Sustainable hydrothermal self-assembly of zirconium and waste shell for biomass reductive upgrade

Abstract

The conversion of biomass-derived aldehydes via waste shell-derived catalysts is vital for sustainable chemistry, yet green batch synthesis of such catalysts from raw biomass remains underexplored. This study uses crab shells, a kitchen waste, combined with ZrCl₄ via non-toxic hydrothermal synthesis to scale-prepare Zr-containing polyphenolic biopolymer catalyst (Zr-Ch). Comprehensive characterizations revealed that the robust coordination between Zr⁴⁺ ions and phenolic hydroxyl groups in waste shell resulted in the formation of potent Lewis acid-base pair sites (Zr⁴⁺-O²⁻). The synergistic effect of diverse acid-base sites in Zr-Ch enabled exceptional catalytic efficiency for the Meerwein-Ponndorf-Verley (MPV) reaction of furfural (FF) to furfuryl alcohol (FA) with a remarkably lower activation energy of 22.2 kJ/mol, which greatly reduced the reaction temperature to 100 °C. Consequently, a quantitative yield of FA as high as 94.9% and a selectivity for FA of 98.9% were achieved. This research expanded waste shell applications and illuminated acid-base interaction mechanisms in biomass molecule reduction.

Keywords

waste shell / green catalyst / biomass upgrade / Meerwein-Ponndorf-Verley reaction / reaction mechanism

References

[1] Kunkes E L, Simonetti D A, West R M, et al.. Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel classes [J]. Science, 2008, 322(5900): 417-421

[2] Wu J-c, Xu L-t, Li Y-y, et al.. Anodic cross-coupling of biomass platform chemicals to sustainable biojet fuel precursors [J]. Journal of the American Chemical Society, 2022, 144(51): 23649-23656

[3] Lu L-y, Wen C-y, Wang H-y, et al.. Tailoring the electron structure and substrate adsorption energy of Ni hydroxide via Co doping to enhance the electrooxidation of biomass-derived chemicals [J]. Journal of Catalysis, 2023, 424: 1-8

[4] Wu J-c, Kong Z-j, Li Y-y, et al.. Unveiling the adsorption behavior and redox properties of PtNi nanowire for biomass-derived molecules electrooxidation [J]. ACS Nano, 2022, 16(12): 21518-21526

[5] Wu J-c, Liu C-w, Zhu Y-t, et al.. Understanding the geometric and electronic factors of PtNi bimetallic surfaces for efficient and selective catalytic hydrogenation of biomass-derived oxygenates [J]. Journal of Energy Chemistry, 2021, 60: 16-24

[6] Viar N, Agirre I, Gandarias I. Process design, kinetics, and techno-economic assessment of an integrated liquid phase furfural hydrogenation process [J]. Chemical Engineering Journal, 2024, 480: 147873

[7] Wu J-c, Zhang X-h, Chen Q, et al.. One-pot hydrogenation of furfural into tetrahydrofurfuryl alcohol under ambient conditions over PtNi alloy catalyst [J]. Energy & Fuels, 2020, 34(2): 2178-2184

[8] Zhou S-h, Dai F-l, Xiang Z-y, et al.. Zirconium-lignosulfonate polyphenolic polymer for highly efficient hydrogen transfer of biomass-derived oxygenates under mild conditions [J]. Applied Catalysis B: Environmental, 2019, 248: 31-43

[9] Wu M, Liu M, Guo P-f, et al.. The ‘open’ site of Lewis acid zeolites for Meerwein-Ponndorf-Verley-Oppenauer reactions in biomass catalysis [J]. ChemCatChem, 2024, 16(24): e202400896

[10] Zhang H-w, Jaenicke S, Okumura K, et al.. Mechanochemistry-based liquid-assisted synthesis of hydrophobic Zr-beta with high metal loading for Meerwein-Ponndorf-Verley reduction [J]. Journal of Catalysis, 2024, 431: 115398

[11] Hao W-w, Li W-f, Tang X, et al.. Catalytic transfer hydrogenation of biomass-derived 5-hydroxymethyl furfural to the building block 2, 5-bishydroxymethyl furan [J]. Green Chemistry, 2016, 18(4): 1080-1088

[12] Koehle M, Lobo R F. Lewis acidic zeolite beta catalyst for the Meerwein-Ponndorf-Verley reduction of furfural [J]. Catalysis Science & Technology, 2016, 6(9): 3018-3026

[13] Zhu Y-z, Jaenicke S, Chuah G K. Supported zirconium propoxide: A versatile heterogeneous catalyst for the Meerwein-Ponndorf-Verley reduction [J]. Journal of Catalysis, 2003, 218(2): 396-404

[14] Wu J-c, Liang D, Song X-b, et al.. Sulfonic groups functionalized Zr-metal organic framework for highly catalytic transfer hydrogenation of furfural to furfuryl alcohol [J]. Journal of Energy Chemistry, 2022, 71: 411-417

[15] Yan Q, Chen Y, Tang B, et al.. Precise engineering of asymmetric tri-active sites by symbiotic strategy for photocontrolled directional reforming of biomass [J]. Angewandte Chemie (International Ed in English), 2025, 64(26): e202505718

[16] Wu J-c, Zhu Y-t, Liao P-z, et al.. Sustainable metal-lignosulfonate catalyst for efficient catalytic transfer hydrogenation of levulinic acid to γ-valerolactone [J]. Applied Catalysis A: General, 2022, 635: 118556

[17] Yan N, Chen X. Sustainability: Don’t waste seafood waste [J]. Nature, 2015, 524(7564): 155-157

[18] Chen X, Yan N. Novel catalytic systems to convert chitin and lignin into valuable chemicals [J]. Catalysis Surveys from Asia, 2014, 18(4): 164-176

[19] Wu J-c, Xu L-t, Kong Z-j, et al.. Integrated tandem electrochemical-chemical-electrochemical coupling of biomass and nitrate to sustainable alanine [J]. Angewandte Chemie (International Ed in English), 2023, 62(45): e202311196

[20] Cira L A, Huerta S, Hall G M, et al.. Pilot scale lactic acid fermentation of shrimp wastes for chitin recovery [J]. Process Biochemistry, 2002, 37(12): 1359-1366

[21] Zhou Y-y, Zhang Y, Nie Y-x, et al.. Recent advances and perspectives in functional chitosan-based composites for environmental remediation, energy, and biomedical applications [J]. Progress in Materials Science, 2025, 152: 101460

[22] Wang T-l, He J-h, Zhang Y-tao. Production of γ-valerolactone from one-pot transformation of biomass-derived carbohydrates over chitosan-supported ruthenium catalyst combined with zeolite ZSM-5 [J]. European Journal of Organic Chemistry, 2020, 2020(11): 1611-1619

[23] Li Y-t, Li M-t, Xu Z-b, et al.. Dehydration kinetics and thermodynamics of ZrO(NO₃)₂-doped Ca(OH)₂ for chemical heat storage [J]. Chemical Engineering Journal, 2020, 399: 125841

[24] Su H-s, Liu Y-w, Tian H, et al.. Selective C - H bond activation in propane with molecular oxygen over Cu (I)-ZSM-5 at ambient conditions [J]. Journal of the American Chemical Society, 2024, 146(25): 17170-17179

[25] Xie Y-f, Luo R, Sun G-d, et al.. Facilitating the reduction of V-O bonds on VO/ZrO₂ catalysts for non-oxidative propane dehydrogenation [J]. Chemical Science, 2020, 11(15): 3845-3851

[26] Binias D, Wyszomirski M, Binias W, et al.. Supermolecular structure of chitin and its derivatives in FTIR spectroscopy studies [J]. Polish Chitin Society, 2007, 12: 95-108

[27] Cárdenas G, Cabrera G, Taboada E, et al.. Chitin characterization by SEM, FTIR, XRD, and ¹³C cross polarization/mass angle spinning NMR [J]. Journal of Applied Polymer Science, 2004, 93(4): 1876-1885

[28] Ling S-l, Slater B. Dynamic acidity in defective UiO-66 [J]. Chemical Science, 2016, 7(7): 4706-4712

[29] Song J-l, Wu L-q, Zhou B-w, et al.. A new porous Zr-containing catalyst with a phenate group: An efficient catalyst for the catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone [J]. Green Chemistry, 2015, 17(3): 1626-1632

[30] Wu J-c, Murphy B M, Gould N S, et al.. A FTIR study of the acidity of in situ generated Bransted sites on NaY via displacement reactions [J]. Chem Cat Chem, 2019, 11(14): 3253-3263

[31] He J, Yang S, Riisager A. Magnetic nickel ferrite nanoparticles as highly durable catalysts for catalytic transfer hydrogenation of bio-based aldehydes [J]. Catalysis Science & Technology, 2018, 8(3): 790-797

[32] Li H, Liu X-f, Yang T-t, et al.. Porous zirconium-furandicarboxylate microspheres for efficient redox conversion of biofuranics [J]. Chem Sus Chem, 2017, 10(8): 1761-1770

[33] Panagiotopoulou P, Martin N, Vlachos D G. Inside cover: Liquid-phase catalytic transfer hydrogenation of furfural over homogeneous Lewis acid-Ru/C catalysts [J]. Chem Sus Chem, 2015, 8(12): 1990

[34] Song J-l, Zhou B-w, Zhou H-c, et al.. Porous zirconium-phytic acid hybrid: A highly efficient catalyst for Meerwein-Ponndorf-Verley reductions [J]. Angewandte Chemie (International Ed in English), 2015, 54(32): 9399-9403

[35] Gilkey M J, Panagiotopoulou P, Mironenko A V, et al.. Mechanistic insights into metal Lewis acid-mediated catalytic transfer hydrogenation of furfural to 2-methylfuran [J]. ACS Catalysis, 2015, 5(7): 3988-3994

[36] Liu S-h, Govindarajan N, Chan K-ren. Understanding activity trends in furfural hydrogenation on transition metal surfaces [J]. ACS Catalysis, 2022, 12(20): 12902-12910

[37] Zhou S-h, Chen G-x, Feng X, et al.. In situ MnO/N-doped carbon aerogels from cellulose as monolithic and highly efficient catalysts for the upgrading of bioderived aldehydes [J]. Green Chemistry, 2018, 20(15): 3593-3603

RIGHTS & PERMISSIONS

Central South University