PREPARATION OF ELECTRICAL CONDHCTIVE MOLYBDENUM OXIDE BY THERMAL DECOMPOSITION OE HYDRAZINE-CONTAINING MOLYBDENUM SALT

A new method of preparing electrical conductive molybdenumoxide by thermal decomposition from hydrazine-containing molybdenum saltwas described.The process of the thermal decomposition of hydrazine-containing molybdemum salt was investigated by thermal analysis(TG and DTA)and the thermally decomposed product was studied by S.E.M.and chemicalanalysis.The result indicated that the molybdenum oxide obtained in thisway was electrical conductive.     

氧化铝薄膜表面羰基钼物种的可逆再生

 通过Mo(CO)6的热分解制备了Al2O3薄膜负载的金属钼模型催化剂,并采用热脱附谱(TDS)和X射线光电子能谱(XPS)原位研究了CO在金属态Mo/Al2O3模型催化剂表面的化学吸附. 结果表明,在低温下CO可与Al2O3表面的金属钼纳米粒子发生多重配位形成类似于羰基钼的物种. CO在Mo/Al2O3模型催化剂表面的吸附导致Mo 3d XPS峰向高结合能方向位移,所生成的羰基钼物种表现为TDS谱中在240 K处有脱附峰. 负载的金属钼模型表面与体相金属钼的化学性质完全不同,表现出明显的粒子尺寸效应.     

Methane Decomposition on the Surface of Molybdenum Nanoparticles at Room Temperature

The decomposition of methane on molybdenum nanoparticles was studied experimentally at room temperature. The molybdenum nanoparticles were synthesized in the gas phase using UV laser photolysis of Mo(CO)6 vapor in a flow reactor. The working part of the flow reactor was equipped with quartz windows for introducing the radiation from a pulsed Nd:YaG laser operating at the fourth harmonic (266 nm) at a frequency of 10 Hz. Methane was used as a carrier gas. As a result of irradiation of a mixture of methane with Mo(CO)6 vapors in the gas phase at room temperature, nanoparticles with sizes of 2–50 nm were synthesized. The phase composition of the nanoparticles included pure molybdenum, molybdenum carbide Mo2C, and molybdenum oxide MoO3. During the reaction, the hydrogen yield was measured with a VG-7 highly sensitive hydrogen analyzer based on a semiconductor metal–dielectric sensor. The measured H2 concentration varied from 5 to 25 ppm depending on the concentration of Mo(CO)6. The possibility of methane decomposition on molybdenum nanoparticles at room temperature was discussed based on the obtained data.     

Monitoring Silica Supported Molybdenum Oxide Catalysts at Work: A Raman Spectroscopic Study

The structure of silica SBA‐15‐supported molybdenum oxide catalysts is investigated during selective oxidation of propylene at 500 °C using operando Raman spectroscopy. The active catalysts contain mixtures of dispersed molybdenum oxide species exhibiting monooxo and dioxo structure. An increase in molybdenum oxide loading results in a decrease of the ratio of dioxo and monooxo species from 3.8 to 1.9, as determined by quantitative analysis of Raman spectra. Additional in situ Raman studies at 500 °C reveal that the dioxo/monooxo ratio increases in the presence of steam at higher molybdenum oxide loadings. The observed structural changes are assigned to shifts in the equilibrium between dioxo and monooxo species resulting from hydration/dehydration of the catalyst. This study demonstrates that the detailed structure of nanostructured molybdenum oxide catalysts depends on temperature, gas‐phase composition, and molybdenum oxide loading.     

Molybdenum oxide-mediated facile aliphatic nucleophilic fluorination

A facile aliphatic nucleophilic fluorination with cesium fluoride in the presence of molybdenum oxide as a catalyst has been demonstrated. Reactivity of molybdenum oxide in nanocrystal form was found to be chemoselective in the presence of water. Furthermore, the reaction is highly specific with alkyl sulfonate substrates.     

Effect of the Conditions of Thermal Treatment of Molybdenum–Titanium and Vanadium–Molybdenum–Titanium Oxide Catalysts on Pore Structure Formation

The effect of the conditions of thermal treatment on the texture formation in molybdenum–titanium oxide (Mo–Ti–O) and vanadium–molybdenum–titanium oxide (V–Mo–Ti–O) catalysts was studied. It was found that the presence of MoO₃ in the Mo–Ti–O catalyst resulted in the stabilization of the surface area of anatase and in the retention of the fine pore structure upon thermal treatment because of the insertion of highly dispersed molybdenum crystallites into the aggregates of anatase crystallites, preventing from their agglomeration over a wide range of temperatures. In the presence of MoO₃ and V₂O₅ in the catalyst, anatase particles underwent agglomeration as the temperature was increased. This resulted in a more drastic decrease in the specific surface area and an increase in the pore size, as compared with binary samples, because of the formation of a thermally labile vanadium–molybdenum compound at the surface of anatase.     

The Preparation of Perovskite Nano Powder by Sol-gel from DTPA and the Mechanism of Thermal Decomposition

Dy0.8Sr0.2FeO3 nano powder, a synthetic oxide, is made by sol-gel method from metal nitrate and diethylenetriaminepentaaeetic acid (DTPA), and the processing parameters are optimized.The process of the preparation, thermal decomposition and the property of the powder are studied by TG-DTA, IR, TEM, and XRD. The diameter of the average grain is about 70 nm. This new technique can be used in the preparation and the studying of ha‘no materials in the complex oxide system.     

Highly Efficient Micro-Scale Liquid-Liquid In-Flow Extraction of 99mTc from Molybdenum

The trend to achieve even more compact-sized systems is leading to the development of micro-scale reactors (lab-on-chip) in the field of radiochemical separation and radiopharmaceutical production. Technetium-99m extraction from both high and low specific activity molybdenum could be simply performed by MEK-driven solvent extraction if it were not for unpractical automation. The aim of this work is to develop a solvent extraction and separation process of technetium from molybdenum in a micro-scale in-flow chemistry regime with the aid of a capillary loop and a membrane-based separator, respectively. The developed system is able to extract and separate quantitatively and selectively (91.0 ± 1.8% decay corrected) the [^99mTc]TcO₄Na in about 20 min, by using a ZAIPUT separator device. In conclusion, we demonstrated for the first time in our knowledge the high efficiency of a MEK-based solvent extraction process of ^99mTc from a molybdenum-based liquid phased in an in-flow micro-scale regime.     

钴掺杂对碳化钼催化噻吩加氢脱硫性能的影响

以MoO3和CoMo混合氧化物为前驱体, 制备了碳化钼和碳化钼-钴催化剂, 采用XRD, BET, SEM和XPS等技术对其进行了表征, 研究了Co掺杂对碳化钼催化剂噻吩加氢脱硫性能的影响. 结果表明, 掺入适量的Co后制得的CoMo双金属混合氧化物为MoO3和CoMoO4的两相混合体, 经CH4/H2气氛程序升温还原碳化反应生成共生共存的Co-Mo2C, Co以金属细颗粒的形态均匀地分散在生成的Mo2C组分之间. 在共生过程中含Co物种的掺入可降低制备碳化钼所需要的还原碳化温度, 使制备的碳化钼颗粒变小, 比表面积增大, 表面Mo2+含量增多, 从而对碳化钼的噻吩加氢脱硫活性有较好的促进作用, Co的添加量以Co/Mo摩尔比为0.2左右较为适宜. 用化学共沉淀法制得的Co-Mo2C共生共存体系的噻吩加氢脱硫反应活性, 好于由金属Co与Mo2C机械混合法制得的Co+Mo2C二相共存体系. 这表明当两个活性相共存时, 只有经过相互共生过程才能发挥其最佳的协同效应.     

Iron-Containing Metalworking Wastes as a Chemosorbent for Wastewater Treatment from Molybdenum Ions

The extraction mechanism of molybdenum(VI) ions from model solutions with iron-containing metalworking wastes is studied. The experimental X-ray phase analysis and energy dispersive microanalysis data indicate that iron(III) molybdate appears in the first chemisorption stages with the subsequent formation of layers enriched in molybdenum(VI) oxide. The kinetics of the chemisorption of molybdenum(VI) ions from model solutions with iron-containing metalworking wastes is studied. We showed that the total exchange capacity of the modified steel chips having a specific surface of more than 15 cm2/g relative to molybdenum(VI) ions is limited only by the corrosion rate of steel chips and is achieved after its complete dissolution. The effectiveness of the chemisorption process is found. We also showed that iron-containing metalworking waste may be used for the purification of wastewater from molybdenum(VI) ions to the standard values.     

Effect of Concentration of the Diazoalcene Molybdenum Complex Immobilized in Ureasil Matrix

The complex trans-[FMo(NNCHCHCHCH₂CH₃)(Ph₂PCH₂CH₂PPh₂)₂][BPh₄], was dispersed in a hybrid matrix synthesized by a sol-gel process. The host matrix of the so-called ureasil is a network of silica to which oligopolyoxyethylene chains [POE, (OCH₂CH₂)_n] are grafted by means of urea cross-links. The free complex and sol-gel materials were characterized by thermal analysis (DSC), surface analysis (XPS) and spectroscopic methods (FT-IR and UV/Vis). The data gathered indicates that the molybdenum(IV) complex is immobilized in the host matrix, and it exhibits structural properties different from those of the free form. These differences could arise either from distortions caused by steric effects imposed by the structure of hybrid matrix or by interactions with the matrix. These materials shows potential applications in heterogeneous catalysis in mild conditions.     

Sol-gel route for obtaining bismuth high T c superconducting oxide compounds

Bismuth high T _c superconducting oxide compounds were obtained by sol-gel method using acetate precursors. A study of the decomposition of quasi-amorphous acetates has been carried out to establish the conditions of superconducting phase formation. A comparison of the acetate sol-gel route with the oxalate coprecipitation method (previously used by the authors) reveals comparable results. Both methods require much shorter periods of thermal treatment for the formation of superconducting phases, as compared with the solid state reactions. The sol-gel route leads to better results from this point of view.     

The Role of Active Oxygen Transfer through the Gas Phase in Propylene Oxidation over a Bismuth–Molybdenum Catalyst

The transfer of atomic oxygen from the surface of bismuth oxide onto molybdenum oxide through the gas phase, including the case when ozone was fed to the catalyst bed, is experimentally studied. It is found that the transfer of atomic oxygen through the gas phase only leads to the formation of the products of complete oxidation of propylene under conditions of heterogeneous propylene oxidation on the mixture of molybdenum and bismuth oxides. No new sites are formed on the surface of molybdenum oxide.     

Studies on the Preparation and Properties of Some Phenolic Derivatives of Biscyclopentadienyl Molybdenum (VI) and Bisindenyl Molybdenum (VI) Oxide Dichloride

Reactions of biscyclopentadenyl molybdenum (VI) oxide dichloride (I) and bisindenyl molybdenum (VI) oxide dichloride (II) with mono-, di- and trihydroxy phenols have been studied and the phenoxide derivatives so formed have been isolated. Infrared spectra and some phenolic derivatives of these compounds have been studied.     

Thermogravimetric study of yttrium isopropoxide and dispersant burnout in aluminum nitride ceramic processing

Yttrium isopropoxide, an yttrium oxide precursor, is sometimes used as a sintering aid for producing aluminum nitride ceramics. In the present work, this sintering aid was used with isopropanol as the solvent and polyethyleneimine as the dispersing agent. After initial ball milling and drying steps, the burnout behaviour of samples taken from isostatically pressed pellets was studied by thermal analysis in nitrogen and air. In addition to the milled and pressed pellets, each component was also analyzed separately. Complete conversion to yttrium oxide, with no residual carbon, would be a desirable property of this system. However, during the preparation of the aluminum nitride pellet, there was only partial yttrium isopropoxide decomposition. The nitrogen burnout residue contained carbon formed from the yttrium isopropoxide and dispersant overlapping thermal decomposition, mostly from an intermediary decomposition stage of the former that occurs between 300 and 550°C. The residual carbon content and the previous yttrium isopropoxide decomposition were estimated by thermogravimetry.     

The influence of trace water concentration on iron oxide nanoparticle size

The size of iron oxide nanoparticles, prepared from the thermal decomposition of Fe(CO)(5) in a high boiling solvent in the presence of oleic acid, is affected by water concentration, giving particles from sizes of 5.6 nm to as low as 2.2 nm.     

A study on Zn-based catal-sorbents for the simultaneous removal of hydrogen sulfide and ammonia at high temperature

To simultaneously remove hydrogen sulfide and ammonia from hot coal gases, the ammonia decomposition abilities of various metal oxide catalysts were tested in the absence/presence of hydrogen sulfide, at 650 °C. Cobalt oxide, molybdenum oxide, and nickel oxide have high ammonia decomposition abilities (>95%) in the absence of hydrogen sulfide, but such abilities rapidly decreased during the reaction in the presence of hydrogen sulfide. To improve the simultaneous removal abilities of metal oxides, Zn-based catal sorbents were prepared via impregnation with various metals, such as cobalt, nickel, and molybdenum, on zinc oxide. The CZ-30 (promoted with 30 wt% cobalt oxide on zinc oxide) and NZ-30 (promoted with 30 wt% nickel oxide on zinc oxide) catal sorbents showed excellent sulfur removal capacities, which, calculated until the breakthrough point, were 0.35 and 0.39 g S/g catal sorbent, respectively, while MZ-30 promoted with molybdenum showed a low sulfur removal capacity of 0.08 g S/g catal sorbent. The ammonia decomposition ability of CZ-30, however, increased more than 18 times compared with Co₃O₄, whose ammonia decomposition ability was more than 95% until 465 min, even though the ammonia decomposition ability of NZ-30 sharply decreased after 30 min. The CZ catal sorbent is a good candidate for the simultaneous removal of ammonia and hydrogen sulfide.     

Preparation and Characterization of Molybdenum Oxide Thin Films by Sol-Gel Process

This paper presents a new sol-gel process to prepare molybdenum oxide thin films. A molybdenum acetylacetonate sol was prepared by employing the system CH₃COCH₂COCH₃/MoO₃/C₆H₅CH₃/HOCH₂CH₂OCH₃. A molybdenum acetylacetonate gel was prepared by addition of aqueous NH₃. Thermal gravimetry (TG) and differential thermal analyses (DTA) of the gel suggested that crystallization of MoO₃ occurs in a 140 K temperature range around 508°C. MoO₃ films were prepared on fused silica, Si (111) and Al₂O₃ (012) substrates by annealing spin coating films of the sol in oxygen environment at 508°C. X-ray diffraction (XRD) showed that all films crystallize in -MoO₃ structure, and crystallites on fused silica substrate are arbitrarily oriented while those on Si (111) and Al₂O₃(012) substrates oriented in the (010) direction. SEM investigations showed that MoO₃ grains of all films are randomly distributed, with a longitudinal dimension of about 1–5 m and the film thickness is about 1 m.     

Electrolytic Deposition of Molybdenum Oxide from Aqueous Solutions at Room Temperature

The conditions of electrolytic deposition of molybdenum oxide from aqueous solutions at room temperature were studied and the optimal parameters of electrolysis, which provide deposits with necessary physical and structural characteristics, were chosen.     

The chemical analysis of ternary alloys of plutonium with Molybdenum and Uranium

It is shown that the absorptiometric determination of molybdenum as thiocyanate may be used in the presence of plutonium. Molybdenum interferes with previously published methods for determining uranium and plutonium but conditions have been established for its complete removal by solvent extraction of the compound with a-benzoin oxime. The previous methods for uranium and plutonium are satisfactory when applied to the residual aqueous phase following this solvent extraction.