Efficient conversion of lignin to alkylphenols over highly stable inverse spinel MnFe<sub>2</sub>O<sub>4</sub> catalysts

doi:10.1007/s11705-022-2236-1

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (8) : 1085-1095 https://doi.org/10.1007/s11705-022-2236-1

RESEARCH ARTICLE

Efficient conversion of lignin to alkylphenols over highly stable inverse spinel MnFe₂O₄ catalysts

Yi Qi, Xuezhi Zeng, Lingyingzi Xiong, Xuliang Lin(

), Bowen Liu, Yanlin Qin(

)

Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China

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Abstract

The aromatic properties of lignin make it a promising source of valuable chemicals and fuels. Developing efficient and stable catalysts to effectively convert lignin into high-value chemicals is challenging. In this work, MnFe₂O₄ spinel catalysts with oxygen-rich vacancies and porous distribution were synthesized by a simple solvothermal process and used to catalyze the depolymerization of lignin in an isopropanol solvent system. The specific surface area was 110.5 m²∙g^–1, which substantially increased the active sites for lignin depolymerization compared to Fe₃O₄. The conversion of lignin reached 94%, and the selectivity of alkylphenols exceeded 90% after 5 h at 250 °C. Underpinned by characterizations, products, and density functional theory analysis, the results showed that the catalytic performance of MnFe₂O₄ was attributed to the composition of Mn and Fe with strong Mn–O–Fe synergy. In addition, the cycling experiments and characterization showed that the depolymerized lignin on MnFe₂O₄ has excellent cycling stability. Thus, our work provides valuable insights into the mechanism of lignin catalytic depolymerization and paves the way for the industrial-scale application of this process.

Keywords lignin depolymerization spinel catalysts hydrogenation

Corresponding Author(s): Xuliang Lin,Yanlin Qin

Online First Date: 06 March 2023 Issue Date: 20 July 2023

Cite this article:

Yi Qi,Xuezhi Zeng,Lingyingzi Xiong, et al. Efficient conversion of lignin to alkylphenols over highly stable inverse spinel MnFe₂O₄ catalysts[J]. Front. Chem. Sci. Eng., 2023, 17(8): 1085-1095.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2236-1
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I8/1085

Scheme1 Schematic diagram of MnFe₂O₄ spinel catalyst synthesis.

Fig.1 (a) XRD patterns of MnFe₂O₄ and Fe₃O₄; (b) nitrogen adsorption?desorption isotherm of MnFe₂O₄ and Fe₃O₄. Inset showed the BJH pore-size distribution curve of the MnFe₂O₄ and Fe₃O₄.

Fig.2 (a, b) SEM images of MnFe₂O₄ at different magnifications, (c) TEM images of MnFe₂O₄ at different magnifications (the inset shows an enlarged view of the spinel catalyst surface), (d) HRTEM image, (e) HAADF-STEM image and corresponding elemental mappings of Mn, Fe, and O.

Fig.3 (a) Full range XPS spectra of MnFe₂O₄ and Fe₃O₄, (b) high-resolution Mn 2p spectra of MnFe₂O₄, (c) high-resolution Fe 2p spectra of MnFe₂O₄ and Fe₃O₄, (d) high-resolution O 1s spectra of MnFe₂O₄ and Fe₃O₄.

Fig.4 (a) Total ion chromatograms and corresponding structures of the liquid products obtained by depolymerization of lignin on MnFe₂O₄, (b) schematic representation of the proposed bond-breaking based on the lignin depolymerization product, (c) total aromatic monomer selectivity and lignin conversion obtained during lignin depolymerization with and without catalysts, (d) lignin conversion under different conditions of experimental parameters.

Fig.5 Conversion rate selectivity of PPE and BPE in MnFe₂O₄ catalyzed depolymerization.

Fig.6 (a, b) Fracture energy of PPE and BPE on the crystal surface of MnFe₂O₄; (c, d) Fracture energy of PPE and BPE on the crystal surface of Fe₃O₄.

Fig.7 (a) Stability test of lignin in MnFe₂O₄ catalyzed conversion. (b) XRD spectrum of the cyclic catalytic conversion of MnFe₂O₄.

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