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离子液体促进过氯酸根在光热协同作用下促进碱木质素中 C-C/C-O 键的断裂。

The ionic liquids upon perchlorate to promote the C-C/C-O bonds cleavage in alkali lignin under photothermal synergism.

机构信息

Beijing Key Laboratory of Ionic Liquids Clean Process, CAS Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China; School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100190, China.

Beijing Key Laboratory of Ionic Liquids Clean Process, CAS Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China; School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100190, China.

出版信息

Int J Biol Macromol. 2024 Jan;255:128125. doi: 10.1016/j.ijbiomac.2023.128125. Epub 2023 Nov 19.

Abstract

Transforming lignin into aromatic monomers is critically attractive to develop green and sustainable energy supplies. However, the usage of the additional catalysts like metal or base/acid is commonly limited by the caused repolymerized and environmental issues. The key step is to mediate electron transfer in lignin to trigger lignin C-C/C-O bonds cleavage without the catalysts mentioned above. Here, we report that the ionic liquids [BMim][ClO] was found to trigger lignin electron transfer to cleave the C-C/C-O bonds for aromatic monomers without any additional catalyst. The proton transfer from [BMim] to [ClO] could polarize the anion and decrease its structure stability, upon which the active hydroxyl radical generated and induced lignin C-C/C-O bonds fragmentation via free radical-mediated routes with the assistance of photothermal synergism. About 4.4 wt% yields of aromatic monomers, mainly composed of vanillin and acetosyringone, are afforded in [BMim][ClO] under UV-light irradiation in the air at 80 °C. This work opens the way to produce value-added aromatic monomers from lignin using an eco-friendly, energy-efficient, and simple route that may contribute to the sustainable utilization of renewable natural resources.

摘要

将木质素转化为芳香族单体对于开发绿色可持续能源具有重要吸引力。然而,金属或酸碱等附加催化剂的使用通常受到重新聚合和环境问题的限制。关键步骤是在木质素中进行电子转移,以触发木质素 C-C/C-O 键的断裂,而无需使用上述催化剂。在这里,我们报告发现离子液体[BMim][ClO]可以引发木质素的电子转移,从而在没有任何附加催化剂的情况下裂解 C-C/C-O 键,生成芳香族单体。[BMim]向[ClO]的质子转移可以使阴离子极化并降低其结构稳定性,从而产生活性羟基自由基,并通过光热协同作用辅助下的自由基介导途径诱导木质素 C-C/C-O 键的断裂。在 80°C 的空气中,使用 UV 光在[BMim][ClO]中可得到约 4.4wt%的芳香族单体收率,主要由香草醛和乙酰丁香酮组成。这项工作为使用环保、高效和简单的路线从木质素中生产高附加值的芳香族单体开辟了道路,可能有助于可再生自然资源的可持续利用。

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