One-pot synthesis of 2,5-bis(hydroxymethyl)furan from biomass derived 5-(chloromethyl)furfural in high yield

5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.

Catalyst design strategy toward the efficient heterogeneously-catalyzed selective oxidation of 5-hydroxymethylfurfural

The selective oxidation of 5-hydroxymethylfurfural(HMF),a versatile bio-based platform molecule,leads to the formation of several intriguing and useful downstream chemicals,such as 2,5-diformylfuran(DFF),5-hydroxymethyl-2-furancarboxylic acid(HMFCA),formyl 2-furancarboxylic acid(FFCA),2,5-furandicarboxylic acid(FDCA) and furan-2,5-dimethylcarboxylate(FDMC).These products have been extensively employed to fabricate novel polymers,pharmaceuticals,sustainable dyes and many other value-added fine chemicals.The heart of the developed HMF oxidation processes is always the catalyst.In this regard,this review comprehensively summarized the established heterogeneous catalyst design strategy for the selective oxidation of HMF via thermo-catalysis.Particular attention has been focused on the reaction mechanism of HMF oxidation over different catalysts as well as enhancing the catalytic performance of the catalyst through manipulating the properties of the support and fabricating of multi-component metal nano-particles and oxides.The current challenges and possible research directions for the catalytic oxidation of HMF in the future are also discussed.

Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol with formic acid as hydrogen donor over CuCs-MCM catalyst

Catalytic transfer hydroge nation(CTH)of furfural(FF)to furfu ryl alcohol(FFA)has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6%FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.

Construction of Synergistic Co and Cu Diatomic Sites for Enhanced Higher Alcohol Synthesis

Higher alcohol synthesis(HAS)from syngas could efficiently alleviate the dependence on the traditional fossil resources.However,it is still challenging to construct high-performance HAS catalysts with satisfying selectivity,space–time yield(STY),and stability.Herein,we designed a diatomic catalyst by anchoring Co and Cu sites onto a hierarchical porous N-doped carbon matrix(Co/Cu–N–C).The Co/Cu–N–C is efficient for HAS and is among the best catalysts reported.With a COconversion of 81.7%,C2+OHselectivity could reach 58.5%with an outstanding C2+OH STY of 851.8 mg/g·h.We found that the N4–Co1 and Cu1–N4 showed an excellent synergistic effect.The adsorption of CO occurred on the Co site,and the surrounding nitrogen sites served as a hydrogen reservoir for the CO reduction reactions to form CHxCo.Meanwhile,the Cu sites stabilized a CHOCu species to interact with CHxCo,facilitating a barrier-free formation of C2 species,which is responsible for the high selectivity of higher alcohols.