry by means of Monte Carlo simulations. From the viewpoint of application to the technology of surface modification, we have considered a quasi-two-dimensional suspension in thermodynamic equilibrium. As the magnetic interaction strength is increased, the effects of the thermal energy are reduced and the particles tend to aggregate together. These aggregates of cubic particles are not chain-like, but are designated as closely packed clusters. An applied magnetic field tends to enhance the formation of clusters along the field direction but does not significantly regularise the internal structure of the cluster. This is mainly due to the preference of a face-to-face contact configuration for the alignment of particles with cubic geometry. The regime of the internal structure of aggregates has a significant effect on the characteristics of the alignment of the magnetic moments with regard to the external magnetic field direction. Our simulations indicate that larger closely packed clusters are formed with increasing volumetric fraction, whereas the internal structure of the closely packed clusters is not found to be significantly influenced by the change in the volumetric fraction.     

Simulations to Cover the Waterfront for Iron Oxide Catalysis

Hematite has been widely studied for catalytic water splitting, but the role of the interactions between catalytic sites is unknown. In this paper, we calculate the oxygen evolution reaction free energies and the surface adsorption distribution using a combination of density functional theory and Monte Carlo simulations to “cover the waterfront,” or cover a wide range of properties with a simulation of the hematite surface under working conditions. First, we show that modeling noninteracting catalytic sites provides a poor explanation of hematite's slow reaction kinetics. The interactions between the catalytic site may hinder catalysis through the strong interactions of *OH₂ and *OOH intermediates, which cause the reaction to revert back to the *O intermediate. Hence, neighboring interactions may be a possible reason for the abundant, experimentally observed *O intermediate on the surface. This study demonstrates how neighboring sites impact the energy required for catalytic steps, thus providing new avenues to improve catalysis by controlling neighboring site interactions.     

Extended light absorption and enhanced photoelectrochemical activity of palladium‐decorated hematite nanotubes prepared by photodeposition method

Palladium particles were deposited on hematite nanotube surfaces via a facile photodeposition method. Anodization method was then used for direct vertical growth of hematite nanotube arrays (HNTs) on a pretreated iron substrate. Field emission scanning electron microscopy, X‐ray diffraction, diffraction reflection spectroscopy and X‐ray photoelectron spectroscopy analyses were then used to carry out morphological and structural investigations. Compared with the bare HNTs, Pd‐decorated hematite films (Pd/HNTs) exhibit intense visible light absorption and show a red shift of the band edge. Pd/HNTs are more photoelectrochemically active than the non‐decorated films, according to chronoamperometry measurements. Thus, a promising methodology has been developed for the design of a simple and effective photoelectrode for application in photoelectrochemical water splitting systems.     

Iron ore sintering

Differential scanning and high temperature reaction calorimetry have been used to characterize a series of natural iron ore and flux samples commonly used during iron ore sintering. Most iron ore samples were shown to contain measurable quantities of goethite, with a characteristic dehydration peak in DSC and TG between 200 and 400°C. At higher temperatures, all samples decomposed to produce magnetite with an accompanying mass loss in the TG profile due to the evolution of oxygen. High temperature reaction calorimetry has been used to measure the heat of solution of the ore in the melt formed during iron ore sintering. The dehydration and calcination of iron ore and flux samples was also examined using high-temperature reaction calorimetry. The results support the DSC/TG findings.