title: Morphology Tailoring of Sulfonic Acid Functionalized Organosilica Nanohybrids for the Synthesis of Biomass-Derived Alkyl Levulinates.
abstract: Morphology evolution of sulfonic acid functionalized organosilica nanohybrids (Si(Et)Si-Pr/ArSO3 H) with a 1D tubular structure (inner diameter of ca. 5 nm), a 2D hexagonal mesostructure (pore diameter of ca. 5 nm), and a 3D hollow spherical structure (shell thickness of 2-3 nm and inner diameter of ca. 15 nm) was successfully realized through P123-templated sol-gel cocondensation strategies and fine-tuning of the acidity followed by aging or a hydrothermal treatment. The Si(Et)Si-Pr/ArSO3 H nanohybrids were applied in synthesis of alkyl levulinates from the esterification of levulinic acid and ethanolysis of furfural alcohol. Hollow spherical Si(Et)Si-Pr/ArSO3 H and hexagonal mesoporous analogues exhibited the highest and lowest catalytic activity, respectively, among three types of nanohybrids; additionally, the activity was influenced by the -SO3 H loading. The activity differences are explained in terms of different Brønsted acid and textural properties, reactant/product diffusion, and mass transfer rate, as well as accessibility of -SO3 H sites to the reactant molecules. The reusability of the nanohybrids was also evaluated.
authors.affiliation: School of Chemistry, Northeast Normal University, 5268 Renmin Street, Changchun 130024 (P.R. China).
authors.forename: Sai
authors.initials: S
authors.lastname: An
authors.affiliation: School of Chemistry, Northeast Normal University, 5268 Renmin Street, Changchun 130024 (P.R. China).
authors.forename: Daiyu
authors.initials: D
authors.lastname: Song
authors.affiliation: School of Chemistry, Northeast Normal University, 5268 Renmin Street, Changchun 130024 (P.R. China).
authors.forename: Bo
authors.initials: B
authors.lastname: Lu
authors.affiliation: School of Environment, Northeast Normal University, 2555 Jingyue Street, Changchun 130117 (P.R. China), Fax: (+86) 431-89165626.
authors.forename: Xia
authors.initials: X
authors.lastname: Yang
authors.affiliation: School of Environment, Northeast Normal University, 2555 Jingyue Street, Changchun 130117 (P.R. China), Fax: (+86) 431-89165626. guoyh@nenu.edu.cn.
authors.forename: Yi-Hang
authors.initials: YH
authors.lastname: Guo
mesh_terms: D018533:Biomass; D002384:Catalysis; D007982:Levulinic Acids / Q000138:chemical synthesis* / Q000302:isolation & purification; D049329:Nanostructures / Q000737:chemistry* / Q000648:ultrastructure; D017646:Organosilicon Compounds / Q000737:chemistry*; D016062:Porosity; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D007982:Levulinic Acids; D017646:Organosilicon Compounds; D013451:Sulfonic Acids; C032246:levulinic acid
keywords: biomass; heterogeneous catalysis; nanostructures; organic-inorganic hybrid composites; silicates