The aldol-condensation reaction of biomass-derived furfural and cyclopentanone coupled with hydrogenation/hydrodeoxygenation is a promising route for the production of renewable high-quality diesel or jet fuel. In this paper, we focus on the heterogeneously catalyzed aldol condensation of furfural with cyclopentanone, in order to maximize the yield of 2,5-bis(2-furylmethylidene)cyclopentan-1-one (F2C, a C15 fuel precursor). Experiments were conducted over a series of solid-base catalysts and it was found that potassium fluoride impregnated alumina shown the highest catalytic efficiency. We further investigated the effect of different parameters on the performance of KF/γ-Al2O3, including KF loading amount, solvent, reaction time and temperature. Over KF/γ-Al2O3 with a 33% KF loading amount, the aldol reaction achieved an F2C molar yield up to 95.4% at 333 K within 2 h. Under the nearly optimal condition, the separated solid product is almost F2C with a purity of 100%, providing a high-quality biofuel precursor for the next processing step.
The photocatalytic depolymerization of lignin is a sustainable strategy to produce high-value aromatic chemicals. The selective and efficient cleavage of β-O-4 bonds under mild conditions remains one of the challenges in lignin valorization. Herein, an efficient and mild strategy was employed for one-step photocatalytic depolymerization of lignin and β-O-4 model compounds over novel Z-scheme heterojunction g-C3N4/carbon quantum dot/CdZnS (CN/CQD/CZS) under simulated solar light. The total yield of vanillin and vanillic acid from lignin depolymerization was 36.3 mg g−1 lignin when the volume ratio of SDS-8 (sodium dodecyl sulfate solution with a mass fraction of 0.08%) to HCOOH was 4 : 1 within 2 h. The depolymerization mechanism of lignin was investigated using β-O-4 model compounds. The β-O-4 model compounds were converted into phenolic monomers over optimized CN/CQD/CZS, yielding 84% substrate conversion and ∼100% C–O bond cleavage selectivity. Three extractive natural lignin samples were applied to this system and successfully depolymerized. A combination of experimental results and theoretical calculations illustrated that CQDs played a crucial role in accelerating photogenerated electron transfer at the CN/CZS interface via the Z-scheme electron pathway, which effectively promoted the separation and transfer of photoexcited hole–electron pairs. Mechanistic studies demonstrated that the selective cleavage of the β-O-4 bond mainly involved a photogenerated electron–hole coupled redox mechanism. The construction of the Z-scheme CN/CQD/CZS heterojunction is essential to enhance the kinetics of electron transport and maintain strong redox ability. The approach in this work offers a useful guidance for the construction of Z-scheme heterojunction photocatalysts with a carbon-based electron mediator and the selective breakage of C–O bonds in lignin.