Periodic Mesoporous Organosilicas: A Type of Hybrid Support for Water-Mediated Reactions

Hybrid mesoporous periodic organosilicas (Ph‐PMOs) with phenylene moieties embedded inside the silica matrix were used as a heterogeneous catalyst for the Ullmann coupling reaction in water. XRD, N2 sorption, TEM, and solid‐state NMR spectroscopy reveal that mesoporous Ph‐PMO supports and Pd/Ph‐PMO...

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Bibliographic Details
Published in:Chemistry, an Asian journal an Asian journal, 2007-07, Vol.2 (7), p.875-881
Main Authors: Wan, Ying, Zhang, Dieqing, Zhai, Yunpu, Feng, Cuimiao, Chen, Jia, Li, Hexing
Format: Article
Language:English
Subjects:
catalyst supports
hydrophobic effect
mesoporous materials
organosilicas
water
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Summary:Hybrid mesoporous periodic organosilicas (Ph‐PMOs) with phenylene moieties embedded inside the silica matrix were used as a heterogeneous catalyst for the Ullmann coupling reaction in water. XRD, N2 sorption, TEM, and solid‐state NMR spectroscopy reveal that mesoporous Ph‐PMO supports and Pd/Ph‐PMO catalysts have highly ordered 2D hexagonal mesostructures and covalently bonded organic–inorganic (all Si atoms bonded with carbon) hybrid frameworks. In the Ullmann coupling reaction of iodobenzene in water, the yield of biphenyl was 94 %, 34 %, 74 % and for palladium‐supported Ph‐PMO, pure silica (MCM‐41), and phenyl‐group‐modified Ph‐MCM‐41 catalysts, respectively. The selectivity toward biphenyl reached 91 % for the coupling of boromobenzene on the Pd/Ph‐PMO catalyst. This value is much higher than that for Pd/Ph‐MCM‐41 (19 %) and Pd/MCM‐41 (0 %), although the conversion of bromobenzene for these two catalysts is similar to that for Pd/Ph‐PMO. The large difference in selectivity can be attributed to surface hydrophobicity, which was evaluated by the adsorption isotherms of water and toluene. Ph‐PMO has the most hydrophobic surface, and in turn selectively adsorbs the reactant haloaryls from aqueous solution. Water transfer inside the mesochannels is thus restricted, and the coupling reaction of bromobenzene is improved. Support network: Hybrid mesoporous periodic organosilicas (Ph‐PMOs) with embedded phenylene moieties can be used in heterogeneous catalysis for Ullmann coupling in water. The Pd/Ph‐PMO catalyst exhibits much higher activity than the related pure silica (MCM‐41) and phenyl‐modified silica (Ph‐MCM‐41) catalysts. This could be due to the hydrophobic surface of Ph‐PMO, which selectively adsorbs haloaryls from aqueous solution.
ISSN:1861-4728
1861-471X
DOI:10.1002/asia.200700057