A turbidimetric method to measure isoelectric points and particles deposition onto massive substrates

A simple experimental approach was developed to determine the adhesion rate of particles onto massive substrate. Turbidimetry measurements are used to follow the evolution of particle concentration in a suspension in dynamic contact with the walls of a vessel made of different materials. This method allows to rapidly obtain qualitative results about the adhesion of metallic oxides particles on massive substrates. Adhesion of particles of charged latex onto glass was used to validate the approach and was shown to be a method to determine isoelectric points (IEP) of massive substrates. Then, the adhesion of an iron oxide (hematite) particles onto several substrates was studied to determine the reactivity of current labware (glass, polypropylene) and on a metal (aluminum) commonly found in industrial fouling problems. Adhesion of hematite was found to be pH-dependant, and occurs only below ca. 6 (glass) or 7 (polypropylene), and above 7 (aluminum). DLVO calculations were performed to model the hematite/water/glass system and are consistent with the experimental results. Experiments at temperature 7–50 °C have shown an increasing of the adhesion rate from 7 to 40 °C, then a constant value until 50 °C.     

Development of chromium-free iron-based catalysts for high-temperature water-gas shift reaction

Chromium-free iron-based catalysts were prepared and studied in regard to their performance in the high-temperature water-gas shift reaction (HTS). The effects of various catalyst preparation variables (i.e., Fe/promoter ratio, pH of precipitation medium, calcination and reduction temperatures) and preparation methods were investigated. Aluminum is a potential chromium replacement in HTS catalysts. Further improvement in WGS activity of Fe–Al catalysts can be achieved by the addition of small amounts of copper or cobalt. Catalysts were characterized using BET surface area measurements, temperature-programmed reduction (TPR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). As a textural promoter, aluminum and chromium prevent the sintering of iron oxides and stabilize magnetite phase by retarding its further reduction to FeO and metallic Fe. The promotional effect of Cu is found to be strongly dependent on the preparation method.     

Characterization of colloidal hematite particle shape and dispersion behavior

An elliptically polarized light scattering (EPLS) technique for the size and shape characterization of ellipsoidal hematite particles is presented. The hematite particles are synthesized by aging aqueous FeCl(3) or Fe(NO(3))(3) solutions at 100 degrees C. Different reaction conditions create particles of aspect ratios between 1 (spherical) and 8 (elongated). Cross-sectional diameter and aspect ratio are observed as a function of reaction (aging) time. Growth of the elongated particles, as well as their fractal aggregation behavior, is characterized using EPLS and comparisons are made with photon correlation spectroscopy and TEM measurements.     

Prospects of electrochemically synthesized hematite photoanodes for photoelectrochemical water splitting: A review

Hematite (α-Fe₂O₃) is found to be one of the most promising photoanode materials used for the application in photoelectrochemical (PEC) water splitting due to its narrow band gap energy of 2.1 eV, which is capable to harness approximately 40% of the incident solar light. This paper reviews the state-of-the-art progress of the electrochemically synthesized pristine hematite photoanodes for PEC water splitting. The fundamental principles and mechanisms of anodic electrodeposition, metal anodization, cathodic electrodeposition and potential cycling/pulsed electrodeposition are elucidated in detail. Besides, the influence of electrodeposition and annealing treatment conditions are systematically reviewed; for examples, electrolyte precursor composition, temperature and pH, electrode substrate, applied potential, deposition time as well as annealing temperature, duration and atmosphere. Furthermore, the surface and interfacial modifications of hematite-based nanostructured photoanodes, including elemental doping, surface treatment and heterojunctions are elaborated and appraised. This review paper is concluded with a summary and some future prospects on the challenges and research direction in this cutting-edge research hotspot. It is anticipated that the present review can act as a guiding blueprint and providing design principles to the scientists and engineers on the advancement of hematite photoanodes in PEC water splitting to resolve the current energy- and environmental-related concerns.     

提高氧化铁光电催化分解水效率的策略进展

为了解决能源危机与环境污染问题,发展一种可再生的清洁能源至关重要.太阳能是一种取之不尽用之不竭的清洁能源,而氢气是一种良好的能源载体.利用太阳能光电催化水分解制氢,是一项有望能够解决能源与环境问题的技术,具有很大的应用前景.其中,氧化铁因为具有合适的能带位置与带隙、良好的稳定性与廉价无毒等优点,成为一种理想的光阳极材料.但是,在实际的测试中,氧化铁仅仅只能得到一个较低的光电转换效率,这可能是因为其较短的空穴扩散距离、较低的电导率以及极度缓慢的水氧化反应动力学所致.整个光电催化水氧化可分为三个过程,即光吸收过程、电荷分离过程以及表面空穴注入过程.这三个过程的效率共同决定了器件的太阳能转化效率.鉴于此,本文将从如何提高这三个效率的角度出发,总结近期研究报道中提高氧化铁光电催化分解水效率的一些策略.光吸收过程是指半导体中价带的电子在吸收具有一定能量的光子后发生跃迁,产生空穴-电子对的过程.其光子的损失主要来源于光的反射、透射以及半导体吸收边的限制.提高光吸收效率的主要策略包括制备具有特定纳米结构的氧化铁电极、利用表面等离子体共振效应以及组成双光吸收系统和掺杂等.电荷分离过程指的是受光激发产生的空穴电子对,在内建电场的作用下发生电荷分离,即光生空穴流向电极表面,光生电子流向半导体内部并从外电路导出.电荷分离效率的损失主要来源于光生载流子在迁移过程中的复合.因此,为了提高电荷分离效率,常见的策略是提高载流子在电荷分离过程中的复合时间τ₁和减少电荷迁移到表面(空穴)或者基底(电子)的时间τ₂.具体的策略包括制备特定的纳米结构(缩短体表相距离,减少τ₂)、构建异质结(增强能带弯曲,提高τ₁和减少τ₂)、掺杂(减少τ₂)和钝化复合中心(提高τ₁)等.表面空穴注入是指到达表面的光生空穴发生水氧化反应生成氧气的过程.除了空穴注入外,表面还可能存在复合与逆反应过程.因此,为了提高表面空穴注入效率,我们既可以提高水氧化反应动力学,具体的手段包括引入水氧化催化剂、F掺杂和碱处理等;也可以采用减少复合反应的策略,具体的方法包括引入钝化层、酸处理和高温热处理等;还可以采用减少逆反应的方法,最常见的手段就是在基底与氧化铁层之间引入电子阻挡层.上述三种途径都能提高表面空穴注入效率.最后,通过结合上述的一些策略,目前得到的最高性能的氧化铁电极在1.23 V(相对于可逆氢电极)能够达到6 mA cm^?2的光电催化分解水电流,但这个值依然明显低于氧化铁的理论值(12.6 mA cm^?2).这可能是由于体相复合所致.除此之外,氧化铁表面的水氧化机理现在依然不清晰,这些都是需要我们在未来解决的问题.     

A co-activation strategy for enhancing the performance of hematite in photoelectrochemical water oxidation

Hematite(α-Fe_2O_3) is a promising photoanode for photoelectrochemical(PEC) water splitting.However,the severe charge recombination and sluggish water oxidation kinetics extremely limit its use in photohydrogen conversion.Herein,a co-activation strategy is proposed,namely through phosphorus(P)doping and the loading of CoAl-layered double hydroxides(CoAl-LDHs) cocatalysts.Unexpectedly,the integrated system,CoAl-LDHs/P-Fe_2O_3 photoanode,exhibits an outstanding photocurrent density of 1.56 mA/cm~2 at 1.23 V(vs.reversible hydrogen electrode,RHE),under AM 1.5 G,which is 2.6 times of pureα-Fe_2O_3.Systematic studies reveal that the remarkable PEC performance is attributed to accelerated surface OER kinetics and enhanced carrier separation efficiency.This work provides a feasible strategy to enhance the PEC performance of hematite photoanodes.     

Detection of Dexamethasone Sodium Phosphate in Blood Plasma: Application of Hematite in Electrochemical Sensors

We studied sensor application of a graphene oxide and hematite (α‐Fe₂O₃/GO) composite electrode well‐characterized by the SEM and XRD. Through differential pulse voltammetry (DPV), oxidation of dexamethasone sodium phosphate (DSP) was studied at the surface of a glassy carbon electrode (GCE) modified with graphene oxide nanosheets (GO) and the α‐Fe₂O₃/GO composite. The values of the transfer coefficient (α) and the diffusion coefficient (D) of DSP were 0.5961 and 4.71×10^?5 cm² s^?1 respectively. In the linear range of 0.1–50 μM, the detection limit (DL) was 0.076 μM. In the second step, a GCE was modified with α‐Fe₂O₃/GO composite and the DSP measurement step was repeated to analyzed and compare the effects of hematite nanoparticles present on graphene oxide surfaces. According to the results, α and D were 0.52 and 2.406×10^?4 cm² s^?1 respectively and the DL was 0.046 μM in the linear range of 0.1–10.0 μM. The sensor is simple, inexpensive and uses blood serum.     

The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the anionic media

The transformation from ferrihydrite to various iron oxides and iron oxyhydroxides has been given much attention not only in environmental science and geochemistry but also in biology and material science. This laboratory study attempted to investigate Fe(II)-induced transformation of ferrihydrite in sulfate-rich medium. The results indicate that the transformation in sulfate-rich medium differs from that in Cl⁻ medium in the species, the amount and the morphology of products and transformation rate. Lepidocrocite is a main ingredient in the product in Cl⁻ medium at room temperature (RT), while goethite is the only product in SO₄²⁻ medium at RT. Goethite particles obtained in Cl⁻ medium are star-like but rod-like in SO₄²⁻ medium. The transformation rate in the latter medium is obviously slower than that in the former medium. The formation of lepidocrocite depends on both the ionic strength of the system and the dissolution rate of ferrihydrite.     

Influence of Sn and Sn/Mg doping on structural features and visible absorption properties of α-Fe2O3 hematite

Pure, Sn-doped and Mg/Sn co-doped α-Fe₂O₃ hematite samples were synthesized by precipitation process. Fe₂O₃ is the most popular red mineral pigment which is used largely in traditional ceramics, tar and concrete. The compounds were characterized by powder X-ray diffraction (XRD), scanning transmission electronic microscopy (energy dispersive X-ray cartography), Mössbauer spectroscopy, magnetic investigations versus temperature and visible-NIR spectroscopy. Both ⁵⁷Fe and ¹¹⁹Sn Mössbauer analyses combined with rietveld XRD refinements are the ideal techniques to characterize tin-iron oxides. Hence, thanks to these techniques it was shown how the synthesis temperature influences directly the grain size and the dopants concentration limit which can be incorporated into the host hematite matrix. The stabilization of these tetravalent and divalent dopants into the hematite framework leads to reduce the crystal growth and to limit the (AF) ordering due to the formation of cationic vacancies. The study of the Morin magnetic transition emphasizes this demonstration. In a second part, the influence of the dopants incorporation on the material color was investigated in order to show which key parameters allow improving the red color saturation of iron oxides. In order to improve the red color of the hematites, it was shown that the introduction of cationic vacancies—limiting the octahedral distortion thanks to the interruption of the dissymmetric metal-metal orbital coupling—is the key point. Vacancies are created by Sn⁴⁺, doping for an increase of the introduced Sn⁴⁺ concentration; it acts to the detriment of the color saturation.     

Synthesis and Characterization of Uniform Fine Particles of Iron(III) Hydroxide/Oxide

Iron(III) hydroxide was precipitated from the homogeneous solutions, containing variuos amounts of iron(III) nitrate, potassium sulfate, and urea, by heating at 85 °C for different periods of time (5‐30 min). The precipitated solids were either in the form of gel or dispersed particles of different shapes and sizes, depending upon the composition of the reactant mixtures. The as‐prepared solids were amorphous in nature and were formulated as Fe(OH)₃.H₂O. On calcinations at 800 °C for 1 h, the latter converted into crystalline compound, composed of α‐Fe₂O₃ (hematite). The calcined particles retained the original features of their precursors to a maximum extent.