ナノ細孔をもつ光・酸化および水素化触媒の構築と地球環境改善への展開(2004年度神奈川大学総合理学研究所共同研究助成論文)

概要

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Novel microporous rhodium(II) carboxylate polymer complexes having metal-loporphyrin, Rh_2[MTCPP] (M = H_2 1, Cu^<2+> 2, Ni^<2+> 3, Pd^<2+> 4) (H_2TCPP - 4,4',4'',4'''t-(21H;23H-porphine-5,10,15,20-tetrayl)tetrakis benzole acid), were synthesized and completely characterized by elemental analysis, TG/DTA, magnetic susceptibilities, FT-IR, DR-UV-vis, XRPD, BET analysis, and nitrogen adsorption measurements. These complexes possess carboxylate bridged dinuclear rhodium(II) sites and mononuclear copper(II), nickel(II), and palladium(II) centers in the porphyrin ring to form uniform micropores of ca. 5.0 Å. Furthermore, they show high surface areas and high nitrogen adsorption capacities, and act as efficient heterogeneous catalysts for hydrogenation of olefins at approximately 200 K. The unique bimetallic effects shown by metalloporphyrin and dinuclear rhodium sites in micropores were investigated by kinetic studies and hydrogen and propene adsorption-desorption measurements; the priority coordination of olefins onto metalloporphyrins and the intramolecular transfer of hydrogen from rhodium center to the olefin molecule coordinated onto metalloporphyrin remarkably reflects the catalytic activities in hydrogenation.
神奈川大学の論文
2005-05-25