Synergistic Ti-Fe Oxides on Fishbone-Derived Carbon Sulfonate: Enhanced Styrene Oxidation Catalysis

Mukhamad Nurhadi(1*), Ratna Kusumawardani(2), Teguh Wirawan(3), Sin Yuan Lai(4), Hadi Nur(5)

(1) Department of Chemical Education, Universitas Mulawarman, Kampus Gunung Kelua, Samarinda 75119, Indonesia
(2) Department of Chemical Education, Universitas Mulawarman, Kampus Gunung Kelua, Samarinda 75119, Indonesia
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Mulawarman, Samarinda 75119, Indonesia
(4) School of Energy and Chemical Engineering, Xiamen University Malaysia, Selangor Darul Ehsan 43900, Malaysia; Kelip-kelip! Center of Excellence for Light Enabling Technologies, Xiamen University Malaysia, Bandar Sunsuria, Sepang 43900, Malaysia; College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
(5) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Negeri Malang, Jl. Semarang No. 5, Malang 65145, Indonesia; Center of Advanced Materials for Renewable Energy (CAMRY), Universitas Negeri Malang, Jl. Semarang No. 5, Malang 65145, Indonesia
(*) Corresponding Author


Fishbone-derived carbon sulfonate, modified through incipient wetness impregnation with titanium tetraisopropoxide and iron nitrate salts, displays catalytic activity in the oxidation of styrene with hydrogen peroxide (H2O2) as an oxidant. This was done to develop a cost-effective, non-toxic, and environmentally friendly bimetallic oxide catalyst, incorporating titanium and iron oxides on mesoporous-derived carbon fishbone to enhance styrene conversion and benzaldehyde selectivity in styrene oxidation using aqueous H2O2. The catalyst, featuring a combination of titanium and iron oxides on the surface of the fishbone-derived carbon sulfonate, demonstrates higher catalytic activity than single oxide catalysts, such as titanium or iron oxides alone. Factors influencing the catalyst's performance are investigated by using FTIR, XRD, XRF, SEM, and BET surface area. The results reveal that the presence of both titanium and iron oxides on the surface of the fishbone-derived carbon sulfonate and the catalyst's surface area creates a synergistic effect, the primary factors affecting its catalytic activity in styrene oxidation using H2O2 as an oxidant.


iron; oxidation; styrene; synergistic effect; titanium

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[1] Ito, S., Kon, Y., Nakashima, T., Hong, D., Konno, H., Ino, D., and Sato, K., 2019, Titania-catalyzed H2O2 thermal oxidation of styrenes to aldehydes, Molecules, 24 (14), 2520.

[2] Batra, M.S., Dwivedi, R., and Prasad, R., 2019, Recent developments in heterogeneous catalyzed epoxidation of styrene to styrene oxide, ChemistrySelect, 4 (40), 11636–11673.

[3] Andrade, M.A., and Martins, L.M.D.R.S., 2021, Selective styrene oxidation to benzaldehyde over recently developed heterogeneous catalysts, Molecules, 26 (6), 1680.

[4] Aberkouks, A., Mekkaoui, A.A., Boualy, B., El Houssame, S., Ait Ali, M., and El Firdoussi, L., 2018, Selective oxidation of styrene to benzaldehyde by Co-Ag codoped ZnO catalyst and H2O2 as oxidant, Adv. Mater. Sci. Eng., 2018, 2716435.

[5] Xie, L., Wang, H., Lu, B., Zhao, J., and Cai, Q., 2018, Highly selective oxidation of styrene to benzaldehyde over Fe3O4 using H2O2 aqueous solution as oxidant, React. Kinet., Mech. Catal., 125 (2), 743–756.

[6] Sakthivel, B., Josephine, D.S.R., Sethuraman, K., and Dhakshinamoorthy, A., 2018, Oxidation of styrene using TiO2-graphene oxide composite as solid heterogeneous catalyst with hydroperoxide as oxidant, Catal. Commun., 108, 41–45.

[7] Hulea, V., and Dumitriu, E., 2004, tyrene oxidation with H2O2 over Ti-containing molecular sieves with MFI, BEA and MCM-41 topologies, Appl. Catal., A, 277 (1-2), 99–106.

[8] Jafarpour, M., Ghahramaninezhad, M., and Rezaeifard, A., 2014, Catalytic activity and selectivity of reusable α-MoO3 nanobelts toward oxidation of olefins and sulfides using economical peroxides, RSC Adv., 4 (4), 1601–1608.

[9] Wang, H., Qian, W., Chen, J., Wu, Y., Xu, X., Wang, J., and Kong, Y., 2014, Spherical V-MCM-48: The synthesis, characterization and catalytic performance in styrene oxidation, RSC Adv., 4 (92), 50832–50839.

[10] Cancino, P., Paredes-García, V., Aguirre, P., and Spodine, E., 2014, A reusable CuII based metal–organic framework as a catalyst for the oxidation of olefins, Catal. Sci. Technol., 4 (8), 2599–2607.

[11] Zhang, Y., Wei, N., Xing, Z., and Han, Z.B., 2020, Functional hexanuclear Y(III) cluster-based MOFs supported Pd(II) single site catalysts for aerobic selective oxidation of styrene, Appl. Catal., A, 602, 117668.

[12] Nurhadi, M., Kusumawardani, R., Wirawan, T., Sumari, S., Lai, S.Y., and Nur, H., 2021, Catalytic performance of TiO2–carbon mesoporous-derived from fish bones in styrene oxidation with aqueous hydrogen peroxide as an oxidant, Bull. Chem. React. Eng. Catal., 16 (1), 88–96.

[13] Tanglumlert, W., Imae, T., White, T.J., and Wongkasemjit, S., 2009, Styrene oxidation with H2O2 over Fe- and Ti-SBA-1 mesoporous silica, Catal. Commun., 10 (7), 1070–1073.

[14] Kusumawardani, R., Nurhadi, M., Wirawan, T., Prasetyo, A., Agusti, N.N., Lai, S.Y., and Nur, H., 2022, Kinetic study of styrene oxidation over titania catalyst supported on sulfonated fish bone-derived carbon, Bull. Chem. React. Eng. Catal., 17 (1), 194–204.

[15] Ha, Y., Mu, M., Liu, Q., Ji, N., Song, C., and Ma, D., 2017, Mn-MIL-100 heterogeneous catalyst for the selective oxidative cleavage of alkenes to aldehydes, Catal. Commun., 103, 51–55.

[16] Ghosh, R., Son, Y.C., Makwana, V.D., and Suib, S.L., 2004, Liquid-phase epoxidation of olefins by manganese oxide octahedral molecular sieves, J. Catal., 224 (2), 288–296.

[17] Zou, H., Xiao, G., Chen, K., and Peng, X., 2018, Noble metal free V2O5/g-C3N4 composite for selective oxidation of olefins using hydrogen peroxide as oxidant, Dalton Trans., 47 (38), 13565–13572.

[18] Saux, C., and Pierella, L.B., 2011, Studies on styrene selective oxidation to benzaldehyde catalyzed by Cr-ZSM-5: Reaction parameters effects and kinetics, Appl. Catal., A, 400 (1-2), 117–121.

[19] Fiorenza, R., 2020, Bimetallic catalysts for volatile organic compound oxidation, Catalysts, 10 (6), 661.

[20] Vetrivel, S., and Pandurangan, A., 2005, Supported metal oxide catalysts: Their activity to vapor phase oxidation of ethylbenzene, Ind. Eng. Chem. Res., 44 (4), 692–701.

[21] Das, S., Gupta, A., Singh, D., and Mahajani, S., 2019, La/Zn bimetallic oxide catalyst for epoxidation of styrene by cumene hydroperoxide: Kinetics and reaction engineering aspects, Ind. Eng. Chem. Res., 58, 7448–7460.

[22] Zhang, Y., Wang, H., Li, S., Lu, B., Zhao, J., and Cai, Q., 2021, Catalytic oxidation of styrene and its reaction mechanism consideration over bimetal modified phosphotungstates, Mol. Catal., 515, 111940.

[23] Huang, K., Yu, S., Li, X., and Cai, Z., 2020, One-pot synthesis of bimetal MOFs as highly efficient catalysts for selective oxidation of styrene, J. Chem. Sci., 132 (1), 139.

[24] Zou, H., Hu, C., Chen, K., Xiao, G., and Peng, X., 2018, Cobalt vanadium oxide supported on reduced graphene oxide for the oxidation of styrene derivatives to aldehydes with hydrogen peroxide as oxidant, Synlett, 29 (16), 2181–2184.

[25] Nurhadi, M., 2017, Modification of coal char-loaded TiO2 by sulfonation and alkylsilylation to enhance catalytic activity in styrene oxidation with hydrogen peroxide as oxidant, Bull. Chem. React. Eng. Catal., 12 (1), 55–61.

[26] Nurhadi, M., Efendi, J., Lee, S.L., Indra Mahlia, T.M., Chandren, S., Ho, C.S., and Nur, H., 2015, Utilization of low rank coal as oxidation catalyst by controllable removal of its carbonaceous component, J. Taiwan Inst. Chem. Eng., 46, 183–190.

[27] Nurhadi, M., Chandren, S., Yuan, L.S., Ho, C.S., Indra Mahlia, T.M., and Nur, H., 2017, Titania-loaded coal char as catalyst in oxidation of styrene with aqueous hydrogen peroxide, Int. J. Chem. React. Eng., 15 (1), 20160088.

[28] Chakraborty, R., and Chowdhury, D.R., 2013, Fish bone derived natural hydroxyapatite-supported copper acid catalyst: Taguchi optimization of semibatch oleic acid esterification, Chem. Eng. J., 215-216, 491–499.

[29] Patel, S., Han, J., Qiu, W., and Gao, W., 2015, Synthesis and characterisation of mesoporous bone char obtained by pyrolysis of animal bones, for environmental application, J. Environ. Chem. Eng., 3 (4, Part A), 2368–2377.

[30] Yin, T., Park, J.W., and Xiong, S., 2015, Physicochemical properties of nano fish bone prepared by wet media milling, LWT - Food Sci. Technol., 64 (1), 367–373.

[31] Zayed, E.M., Sokker, H.H., Albishri, H.M., and Farag, A.M., 2013, Potential use of novel modified fishbone for anchoring hazardous metal ions from their solutions, Ecol. Eng., 61, 390–393.

[32] Lestari, S., Nurhadi, M., Kusumawardani, R., Saputro, E., Pujisupiati, R., Muskita, N.S., Fortuna, N., Purwandari, A.S., Aryani, F., Lai, S.Y., and Nur, H., 2022, Comparative adsorption performance of carbon-containing hydroxyapatite derived tenggiri (Scomberomorini) and belida (Chitala) fish bone for methylene blue, Bull. Chem. React. Eng. Catal., 17 (3), 565–576.

[33] Nurhadi, M., Kusumawardani, R., Nurhadi, M., Wirhanuddin, W., Gunawan, R., and Nur, H., 2019, Carbon-containing hydroxyapatite obtained from fish bone as low-cost mesoporous material for methylene blue adsorption, Bull. Chem. React. Eng. Catal., 14 (3), 660–671.

[34] Jaber, H.L., Hammood, A.S., and Parvin, N., 2018, Synthesis and characterization of hydroxyapatite powder from natural Camelus bone, J. Aust. Ceram. Soc., 54 (1), 1–10.

[35] Abdullah, N.H., Mohamed Noor, A., Mat Rasat, M.S., Mamat, S., Mohamed, M., Mohd Shohaimi, N.A., Ab Halim, A.Z., Mohd Shukri, N., Azhar Abdul Razab, M.K., and Mohd Amin, M.F., 2020, Preparation and characterization of calcium hydroxyphosphate (hydroxyapatite) from tilapia fish bones and scales via calcination method, Mater. Sci. Forum, 1010, 596–601.

[36] Goulas, K.A., Sreekumar, S., Song, Y., Kharidehal, P., Gunbas, G., Dietrich, P.J., Johnson, G.R., Wang, Y.C., Grippo, A.M., Grabow, L.C., Gokhale, A.A., and Toste, F.D., 2016, Synergistic effects in bimetallic palladium−copper catalysts improve selectivity in oxygenate coupling reactions, J. Am. Chem. Soc., 138 (21), 6805–6812.

[37] He, L., Gong, X., Ye, L., Duan, X., and Yuan, Y., 2016, Synergistic effects of bimetallic Cu-Fe/SiO2 nanocatalysts in selective hydrogenation of diethyl malonate to 1,3-propanediol, J. Energy Chem., 25 (6), 1038–1044.

[38] Stucchi, M., Capelli, S., Cardaci, S., Cattaneo, S., Jouve, A., Beck, A., Sáfrán, G., Evangelisti, C., Villa, A., and Prati, L., 2020, Synergistic effect in Au-Cu bimetallic catalysts for the valorization of lignin-derived compounds, Catalysts, 10 (3), 332.

[39] Ehsan, M.A., Hakeem, A.S., and Rehman, A., 2020, Synergistic effects in bimetallic Pd–CoO electrocatalytic thin films for oxygen evolution reaction, Sci. Rep., 10 (1), 14469.


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