STRUCTURAL AND ELECTRONICAL CONTROL OF METAL IONS SUPPORTED ON OXIDES

1.在二氧化硅负载的氧化铜催化剂的制备中乙酸铜与二氧化硅载体的相互作用：研究了乙酸铜（铜离子的前体）与二氧化硅载体以及单-、二-和三-氯乙酸铜的相互作用。通过红外光谱和电子自旋共振（ESR）技术研究发现，二氧化硅表面的OH-基团通过与配合物的末端配位而起到稳定配合物的作用.铜-吡啶络合物固定在硅胶或分子筛上，其结构和催化性能：发现铜-吡啶络合物Cu（Py）_nn = 3-4固定在硅胶或2-[2-（三氯硅基）乙基]吡啶改性的分子筛上。该配合物易被还原和氧化，在硅胶上或沸石中形成Cu：O_2 = 2：1或1：1的氧加合物，对苯酚的二聚或多聚反应具有特定的催化活性和选择性。分子筛超笼的连续甲基化利用分子筛的疏水性提高了分子筛的催化活性，这与酶促反应相似.氧化硅载体在氧化硅负载钼催化剂中的作用：在CO气氛下，氧化硅上的钼物种被发现容易被光还原成其四面体结构，这是由氧化硅的四面体结构诱导的。将其暴露于水得到在二氧化硅上的12-羟基喹啉酸，其显示固体酸的催化性质。钴离子或钴卟啉配合物在无机基质上的固定及其对CO_2还原的催化性能：用4-[2-（三氯硅基）乙基]吡啶或氯化亚砜的吡啶衍生物修饰氧化锡或玻碳，研究了四苯基卟啉钴（CoTPP）的固定及其结构和对CO_2还原的电催化性能。通过光谱法确认CoTPP/Py的形成。该催化剂对CO_2的电还原具有很高的催化活性。

1. Interaction of cupric acetate with silica support in the preparation of a silica- supported copper oxide catalyst: Interaction of with cupric acetate, a precursor of cupric ions, with silica support was studied as well as cupric mono-, di- and tri-chloro acetate. An OH- group on silica was found to stabilize the complexes by coordinating it to the terminal position by an IR or ESR technique.2. Copper-pyridine complex fixed on silica or in zeolite, and its structural and catalytic properties: Copper-pyridine complex, Cu(Py)_n n = 3-4, was found to be fixed on silica or in zeolite modified with 2-[2-(tricnlotosilyl)-ethyl] pyridine. This complex showed to be reduced and oxidized easily, to form its oxygen adducts of Cu:O_2 = 2:1 on silica or 1:1 in zeolite, and to give specific catalytic activity and selectivity in dimerization or polimerization of phenol. Successive methylation of supercage of zeolite increased its catalytic activity by its hydrophobic property, indicating the similarity with an enzymic reaction.3. Role of silica support in a silica-supported molybdenum catalyst: Molybdenum species on silica was found to be photoreduced easily in its terahedral structure induced by that of silica under CO atmosphere. Exposure of it to water gave 12 molybdosilic acid on silica, which showed catalytic property of a solid acid.4. Cobalt ions or cobalt porphyrine complex fixed on inorganic matrix and their catalytic property to reduction of CO_2: Fixation of cobalt tetraphenyl porphyrine ( CoTPP ) was carried out on tin oxide or glassy carbon modified with 4-[2-(trichlorosilyl)ethyl] pyridine or pyridine derivative of thionyl chloride with studies of its structure and electro- catalytic properties to reduction of CO_2. Formation of CoTPP/Py was confirmed spectroscopically. High catalytic activity was found to electroreduction of CO_2.