Uniformly dispersed Co-Corrin/C catalysts for the study of β-O-4 bonding activity in lignin

IF 5.8 2区 化学 Q1 CHEMISTRY, ANALYTICAL Journal of Analytical and Applied Pyrolysis Pub Date : 2024-10-01 DOI:10.1016/j.jaap.2024.106826
Shuang Wang , Huihui Zhang , Chunyan Yu , Yue Liu , Yanju Lu , Lu Li
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Abstract

In this study, Co-Corrin/C catalysts with corrin active skeleton were prepared by pyrolysis under anaerobic conditions using vitamin B12 (VB12) as a precursor and activated carbon with rich mesoporous structure as a carrier. The Co-Corrin/C catalyst was applied to the oxidative cleavage reaction of lignin, showing a 92.74 % breakage of β-O-4 bonds. Density functional theory (DFT) calculations indicate that the low energy gap difference of Co-Corrin/C promotes electron transfer between Co and O. Meanwhile, the pyrrole ring in the corrin structure will be adsorbed and bonded to oxygen, which promotes the generation of large amounts of oxygen free radicals. The Cα-OH bond in the lignin aliphatic chain is oxidized to Cα=O bond under the action of oxygen radicals, which reduces the dissociation energy of the β-O-4 bond and significantly improves the oxidation efficiency. Cycling experiments proved that Co-Corrin/C has good stability.
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用于研究木质素中 β-O-4 键合活性的均匀分散 Co-Corrin/C 催化剂
本研究以维生素 B12 (VB12) 为前驱体,以具有丰富介孔结构的活性炭为载体,在厌氧条件下通过热解制备了具有珊瑚酸活性骨架的 Co-Corrin/C 催化剂。Co-Corrin/C 催化剂被用于木质素的氧化裂解反应,β-O-4 键的断裂率为 92.74%。密度泛函理论(DFT)计算表明,Co-Corrin/C 的低能隙差促进了 Co 和 O 之间的电子转移,同时 Corrin 结构中的吡咯环会吸附并键合到氧上,从而促进大量氧自由基的生成。在氧自由基的作用下,木质素脂肪链中的 Cα-OH 键被氧化成 Cα=O 键,从而降低了 β-O-4 键的解离能,显著提高了氧化效率。循环实验证明 Co-Corrin/C 具有良好的稳定性。
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来源期刊
CiteScore
9.10
自引率
11.70%
发文量
340
审稿时长
44 days
期刊介绍: The Journal of Analytical and Applied Pyrolysis (JAAP) is devoted to the publication of papers dealing with innovative applications of pyrolysis processes, the characterization of products related to pyrolysis reactions, and investigations of reaction mechanism. To be considered by JAAP, a manuscript should present significant progress in these topics. The novelty must be satisfactorily argued in the cover letter. A manuscript with a cover letter to the editor not addressing the novelty is likely to be rejected without review.
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