One-Step Conversion of Biomass-Derived 5-Hydroxymethylfurfural to 1,2,6-Hexanetriol Over Ni–Co–Al Mixed Oxide Catalysts Under Mild Conditions

Abstract

The conversion of biomass-derived 5-hydroxymethylfurfural (HMF) was examined over Ni–Co–Al mixed oxide catalysts derived from corresponding hydrotalcite-like compounds (HTlcs). 1,2,6-Hexanetriol (1,2,6-HT) was obtained in 64.5% yield under mild reaction conditions. The catalysts were characterized by X-ray powder diffraction (XRD), CO2 temperature-programmed desorption (CO2–TPD), N2 physical adsorption, and H2 temperature-programmed reduction (H2–TPR), and the reaction product distribution was correlated with the catalyst composition and reaction conditions. The reaction pathway was proposed based on the results. In all cases, the conversion of HMF proceeds according to a pathway that begins with the aldehyde group being hydrogenated to form 2,5-dihydroxymethylfuran (2,5-DHF). This product then undergoes a ring-opening reaction to form 1,2,6-HT. A synergetic effect between Ni and Co was observed, which significantly promoted catalytic activity and selectivity.

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

“…Hence, aw ide range of catalysts based on the metal such as Pt, Pd, Ru, Ir,R e, and Ni have been explored extensively for the production of diverse open ring products from biomass-derived furans. [138][139][140][141][142][143][144][145][146][147][148][149][150] Mizugaki et al reported hydrotalcite supported Pt nanoparticles for an efficient transfor-mation of furfural to 1,2-PeD in 73 %y ield at 423 K using 3MPa H 2 in 2-propanol. [140] The observed high yield of open ring 1,2-PeD was attributed to the cooperation of Pt nanoparticles and hydrotalcite support, where the basic surface of hydrotalcite facilitated strong interactions between the hydroxyl group of the intermediate furfuryl alcohol and the support, while furan ring interacted with metal Pt.…”

Functionalized silica nanoparticles for conversion of fructose to 5-hydroxymethylfurfural

“…[3][4][5] As one of the most important biomass carbohydrate-derived chemicals, 5-hydroxymethylfurfural (5-HMF) has been considered as a versatile platform molecule because of its easily transformation to a variety of high value-added chemicals, such as, 2,5-dimethylfuran, [6,7] 2,5-diformylfuran, [8][9][10] 2,5-furandicarboxylic acid, [11][12][13] C 9 -C 15 alkanes [14] and others. [15] Therefore, the transformation of carbohydrates into 5-HMF is a key pathway in integrated utilization of biomass resource.…”

Catalytic Response and Stability of Nickel/Alumina for the Hydrogenation of 5‐Hydroxymethylfurfural in Water

“…[53] The presence of Ni must favour the adsorption of the intermediate (FDM) with its molecular plane parallel to the surface, which facilitates the hydrogenation of the ring. [16] Figure 4a presents the selectivity (S)o btained towards FDM and THFDM as af unction of HMF conversion (X), combining data obtainedo ver the four catalysts where the mass of catalyst was varied in the range 0.01 g m 0.06 ga nd samples were taken every 40 minu pt o6h. The collected data points overlay one another,s uggesting that the selectivity is independento ft he catalyst's composition,i nitial mass of catalysts and time but varies consistently with X.H MF is first converted to FDM, as S FDM = 100 %when X < 5%.FDM is then progressively converted to THFDM and S THFDM = 40 %w hen X % 98 %.…”

“…This chemicalf inds application as as olvent (e.g., for the dehydration of fructose), ab uildingb lock for the synthesis of polymers (e.g.,s ynthesis of polyesters via caprolactone) [12] and high-value chemicals (e.g.,8 -oxa-3-aza-bicyclo(3.2.1)octane hydrochloride). [13] An umber of factors have been proposed to influence the catalytic response, including the nature of the catalysts and reaction conditions, that is, the solvent, [14] pH value (acidic or neutral), [15] hydrogen partial pressure, [16] temperature, [16] metal, isoelectricp oint (IEP), acid and basic properties of the support. [7,15] Indeed, the nature of the metal affects the selectivity for which Cu-and Ru-based catalysts can be selective for CÀO hydrogenolysis with formation of dimethyl furan [17,18] whereas polymerisation of the intermediate (furan-2,5-diyldimethanol (FDM);Scheme 1) occurs over Pd and Pt catalysts.…”