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

Abstract

The catalytic conversion of 5-hydroxymethylfufural (HMF), one of the vital platform chemicals in biomass upgrading, holds great promise for producing highly valuable chemicals through sustainable routes, thereby alleviating the dependence on fossil feedstocks and reducing CO 2 emissions. The reductive upgrading (hydrogenation, hydrogenolysis, ring-opening, ring-rearrangement, amination, etc.) of HMF has exhibited great potential to produce monomers, liquid fuel additives, and other valuable chemicals. Thermocatalytic conversion has a significant advantage over photocatalysis and electrocatalysis in productivity. In this Review, the recent achievements of thermo-reductive transformation of HMF to various chemicals using heterogeneous catalytic systems are presented, including the catalytic systems (catalyst and solvent), reaction conditions, (reaction temperature, pressure, etc.), and reaction mechanisms. The current challenges and future opportunities are discussed as well, aiming at guiding the catalyst design and practical scalable productions.

Catalytic Hydroconversion of 5‐HMF to Value‐Added Chemicals: Insights into the Role of Catalyst Properties and Feedstock Purity

“…Surprisingly, HMF impurities play an overlooked but crucial role in its catalytic upgrading. In this Review, we focused mainly on the selective HMF hydroconversion towards BHMF, BHMTHF, and DMTHF, while DMF synthesis from HMF is already extensively covered elsewhere [17][18][19][20] and thus not discussed in the present work.…”

“…[16] Several outstanding Reviews on the production of HMF-derived biofuels mainly including DMF have been already published. [17][18][19][20] Generally, transformation of HMF to valuable chemicals proceeds via various techniques, of which heterogeneous and biocatalysis are most frequently used compared to other approaches. The topic of HMF biotransformation to numerous derivatives is widely covered in recent literature reports.…”

“…Among mentioned chemicals, DMF is the most promising biofuel candidate due to its excellent combustibility, high energy density, low volatility, and low water solubility, while being renewable [16] . Several outstanding Reviews on the production of HMF‐derived biofuels mainly including DMF have been already published [17–20] . Generally, transformation of HMF to valuable chemicals proceeds via various techniques, of which heterogeneous and biocatalysis are most frequently used compared to other approaches.…”

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

“…Recently, many excellent Reviews involving the heterogeneous conversion of HMF have been published from various aspects. Wan and Lee reviewed the HMF upgrading to fuels and fine chemicals via reductive processes [6b] . Lin et al.…”

Base‐free Oxidative Esterification of HMF over AuPd/nNiO‐TiO2. When Alloying Effects and Metal‐support Interactions Converge in Producing Effective and Stable Catalysts

“…Specifically, it can be easily synthesized through selective oxidation of hydroxymethyl furfural (HMF), a valuable platform chemical extracted from lignocellulosic biomass. [6] Heterogeneously catalyzed oxidation of HMF with molecular oxygen (O 2 ) or air is preferred over the use of stoichiometric oxidants or homogeneous catalysts (e. g. Co(OAc) 2 and Mn-(OAc) 2 in AMOCO process [7] ) for a more sustainable, energy saving and environmentally friendly process. [8,9] Almost quantitative yields to FDCA have been achieved over supported noble-metal (Au, Ru, Pd, Pt) nanoparticles as catalysts under relatively mild conditions in the presence of an alkaline medium.…”