Direct Synthesis of 1,6‐Hexanediol from HMF over a Heterogeneous Pd/ZrP Catalyst using Formic Acid as Hydrogen Source

Abstract

A new approach is developed for hydrogenolytic ring opening of biobased 5-hydroxymethylfurfural (HMF), dehydration product of hexoses, towards 1,6-hexanediol (HDO) under atmospheric pressure. The highest yield of HDO, 43%, is achieved over reusable Pd/zirconium phosphate (ZrP) catalyst at 413 K in the presence of formic acid as hydrogen source. In comparison with various Brønsted and/or Lewis acidic supports, the specific Brønsted acidity on ZrP support effectively accelerated the cleavage of C-O bond in a furan ring.

Catalytic Conversion of Biomass-derived Carbohydrates into 5-Hydroxymethylfurfural using a Strong Solid Acid Catalyst in Aqueous γ-Valerolactone

“…It can be used to produce many important chemicals, such as 2,5-diformylfuran (Zhang et al 2014b), 2,5-furandicarboxylic acid (Wang et al 2015), 1,6-hexanediol (Tuteja et al 2014), levulinic acid, and γ-valerolactone (Heeres et al 2009). HMF has built a bridge between raw biomass materials and liquid fuels or chemicals, and it has a large market potential with a promising future.…”

Catalytic Transfer Hydrogenolysis as an Effective Tool for the Reductive Upgrading of Cellulose, Hemicellulose, Lignin, and Their Derived Molecules

“…Tuteja and co-workers [94] reported the CTH process of HMF to 1,6-hexanediol (HDO) under atmospheric pressure in the presence of Pd/ZrP (zirconium phosphate) with FA as a hydrogen source. A 43% yield of HDO at 140 • C in 21 h was obtained.…”

Zirconium Phosphate Catalysts in the XXI Century: State of the Art from 2010 to Date

“…Cr(III) immobilized on m-ZrP Oxidation of allylic and benzylic compounds [39] Conversion of fructose into HMF [40] Fe(III) immobilized on window-type organic zirconium phosphonate Formaldehyde decomposition [41] Fe(Salen) and Cu(Salen) complexes supported on microcystalline ZrP Cyclohexene oxidation [42,43] Rh(III) and Ir(III) complexes intercalated into ZrP Visible light driven H 2 production [44] ClRh(PPh 3 ) 3 immobilized on ethoxysilane-modified ZrP Olefin hydrogenation [45] Co-Ru immobilized on ZrP/SiO 2 Fischer-Tropsch reaction [46] Pd NPs supported on ZrP Synthesis of 1,6-hexanediol from HMF [47] Heck reaction [48] Pd NPs supported on zirconium phosphonates Suzuki-Miyaura coupling reaction [49] Pd fluorinated complexes intercalated into microcrystalline ZrP Sonogashira and Heck reactions [50] TiO 2 pillared ZrP Degradation of methyl orange [51] TiO 2−x clusters grafted on ZrP nanosheets Degradation of methylene blue [52] Ag@AgCl/nanosized ZrP Degradation of Rhodamine B [53] Vanadium phosphorus oxide supported on ZrP dehydration of glycerol [54] 1-butyl-3-methylimidazolium chloride intercalated into layered θ-ZrP synthesis of propylene carbonate from CO 2 and propylene oxide [55] Mo et al immobilized Fe(III) ions on a new window-type porous organic zirconium phosphonate hybrid material having the formula Zr 5 (HPO 4 ) 6 [O 3 PCH 2 N(CH 2 CH 2 COOH)CH 2 PO 3 ] (ZrNCP), based on b-alanine-N,N-dimethylidenephosphonate groups bonded to adjacent inorganic layers, thus creating windows and, therefore, porosity [41]. Moreover, the presence of both nitrogen atoms and carbonyl groups in the organic chains allowed the coordination of metal ions with the wall of pores by ion exchange.…”

“…Ebitani et al in 2014 used a composite heterogeneous catalyst based on ZrP supporting Pd nanoparticles for the synthesis of 1,6-Hexanediol (HDO) from HMF by using formic acid as a hydrogen source [47]. HDO is used in the production of polyesters for polyurethane elastomers, coatings, adhesives, and polymeric plasticizers.…”