Мақола

Sustainable production of C6 phenols from lignin via sequential C O and C C bond cleavage over Ni-MgO/hydroxyapatite catalyst

Shitong YuMOE Key Laboratory of Energy Thermal Conversion & Control, School of Energy and Environment, Southeast University, Nanjing 210096, ChinaZhitong GeMOE Key Laboratory of Energy Thermal Conversion & Control, School of Energy and Environment, Southeast University, Nanjing 210096, ChinaHaowei HuangMOE Key Laboratory of Energy Thermal Conversion & Control, School of Energy and Environment, Southeast University, Nanjing 210096, ChinaJulian A. SteeleAustralian Institute for Bioengineering and Nanotechnology, University of Queensland, Brisbane, QLD 4072, AustraliaFrancis KemausuorDepartment of Agricultural and Biosystems Engineering, Kwame Nkrumah University of Science and Technology, Kumasi, GhanaEmad M. HafezDepartment of Agronomy, Faculty of Agriculture, Kafrelsheikh University, Kafr El-Sheikh 33516, EgyptObid TursunovDepartment of Power Supply and Renewable Energy Sources, National Research University TIIAME, 39 Kari Niyazov, Tashkent 100000, UzbekistanZhicheng LuoMOE Key Laboratory of Energy Thermal Conversion & Control, School of Energy and Environment, Southeast University, Nanjing 210096, China

Chemical Engineering Journaljournal2025en

ABI

Аннотация

Lignin, the only renewable source of aromatic compounds, remains underutilized due to its structural complexity. Self-supplied hydrogenolysis (SSH), which leverages endogenous hydroxyl groups as hydrogen donors, has emerged as a promising strategy for lignin valorization. However, conventional SSH predominantly yields C8/C9 alkylphenols rather than the more valuable C6 phenols due to rapid catalyst-driven hydrodeoxygenation. Here, we report a carbonyl-stabilization strategy using a non-noble Ni–MgO/hydroxyapatite (HAP) catalyst that enables sequential cleavage of C β -O and C 1 -C α bonds, achieving 74.4 % selectivity for C6 phenolic monomers. Mechanistic studies reveal that basic sites on MgO/HAP facilitate oxygen adsorption at C α sites, promoting Ni-catalyzed C α H–OH dehydrogenation to C α = O groups, which lowers the dissociation energy of C β –O bonds, enabling efficient cleavage. Furthermore, the limited hydrodeoxygenation activity of Ni–MgO/HAP stabilizes C8/C9 carbonyl intermediates, allowing C 1 -C α bond scission via high-temperature hydrogen-driven carbocation formation. This strategy represents a paradigm shift in lignin depolymerization, offering a direct, hydrogen-efficient route to C6-based platform chemicals. By maximizing lignin-derived product value while reducing reliance on external hydrogen, this work advances sustainable biomass conversion and green chemical manufacturing. • Lignin is selectivity converted into C6 phenols via carbonyl-stabilization strategy during self-supplied hydrogenolysis. • Nickel promotes the dehydrogenation of C α H-OH groups, aided by basic sites on MgO/hydroxyapatite (HAP). • Mg doping increases the number of basic sites and enhances the availability of Ni 0 active sites on the catalyst surface. • Low-loading Ni stabilize the C8/C9 carbonyl-containing phenolic intermediates by preventing over-hydrogenation. • High-temperature hydrogen protons facilitate the activation and cleavage of C 1 -C α bonds.

Ҳали таржима қилинмаган

Мавзулар

Lignin and Wood Chemistry Catalysis for Biomass Conversion Catalysis and Hydrodesulfurization Studies

Идентификаторлар

DOI: 10.1016/j.cej.2025.164669

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