The synthesis of fuels, fuel additives, commercial and potential products from platform molecules generated by the hydrolysis of lignocellulosic biomass is a promising strategy toward the utilization of renewable feedstocks. Significant advances have been made on the various transformations (e.g., hydrogenation, oxidation, aldol condensation, rehydration, amination, polymerization, etherification and decarbonylation) of biomass-derived 5-hydroxymethylfurfural (HMF). This review firstly gives an overview of these various transformations of HMF to produce a number of fuels and chemicals, wherein the fundamental aspects of reaction mechanisms, recent progress and challenges are highlighted. Different types of catalysts are also summarized and compared in tables. One objective is to comment on the synthesis of value-added commercial and potential chemicals (e.g., furan-based polyester platform 2,5-furandicarboxylic acid (FDCA), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 2,5-diformylfuran (DFF)). Another purpose of the review is to comment on fuels and fuel additives, including the gasoline blendstock 2,5-dimethylfuran (DMF), ethyl levulinate (EL), gamma-valerolactone (GVL), methylfuran (MF) and so on. These obtained chemicals could replace the products from petrochemical resources, reducing CO2 emissions.
Selective cleavage of C-C bonds is very important in organic chemistry, but remains challenging because of their inert chemical nature. Herein, we report that Zn/NC-X catalysts, in which Zn2+ coordinate with N species on microporous N-doped carbon (NC) and X denotes the pyrolysis temperature, can effectively catalyze aerobic oxidative cleavage of C(CO)-C bonds and quantitatively convert acetophenone to methyl benzoate with a yield of 99% at 100 °C. The Zn/NC-950 can be applied for a wide scope of acetophenone derivatives as well as more challenging alkyl ketones. Detail mechanistic investigations reveal that the catalytic performance of Zn/NC-950 can be attributed to the coordination between Zn2+ and N species to change the electronic state of the metal, synergetic effect of the Zn single sites with their surrounding N atoms, as well as the microporous structure with the high surface area and structural defects of the NC.
Efficient conversion of renewable biomass into value-added chemicals and biofuels is regarded as an alternative route to reduce our high dependence on fossil resources and the associated environmental issues. In this context, biomass-based furfural and levulinic acid (LA) platform chemicals are frequently utilized to synthesize various valuable chemicals and biofuels. In this review, the reaction mechanism and catalytic system developed for the generation of furfural and levulinic acid are summarized and compared. Special efforts are focused on the different catalytic systems for the synthesis of furfural and levulinic acid. The corresponding challenges and outlooks are also observed.
10 September 2024 in Applied Catalysis B: Environment and Energy