Synthesis and characterization of molybdenum incorporated mesoporous aluminophosphate

A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of ²⁷Al and ³¹P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m²/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo⁴⁺ and Mo⁶⁺ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination.     

Heat-treatment studies of molybdenum oxide-monohydrate

The dehydration of molybdic acid, MoO₃---H₂O, was studied by thermal analysis, X-ray diffractometry and FTIR spectroscopy. The results show that an intermediate phase, MoO₃-2/3H₂O is formed at 216 °C and the monoclinic form of MoO₃ is grown above 350 °C. The mechanism of dehydration and structural rearrangement were confirmed by the features of the infrared spectra showing formation of corner-shared MoO₆ octahedra.     

Synthese und Eigenschaften von Sr3Mo1.5Zn0.5O7‐δ, einer Phase mit perowskitverwandter Schichtstruktur

Synthesis and Properties of the Layered Perovskite Phase Sr₃Mo_1.5Zn_0.5O_7‐δ The new layered perovskite phase Sr₃Mo_1.5Zn_0.5O_7‐δ was synthesized by solid state reaction using a Zn/ZnO oxygen buffer. The crystal structure was refined from X‐ray powder pattern by the Rietveld method. The compound crystallizes tetragonal in the space group I4/mmm (no. 139) with the lattice parameters a = 3.9631(3) Å, c = 20.583(1) Å. An oxygen deficiency corresponding to δ ≈ 0.25 was determinated, indicating the presence of molybdenum in mixed valence (Mo⁴⁺ and Mo⁶⁺).     

硫酰胺的快速分析（Ⅱ） 

硫酰胺生产过程中副产的大量氯化铵要干扰硫酰胺的测定，采用四苯硼钠将全部氯化铵呈沉淀析出，再用次溴酸钠把滤液中的硫酰胺分解成氮气，测其体积，计算出硫酰胺的含量。对样品进行测定的结果表明，该法重现性好、准确度高、分析周期在３５ｍｉｎ内，相对误差在±１％以内。     

Vapour and plasma ignition thresholds for visible pulsed-laser ablation of metallic targets

The coupling of visible nanosecond laser pulses to metallic targets irradiated in vacuum is studied. The expressions of the vapour and plasma ignition times are obtained. Two cases for vapour breakdown in the plasma ignition process are considered. The first case is that 40 generations of new electrons are born in vapour generation time before plasma formation as assumed in the literature. The second case is that 10 generations of new electrons are born in vapour generation time. Molybdenum (Mo), niobium (Nb) and aluminium (Al) targets are considered for illustrations of our results. The expression of the plasma ignition time for the Al target is substantially different from that reported in the literature. The vapour and plasma ignition threshold laser intensities are calculated and compared with those reported in the literature. Reasons for disagreement are discussed. The plasma ignition threshold estimated in the second case is noted to be in good agreement with the reported experimental result.     

A photoemission study of molybdenum hexacarbonyl adsorption and decomposition on TiO2(1 1 0) surface

The adsorption and decomposition of molybdenum hexacarbonyl on (1 1 0) TiO₂ surfaces were studied using both core levels and valence band photoemission spectroscopies. It was found that after an adsorption at 140 K, when going back to room temperature, only a small part of molybdenum compounds, previously present at low temperature, remained on the TiO₂ surface. This indicates that the desorption temperature on such a surface is lower than the decomposition one. The use of photon irradiation to decompose the hexacarbonyl molecule was also studied. It was shown that during such a decomposition molecular fragments were chemisorbed on the surface allowing a higher amount of metal to remain on the surface. It was also shown that it was possible to get rid of adsorbed subcarbonyl groups and to organize the metal atoms by thermal treatments at temperatures as low as 400 K, i.e. much lower than the one needed to obtain the same structures using physical vapour deposition (PVD). Moreover, due to lower used temperatures, this chemical way of deposition allows a better control of the interface than during PVD growth.     

Electrolytical production of Ni + Mo + Si composite coatings with enhanced content of Si

Ni + Mo + Si composite coatings were prepared by co-deposition of nickel with molybdenum and silicon powders from a nickel solution in which Mo and Si particles were suspended by stirring. The layers have been deposited on a carbon steel substrate (St3S) under galvanostatic conditions. The content of Si in deposited layers was about 2-5 wt.% depending on deposition current density and the value of electric charge. For comparison Ni + Mo composite coatings were obtained under analogous current conditions. Composite coatings of enhanced Si content (15 wt.%) were deposited from an electrolyte in which 40 g/dm³ of Si covered with electroless plated nickel was dispersed. Deposition current density was equal 0.1 A/cm² and the value of electric charge Q = 500 C/cm². The thickness of the coatings was about 100-300 μm depending on their kind, electric charge and the deposition current density. Surface and cross-section morphology were investigated by scanning electron microscope (SEM). All deposited coatings are characterized by great, developed surface area. No internal stresses causing their cracking were observed. Chemical composition of the layers was determined by X-ray fluorescence spectroscopy (XRF) method and quantitative X-ray analysis (QXRD). It was stated, that the content of molybdenum and silicon in Ni + Mo + Si coatings depends on deposition current density and the amount of the powder in bath. The results of structural investigation of the obtained layers by the X-ray diffraction (XRD) method show, that they consist in crystalline Mo or Mo and Si phases built into Ni matrix. Moreover, Ni + Mo + Si composite coatings were modified by thermal treatment. It has been found that the thermal treatment of Ni + Mo + Si composite coatings caused that the new phases (NiSi, Mo₂Ni₃Si and Ni₆Mo₆C_1.06) were obtained.     

Synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine and (±)-convolutamydines A and E, through enolization-Claisen rearrangement of 2-allyloxyindolin-3-ones

Claisen rearrangement triggered by enolization of 2-allyloxyindolin-3-ones with DBU was performed in order to prepare 3-allyl-3-hydroxyindolin-2-ones. Total synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine, as well as (±)-convolutamydines A and E, was achieved by transformation of the allyl moiety of 3-allyl-3-hydroxyindolin-2-ones.     

若干具有[(PO4)2Mo5O15]簇骼的化合物的光谱研究

本文对所合成的具有 [(PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5[(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·[(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·[Cu(en) ][(PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 [(PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 [(PO4 ) 2 Mo5O1 5]簇骼基元是由 [Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 [Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。     

Influence of boric acid on the electrochemical deposition of Ni

The electrolytic deposition of Ni onto a paraffin-impregnated graphite electrode from supporting chloride electrolyte (0.5 mol dm⁻³ NaCl) adjusted to the required pH using dilute HCl is investigated. The effect of electrolyte composition on the Ni electrodeposition is studied using linear sweep voltammetry in the cathodic region. An elimination voltammetry procedure was applied to evaluate the polarization curves. The aim of this work was to deduce the mechanism of Ni reduction in the chloride bath as well as the influence of boric acid on this. Positively-charged NiCl⁺ ions were found to be the electroactive particles in the Ni reduction mechanism. The strong competition between the NiCl⁺, Cl⁻ and H⁺ ions for active sites at the electrode is discussed. Kinetically-controlled adsorption/desorption processes of various species were also confirmed using elimination voltammetry with a linear scan. The evolution of gaseous hydrogen, catalyzed by the freshly-deposited Ni, accompanies the electrodeposition process. The presence of boric acid at a sufficiently high concentration inhibits the deposition of Ni and, at the same time, improves the morphology and brightness, as well as the adhesion of the deposited Ni. Elimination voltammetry with a linear scan is an efficient way to evaluate current–potential curves that reflect the electrodeposition of one-component Ni coatings. By eliminating selected currents, additional interesting and useful information can be obtained from voltammetric data.