Abstract
Peroxo-heteropoly compound PO(4)[W(O)(O(2))(2)] was synthesized on calcium-deficient hydroxyapatite using a reaction of surface [HPO(4)](2-) groups on hydroxyapatite with a Na(2)[W(2)O(3)(O(2))(4)] aqueous solution. The vibration of [HPO(4)](2-) at 875 cm(-1) became very weak, and the vibration of the peroxo-oxygen bond [O-O](2-) at 845 cm(-1) appeared in the FT-IR spectrum of the solid product, indicating that PO(4)[W(O)(O(2))(2)] was formed on the surface of hydroxyapatite. The formed solid sample was further reacted with PdCl(2)(PhCN)(2) in an acetone solution to fix PdCl(2) between the O sites on the hydroxyapatite. Elemental analyses proved that the resultant solid contained 1.2 wt.% Pd, implying that PdCl(2) molecules were immobilized on the surface of hydroxyapatite. The hydroxyapatite-based hybrid compound containing Pd and PO(4)[W(O)(O(2))(2)] was used as a heterogeneous catalyst in a methanol solvent for propylene epoxidation by molecular oxygen in an autoclave batch reaction system. A propylene conversion of 53.4% and a selectivity for propylene oxide of 88.7% were obtained over the solid catalyst after reaction at 363 K for 8 h. The novel catalyst could be reused by a simple centrifugal separation, and the yield of propylene oxide did not decrease after the reaction for five runs. By prolonging the reaction time to 13 h, the highest yield of propylene oxide at 363 K over the solid catalyst was obtained as 53.8%, which was almost the same as that of the homogeneous catalyst containing PdCl(2)(PhCN)(2) and [(C(6)H(13))(4)N](2){HPO(4)[W(O)(O(2))(2)](2)} for the propylene epoxidation. Methanol was used as a solvent as well as a reducing agent in the propylene epoxidation by molecular oxygen. Small particles of Pd metal were formed on the surface of the hybrid solid catalyst during the reaction, and acted as active species to achieve the catalytic turnover of PO(4)[W(O)(O(2))(2)] in the propylene epoxidation by molecular oxygen in methanol.