Selective hydrogenation of 5-(hydroxymethyl)furfural to 5-methylfurfural over single atomic metals anchored on Nb2O5

Abstract

Abstract5-Methylfurfural (MF) is a very useful chemical. Selective hydrogenation of biomass platform molecule 5-(hydroxymethyl)furfural (HMF) to MF using H2 as the reducing agent is very attractive, but challenging because hydrogenation of C=O bond in HMF is more favourable than C–OH both kinetically and thermodynamically, and this route has not been realized. In this work, we prepare isolated single atomic catalysts (SACs) Pt1/Nb2O5-Ov, Pd1/Nb2O5-Ov, and Au1/Nb2O5-Ov, in which single metal atoms are supported on oxygen defective Nb2O5 (Nb2O5-Ov). It is discovered that the SACs can efficiently catalyze the hydrogenation of HMF to MF using H2 as the reducing agent with MF selectivity of >99% at complete conversion, while the selectivities of the metal nanocatalysts supported on Nb2O5 are very poor. A combination of experimental and density function theory (DFT) studies show that the unique features of the SACs for the reaction result from the cooperation of the Nb and Pt sites near the interface in the Pt1/Nb2O5-Ov. The Pt atoms are responsible for the activation of H2 and the Nb sites activate C-OH in the reaction. This work opens the way for producing MF by direct hydrogenation of biomass-derived HMF using H2 as the reductant.

Subnanometric Cu clusters on atomically Fe-doped MoO2 for furfural upgrading to aviation biofuels

“…The distinctive structure and properties of the Cu 4 /Fe 0.3 Mo 0.7 O 2 @C material inspired us to investigate its catalytic performance. Furfural (FFA) is a commercialized biomass platform molecule, which may be chemically converted into over 80 kinds of valuable chemicals/biofuels 37 – 40 . One of the most promising strategies for FFA valorization is the aldol condensation of FFA with aldehydes/ketones (e.g., acetone) for the production of α,β-unsaturated aldehydes/ketones, which are well-known as critical intermediates for the production of aviation biofuels (C 8 ~C 15 alkanes) via a hydrodeoxygenation process 41 – 44 .…”

Subnanometric Cu Clusters on Atomically Fe-doped MoO2 for Furfural Upgrading to Aviation Biofuels

“…Furfural (FFA) is a commercialized biomass platform molecule, which may be chemically converted into over 80 kinds of valuable chemicals/bio-fuels. [37][38][39][40] One of the most promising strategies for FFA valorization is the aldol condensation of FFA with aldehydes/ketones (e.g., acetone) for the production of α,β-unsaturated aldehydes/ketones, which are well-known as critical intermediates for the production of aviation biofuels (C 8 ~C15 alkanes) via a hydrodeoxygenation process. [41][42][43][44] From a green, economic, and sustainable viewpoint, the direct reaction of saturated monobasic alcohols with FFA may be the most preferred and promising, due to the availability and low cost of alcohols in comparison with their oxidation products such as aldehydes and ketones.…”

Energy Densification of Biomass-Derived Furfurals to Furanic Biofuels by Catalytic Hydrogenation and Hydrodeoxygenation Reactions

“…Among various metal atoms employed, a complete conversion of HMF was achieved using platinum metal. It was concluded that the selectivity of 5MF is independent of H 2 pressure and reaction temperature [156].…”