Selective hydrodeoxygenation of guaiacol to cyclohexanol using activated hydrochar-supported Ru catalysts

Abstract

Lignin, an abundant aromatic polymer in nature, has received significant attention for its potential in the production of bio-oils and chemicals owing to increased resource availability and environmental issues. The hydrodeoxygenation of guaiacol, a lignin-derived monomer, can produce cyclohexanol, a nylon precursor, in a carbon-negative and environmentally friendly manner. This study explored the porous properties and the effects of activation methods on the Ru-based catalyst supported by environmentally friendly and cost-effective hydrochar. Highly selective cleavage of C_aryl–O bonds was achieved under mild conditions (160 °C, 0.2 MPa H₂, and 4 h), and alkali activation further improved the catalytic activity. Various characterization methods revealed that hydrothermal treatment and alkali activation relatively contributed to the excellent performance of the catalysts and influenced their porous structure and Ru dispersion. X-ray photoelectron spectroscopy results revealed an increased formation of metallic ruthenium, indicating the effective regulation of interaction between active sites and supports. This synergistic approach used in this study, involving the valorization of cellulose-derived hydrochar and the selective production of nylon precursors from lignin-derived guaiacol, indicated the comprehensive and sustainable utilization of biomass resources.

Graphical abstract

Keywords

hydrochar / guaiacol / cyclohexanol / activation / full-component utilization

References

[1] Zakzeski J , Bruijnincx P C , Jongerius A L , Weckhuysen B M . The catalytic valorization of lignin for the production of renewable chemicals. Chemical Reviews, 2010, 110(6): 3552–3599

[2] Liu W , Jiang H , Yu H . Thermochemical conversion of lignin to functional materials: a review and future directions. Green Chemistry, 2015, 17(11): 4888–4907

[3] Zhou Y , Zeng Q , He H , Wu K , Liu F , Li X . Role of methoxy and C_α-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds. Green Energy & Environment, 2024, 9(1): 114–125

[4] Kumar A , Anushree J , Kumar T . Utilization of lignin: a sustainable and eco-friendly approach. Journal of the Energy Institute, 2020, 93(1): 235–271

[5] Liu W , You W , Sun W , Yang W , Korde A , Gong Y , Deng Y . Ambient-pressure and low-temperature upgrading of lignin bio-oil to hydrocarbons using a hydrogen buffer catalytic system. Nature Energy, 2020, 5(10): 759–767

[6] Zhou H , Wang H , Perras F A , Naik P , Pruski M , Sadow A D , Slowing I I . Two-step conversion of kraft lignin to nylon precursors under mild conditions. Green Chemistry, 2020, 22(14): 4676–4682

[7] Zhou M , Wang Y , Wang Y , Xiao G . Catalytic conversion of guaiacol to alcohols for bio-oil upgrading. Journal of Energy Chemistry, 2015, 24(4): 425–431

[8] Sharma V , Getahun T , Verma M , Villa A , Gupta N . Carbon based catalysts for the hydrodeoxygenation of lignin and related molecules: a powerful tool for the generation of non-petroleum chemical products including hydrocarbons. Renewable & Sustainable Energy Reviews, 2020, 133: 110280

[9] Liu X , Jia W , Xu G , Zhang Y , Fu Y . Selective hydrodeoxygenation of lignin-derived phenols to cyclohexanols over Co-based catalysts. ACS Sustainable Chemistry & Engineering, 2017, 5(10): 8594–8601

[10] Xue G , Yin L , Shao S , Li G . Recent progress on selective hydrogenation of phenol toward cyclohexanone or cyclohexanol. Nanotechnology, 2022, 33(7): 072003

[11] Zhang K , Meng Q , Wu H , Yan J , Mei X , An P , Zheng L , Zhang J , He M , Han B . Selective hydrodeoxygenation of aromatics to cyclohexanols over Ru single atoms supported on CeO₂. Journal of the American Chemical Society, 2022, 144(45): 20834–20846

[12] Vomeri A , Stucchi M , Villa A , Evangelisti C , Beck A , Prati L . New insights for the catalytic oxidation of cyclohexane to KA oil. Journal of Energy Chemistry, 2022, 70: 45–51

[13] Karimi Estahbanati M R , Feilizadeh M , Babin A , Mei B , Mul G , Iliuta M C . Selective photocatalytic oxidation of cyclohexanol to cyclohexanone: a spectroscopic and kinetic study. Chemical Engineering Journal, 2020, 382: 122732

[14] Chiu C C , Genest A , Borgna A , Rösch N . Hydrodeoxygenation of guaiacol over Ru (0001): a DFT study. ACS Catalysis, 2014, 4(11): 4178–4188

[15] Laurenti D , Afanasiev P , Geantet C . Hydrodeoxygenation of guaiacol with CoMo catalysts. Part I: Promoting effect of cobalt on HDO selectivity and activity. Applied Catalysis B: Environmental, 2011, 101(3-4): 239–245

[16] Singh D , Dhepe P L . Understanding the influence of alumina supported ruthenium catalysts synthesis and reaction parameters on the hydrodeoxygenation of lignin derived monomers. Molecular Catalysis, 2020, 480: 110525

[17] Han B , Bao Z , Liu T , Zhou H , Zhuang G , Zhong X , Deng S , Wang J . Enhanced catalytic performances for guaiacol aqueous phase hydrogenation over ruthenium supported on mesoporous TiO₂ hollow spheres embedded with SiO₂ nanoparticles. ChemistrySelect, 2017, 2(29): 9599–9606

[18] Nakagawa Y , Ishikawa M , Tamura M , Tomishige K . Selective production of cyclohexanol and methanol from guaiacol over Ru catalyst combined with MgO. Green Chemistry, 2014, 16(4): 2197–2203

[19] Xu Q , Shi Y , Yang L , Fan G , Li F . The promotional effect of surface Ru decoration on the catalytic performance of Co-based nanocatalysts for guaiacol hydrodeoxygenation. Molecular Catalysis, 2020, 497: 111224

[20] Yu S , Dong X , Zhao P , Luo Z , Sun Z , Yang X , Li Q , Wang L , Zhang Y , Zhou H . Decoupled temperature and pressure hydrothermal synthesis of carbon sub-micron spheres from cellulose. Nature Communications, 2022, 13(1): 3616

[21] Adilina I B , Widjaya R R , Hidayati L N , Supriadi E , Safaat M , Oemry F , Restiawaty E , Bindar Y , Parker S F . Understanding the surface characteristics of biochar and its catalytic activity for the hydrodeoxygenation of guaiacol. Catalysts, 2021, 11(12): 1434

[22] Chen M , Li H , Wang Y , Tang Z , Dai W , Li C , Yang Z , Wang J . Lignin depolymerization for aromatic compounds over Ni-Ce/biochar catalyst under aqueous-phase glycerol. Applied Energy, 2023, 332: 120489

[23] Li T , Li H , Huang G , Shen X , Wang S , Li C . Transforming biomass tar into a highly active Ni-based carbon-supported catalyst for selective hydrogenation-transalkylation of guaiacol. Journal of Analytical and Applied Pyrolysis, 2021, 153: 104976

[24] Zhou M , Ye J , Liu P , Xu J , Jiang J . Water-assisted selective hydrodeoxygenation of guaiacol to cyclohexanol over supported Ni and Co bimetallic catalysts. ACS Sustainable Chemistry & Engineering, 2017, 5(10): 8824–8835

[25] Gollakota A R , Reddy M , Subramanyam M D , Kishore N . A review on the upgradation techniques of pyrolysis oil. Renewable & Sustainable Energy Reviews, 2016, 58: 1543–1568

[26] Song W , Liu Y , Baráth E , Zhao C , Lercher J A . Synergistic effects of Ni and acid sites for hydrogenation and C–O bond cleavage of substituted phenols. Green Chemistry, 2015, 17(2): 1204–1218

[27] Latifi E , Marchese A D , Hulls M C W , Soldatov D V , Schlaf M . [Ru(triphos)(CH₃CN)₃](OTf)₂ as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium. Green Chemistry, 2017, 19(19): 4666–4679

[28] Bjelić A , Grilc M , Likozar B . Catalytic hydrogenation and hydrodeoxygenation of lignin-derived model compound eugenol over Ru/C: intrinsic microkinetics and transport phenomena. Chemical Engineering Journal, 2018, 333: 240–259

[29] Ishikawa M , Tamura M , Nakagawa Y , Tomishige K . Demethoxylation of guaiacol and methoxybenzenes over carbon-supported Ru-Mn catalyst. Applied Catalysis B: Environmental, 2016, 182: 193–203

[30] Yu S , Zhao P , Yang X , Li Q , Mohamed B A , Saad J M , Zhang Y , Zhou H . Low-temperature hydrothermal carbonization of pectin enabled by high pressure. Journal of Analytical and Applied Pyrolysis, 2022, 166: 105627

[31] Wang X , Arai M , Wu Q , Zhang C , Zhao F . Hydrodeoxygenation of lignin-derived phenolics—a review on the active sites of supported metal catalysts. Green Chemistry, 2020, 22(23): 8140–8168

[32] Song W , He Y , Lai S , Lai W , Yi X , Yang W , Jiang X . Selective hydrodeoxygenation of lignin phenols to alcohols in the aqueous phase over a hierarchical Nb₂O₅-supported Ni catalyst. Green Chemistry, 2020, 22(5): 1662–1670

[33] Yu S , Yang X , Li Q , Zhang Y , Zhou H . Breaking the temperature limit of hydrothermal carbonization of lignocellulosic biomass by decoupling temperature and pressure. Green Energy & Environment, 2023, 8(4): 1216–1227

[34] Sevilla M , Fuertes A B . The production of carbon materials by hydrothermal carbonization of cellulose. Carbon, 2009, 47(9): 2281–2289

[35] Lin Q , Zhang C , Wang X , Cheng B , Mai N , Ren J . Impact of activation on properties of carbon-based solid acid catalysts for the hydrothermal conversion of xylose and hemicelluloses. Catalysis Today, 2019, 319: 31–40

[36] Chieng B W , Lee S H , Ibrahim N A , Then Y Y , Loo Y Y . Isolation and characterization of cellulose nanocrystals from oil palm mesocarp fiber. Polymers, 2017, 9(12): 355

[37] Norouzi O , Pourhosseini S , Naderi H R , Di Maria F , Dutta A . Integrated hybrid architecture of metal and biochar for high performance asymmetric supercapacitors. Scientific Reports, 2021, 11(1): 5387

[38] Eun K S , Hu K J , Keun K D , Chul H H , Lee K Y , Joo K H . Na-modified carbon nitride as a leach-resistant and cost-effective solid base catalyst for biodiesel production. Fuel, 2023, 341: 127548

[39] Wang L , Zhang H , Cao G , Zhang W , Zhao H , Yang Y . Effect of activated carbon surface functional groups on nano-lead electrodeposition and hydrogen evolution and its applications in lead-carbon batteries. Electrochimica Acta, 2015, 186: 654–663

[40] Mandrino D , Podgornik B . XPS investigations of tribofilms formed on CrN coatings. Applied Surface Science, 2017, 396: 554–559

[41] Chen X , Wang X , Fang D . A review on C1s XPS-spectra for some kinds of carbon materials. Fullerenes, Nanotubes, and Carbon Nanostructures, 2020, 28(12): 1048–1058

[42] Dang Y , Wang J , He J , Feng X , Tobin Z , Achola L A , Zhao W , Wen L , Suib S L . RuO₂-NiO nanosheets on conductive nickel foam for reliable and regeneratable seawater splitting. ACS Applied Nano Materials, 2022, 5(9): 13308–13318

[43] Silva C C C , Ribeiro N F , Souza M M , Aranda D A . Biodiesel production from soybean oil and methanol using hydrotalcites as catalyst. Fuel Processing Technology, 2010, 91(2): 205–210

[44] Long J , Shu S , Wu Q , Yuan Z , Wang T , Xu Y , Zhang X , Zhang Q , Ma L . Selective cyclohexanol production from the renewable lignin derived phenolic chemicals catalyzed by Ni/MgO. Energy Conversion and Management, 2015, 105: 570–577

[45] Zhang C , Jia C , Cao Y , Yao Y , Xie S , Zhang S , Lin H . Water-assisted selective hydrodeoxygenation of phenol to benzene over the Ru composite catalyst in the biphasic process. Green Chemistry, 2019, 21(7): 1668–1679

[46] Hossain M A , Phung T K , Rahaman M S , Tulaphol S , Jasinski J B , Sathitsuksanoh N . Catalytic cleavage of the β-O-4 aryl ether bonds of lignin model compounds by Ru/C catalyst. Applied Catalysis A, General, 2019, 582: 117100

[47] Gilkey M J , Panagiotopoulou P , Mironenko A V , Jenness G R , Vlachos D G , Xu B . Mechanistic insights into metal lewis acid-mediated catalytic transfer hydrogenation of furfural to 2-methylfuran. ACS Catalysis, 2015, 5(7): 3988–3994

[48] Zhang M , Xiang L , Fan G , Yang L , Li F . Unveiling the role of surface basic sites on ruthenium-based nanocatalysts for enhanced hydrodeoxygenation of guaiacol. Molecular Catalysis, 2022, 533: 112794

[49] Xu H , Ju J , Li H . Toward efficient heterogeneous catalysts for in-situ hydrodeoxygenation of biomass. Fuel, 2022, 320: 123891

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

The financial support from the National Natural Science Foundation of China (Grant No. 52276202), the National Key R&D Program of China (Grant No. 2020YFC1910100), the Tsinghua University-Shanxi Clean Energy Research Institute Innovation Project Seed Fund, Huaneng Group Science and Technology Research Project (Grant No. KTHT-U22YYJC12), the International Joint Mission On Climate Change and Carbon Neutrality, Tsinghua-Toyota Joint Research Fund, and State Key Laboratory of Chemical Engineering (Grant No. SKL-ChE-22A03) are gratefully acknowledged.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s11705-024-2409-1 and is accessible for authorized users.

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