Producing monomeric phenols from lignin biopolymer depolymerization in a detachable and efficient manner comes under the spotlight on the fullest utilization of sustainable lignocellulosic biomass. Here, we report a low-loaded and highly dispersed Ru anchored on a chitosan-derived N-doped carbon catalyst (RuN/ZnO/C), which exhibits outstanding performance in the reductive catalytic fractionation of lignocellulose. Nearly theoretical maximum yields of phenolic monomers from lignin are achieved, corresponding to TON as 431 molphenols molRu−1, 20 times higher than that from commercial Ru/C catalyst; high selectivity toward propyl end-chained guaiacol and syringol allow them to be readily purified. The RCF leave high retention of (hemi)cellulose amenable to enzymatic hydrolysis due to the successful breakdown of biomass recalcitrance. The RuN/ZnO/C catalyst shows good stability in recycling experiments as well as after a harsh hydrothermal treatment, benefiting from the coordination of Ru species with N atoms. Characterizations of the RuN/ZnO/C imply a transformation from Ru single atoms to nanoclusters under current reaction conditions. Time-course experiment, as well as reactivity screening of a series of lignin model compounds, offer insight into the mechanism of current RCF over RuN/ZnO/C. This work opens a new opportunity for achieving the valuable aromatic products from lignin and promoting the industrial economic feasibility of lignocellulosic biomass.
An eco-friendly and low-cost lignosulfonate-based acidic carbonaceous catalyst (LS-SO 3 H) was effectively fabricated using the sulfite pulping by-product of sodium lignosulfonate as a precursor by facile one-step simultaneous carbonization and sulfonation, and employed for the synthesis of promising biofuel furan derivatives from biorenewable feedstocks. The catalyst preparation conditions significantly affected the preparation and properties of LS-SO 3 H. A relatively high catalyst preparation yield (40.4%) with strong -SO 3 H density (1.33 mmol g À1 ) were achieved when the lignosulfonate was treated in concentrated H 2 SO 4 solution at 120 C for 6 h. The preparation yield of LS-SO 3 H was nearly twice as much as that of one-step prepared catalyst using alkaline lignin (another technical lignin from pulping) as a precursor.The as-prepared LS-SO 3 H had similar textural characteristics to the frequently-used two-step prepared carbonaceous catalyst involving pyrolysis carbonization and sulfonation. LS-SO 3 H was found to show good catalytic activity for the synthesis of 5-ethoxymethylfurfural (EMF) in ethanol medium, affording around 86%, 57% and 47% yields from 5-hydroxymethylfurfural (HMF), fructose and inulin, respectively. Also, a high HMF yield of 83% could be obtained from fructose when DMSO was replaced as reaction medium. The used LS-SO 3 H was readily recovered by filtration, and remained active in recycle runs.
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