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In recent years,much effort has been made on the development of novel porous monolithic materials for separation science,with advantages of high permeability to flow and low back pressure of preparation.Among various monoliths,organic-inorganic hybrid monoliths have drawn much more attention due to their improved chemical stability in wide pH ranging compared with silica monoliths,and relatively high surface area(typically around 300 m2·g-1)compared to polymer monoliths.Recently,hybrid materials with organic bridged-bonded alkoxysilane precursors((RO)3Si–R–Si(OR)3,R: CH2CH3,CH2=CH2 or C6H4,R: methyl or ethyl)have attracted more and more attention,due to their unique features of high-loading of organic content,insignificant pore blockage,homogeneously distributed functional groups and good chemical stability with C-C bonds in the framework of structures.In this study,we synthesized a novel kind of hierarchically porous hybrid monolith with 100% vinyl groups in the framework by one-step “sol-gel” condensation of ethylene-bridged alkoxysilane precursor.Such monolith possesses good chemical stability within the pH range of 2-10 and large surface area as high as 1707 m2·g-1.With vinyl groups homogeneously distributed in the skeleton of the monolith,it can be easily functionalized with various thiol groups by thiol-ene “click” chemistry reaction for widespread applications.