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Converting lignin into specific aromatic chemicals for utilization through depolymerization of lignin is an effective way to achieve high-value applications. There are many depolymerization methods that can do this, but there are problems such as harsh reaction conditions, low depolymerization efficiency and uncontrollable target products that need to be solved. This study reports a novel system for the oxidative depolymerization of alkali lignin using Fe- and Mn- modified TS-1 as a catalyst to assist in the highly selective production of vanillin. We also proposed a possible reaction pathway for the oxidative depolymerization of alkali lignin to produce vanillin catalyzed by Fe-Mn/TS-1 catalyst. The catalytic effects of TS-1, Fe/TS-1, and Fe-Mn/TS-1 catalysts on the oxidative depolymerization of lignin to produce phenolic monomers and vanillin were investigated. The results show that the modified catalysts can effectively improve the efficiency of linkage bond breaking in lignin, especially the β-O-4 bond, in which the inter-band transitions of Fe and Mn play an important role. The synergistic effect of the bimetallic-loaded catalyst (Fe-Mn/TS-1) could catalyze the oxidative depolymerization of lignin more efficiently than the monometallic-loaded catalyst (Fe/TS-1). This lignin oxidative depolymerization system produced 40.59 wt% bio-oil including 12.24 wt% phenolic monomers and 16.17 wt% re-lignin after the addition of Fe-Mn/TS-1 catalyst, owning the highest phenolic monomer yield. Surprisingly, this lignin oxidative depolymerization system exhibited high yield for vanillin (8.36 wt%) production. These results demonstrated that the Fe-Mn/TS-1 catalytic system has potential to produce vanillin from lignin under mild conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Pine kraft-anthraquinone (kraft-AQ) pulp was bleached in alkaline solution with hydrogen peroxide catalyzed by either [L(1)Mn(IV)(micro-O)(3)Mn(IV)L(1)](PF(6))(2)] (C1) or [LMn(IV)(2)(micro-O)(3)] (ClO(4))(2) (C2) at 60 and 80 degrees C for 120 min with a catalyst charge of 10 ppm on pulp. The resulting bleached pulp was hydrolyzed with cellulase to obtain insoluble and soluble residual lignins. The alkaline bleaching effluents were acidified to precipitate alkaline-soluble lignins. These lignin preparations were then characterized by 2D heteronuclear multiple-quantum coherence (HMQC) NMR spectroscopic techniques. The results showed that biphenyl (5-5) and stilbene structures of the residual lignin in the pulp are preferentially degraded in both the C1- and C2-catalyzed bleachings, whereas beta-O-4, beta-5, and beta-beta structures undergo degradation to a lesser extent. In both cases, the degradation of the residual lignin increased with the increase in reaction temperature from 60 to 80 degrees C. Thus, the result of C1-catalyzed delignification is not in agreement with the observed decrease in the disappearance rate for substrates in the C1-catalyzed oxidation of lignin model compounds with hydrogen peroxide when the reaction temperature is increased from 60 to 80 degrees C. In addition, the resulting residual lignins in the C2-catalyzed bleaching at 80 degrees C are less degraded than the corresponding lignins in the C1-catalyzed bleaching at both 60 and 80 degrees C. Thus, C1 is more effective than C2 as catalyst in the binucleus Mn(IV) complex-catalyzed bleaching of pine kraft-AQ pulp with hydrogen peroxide.

Culture supernatants of the white-rot fungus Trametes versicolor were found to contain Mn(III)-complexing agents able to effectively promote manganese-dependent peroxidase (MnP)-mediated oxidation of phenol red. The high molecular weight fractions of these supernatants contained carbohydrate polymers that functioned as effective Mn(III)-complexing agents. Gluconic and glucuronic acids were also found to be effective Mn(III)-complexing ligands capable of supporting MnP-mediated phenol red oxidation, as was the cellobionic acid formed from cellobiose by cellobiose:quinone oxidoreductase (CBQase) (EC 1.1.5.1). The formation of cellulose-derived sugar acid manganese-complexing agents by CBQase increased in the presence of wood pulp and cellulolytic enzymes. CBQase, while oxidizing cellobiose, reduced insoluble Mn(IV)O2 to Mn(II) or Mn(III) by a reaction whose rate is determined by the nature of the manganese-complexing agents present. A model is proposed to explain how oxidation of carbohydrate and reduction of MnO2 and quinones by CBQase may complement oxidation by MnP, thus promoting lignin biodegradation.

Many ligninolytic basidiomycete fungi have been shown to secrete a group of peroxidase isozymes whose sole function appears to be the peroxide-dependent oxidation of manganous [Mn(II)] to manganic [Mn(III)] ions. Manganic chelates and these Mn peroxidases have been implicated as central to the degradation of various natural and synthetic lignins and lignin-containing effluents by white rot (ligninolytic) fungi. Another group of enzymes, the laccases, are commonly secreted by wood-rotting fungi, but are generally regarded as being able to oxidize (and usually polymerize) only phenolic substrates. In this report it is shown that in the presence of appropriate oxidizable phenolic accessory substances or primary substrates, a variety of laccases and peroxidases catalyzing one-electron oxidations can also produce Mn(III) chelates from Mn(II).