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Preparation of various transition metal coordination polymer complexes and their catalytic behavior as nanospace catalysts

多种过渡金属配位聚合物配合物的制备及其纳米空间催化剂的催化性能

基本信息

批准号：
14350428
负责人：
NAITO Shuichi
金额：
$ 8.77万
依托单位：
KANAGAWA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

We have investigated the catalytic behavior as well as adsorption behavior over coordination polymer complexes of Rh(dicarboxilate), Co(bipyridyl) and metal encapsulated silica and titania nanotube catalysts.When fumalic acid, thelephalic acid, nathalene dicarboxylic acid, mucone acid were used as ligands, Rh dicroboxylic complexes exhibited gas occlusion ability such as H_2, CO, NO, various olefins and pallafines (several molecules per one Rh metal). The amount of occlusion depended on the sizes of ligands as well as absorbent molecules, however, gradual crystallization of the polymer complexes took place, which caused the decrease of the amount of occlusion. H_2-D_2 hydrogen exchange reaction took place as low temperatures as 200 K, and two different exchange mechanisms were observed between dissociatively adsorbed H(a) and D(a) and between D(a) and hydrogen in ligand molecules. Hydrogen exchange and hydrogenation of olefin also took place below room temperatures, where former exchan … More ge proceeded only inside the pores of the polymer complexes although the latter exchange proceeded both inside the pores and over outer surfaces of the complexes. The gradual crystallization of the complexes again took place with the repeated catalytic reactions. TEM observation revealed uniform sphere particles rather than sheet structures.In the case of Co(bipyridyl) coordination polymer complexes, a large amount of NH_3 occlusion was observed, which accelerated the reduction of NO by NH_3, showing a important role of pore structures for NO-NH_3 reaction to form N_2 selectivery.Selective permeation property of H_2 took place progressively by higher temperature evacuation of Pt-SiO_2 nanotubes, indicating the formation ultra micro pores inside the network of silica walls. There existed a few ten nm Pt particles inside the tubes and sub-nm Pt clusters inside the silica networks of the wall, and the latter Pt might be responsible for the characteristic catalytic behavior in CO-H_2 reaction. Pt encapsulated TiO_2 nanotubes exhibited one order of magnitude larger TOF in CO-H_2O and CO-H_2 reactions than conventional impregnated Pt/TiO_2 catalysts. More than 90% selectivity for methanol formation was acheved in CO-H_2 reaction in the case of nanotube catalysts. Exceptionally strongly adsorbed CO, which was observed by FT-IR may be responsible for these unique catalytic behavior of these nanotube catalysts. Less

我们研究了Rh配位聚合物配合物的催化行为和吸附行为（二羧酸），钴以富马酸、噻吩二甲酸、萘二甲酸、粘酮酸为配体时，Rh二羧酸配合物表现出对H_2、CO、NO等气体的吸附能力，各种烯烃和钯（每种Rh金属几个分子）。吸藏量与配体和吸附剂分子的大小有关，但随着聚合物的逐渐结晶，吸藏量逐渐减少。H_2-D_2氢交换反应在200 K低温下发生，解离吸附的H（a）与D（a）之间以及D（a）与配体分子中的氢之间存在两种不同的交换机理。氢交换和烯烃加氢也发生在室温以下， ...更多信息 Ge仅在聚合物络合物的孔内进行，尽管后者的交换在孔内和络合物的外表面上都进行。随着重复的催化反应，络合物的逐渐结晶再次发生。透射电镜观察显示均匀的球形颗粒，而不是片状结构。（联吡啶）配位聚合物配合物中，大量的NH_3吸附在配合物上，加速了NH_3对NO的还原，Pt-SiO_2催化剂的孔结构对NO-NH_3反应生成N_2的选择性起着重要的作用。2纳米管，表明二氧化硅壁网络内部形成超微孔。在管壁的二氧化硅网络中，存在少量的10 nm Pt颗粒和亚nm Pt团簇，后者可能是CO-H_2反应的特征催化剂。在CO-H_2 O和CO-H_2反应中，Pt/TiO_2纳米管的飞行时间比传统的浸渍Pt/TiO_2催化剂大一个数量级。在碳纳米管催化剂上，CO-H_2反应的甲醇选择性大于90%。FT-IR分析表明，这些纳米管催化剂的催化性能与CO的强烈吸附有关。少