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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2023, Vol. 17 Issue (8): 1085-1095   https://doi.org/10.1007/s11705-022-2236-1
  本期目录
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.

Key wordslignin depolymerization    spinel    catalysts    hydrogenation
收稿日期: 2022-07-19      出版日期: 2023-07-20
Corresponding Author(s): Xuliang Lin,Yanlin Qin   
 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2023, 17(8): 1085-1095.
Yi Qi, Xuezhi Zeng, Lingyingzi Xiong, Xuliang Lin, Bowen Liu, Yanlin Qin. Efficient conversion of lignin to alkylphenols over highly stable inverse spinel MnFe2O4 catalysts. Front. Chem. Sci. Eng., 2023, 17(8): 1085-1095.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-022-2236-1
https://academic.hep.com.cn/fcse/CN/Y2023/V17/I8/1085
  
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1 M K Islam, H Wang, S Rehman, C Dong, H Y Hsu, C S K Lin, S Y Leu. Sustainability metrics of pretreatment processes in a waste derived lignocellulosic biomass biorefinery. Bioresource Technology, 2020, 298: 122558
2 S Wang, J Bai, M T Innocent, Q Wang, H Xiang, J Tang, M Zhu. Lignin-based carbon fibers: formation, modification and potential applications. Green Energy & Environment, 2022, 7(4): 578–605
3 X Shen, C Zhang, B Han, F Wang. Catalytic self-transfer hydrogenolysis of lignin with endogenous hydrogen: road to the carbon-neutral future. Chemical Society Reviews, 2022, 51(5): 1608–1628
4 X Lin, J Liu, L Wu, L Chen, Y Qi, Z Qiu, S Sun, H Dong, X Qiu, Y Qin. In situ coupling of lignin-derived carbon-encapsulated CoFe–CoxN heterojunction for oxygen evolution reaction. AIChE Journal, 2022, e17785
5 C Cheng, D Shen, S Gu, K H Luo. State-of-the-art catalytic hydrogenolysis of lignin for the production of aromatic chemicals. Catalysis Science & Technology, 2018, 8: 6275–6296
6 C Espro, B Gumina, E Paone, F Mauriello. Upgrading lignocellulosic biomasses: hydrogenolysis of platform derived molecules promoted by heterogeneous Pd–Fe catalysts. Catalysts, 2017, 7(12): 78
7 R Behling, S Valange, G Chatel. Heterogeneous catalytic oxidation for lignin valorization into valuable chemicals: What results? What limitations? What trends?. Green Chemistry, 2016, 18(7): 1839–1854
8 Z Dou, Z Zhang, M Wang. Self-hydrogen transfer hydrogenolysis of native lignin over Pd–PdO/TiO2. Applied Catalysis B: Environmental, 2022, 301: 120767
9 Y Qi, X Xiao, Y Mei, L Xiong, L Chen, X Lin, Z Lin, S Sun, B Han, D Yang, Y Qin, X Qiu. Modulation of brønsted and lewis acid centers for NixCo3−xO4 spinel catalysts: towards efficient catalytic conversion of lignin. Advanced Functional Materials, 2022, 32: 2111615
10 P Liu, Y Liu, Y Lv, W Xiong, F Hao, H Luo. Zinc modification of Ni–Ti as efficient NixZnyTi1 catalysts with both geometric and electronic improvements for hydrogenation of nitroaromatics. Frontiers of Chemical Science and Engineering, 2021, 16(4): 461–474
11 L P Xiao, S Wang, H Li, Z Li, Z J Shi, L Xiao, R C Sun, Y Fang, G Song. Catalytic hydrogenolysis of lignins into phenolic compounds over carbon nanotube supported molybdenum oxide. ACS Catalysis, 2017, 7(11): 7535–7542
12 T Li, H Lin, X Ouyang, X Qiu, Z Wan, T Ruan. Impact of nitrogen species and content on the catalytic activity to C–O bond cleavage of lignin over N-doped carbon supported Ru-based catalyst. Fuel, 2020, 278: 118324
13 W Guan, X Chen, C W Tsang, H Hu, C Liang. Highly dispersed Rh/NbOx invoking high catalytic performances for the valorization of lignin monophenols and lignin oil into aromatics. ACS Sustainable Chemistry & Engineering, 2021, 9(9): 3529–3541
14 L Li, L Dong, D Li, Y Guo, X Liu, Y Wang. Hydrogen-free production of 4-alkylphenols from lignin via self-reforming-driven depolymerization and hydrogenolysis. ACS Catalysis, 2020, 10(24): 15197–15206
15 H Li, X Zheng, H Zhang, X Li, J Long. Selective cleavage of ester linkages in lignin catalyzed by La-doped Ni/MgO. ACS Sustainable Chemistry & Engineering, 2020, 8(41): 15685–15695
16 Y Cao, S S Chen, D C W Tsang, J H Clark, V L Budarin, C Hu, K C W Wu, S Zhang. Microwave-assisted depolymerization of various types of waste lignins over two-dimensional CuO/BCN catalysts. Green Chemistry, 2020, 22(3): 725–736
17 X Li, G Chen, C Liu, W Ma, B Yan, J Zhang. Hydrodeoxygenation of lignin-derived bio-oil using molecular sieves supported metal catalysts: a critical review. Renewable & Sustainable Energy Reviews, 2017, 71: 296–308
18 W Li, X Dou, C Zhu, J Wang, H M Chang, H Jameel, X Li. Production of liquefied fuel from depolymerization of kraft lignin over a novel modified nickel/H-beta catalyst. Bioresource Technology, 2018, 269: 346–354
19 X Dou, W Li, C Zhu, X Jiang. Catalytic waste kraft lignin hydrodeoxygenation to liquid fuels over a hollow Ni–Fe catalyst. Applied Catalysis B: Environmental, 2021, 287: 119975
20 Y Ge, Y Dong, S Wang, Y Zhao, J Lv, X Ma. Influence of crystalline phase of Li–Al–O oxides on the activity of Wacker-type catalysts in dimethyl carbonate synthesis. Frontiers of Chemical Science and Engineering, 2012, 6(4): 415–422
21 X Dou, W Li, C Zhu. Catalytic hydrotreatment of Kraft lignin into liquid fuels over porous ZnCoOx nanoplates. Fuel, 2021, 283: 118801
22 X Zhang, J Wu, T Li, C Zhang, L Zhu, S Wang. Selective hydrodeoxygenation of lignin-derived phenolics to cycloalkanes over highly stable NiAl2O4 spinel-supported bifunctional catalysts. Chemical Engineering Journal, 2022, 429: 132181
23 H Zhang, G Zhang, X Bi, X Chen. Facile assembly of a hierarchical core@shell Fe3O4@CuMgAl-LDH (layered double hydroxide) magnetic nanocatalyst for the hydroxylation of phenol. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2013, 1(19): 5934
24 C Zhu, X Dou, W Li, X Liu, Q Li, J Ma, Q Liu, L Ma. Efficient depolymerization of Kraft lignin to liquid fuels over an amorphous titanium–zirconium mixed oxide supported partially reduced nickel–cobalt catalyst. Bioresource Technology, 2019, 284: 293–301
25 Z Ma, S Kasipandi, Z Wen, L Yu, K Cui, H Chen, Y Li. Highly efficient fractionation of corn stover into lignin monomers and cellulose-rich pulp over H2WO4. Applied Catalysis B: Environmental, 2020, 284: 119731
26 G Kresse, J Furthmuller. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B, 1996, 54: 11169–11186
27 G Kresse, J Furthmiiller. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 1996, 6: 15–50
28 G Kresse, D Joubert. From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 1999, 59: 1758–1775
29 Y Liu, N Zhang, C Yu, L Jiao, J Chen. MnFe2O4@C nanofibers as high-performance anode for sodium-ion batteries. Nano Letters, 2016, 16(5): 3321–3328
30 Q Chen, J Zheng, Q Yang, Z Dang, L Zhang. Insights into the glyphosate adsorption behavior and mechanism by a MnFe2O4@cellulose-activated carbon magnetic hybrid. ACS Applied Materials & Interfaces, 2019, 11(17): 15478–15488
31 X Wei, X Wen, Y Liu, C Chen, C Xie, D Wang, M Qiu, N He, P Zhou, W Chen, J Cheng, H Lin, J Jia, X-Z Fu, S Wang. Oxygen vacancy-mediated selective C–N coupling toward electrocatalytic urea synthesis. Journal of the American Chemical Society, 2022, 144(26): 11530–11535
32 L Feng, X Li, Z Wang, B Liu. Catalytic hydrothermal liquefaction of lignin for production of aromatic hydrocarbon over metal supported mesoporous catalyst. Bioresource Technology, 2021, 323: 124569
33 B Tang, W Li, X Zhang, B Zhang, H Zhang, C Li. Depolymerization of Kraft lignin to liquid fuels with MoS2 derived oxygen-vacancy-enriched MoO3 in a hydrogen-donor solvent system. Fuel, 2022, 324: 124674
34 Z Wang, C Lai, L Qin, Y Fu, J He, D Huang, B Li, M Zhang, S Liu, L Li, W Zhang, H Yi, X Liu, X Zhou. ZIF-8-modified MnFe2O4 with high crystallinity and superior photo-Fenton catalytic activity by Zn–O–Fe structure for TC degradation. Chemical Engineering Journal, 2020, 392: 124851
35 L Qin, Z Wang, Y Fu, C Lai, X Liu, B Li, S Liu, H Yi, L Li, M Zhang, Z Li, W Cao, Q Niu. Gold nanoparticles-modified MnFe2O4 with synergistic catalysis for photo-Fenton degradation of tetracycline under neutral pH. Journal of Hazardous Materials, 2021, 414: 125448
36 X Wang, A Wang, J Ma. Visible-light-driven photocatalytic removal of antibiotics by newly designed C3N4@MnFe2O4-graphene nanocomposites. Journal of Hazardous Materials, 2017, 336(15): 81–92
37 Y Zhou, B Xiao, S Q Liu, Z Meng, Z G Chen, C Y Zou, C B Liu, F Chen, X Zhou. Photo-Fenton degradation of ammonia via a manganese-iron double-active component catalyst of graphene-manganese ferrite under visible light. Chemical Engineering Journal, 2016, 283: 266–275
38 Z Wang, H Ma, C Zhang, J Feng, S Pu, Y Ren, Y Wang. Enhanced catalytic ozonation treatment of dibutyl phthalate enabled by porous magnetic Ag-doped ferrospinel MnFe2O4 materials: performance and mechanism. Chemical Engineering Journal, 2018, 354: 42–52
39 D Ricciarelli, D Meggiolaro, P Belanzoni, A A Alothman, E Mosconi, F De Angelis. Energy vs charge transfer in manganese-doped lead halide perovskites. ACS Energy Letters, 2021, 6(5): 1869–1878
40 Y Sun, S Sun, H Yang, S Xi, J Gracia, Z Xu. Spin-related electron transfer and orbital interactions in oxygen electrocatalysis. Advanced Materials, 2020, 32: 2003297
41 S R Pouya, P Young-Kwon. Catalytic hydropyrolysis of lignin: suppression of coke formation in mild hydrodeoxygenation of lignin-derived phenolics. Chemical Engineering Journal, 2019, 386: 121348
42 L Li, J Kong, H Zhang, S Liu, Q Zeng, Y Zhang, H Ma, H He, J Long, X Li. Selective aerobic oxidative cleavage of lignin C–C bonds over novel hierarchical Ce–Cu/MFI nanosheets. Applied Catalysis B: Environmental, 2020, 279: 119343
43 F Yan, R Ma, X Ma, K Cui, K Wu, M Chen, Y Li. Ethanolysis of Kraft lignin to platform chemicals on a MoC1–x/Cu–MgAlOz catalyst. Applied Catalysis B: Environmental, 2017, 202: 305–313
44 C Cheng, P Li, W Yu, D Shen, S Gu. Catalytic hydrogenolysis of lignin in ethanol/isopropanol over an activated carbon supported nickel–copper catalyst. Bioresource Technology, 2021, 319: 124238
45 T Li, J Su, H Wang, C Wang, W Xie, K Wang. Catalytic hydropyrolysis of lignin using NiMo-doped catalysts: catalyst evaluation and mechanism analysis. Applied Energy, 2022, 316: 119115
46 J Lu, M Wang, X Zhang, A Heyden, F Wang. β-O-4 bond cleavagemechanism for lignin model compounds over Pd catalysts identified by combination of first-principles calculations and experiments. ACS Catalysis, 2016, 6: 5589–5598
47 X Zou, J Chen, Z Rui, H Ji. Sequential growth reveals multi-spinel interface promotion for methane combustion over alumina supported palladium catalyst. Applied Catalysis B: Environmental, 2020, 273: 119071
48 T Xiao, X Dai, X Wang, S Chen, B Dong. Enhanced sludge dewaterability via ozonation catalyzed by sludge derived biochar loaded with MnFe2O4: performance and mechanism investigation. Journal of Cleaner Production, 2021, 323: 129182
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