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Depolymerization of Lignin into Monophenolics by Ferrous/Persulfate Reagent under Mild Conditions

Hanxi Bao, William Joe Sagues, Yigui Wang, Wenbo Peng, Lin Zhang, Shunchang Yang, Dequan Xiao, Zhaohui Tong

2020ChemSusChem24 citationsDOIOpen Access PDF

Abstract

Abstract This study aimed to use a persulfate together with transition metal ions as the reagent to effectively depolymerize lignin into monophenolic compounds under mild conditions (ambient pressure, temperature <100 °C). The Box‐Behnken experimental design in combination with the response surface methodology was applied to obtain optimized reaction conditions. The results showed that this reagent could depolymerize up to 99 % of lignin dimers to mainly veratraldehyde. This reaction also successfully depolymerized industrial lignins with a high yield of phenolic oils and monophenolic compounds. Quantum chemistry calculations using the density functional theory level indicated that the persulfate free radical attacks C β to break the β‐O‐4 bond of lignin through a five‐membered ring mechanism. This mechanism using persulfate free radicals has a lower activation barrier than that using hydroxyl radicals. Gel permeation chromatography and 2D‐NMR spectroscopy demonstrated the effective cleavage of the β‐O‐4 bonds of lignin after depolymerization.

Topics & Concepts

DepolymerizationChemistryPersulfateReagentLigninRadicalFerrousBond cleavageGel permeation chromatographyOrganic chemistryReaction mechanismYield (engineering)PhotochemistryCatalysisPolymerMaterials scienceMetallurgyLignin and Wood ChemistryBiochemical and biochemical processesEnzyme-mediated dye degradation
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