Error message

  • Deprecated function: Unparenthesized `a ? b : c ? d : e` is deprecated. Use either `(a ? b : c) ? d : e` or `a ? b : (c ? d : e)` in include_once() (line 1439 of /home/science2016/public_html/includes/bootstrap.inc).
  • Deprecated function: Array and string offset access syntax with curly braces is deprecated in include_once() (line 3557 of /home/science2016/public_html/includes/bootstrap.inc).
  • Deprecated function: Unparenthesized `a ? b : c ? d : e` is deprecated. Use either `(a ? b : c) ? d : e` or `a ? b : (c ? d : e)` in include_once() (line 1439 of /home/science2016/public_html/includes/bootstrap.inc).
  • Deprecated function: Array and string offset access syntax with curly braces is deprecated in include_once() (line 3557 of /home/science2016/public_html/includes/bootstrap.inc).

Oxidation of 1,7-Octadiene by Molecular Oxygen in Liquid-Phase in the Presence of Metal Silicides at the Initial Stages

Oksana Makota1, Zoryana Komarenska1, Lilianna Oliynyk1
Affiliation: 
1 Institute of Chemistry and Chemical Technologies, Lviv Polytechnic National University, 12 S. Bandery St., Lviv 79013, Ukraine oksana.i.makota@lpnu.ua
DOI: 
https://doi.org/10.23939/chcht20.01.072
AttachmentSize
PDF icon full_text.pdf752.92 KB
Abstract: 
The effect of metal silicides, TiSi2, VSi2, MoSi2, HfSi2, TaSi2, and WSi2, on the initial stages of the liquid-phase oxidation processes of 1,7-octadiene by molecular oxygen was investigated. It was established that the presence of a homogeneous initiator of radical processes, tert-butyl hydroperoxide, was necessary for the oxidation reaction to proceed. VSi2 is the best catalyst for the oxidation of 1,7-octadiene by O2. VSi2 and MoSi2 exhibited excellent reusability over five cycles of use without significant loss in their catalytic activity. VSi2 and MoSi2 before and after the oxidation reaction were characterized by XRD and FTIR.
References: 

[1] Kang, J.; Park, E.D. Liquid-Phase Selective Oxidation of Methane to Methane Oxygenates. Catalysts 2024, 14, 167. https://doi.org/10.3390/catal14030167
https://doi.org/10.3390/catal14030167

[2] Ciriminna, R.; Albanese, L.; Meneguzzo, F.; Pagliaro, M. Hydrogen Peroxide: A Key Chemical for Today's Sustainable Development. ChemSusChem 2016, 9, 3374-3381. https://doi.org/10.1002/cssc.201600895
https://doi.org/10.1002/cssc.201600895

[3] Kim, M.S.; Yang, G.S.; Park, E.D. Effects of Cu Species on Liquid-Phase Partial Oxidation of Methane with H₂O₂ over Cu-Fe/ZSM-5 Catalysts. Catalysts 2022, 12, 1224. https://doi.org/10.3390/catal12101224
https://doi.org/10.3390/catal12101224

[4] Liu, R.; Wu, H.; Shi, J.; Xu, X.; Zhao, D.; Ng, Y.H.; Zhang, M.; Liu, S.; Ding, H. Recent Progress on Catalysts for Catalytic Oxidation of Volatile Organic Compounds: A Review. Catal. Sci. Technol. 2022, 12, 6945-6991. https://doi.org/10.1039/D2CY01181F
https://doi.org/10.1039/D2CY01181F

[5] Rizescu, C.; El Fergani, M.; Eftemie, D.-I. Liquid Phase Oxidation of Alkenes and Glycerol with Molecular Oxygen over Mixed-Ligand Copper(II) Complexes Grafted on GO as Catalysts. Appl. Catal. A Gen. 2023, 663, 119302. https://doi.org/10.1016/j.apcata.2023.119302
https://doi.org/10.1016/j.apcata.2023.119302

[6] Denekamp, I.M.; Antens, M.; Slot, T.K.; Rothenberg, G. Selective Catalytic Oxidation of Cyclohexene with Molecular Oxygen: Radical versus Nonradical Pathways. ChemCatChem 2018, 10, 1035-1041. https://doi.org/10.1002/cctc.201701538
https://doi.org/10.1002/cctc.201701538

[7] Vidal, F.; Smith, S.; Williams, C.K. Ring Opening Copolymerization of Boron-Containing Anhydride with Epoxides as a Controlled Platform to Functional Polyesters. J. Am. Chem. Soc. 2023, 145, 13888-13900. https://doi.org/10.1021/jacs.3c03261
https://doi.org/10.1021/jacs.3c03261

[8] Hanif, M.; Zahoor, A.F.; Saif, M.J.; Nazeer, U.; Ali, K.G.; Parveen, B.; Mansha, A.; Chaudhry, A.R.; Irfan, A. Exploring the Synthetic Potential of Epoxide Ring Opening Reactions toward the Synthesis of Alkaloids and Terpenoids: A Review. RSC Adv. 2024, 14, 13100-13128. https://doi.org/10.1039/D4RA01834F
https://doi.org/10.1039/D4RA01834F

[9] Printz, G.; Shuvo, R.G.; Schweizer, A.; Ryzhakov, D.; Gourlaouen, C.; Lantigner, L.; Jacques, B.; Messaoudi, S.; Le Bideau, F.; Dagorne, S. N-Heterocyclic Carbene-Initiated Epoxide/Anhydride Ring-Opening Copolymerization: Effective and Selective Organoinitiators for the Production of Various Polyesters. Polym. Chem. 2024, 15, 3901-3906. https://doi.org/10.1039/D4PY00778F
https://doi.org/10.1039/D4PY00778F

[10] Mitani, R.; Yamamoto, H.; Sumimoto, M. Theoretical Study of the Reaction Mechanism of Phenol-Epoxy Ring-Opening Reaction Using a Latent Hardening Accelerator and a Reactivity Evaluation by Substituents. Molecules 2023, 28, 694. https://doi.org/10.3390/molecules28020694
https://doi.org/10.3390/molecules28020694

[11] Kayano, K.; Tsutsumi, T.; Murata, Y.; Ogasa, C.; Watanabe, T.; Sato, R.; Karanjit, S.; Namba, K. Epoxide Ring-Opening Reactions for Abundant Production of Mugineic Acids and Nicotianamine Probes. Angew. Chem. Int. Ed. 2024, 63, e202401411. https://doi.org/10.1002/anie.202401411
https://doi.org/10.1002/anie.202401411

[12] Zhao, Y.; Yu, Y.; Li, J.; Xie, J.; He, C. Hydrodechlorination under O₂ Promotes Catalytic Oxidation of CVOCs over Pt/TiO₂ Catalyst at Low Temperature. Chem. Commun. 2025, 61, 4710-4713. https://doi.org/10.1039/D4CC06366J
https://doi.org/10.1039/D4CC06366J

[13] He, X.; Zhang, Y.; Wang, L.; Li, J.; Liu, Y. Propene Epoxidation with Molecular Oxygen: Advancements from Nanoparticle to Single-Atom Catalysts. Smart Molecules 2024, 3, 25. https://doi.org/10.1002/smo.20240025
https://doi.org/10.1002/smo.20240025

[14] Yu, X.; Mao, J.; Wu, B.; Wei, Y.; Sun, Y.; Zhong, L. Boosting Direct Oxidation of Methane with Molecular Oxygen at Low Temperature over Rh/ZSM-5 Catalyst. ChemCatChem 2023, 15, e202300077. https://doi.org/10.1002/cctc.202300077
https://doi.org/10.1002/cctc.202300077

[15] Yan, L.; Wang, S.; Qian, C.; Zhou, S. Enhancing Oxygen Activation toward Promoted Photocatalytic Oxidation of Methane to Liquid Oxygenates with ReO₂@TiO₂: The Regulation of Oxygen Affinity. J. Mater. Chem. A 2025, 13, 4662-4672. https://doi.org/10.1039/D4TA07559E
https://doi.org/10.1039/D4TA07559E

[16] Wang, H.; Xin, W.; Zheng, X.; Zhang, Y.; Li, J.; Wang, X. Mild Oxidation of Methane to Oxygenates with O₂ and CO on Fluorine Modified TS-1 Supported Rh Single-Atom Catalyst in a Flow Reactor. Catal. Lett. 2024, 154, 259-269. https://doi.org/10.1007/s10562-023-04298-y
https://doi.org/10.1007/s10562-023-04298-y

[17] He, F.; Xu, L.; Wang, H.; Jiang, C. Recent Progress in Molecular Oxygen Activation by Iron-Based Materials: Prospects for Nano-Enabled In Situ Remediation of Organic-Contaminated Sites. Toxics 2024, 12, 773. https://doi.org/10.3390/toxics12110773
https://doi.org/10.3390/toxics12110773

[18] Yang, X.; Li, Y.; Zhang, Y.; Wang, Y.; Liu, Y.; Xu, Y.; Zhang, Y.; Wang, X. Controlling Metal-Oxide Reducibility for Efficient C-H Bond Activation in Hydrocarbons. Angew. Chem. Int. Ed. 2023, 62, e202310062. https://doi.org/10.1002/anie.202310062
https://doi.org/10.1002/anie.202310062

[19] Wang, Y.; Liu, Y.; Su, Q.; Li, Y.; Deng, L.; Dong, L.; Fu, M.; Liu, S.; Cheng, W. Poly(Ionic Liquid) Materials Tailored by Carboxyl Groups for the Gas Phase-Conversion of Epoxide and CO₂ into Cyclic Carbonates. J. CO₂ Util. 2022, 60, 101976. https://doi.org/10.1016/j.jcou.2022.101976
https://doi.org/10.1016/j.jcou.2022.101976

[20] Doiuchi, Y.; Nakamura, Y.; Kato, M.; Oi, S. Acid-Cooperative Transition Metal-Catalysed Oxygen-Atom-Transfer: Ruthenium-Catalysed C-H Oxygenation. Adv. Synth. Catal. 2024, 366, 1005-1013. https://doi.org/10.1002/adsc.202301453
https://doi.org/10.1002/adsc.202301453

[21] Etim, U.J.; Bai, P.; Gazit, O.M.; Zhong, Z. Low-Temperature Heterogeneous Oxidation Catalysis and Molecular Oxygen Activation. Catal. Rev. 2023, 65, 239-425. https://doi.org/10.1080/01614940.2021.1919044
https://doi.org/10.1080/01614940.2021.1919044

[22] Makota, O.; Lisnichuk, M.; Briančin, J.; Bednarčík, J.; Bondarchuk, O.; Melnyk, I. Magnetically Enhanced Fe₃O₄@ZnO and Fe₃O₄@ZnO@Bi₂O₂.₇ Composites for Efficient UV and Visible Light Photodegradation of Methyl Orange and Ofloxacin. Chemosphere 2025, 377, 144365. https://doi.org/10.1016/j.chemosphere.2025.144365
https://doi.org/10.1016/j.chemosphere.2025.144365

[23] Makota, O.; Dutková, E.; Briančin, J.; Bednarcik, J.; Lisnichuk, M.; Yevchuk, I.; Melnyk, I. Advanced Photodegradation of Azo Dye Methyl Orange Using H₂O₂-Activated Fe₃O₄@SiO₂@ZnO Composite under UV Treatment. Molecules 2024, 29, 1190. https://doi.org/10.3390/molecules29061190
https://doi.org/10.3390/molecules29061190

[24] Makota, O.; Yankovych, H. B.; Bondarchuk, O.; Saldan, I.; Melnyk, I. Sphere-Shaped ZnO Photocatalyst Synthesis for Enhanced Degradation of the Quinolone Antibiotic, Ofloxacin, under UV Irradiation. Environ. Sci. Pollut. Res. 2024, 31, 33619. https://doi.org/10.1007/s11356-024-33619-w
https://doi.org/10.1007/s11356-024-33619-w

[25] Komarenska, Z.; Oliynyk, L.; Makota, O. Activation of Mo₂B Catalyst in the Epoxidation Reaction of α-Ethylallyl Ethyl Acrylate with tert-Butyl Hydroperoxide. Chem. Chem. Technol. 2023, 17, 18-23. https://doi.org/10.23939/chcht17.01.018
https://doi.org/10.23939/chcht17.01.018

[26] Ischenko, O. V.; Dyachenko, A. G.; Saldan, I.; Lisnyak, V. V.; Diyuk, V. E.; Vakaliuk, A. V.; Yatsymyrskyi, A. V.; Gaidai, S. V.; Zakharova, T. M.; Makota, O.; et al. Methanation of CO₂ on Bulk Co-Fe Catalysts. Int. J. Hydrogen Energy 2021, 46, 37860-37871. https://doi.org/10.1016/j.ijhydene.2021.09.034
https://doi.org/10.1016/j.ijhydene.2021.09.034

[27] Khalameida, S.; Samsonenko, M.; Sydorchuk, V.; Zakutevskyy, O.; Starchevskyy, V.; Lakhnik, A. Improving the Photocatalytic Properties of Tin Dioxide Doped with Titanium and Copper in the Degradation of Rhodamine B and Safranin T. React. Kinet. Mech. Catal. 2022, 135, 1665-1685. https://doi.org/10.1007/s11144-022-02206-w
https://doi.org/10.1007/s11144-022-02206-w

[28] Starchevskyy, V.; Shparij, M.; Hrynchuk, Y.; Reutskyy, V.; Kurta, S.; Hatsevych, O. Modification of the Catalytic System for the Industrial Chlorine Processing of Ethylene in 1,2-Dichloroethane. Chem. Chem. Technol. 2020, 14, 394-402. https://doi.org/10.23939/chcht14.03.394
https://doi.org/10.23939/chcht14.03.394

[29] Shpariy, M.; Starchevskyy, V.; Znak, Z.; Mnykh, R.; Poliuzhyn, I. Extraction of Iron-Containing Catalyst from Chlororganic Wastes Generated by Ethylene Chlorination. East.-Eur. J. Enterp. Technol. 2020, 2(10(104)), 19-26. https://doi.org/10.15587/1729-4061.2020.201696
https://doi.org/10.15587/1729-4061.2020.201696

[30] Khalameida, S.V.; Samsonenko, M.N.; Sydorchuk, V.V.; Starchevskyy, V.L.; Zakutevskyy, O.I.; Khyzhun, O.Yu. Photocatalytic Properties of Tin Dioxide Doped with Chromium(III), Silver and Zinc Compounds in the Oxidation of Organic Substrates by the Action of Visible Light. Theor. Exp. Chem. 2017, 53, 40-46. https://doi.org/10.1007/s11237-017-9499-5
https://doi.org/10.1007/s11237-017-9499-5

[31] Nikipanchuk, M.V.; Komarenskaya, Z.M.; Cherniy, M.O. On the Activation of Mo2B and MoB Catalysts in Oct-1-ene Epoxidation with tert-Butyl Hydroperoxide. Kinet. Catal. 2014, 55, 212-216. https://doi.org/10.1134/S0023158414020062
https://doi.org/10.1134/S0023158414020062

[32] Ahmad, I.; Aftab, M. A.; Fatima, A.; Mekkey, S. D.; Melhi, S.; Ikram, S. A Comprehensive Review on the Advancement of Transition Metals Incorporated on Functional Magnetic Nanocomposites for the Catalytic Reduction and Photocatalytic Degradation of Organic Pollutants. Coord. Chem. Rev. 2024, 514, 215904. https://doi.org/10.1016/j.ccr.2024.215904
https://doi.org/10.1016/j.ccr.2024.215904

[33] Chen, X.; Liang, C. Transition Metal Silicides: Fundamentals, Preparation and Catalytic Applications. Catal. Sci. Technol. 2019, 9, 4785-4820. https://doi.org/10.1039/C9CY00533A
https://doi.org/10.1039/C9CY00533A

[34] Yang, K.; Chen, X.; Wang, L.; Zhang, L.; Jin, S.; Liang, C. SBA-15-Supported Metal Silicides Prepared by Chemical Vapor Deposition as Efficient Catalysts Towards the Semihydrogenation of Phenylacetylene. ChemCatChem 2017, 9, 348-355. https://doi.org/10.1002/cctc.201601653
https://doi.org/10.1002/cctc.201601653

[35] Su, Y.; Xie, Y.; Qin, H.; Huang, Z.; Yin, Q.; Li, Z.; Zhang, R.; Zhao, Z.; Wu, F.; Ou, G. Ultrafine Molybdenum Silicide Nanoparticles as Efficient Hydrogen Evolution Electrocatalyst in Acidic Medium. Int. J. Hydrogen Energy 2022, 47, 28924-28931. https://doi.org/10.1016/j.ijhydene.2022.06.218
https://doi.org/10.1016/j.ijhydene.2022.06.218

[36] Yang, X.; Wan, Y.; Li, J.; Liu, J.; Wang, M.; Tao, X. High Emissivity MoSi2-SiC-Al2O3 Coating on Rigid Insulation Tiles with Enhanced Thermal Protection Performance. Materials 2024, 17, 220. https://doi.org/10.3390/ma17010220
https://doi.org/10.3390/ma17010220

[37] Trach, Y. B. Specifics of Oxidation of Octene-1 with Molecular Oxygen on Vanadium Disilicide. Petrol. Chem. 2009, 49, 393-396. https://doi.org/10.1134/S0965544109050107
https://doi.org/10.1134/S0965544109050107

[38] Makota, O.I.; Trach, Y.B. Catalysis of 1-Octene Hydroperoxide Epoxidation Reaction by Metal Disilicides. Pol. J. Chem. 2008, 82, 345-352.

[39] Milas, N.A.; Surgenor, D.M. Studies in Organic Peroxides. VIII. t-Butyl Hydroperoxide and Di-t-butyl Peroxide. J. Am. Chem. Soc. 1946, 68, 205-208. https://doi.org/10.1021/ja01206a017
https://doi.org/10.1021/ja01206a017

[40] Liang, Y.; Ouyang, J.; Wang, H.; Wang, W.; Chui, P.; Sun, K. Synthesis and Characterization of Core-Shell Structured SiO₂@YVO₄:Yb³⁺,Er³⁺ Microspheres. Appl. Surf. Sci. 2012, 258, 3689-3694. https://doi.org/10.1016/j.apsusc.2011.12.006
https://doi.org/10.1016/j.apsusc.2011.12.006

[41] Trach, Y.; Makota, O.; Skubiszewska-Zięba, J.; Borowiecki, T.; Leboda, R. FTIR Investigation into Transition Metal Disilicides as Catalysts for tert-Butyl Hydroperoxide Decomposition. Transit. Met. Chem. 2010, 35, 345-348. https://doi.org/10.1007/s11243-010-9333-6
https://doi.org/10.1007/s11243-010-9333-6

[42] Makota, O.; Trach, Y.; Leboda, R.; Skubiszewska-Zięba, J. The Study of Cyclooctene Oxidation with Molecular Oxygen Catalyzed by VSi₂. Cent. Eur. J. Chem. 2009, 7, 731-738. https://doi.org/10.2478/s11532-009-0096-x
https://doi.org/10.2478/s11532-009-0096-x

[43] Shafeeq, K.M.; Athira, V.P.; Raj Kishor, C.H.; Aneesh, P.M. Structural and Optical Properties of V₂O₅ Nanostructures Grown by Thermal Decomposition Technique. Appl. Phys. A 2020, 126, 586. https://doi.org/10.1007/s00339-020-03770-5
https://doi.org/10.1007/s00339-020-03770-5

[44] Wen, A.; Cai, Z.; Zhang, Y.; Liu, H. A Novel Method of Preparing Vanadium-Based Precursors and Their Enhancement Mechanism in Vanadium Nitride Preparation. RSC Adv. 2022, 12, 13093-13101. https://doi.org/10.1039/d2ra00584k
https://doi.org/10.1039/D2RA00584K

[45] Musić, S.; Filipović-Vinceković, N.; Sekovanić, L. Precipitation of Amorphous SiO₂ Particles and Their Properties. Braz. J. Chem. Eng. 2011, 28, 89-94. https://doi.org/10.1590/S0104-66322011000100011
https://doi.org/10.1590/S0104-66322011000100011

[46] Jun, S.E.; Choi, S.; Choi, S.; Lee, T. H.; Kim, C.; Yang, J. W.; Choe, W.-O.; Im, I.-H.; Kim, C.-J.; Jang, H.W. Direct Synthesis of Molybdenum Phosphide Nanorods on Silicon Using Graphene at the Heterointerface for Efficient Photoelectrochemical Water Reduction. Nano-Micro Lett. 2021, 13, 81. https://doi.org/10.1007/s40820 021 00605 7
https://doi.org/10.1007/s40820-021-00605-7