title: Orderly Layered Zr-Benzylphosphonate Nanohybrids for Efficient Acid-Base-Mediated Bifunctional/Cascade Catalysis.
abstract: The development of functional metal-organic materials that are robust and active for bifunctional/cascade catalysis is of great significance. Herein, a series of mesoporous and orderly layered nanohybrids were synthesized for the first time through simple and template-free assembly of ortho-, meta-, or para-xylylenediphosphonates (o-, p-, or m-PhP) containing zirconium. It was found that m-PhPZr nanoparticles (20-50 nm) with mesopores centered at 7.9 nm and high Lewis acid-base site ratio (1:0.7) showed excellent performance under mild conditions (as low as 82 °C) in transfer hydrogenation of carbonyl compounds, including bioaldehydes and alcohols, with near quantitative yields and little Zr leaching. Isotopic labeling studies indicated the occurrence of direct hydrogen transfer rather than metal hydride route by bifunctional catalysis. Lewis acidic (Zr) and basic (PO3) centers of the heterogeneous catalyst were further revealed to play a synergistic role in one-pot cascade transformations, for example, of ethyl levulinate to γ-valerolactone and glucose to 5-hydroxymethylfurfural.
authors.affiliation: Biomass Group, College of Engineering, Nanjing Agricultural University, 40 Dianjiangtai Road, Nanjing, Jiangsu, 210031, P.R. China.|State-Local Joint Engineering Laboratory for Comprehensive Utilization of Biomass, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering (Ministry of Education), Center for R&D of Fine Chemicals, Guizhou University, Guiyang, 550025, P.R. China.
authors.forename: Hu
authors.initials: H
authors.lastname: Li
authors.affiliation: Biomass Group, College of Engineering, Nanjing Agricultural University, 40 Dianjiangtai Road, Nanjing, Jiangsu, 210031, P.R. China.
authors.forename: Zhen
authors.identifier: 0000-0002-7391-372X
authors.initials: Z
authors.lastname: Fang
authors.affiliation: State-Local Joint Engineering Laboratory for Comprehensive Utilization of Biomass, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering (Ministry of Education), Center for R&D of Fine Chemicals, Guizhou University, Guiyang, 550025, P.R. China.
authors.forename: Jian
authors.initials: J
authors.lastname: He
authors.affiliation: State-Local Joint Engineering Laboratory for Comprehensive Utilization of Biomass, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering (Ministry of Education), Center for R&D of Fine Chemicals, Guizhou University, Guiyang, 550025, P.R. China.
authors.forename: Song
authors.initials: S
authors.lastname: Yang
mesh_terms: D002384:Catalysis; D004164:Diphosphonates / Q000737:chemistry; D006865:Hydrogenation; D058116:Lewis Acids / Q000737:chemistry; D058115:Lewis Bases / Q000737:chemistry; D049329:Nanostructures / Q000737:chemistry; D063065:Organophosphonates / Q000737:chemistry*; D014992:Xylenes / Q000737:chemistry; D015040:Zirconium / Q000737:chemistry*
chemical_list: D004164:Diphosphonates; D058116:Lewis Acids; D058115:Lewis Bases; D063065:Organophosphonates; D014992:Xylenes; C475503:benzylphosphonic acid; D015040:Zirconium
keywords: biomass conversion; cascade reaction; heterogeneous catalysis; mesoporous material; nanoparticles