Property and Activity of Molybdates Dispersed on Silica Obtained from Various Synthetic Procedures

The synthesis and characterization of several dispersed molybdena catalysts on silica support (MoO3-SiO2) prepared from a variety of precursors (Mo(VI)-acetylacetonate, oxo-peroxo Mo-species, hydrated ammonium heptamolybdate) and preparation methods (deposition of the Mo-phase on finite SiO2 support by aqueous and methanol impregnations, by adsorption, by oxo-peroxo route-like, and by one-step synthesis of MoO3-SiO2 system with molecular precursors) are presented. The molybdena concentration on silica was comprised in a large interval (1.5 - 14 wt%) depending on the preparation method which governed the Mo-loading on silica. Convenient comparisons among samples at similar Mo-concentration have been made discussing the morphologic-structural (XRD, XPS, UV-vis-DRS, and N2-adsorption) and physicochemical (TG-DTG, TPR, and n-butylamine-TPD) sample properties. Polymeric octahedral polymolybdate aggregates predominated in the samples prepared by aqueous and methanol impregnations, which were at high Mo-concentration. On the contrary, isolated Mo(VI) species in distorted Td symmetry predominated in the sample prepared by adsorption which was at very low Mo-concentration. The sample acidity was composed of a weak acidy site population, associated with the silica support, and a strong acid site population associated with the Mo-dispersed phase. Oxidation tests of formaldehyde, an oxygen-containing VOC (Volatile Organic Compound), were performed to determine the prevalent redox or acidic function of the Mo-species at the surface of the catalysts.

合成氨工业催化剂的一种新型前躯体—维氏体

关于合成氨铁系催化剂最佳氧化态前躯体相矛盾的实验结果推动了当前以维氏体和磁铁矿为母体的催化剂的比较研究。测定了两种催化剂的许多物理性质(密度、孔结构、晶相、还原速率、金属表面、磨耗量)和催化性能(动力学常数、耐热性)。证明了以维氏体为母体的催化剂具有更高的活性,尤其是在低温下,除了在高转化率情况下之外,可以达到Ru/C催化剂的性能。本文讨论了以维氏体为母体的催化剂具有这种特性的可能原因,并且建议有必要对合成氨铁系催化剂现有统一的理论知识进行重新考虑。