اکسایش بنزیل الکل به بنزآلدهید تحت شرایط بدون حلال با استفاده از نانوذرات مخلوط روتنیوم-سریم اکسید

نویسنده

Nano Technology and Advanced Materials, Materials and Energy Research Center

چکیده

در این مطالعه، ترکیب سریم اکسید و مخلوط روتنیوم- سریم اکسید با استفاده از روش رسوب‎گذاری در محیط قلیایی و نانوذرات مخلوط روتنیوم- سریم اکسید با استفاده از روش مایسل معکوس سنتز گردیدند. تمامی نمونه‎ها با استفاده از روش‎های XRD و BET شناسایی گردیدند. اندازه نانوذرات به‌دست آمده با استفاده از تصاویر TEM اندازه‌گیری گردید. در مرحله بعد فعالیت کاتالیزوری نمونه‎های سنتزی در واکنش اکسایش بنزیل الکل در حضور اکسیژن مولکولی و تحت شرایط بدون حلال مورد بررسی قرار گرفت. نتایج به‌دست آمده نشان داد نانوکاتالیزور سنتز شده بهترین گزینه در واکنش اکسایش بنزیل الکل به بنزآلدهید می‌باشد. هم‌چنین عوامل موثر بر واکنش مانند دمای واکنش، مقدار کاتالیزور و مدت زمان واکنش جهت رسیدن به بالاترین درصد تبدیل بنزیل الکل بهینه گردیدند. تحت شرایط بهینه بالاترین درصد تبدیل بنزیل الکل 99 درصد با گزینش‌‎پذیری 94 درصد برای محصول بنزآلدهید در حضور نانوذرات مخلوط روتنیوم- سریم اکسید در دمای 80 درجه سانتی-گراد و مدت زمان سه ساعت به‎دست آمد.

کلیدواژه‌ها


عنوان مقاله [English]

Solvent Free Oxidation of Benzyl Alcohol to Benzaldehyde over RuO2/CeO2 Nano-Mixed Oxide

چکیده [English]

In this study, Ce oxide and Ru-Ce mixed oxide were prepared by co-precipitation method in alkaline media. Also, the Ru-Ce mixed oxide nanoparticles were synthesized by a reverse micelle approach. All of the samples were characterized with XRD and BET methods and the size of nanoparticles synthesized in the reverse micelle was measured by the TEM technique. The catalytic activities of synthesized samples were investigated for oxidation of benzyl alcohol in the presence of molecular oxygen and solvent free condition. The obtained results show that the nano-catalyst is suitable candidates for the oxidation of benzyl alcohol to the benzaldehyde. In order to obtain maximum conversion of benzyl alcohol, the reaction parameters, like reaction temperature, amount of catalyst and reaction time, were optimized. Under the optimized conditions, a maximum of 99%benzyl alcohol conversion and 94 % selectivity for benzaldehyde was achieved with Ru-Ce nano mixed oxide as catalyst, at 80 oC and 3h.

کلیدواژه‌ها [English]

  • Benzyl alcohol
  • Solvent free oxidation
  • Benzaldehyde
  • Nanoparticles Ru-Ce mixed oxide
  • Reverse Micelle

1. Parreira, L.A., Bogdanchikova, N., Pestryakov, A., Zeped, T.A., Tuzovskaya, I., Farias, M.H., Gusevskaya, E.V., Nanocrystalline gold supported on Fe-, Ti- and Ce-modified hexagonal mesoporous silica as a catalyst for the aerobic oxidative esterification of benzyl alcohol. Appl Catal A, 2011, 397, 145–152.

 

2.   Yu, H., Fu, X., Zhou, C., Peng, F., Wang, H., Yang, J., Capacitance dependent catalytic activity of RuO2 xH2O/CNT, nano catalysts for aerobic oxidation of benzyl alcohol. Chem Commun, 2009, 2408–10.

 

3.   Sudarsanam, P., Mallesham, B., Durgasri, D.N., Reddy, B.M. Physicochemical and catalytic properties of nano sized Au/CeO2catalysts for eco-friendly oxidation of benzyl alcohol, J Ind Eng Chem, 2014, 20, 3115-21.

 

4.   Arena, F., Gumina, B., Lombardo, A.F., Espro, C., Patti, A., Spadaro, L., Spiccia L.Nanostructured MnOx catalysts in the liquid phase selective oxidation of benzyl alcohol with oxygen: Part I. Effects of Ce and Fe addition on structure and reactivity, Appl Catal B: Environmen, 2015, 162 , 260–7.

 

5.   Bruhne, F., Wright, E., Benzaldehyde, Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, Germany, 2000.

 

6.   Beier, M.J., Hansen, T.W., Grunwaldt, J.D., Selective liquid-phase oxidation of alcohols catalyzed by a silver-based catalyst promoted by the presence of ceria. J Cata,l 2009, 266, 320–30.

 

7.   Zhu, C., Ji, L., Wei, Y., Clean and selective oxidation of alcohols with n-Bu4NHSO5 catalyzed by ionic liquid immobilized TEMPO in ionic liquid [bmim][PF6]. Catal Commun, 2010, 11, 1017–20.

 

8.   Bose, S., Pariyar, A., Biswas, A.N., Das, P., Bandyopadhyay, P., Manganese(III) corrole catalyzed selective oxidation of alcohols to carbonyl compounds by tert-butyl hydroperoxide under mild condition. Catal Commun, 2011, 12:446–9.

 

9.   García-Suárez, E.J., Tristany, M., García, A.B., Collière, V., Philippot, K., Carbon-supported Ru and Pd nanoparticles: Efficient and recyclable catalysts for the aerobic oxidation of benzyl alcohol in water. Micropor Mesopor Mat, 2012, 153, 155–62.

 

10. Pagadala, R., Maddila, S., Rana, S., Jonnalagadda, S.B., Ce-Zr/SiO2: A versatile reusable heterogeneous catalyst for three-component synthesis and solvent free oxidation of benzyl alcohol. RSC Adv, 2014, 4, 6602-7.

 

11. Nascimento, L.F., Rosolen, J.M., Matsubara, E.Y., Donate, P.M., Catalytic behavior of ruthenium anchored on micronanostructured composite in selective benzyl alcohol oxidation, Reac Kinet Mech Cat, 2013, 110, 471–83.

 

12. Kanada, A., Idaka, N., Nishiyama, S., Tsuruya, S., Masai, M., Oxidation activity of cerium supported NaZSM-5 zeolites with and without added alkali metals in the gas-phase catalytic oxidation of benzyl alcohol. Phys Chem Chem Phys, 1999, 1, 373-81.

 

13. Deori, K., Kalita, C., Deka, S., surface exposed CeO2 Nanocube as Efficient Heterogeneous Catalyst in Tandem Oxidation of Benzyl Alcohol, para -Chlorobenzyl Alcohol and Toluene to Corresponding Aldehydes Selectively, J. Mater Chem A, 2015, 3, 6909-20.

 

14. Mallick, S., Rana, S., Parida, K., Facile Method for the Synthesis of Phosphomolybdic Acid Supported on Zirconia − Ceria Mixed Oxide and Its Catalytic Evaluation in the Solvent-Free Oxidation of Benzyl Alcohol, Ind Eng Chem Res, 2012, 51, 7859-66.

 

15. Pal, N,N., Cho, E.B., Kim, D., Synthesis of ordered mesoporous silica/ceria –silica composites and their high catalytic performance for solvent-free oxidation of benzyl alcohol at room temperature, RSC Adv, 2014, 4, 9213–22.

 

16. Hosokawa, S., Hayashi, Y., Imamura, S., Wada, K., Inoue, M., Effect of the Preparation Conditions of Ru/CeO2Catalysts for the Liquid Phase Oxidation of Benzyl Alcohol, Catal Lett, 2009, 129, 394–399.

 

17. Seiki T, Nakato A, Nishiyama S, Tsuruya S, Effect and role of alkali metals added to cobalt ion-exchanged X and Y zeolite catalysts in the gas-phase catalytic oxidation of benzyl alcohol. Phys Chem Chem Phys 2003; 5: 3818–26.

 

18. Mandal S, Santra C,. Bando K K, James O O, Maity S, Mehta D,Chowdhury B. Effect and role of alkali metals added to cobalt ion-exchanged X and Y zeolite catalysts in the gas-phase catalytic oxidation of benzyl alcohol. J Molecul Catal A Chem2013;378: 47– 56.

 

19. Chen, Y., Zheng, H., Guo, Z., Zhou, C., Wang, C., Borgna, A., Yang, Y., Pd catalysts supported on Mn CeOx mixed oxides and their catalytic application in solvent-free aerobic oxidation of benzyl alcohol: Support composition and structure sensitivity. J Catal 2011, 283, 34–44.

 

20. Paul, A., Hull, J.F., Norris, M.R., Chen, Z., Ess, D.H., Concepcion, J.J., Meye, T.J., Multiple Pathways for Benzyl Alcohol Oxidation by Ruv=O3+and RuIV= O2+, Inorg Chem, 2011, 50, 1167-1169.

 

21. Hornstein, B.J., Dattelbaum, D.M., Schoonover, J.R., Meyer, T.J., Reactivity of an Adsorbed Ru(VI)-Oxo Complex: Oxidation of Benzyl Alcohol, Inorg Chem. 2007, 46, 8139-45.

 

22. Alhumaimess, M., Dummer, N.F., Lin, Z., Taylor, S.H., Weng, W., Dimitratos, N., Bartley, J.K., Kiely, C.J., Hutchings, G.J., Oxidation of Benzyl Alcohol by using Gold Nanoparticles Supported on Ceria Foam, ChemSus Chem, 2012, 5, 125 –31.

 

23. Bavykin, D.V., Lapkin, A.A., Kolaczkowski, S.T., Plucinski, P.K., Selective oxidation of alcohols in a continuous multifunctional reactor: Ruthenium oxide catalyzed oxidation of benzyl alcohol, Appl Catal A Gen, 2005, 288, 175–84.

 

24. Tang, T., Yin, C., Xiao, N., Guo, M., Xiao, F.S., High Activity in Catalytic Oxidation of Benzyl Alcohol with Molecular Oxygen over Carboxylic-Functionalized Carbon Nanofiber-Supported Ruthenium Catalysts. Catal Lett, 2009, 127, 400–5.

 

25. Li, B., Zhang, B., Nie, S., Shao, L., Hu, L., Optimization of plasmon-induced photocatalysis in electrospun Au/CeO2 hybrid nanofibers for selective oxidation of benzyl alcohol, Journal of Catalysis 2017, 348, 256-264.

 

26. Jung, D., Lee, L., Na, N., RuO2 supported NaY zeolite catalysts: Effect of preparation methods on catalytic performance during aerobic oxidation of benzyl alcohol, Solid State Sciences, 2017, 72, 150-155.

 

27. Renard, B., Barbier, J, Jr., Duprez, D., Durecu, S., Catalytic wet air oxidation of stearic acid on cerium oxide supported noble metal catalysts, Appl Catal B: Environ, 2005, 55, 1-10.

 

28. Hosokawa, S., Nogawa, S., Taniguchi, M., Utani, K., Kanai, H., Imamura, S., Oxidation characteristics of Ru/CeO2 catalyst, Appl Catal A: General, 2005, 288, 67-73.

 

29. Sheldon, R.A., Wallau, M., Arendes IWCE, Schuchardt U, Heterogeneous Catalysts for Liquid-Phase Oxidations: Philosophers’ Stones or Trojan Horses?"Acc. Chem. Res, 1998, 31, 485-493.

 

30. Ebitani, K., Mizugaki, H., Kaneda K., Highly active trimetallic Ru/CeO2/CoO(OH) catalyst for oxidation of alcohols in the presence of molecular oxygen, J Mol Catal A: Chem, 2004, 212, 161–170.

 

31. Yamaguchi, K., Mizuno, N., Supported Ruthenium Catalyst for the Heterogeneous Oxidation of Alcohols with Molecular Oxygen, Angew Chem Int Ed 2002, 41, 4538-42.

 

32. Shapley, P.A., Zhang, N., Allen, J.L., Pool, D.H., Liang, H.C., Selective Alcohol Oxidation with Molecular Oxygen Catalyzed by Os−Cr and Ru−Cr Complexes, J Am Chem Soc, 2000, 122, 1079-91.