Development of Metal Cluster Catalysts Supported on Porous Chelate Resins

1. 螯合树脂上金属团簇的固定化将六氯铂酸盐离子固定在螯合树脂的铝络合物上，交联含有亚氨基二乙酸基团的聚苯乙烯，然后用硼化锂连续还原铂（IV）离子，得到树脂负载的铂团簇催化剂。通过与铝（III）离子交换得到钠(I)和镁（II）衍生物。用硼氢化锂固定钯离子，制备了络合树脂负载钯簇催化剂。螯合树脂配合物负载金属簇的表征螯合树脂配合物以及含金属簇的螯合树脂配合物的表面积随着所涉及金属离子的价态而增加。螯合树脂的Al （III）配合物簇簇直径大多为40 A，而铂簇簇的平均直径为26 A，说明簇簇颗粒占据了孔隙。树脂中的金属离子也会影响团簇的分布。螯合树脂络合物负载金属团簇的催化作用由此得到的铂和钯团簇在温和条件下作为烯烃和二烯加氢的催化剂具有活性。催化活性随树脂表面积的增加而增加。氢化速率还取决于基质-载体的相互作用和载体中团簇的分布。

1. Immobilization of Metal Clusters on Chelate ResinImmobilization of hexachloroplatinate ions on the aluminum complex of the chelate resin, crosslinked polystyrene containing iminodiacetic acid moieties, and then successive reduction of the platinum (IV) ions by lithium borotydride gave the resin-supported platinum cluster catalyst. Sodium (I) and magnesium (II) derevatives were obtained by ion exchange with aluminum (III). The chelate resin complex-supported palladium cluster catalysts were prerared by immobilization of palladium (II) ions with lithium borohydride.2. Characterization of Chelate Resin Complex-Supported Metal ClusrersThe surface area of the chelate resin complex as well as the metal cluster-containing chelate resin complex increases with the valency of the metal ion involved. Most of the porse of the Al (III) complex of the chelate resin are 40 A in diameter, while the platinum cluster has the average diameter of 26 A, which suggests the cluster particles occupy the pores. The metal ion involved in the resin can affect the distribution of clusters, too.3. Catalyses of Chelate Resin Complex-Supported Metal ClustersThe platinum and palladium clusters thus obtained are active as the catalysts for hydrogenation of olefin and diene under mild conditions. The catalytic activity increases with increase of the surface area of the resin. The hydrogenation rate also depends both on the substrate-support interaction and on the distribution of the clusters in the support.