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Guo, Dayi; Wang, Shuai; Dong, Shuailong; Feng, Junfeng; Pan, Hui
Chemical engineering journal (Lausanne, Switzerland : 1996), 05/2024, Volume: 487Journal Article
•5CuO/Al2O3 catalysts can be prepared without hydrogen pre-treatment.•The strong interaction is beneficial for in situ reduction of catalysts.•Surface CuO species can be reduced to Cu0 and Cu+ in situ during the reaction.•The high catalytic activity be ascribed to the synergistic between Cu0 and Cu+.•Efficient hydrodeoxygenation of VN to MMP under mild conditions. A new method for the hydrodeoxygenation of vanillin to 2-methoxy-4-methylphenol (MMP) by in-situ reduced CuO/Al2O3 catalysts was developed. The CuO/Al2O3 catalysts with different CuO contents were prepared by simple wet impregnation and could provide complete vanillin conversion with 99 % MMP selectivity under mild conditions (120 °C, 0.5 MPa H2, 8 h). The results from XPS and H2-TPR characterizations of the CuO/Al2O3 catalysts suggested that CuO species had a strong interaction with the Al2O3 support, which was beneficial for the in-situ reduction of CuO to Cu+ and Cu0 species during the hydrodeoxygenation reaction. The synergistic effect of Cu+ and Cu0 species was believed to promote the hydrodeoxygenation of vanillin, in which Cu0 accounts for the hydrogenation reaction, while Cu+ is responsible for the adsorption of vanillin and 4-hydroxy-3-methoxybenzyl alcohol to facilitate the further dehydration of 4-hydroxy-3-methoxybenzyl alcohol. In addition, the CuO/Al2O3 catalyst could maintain high catalytic activity after three reaction cycles and showed versatility for various lignin derivatives. The development of this in-situ reduceable catalyst could provide a cost-effective approach for the upgrading of biomass derived products.
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