Synthesis of Sulfated and CaO-Modified UiO-66 Bifunctional Catalysts from Zircon Sand for Conversion of Waste Cooking Oil
DOI:
https://doi.org/10.22437/chp.v10i1.49575Kata Kunci:
Biodiesel, heterogeneous catalyst, UiO-66, waste cooking oil, zircon sandAbstrak
Zircon-based UiO-66 metal–organic frameworks (MOFs) were synthesized from Central Kalimantan zircon sand and modified into bifunctional catalysts for two-step biodiesel production from waste cooking oil (WCO). Zirconium oxychloride (ZrOCl₂·8H₂O), obtained via acid leaching of zircon sand, served as the precursor for solvothermal UiO-66 synthesis using terephthalic acid (H₂BDC) as a linker. Post-synthetic modifications yielded sulfated UiO-66 (UiO-66/SO₄) as an acid catalyst and CaO-modified UiO-66 (UiO-66/CaO) as a base catalyst. XRD analysis displayed sharp reflections at 2θ = 7.4°, 8.5°, 25.8°, and 30.8° for UiO-66, with additional peaks at 17.7°, 33.8°, and 46.8° corresponding to CaO and Ca(OH)₂ phases, and a new band at 1114 cm-1 confirming sulfate incorporation—indicating successful formation of acid–base composite structures. Catalytic tests were conducted at varying catalyst loadings of 0.25%, 0.5%, and 0.75%. The UiO-66/SO₄ catalyst achieved the highest esterification efficiency at 0.5% loading, reducing the free fatty acid (FFA) content by 51.7%. Similarly, UiO-66/CaO exhibited optimum transesterification activity at 0.5% loading, yielding 61.82% biodiesel. FTIR spectra of the products confirmed fatty acid methyl ester (FAME) formation with characteristic C=O (1744 cm-1), C–O (1165, 1031 cm-1), and CH₃ (1456 cm-1) vibrations. These results demonstrate that zircon-sand-derived UiO-66 catalysts possess excellent structural stability, synergistic acid–base functionality, and strong catalytic efficiency, providing a sustainable pathway for biodiesel production from waste cooking oil.
Referensi
[1] Dinçer S. Alternative Renewable Energy Sources In The Context of Global Energy Crises and Sustainable Environment,” Kapanaltı Dergisi, 2025, 7:9–30, doi: 10.62080/kmfed.1642736.
[2] Khairati M. Biodiesel: An Overview. International Journal of Research and Review, 2023, 10(11):228–236, doi: 10.52403/ijrr.20231127
[3] Linganiso EC, Tlhaole B, Magagula LP, Dziike S, Linganiso LZ, Motaung TE, Moloto N, Tetana ZN. Biodiesel Production from Waste Oils: A South African Outlook. Sustainability. 2022; 14(4):1983. https://doi.org/10.3390/su14041983
[4] Lam MK., Lee KT., and Mohamed AR. Homogeneous, heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: A review. Biotechnology Advances. 2010, 28(4): 500–518,
doi: 10.1016/j.biotechadv.2010.03.002
[5] Wong SF., Tiong ANT., and Chin YH. Pre-treatment of waste cooking oil by combined activated carbon adsorption and acid esterification for biodiesel synthesis via two-stage transesterification. Biofuels, 2023. 14(9):967–977. doi:10.1080/17597269.2023.2196804
[6] M. Mulyatun, J. Prameswari, I. Istadi, and W. Widayat, “Production of non-food feedstock based biodiesel using acid-base bifunctional heterogeneous catalysts: A review,” Fuel, vol. 314, p. 122749, Apr. 2022, doi: 10.1016/j.fuel.2021.122749.
[7] Cavka JH, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S, Lillerud KP. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. Journal of the American Chemical Society. 2008. 130(42):13850–13851,doi: 10.1021/ja8057953.
[8] Murtadho I, Muslih EY, and Kusuma DY. Zirconia content enrichment of Indonesian zircon sand by using alkali fusion followed by water leaching and sulfuric acid leaching. 2022, 30006. doi: C10.1021/ja8057953.
[9] Butova VV, Burachevskaia OA, Drenchev NL, Tereshchenko AA, and Hadjiivanov KI. Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO2 via Adsorptive FTIR Spectroscopy. Nanomaterials. 2025. 15(11): 779, doi: 10.3390/nano15110779.
[10] Liu W, Wang F, Meng P, and Zang SQ. Sulfonic Acids Supported on UiO-66 as Heterogeneous Catalysts for the Esterification of Fatty Acids for Biodiesel Production. Catalysts. 2020. 10(11):1271, doi: 10.3390/catal10111271.
[11] Lee HV, Juan JC, and Taufiq-Yap YH. Preparation and application of binary acid-base CaO-La2O3 catalyst for biodiesel production. Renewable Energy, 2015. 74:124–132, doi: 10.1016/j.renene.2014.07.017.
[12] Li H, Wang Y, Ma X, Guo M, Li Y, Li G, Cui P, Zhou S, Yu M. Synthesis of CaO/ZrO2 based catalyst by using UiO–66(Zr) and calcium acetate for biodiesel production. Renewable Energy, 2022. 185:970–977, doi: 10.1016/j.renene.2021.12.096.
[13] Djustiana N, Febrida R, Panatarani C, Imarundha Y, Karlina E, and Joni IM. Microstructure Analysis of Zirconia-Alumina-Silica Particles Made from Indonesia Natural Sand Synthesized Using Spray Pyrolysis Method. Key Engineering Materials, 2016. 720: 285–289. doi: 10.4028/www.scientific.net/KEM.720.285.
[14] Li H, Chu H, Ma X, Wang G, Liu F, Guo M, Lu W, Zhou S, Yu M. Efficient heterogeneous acid synthesis and stability enhancement of UiO-66 impregnated with ammonium sulfate for biodiesel production. Chemical Engineering Journal, 2021, 408, 127277, doi: 10.1016/j.cej.2020.127277.
[15] Pratama DY, Valhalla ABG, Ely S, Hatta AM, and Suminar P. Temperature and Molarity Effects on the Synthesized Zircon Crystal Cells. Materials Science Forum, 2023, 1094: 71–75, doi: 10.4028/p-CgaJ4B.
[16] Chen Q, He Q, Lv M, Xu Y, Yang H, Liu X, Wei F. Selective adsorption of cationic dyes by UiO-66-NH2. Applied Surface Science, 2015, 327:77–85, doi:10.1016/j.apsusc.2014.11.103
[17] Pratika RA, Nafisah Z, Yuliana Y, Syarpi S, Iqba RM, Ysrafil Y, Wijaya K. Conversion of Used Cooking Oil into Biodiesel by Utilizing Zirconia Catalyst as Acid Catalyst (SO4/ZrO2) and Base Catalyst (ZrO2/CaO). Arabian Journal for Science and Engineering. 2025. 50(9):6595–6608, doi: 10.1007/s13369-024-09520-6.
[18] Nielsen RH, and Wilfing G. Zirconium and Zirconium Compounds, ”in Ullmann’s Encyclopedia of Industrial Chemistry, Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2010. doi: 10.1002/14356007.a28_543.pub2.
[19] Wang Y, Yang Z, Wu X, Quan W, Chen Q, and Wang A. UiO-66 with Both Brønsted and Lewis Acid Sites for Catalytic Synthesis of Biodiesel. Molecules, 2024. 29(17): 4195, doi: 10.3390/molecules29174195.
[20] Tatay S, Martinex-Gimenez S, Rubio-Gaspar A, Gómez-Oliveira E, Castells-Gil J, Dong Z, Mayoral A, Almora-Barrios N, Padial NM, Martí-Gastaldo C. Synthetic control of correlated disorder in UiO-66 frameworks,” Nature Communication, 2023. 14(1):6962, doi: 10.1038/s41467-023-41936-w.
[21] Biswas S and Der Voort PV. A General Strategy for the Synthesis of Functionalised UiO‐66 Frameworks: Characterisation, Stability and CO Adsorption Properties. European Journal of Inorganic Chemistry. 2013.12:2154–2160, doi:10.1002/ejic.201201228.
[22] Bauza M, Leo P, Cabello CP, Martin A, Orcajo G, Palomino GT, Martinez F. Catalytic Advantages of SO3H-Modified UiO-66(Zr) Materials Obtained via Microwave Synthesis in Friedel–Crafts Acylation Reaction. Inorganic Chemistry. 2024. 63(38):17460–17468, doi: 10.1021/acs.inorgchem.4c01792.
[23] Fernández-Morales JM, Lozano LA, Castillejos-López E, Rodríguez-Ramos I, Guerrero-Ruiz A, and Zamaro JM. Direct sulfation of a Zr-based metal-organic framework to attain strong acid catalysts,” Microporous and Mesoporous Materials. 2019. 290, 109686, doi: 10.1016/j.micromeso.2019.109686.
[24] Dhakshinamoorthy A, Santiago‐Portillo A, Asiri AM, and Garcia H. Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis. ChemCatChem, 2019, 11(3): 899–923, doi: 10.1002/cctc.201801452.
[25] Perfecto-Irigaray M, Beodibe G, Castillo O, da Silva I, García-Lojo D, Luque A, Mendia A, Pérez-Yáñez S. [Zr6O4(OH)4(benzene-1,4-dicarboxylato)6]n: a hexagonal polymorph of UiO-66. Chemical Communications. 2019. 55(42):5954–5957,doi:10.1039/C9CC00802K.
[26] Chen X, Yongjie L, Fu Q, Qin H, Lv J, Yang K, Zhang Q, Zhang H, Wang M. An efficient modulated synthesis of zirconium metal–organic framework UiO-66. RSC Advances. 2022. 12(10): 6083–6092, 2022, doi: 10.1039/D1RA07848H.
[27] Liu B, Chen X, Huang N, Liu S, Shen B, Wei F, Wang T. Interaction between Single Metal Atoms and UiO-66 Framework Revealed by Low-Dose Imaging. Nano Letters. 2023. 23(5): 1787–1793, doi: 10.1021/acs.nanolett.2c04569.
[28] Garzón‐Tovar L, Pérez‐Carvajal J, Imaz I, Maspoch D. Composite Salt in Porous Metal‐Organic Frameworks for Adsorption Heat Transformation. Advanced Functional Materials. 2017. 27(21), doi: 10.1002/adfm.201606424.
[29] Liu J, Cui H, Li J, and Chen M. A research on the cadmium ions adsorption of Sulfhydryl- and sulfo-functionalized UIO-66 with silica layer from water. Journal of Environmental Chemical Engineering. 2021. 9(1). 104621, doi: 10.1016/j.jece.2020.104621.
[30] Das RS, Warkhade SK, Kumar A, and Wankhade AV. Graphene oxide-based zirconium oxide nanocomposite for enhanced visible light-driven photocatalytic activity. Research on Chemical Intermediates, 2019. 45(4): 1689–1705,doi: 10.1007/s11164-018-3699-z.
[31] Pratika RA, Wijaya K, and Trisunaryanti W. Hydrothermal treatment of SO4/TiO2 and TiO2/CaO as heterogeneous catalysts for the conversion of Jatropha oil into biodiesel. Journal of Environmental Chemical Engineering. 2021. 9(6):106547, doi: 10.1016/j.jece.2021.106547.
[32] Liu H, Zhang M, Zhao H, Jiang Y, Liu G, and Gao J. Enhanced dispersibility of metal–organic frameworks (MOFs) in the organic phase via surface modification for TFN nanofiltration membrane preparation,” RSC Advances. 2020. 10(7):4045–4057, 2020, doi: 10.1039/C9RA09672H.
[33] Chu J, Ke FS, Wang Y, Feng X, Chen W, Ai x, Yang H, Cao. Facile and reversible digestion and regeneration of zirconium-based metal-organic frameworks, Communications Chemistry, 2020. 3(1):5, doi: 10.1038/s42004-019-0248-7.
[34] Mohamed F, Shaban M, Aljohani G, and Ahmed AM. Synthesis of novel eco-friendly CaO/C photocatalyst from coffee and eggshell wastes for dye degradation. Journal of Materials Research and Technology, 2021, 14:3140–3149, doi: 10.1016/j.jmrt.2021.08.055.
[35] Chi C, Li Y, Ma X, and Duan L. CO2 capture performance of CaO modified with by-product of biodiesel at calcium looping conditions. Chemical Engineering Journal, 2017, 326:378–388, doi: 10.1016/j.cej.2017.05.163
[36] Beitollahi A. Eiffect of the addition of Ca2+ on the structure, mcrostructure and ferroelectric properties of (Pb1 − y Ca y )(Zr0.8Ti0.2)O3 system with y = 0.0, 0.02, 0.05 and 0.1, Journal of Materials Science. 2003. 38(6): 1219–1229, doi:10.1023/A:1022809820833
[37] Abou-Elyazed AS, Ye G, Sun Y, and El-Nahas AM. A Series of UiO-66(Zr)-Structured Materials with Defects as Heterogeneous Catalysts for Biodiesel Production. Industrial and Engineering Chemistry Research. 2019. 58(48):21961–21971, doi:10.1021/acs.iecr.9b04344.
[38] Rezaie MA, Khojastehnezhad A, and Shiri A. Post-synthetic modification of Zr-based metal organic framework by schiff base zinc complex for catalytic applications in a click reaction. Scientific Reports. 2024.14(1): 24644, Oct. 2024, doi: 10.1038/s41598-024-76199-y.
[39] Andreo-Martínez P, Ortiz-Martínez VM, Salar-García MJ, Veiga-del-Baño JM, Chica A, and Quesada-Medina J. Waste animal fats as feedstock for biodiesel production using non-catalytic supercritical alcohol transesterification: A perspective by the PRISMA methodology. Energy for Sustainable Development, 2022. 69:150–163, doi:10.1016/j.esd.2022.06.004.
[40] Machmudah S, Wahyudiono W, Suprapto S, Budikarjono K, Roesyadi A, Sasaki M, Goto M. Transesterification Of Vegetables Oil Using Sub- and Supercritical Methanol. Reaktor, 2012. 14(2):123, doi:10.14710/reaktor.14.2.123-128.
[41] Kedir WM, Wondimu KT, and Weldegrum GS. Optimization and characterization of biodiesel from waste cooking oil using modified CaO catalyst derived from snail shell. Heliyon, 2023. 9(5): e16475, doi: 10.1016/j.heliyon.2023.e16475.
[42] Puhan D, Casford MTL, and Davies PB. Evaluation of Structural and Compositional Changes of a Model Monoaromatic Hydrocarbon in a Benchtop Hydrocracker Using GC, FTIR, and NMR Spectroscopy. ACS Omega, 2023. 8(39):35988–36000, doi:10.1021/acsomega.3c03833.
[43] Yusuff AS, Owolabi JO. Synthesis and characterization of alumina supported coconut chaff catalyst for biodiesel production from waste frying oil,” South African Journal of Chemical Engineering. 2019. 30:42–49, doi: 10.1016/j.sajce.2019.09.001.
[44] Paul R, Shit SC, Fovanna T, Ferri D, Srinivasa Rao B, Gunasooriya GTKK, Dao DQ, Le QV, Shown I, Sherburne MP, Trinh QT, Mondal J. Realizing Catalytic Acetophenone Hydrodeoxygenation with Palladium-Equipped Porous Organic Polymers. ACS Applied Materials and Interfaces. 2020.12(45): 50550–50565, doi: 10.1021/acsami.0c16680.
