Analytical Investigation of Oleic Acid Double Bond Cleavage Using Cu-BiVO4 Photocatalyst in Water/Ethanol System Using GC-MS Analysis

Annisa Aulia Rahmah; Bambang Prijamboedi; Fainan Failamani

doi:10.21009/JRSKT.121.02

Authors

Annisa Aulia Rahmah Chemistry Department, Faculty of Mathematics and Natural Sciences, Universitas Negeri Jakarta, Jl. Rawamangun Muka, Rawamangun, Jakarta Timur, DKI Jakarta 13220
Bambang Prijamboedi Inorganic and Physical Chemistry Research Division, Faculty of Mathematics and Natural Sciences, Bandung Institute of Technology, Jl. Ganesha 10, Bandung, 40132, Indonesia.
Fainan Failamani Inorganic and Physical Chemistry Research Division, Faculty of Mathematics and Natural Sciences, Bandung Institute of Technology, Jl. Ganesha 10, Bandung, 40132, Indonesia.

DOI:

https://doi.org/10.21009/JRSKT.121.02

Keywords:

BiVO4-phtocatalyst, fatty acid, GC-MS analysis, Oleic acid oxidation, Photocatalytic cleavage

Abstract

The oxidative cleavage of unsaturated fatty acids is a promising pathway for producing value-added chemicals; however, its photocatalytic conversion remains limited by catalyst efficiency. This study investigates the performance of BiVO₄ and Cu-modified BiVO₄ (Cu–BiVO₄) in promoting the photocatalytic cleavage of oleic acid in a water–ethanol system under visible light irradiation. The catalysts were synthesized via hydrothermal and impregnation methods, followed by photocatalytic reactions for 24 h. Product distribution and transformation pathways were analyzed using GC–MS. The results show that pristine BiVO₄ exhibits limited catalytic activity, while Cu–BiVO₄ significantly enhances the formation of C14 and C16 saturated fatty acids along with various oxidative cleavage products. This improvement is attributed to enhanced charge separation and increased generation of reactive oxygen species. These findings demonstrate that Cu–BiVO₄ is a more effective photocatalyst for the oxidative transformation of unsaturated fatty acids.

References

Alkahlawy, A., & Gaffer, A. (2025). Novel sustainable biodiesel production from low-grade oleic acid via esterification catalyzed by characterized crystalline ZrO2/Al2O3. BMC Chemistry, 19(1). https://doi.org/10.1186/s13065-024-01360-7

Chen, H. F., Chen, J. M., & Pan, Z. X. (2016). Preparation and Photocatalytic Activity of Cu/BiVO4 by Solid State Grinding Method for Degradation of Methyl Orange. Key Engineering Materials, 703, 321–325. https://doi.org/10.4028/www.scientific.net/KEM.703.321

Cui, J., Wang, G., Liu, W., Ke, P., Tian, Q., Li, X., & Tian, Y. (2021). Synthesis BiVO4 modified by CuO supported onto bentonite for molecular oxygen photocatalytic oxidative desulfurization of fuel under visible light. Fuel, 290, 120066. https://doi.org/https://doi.org/10.1016/j.fuel.2020.120066

Enferadi Kerenkan, A., Béland, F., & Do, T. O. (2016). Chemically catalyzed oxidative cleavage of unsaturated fatty acids and their derivatives into valuable products for industrial applications: A review and perspective. In Catalysis Science and Technology (Vol. 6, Number 4, pp. 971–987). Royal Society of Chemistry. https://doi.org/10.1039/c5cy01118c

Gardner, H. W. (1989). OXYGEN RADICAL CHEMISTRY OF POLYUNSATURATED FATTY ACIDS. In Free Radical Biology & Medicine (Vol. 7). https://doi.org/10.1016/0891-5849(89)90102-0

Garti, N., & Avni, E. (1982). The oxidation of oleic acid by permanganate in oil in water emulsion. Colloids and Surfaces, 4(1), 33–41. https://doi.org/10.1016/0166-6622(82)80087-5

Gomes, L. E., Plaça, L. F., Rosa, W. S., Gonçalves, R. V., Ullah, S., & Wender, H. (2022). Increasing the Photocatalytic Activity of BiVO4 by Naked Co(OH)2 Nanoparticle Cocatalysts. Photochem, 2(4), 866–879. https://doi.org/10.3390/photochem2040055

Hajra, B., Sultana, N., Guria, C., Pathak, A. K., & Saxena, V. K. (2017). Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex. JAOCS, Journal of the American Oil Chemists’ Society, 94(12), 1463–1480. https://doi.org/10.1007/s11746-017-3048-1

Han, S. S., Park, J. Y., Hwang, H. S., Choe, H. R., Nam, K. M., & Cho, E. J. (2019). Facile Synthesis of BiVO4 for Visible-Light-Induced C−C Bond Cleavage of Alkenes to Generate Carbonyls. ChemSusChem, 12(13), 3018–3022. https://doi.org/10.1002/cssc.201900439

Hewavitharana, G. G., Perera, D. N., Navaratne, S. B., & Wickramasinghe, I. (2020). Extraction methods of fat from food samples and preparation of fatty acid methyl esters for gas chromatography: A review. In Arabian Journal of Chemistry (Vol. 13, Number 8, pp. 6865–6875). Elsevier B.V. https://doi.org/10.1016/j.arabjc.2020.06.039

Hilbrands, A. M., Goetz, M. K., & Choi, K.-S. (2023). C–C Bond Formation Coupled with C–C Bond Cleavage during Oxidative Upgrading of Glycerol on a Nanoporous BiVO 4 Photoanode. Journal of the American Chemical Society, 145(46), 25382–25391. https://doi.org/10.1021/jacs.3c09631

Jin, L., Chen, Y., Tian, H., Liu, X., Huang, Y., Li, R., Chen, C., Dai, Z., & Huang, D. (2023). Unveiling the selective cleavage-bond mechanism during the photocatalytic degradation process with pH-mediated BiVO4/BiPO4 dipole controlled and changed glyphosate electron cloud distribution. Separation and Purification Technology, 320, 124164. https://doi.org/10.1016/j.seppur.2023.124164

Jin, X., Li, R., Zhao, Y., Liu, X., Wang, X., Jiao, H., & Li, J. (2018). Spatial separation of dual-cocatalysts on bismuth vanadate for selective aerobic oxidation of benzylalcohols to benzaldehydes under visible light irradiation. Catalysis Science and Technology, 8(23), 6173–6179. https://doi.org/10.1039/c8cy01778f

Kamble, G. S., Natarajan, T. S., Patil, S. S., Thomas, M., Chougale, R. K., Sanadi, P. D., Siddharth, U. S., & Ling, Y. C. (2023). BiVO4 As a Sustainable and Emerging Photocatalyst: Synthesis Methodologies, Engineering Properties, and Its Volatile Organic Compounds Degradation Efficiency. In Nanomaterials (Vol. 13, Number 9). MDPI. https://doi.org/10.3390/nano13091528

Lestari, A. Z., & Maulida, N. (2024). Analisis Kandungan Logam Dan Ftalat pada Komponen Eletronik menggunakan XRF dan Py/GC-MS. JRSKT - Jurnal Riset Sains Dan Kimia Terapan, 10(1), 99–106. https://doi.org/10.21009/jrskt.101.02

Li, X., Choo Ping Syong, J., & Zhang, Y. (2018). Sodium stannate promoted double bond cleavage of oleic acid by hydrogen peroxide over a heterogeneous WO3 catalyst. Green Chemistry, 20(15), 3619–3624. https://doi.org/10.1039/C8GC00949J

Lih, T. K., Zheng, A. L. T., Tan, H. Y., Sarbini, S. R., Seng, K. W. K., Chung, E. L. T., Andou, Y., & Tan, K. B. (2025). Low intensity UV driven dual functional Cu doped BiVO4 for enhanced methylene blue degradation and Staphylococcus aureus inactivation. Scientific Reports, 15(1). https://doi.org/10.1038/s41598-025-17994-z

Liu, Y., Shang, H., Zhang, B., Yan, D., & Xiang, X. (2024). Surface fluorination of BiVO4 for the photoelectrochemical oxidation of glycerol to formic acid. Nature Communications , 15(1). https://doi.org/10.1038/s41467-024-52161-4

Onwudiwe, D. C., Phadi, B. M., & Oyewo, O. A. (2021). Ce2O3/BiVO4 Embedded in rGO as Photocatalyst for the Degradation of Methyl Orange under Visible Light Irradiation. J, 4(2), 154–168. https://doi.org/10.3390/j4020013

Phuruangrat, A., Wannapop, S., Sakhon, T., Kuntalue, B., Thongtem, T., & Thongtem, S. (2023). Characterization and photocatalytic properties of BiVO4 synthesized by combustion method. Journal of Molecular Structure, 1274, 134420. https://doi.org/https://doi.org/10.1016/j.molstruc.2022.134420

Prasetiyo, H., Nanda, F. N., Rudi, M., & Razak, N. A. (2025). Screening of Bioactive Compounds of Spirulina platensis as Potential Antioxidants: An In-silico Approach. JRSKT - Jurnal Riset Sains Dan Kimia Terapan, 11(2), 41–52. https://doi.org/10.21009/jrskt.112.05

Sajid, M. M., Khan, S. B., Shad, N. A., Amin, N., & Zhang, Z. (2018). Visible light assisted photocatalytic degradation of crystal violet dye and electrochemical detection of ascorbic acid using a BiVO4/FeVO4 heterojunction composite. RSC Advances, 8(42), 23489–23498. https://doi.org/10.1039/c8ra03890b

Soutelo-Maria, A., Dubois, J. L., Couturier, J. L., & Cravotto, G. (2018a). Oxidative cleavage of fatty acid derivatives for monomer synthesis. Catalysts, 8(10). https://doi.org/10.3390/catal8100464

Spannring, P., Bruijnincx, P. C. A., Weckhuysen, B. M., & Gebbink, R. J. M. K. (2014). Transition metal-catalyzed oxidative double bond cleavage of simple and bio-derived alkenes and unsaturated fatty acids. In Catalysis Science and Technology (Vol. 4, Number 8, pp. 2182–2209). Royal Society of Chemistry. https://doi.org/10.1039/c3cy01095c

Upadhyay, R., Rana, R., Sood, A., Singh, V., Kumar, R., Srivastava, V. C., & Maurya, S. K. (2021). Heterogeneous vanadium-catalyzed oxidative cleavage of olefins for sustainable synthesis of carboxylic acids. Chemical Communications, 57(44), 5430–5433. https://doi.org/10.1039/d1cc01742j

Wang, Z., Lu, S., Wu, T., Hu, T., & Chen, G. (2025). HS-SPME/GC-MS-based multivariate statistics to discriminate differences in volatile flavors, amino acids, and fatty acids during oat fermentation. Journal of Cereal Science, 126, 104286. https://doi.org/10.1016/j.jcs.2025.104286

Xiao, L., Wang, S., Wang, Y., Wang, B., Ji, C., Lin, X., Liang, H., Zhang, S., Xu, X., & Dong, L. (2023). Density functional theory studies on the oleic acid thermal oxidation into volatile compounds. Food Chemistry: X, 19. https://doi.org/10.1016/j.fochx.2023.100737

Xu, H., Li, H., Wu, C., Chu, J., Yan, Y., & Shu, H. (2008). Preparation, characterization and photocatalytic activity of transition metal-loaded BiVO4. Materials Science and Engineering: B, 147(1), 52–56. https://doi.org/10.1016/j.mseb.2007.11.011

Yun, D., Ayla, E. Z., Bregante, D. T., & Flaherty, D. W. (2021a). Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H2O2over Tungsten Oxide Catalysts. ACS Catalysis, 11(5), 3137–3152. https://doi.org/10.1021/acscatal.0c05393

Yun, D., Ayla, E. Z., Bregante, D. T., & Flaherty, D. W. (2021b). Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H2O2over Tungsten Oxide Catalysts. ACS Catalysis, 11(5), 3137–3152. https://doi.org/10.1021/acscatal.0c05393

Zhang, S., Jiang, X., Jiang, Y., Jiang, C., & Yao, X. (2023). Hybridization of CuO with BiVO4 as an Efficient and Stable Photocatalyst for Selective Cleavage of Lignin C–C Bonds. Industrial & Engineering Chemistry Research, 62(3), 1277–1285. https://doi.org/10.1021/acs.iecr.2c03595

Zhao, J., Yang, H., Chen, C., You, T., Yu, X., Zhang, Y., Liu, H., & Zhu, Y. (2025). Fabrication of CuO/BiVO4 composites for enhanced visible-light-driven photocatalytic antibacterial activity. RSC Advances, 15(53), 45038–45047. https://doi.org/10.1039/D5RA06653K

Zhu, S., Tang, Y., & Wei, M. (2016). Preparation and Visible Light-Induced Photocatalytic Activity of BiVO4 with Olive-Like Morphology. Hans Journal of Chemical Engineering and Technology, 06(03), 64–70. https://doi.org/10.12677/hjcet.2016.63008