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Abstract
The catalytic properties of reduced graphene oxide (rGO) deposited on aluminum and magnesium oxides were investigated in acetylene hydrogenation. Catalysts with different rGO loadings were prepared by impregnating γ-Al₂O₃ and MgO with aqueous graphene oxide suspensions, followed by reduction in hydrogen at 400 °C. The materials were characterized by FTIR, Raman spectroscopy, and SEM. FTIR spectra confirmed the successful deposition of rGO on both supports, and for MgO-based samples, FTIR also revealed partial hydration of surface Mg–O groups, forming Mg(OH)₂ and a hydroxide–graphene interfacial layer that improves anchoring and stabilizes the structure. Raman spectroscopy verified the formation of a graphene-based phase on both oxides and showed that the defect level of the deposited graphene remains constant with varying rGO loading. SEM analysis indicated that on MgO, rGO forms thin film-like structures and irregular folds that create partially covered regions, while on γ-Al₂O₃ it forms continuous films in some areas and isolated folds in others. Modification of γ-Al₂O₃ and MgO with rGO enhanced catalytic activity in acetylene hydrogenation, with the highest rates observed for samples with low rGO content. Both rGO/Al₂O₃ and rGO/MgO exhibited full (100 %) selectivity to ethylene in the 250–400 °C range. The improved performance is attributed to rGO-derived surface structures that ensure effective contact between carbon and oxide phases and facilitate activation of acetylene and hydrogen. Overall, the catalytic behavior of rGO-modified oxides is governed by the acid–base properties of the support and the structural features of the deposited graphene layer, which determine the activation temperature and thermal stability of the system.
References
Studt F., Calle-Vallejo F., Luo J., Hansen H.A., Nørskov J.K., Bligaard T. On the role of surface structure for catalyst selectivity by first-principles theory. ChemCatChem, 2012, 4(11), 1809-1815.
Borodziński A., Bond G.C. Selective hydrogenation of ethyne in ethene-rich streams on palladium catalysts. Part 1: Oxide supports. Catal. Rev., 2006, 48(1), 91-144.
https://doi.org/10.1080/01614940500364909
Liu Y., Wang Z., Zhang X. Review on graphene-based metal-free catalysts: Synthesis and applications. Chem. Eng. J., 2015, 270, 1-25.
Chen X., Park J., Ruoff R.S. Chemical functionalization of graphene and its applications. Chem. Rev., 2016, 116(14), 704-711.
Dreyer D.R., Park S., Bielawski C.W., Ruoff R.S. The chemistry of graphene oxide. Chem. Soc. Rev., 2010, 39(1), 228-240.
https://doi.org/10.1039/B917103G
Loh K.P., Bao Q., Eda G., Chhowalla M. Graphene oxide as a chemically tunable platform for optical applications. Nat. Chem., 2010, 2(12), 1015-1024.
https://doi.org/10.1038/nchem.907
Stankovich S., Dikin D.A., Piner R.D., et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon, 2007, 45(7), 1558-1565.
https://doi.org/10.1016/j.carbon.2007.02.034
Abakumov A., Bychko I.B., Selyshchev O.V., Zahn D.R.T., Qi X., Tang J., Stryzhak P.Ye. Highly selective hydrogenation of acetylene over reduced graphene oxide carbocatalyst. Materialia, 2021, 18, 101163.
https://doi.org/10.1016/j.mtla.2021.101163
Zhu C., Sheng J., Lu R. Metal-free hydrogenation of alkynes using nitrogen-doped graphene as a catalyst. ACS Catal., 2018, 8(10), 10081-10088.
Primo A., Neatu F., Florea M., Parvulescu V., Garcia H. Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation. Nat. Commun., 2014, 5, 5291.
https://doi.org/10.1038/ncomms6291
Nosach V.V., Bychko I.B., Stryzhak P.Ye. Catalytic properties of reduced graphene oxide deposited on aluminum oxide in ethane dehydrogenation. Theor. Exp. Chem., 2025, 61(2), 121-126. [in Ukranian].
https://doi.org/10.1007/s11237-025-09860-w
Kheirandish E., Taherzadeh M. Quasi-2D crystalline γ-alumina grown by graphene-templated method. Adv. Mater. Interfaces, 2020, 7(3), 2000561.
https://doi.org/10.1002/admi.202000561
Gómez-Navarro C., Burghard M., Kern K. Atomic structure of reduced graphene oxide. Nano Lett., 2010, 10(4), 1144-1148.
https://doi.org/10.1021/nl9031617
Long Y., Zhang Z., Zhao X., Wang D. Field emission of MgO-coated graphene sheets prepared by atomic layer deposition. J. Vac. Sci. Technol. B, 2015, 33(1), 012204.
https://doi.org/10.1116/1.4905094
Busca G. Acid-base properties of metal oxide surfaces and their characterization by IR spectroscopic methods. Adv. Catal., 2014, 57, 319-404.
Navalon S., Dhakshinamoorthy A., Alvaro M., García H. Carbocatalysis by graphene-based materials. Chem. Rev., 2014, 114(12), 6179-6212.
https://doi.org/10.1021/cr4007347
Acik M., Lee G., Mattevi C., Chhowalla M., Cho K., Chabal Y.J. Unusual infrared-absorption mechanism in thermally reduced graphene oxide. Nat. Mater., 2010, 9(10), 840-845.
https://doi.org/10.1038/nmat2858
Ferrari A.C. Raman spectroscopy of graphene and graphite: Disorder, electron-phonon coupling, doping and nonadiabatic effects. Solid State Commun., 2007, 143(1-2), 47-57.
https://doi.org/10.1016/j.ssc.2007.03.052
Eckmann A., Felten A., Mishchenko A., Britnell L., Krupke R., Novoselov K.S., Casiraghi C. Probing the nature of defects in graphene by Raman spectroscopy. Nano Lett., 2012, 12(8), 3925-3930.
https://doi.org/10.1021/nl300901a
Mohiuddin T.M.G., Lombardo A., Nair R.R., Bonetti A., Savini G., Jalil R., Ferrari A.C. Uniaxial strain in graphene by Raman spectroscopy. Phys. Rev. B, 2009, 79(20), 205433.
https://doi.org/10.1103/PhysRevB.79.205433
Busca G. The surface of transitional aluminas: A critical review. Catal. Today, 2014, 226, 2-13.
https://doi.org/10.1016/j.cattod.2013.08.003
Gotić M., Ivanda M., Sekulić A., Musić S., Matthews A., Popović S. Raman spectroscopic study of MgO and Mg(OH)₂ under high pressure. J. Mol. Struct., 2000, 555(1-3), 353-360.
Frost R.L., Kloprogge J.T. Vibrational spectroscopy of hydroxyl groups in MgO-H₂O system. Spectrochim. Acta A, 1999, 55(12), 2195-2205.
https://doi.org/10.1016/S1386-1425(99)00016-5
Liu P., Yan Y. Preparation and characterization of reduced graphene oxide and its composite with TiO₂ by FTIR and Raman spectroscopy. Appl. Surf. Sci., 2010, 256(9), 2810-2814.
Reddy B.M., Khan A. Promoted MgO catalysts for organic transformations: FTIR characterization of carbonate and carboxylate species on MgO. J. Mol. Catal. A, 2005, 230(1-2), 33-39.
Hu Y., Shen J., Li N., Ma H., Shi M., Ye M. Microwave-assisted reduction and functionalization of graphene oxide on MgO surfaces. J. Phys. Chem. C, 2010, 114(20), 9308-9313.
https://doi.org/10.1021/jp909756r
Gao J., Chen S., Wang H. Effect of support acidity on catalytic performance of Pt-based catalysts for selective hydrogenation of acetylene. Catal. Today, 2017, 295, 110-118.
Santos A.L.R., et al. Quantification of hydroxyl groups on alumina supports and their role in catalytic activity. Braz. J. Anal. Chem., 2018, 5(20), 48-59.
https://doi.org/10.30744/brjac.2179-3425.2018.5.20.48-59
Kwon O., Park J., Kim J., Song I. Acid-base properties of metal oxides and their influence on catalytic hydrogenation reactions. J. Mol. Catal. A, 2015, 398, 156-164.
Busca G. Bases and basic materials in heterogeneous catalysis: MgO, CaO, hydrotalcites and related materials. Catal. Today, 2009, 143, 2-8.
Torshizi H.O., Nakhaei Pour A., Mohammadi A., Zamani Y., Shahri S.M.K., Kamali Shahri S.M. Fischer-Tropsch synthesis by reduced graphene oxide nanosheets supported cobalt catalysts. Front. Chem. Sci. Eng., 2021, 15, 299-309.
https://doi.org/10.1007/s11705-020-1925-x
Grigoriev S.A., et al. Reduced graphene oxide (RGO) and its modifications as catalyst supports: Effects of loading and layer thickness. Materials, 2018, 11(8), 1405.