Phase composition of manganese-alumina catalysts for the reactions of deep oxidation

X-ray powder diffraction, transmission electron microscopy and differential dissolution were used for investigation of the phase transformation peculiarities of biphasic manganese-alumina catalysts during their thermal treatment. An effect of interaction between aluminium and manganese oxides depending on the sample preparation procedure was found.     

Nano-sized manganese oxide: a proposed catalyst for water oxidation in the reaction of some manganese complexes and cerium(iv) ammonium nitrate

According to UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy, nano-sized manganese oxides are proposed as active catalysts for water oxidation in the reaction of some manganese complexes and cerium(iv) ammonium nitrate.     

Nanoscale manganese oxide within Faujasite zeolite as an efficient and biomimetic water oxidizing catalyst

Nanoscale manganese oxides within Faujasite zeolite have been synthesized with a simple method and characterized by scanning electron microscopy, X-ray diffraction spectrometry, N(2) adsorption-desorption isotherms, transmission electron microscopy, and atomic absorption spectroscopy. These oxides showed efficient water oxidizing activity in the presence of cerium(iv) ammonium nitrate as a non-oxo transfer oxidant.     

A very simple method to synthesize nano-sized manganese oxide: an efficient catalyst for water oxidation and epoxidation of olefins

Nano-sized particles of manganese oxides have been prepared by a very simple and cheap process using a decomposing aqueous solution of manganese nitrate at 100 °C. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction spectrometry have been used to characterize the phase and the morphology of the manganese oxide. The nano-sized manganese oxide shows efficient catalytic activity toward water oxidation and the epoxidation of olefins in the presence of cerium(iv) ammonium nitrate and hydrogen peroxide, respectively.     

Reaction of gaseous hydrogen fluoride with aluminium and its compounds

The reaction of metallic aluminium surfaces, aluminium oxides, hydrated oxides and sulphate with gaseous anhydrous hydrogen fluoride was studied at 470°C and pressures between 10 and 100 torr. The complementary analytical techniques of X-ray induced photoelectron spectra, X-ray and electron diffraction, and electron microscopy were used for identifying the (frequently unexpected) products.     

Role of MnO on the Mullitization Behavior of Al2 O3-SiO2 Gels

Gels were synthesized from solutions of tetraethylorthosilicate (TEOS) and aluminium nitrate (with and without manganese nitrate).The structural evolution of the gels as a function of manganese content and heat-treatment temperature was studied by visible spectrophotometry (VIS), electron paramagnetic resonance (EPR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the presence of manganese can induce mullitization at lower temperatures. However, the effect of manganese depends on its content and how it enters into the mullite structure.     

Catalytic graphitization of PAN-based carbon fibers by spontaneously deposited manganese oxides

A simple method for the spontaneous deposition of manganese oxides on the surface of polyacrylonitrile (PAN)-based carbon fibers by a direct redox reaction between carbon fibers and permanganate ions is described. Catalytic graphitization of the PAN-based carbon fibers coated with manganese oxides was investigated by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. The results indicate that the graphitization of the PAN-based carbon fibers was accelerated in the presence of the manganese oxides even at the relatively low temperature of 1,600 °C.     

Differentiation of Spanish brandies according to their metal content

Eleven metals, namely, aluminium, calcium, cadmium, copper, iron, lead, magnesium, manganese, potassium, sodium and zinc were determined in twenty samples of Sherry brandies and twelve samples of Penedés brandies by applying atomic spectrometry techniques. Flame atomic absorption spectrometry was used for quantitating calcium, copper, iron, magnesium, manganese and zinc; atomic emission spectrometry to determine potassium and sodium; and graphite furnace atomic absorption spectrometry to analyse aluminium, cadmium and lead. A chemometric approach was followed to study the discrimination between brandies from Sherry or Penedés according to the metal profile.     

Silicate‐based post‐anodic treatment for lithographic application

Sodium silicate solutions are widely used chemicals for a variety of applications. In particular, they are commonly used in pre‐treatments of aluminium alloys as cleaners and corrosion inhibitors. Another application is found in offset printing, where after graining and anodising, a silicate‐based post‐anodic treatment (PAT) is considered to optimise the aluminium plate characteristics. It is, however, not clear what type of interaction takes place between the oxide‐covered aluminium and the silicate solution. In this work, silicate‐based PAT is studied. Different barrier‐type and porous‐type aluminium oxides are silicate‐treated by dipping in a water‐based sodium silicate solution and the effect of time on the deposition is studied. Particular attention is given to the role of rinsing when the alumina surface is washed in water after the silicate treatment. A good understanding of the role of rinsing allows us to obtain information on the characteristics of the silicate layer which is formed after dipping. The surface modifications induced by the silicate treatment on the aluminium oxides were monitored by means of field emission scanning electron microscopy and infrared spectroscopic ellipsometry. Quantitative measurements on the amount of deposited silicate were taken by X‐ray fluorescence, and relative comparisons between different oxides are shown. Auger electron spectroscopy was used to study the in‐depth composition of the silicate deposition. Experiments show a high affinity of the silicate to the anodic oxide film. A thin nanometric chemisorbed (alumino)silicate layer is present on the surface after rinsing, while the physisorbed part of the layer is washed away. Copyright © 2009 John Wiley & Sons, Ltd.     

选择性刻蚀制备铜锰复合氧化物及其CO催化氧化性能

由于在工业、环保和能源等诸多领域的潜在应用,低温CO催化氧化催化剂的研发引起了广泛关注.尽管贵金属表现出优越的CO氧化活性和稳定性,但是其有限储量和高昂价格一直限制着它们的实际应用.铜锰氧化物是著名的霍加拉特催化剂的主组分,价格低廉,催化氧化CO活性高,可高效替代贵金属催化剂.大量研究已证实, CO在铜锰氧化物上的氧化遵循氧化-还原机理,因此调变铜锰氧化物催化剂的氧化-还原性能对于改善其CO氧化活性至关重要.本文报道了一种简单的选择性刻蚀技术,即在铜、锰前驱物共沉淀过程中引入氨水作为刻蚀剂,利用氨水与铜离子的强络合作用选择性刻蚀铜组分,调变铜锰氧化物的铜锰比,有效改善了铜锰氧化物的氧化-还原特性,从而提高了其CO氧化性能. X射线粉末衍射(XRD)测试结果表明,初始制备的样品结晶弱,主要物相包含铜锰复合氧化物和氧化锰,此外还存在少量碳酸锰.不同浓度氨水刻蚀几乎未改变铜锰氧化物的物相组成.透射电子显微(TEM)照片中几乎没有发现晶格相,进一步证实这些铜锰氧化物的弱结晶本质.扫描电子显微(SEM)照片显示初始制备的铜锰复合氧化物主要由1.5?m左右的球形颗粒堆积而成,氨水刻蚀后颗粒形状变得不规则,表面更加粗糙,样品比表面积也从刻蚀前的85 m2/g增加到139 m2/g.理论上,氨水与铜的络合作用更强,样品主体和表面组成分析结果显示,随着氨刻蚀量增加,铜含量逐步降低,这清晰证实了氨有效地选择性刻蚀了铜组分. 进一步运用X射线光电子能谱(XPS)、氢程序升温还原(H2-TPR)、CO程序升温还原(CO-TPR)和氧程序升温脱附(O2-TPD)等测试手段表征了铜锰氧化物的氧化和还原特性,特别是氨刻蚀后催化剂氧化-还原性能. XPS分析显示铜锰氧化物中铜和锰物种的氧化态分别为+2和+3,氨刻蚀并没有改变两物种的氧化态. H2-TPR和CO-TPR证实氨刻蚀有效促进了铜锰氧化物中晶格氧从锰到铜物种的迁移,氨刻蚀同时还增强了与铜和锰键合的晶格氧物种的反应活性. O2-TPD结果进一步表明,氨刻蚀显著改善了铜锰氧化物中与铜键合晶格氧的释放.综合来看,氨刻蚀可有效促进铜锰氧化物的晶格氧迁移、释放和反应等氧化-还原特性. CO氧化反应研究显示,氨刻蚀大幅度促进了铜锰氧化物的催化活性.当反应温度在30?C时,相比于初始制备的铜锰氧化物催化剂,氨水刻蚀的样品上CO转化率提高了30%,达到90%转化率时的温度降低了20?C.关联催化剂结构表征和CO氧化性能数据发现,以表面Cu量归一化的CO氧化反应速率与催化剂的氧化-还原性能正相关.这一结果清晰证实氨刻蚀能显著改善铜锰氧化物的氧化-还原特性,进而有效促进其CO氧化活性.     

Characteristics of manganese-coated sand using SEM and EDAX analysis

"Manganese-coated sand" is a type of silica medium coated with manganese oxides, formed from the sorption of manganese oxides during long-term filtration via the process of rapid sand filtration, followed by aeration in a water treatment plant. Locally available manganese-coated sand, both for packing and as a byproduct of filtration processes for water treatment plants in Taiwan, was found to be a low-cost and promising adsorbent for removal of Mn(2+) from raw water. This study was conducted to build the basic data for coating hydrated manganese oxide on the sand surface to utilize the adsorbent properties of the coating and the filtration properties of the sand. In this study, gas adsorption porosimetry and scanning electron microscopy analyses were used to investigate the surface properties of the coated layer. An energy dispersive X-ray (EDAX) technique of analysis was used to characterize metal adsorption sites on a manganese-coated sand surface. Results indicated that manganese-coated sand had more micropores and higher specific surface area, owing to attachment of manganese sand. Manganese ions penetrated into the micropores and mesopores of manganese oxide on a sandy surface; regeneration of manganese-coated sand could be achieved by soaking with pH < 2.0 acid solution. Results of EDAX analysis showed that the interfacial layer constructed the interface of manganese-coated sand. Acid and alkali resistance tests interpret a wide application range of pH for manganese-coated sand, and general temperature conditions do not affect the performance of this sand. Manganese-coated sand is potentially suitable for application as a packed bed for treatment of heavy metals from water. The results of this study can also benefit plant operational capacity data for engineering design.     

溶剂热法制备纳米MnOOH

MnOOH在常温常压下为黑色固体粉末,经氧化或还原可制成电子工业中生产锰锌铁氧体软磁材料的重要原料.以KMnO4与MnSO4为原料,在水与正丙醇混合溶剂中反应制备了MnOOH纳米棒;采用X射线粉末衍射仪(XRD)、差热-热重(DTA-TG)分析系统、红外光谱仪(IR),以及扫描电镜(SEM)、透射电镜(TEM)、X射线...     

Influence of cation (NH 4 + ) on electrochemical characteristics of MnO2 nanowire synthesized by hydrothermal method

Nanowires of MnO₂ were prepared by a simple method in which the commercial granular -MnO₂ powders were hydrothermally treated in water or ammonia solution at 150 °C. These 1D nanostructured manganese oxides were characterized physically by X-ray diffraction, scanning electron microscopy and transmission electron microscopy tests. Cyclic voltammetry and constant current discharge experiments were employed to explore the diversity of electrochemical performances; and the reasons for the difference are discussed. The experimental results indicate that the existence of NH₄⁺ in the preparation solution has depressed the electrochemical performances of the final product; This is further confirmed by the electrochemical impedance spectra of the electrodes.     

Pentatomie heteroaromatic cations. Note II. Chemical properties of 2-phenyl-1,3-benzoxathiolium perchlorate

The reactions of 2-phenyl-1,3-benzoxathiolium perchlorate with common nucleophilic reagents (water, sodium hydroxide, ethanol, thiophenol, morpholine, phenylmagnesium bromide), with reducing agents (zinc, lithium aluminium hydride) and with manganese dioxide, were studied. In every case the reactions proceed by attack of the reagents at the C-2 position of the cationic system, giving rise either to 1,3-benzoxathiole derivatives or to ring-opening products. The 1,3-benzoxathiolium salts were shown to be suitable intermediates for converting the carboxylic acids into aldehydes and ketones.     

An investigation on characterization and thermal analysis of the Aughinish red mud

Summary Red mud is insoluble, fine-grained waste residue which is generated as a by product during the production of alumina from the Bayer process. In this article, the thermal behavior of Aughinish red mud was investigated using thermal gravimetric analysis (TG) and differential thermal analysis (DTA). For identification of oxide and mineral phases in the red mud sample, XRD method, scanning electron microscopy (SEM), EDAX were used. Iron (30.4%), aluminium (23.6%) and titanium (17.85%) oxides are major oxides in the sample. Two endothermic peaks were shown on DTA curve. The total mass loss in the red mud was found to be 10.1%, which was associated with moisture and water molecules in gibbsite and boehmite phases.     

Synthesis of nanocrystalline zinc manganese oxide by thermal decomposition of new dinuclear manganese(III) precursors

Nanocrystalline manganese-doped zinc oxide was synthesized by thermal decomposition of a zinc oxide sol with two new dinuclear manganese(III) complexes as precursor. Thermal analysis results indicated that the decomposition of manganese precursors occurred at 269 and 314 °C. X-ray structural analysis shows the presence of dimanganese core in the complexes and the binding of the ligands to the manganese(III) is through N₂O₂. The manganese-doped zinc oxide composite was characterized by means of X-ray diffraction, scanning electron microscopy, and UV–Vis spectroscopy. Structural properties of the composites elucidated that the manganese ions have substituted the zinc ions without changing the wurtzite structure of zinc oxide.     

Reactions of Oxides of Some 3d Elements with Ammonium Hydrogen Difluoride

Reactions of iron, manganese(II), manganese(IV), copper, and zinc oxides with ammonium hydrogen difluoride were studied by thermogravimetry, X-ray phase analysis, IR spectrometry, and chemical analysis.     

Direct Observation of an Anomalous Spinel‐to‐Layered Phase Transition Mediated by Crystal Water Intercalation

The phase transition of layered manganese oxides to spinel phases is a well‐known phenomenon in rechargeable batteries and is the main origin of the capacity fading in these materials. This spontaneous phase transition is associated with the intrinsic properties of manganese, such as its size, preferred crystal positions, and reaction characteristics, and it is therefore very difficult to avoid. The introduction of crystal water by an electrochemical process enables the inverse phase transition from spinel to a layered Birnessite structure. Scanning transmission electron microscopy can be used to directly visualize the rearrangement of lattice atoms, the simultaneous insertion of crystal water, the formation of a transient structure at the phase boundary, and layer‐by‐layer progression of the phase transition from the edge. This research indicates that crystal water intercalation can reverse phase transformation with thermodynamically favored directionality.     

高度分散二氧化锰纳米纤维的水热合成和对双氧水电流检测

采用水热还原氧化法合成了高度分散的具有纳米纤维结构的钾矿型二氧化锰,并将其用来制作检测双氧水浓度的传感器.运用X射线衍射(XRD)仪、电子扫描显微镜(SEM)、透射电子显微镜(TEM)和比表面积(BET)及孔隙度分析仪观察和表征二氧化锰纳米纤维的结构和表面形貌;用电化学工作站(EW)检测其传感性能.结果表明:在pH为7.4的磷酸缓冲溶液中,开路电压为0.2V的条件下对0.1%(w,质量分数)的二氧化锰纳米纤维修饰的玻碳电极(GCE)进行测试,测试结果为随着双氧水的浓度每增加0.1mmo·lL-1,响应电流的峰值就增加约1.3μA,在双氧水的浓度在0.1-1.5mmo·lL-1范围内得到的线性相关系数为0.996,这种电极的高灵敏度和优异的电化学活性可能归因于钾矿型二氧化锰纳米纤维的特殊纳米结构.这种传感器有很高的灵敏度和很好的重现性.综上说明这种廉价并且有很好的电化学活性的材料为设计新型电极生物传感器提供了更大可能.     

Influence of aluminium precursor on physico-chemical properties of aluminium hydroxides and oxides

The paper concerns aluminium hydroxides precipitated during hydrolysis of aluminium acetate in ammonia medium, as well as aluminium oxides obtained through their calcination at 550, 900 or 1200°C for 2 h. The following techniques were used for analysing of obtained materials: thermal analysis, IR spectroscopy, X-ray diffraction, low-temperature nitrogen adsorption, adsorption-desorption of benzene vapours and scanning electron microscopy. Freshly precipitated boehmite/pseudoboehmite had high value of S _BET, very good sorption capacity for benzene vapours, developed mesoporous structure and hydrophilic character. After prolonged refluxing at elevated temperature its crystallinity increased which was accompanied by a decrease of specific surface determined from nitrogen adsorption, decrease of sorption capacity for benzene vapours and weakening of the hydrophilic character. Calcination of all hydroxides at the temperature up to 1200°C resulted in the formation of α-Al₂O₃ via transition forms of γ-, δ-and θ-Al₂O₃. The samples of aluminium oxides obtained after calcination at 550 and 900°C were characterised with high values of specific surface area and displayed quite high heat resistance, probably due to a specific morphology of starting hydroxides. The process of ageing at elevated temperature developed thermal stability of aluminium oxides.