title: Direct Production of 5-Hydroxymethylfurfural via Catalytic Conversion of Simple and Complex Sugars over Phosphated TiO2.
abstract: A water-THF biphasic system containing N-methyl-2-pyrrolidone (NMP) was found to enable the efficient synthesis of 5-hydroxymethylfurfural (HMF) from a variety of sugars (simple to complex) using phosphated TiO2 as a catalyst. Fructose and glucose were selectively converted to HMF resulting in 98 % and 90 % yield, respectively, at 175 °C. Cellobiose and sucrose also gave rise to high HMF yields of 94 % and 98 %, respectively, at 180 °C. Other sugar variants such as starch (potato and rice) and cellulose were also investigated. The yields of HMF from starch (80-85 %) were high, whereas cellulose resulted in a modest yield of 33 %. Direct transformation of cellulose to HMF in significant yield (86 %) was assisted by mechanocatalytic depolymerization-ball milling of acid-impregnated cellulose. This effectively reduced cellulose crystallinity and particle size, forming soluble cello-oligomers; this is responsible for the enhanced substrate-catalytic sites contact and subsequent rate of HMF formation. During catalyst recyclability, P-TiO2 was observed to be reusable for four cycles without any loss in activity. We also investigated the conversion of the cello-oligomers to HMF in a continuous flow reactor. Good HMF yield (53 %) was achieved using a water-methyl isobutyl ketone+NMP biphasic system.
authors.affiliation: Australian Institute for Bioengineering&Nanotechnology, Nanomaterials Center and School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072 (Australia).
authors.forename: Luqman
authors.initials: L
authors.lastname: Atanda
authors.affiliation: Australian Institute for Bioengineering&Nanotechnology, Nanomaterials Center and School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072 (Australia).|Catalysis Research Center, Hokkaido University, Kita 21 Nishi 10, Kita-Ku, Sapporo 001-0021 (Japan).
authors.forename: Abhijit
authors.initials: A
authors.lastname: Shrotri
authors.affiliation: Australian Institute for Bioengineering&Nanotechnology, Nanomaterials Center and School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072 (Australia).
authors.forename: Swathi
authors.initials: S
authors.lastname: Mukundan
authors.affiliation: Australian Institute for Bioengineering&Nanotechnology, Nanomaterials Center and School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072 (Australia).
authors.forename: Qing
authors.initials: Q
authors.lastname: Ma
authors.affiliation: Australian Institute for Bioengineering&Nanotechnology, Nanomaterials Center and School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072 (Australia).
authors.forename: Muxina
authors.initials: M
authors.lastname: Konarova
authors.affiliation: Australian Institute for Bioengineering&Nanotechnology, Nanomaterials Center and School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072 (Australia). j.beltramini@uq.edu.au.
authors.forename: Jorge
authors.initials: J
authors.lastname: Beltramini
mesh_terms: D002241:Carbohydrates / Q000737:chemistry*; D002384:Catalysis; D005662:Furaldehyde / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D046529:Microscopy, Electron, Transmission; D010710:Phosphates / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D014025:Titanium / Q000737:chemistry*
chemical_list: D002241:Carbohydrates; D010710:Phosphates; C009495:titanium dioxide; C008046:5-hydroxymethylfurfural; D014025:Titanium; D005662:Furaldehyde
keywords: biphasic systems; heterogeneous catalysis; mesoporous materials; solvents; sugars