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Preparation of Nitrogen-Doped Carbon-Supported Co-V Catalyst for Catalys-tic Depolymerization of Lignin to Produce Monophenolic Compounds

Received Date:2024-03-01 Revised Date:2024-04-10 Accepted Date:2024-04-15

DOI:10.20078/j.eep.20240403

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    Abstract:Lignin, a renewable biomass component, holds promise as a fossil fuel alternative throughits depolymerization into monop... Open+
    Abstract:

    Lignin, a renewable biomass component, holds promise as a fossil fuel alternative throughits depolymerization into monophenolic compounds for liquid fuel production. However, its complexchemical structure presents significant challenges to efficient degradation. This study addresses thislimitation by developing a nitrogen-doped carbon-supported Co-V catalyst, synthesized using cobaltnitrate hexahydrate, ammonium metavanadate, and melamine as precursors. The synthesis capitalizedon vanadium-nitrogen coordination and the inherent stability of vanadium nitride, eliminating the needfor an external carbon source. By regulating the mass ratio of melamine to metal salts, the structuralEnergy Environmental Protectionmorphology and the types and contents of Co and N in the catalyst were precisely controlled. Theoptimized Co-V/NC (30) catalyst exhibited abundant defect sites, a high specific surface area, largepore volume, and hierarchical porous structure comprising micropores, mesopores, and macropores.The catalyst also featured a high content of pyridinic nitrogen and metallic cobalt (Co), along with arelatively low content of Co-N species. Synergistic interactions between the active components Co andV, coupled with nitrogen-mediated anchoring, ensured uniform dispersion of active sites, therebyenhancing catalytic activity and stability. Under optimized reaction conditions (180 ℃, 0.5 MPa O,8 h), the catalyst achieved 86.3% bio-oil yield and 28.8% monophenolic compounds from organosolvlignin. Notably, Co-V/NC (30) outperformed commercial catalysts (Co-V/AC and Co-V/ZSM-5),demonstrating the critical role of nitrogen-doped carbon in anchoring and dispersing metal activecomponents. 2D-HSQC NMR analysis confirmed the catalyst′s exceptional activity in cleaving bothC—O and C—C bonds between lignin structural units, enabling efficient degradation intomonophenolic compounds. Mechanistic investigations using a β-1 lignin model compound(diphenylethanone) revealed that the cleavage of C—C bonds proceeds via two pathways: (1) O isreduced on the catalyst surface to generate reactive oxygen species, which coordinates with the C—Hbond to form a peroxide intermediate. This intermediate undergoes dimerization to benzil, followed byC—C bond cleavage; (2) alternatively, homolytic cleavage of the peroxide O—O bond generatesoxygen-centered radicals, directly breaking the C—C bond. Structural characterization via X-raydiffraction (XRD), Brunauer-Emmett-Teller (BET) analysis, and transmission electron microscopy(TEM) confirmed that the catalyst retained its crystalline structure, high surface area, and hierarchicalporosity, even after five reuse cycles. Notably, active components (Co and V) remained uniformlydispersed without aggregation, contributing to sustained catalytic performance. This work provides ascalable synthesis strategy for robust, low-cost catalysts and elucidates a reaction pathway for lignin-to-aromatic conversion, thereby advancing biomass utilization in renewable energy. These findingsunderscore the potential of Co-V-NC systems to replace fossil-derived catalysts for sustainablechemical production.

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    Authors:

    • MA Yuqiao
    • LIU Xingwang
    • QIAN Yong*
    • OUYANG Xinping*

    Units

    • School of Chemistry & Chemical Engineering, South China University of Technology,Guangzhou 510640, China

    Keywords

    • Lignin
    • Catalytic oxidation
    • Depolymerization
    • Nitrogendoped carbon support
    • Monophenolic compounds

    Citation

    MA Yuqiao, LIU Xingwang, QIAN Yong, et al. Preparation of Nitrogen-Doped Carbon-Supported Co-V Catalyst for Catalystic Depolymerization of Lignin to Produce Monophenolic Compounds[J]. EnergyEnvironmental Protection, 2025, 39(2): 120−136.

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