Synthesis of manganese titanate and its precursors from xerogel

An overview of research on the synthesis of manganese titanates is presented. The xerogel of Mn–Ti–O–C–H composition was synthesized from manganese acetate and titanium tetrabutylate via liquid-phase method using organic solvents. The calcination of xerogel in air at 450 °C and 700 °C yielded manganese titanate precursors in the form of a nanostructured mixture of Mn₂O₃ and TiO₂. Annealing at 1000 °C, manganese metatitanate MnTiO₃ was obtained. Reference experiments with initial reagents included, separately, thermal decomposition of Mn(CH₃COO)₂×4H₂O and the product of Ti(OC₄H₉)₄ hydrolysis. The composition, structure, and properties of the products were studied using X-ray diffraction, scanning electron microscopy, elemental analysis, diffuse reflectance IR Fourier spectroscopy, thermogravimetry, and by measuring specific surface area. The data presented by these different techniques are basically consistent with each other (with an increase in the annealing temperature, an increase in globule size and decrease in specific surface area are observed; structuring occurs within the long- and short-range order; the size of the crystallites does not exceed that of the globules; elemental composition correlates with phase composition; the endothermic character of the reaction of MnTiO₃ formation at 900 °C is confirmed by a thermodynamic calculation). Nevertheless, some unexpected effects were revealed (based on the FTIR diffuse reflection spectra, mixed oxide Mn–Ti–O is formed in the surface layer of particles already at 450 °C and 700 °C; etc.). Application of the proposed technique for modifying Al₂O₃ powders, with the aim of implementing low-temperature sintering of corundum ceramics, is discussed.     

Manganese ferrite-polyaniline hybrid materials: Electrical and magnetic properties

Magnetic MnFe₂O₄ nanopowders were synthesized by an original solvothermal method in the absence and in the presence of tetra-n-butylammonium bromide (TBAB) and Tween 80 (TW) as surfactants. Manganese ferrite/polyaniline (PANI) hybrid materials were synthesized by in situ polymerization of aniline on the surface of MnFe₂O₄ using ammonium persulfate as oxidant. The purpose of the study was to investigate the influence of the two surfactants on the properties of the MnFe₂O₄ powders and of their composites with PANI. The specific surface area, the cumulative surface area of pores and the cumulative volume of pores are influenced by the nature of surfactant in case of MnFe₂O₄ powders and are higher by comparison to those of the MnFe₂O₄/PANI hybrid materials. The values of saturation magnetization in case of MnFe₂O₄ powders are higher than those of the hybrid materials and are not influenced by the surfactant nature. These features revealed that MnFe₂O₄ powders can be efficiently used as adsorbents for the purification of wastewaters. The values of the electrical conductivity of the composites exhibit a significant increase in comparison to the MnFe₂O₄ powders and depend on the surfactant nature. The highest value of electrical conductivity was achieved by the composite obtained using Tween 80 as surfactant (σ_DC = 54.5·10^?5S?m^?1) which was close to that of PANI (σ_DC = 61.2·10^?5 S?m^?1). The fact that the magnetic and electric properties of the synthesized MnFe₂O₄/PANI composites can be changed by design, demonstrate the high potential of these materials to be used in magneto-electric applications.     

斗南锰矿选矿厂设计中几个问题的处理

作者在斗南锰矿选矿厂设计中,针对当前锰选厂生产的经验和存在的问题,从工艺角度分别对干、湿筛分、CS-2强磁机的处理量、矿泥强磁选机的选型、以及在强磁选前设置脱除强磁性物质装置等作了分析,并提出了作者的看法。     

Effect of the addition of silver compounds during the pyrolysis of manganese nitrate on tantalum anodic oxide film

A study of the pyrolysis of an aqueous solution of manganese nitrate in the presence of silver compounds has been carried out. Thermal analysis showed that the MnO₂ formation temperature and the transformation temperature from MnO₂ to Mn₂O₃ shifted towards a lower temperature in the presence of silver acetate. A large particle-size and high crystallinity MnO₂ was formed; this may be a useful method of making an excellent tantalum capacitor with high capacitance.     

Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

Lattice Effects and Irreversible Magnetoresistance in Gd Doped La—Ca—Mn—O

The Gd substituting effects for La in La0.67Ca0.33MnO3 has been studied .With increasing the substituting amount of Gd,the phase transition temperature of metal-isolator for the samples decreases,the corresponding peak resistivity increases,the Curie temperature decreases monotonically.The substitution of La-Ca-Mn-O with 11% Gd for La improved the magnetoresistance ratio by an order of magnitude.The effects of substituting Gd can be explained in terms of the lattice effects.An irreversible MR behaviour was observed in Gd-substituting compounds.This effect became marked when the substituting amount of Gd was greater than 7%.A maximum irreversible increment of MR ratio as large as 91% was obtained when Gd substituting amount was 11%.     

Epoxidation of olefines with PDMS membranes containing zeolite occluded manganese diimine complexes

A new composite catalyst for selective epoxidation of olefins with tert-butyl hydroperoxide (tBHP) is reported. The catalyst contains manganese diimine complexes (cis-Mn bis-2,2′-Bipyridyl), occluded within a NaY zeolite, in turn incorporated in a polydimethylsiloxane membrane (cis-[Mn(bpy)₂]²⁺-NaY-PDMS). The three-step synthesis consists of a Mn²⁺exchange of NaY, ligand sorption to form cis-[Mn(bpy)₂]²⁺-NaY and incorporation of the latter in a PDMS membrane. The major differences between [Mn(bpy)₂]²⁺-NaY as such and occluded in PDMS are observed in the sorption and catalytic characteristics. With the membrane system, the use of a solvent becomes obsolete. Whereas optimal cyclohexene oxidation with [Mn(bpy)₂]²⁺-NaY occurs with hydrogen peroxide in acetone, tBuOOH proves to be a better oxidant for [Mn(bpy)₂]²⁺-NaY-PDMS. The reactions in batch and fed-batch reactors are discussed. A simple regeneration procedure, monitored by FT-IR spectroscopy is proposed.     

添加高效粘结剂的氧化锰矿粉冷固成团

以氧化锰矿粉为原料，添加ＺＢ粘结剂进行冷固成团，所得冷固团块不仅具有足够的机械强度，而且具有良好的耐湿性，适用于长距离运输和露天堆存，是一种可与块矿性能相媲美的优质炉料，为充分利用矿山及冶炼厂的锰矿粉找到了一条良好的途径．     

Mn-containing catalytic materials for the total combustion of toluene: The role of Mn localisation in the structure of LDH precursor

Mg/Mn/Al mixed oxide systems of similar atomic ratios close to 2/0.5/1 were obtained by calcination of Mg,Al layered double hydroxide (LDH) type precursors containing Mn either in the cationic form within the brucite layer or as permanganate anions in the interlayer. The materials were characterised with PXRD, thermal analysis, XPS, ESR, TPR and BET. In mixed oxides derived from interlayer-doped precursor PXRD identified MgO–MnO solid solution and poorly crystalline Al-rich spinel phase, while those obtained from layer-doped LDH contained a better crystalline Mn-rich spinel. Surface of both materials was covered with poorly crystalline and/or amorphous Mn⁴⁺-containing phases. Higher reducibility of this surface coat in calcined layer-doped catalyst, as compared to interlayer-doped one, was attributed to the differences in the nature of underlying crystalline phases, and was considered the chief reason for the higher catalytic activity of this catalyst in the total oxidation of toluene.