Catalytic transfer hydrogenation of biomass-derived 5-hydroxymethylfurfural into 2,5-bis(hydroxymethyl)furan over tunable Zr-based bimetallic catalysts

Abstract

ZrBa-SBA is highly efficient for the MPV reduction of HMF to BHMF, as the etherification of BHMF was suppressed.

On demand production of ethers or alcohols from furfural and HMF by selecting the composition of a Zr/Si catalyst

“…However, strong Brønsted acid sites may cause side-reactions, such as the hydrolytic ring-opening to form levulinate products, especially at high reaction temperature. 28,61,65,71,72,74,75,92 Hence, a material constituted only by Brønsted acid sites should be effective for direct etherification to form product 7, being unable to activate the hydrogen transfer process. In contrast, hydrogen transfer by the MPV mechanism is favored over solid catalysts with a Lewis acid site and a neighboring base site.…”

“…9 In a previous study, some of us reported that pure Lewis acid solids, such as Cu/SiO 2 prepared by a chemisorption-hydrolysis method, express limited activity in the CTH of furfural and low selectivity, due to ether formation, but catalysts with acid-base pairs, such as ZrO 2 , are definitely more active and selective. 51 In some cases, pure Lewis acidity accounts also for ether formation, 28,72,74 even though the mechanism is still poorly understood. 75,93 Catalysis Science & Technology Paper…”

“…9 Also the reaction selectivity can be improved if CTH occurs through a concerted Meerwein-Ponndorf-Verley (MPV) mechanism, that is without the evolution of molecular hydrogen, by which the reduction has an exclusive selectivity towards the transformation of a carbonyl group into a hydroxyl group. 28 Different catalytic systems active in the CTH processes of furfural and HMF for the synthesis of furfuryl alcohol and BHMF are reported in the literature. Alongside precious metal and/or expensive complicated materials, [29][30][31][32][33][34][35][36][37][38][39][40] cheaper catalysts based on Cu, Co, Fe, Hf, Mn, Zr, or zeolites (e.g.…”

Efficient synthesis of bio‐based monomer 2,5‐bishydroxymethylfuran by the solvent‐free hydrogenation of 5‐hydroxymethylfurfural‐based deep eutectic mixture

“…In bio‐refining, lignocellulosic biomass is deemed as a promising raw material that allows the production of a number of all‐purpose platform molecules, such as levulinic acid or 5‐hydroyxmethylfurfural (HMF), by chemical and/or biological routes . Particularly, HMF holds great promise to address numerous high volume markets for chemicals, materials, and fuels . For example, 2,5‐bishydroxymethylfuran (BHMF), synthesized by selective hydrogenation of HMF, is a versatile building block for the production of polyurethane foams, value‐added pharmaceuticals and bio‐based polymers …”

Carbonate-Catalyzed Room-Temperature Selective Reduction of Biomass-Derived 5-Hydroxymethylfurfural into 2,5-Bis(hydroxymethyl)furan

“…The employed metallic catalysts are typically expensive, with relatively harsh reaction conditions [20,25]. Likewise, transfer hydrogenation using alcohol (e.g., ethanol, 2-propanol) or formic acid as the liquid hydrogen source has also attracted much attention from many researchers [21,25,[29][30][31][32]. However, the use of formic acid may lead to the corrosion of the equipment and metal leaching, while the alcohol can further react with BHMF by etherification to reduce its selectivity [33].…”