Efficient synthesis of 2,5-dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxymethylfurfural using mineral-derived Cu catalysts as versatile catalysts

Abstract

Selective conversion of 5-hydroxymethylfurfural (HMF) can produce sustainable fuels and chemicals.Herein, Cu-ZnO catalysts derived from minerals (malachite, rosasite and aurichalcite) were employed for selective hydrogenation of HMF for the first time. High yields of 2,5-dihydroxymethylfuran (~99.1%) and 2,5-dimethylfuran (~91.8%) were obtained tunably over the catalyst with a Cu/Zn molar ratio of 2, due to the well-dispersed metal sites tailored by mineral precursors, well-controlled surface sites and optimized reaction conditions. The relationship between catalytic performance and catalyst properties was elucidated by characterization based on the composition and the structural and surface properties, and catalytic tests.The catalyst can also be extended to selective hydrogenation of other bio-derived molecules (furfural and 5-methylfurfural) to target products. The construction of mineral-derived Cu-ZnO catalysts and the revelation of the structure-performance relationship can be applied to further rational design and functionalization of non-noble Cu catalysts for selective conversion of bio-derived compounds.Catal. Sci. Technol. This journal is

Efficient Synthesis of Furfuryl Alcohol and 2‐Methylfuran from Furfural over Mineral‐Derived Cu/ZnO Catalysts

“…The structures of the synthesized samples could also be demonstrated by Raman spectra shown in Figure (c). The band at 1070 cm −1 corresponds to the CO 3 2− symmetric stretching mode of aurichalcite whereas the peaks at 1100 cm −1 , 1370 cm −1 and 1500 cm −1 can be assigned to the zincian malachite phase . Based on the results of XRD patterns and Raman spectra, the synthesized samples were verified to be the presupposed precursors that mainly consisted of aurichalcite and zincian malachite, respectively.…”

Selective Hydrodeoxygenation of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Heterogeneous Iron Catalysts

“…If THF was used as the solvent, only 34.7 %y ield of the target product DMF was obtained after 12 h. MF was observeda st he major byproduct, achievingamaximumy ield of 60.6 %a t6h and then decreasing gradually.T his product distribution demonstrated that the reaction rate of the HDO of HMF to MF was much highert han that of the HDO of MF to DMF,l eadingt o the accumulationo fM Fi nt he solution. [42] The HDO of MF andM FM overF e/C-800 in n-butanolw as explored to investigate the role of FeN x species in the HDO of C=Oa nd CÀOb onds (see FigureS5).T he DMF yields were 44 and 53 %f or the HDO of MF andM FM, respectively.T he inferior catalytic performance demonstrated thatt he presence of FeN x species was critical for both HDO reactions. If n-butanol was used as the solvent, the productionr ate of DMF was enhanced significantly,a nd am aximum yield of 86.2 %w as obtained within 5h.M Fa chieved am aximum yield of 9.9 %a t 1h and was then converted completely after 6h.I na ddition, DFF,w hich is the dehydrogenation product of HMF,a chieved am aximum yield of 4.4 %i nT HF but could not be detected with n-butanol as the solvent.…”

“…[32] Considering the high cost and scarcityo fn oble metals, the HDO of HMF to DMF over non-noble-metal catalysts was investigated recently.T he activities and stabilities of six carbon-supported noble-o rn on-noble-metalc atalysts were comparedi n ac ontinuous-flow reactor by Gorte and co-workers. [39][40][41][42] They also studied the one-step continuous conversiono ff ructoset o DMF over combined HY zeolite and HT-Cu/ZnO/Al 2 O 3 in af ixed-bed reactor with aD MF yield of 40.6 %. [34] Subsequently,t hey studied the conversion of HMF over Cu 0.61 Mg 2.33 Al 0.98 Ru 0.02 and CuÀZn nanoalloy catalysts, and up to 97 %c ombined product yields were obtained at 200-220 8Ca nd 20-30 bar H 2 .…”

Hydrogenolysis of Biomass‐Derived 5‐Hydroxymethylfurfural to Produce 2,5‐Dimethylfuran Over Ru‐ZrO2‐MCM‐41 Catalyst

“…Zhu et al . reported the synthesis of 2,5‐dihydroxymethylfuran and 2,5‐dimethylfuran from 5 hydroxymethylfurfural using Cu–ZnO as catalysts . Nagpure et al .…”