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J Am Chem Soc ; 123(43): 10502-10, 2001 Oct 31.
Article in English | MEDLINE | ID: mdl-11673981

ABSTRACT

Impregnation of hyper-cross-linked polystyrene (HPS) with tetrahydrofuran (THF) or methanol (ML) solutions containing platinic acid results in the formation of Pt(II) complexes within the nanocavities of HPS. Subsequent reduction of the complexes by H2 yields stable Pt nanoparticles with a mean diameter of 1.3 nm in THF and 1.4 nm in ML. The highest selectivity (98% at 100% conversion) measured during the catalytic oxidation of L-sorbose in water is obtained with the HPS-Pt-THF complex prior to H2 reduction. During an induction period of about 100 min, L-sorbose conversion is negligible while catalytic species develop in situ. The structure of the catalyst isolated after the induction period is analyzed by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. Electron micrographs reveal a broad distribution of Pt nanoparticles, 71% of which measure less than or equal to 2.0 nm in diameter. These nanoparticles are most likely responsible for the high catalytic activity and selectivity observed. The formation of nanoparticles measuring up to 5.9 nm in diameter is attributed to the facilitated intercavity transport and aggregation of smaller nanoparticles in swollen HPS. The catalytic properties of these novel Pt nanoparticles are highly robust, remaining stable even after 15 repeated uses.


Subject(s)
Cross-Linking Reagents/chemistry , Organoplatinum Compounds/chemistry , Polystyrenes/chemistry , Sorbose/chemistry , Catalysis , Cross-Linking Reagents/chemical synthesis , Kinetics , Magnetic Resonance Spectroscopy , Nanotechnology , Organoplatinum Compounds/chemical synthesis , Oxidation-Reduction , Polystyrenes/chemical synthesis , Sugar Acids/chemistry
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