环保型催化材料氮化钼的合成与表征

采用溶胶-凝胶法制备了负载型氮化钼的前驱体,采用流化氮化新工艺制备了氮化钼。通过单因素和正交实验,确定了较优氮化条件:升温速率为1.2℃/min,H2∶N2=4.0∶1,空速70×103h-1,氮化终温为650℃,活性组分MoO3含量为10%。并采用BET、XRD、SEM等对制备的氮化钼及前驱体进行了表征。     

Selectivities in methanol oxidation over silica supported molybdena

Selectivities in methanol oxidation over silica supported molybdenum oxide catalysts were investigated in relation with the phase distribution. The supported catalysts were prepared by impregnation with ammonium heptamolybdate. In addition to crystalline MoO₃, Mo containing cluster species of 1–2 nm size were observed by STEM even from a used catalyst with 13% catalyst loading. The percentage of Mo present as crystalline MoO₃ increases with the catalyst loading. An ESCA study indicates that part of surface Mo in the supported catalysts is reduced to Mo⁵⁺. The dimethyl ether selectivity increases with the catalyst loading and its formation occurs over the crystalline MoO₃ phase. The Selectivities to CO and methyl formate are greatly enhanced because of the presence of support, and are relatively independent of the catalyst loading and phase distribution. The dependence and independence of the Selectivities of different byproducts on the loading make the silica supported catalysts with high catalyst loadings less selective for the partial oxidation of methanol to formaldehyde.     

Hardness and Fracture Toughness of SiC-Particle-Reinforced MoSi2 Composites

The indentation technique has been used to evaluate the hardness and fracture toughness of SiC-reinforced MoSi₂ composites made by hot-pressing. It is seen that the toughness increases with increasing indentation crack length (under increasing load) and a probable mechanism responsible for this behavior is described. It is also observed that there is an optimum volume fraction of SiC particles for which the maximum fracture toughness of the composite can be achieved.     

甲烷磺酰氯的合成研究

阐述了利用二甲基二硫在相转移催化剂作用下，于盐酸介质中经氯气直接氧化，一步合成甲烷磺酰氯的工艺过程，讨论了几个主要反应因素对产物收率的影响，确定了适宜的工艺条件。表明了产品的检测方法     

酯对钼系Ziegler-Natta催化剂引发丁二烯聚合的影响

以MoCl_4(Mo)为主催化剂,甲苯氧基二异丁基铝(Al)为助催化剂,在加氢汽油溶剂中,研究了8种酯对丁二烯(Bd)聚合的影响。结果表明,凡是能够溶解在酯中的Mo与Al所组成的二元催化体系,大多能很好地引发Bd聚合,并有较高的催化活性。酯的主要作用是增加Mo在加氢汽油中的溶解性,对聚合物的分子量影响不大,对微观结构几乎无影响。     

Kinetics of Solid-State Reactions in Heterogeneous Catalysis from Time-Resolved X-Ray Absorption Spectroscopy

The potentials of X-ray absorption spectroscopy (XAS) (quantitative phase composition and average valence together with a short-range order structure analysis) combined with a time-resolution in the second range make time-resolved (TR-) XAS a powerful tool for investigating the reactivity of solids in catalysis and solid-state chemistry. General aspects of TR-XAS investigations are discussed (i.e., instrumentation, data analysis). In addition, some experiments illustrate how the kinetics of solid-state reactions in heterogeneous catalysis can be elucidated from TR-XAS studies.     

甲醇在聚苯胺修饰铂钼共沉积电极上的催化氧化

用恒电位法和循环伏安法在铂电极上分别制备了聚苯胺修饰的分散氢钼青铜电极和分散铂电极,以及聚苯胺修饰的不同铂钼比例的铂与氢钼青铜共沉积电极。用循环伏安法研究了制备电极在c(H2SO4)=0.5mol/L水溶液中的电化学行为,以及对c(CH3OH)=0.1 mol/L的催化氧化行为。其中,分散氢钼青铜电极对甲醇无催化氧化的作用,铂与氢钼青铜共沉积电极对甲醇的催化氧化效果优于分散铂电极。铂-氢钼青铜共沉积电极对甲醇氧化的催化能力与共沉积铂钼的比例有关,当制备电极所用的溶液中n(氯铂酸)∶n(钼酸钠)=2∶1时,共沉积电极对甲醇的催化氧化活性最高,此时甲醇在共沉积电极上的氧化峰电流是单纯铂电极的2.632倍。     

钼矿尾矿铜铅重金属离子溶出规律研究

为了评估钼矿尾矿的环境危害,通过105 d连续静态浸泡试验,定期监测钼矿尾矿浸泡液的pH值及其铜铅重金属离子浓度,研究了尾矿的离子溶出规律.结果表明,尾矿对酸性溶液有很强的中和能力,可将pH=3.5～6的酸性溶液在8 d内中和到pH=7的中性状态,并维持不变.液固比为1:10的浸泡液中Cu~(2+)和Pb~(2+)的浓度都在25 d内达到最大值(分别为29.52和9.40μg/L),此后浓度下降,并发生震荡,但Cu~(2+)和Pb~(2+)的浓度随时间的变化趋势不同.浸泡液中Cu~(2+)和Pb~(2+)的平均浓度分别为19.37和4.29μg/L,尾矿中Cu和Pb的平均溶出率分别为0.097%和0.043%.钼矿尾矿可在中性条件下长期释放Cu~(2+)和Pb~(2+),且Cu比Pb更容易溶出.     

蛋白质增敏钼-邻苯二酚紫体系的研究及应用

在pH=2.8的clark-lubs缓冲介质中,牛血清白蛋白能显著增敏钼-邻苯二酚紫的显色体系,据此建立了分光光度法测定钼的新方法。仔细考察了反应酸度、邻苯二酚紫浓度、牛血清白蛋白浓度及反应时间等因素对测定的影响。最大吸收波长在680 nm处,与钼-邻苯二酚紫体系相比,红移了120 nm。10 mL溶液中,钼质量在0～40μg范围内服从比尔定律,测定的表观摩尔吸光系数为2.11×104L/(mol.cm)。所拟方法简便、快速、灵敏度高,用于合金钢样品中微量钼的测定,结果与认定值一致。     

福建某钼矿的工艺矿物学研究

研究了福建某钼矿的工艺矿物学特征,分析了矿石的化学组成,对矿石中钼和硫矿物的种类、成分、粒度、嵌布特征进行测定和统计,根据钼和硫的工艺矿物学研究结果,提出提高钼和硫的选矿回收率的建议．