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

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.

Graphical abstract

Keywords

lignin depolymerization / spinel / catalysts / hydrogenation

References

[1] Islam M K, Wang H, Rehman S, Dong C, Hsu H Y, Lin C S K, Leu S Y. Sustainability metrics of pretreatment processes in a waste derived lignocellulosic biomass biorefinery. Bioresource Technology, 2020, 298: 122558

[2] Wang S, Bai J, Innocent M T, Wang Q, Xiang H, Tang J, Zhu M. Lignin-based carbon fibers: formation, modification and potential applications. Green Energy & Environment, 2022, 7(4): 578–605

[3] Shen X, Zhang C, Han B, Wang F. Catalytic self-transfer hydrogenolysis of lignin with endogenous hydrogen: road to the carbon-neutral future. Chemical Society Reviews, 2022, 51(5): 1608–1628

[4] Lin X, Liu J, Wu L, Chen L, Qi Y, Qiu Z, Sun S, Dong H, Qiu X, Qin Y. In situ coupling of lignin-derived carbon-encapsulated CoFe–Co_xN heterojunction for oxygen evolution reaction. AIChE Journal, 2022, e17785

[5] Cheng C, Shen D, Gu S, Luo K H. State-of-the-art catalytic hydrogenolysis of lignin for the production of aromatic chemicals. Catalysis Science & Technology, 2018, 8: 6275–6296

[6] Espro C, Gumina B, Paone E, Mauriello F. Upgrading lignocellulosic biomasses: hydrogenolysis of platform derived molecules promoted by heterogeneous Pd–Fe catalysts. Catalysts, 2017, 7(12): 78

[7] Behling R, Valange S, Chatel G. Heterogeneous catalytic oxidation for lignin valorization into valuable chemicals: What results? What limitations? What trends?. Green Chemistry, 2016, 18(7): 1839–1854

[8] Dou Z, Zhang Z, Wang M. Self-hydrogen transfer hydrogenolysis of native lignin over Pd–PdO/TiO₂. Applied Catalysis B: Environmental, 2022, 301: 120767

[9] Qi Y, Xiao X, Mei Y, Xiong L, Chen L, Lin X, Lin Z, Sun S, Han B, Yang D, Qin Y, Qiu X. Modulation of brønsted and lewis acid centers for Ni_xCo_3−xO₄ spinel catalysts: towards efficient catalytic conversion of lignin. Advanced Functional Materials, 2022, 32: 2111615

[10] Liu P, Liu Y, Lv Y, Xiong W, Hao F, Luo H. Zinc modification of Ni–Ti as efficient Ni_xZn_yTi₁ catalysts with both geometric and electronic improvements for hydrogenation of nitroaromatics. Frontiers of Chemical Science and Engineering, 2021, 16(4): 461–474

[11] Xiao L P, Wang S, Li H, Li Z, Shi Z J, Xiao L, Sun R C, Fang Y, Song G. Catalytic hydrogenolysis of lignins into phenolic compounds over carbon nanotube supported molybdenum oxide. ACS Catalysis, 2017, 7(11): 7535–7542

[12] Li T, Lin H, Ouyang X, Qiu X, Wan Z, Ruan T. 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] Guan W, Chen X, Tsang C W, Hu H, Liang C. Highly dispersed Rh/NbO_x 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] Li L, Dong L, Li D, Guo Y, Liu X, Wang Y. Hydrogen-free production of 4-alkylphenols from lignin via self-reforming-driven depolymerization and hydrogenolysis. ACS Catalysis, 2020, 10(24): 15197–15206

[15] Li H, Zheng X, Zhang H, Li X, Long J. Selective cleavage of ester linkages in lignin catalyzed by La-doped Ni/MgO. ACS Sustainable Chemistry & Engineering, 2020, 8(41): 15685–15695

[16] Cao Y, Chen S S, Tsang D C W, Clark J H, Budarin V L, Hu C, Wu K C W, Zhang S. Microwave-assisted depolymerization of various types of waste lignins over two-dimensional CuO/BCN catalysts. Green Chemistry, 2020, 22(3): 725–736

[17] Li X, Chen G, Liu C, Ma W, Yan B, Zhang J. Hydrodeoxygenation of lignin-derived bio-oil using molecular sieves supported metal catalysts: a critical review. Renewable & Sustainable Energy Reviews, 2017, 71: 296–308

[18] Li W, Dou X, Zhu C, Wang J, Chang H M, Jameel H, Li X. Production of liquefied fuel from depolymerization of kraft lignin over a novel modified nickel/H-beta catalyst. Bioresource Technology, 2018, 269: 346–354

[19] Dou X, Li W, Zhu C, Jiang X. Catalytic waste kraft lignin hydrodeoxygenation to liquid fuels over a hollow Ni–Fe catalyst. Applied Catalysis B: Environmental, 2021, 287: 119975

[20] Ge Y, Dong Y, Wang S, Zhao Y, Lv J, Ma X. 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] Dou X, Li W, Zhu C. Catalytic hydrotreatment of Kraft lignin into liquid fuels over porous ZnCoO_x nanoplates. Fuel, 2021, 283: 118801

[22] Zhang X, Wu J, Li T, Zhang C, Zhu L, Wang S. Selective hydrodeoxygenation of lignin-derived phenolics to cycloalkanes over highly stable NiAl₂O₄ spinel-supported bifunctional catalysts. Chemical Engineering Journal, 2022, 429: 132181

[23] Zhang H, Zhang G, Bi X, Chen X. 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] Zhu C, Dou X, Li W, Liu X, Li Q, Ma J, Liu Q, Ma L. 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] Ma Z, Kasipandi S, Wen Z, Yu L, Cui K, Chen H, Li Y. Highly efficient fractionation of corn stover into lignin monomers and cellulose-rich pulp over H₂WO₄. Applied Catalysis B: Environmental, 2020, 284: 119731

[26] Kresse G, Furthmuller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B, 1996, 54: 11169–11186

[27] Kresse G, Furthmiiller J. 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] Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 1999, 59: 1758–1775

[29] Liu Y, Zhang N, Yu C, Jiao L, Chen J. MnFe₂O₄@C nanofibers as high-performance anode for sodium-ion batteries. Nano Letters, 2016, 16(5): 3321–3328

[30] Chen Q, Zheng J, Yang Q, Dang Z, Zhang L. 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] Wei X, Wen X, Liu Y, Chen C, Xie C, Wang D, Qiu M, He N, Zhou P, Chen W, Cheng J, Lin H, Jia J, Fu X-Z, Wang S. Oxygen vacancy-mediated selective C–N coupling toward electrocatalytic urea synthesis. Journal of the American Chemical Society, 2022, 144(26): 11530–11535

[32] Feng L, Li X, Wang Z, Liu B. Catalytic hydrothermal liquefaction of lignin for production of aromatic hydrocarbon over metal supported mesoporous catalyst. Bioresource Technology, 2021, 323: 124569

[33] Tang B, Li W, Zhang X, Zhang B, Zhang H, Li C. 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] Wang Z, Lai C, Qin L, Fu Y, He J, Huang D, Li B, Zhang M, Liu S, Li L, Zhang W, Yi H, Liu X, Zhou X. 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] Qin L, Wang Z, Fu Y, Lai C, Liu X, Li B, Liu S, Yi H, Li L, Zhang M, Li Z, Cao W, Niu Q. Gold nanoparticles-modified MnFe₂O₄ with synergistic catalysis for photo-Fenton degradation of tetracycline under neutral pH. Journal of Hazardous Materials, 2021, 414: 125448

[36] Wang X, Wang A, Ma J. Visible-light-driven photocatalytic removal of antibiotics by newly designed C₃N₄@MnFe₂O₄-graphene nanocomposites. Journal of Hazardous Materials, 2017, 336(15): 81–92

[37] Zhou Y, Xiao B, Liu S Q, Meng Z, Chen Z G, Zou C Y, Liu C B, Chen F, Zhou X. 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] Wang Z, Ma H, Zhang C, Feng J, Pu S, Ren Y, Wang Y. 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] Ricciarelli D, Meggiolaro D, Belanzoni P, Alothman A A, Mosconi E, De Angelis F. Energy vs charge transfer in manganese-doped lead halide perovskites. ACS Energy Letters, 2021, 6(5): 1869–1878

[40] Sun Y, Sun S, Yang H, Xi S, Gracia J, Xu Z. Spin-related electron transfer and orbital interactions in oxygen electrocatalysis. Advanced Materials, 2020, 32: 2003297

[41] Pouya S R, Young-Kwon P. Catalytic hydropyrolysis of lignin: suppression of coke formation in mild hydrodeoxygenation of lignin-derived phenolics. Chemical Engineering Journal, 2019, 386: 121348

[42] Li L, Kong J, Zhang H, Liu S, Zeng Q, Zhang Y, Ma H, He H, Long J, Li X. Selective aerobic oxidative cleavage of lignin C–C bonds over novel hierarchical Ce–Cu/MFI nanosheets. Applied Catalysis B: Environmental, 2020, 279: 119343

[43] Yan F, Ma R, Ma X, Cui K, Wu K, Chen M, Li Y. Ethanolysis of Kraft lignin to platform chemicals on a MoC_1–x/Cu–MgAlO_z catalyst. Applied Catalysis B: Environmental, 2017, 202: 305–313

[44] Cheng C, Li P, Yu W, Shen D, Gu S. Catalytic hydrogenolysis of lignin in ethanol/isopropanol over an activated carbon supported nickel–copper catalyst. Bioresource Technology, 2021, 319: 124238

[45] Li T, Su J, Wang H, Wang C, Xie W, Wang K. Catalytic hydropyrolysis of lignin using NiMo-doped catalysts: catalyst evaluation and mechanism analysis. Applied Energy, 2022, 316: 119115

[46] Lu J, Wang M, Zhang X, Heyden A, Wang F. 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] Zou X, Chen J, Rui Z, Ji H. Sequential growth reveals multi-spinel interface promotion for methane combustion over alumina supported palladium catalyst. Applied Catalysis B: Environmental, 2020, 273: 119071

[48] Xiao T, Dai X, Wang X, Chen S, Dong B. Enhanced sludge dewaterability via ozonation catalyzed by sludge derived biochar loaded with MnFe₂O₄: performance and mechanism investigation. Journal of Cleaner Production, 2021, 323: 129182

Acknowledgements

We gratefully acknowledge the financial supports from the National Natural Science Foundation of China (Grant Nos. 22038004 and 22078069).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2236-1 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2023 Higher Education Press