Selective Hydrogenation of 5-Hydroxymethylfurfural via Zeolite Encapsulation to Avoid Further Hydrodehydroxylation

Abstract

Pt nanoparticles encapsulated into zeolite Y (denoted as Pt@Y) exhibited approaching 100% catalytic selectivity to 2,5-bis-(hydroxymethyl)-furan (BHMF) at full conversion of 5-hydroxymethylfurfural (HMF) in the presence of H2, coupled with good reusability. Zeolite Y constrained HMF to be adsorbed on encapsulated Pt nanoparticle surface via either the end of aldehyde groups or hydroxyl groups in thermodynamically unfavorable end-on mode to enlarge the gap in the activation energies between hydrogenation of aldehyde groups and hydrodehydroxylation of hydroxyl groups to favor selectivity enhancement via avoidance of further hydrodehydroxylation at moderate conditions, which provide a general method to avoid thermodynamics-regulated flat-lying conformation for simultaneous activation on the furan ring, aldehyde, and hydroxyl groups.

Catalytic Conversion of 5‐Hydroxymethylfurfural to High‐Value Derivatives by Selective Activation of C−O, C=O, and C=C Bonds

“…encapsulated Pt nanoparticles into zeolite Y to avoid over‐hydrogenation, and they gave the near 100 % selectivity of DHMF at full conversion of HMF in the presence of H 2 . This remarkable selectivity was distinctly ascribed to the confinement effect of zeolite Y to compel HMF to adsorb on encapsulated Pt surface via the end of the aldehyde or hydroxy group [18] . Moreover, Feng et al.…”

“…This remarkable selectivity was distinctly ascribed to the confinement effect of zeolite Y to compel HMF to adsorb on encapsulated Pt surface via the end of the aldehyde or hydroxy group. [18] Moreover, Feng et al prepared highly dispersed Cu NPs with small size by encapsulating Cu NPs into ZIF-8. A 99.0 % yield of DHMF was achieved under a relatively low hydrogen pressure and short reaction time; the excellent performance was attributed to the coexistence of Cu I À Cu 0 bicomponent in ZIF-8.…”

Recent Advances in Reductive Upgrading of 5‐Hydroxymethylfurfural via Heterogeneous Thermocatalysis

“…In this case, either the end of the aldehyde moiety or the hydroxy group of the HMF reactant adsorbed on the encapsulated Pt nanoparticles. Simultaneously, the far lower activation energy for hydrogenation of solely chemisorbed −CHO than the separately chemisorbed −OH prevented forming DMF and 5‐methylfurfuryl alcohol over Pt@Y at mild reaction conditions (353 K and 2 MPa of H 2 ) [29] . Improving the dispersion of Pt particles and enhancing the interaction between Pt and support are also effective strategies.…”

Advanced Room-Temperature Synthesis of 2,5-Bis(hydroxymethyl)furan—A Monomer for Biopolymers—from 5-Hydroxymethylfurfural

“…12,13 The high reactivity of 5-HMF is attributed to the presence of three functional groups at once: the carbonyl group, the hydroxyl group, and the furan ring. 14,15 The product of selective hydrogenation of the carbonyl bond2,5-bis(hydroxymethyl)furan (BHMF)draws special attention because of the possibility of its further polymerization for polyesters and polyurethanes production (Scheme 1). 16−20 On the other hand, hydrogenation of BHMF can give dimethylfuran (DMF)an organic compound, which has great potential as modern biofuel.…”

“…Renewable sources include the so-called “bio-platform molecules”, such as glycerol, , levulinic acid, 5-hydroxymethylfurfural (5-HMF), − and others. 5-HMF obtained from various bioavailable raw materials − is known as a “sleeping giant” for its huge potential in the synthesis of a wide range of valuable organic derivatives. , The high reactivity of 5-HMF is attributed to the presence of three functional groups at once: the carbonyl group, the hydroxyl group, and the furan ring. , The product of selective hydrogenation of the carbonyl bond2,5-bis­(hydroxymethyl)­furan (BHMF)draws special attention because of the possibility of its further polymerization for polyesters and polyurethanes production (Scheme ). − On the other hand, hydrogenation of BHMF can give dimethylfuran (DMF)an organic compound, which has great potential as modern biofuel …”