Theoretical insight into the hydrogenolysis mechanism of lignin dimer compounds based on experiments. (January 2021)

• Record Type: Journal Article
• Authors: Zhu, Chen; Cao, Jing-Pei; Feng, Xiao-Bo; Zhao, Xiao-Yan; Yang, Zhen; Li, Jun; Zhao, Ming; Zhao, Yun-Peng; Bai, Hong-Cun
• Is Part Of: Renewable energy. Volume 163(2021)
• Page Start: 1831
• Page End: 1837
• Publication Date: 2021-01
• Subjects: Lignin model compounds -- Density functional theory -- Fukui function -- Average local ionization energy -- Kinetic; Renewable energy sources -- Periodicals; Power resources -- Periodicals; Énergies renouvelables -- Périodiques; Ressources énergétiques -- Périodiques; 333.794
• DOI: 10.1016/j.renene.2020.10.094
• Languages: English
• ISSNs: 0960-1481

Abstract

Abstract: Deep insight of reaction mechanism in lignin model compounds is helpful to achieve the directed depolymerization of lignin or biomass to chemicals or fuels. In this study, the density functional theory (DFT) calculation was employed to investigate the cleavage mechanism of the C –O bonds in lignin dimers. Additionally, the intrinsic chemical reactivity of molecular in term of the Fukui function was applied to predict the most probable sites which react with hydrogen free radicals (H·). It was found that the O atoms in lignin dimers are the most reaction site involving H· because of the large f (0). By this method, the most rational path from a series of reaction paths was screen out. Apart from the Fukui function, the average local ionization energy (ALIE) was analyzed to prove the reliability of Fukui function. The kinetic analysis of the reaction path was performed to further understand the impact of temperature on the reaction rate constant (K TST ). It is observed that benzyl phenyl ether (BPE) with higher K TST could be easily cleaved because of the relatively low energy barrier. Graphical abstract: Image 1 Highlights: The reaction paths of lignin dimers hydrogenolysis was simulated by DFT. The Fukui function and average local ionization energy of molecule were calculated. The reaction sites with H· radicals was predicted based on f (0) and ALIE. The kinetic studies of lignin dimers hydrogenolysis were explored.