Liquid Phase Hydrogenation of p-Chloronitrobenzene on Au-Pd/TiO₂ Catalysts: Effects of Reduction Methods

Yu-Wen Chen, Der-Shing Lee

Department of Chemical and Materials Engineering, National Central University, Jhongli City, Chinese Taipei.

DOI: 10.4236/mrc.2013.22004                

Abstract

The effects of palladium addition and the reduction methods on Au/TiO₂ were investigated. Pd was loaded on TiO₂ firstly by incipient-wetness impregnation, Au was then loaded by deposition-precipitation method. The nominal loadings of Au and Pd were 1 wt% and 0.01 wt%. The bimetallic catalysts were reduced by heating at 453 K, by flowing H₂ at 423 K, or by NaBH₄ at 298 K. The catalysts were characterized by ICP, XRD, TEM, HRTEM, TPR and XPS. Hydrogenation of p-chloronitrobenzene was carried out at 1.2 MPa H₂ pressure and 353 K. The results showed that even adding very small amount of Pd could enhance activity and selectivity of p-chloroaniline significantly. Pd and Au formed alloy and Pd could donate partial electron to Au. Pd metal on the surface of alloy could adsorb hydrogen and enhanced the activity. The pretreatment methods did not change particle size significantly, all were below 4 nm. The sample reduced by NaBH₄ could have higher concentration of Au⁰ and sustain small Au particle size, resulting in high activity.

Keywords

Nanoalloy; Gold Catalyst; Au-Pd Catalysts; Hydrogenation of Chloronitrobenzene; Chloroaniline

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Y. C. Liu and Y. W. Chen, “Hydrogenation of p-Chloronitrobenzene on La-promoted NiB Nanometal Catalysts,” Industrial and Engineering Chemistry Research, Vol. 45, No. 9, 2006, pp. 2973-2980. doi:10.1021/ie0509847
[2]	Y. C. Liu, C. Y. Huang and Y. W. Chen, “Hydrogenation of p-choloronitrobenzene Ni-B on Nanometal Catalysts,” Journal of Nanoparticle Research, Vol. 8, No. 2, 2006, pp. 223-234. doi:10.1007/s11051-005-5944-9
[3]	L. F. Chen and Y. W. Chen, “Effect of Additive (W, Mo, and Ru) on Ni-B Amorphous Alloy Catalyst in Hydrogenation of p-Chloronitrobenzene,” Industrial and Engineering Chemistry Research, Vol. 45, No. 26, 2006, pp. 8866-8873. doi:10.1021/ie060751v
[4]	W. J. Wang, J. H. Shen and Y. W. Chen, “Hydrogenation of p-Chloronitrobenzene on Ni-P-B Nanoalloy Catalysts,” Industrial and Engineering Chemistry Research, Vol. 45, No. 26, 2006, pp. 8860-8865. doi:10.1021/ie0605736
[5]	J. H. Shen and Y. W. Chen, “Catalytic Properties of Bimetallic NiCoB Nanoalloy Catalysts for Hydrogenation of p-Chloronitrobenzene,” Journal of Molecular Catalysis A: Chemical, Vol. 273, No. 1-2, 2007, pp. 265-276. doi:10.1016/j.molcata.2007.04.015
[6]	Y. W. Chen and N. Sasirekha, “Preparation of NiFeB Nanoalloy Catalysts and Its Applications in Liquid Phase Hydrogenation of p-Chloronitrobenzene,” Industrial and Engineering Chemistry Research, Vol. 48, No. 13, 2009, pp. 6248-6255. doi:10.1021/ie801624a
[7]	Y. W. Chen, N. Sasirekha and Y. C. Liu, “Hydrogenation of p-Chloronitrobenzene over NiPtB Nanoalloy Catalysts,” Journal of Non-Crystalline Solids, Vol. 355, No. 22-23, 2009, pp. 1193-1201.
[8]	M. H. Lin, B. Zhao and Y. W. Chen, “Hydrogenation of p-Chloronitrobenzene over Mo-modified NiCoB Nanoalloy Catalysts: Effect of Mo Content,” Industrial and Engineering Chemistry Research, Vol. 48, No. 15, 2009, pp. 7037-7043. doi:10.1021/ie900019d
[9]	B. Zhao and Y. W. Chen, “Hydrogenation of p-Chloronitrobenzene on Mo, La, Fe, and W-Modified NiCoB Nanoalloy Catalysts,” Journal of Non-Crystalline Solids, Vol. 356, No. 18-19, 2010, pp. 839-847.
[10]	B. Zhao, C. J. Chou and Y. W. Chen, “Hydrogenation of p-Chloronitrobenzene on Tungsten-Modified NiCoB Catalyst,” Industrial and Engineering Chemistry Research, Vol. 49, No. 4, 2010, pp. 1669-1676. doi:10.1021/ie901606b
[11]	B. Zhao and Y. W. Chen, “The Effect of Poly-N-vinylpyrrolidone Modification on NiCoB Catalysts for Hydrogenation of p-Chloronitrobenzene,” Materials Chemistry and Physics, Vol. 125, No. 3, 2011, pp. 763-768. doi:10.1016/j.matchemphys.2010.09.061
[12]	J. F. Su, B. Zhao and Y. W. Chen, “Hydrogenation of p-Chloronitrobenzene on Mo-Doped NiB Cluster Catalysts,” Industrial and Engineering Chemistry Research, Vol. 50, No. 3, 2011, pp. 1580-1587. doi:10.1021/ie1016865
[13]	Y. W. Chen and D. S. Lee, “Hydrogenation of p-Chloronitrobenzene on Nanosized Modified NiMoB Catalysts,” Catalysis Surveys from Asia, Vol. 16, No. 4, 2012, pp. 198-209. doi:10.1007/s10563-012-9144-1
[14]	C. P. Li, Y. W. Chen and W. J. Wang, “Nitrobenzene Hydrogenation over Aluminum Borate-supported Platinum Catalyst,” Applied Catalysis A: General, Vol. 119, No. 2, 1994, pp. 185-194. doi:10.1016/0926-860X(94)85190-5
[15]	R. Baltzly and A. R. Phillips, “The Catalytic Hydrogenolysis of Halogen Compounds,” Journal of American Chemical Society, Vol. 68, No. 2, 1946, pp. 261-265. doi:10.1021/ja01206a034
[16]	J. R. Kosak, “Catalytic Hydrogenation of Aromatic Halonitro Compounds,” Annals of the New York Academy of Sciences, Vol. 172, 1970, pp. 175-186. doi:10.1111/j.1749-6632.1970.tb34975.x
[17]	M. M. Dell’Anna, V. Gallo, P. Mastrorilli and G. Romanazzi, “A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions,” Molecules, Vol. 15, No. 5, 2010, pp. 3311-3318. doi:10.3390/molecules15053311
[18]	M. Liu, W. Yu, H. Liu and J. Zheng, “Preparation and Characterization of Polymer-Stabilized Ruthenium-Platinum and Ruthenium-Palladium Bimetallic Colloids and Their Catalytic Properties for Hydrogenation of o-Chloronitrobenzene,” Journal of Colloid and Interface Science, Vol. 214, No. 2, 1999, pp. 231-240. doi:10.1006/jcis.1999.6186
[19]	P. A. Sermon, G. C. Bond and P. B. Wells, “Hydrogenation of Alkenes over Supported Gold,” Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, 1979, pp. 385-392. doi:10.1039/f19797500385
[20]	R. S. Yolles, B. J. Wood and H. Wise, “Hydrogenation of Alkenes on Gold,” Journal of Catalysis, Vol. 21, No. 1, 1971, pp. 66-72. doi:10.1016/0021-9517(71)90121-7
[21]	M. Haruta, “Gold as a Novel Catalyst in the 21st Century: Preparation, Working Mechanism and Application,” Gold Bulletin, Vol. 37, No. 1-2, 2004, pp. 27-54. doi:10.1007/BF03215514
[22]	Z. Li, F. Gao, Y. Wang, F. Calaza, L. Burkholder and W. T. Tysoe, “Formation and Characterization of Au/Pd Surface Alloys on Pd(111),” Surface Science, Vol. 601, No. 8, 2007, pp. 1898-1908. doi:10.1016/j.susc.2007.02.028
[23]	F. Cárdenas-Lizana, S. Gómez-Quero and M. A. Keane, “Ultra-selective Gas Phase Catalytic Hydrogenation of Aromatic Nitro Compounds over Au/Al2O3,” Catalysis Communications, Vol. 9, No. 3, 2008, pp. 475-482. doi:10.1016/j.catcom.2007.07.032
[24]	F. Cárdenas-Lizana, S. Gómez-Quero and M. A. Keane, “Exclusive Production of Chloroaniline from Chloronitrobenzene over Au/TiO2 and Au/Al2O3,” Sustainable Chemistry & Green Chemistry, Vol. 1, No. 3, 2008, pp. 215-223. doi:10.1002/cssc.200700105
[25]	F. Cardenas-Lizana, S. Gomez-Quero, A. Hugon, L. Delannoy, C. Louis and M. A. Keane, “Pd-Promoted Selective Gas Phase Hydrogenation of p-Chloronitrobenzene over Alumina Supported Au,” Journal of Catalysis, Vol. 262, No. 2, 2009, pp. 235-243. doi:10.1016/j.jcat.2008.12.019
[26]	F. Cardenas-Lizana, S. Gomez-Quero and M. A. Keane, “Gas Phase Hydrogenation of m-Dinitrobenzene over Alumina Supported Au and Au-Ni Alloy,” Catalysis Letters, Vol. 127, No. 1-2, 2009, pp. 25-32. doi:10.1007/s10562-008-9660-9
[27]	F. Cardenas-Lizana, S. Gomez-Quero, N. Perret and M. A. Keane, “Support Effects in the Selective Gas Phase Hydrogenation of p-Chloronitrobenzene over Gold,” Gold Bulletin, Vol. 42, No. 2, 2009, pp. 124-132. doi:10.1007/BF03214922
[28]	F. Cardenas-Lizana, S. Gomez-Quero and M. A. Keane, “Clean Production of Chloroanilines by Selective Gas Phase Hydrogenation over Supported Ni Catalyst,” Applied Catalysis A: General, Vol. 334, No. 1-2, 2008, pp. 199-206. doi:10.1016/j.apcata.2007.10.007
[29]	C. Y. Wang, C. Y. Liu, X. Zheng, J. Chen and T. Shen, “The Surface Chemistry of Hybrid Nanometer-Sized Particles: I. Photochemical Deposition of Gold on Ultrafine TiO2 Particles,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 131, No. 1-3, 1998, pp. 271-280. doi:10.1016/S0927-7757(97)00086-1
[30]	Z. K. Yu, S. J. Liao, Y. Xu, B. Yang and D. R. Yu, “Hydrogenation of Nitroaromatics by Polymer-Anchored Bimetallic Palladium-Ruthenium and Palladium-Platinum Catalysts under Mild Conditions,” Journal of Molecular Catalysis A: Chemical, Vol. 120, No. 1-3, 1997, pp. 247-253. doi:10.1016/S1381-1169(96)00420-7