Gold Nanoparticle Immobilized Porous Manganese Oxide Microspheres As Heterogeneous Catalyst for Benzyl Alcohol Oxidation

Yıl 2022, Cilt: 50 Sayı: 1, 85 - 92, 05.01.2022

Kadriye Özlem Hamaloglu

https://doi.org/10.15671/hjbc.962119

Öz

A heterogenous catalyst in the form of Au nanoparticles (Au NPs) immobilized porous manganese oxide (Mn5O8) microspheres was synthesized. The sol-gel templating method was used for the synthesis of Mn5O8 microspheres. The heterogenous catalyst showed good performance when compared with similar catalysts in the oxidation of benzyl alcohol. The heterogenous catalyst (Au@Mn5O8) obtained by the immobilization of Au NPs on Mn5O8 microspheres performed 99.4% of benzyl alcohol conversion and 100 % of benzaldehyde formation yield. Also the heterogenous catalyst showed a good stability and agglomeration resistance in the reusabilty experiments. Au@Mn5O8 microspheres could be reused up to 5 times without remarkable loss in the catalytic activity.

Anahtar Kelimeler

Manganese oxide, Benzyl alcohol oxidation, Gold nanoparticles, Heterogenous catalysis

Teşekkür

The author thanks Prof. Dr. Ali TUNCEL for his valuable help to use his laboratory facilities and Rukiye Babacan Tosun for her valuable help during experiments.

Benzil alkol oksidasyonu için heterojen katalizör olarak altın nanoparçacık immobilize edilmiş gözenekli manganez oksit mikroküreler

Öz

Altın nanopartiküllerle (Au NP'ler) dekore edilmiş gözenekli manganez oksit (Mn5O8) mikroküreleri formunda heterojen bir katalizör sentezlenmiştir. Mn5O8 mikrokürelerinin sentezi için sol-jel kalıplama yöntemi kullanılmıştır. Sentezlenen heterojen katalizör, benzil alkol oksidasyonunda benzer katalizörlerle karşılaştırıldığında iyi performans göstermiştir. Au NP'lerin Mn5O8 mikroküreleri üzerinde immobilizasyonu ile elde edilen heterojen katalizör (Au@Mn5O8) ile %99.4 benzil alkol dönüşümü ve %100 benzaldehit oluşum verimi elde edilmiştir. Ayrıca heterojen katalizör, tekar kullanılabilirlik deneylerinde iyi bir stabilite ve aglomerasyona karşı direnç göstermiştir. Au@Mn5O8 mikroküreleri, katalitik aktivitede kayda değer bir kayıp olmaksızın 5 kata kadar yeniden kullanılabilmiştir.

Anahtar Kelimeler

Manganez oksit, Benzil alkol oksidasyonu, Altın nanopartiküller, Heterojen kataliz

Kaynakça

• Y. Zhang, X. Cui, F. Shi, Y. Deng, Nano-gold catalysis in fine chemical synthesis, Chem. Rev. 112 (2012) 2467–2505.
• C.D. Pina, E. Falletta, M. Rossi, Update on selective oxidation using gold, Chem. Soc. Rev. 41 (2012) 350–369.
• A. Abad, A. Corma, H. Garcia, Catalyst parameters determining activity and selectivity of supported gold nanoparticles for the aerobic oxidation of alcohols: the molecular reaction mechanism, Chem. Eur. J. 14 (2008) 212–222.
• Y. Hui, S. Zhang, W. Wang, Recent progress in catalytic oxidative transformations of alcohols by supported gold nanoparticles, Adv. Synth. Catal., 361(2019) 2215-2235.
• G. Liu, M. Hou, J. Song, T. Jiang, H. Fan, Z. Zhang, B. Han, Immobilization of Pd nanoparticles with functional ionic liquid grafted onto cross-linked polymer for solvent-free Heck reaction, Green Chem., 12 (2010) 65-69.
• M. Zou, M. Du, M. Zhang, T. Yang, H. Zhu, P. Wang, S. Bao, Synthesis and deposition of ultrafine noble metallic nanoparticles on amino-functionalized halloysite nanotubes and their catalytic application, Mater. Res. Bull., 61 (2015) 375-382.
• L. Chen, J. Yan, Z. Tong, S. Yu, J. Tang, B. Ou, L. Yue, L. Tian, Nanofiber-like mesoporous alumina supported palladium nanoparticles as a highly active catalyst for base-free oxidation of benzyl alcohol, Micropor. Mesopor. Mat., 266 (2018) 126-131.
• S. Niu, W. Guo, T.W. Lin, W. Yu, Y. Wu, X. Ji, L. Shao, Nanoscale Pd supported on 3D porous carbon for enhanced selective oxidation of benzyl alcohol, RSC Adv., 7 (2017) 25885-25890.
• Z. Hu, G. Zhou, L. Xu, J. Yang, B. Zhang, X. Xiang, Preparation of ternary Pd/CeO2-nitrogen doped graphene composites as recyclable catalysts for solvent-free aerobic oxidation of benzyl alcohol, Appl. Surf. Sci., 471 (2019) 852-861.
• K. Morgan, A. Goguet, C. Hardacre, Metal redispersion strategies for recycling of supported metal catalysts: a perspective, ACS Catal., 5 (2015) 3430-3445.
• L. Wolski, G. Nowaczyk, S. Jurga, M. Ziolek, Influence of co-precipitation agent on the structure, texture and catalytic activity of Au-CeO2 catalysts in low-temperature oxidation of benzyl alcohol, Catalysts, 11 (2021), 641-656.
• X. Li, J. Feng, M. Perdjon, R. Oh, W. Zhao, X. Huang, S. Liu, Investigations of supported Au-Pd nanoparticles on synthesized CeO2 with different morphologies and application in solvent-free benzyl alcohol oxidation, Appl. Surf. Sci., 505 (2020) 144473.
• S. Mandal, C. Santra, K.K. Bando, O.O. James, S. Maity, D. Mehta, B. Chowdhury, Aerobic oxidation of benzyl alcohol over mesoporous Mn-doped ceria supported Au nanoparticle catalyst, J. Mol. Catal. A: Chem., 378 (2013) 47-56.
• A. Mahdavi-Shakib, J. Sempel, M. Hoffman, A. Oza, E. Bennett, J.S. Owen, A.R. Chokanlu, B.G. Frederick, R.N. Austin, Au/TiO2-catalyzed benzyl alcohol oxidation on morphologically precise anatase nanoparticles, ACS Appl. Mater. Interfaces, 13 (2021) 11793-11804.
• R.H. Adnan, V.B. Golovko, Benzyl alcohol oxidation using gold catalysts derived from Au8 clusters on TiO2, Catal. Lett., 149 (2019) 449-455.
• P. Verma, K. Mori, Y. Kuwahara, S.J. Cho, H. Yamashita, Synthesis of plasmonic gold nanoparticles supported on morphology-controlled TiO2 for aerobic alcohol oxidation, Catal. Today, 352 (2020) 255-261.
• L.C. Wang, Y.M. Liu, M. Chen, Y. Cao, H.Y. He, K.N. Fan, MnO2 nanorod supported gold nanoparticles with enhanced activity for solvent-free aerobic alcohol oxidation, J. Phys. Chem. A, 112 (2008) 6981-6987.
• B. Das, M. Sharma, M.J. Baruah, B.P. Mounash, G.V. Karunakar, K.K. Bania, Gold nanoparticle supported on mesoporous vanadium oxide for photo-oxidation of 2-naphthol with hydrogen peroxide and aerobic oxidation of benzyl alcohols, J. Environ. Chem. Eng., 8 (2020) 104268.
• G. Nagy, A. Beck, G. Sáfrán, Z. Schay, S. Liu, T. Li, B. Qiao, J. Wang, K. Lázár, Nanodisperse gold catalysts in oxidation of benzyl alcohol: comparison of various supports under different conditions, React. Kinet. Mech. Catal., 128 (2019) 71-95.
• J.A. Gualteros, M.A. Garcia, A.G. da Silva, T.S. Rodrigues, E.G. Cândido, F.A. e Silva, F.C. Fonseca, J. Quiroz, D.C. de Oliveira, S.I.C. de Torresi, C.V.R. de Moura, P.H.C. Camargo, E.M. de Moura, Synthesis of highly dispersed gold nanoparticles on Al2O3, SiO2, and TiO2 for the solvent-free oxidation of benzyl alcohol under low metal loadings, J. Mater. Sci., 54 (2019) 238-251.
• X. Rao, A. Abou-Hassan, C. Guyon, E.O.M Ruiz, M. Tatoulian, S. Ognier, Synthesis of benzaldehyde with high selectivity using immobilized AuNPs and AuNPs@ zeolite in a catalytic microfluidic system, Lab on a Chip, 19 (2019) 2866-2873.
• L. Liu, H. Li, Y. Tan, X. Chen, R. Lin, W. Yang, C. Huang, S. Wang, X. Wang, X.Y. Liu, M. Zhao, Y. Ding, Metal-support synergy of supported gold nanoclusters in selective oxidation of alcohols, Catalysts, 10 (2020) 107-127.
• M. Haruta, Gold as a low-temperature oxidation catalyst: factors controlling activity and selectivity, Stud. Surf. Sci. Catal., 110 (1997) 123-134.
• L.I. Jinwei, L.I. Weibin, Effect of preparation method on the catalytic activity of Au/CeO2 for VOCs oxidation, J. Rare Earth, 28 (2010) 547-551.
• C. Santra, S. Rahman, S. Bojja, O.O. James, D. Sen, S. Maity, A.K. Mohanty, S. Mazumder, B. Chowdhury, Barium, calcium and magnesium doped mesoporous ceria supported gold nanoparticle for benzyl alcohol oxidation using molecular O2, Catal. Sci. Technol., 3 (2013) 360-370.
• S. Mandal, K.K. Bando, C. Santra, S. Maity, O.O. James, D. Mehta, B. Chowdhury, Sm-CeO2 supported gold nanoparticle catalyst for benzyl alcohol oxidation using molecular O2, Appl. Catal. A: Gen., 452 (2013) 94-104.
• R.B. Tosun, Ç. Kip, A. Tuncel, Polymeric template assisted synthesis of monodisperse-porous manganese oxide microspheres: a new nanozyme with oxidase-like activity allowing biomolecule determination via bimodal sensing, New J. Chem., 43 (2019) 18505-18516.
• R.B. Tosun, K.Ö. Hamaloğlu, P.A. Kavaklı, C. Kavaklı, A. Tuncel, A synergistic catalyst based on a multivalence monodisperse-porous microspheres with oxygen vacancies for benzyl alcohol oxidation, Mol. Catal., 497 (2020) 111227.
• C. Keresszegi, D. Ferri, T. Mallat, A. Baiker, Unraveling the surface reactions during liquid-phase oxidation of benzyl alcohol on Pd/Al2O3: an in situ ATR− IR study, J. Phys. Chem. B, 109 (2005) 958-967.
• A. Savara, C.E. Chan‐Thaw, I. Rossetti, A.Villa, L. Prati, Benzyl alcohol oxidation on carbon‐supported Pd nanoparticles: Elucidating the reaction mechanism, ChemCatChem, 6 (2014) 3464-3473.
• C.E. Chan-Thaw, A. Savara, A. Villa, Selective benzyl alcohol oxidation over Pd catalysts, Catalysts, 8 (2018), 431-452.
• F. Galvanin, M. Sankar, S. Cattaneo, D. Bethell, V. Dua, G.J. Hutchings, A. Gavriilidis, On the development of kinetic models for solvent-free benzyl alcohol oxidation over a gold-palladium catalyst. Chem. Eng. J., 342 (2018) 196-210.