SHIP-IN-BOTTLE SYNTHESIS OF PT9-PT15 CARBONYL CLUSTERS INSIDE NAY AND NAX ZEOLITES, INSITU FTIR AND EXAFS CHARACTERIZATION AND THE CATALYTIC BEHAVIORS IN (CO)-C-13 EXCHANGE-REACTION AND NO REDUCTION BY CO

[Pt9(CO)18]2-/NaY (orange-brown, 2056 and 1798 cm-1), [Pt12(CO)24]2-/NaY (dark-green, 2080 and 1824 cm-1 and [Pt15(CO)30]2-/NaX (yellow-green, 2100 and 1865 cm-1) were stoichiometrically synthesized by the reductive carbonylation of [Pt(NH3)4]2+/NaY, Pt2+/NaY and Pt2+/NaX, respectively. The IR bands characteristic of their linear carbonyls shift to higher frequencies whereas the bridging CO bands to lower frequencies, compared with those on the external zeolites and in solution. In-situ FTIR studies suggested that the subcarbonyl species such as PtO(CO) and "Pt3(CO)3(mu-2 - CO)3" are formed as the proposed intermediates towards [Pt12(CO)24]2-/NaY in the reductive carbonylation of Pt2+/NaY. (CO)-C-13 exchange reaction preceded with the different intrazeolite Pt carbonyl species in the following order of activity at 298-343 K: "Pt3(CO)3(mu-2 - CO)3"/NaY >> PtO(CO)/NaY > [Pt9(CO)18]2-/NaY > [Pt12(CO)24]2-/NaY. Pt-L3-edge EXAFS measurement for these synthesized samples demonstrated that they are consistent with the Pt carbonyl clusters having trigonal prismatic Pt9 and Pt12 frameworks inferred to a series of the Chini complexes such as [NEt4]2[Pt3(CO)6]n (n = 3-5). The intrazeolite Pt9 and Pt12 carbonyl clusters exhibited higher catalytic activity in NO reduction by CO towards N2 and N2O at 473 K, compared with those on the conventional Pt/Al2O3 catalysts. The mechanism of intrazeolite Pt9-Pt15 carbonyl cluster formation are discussed in terms of the intrazeolite basicity and acidity.