The exploration of effective approaches for the valorization of lignin to valuable products attracts broad interests of a growing scientific community. By fully unlocking the potential of the world's most abundant resource of bio-aromatics, it could improve the profitability and carbon efficiency of the entire biorefinery process, thus accelerate the replacement of fossil resources with bioresources in our society. The successful realization of this goal depends on the development of technologies to overcome the following challenges, including: 1) efficient biomass pretreatment and lignin separation technologies that overcomes its diverse structure and complex chemistry challenges to obtain high purity lignin; 2) advanced chemical analysis for precise quantitative characterization of the lignin in chemical transformation processes; 3) novel approaches for conversion of biomass-derived lignin to valuable products. This review summarizes the latest cutting-edge innovations of lignin chemical valorization with the focus on the aforementioned three key aspects.
Graphene oxide obtained by the Hummers method was discovered to be an efficient and recyclable acid catalyst for the conversion of fructose-based biopolymers into 5-ethoxymethylfurfural (EMF). EMF yields of 92%, 71%, 34% and 66% were achieved when 5-hydroxymethylfurfural (HMF), fructose, sucrose and inulin were used as starting materials, respectively.
By thermal treatment in vacuum, graphite oxide prepared from Hummers' method was exfoliated and partially reduced. This procedure imparts the graphene oxide (GO) the high reactivity with 2,2,6,6-tetramethyl-piperidin-1-oxyl (TEMPO) as co-catalyst for selective oxidation of 5-hydroxymethylfrufural (HMF) to 2, 5-diformylfuran (DFF) under certain conditions (100% HMF conversion with HMF selectivity 99.6% at 80 wt.% GO loading, 1 atm air pressure). This study found that GO could function as an oxidant for anaerobic oxidation of HMF during which carboxyl groups in GO were reduced. Importantly, the partially reduced GO material could continue activate molecular oxygen during aerobic oxidation. Further study showed that oxygen functionalities in GO material had a crucial effect on the catalytic oxidation of HMF.By control experiments and molecular analogues tests, a plausible mechanism was proposed in which the high reactivity was attributed to the synergistic effect of the carboxylic acid groups and unpaired electrons at GO edge defects, with TEMPO as the co-catalyst and oxygen as the terminal oxidant.
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