Formation of New Phase at the Metal/Oxide Interface and Its Catalyses

1.第八族金属SiO_2负载双金属氧化物的制备为制备分散均匀的Rh、Ni、Fe单相复合氧化物，对化学混合方法和热混合方法进行了深入的研究。建立了RhNbO_4、RhVO_4、Mn-Rh_2O_4、Mo-Rh_2O_6、NiAl_2O_4、NiTiO_3、NiTA_2O_6、Ni_2V_2O_8、NiNb_2O_6、Fe-NbO_4、FeAl_2O_4和AlNbO_4.2几种负载型氧化物的测定方法。还考察了第VIII族金属负载型双氧化物在催化还原/氧化过程中的化学行为。金属-氧化物相互作用的修饰模型普遍适用于这些双氧化物体系，研究了这些双氧化物在几种催化剂上的SMSI行为，发现了许多有趣的事实，如SMSI极大地加速了乙烯的氢甲酰化活性，MnRh_2O_4和MoH_2O_6对氢解反应具有极高的催化活性等。甲烷部分氧化制合成气传统负载型金属催化剂催化甲烷部分氧化制合成气的研究从金属间催化活性的比较、反应机理的阐明等方面进行了研究。确定了反应途径，即先将CH_4完全氧化成CO_2/H_2O，再由CO_2/H_2O重整CH_4生成CO/H_2。Al_2O_3的载体作用是通过活化CO_2来区分的。采用交替脉冲反应体系，即金属的氧化和用CH_4还原金属，可以降低反应温度。

1. Preparation of SiO_2 Supported Double Oxides of Group VIII MetalsChemical mixing methods as well as thermal ones were investigated intensively to prepare the finely dispersed single phase double oxides of Rh, Ni and Fe. The methods were established for several kinds of supported oxides such as RhNbO_4, RhVO_4, Mn-Rh_2O_4, Mo-Rh_2O_6, NiAl_2O_4, NiTiO_3, NiTa_2O_6, Ni_2V_2O_8, NiNb_2O_6, Fe-NbO_4, FeAl_2O_4 and AlNbO_4.2. Characteristics of Supported Double Oxides of Group VIII Metals on CatalysesChemical behaviors of all these oxides during reduction/oxidation were also examined. The so-called decoration model on metal-oxide interactions was found to be effective generally on these double oxide systems.SMSI behaviors of these double oxides were studied on several catalyses, leading to the findings of many interesting facts, e.g., extreme acceleration of hydorformylation activity of ethylene by SMSI, extremely high catalytic activities of MnRh_2O_4 and MoRh_2O_6 on hydrogenolysis, and so on.3. Synthetic Gas Production by Partial Oxidation of MethaneThe production of synthetic gas by catalytic partial oxidation of methane using conventional supported metal catalysts was studied from the viewpoints of comparisons of catalytic activities among metals, an elucidation of reaction mechanism, and so on. The reaction pathways were confirmed, that is, the complete oxidation of CH_4 to CO_2/H_2O proceeds at first, and then the reforming of CH_4 by CO_2/H_2O does to give CO/H_2. The support effect of Al_2O_3 was distinguished through activation of CO_2. It was able to lower the reaction temper-ature by the application of alternative pulse reaction system, i.e., oxidation of metals and their reduction with CH_4.