title: Periodic mesoporous organosilicas: a type of hybrid support for water-mediated reactions.
abstract: 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.
authors.affiliation: Department of Chemistry, Shanghai Normal University, 100 Guilin Road, Shanghai 200234, China. ywan@shnu.edu.cn
authors.forename: Ying
authors.initials: Y
authors.lastname: Wan
authors.forename: Dieqing
authors.initials: D
authors.lastname: Zhang
authors.forename: Yunpu
authors.initials: Y
authors.lastname: Zhai
authors.forename: Cuimiao
authors.initials: C
authors.lastname: Feng
authors.forename: Jia
authors.initials: J
authors.lastname: Chen
authors.forename: Hexing
authors.initials: H
authors.lastname: Li