摘要
5-Hydroxymethylfurfural (HMF) is an important biomass-based platform molecule, its oxidation product, 2,5-furandicarboxylic acid (FDCA), can be used to produce polyethylene furanoate (PEF) that replace petroleum-based compound polyethylene terephthalate (PET). At present, the development of low-cost and efficient catalytic systems remained a significant challenges. In this work, ZSM-5 and SBA-15 zeolites were used as a composite support with micro-mesopores structure through a simple and efficient mechanical treatment, and then Co–Mn bimetallic sites were loaded on the composites by co-precipitation methods. These catalysts exhibited showed different morphology, distribution of active components, and micro-mesopores structure by adjusting Co/Mn molar ratio, loading amounts and calcination temperature. The effects of pore structure, metal composition and distribution, and electronic structure on the catalytic conversion of HMF were studied. Specially, the valence state and content of Co and Mn active species had a significant impact on the catalytic performance of HMF, and we found that the content of Mn 4+ directly affected the selectivity of FDCA, and with a positive correlation between them into a certain extent. Under optimized conditions, 15Co 2 Mn-ZS-21-400 catalyst achieved 92.2% HMF conversion and 81.7% FDCA yield. Its order micro-mesoporous structures provided rapid reaction kinetics, and the synergistic effect of the bimetallic sites enhanced the catalytic activity. Mechanism study revealed that the Co and Mn species were coordinated through electron transfer during the redox process, thereby enabling the cyclic transformation between Co 3+ and Co 2+ , as well as Mn 4+ and Mn 3+ , and then gradually oxidize HMF into FDCA. In addition, 15Co 2 Mn-ZS-21-400 maintained excellent activity after five cycles, the conversion and yield kept at 89.2% and 79.1%, respectively. This work provided a new strategy for developing highly selective and stable thermal catalysts for HMF to FDCA.
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