Selective Catalytic Production of 5-Hydroxymethylfurfural from Glucose by Adjusting Catalyst Wettability

ChemSusChem (Impact Factor: 7.66). 02/2014; 7(2). DOI: 10.1002/cssc.201301076
Source: PubMed


The development of highly-efficient catalysts for conversion of glucose and fructose to 5-hydroxymethylfurfural (HMF) is of great importance. In this work, theoretical simulations form the basis for rational design and synthesis of a superhydrophobic mesoporous acid, that can completely prevent HMF hydration, giving HMF as sole product from full conversion of fructose. Interestingly, the combined superhydrophobic solid acid and superhydrophilic solid base catalysts are very efficient for one-pot conversion of glucose to HMF, giving a yield as high as 95.4 %. The excellent catalytic data in the conversion of glucose to HMF is attributed to the unique wettabilities of the solid acid and base catalysts.

Download full-text


Available from: James P Lewis, Apr 02, 2014
1 Follower
76 Reads
  • [Show abstract] [Hide abstract]
    ABSTRACT: Report herein is an integrated catalytic process for conversion and upgrading of biomass feedstocks into 5,5′-dihydroxymethyl furoin (DHMF), through self-coupling of 5-hydroxymethyl furfural (HMF) via organocatalysis, and subsequently into n-C12H26 alkane fuel via metal–acid tandem catalysis. The first step of the process involves semicontinuous organocatalytic conversion of biomass (fructose, in particular) to the high-purity HMF. N-Heterocyclic carbenes (NHCs) are found to catalyze glucose-to-fructose isomerization, and the relatively inexpensive thiazolium chloride [TM]Cl, a Vitamin B1 analog, catalyzes fructose dehydration to HMF of good purity (>99% by HPLC), achieving a constant HMF yield of 72% over 10 semicontinuous extraction batch runs. Crystallization of the crude HMF from toluene yields the spectroscopically and analytically pure HMF as needle crystals. The second step of the process is the NHC-catalyzed coupling of C6 HMF produced by the semicontinuous process to C12 DHMF; the most effective organic NHC catalyst produces DHMF in 93% or 91% isolated yield with an NHC loading of 0.70 mol % or 0.10 mol % at 60 °C for 3 h under solvent-free conditions. The third step of the process converts C12 DHMF to linear alkanes via hydrodeoxygenation. With a bifunctional catalyst system consisting of Pd/C + acetic acid + La(OTf)3 at 250 °C and 300 psi H2 for 16 h, DHMF has been transformed to liquid hydrocarbon fuel (78% alkanes), with a 64% selectivity to n-C12H26 and an overall C/H/O % ratio of 84/11/5.0.Keywords: biomass; fructose; glucose; cellulose; biomass upgrading; organocatalysis; biofuel
    ACS Catalysis 05/2014; 4(5):1302-1310. DOI:10.1021/cs500058p · 9.31 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Catalytic transformation of biomass based furfural to valorized chemicals is an alternative route to the on-going fossil feedstock based processes. This work describes catalytic aerobic oxidation of furfural to maleic anhydride, an important polymer starting materials having large market, with H5PV2Mo10O40 and Cu(CF3SO3)2 catalysts. Under the optimized conditions, 54.0% yield of maleic anhydride can be achieved with about 7.5% yield of 5-acetoxyl-2(5H)-furanone formation. Notably, 5-acetoxyl-2(5H)-furanone is a highly valorized, biologically important intermediate which has been applied in pharmaceutical synthesis. The catalytic mechanism for furfural oxidation to maleic anhydride and 5-acetoxyl-2(5H)-furanone has been investigated in detail with identifications of several key intermediates.
    Green Chemistry 07/2014; 16(10). DOI:10.1039/C4GC00829D · 8.02 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Strong acid ionic liquids and sulfonic group bifunctional graphene-like nanoporous carbons (GNC-SO3H-ILs) have been synthesized from treating nitrogen containing graphene-like nanoporous carbons (GNCs) with 1,3-propanesultone, ion exchanging with HSO3CF3 or H2SO4. Introducing nitrogen is important for grafting strong acid ionic liquids and sulfonic group in GNCs, which were synthesized from carbonization of a mixture of dicyandiamide or melamine and glucose. GNC-SO3H-ILs possess abundant nanopores, nanosheet structure, good dispersion and controlled acidity. By themselves, they are capable of enhancing the fast diffusion of reactants and products, while increasing the exposition degree of acidic sites in GNC-SO3H-ILs throughout various reactions. The above characters result in their much improved catalytic activity in biomass transformation such as production biodiesel and depolymerization of crystalline cellulose into sugars, which were even as comparable as those of homogeneous ionic liquid and mineral acids.
    Green Chemistry 09/2014; 17(1). DOI:10.1039/C4GC01052C · 8.02 Impact Factor
Show more