Pressure-induced phase transitions for goethite investigated by Raman spectroscopy and electrical conductivity

We reported two pressure-induced phase transitions of goethite up to ～35?GPa using a diamond anvil cell in conjunction with ac impendence spectroscopy, Raman spectra at room temperature. The first pressure-induced phase transition at ～7.0?GPa is manifested in noticeable changes in six Raman-active modes, two obvious splitting phenomena for the modes and the variations in the slope of conductivity. The second phase transition at ～20?GPa was characterized by an obviously drop in electrical conductivity and the noticeable changes in the Raman-active modes. The variations in activation energy with increasing pressure were also discussed to reveal the electrical properties of goethite at high pressure.     

Goethite nanorods as anode electrode materials for rechargeable Li-ion batteries

Although various transition metal oxides have been reported to act as low potential Li insertion hosts, the oxyhydroxides have remained unexplored to date. We show here that the hydroxide ions present in transition metal oxyhydroxides do not interfere with the lithium uptake and extraction, permitting very good reversibility of the reduction/oxidation reactions. Goethite (α-FeOOH) nanocrystals can uptake and extract large amount of Li via the conversion reaction mechanism, providing a reversible capacity of 500 mA h g⁻¹ at an average potential of 0.85 V vs. Li/Li⁺. The mechanism was examined using a combination of X-ray diffraction, electron microscopy, and the corresponding selected area electron diffractions (SAEDs). The α-FeOOH is reduced into nanoparticles of metallic Fe⁰ embedded in an amorphous matrix of Li₂O and LiOH in the first discharge; the subsequent cyclings are redox reactions between metallic Fe⁰ and Fe₂O₃ clusters.     

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.     

Ultrasonic assisted arsenate adsorption on solvothermally synthesized calcite modified by goethite, α-MnO2 and goethite/α-MnO2

A highly porous calcium carbonate (calcite; sorbent 1) was used as a support for modification with α-FeOOH (calcite/goethite; sorbent 2), α-MnO₂ (calcite/α-MnO₂; sorbent 3) and α-FeOOH/α-MnO₂ (calcite/goethite/α-MnO₂; sorbent 4) in order to obtain a cheap hybrid materials for simple and effective arsenate removal from aqueous solutions. The adsorption ability of synthesized adsorbents was studied as a function of functionalization methods, pH, contact time, temperature and ultrasonic treatment. Comparison of the adsorptive effectiveness of synthesized adsorbents for arsenate removal, under ultrasound treatment and classical stirring method, has shown better performance of the former one reaching maximum adsorption capacities of 1.73, 21.00, 10.36 and 41.94 mg g⁻¹, for sorbents 1–4, respectively. Visual MINTEQ equilibrium speciation modeling was used for prediction of pH and interfering ion influences on arsenate adsorption.     

由27Al的核磁共振谱看高岭土与针铁矿的胶结本质

通过对高岭土与针铁矿的人工胶结样的²⁷ Al核磁田共振谱的分析,认为氢键生成是胶结本质。     

The role of Pb ions doping in the mechanism of chromate adsorption by goethite

Pure and 0.384% Pb²⁺ ions doped goethite samples were prepared in the laboratory by the coprecipitation method. The laboratory-prepared goethite samples were characterized for pH of point of zero charge (pH_pzc), surface area, XRD, TG-DTA, TEM, SEM and FTIR analysis, which suggest that the Pb²⁺ ions are incorporated into the crystals of goethite and are also present on the surface in the hydroxylated form. Chromate adsorption studies were carried out in the concentration range 0.25-2.01 mmol L⁻¹ at pH 3, 5 and 7, which show that maximum chromate is adsorbed at the lowest pH of 3 by both the samples of goethite. Effect of temperature on the adsorption of chromate, in the range 303-323 K, shows that the process of adsorption is endothermic in case of pure goethite and exothermic in case of Pb-doped goethite. The values of isosteric heat of adsorption were positive for pure goethite and negative for Pb-doped goethite, which are consistent with the effect of temperature on the process of adsorption. Langmuir isotherm was found applicable to the experimental data. FTIR analysis and equilibrium pH changes reveal that at pH 3 outersphere while at pH 5 and 7 innersphere complexation is the dominant mechanism for chromate adsorption by both the samples of goethite.     

Effect of fulvic acid on neodymium uptake by goethite

Experimental studies of the interaction of aqueous neodymium (Nd), Suwannee River fulvic acid (FA), and solid phase goethite were conducted. Results from blank systems (individual Nd and FA), binary systems (Nd-goethite, FA-goethite, and Nd-FA), and ternary systems (Nd-FA-goethite) at 0.1 mol/kg and 25 °C are reported.In the binary Nd-goethite system a classic sorption edge is observed, whereby virtually all Nd is removed from solution above the goethite point of zero charge (PZC). Similarly, the binary FA-goethite system exhibits strong FA sorption; However in this system near complete removal of FA from solution is observed below the goethite PZC. In the binary Nd-FA system, both aqueous Nd and FA feature a sharp decrease in concentration at ca. pH 9.Various experiments in the ternary system were conducted. For all concentrations, FA enhanced Nd sorption below the goethite PZC, attributed to the formation of a Type B ternary surface complex (mineral-ligand-metal ion). Notably, the 100 ppm FA ternary system showed anomalously high dissolved Nd in solution above the PZC (i.e., Nd sorption suppression) and a concomitant increase in goethite dissolution (∼9 ppm total Fe³⁺ observed above circa pH 9.5).Our results suggest that Nd-FA complexation plays a key role in Nd uptake by goethite, and that this process is largely governed by pH: Whereas at pHs below the goethite PZC, Nd-FA complexation facilitates Nd sorption, above the PZC, and particularly at elevated FA concentrations, the formation of aqueous Nd-FA complexes suppresses Nd removal. Moreover, under these conditions, goethite dissolution may also play a role in mitigating Nd uptake by goethite.     

和田玉糖玉的致色机理研究

采用X射线粉晶衍射(XRD)、激光剥蚀等离子体质谱(ICP-MS)、拉曼光谱(RAMAN)和高分辨率透射电子显微镜(HRTEM)对和田玉糖玉的致色机理进行研究。结果显示,糖玉的主要矿物成分为透闪石,化学成分中的Fe含量和糖玉黄褐色色调有正相关关系,颜色越深Fe的含量越高,Fe在糖玉中以独立铁质矿物的赋存形式分布于透闪石的颗粒间、微裂隙中。铁质矿物由于其含量低、粒度细小,本文设计实验对其进行富集后进行测试。将铁质矿物富集后的样品进行透射电镜测试,铁质矿物呈云状集合体,电子花样衍射图显示其矿物为针铁矿。因此,针铁矿分布于透闪石颗粒间、微裂隙中致使糖玉呈现黄褐色。拉曼光谱显示糖玉表面少见红褐色矿物颗粒为金红石,由于金红石含量少,仅对颜色成因有部分贡献。     

二氧化钛与针铁矿复合光催化材料的制备与光催化性能

以四氯化钛为钛源,针铁矿(α-FeOOH)为载体,采用水解沉淀法制备了金红石相二氧化钛(Ti₂O)与α-FeOOH的复合光催化材料,并采用X射线衍射、扫描电子显微镜、透射电子显微镜、X射线能量散射谱和X射线光电子能谱对样品进行了表征.结果表明,低温下,金红石相Ti₂O包覆于α-FeOOH表面,并形成复合结构;较高温下,铁离子进入金红石相Ti₂O晶格,并形成铁掺杂金红石相Ti₂O纳米管;中温下,样品兼有复合和掺杂两者特征.在室温下以甲基橙为降解对象,采用钨灯+氘灯(波长200~800nm)为光源,对样品的光催化活性进行了测试.结果表明,样品对甲基橙的光催化降解效果良好;与纯α-FeOOH和金红石相Ti₂O相比,不同结构样品的光催化活性均有所提高,其中,复合兼掺杂型样品的光催化活性最高.由此可见,与α-FeOOH复合和铁掺杂是提高Ti₂O光催化活性的有效途径.     

高岭土与针铁矿胶结样中27Al、29Si NMR谱与其原子电荷关系

由NMR谱实验得高岭土与针铁矿胶结样中²⁷Al、²⁹Si的化学位移较单一高岭土分别正移了2.7ppm和2.33ppm.由CNDO/2方法计算得到胶结样中Al、Si原子电行比高岭土分别减少了0.0787和0.0286.胶结样中Al、Si原子电荷的减少与²⁷Al、²⁹Si NMR谱化学位移相吻合,可以认为在高岭土与外铁矿的界面上形成了氢键而呈现胶结态.