Synthesis of bis(indolyl) methanes using aluminiumoxide(acidic) in dry media

Heterogeneous catalyst aluminium oxide(acidic) is found to be an effective catalyst for the solvent-free condensation reaction of indole with aldehydes in microwave irradiation with shorter reaction time and higher yields.

Oxidation of As^Ⅲ by Several Manganese Oxide Minerals in Absence and Presence of Goethite

Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals of different types, birnessite, todorokite, and hausmannite, could actively oxidize As^Ⅲ to Asv, and greatly varied in their oxidation ability. Layer structured birnessite exhibited the highest capacity of As^Ⅲ oxidation, followed by the tunnel structured todorokite. Lower oxide hansmannite possessed much low capacity of As^Ⅲ oxidation, and released more Mn^2＋ than birnessite and todorokite during the oxidation. The maximum amount of Asv produced during the oxidation of As^Ⅲ by Mn oxide minerals was in the order： birnessite （480.4 mmol/kg） 〉 todorokite （279.6 mmol/kg） 〉 hansmannite （117.9 mmol/kg）. The oxidation capacity of the Mn oxide minerals was found to be relative to the composition, crystallinity, and surface properties. In the presence of goethite oxidation of As^Ⅲ by Mn oxide minerals increased, with maximum amounts of Asv being 651.0 mmol/kg for birnessite, 332.3 mmol/kg for todorokite and 159.4 mmol/kg for hansmannite. Goethite promoted As^Ⅲ oxidation on the surface of Mn oxide minerals through adsorption of the Asv produced, incurring the decrease of Asv concentration in solutions. Thus, the combined effects of the oxidation （by Mn oxide minerals）-adsorption （by goethite） lead to rapid oxidation and immobilization of As in soils and sediments and alleviation of the As^Ⅲ toxicity in the environments.

In-situ electrochemical study on the eff ects of Fe(Ⅲ)on kinetics of pyrite acidic pressure oxidation

Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.

Eu(Ⅲ) complexes involving 1,3,5-triazine diphosphine oxides

The 1,3,5-triazine diphosphine oxide ligands with donor-acceptor properties formed strong complexes with europium（Ⅲ） ion in acetonitrile. Spectrophotometric titrations and mass spectra indicated that two ligands coordinated to one europium ion. The stability constants varied from 11.64 to 14.60 （log 13）. Binary complexes exhibited rather weak luminescence in solution. 1,3,5-triazine diphosphine oxides engaged as co-ligands in Eu（Ⅲ） （2-thenoyltrifluoroacetonate）3 complex contributed to the overall photoluminescence and allowed for excitation with longer wavelengths than the parent complex.

腐殖质对电絮凝体系中As(Ⅲ)氧化去除的影响机制

电絮凝技术可以通过二价铁[Fe(Ⅱ)]的氧化沉淀机制高效氧化去除地下水中的As(Ⅲ)。天然有机质(NOM)广泛存在于高砷地下水中,可能通过络合、电子穿梭、竞争吸附位点等多种途径影响Fe(Ⅱ)的氧化沉淀,但目前天然有机质对电絮凝体系中As(Ⅲ)氧化去除的影响规律和机制尚不清楚。以腐殖酸(humic acid,HA)作为天然有机质的代表,研究了腐殖质对电絮凝体系中As(Ⅲ)氧化去除的影响规律和机制。结果表明:(1)HA可以促进电絮凝体系中Fe(Ⅱ)的氧化沉淀和As(Ⅲ)的氧化去除,且HA浓度越高,促进效果越显著;(2)在不同pH值(6.0、6.5、7.0、7.5)以及不同电解质环境下,HA对Fe(Ⅱ)氧化沉淀和As(Ⅲ)氧化去除的影响有显著的差异,pH值越低HA促进As(Ⅲ)氧化去除的效果越显著,在Na2SiO3电解质环境下HA对As(Ⅲ)的氧化去除作用最为显著;(3)HA促进电絮凝体系中As(Ⅲ)氧化去除的机制是通过加速水相Fe(Ⅱ)的氧化促进Fe的沉淀,从而使Fe(Ⅱ)的氧化沉淀过程主导As(Ⅲ)的氧化和去除。研究结果可为高砷地下水修复提供理论指导。

Aluminum(Ⅲ) triflate-catalyzed selective oxidation of glycerol to formic acid with hydrogen peroxide

Glycerol is a by-product of biodiesel production and is an important readily available platform chemical.Valorization of glycerol into value-added chemicals has gained immense attention.Herein,we carried out the conversion of glycerol to formic acid and glycolic acid using H2O2 as an oxidant and metal(Ⅲ)triflate-based catalytic systems.Aluminum(Ⅲ)triflate was found to be the most efficient catalyst for the selective oxidation of glycerol to formic acid.A correlation between the catalytic activity of the metal cations and their hydrolysis constants(Kh)and water exchange rate constants was observed.At 70 ℃,a formic acid yield of up to 72% could be attained within 12 h.The catalyst could be recycled at least five times with a high conversion rate,and hence can also be used for the selective oxidation of other biomass platform molecules.Reaction kinetics and 1H NMR studies showed that the oxidation of glycerol(to formic acid)involved glycerol hydrolysis pathways with glyceric acid and glycolic acid as the main intermediate products.Both the [Al(OH)x]^n+ Lewis acid species and CF3SO3H Brosted acid,which were generated by the in-situ hydrolysis of Al(OTf)3,were responsible for glycerol conversion.The easy availability,high efficiency,and good recyclability of Al(OTf)3 render it suitable for the selective oxidation of glycerol to high value-added products.

Cr(Ⅲ) removal from simulated solution using hydrous magnesium oxide coated fly ash： Optimization by response surface methodology (RSM)

Hydrous magnesium oxide coated fly ash （MFA） has environmental remediation potential by providing a sub- strate for the adsorption of aqueous Cr（Ⅲ）. Aqueous Cr（Ⅲ） adsorption onto MFA was examined as a function of MFA dosage, pH and initial Cr（Ⅲ） concentration with the Box-Behnken approach used for experimental design and optimization using response surface methodology （RSM）. pH and dosage （dosage and concentration） have significant interactive effects on Cr（Ⅲ） adsorption efficiency. Analysis of variance shows that the response surface quadratic model is highly significant and can effectively predict the experimental outcomes. Cr（Ⅲ） removal effi- ciency of 98% was obtained using optimized conditions of MFA dosage, pH and initial Cr（Ⅲ） concentration of 1,5 7 g. L- 1, 4.11 and 126 mg. L- 1, respectively. Cr（Ⅲ） adsorption onto MFA is mainly attributed to the interaction between Or（Ⅲ） and the functional group --OH of the hydrous magnesium oxide, in all probability caused by chemisorptions. The results of this study can conduce to reveal the interactions between Cr（Ⅲ） pollutant and MFA characteristics, posing important implications for the cost-effective alternative adsorption technology in the treatment of heavy metal containing wastewater.

Mechanical and Abrasive Wear Properties of Anodic Oxide Layers Formed on Aluminium

Aluminium oxide coatings were formed on aluminium substrates in oxalic acid-sulphuric acid bath. Abrasion tests of the obtained anodic layers were carried out on a pin-on-disc machine in accordance with the ISO/DP 825 specifications. The rickets microhardness, D （HV0.2）, and the abrasion weight loss, Wa （mg） were measured. Influence of oxalic acid concentration （Cox）, bath temperature （T） and anodic current density （J） on D and Wa has been examined, and the sulphuric acid concentration （Csul） was maintained at 100 g.L-1. It was found that high microhardness and abrasive wear resistance of oxide layers were produced under low temperatures and high current densities with the addition of oxalic acid. The morphology and the composition of the anodic oxide layer were examined by scanning electron microscopy （SEM）, atomic force microscopy （AFM）, optical microscopy and glow-discharge optical emission spectroscopy （GDOES）. It was found that the chemistry of the anodizing electrolyte, temperature, and current density are the controlling factors of the mechanical properties of the anodic oxide layer.

Deposition of Aluminium Oxide Films by Pulsed Reactive Sputtering

Pulsed reactive sputtering is a novel process used to deposit some compound films, which are not deposited by traditional D.C. reactive sputtering easily. In this paper some experimental results about the deposition of Al oxide films by pulsed reactive sputtering are presented. The hysteresis phenomenon of the sputtering voltage and deposition rate with the change of oxygen flow during sputtering process are discussed.

Electrospark Coatings Based on WC-Co Alloys with Aluminium Oxide and Carbon Additives

The structure and properties of coatings based on WC-Co alloys containing additives of 1% - 5% aluminium oxide and 2.5% - 4.5% carbon were investigated. The coatings had a nanocrystalline structure. Depending on the duration and frequency of the discharge pulses, the ratio between WC and W2C in the coatings was different. The additives in the hard alloy allowed us increase the microhardness and wear resistance of the coatings by a factor of 2 - 3 in comparison to coatings created using a conventional WC-10%Co alloy.

Characteristics of Magnesium-iron-aluminium Composite Oxides and Their Influence on Properties of Magnesia-based Bricks

The composition,structure and micro-morphology of magnesium- iron- aluminum composite oxides were investigated using various methods such as XRF,SEM,EDS,XRD and KMn O4-titration. Compared to hercynite,the composite oxides have completely different phases including solid solution（ Mg O）0. 77（ Fe O）0. 23,composite spinel Mg Fe0. 2Al1. 8O4 and a small amount of Mg Fe2O4. The composite oxides exhibit excellent corrosion resistance to cement clinker and potassium salts.The products produced by magnesite and the composite oxides show better performance than magnesia- hercynite bricks,especially the corrosion resistance and thermal shock resistance.

Microstructure and mechanical properties of ceramic coatings formed on 6063 aluminium alloy by micro-arc oxidation

The microstructure and mechanical properties of ceramic coatings formed on 6063 aluminium alloy obtained in silicate-,borate- and aluminate-based electrolyte without and with nanoadditive Al2O3 and TiO2 by micro-arc oxidation（MAO） were studied by scanning electron microscopy（SEM）,energy-dispersive X-ray spectroscopy（EDS）,X-ray diffraction（XRD）,microhardness and friction-abrasion tests,respectively.SEM results show that coatings with nanoadditive have less porosities than those without nanoadditive.XRD results reveal that nanoadditive-containing coatings contain more oxides compared with nanoadditive-free coatings in all cases,which are consistent with the EDS analysis.Mechanical properties tests show that nanoadditive Al2O3-containing coatings have higher microhardness values compared with the other coatings obtained in silicate-,borate- and aluminate-based electrolyte.On the other hand,nanoadditive has a positive effect on improving the wearing-resistance of MAO coatings in all cases.Furthermore,the borate-MAO coatings present an inferior anti-wearing property compared with the silicate- and aluminate-MAO coatings for both the nanoadditive-free and nanoadditive-containing coatings.

Arsenite oxidation by three types of manganese oxides

Oxidation of As（Ⅲ） by three types of manganese oxides and the effects ofpH, ion strength and tartaric acid on the oxidation were investigated by means of chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals, bimessite, cryptomelane, and hausmannite, which widely occur in soil and sediments, could actively oxidize As（Ⅲ） to As（Ⅴ）. However, their ability in As（Ⅲ）-oxidation varied greatly depending on their structure, composition and surface properties. Tunnel structured cryptomelane exhibited the highest ability of As （Ⅲ） oxidation, followed by the layer structured birnessite and the lower oxide hausmannite. The maximum amount of As （Ⅴ） produced by the oxidation was in the order （mmol/kg） of cryptomelane （824.2） 〉 bimessite （480.4） 〉 hausmannite （117.9）, As pH increased from the very low value（pH 2.5）, the amount of As（Ⅲ） oxidized by the tested Mn oxides was firstly decreased, then negatively peaked in pH 3.0 6.5, and eventually increased remarkably. Oxidation of As（Ⅲ） by the Mn oxides had a buffering effects on the pH variation in the solution. It is proposed that the oxidative reaction processes between As （Ⅲ） and biruessite（or cryptomelane） are as follows： （1） at lower pH condition： （MnO2）x＋ H3AsO3 ＋ 0.5H^＋=0.5H2AsO4^- ＋ 0.5HAsO4^2- ＋Mn〉^2＋ （MnO2）x-1 ＋ H2O; （2） at higher pH condition： （MnO2）x ＋ H3AsO3 = 0.5H2AsO4^- ＋ 0.5HAsO4^2- ＋ 1.5H^＋ ＋ （MnO2）x-1. MnO. With increase of ion strength, the As（Ⅲ） oxidized by bimessite and cryptomelane decreased and was negatively correlated with ion strength. However, ion strength had little influence on As （Ⅲ） oxidation by the hausmarmite. The presence of tartaric acid promoted oxidation of As（Ⅲ） by birnessite. As for cryptomelane and hansmannite, the same effect was observed when the concentration of tartaric acid was below 4 mmol/L, otherwise the oxidized As（Ⅲ） decreased. These findings are of great significance in improving our understanding of As geochemical cycling and controlling As contamination.

Optimizing the micro-arc oxidation (MAO) parameters to attain coatings with minimum porosity and maximum hardness on the friction stir welded AA6061 aluminium alloy welds

Micro-arc oxidation(MAO) technique is capable of producing dense oxide films on the aluminium alloy surface. This oxide film protects the aluminium alloy from the corrosion attack for longer duration.Empirical relationships were derived to evaluate the MAO coating properties(porosity and hardness) by incorporating very important MAO parameters(current density, inter-electrode distance and oxidation time). MAO parameters were also optimized to achieve coatings with minimum porosity and maximum hardness. Further, the effect of MAO parameters on coating characteristics was analysed. From the results, it is found that the current density has greater influence on the responses than the other two parameters.

Role of Bismuth Oxide in Bi-MCo_2O_4(M=Co,Ni,Cu,Zn) Catalysts for Wet Air Oxidation of Acetic Acid

Two series of cobalt(Ⅲ)\|containing spinel catalysts were prepared by the decomposition of the corresponding nitrates. The catalysts doped with bismuth oxide exhibit a higher activity in the wet air oxidation of acetic acid than those without dopant bismuth oxide. The catalysts were investigated by XRD,TEM,ESR,UV\|DRS and XPS,and the interaction between Co and Bi was studied as well. It has been found that nano\|sized bismuth oxide is paved on the surface of cobalt spinel crystal and the structures of cobalt(Ⅲ)\|containing spinel are still maintained. The shift of the binding energy of Bi\-\{\%4f\%\-\{7/2\}\} is related to the catalytic activity of these catalysts doped with bismuth oxide.

Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.

A Composite Catalytic Oxidation-fluorescence Sensing System for 2,4-dichlorophenol Analysis based on Fe(Ⅲ)PcTs-BuOOH-CdTe QDs

The active oxygen species in the catalytic oxidation system of Fe(Ⅲ)PcTs-t-BuOOH were identified,and the mechanism of the catalytic oxidation of phenolic substrates was proposed.Quinone imine molecules,the main products of catalytic oxidation reaction,can be adsorbed on the surface of CdTe QDs,resulting in their fluorescence quenching.A dual function of catalytic oxidation and fluorescence sensing was developed for the determination of dichlorophenol(DCP)based on the Fe(Ⅲ)PcTs-BuOOH-CdTe QDs system.The linear detection range of DCP was 1×10^(-6)-1.3×10^(-4) mol/L,and the detection limit 2.4×10^(-7) mol/L.This method was characterized by high selectivity,good repeatability and desirable stability,presenting promising potentials for analyzing DCP concentration in real water samples.

不同Mn/Fe比例天然含铁锰矿的As(Ⅲ)吸附性能与机制

水体中的砷主要以亚砷酸(As(Ⅲ))形态存在.金属氧化物常用于水体砷的去除,但其对As(Ⅲ)的亲和力较弱,导致水体砷很难去除,因此,寻求高效、廉价、绿色的除As(Ⅲ)材料具有显著的环境意义.天然含铁锰矿是一种高效的砷吸附剂,由于自然形成条件复杂,其不同含铁锰矿对As(Ⅲ)的去除性能存在较大差异.本研究以两种不同Mn/Fe比例的天然含铁锰矿(NFM-L、NFM-H)为研究对象,评估其对As(Ⅲ)的吸附性能,并结合XPS、XRD等光谱学表征手段探究其砷的去除机制.实验结果表明,NFM-L的Fe含量是NFM-H的5.61倍,其As(Ⅲ)的最大吸附量(24.82 mg·g^(−1))与吸附速率亦显著高于NFM-H(18.94 mg·g^(−1)),NFM-L和NFM-H对As(Ⅲ)的等温吸附曲线更符合Freundlich模型.影响因子实验表明,溶液pH值对NFM-L的影响更大,共存离子H_(2)PO_(4)^(−)能够显著抑制两种材料对As(Ⅲ)的吸附,但是材料粒径对As(Ⅲ)去除的影响较小.光谱学表征发现,两种矿物吸附砷后结构并未发生明显变化,但锰氧化物能将As(Ⅲ)氧化为As(V),从而显著提高了铁锰矿对砷的吸附能力.

Reduction of Sulphur-containing Aromatic Nitro Compounds with Hydrazine Hydrate over Iron(III) Oxide-MgO Catalyst

Sulphur-containing aromatic amines were prepared efficiently in good to excellent yields by reduction of the corresponding sulphur-containing aromatic nitro compounds with hydrazine hydrate in the presence of iron（Ⅲ） oxide-MgO catalyst. The catalyst exhibited high activity and stability for the reduction of sulphur-containing aromatic nitro compounds. The yields of sulphur-containing aromatic amines were up to 91-99 % at 355 K after reduction for 1-4 h over this catalyst.

Electrochemical anodic oxidation assisted fabrication of memristors

Owing to the advantages of simple structure,low power consumption and high-density integration,memristors or memristive devices are attracting increasing attention in the fields such as next generation non-volatile memories,neuromorphic computation and data encryption.However,the deposition of memristive films often requires expensive equipment,strict vacuum conditions,high energy consumption,and extended processing times.In contrast,electrochemical anodizing can produce metal oxide films quickly(e.g.10 s) under ambient conditions.By means of the anodizing technique,oxide films,oxide nanotubes,nanowires and nanodots can be fabricated to prepare memristors.Oxide film thickness,nanostructures,defect concentrations,etc,can be varied to regulate device performances by adjusting oxidation parameters such as voltage,current and time.Thus memristors fabricated by the anodic oxidation technique can achieve high device consistency,low variation,and ultrahigh yield rate.This article provides a comprehensive review of the research progress in the field of anodic oxidation assisted fabrication of memristors.Firstly,the principle of anodic oxidation is introduced;then,different types of memristors produced by anodic oxidation and their applications are presented;finally,features and challenges of anodic oxidation for memristor production are elaborated.