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Effect of support on activity of palladium catalysts in nitrobenzene hydrogenation

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Abstract

The effect of two types of catalysts on the activity of the catalytic hydrogenation of nitrobenzene was studied. Catalysts were prepared by the surface deposition of palladium hydroxide with a simultaneous reduction with formaldehyde in a basic environment and were characterised by X-ray powder diffraction, transmission electron microscopy, adsorption-desorption, and catalytic tests — hydrogenation of nitrobenzene in methanol. The influence of the supports’ (activated carbon and a mixture of activated carbon and multi-walled carbon nanotubes) surface area is discussed. Despite having a size comparable (4–5 nm) to crystallites of metallic palladium, the catalyst prepared on a mixture of activated carbon and nanotubes (Pd/C/CNT) was significantly less active than the catalyst prepared on pure activated carbon (Pd/C); the rate of this reaction was approximately 30 % lower than the initial reaction rate. This feature could be attributed to the lower specific surface area of the Pd/C/CNT (531 m2 g−1) in comparison with the Pd/C (692 m2 g−1).

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References

  • Bianchi, C. L., Gotti, E., Toscano, L., & Ragaini, V. (1997). Preparation of Pd/C catalysts via ultrasound: a study of the metal distribution. Ultrasonics Sonochemistry, 4, 317–320. DOI: 10.1016/s1350-4177(97)00035-7.

    Article  CAS  Google Scholar 

  • Belykh, L. B., Titova, Y. Y., Umanets, V. A., & Shmidt, F. K. (2006). Palladium hydrogenation catalysts modified with aluminum- and phosphorus-containing compounds and with alcohols: Effect of modifiers. Russian Journal of Applied Chemistry, 79, 1271–1277. DOI: 10.1134/s1070427206080106.

    Article  CAS  Google Scholar 

  • Bouchenafa-Saïb, N., Grange, P., Verhasselt, P., Addoun, F., & Dubois, V. (2005). Effect of oxidant treatment of date pit active carbons used as Pd supports in catalytic hydrogenation of nitrobenzene. Applied Catalysis A: General, 286, 167–174. DOI: 10.1016/j.apcata.2005.02.022.

    Article  Google Scholar 

  • Campanati, M., Fornasari, G., & Vaccari, A. (2003). Fundamentals in the preparation of heterogeneous catalysts. Catalysis Today, 77, 299–314. DOI: 10.1016/s0920-5861(02)00375-9.

    Article  CAS  Google Scholar 

  • Gelder, E. A., Jackson, S. D., & Lok, C. M. (2002). A study of nitrobenzene hydrogenation over palladium/carbon catalysts. Catalysis Letters, 84, 205–208. DOI: 10.1023/a:10214 32104496.

    Article  CAS  Google Scholar 

  • Gelder, E. A., Jackson, S. D., & Lok, C. M. (2006). Competitive hydrogenation of nitrobenzene, nitrosobenzene and azobenzene. In S. R. Schmidt (Ed.), Catalysis of organic reactions, twenty-first conference (pp. 167–176). Boca Raton, FL, USA: CRC Press.

    Google Scholar 

  • Harada, T., Ikeda, S., Miyazaki, M., Sakata, T., Mori, H., & Matsumura, M. (2007). A simple method for preparing highly active palladium catalysts loaded on various carbon supports for liquid-phase oxidation and hydrogenation reactions. Journal of Molecular Catalysis A: Chemical, 268, 59–64. DOI: 10.1016/j.molcata.2006.12.010.

    Article  CAS  Google Scholar 

  • Hudec, P. (2012). Textúra tuhych materiálov. Charakterizácia adsorbentov a katalyzátorov fyzikálnou adsorpciou dusíka. Bratislava, Slovakia: Slovak Technical University. (in Slovak)

    Google Scholar 

  • Hyde, T. (2008). Crystallite size analysis of supported platinum catalysts by XRD. Platinum Metals Review, 52, 129–130. DOI: 10.1595/147106708x299547.

    Article  Google Scholar 

  • Janssen, H. J., Kruithof, A. J., Steghuis, G. J., & Westerterp, K. R. (1990a). Kinetics of the catalytic hydrogenation of 2,4-dinitrotoluene. 1. Experiments, reaction scheme, and catalyst activity. Industrial & Engineering Chemistry Research, 29, 754–766. DOI: 10.1021/ie00101a008.

    Article  CAS  Google Scholar 

  • Janssen, H. J., Kruithof, A. J., Steghuis, G. J., & Westerterp, K. R. (1990b). Kinetics of the catalytic hydrogenation of 2,4 dinitrotoluene. 2. Modeling of the reaction rates and catalyst activity. Industrial & Engineering Chemistry Research, 29, 1822–1829. DOI: 10.1021/ie00105a013.

    Article  CAS  Google Scholar 

  • Jin, S., Qian, W. Z., Liu, Y., Wei, F., Wang, D. Z., & Zhang, J. C. (2010). Granulated carbon nanotubes as the catalyst support for Pt for the hydrogenation of nitrobenzene. Australian Journal of Chemistry, 63, 131–134. DOI: 10.1071/ch09162.

    Article  CAS  Google Scholar 

  • Kolbe, H. (1871). Ueber die reduzierenden Wirkungen des vom Palladium absorbirtenWasserstoffgases. Journal für Praktische Chemie, 4, 418–419. (in German)

    Google Scholar 

  • Králik, M., Turáková, M., Mačák, I., & Wenchich, Š. (2012). Catalytic hydrogenation of aromatic compounds in the liquid phase. Journal of Chemistry and Chemical Engineering, 6, 1074–1082.

    Google Scholar 

  • Ledoux, M. J., Vieira, R., Pham-Huu, C., & Keller, N. (2003). New catalytic phenomena on nanostructured (fibers and tubes) catalysts. Journal of Catalysis, 216, 333–342. DOI: 10.1016/s0021-9517(02)00108-2.

    Article  CAS  Google Scholar 

  • Li, C. H., Yu, Z. X., Yao, K. F., Ji, S. F., & Liang, J. (2005). Nitrobenzene hydrogenation with carbon nanotubesupported platinum catalyst under mild conditions. Journal of Molecular Catalysis A: Chemical, 226, 101–105. DOI: 10.1016/j.molcata.2004.09.046.

    Article  CAS  Google Scholar 

  • Ma, L., Chen, S., Lu, C. S., Zhang, Q. F., & Li, X. N. (2011). Highly selective hydrogenation of 3,4-dichloronitrobenzene over Pd/C catalysts without inhibitors. Catalysis Today, 173, 62–67. DOI: 10.1016/j.cattod.2011.06.011.

    Article  CAS  Google Scholar 

  • Moreno-Castilla, C., Ferro-Garca, M. A., Joly, J. P., Bautista-Toledo, I., Carrasco-Marin, F., & Rivera-Utrilla, J. (1995). Activated carbon surface modification by nitric acid, hydrogen peroxide, and ammonium peroxydisulfate treatments. Langmuir, 11, 4386–4392. DOI: 10.1021/la00011a035.

    Article  CAS  Google Scholar 

  • Navaladian, S., Viswanathan, B., Varadarajan, T. K., & Viswanath, R. P. (2008). A rapid synthesis of oriented palladium nanoparticles by UV irradiation. Nanoscale Research Letters, 4, 181–186. DOI: 10.1007/s11671-008-9223-4.

    Article  Google Scholar 

  • Nishimura, S. (2001). Handbook of heterogeneous catalytic hydrogenation for organic synthesis. New York, NY, USA: Wiley.

    Google Scholar 

  • Obraztsova, I. I., Eremenko, N. K., & Velyakina, Y. N. (2008). Reaction kinetics of nitrobenzene hydrogenation on a palladium catalyst supported on nanodiamonds. Kinetics and Catalysis, 49, 401–406. DOI: 10.1134/s0023158408030130.

    Article  CAS  Google Scholar 

  • Pham-Huu, C., Keller, N., Ehret, G., Charbonniere, L. J., Ziessel, R., & Ledoux, M. J. (2001). Carbon nanofiber supported palladium catalyst for liquid-phase reactions: An active and selective catalyst for hydrogenation of cinnamaldehyde into hydrocinnamaldehyde. Journal of Molecular Catalysis A: Chemical, 170, 155–163. DOI: 10.1016/s1381-1169(01)00055- 3.

    Article  CAS  Google Scholar 

  • Salman, F., Park, C., & Baker, R. T. K. (1999). Hydrogenation of crotonaldehyde over graphite nanofiber supported nickel. Catalysis Today, 53, 385–394. DOI: 10.1016/s0920-5861(99)00132-7.

    Article  CAS  Google Scholar 

  • Saytzeff, M. (1872). Ueber die Einwirkung des vom Palladium absorbirten Wasserstoffs auf einige organische Verbindungen. Journal für Praktische Chemie, 6, 128–136. (in German)

    Article  Google Scholar 

  • Semikolenov, V. A. (1992). Modern approaches to the preparation of “palladium on charcoal” catalysts. Russian Chemical Reviews, 61, 168–174. DOI: 10.1070/rc1992v061n02abeh000938.

    Article  Google Scholar 

  • Serp, P., Corrias, M., & Kalck, P. (2003). Carbon nanotubes and nanofibers in catalysis. Applied Catalysis A: General, 253, 337–358. DOI: 10.1016/s0926-860x(03)00549-0.

    Article  CAS  Google Scholar 

  • Udayakumar, V., Alexander, S., Gayathri, V., Shivakumaraiah, & Viswanathan, B. (2011). Study on the influence of substituents upon the hydrogenation of nitrobenzene using a polymer-supported palladium-imidazole complex catalyst. Reaction Kinetics Mechanisms and Catalysis, 103, 341–352. DOI: 10.1007/s11144-011-0308-1.

    Article  CAS  Google Scholar 

  • Wan, B. S., Liao, S. J., Xu, Y., & Yu, D. R. (1998). Synergic effect of palladium-based bimetallic catalysts for the hydrogenation of nitroaromatics. Reaction Kinetics and Catalysis Letters, 63, 397–401. DOI: 10.1007/bf02475418.

    Article  CAS  Google Scholar 

  • Watanabe, S., & Arunajatesan, V. (2010). Influence of acid modification on selective phenol hydrogenation over Pd/activated carbon catalysts. Topics in Catalysis, 53, 1150–1152. DOI: 10.1007/s11244-010-9551-3.

    Article  CAS  Google Scholar 

  • Wu, H., Zhuo, L. M., He, Q., Liao, X. P., & Shi, B. (2009). Heterogeneous hydrogenation of nitrobenzenes over recyclable Pd(0) nanoparticle catalysts stabilized by polyphenol-grafted collagen fibers. Applied Catalysis A: General, 366, 44–56. DOI: 10.1016/j.apcata.2009.06.024.

    Article  CAS  Google Scholar 

  • Zaitseva, N. A., Goidin, V. V., Molchanov, V. V., Chesnokov, V. V., Buyanov, R. A., & Utkin, V. A. (2011). Catalysts based on filamentous carbon in the hydrogenation of aromatic compounds. Kinetics and Catalysis, 52, 770–773. DOI: 10.1134/s0023158411050181.

    Article  CAS  Google Scholar 

  • Zhao, Y., Li, C. H., Yu, Z. X., Yao, K. F., Ji, S. F., & Liang, J. (2007). Effect of microstructures of Pt catalysts supported on carbon nanotubes (CNTs) and activated carbon (AC) for nitrobenzene hydrogenation. Materials Chemistry and Physics, 103, 225–229. DOI: 10.1016/j.matchemphys.2007.02.045.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Faculty of Metallurgy, Technical University of Košice, Letná 9, 042 00, Košice, Slovakia

    Ľubomír Pikna, Mária Heželová, Silvia Demčáková, Miroslava Smrčová, Beatrice Plešingerová & Pavel Puliš

  2. VUCHT a.s., Areal Duslo a.s., 927 03, Šaľa, Slovakia

    Michal Štefanko, Milan Králik & Peter Lehocký

  3. Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, 812 37, Bratislava, Slovakia

    Mária Turáková

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  1. Ľubomír Pikna
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  2. Mária Heželová
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  3. Silvia Demčáková
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Pikna, Ľ., Heželová, M., Demčáková, S. et al. Effect of support on activity of palladium catalysts in nitrobenzene hydrogenation. Chem. Pap. 68, 591–598 (2014). https://doi.org/10.2478/s11696-013-0497-3

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  • DOI: https://doi.org/10.2478/s11696-013-0497-3

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