Journal of Nanoparticle Research

, Volume 8, Issue 2, pp 223–234 | Cite as

Hydrogenation of p-chloronitrobenzene on Ni–B Nanometal Catalysts

  • Yu-Chang Liu
  • Chung-Yin Huang
  • Yu-Wen Chen


A series of Ni–B catalysts were prepared by mixing nickel acetate in 50% ethanol/water or methanol/water solution. The solution of sodium borohydride (1 M) in excess amount to nickel was then added dropwise into the mixture to ensure full reduction of nickel cations. The mol ratio of boron to nickel in mother solution was 3 to 1. The effects of preparation conditions such as temperature, stirring speed, and sheltering gas on the particle size, surface compositions, electronic states of surface atoms and catalytic activities of the Ni–B catalysts were studied. Ranel nickel catalyst was included for comparison. These catalysts were characterized by N2 sorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalysts were tested for liquid phase hydrogenation of p-chloronitrobenzene. All of the catalysts prepared in this study had nanosized particles. The preparation condition has significant influence on the particle size and surface compositions of the catalyst. The Ni–B catalyst was passivated by boron; therefore it was more stable than Raney nickel and did not catch fire after exposure to air. The catalysts prepared under N2 flow could suppress the oxidation of Ni by the dissolved oxygen in water and had metallic state of nickel. The catalyst prepared with vigorous stirring at 25°C under N2 stream yielded the smallest particles and resulted in the highest activity. It was much more active than the Raney nickel catalyst. The reaction condition also has pronounced effect on the hydrogenation activity. Using methanol as the reaction solvent increased p-chloronitrobenzene conversion to a large extent, compared to that using ethanol as the reaction medium. The selectivity of main product (p-chloroaniline) was greater than 99% on all of the Ni–B catalysts.

Key words

nanocatalyst nickel liquid phase hydrogenation hydrogenation of p-chloronitrobenzene 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Baltzly R. and Phillips A.P. (1946). The catalytic hydrogenolysis of halogen compounds. J. Am. Chem. Soc. 68: 261–268CrossRefGoogle Scholar
  2. Brown H.C. and Brown C.A. (1963). The reaction of sodium borohydride with nickel acetate in aqueous solution-A convenient synthesis of an active nickel hydrogenation catalyst of low isomerizing tendency. J. Am. Chem. Soc. 85: 1003 CrossRefGoogle Scholar
  3. Carberry J.J. (1987). Physico-chemical aspects of mass and heat transfer in heterogeneous catalysis. In: Anderson, J.R. and Boudart, M. (eds) Catalysis, Science and Technology, pp 131–134. Springer Verlag, BerlinGoogle Scholar
  4. Coq B., Tijani A., Dutartre R. and Figuéras F. (1993). Catalysis by Rh/B system. Part 2: Higly regioselective vapour phase hydroformylation of propene at atmospheric pressure on Rh/B on silica and silica–alumina. J. Mol. Catal. 79: 243–252CrossRefGoogle Scholar
  5. Coq B., Tijani A. and Figuéras F. (1991). Pt/γ-Al2O3 catalytic membranes vs. Pt on γ-Al3 powders in the selective hydrogenation of p-chloronitrobenzene. J. Mol. Catal. 2(68): 331–338Google Scholar
  6. Coq B., Tijani A. and Figuéras F. (1992). Reaction pathways and the role of solvent in the hydrogenation of chloronitrobenzenes. J. Mol. Catal. 71: 317–323CrossRefGoogle Scholar
  7. Deng J.F., Yang J., Sheng S.H., Chen H. and Xing G. (1994). The study of ultrafine Ni–B and Ni–P amorphous alloy powders as catalysts. J. Catal. 150: 434CrossRefGoogle Scholar
  8. Fang Z.G., Shen B.R., Lu J., Fan K.N. and Deng J.F. (1999). DFT study of electron transfer between B and Ni in Ni–B amorphous alloy. Acta Chimica Sinia 57: 894 Google Scholar
  9. Fogler H.S. (1992). Elements of Chemical Reaction Engineering. Prentice-Hall Englewood Cliffs, US, 670Google Scholar
  10. Greenfield H. and Dovell F.S. (1967). Metal sulfide catalysts for hydrogenation of halonitrobenzenes to haloanilines. J. Org. Chem. 32: 3670CrossRefGoogle Scholar
  11. Han X., Zhou R., Lai G., Yue B. and Zheng X. (2003). Influence of rare earth (Ce, Sm, Nd, La, and Pr) on the hydrogenation properties of chloronitrobenzene over Pt/ZrO2 catalyst. Catal. Lett. 89: 255CrossRefGoogle Scholar
  12. Hu S.C. and Chen Y.W. (1997). Partial hydrogenation of benzene to cyclohexene on ruthenium catalysts supported on La2O3–ZnO binary oxides. Ind. Eng. Chem. Res. 36: 5153–5160 CrossRefGoogle Scholar
  13. Hutchinson C.R., Heckendorf A.H., Straughn J.L., Daddona P.E. and Cane D.E. (1979). Biosynthesis of camptothecin. 3. Definition of strictosamide as the penultimate biosynthetic precursor assisted by carbon-13 and deuterium NMR spectroscopy. J. Am. Chem. Soc. 101: 3358–3364CrossRefGoogle Scholar
  14. Lee S.P. and Chen Y.W. (2000). Catalytic properties of Ni–B and Ni–P ultrafine materials. J. Chem. Technol. Biotechnol. 75: 1073–1097CrossRefGoogle Scholar
  15. Lee S.P. and Chen Y.W. (2001). Effects of preparation on the catalytic properties of Ni–P–B ultrafine materials. Ind. Eng. Chem. Res. 40: 1495CrossRefGoogle Scholar
  16. Li C., Chen W. and Wang W.J. (1994). Nitrobenzene hydrogenation over aluminum borate-supported platinum catalyst. Appl. Catal. A: Gen. 119: 185–190 CrossRefGoogle Scholar
  17. Li H., Li H.X., Dai W.L., Wang W., Fang Z. and Deng J.F. (1999). XPS studies on surface electronic characteristics of Ni–B and Ni–P amorphous alloy and its correlation on their catalytic properties. Appl. Surf. Sci. 152: 25–32CrossRefGoogle Scholar
  18. Liao, S., Z. Yu, Y. Xu, B. Yang & D. Yu, 1995. A remarkable synergic effect of polymer-anchored bimetallic palladium–ruthenium catalysts in the selective hydrogenation of p-chloronitrobenzene. J. Chem. Soc. Chem. Commun. 1155Google Scholar
  19. Liu W., Tu H. and Tang Y. (2000). The metal complex effect on the selective hydrogenation of m- and p-chloronitrobenzene over PVP-stabilized platinum colloidal catalysts. J. Mol. Catal. A: Chem. 159: 115–120CrossRefGoogle Scholar
  20. Ma A., W. Lu & E. Min, 2000. Amorphous alloy catalyst containing phosphorus, its preparation and use, U.S. Patent 6,051,528Google Scholar
  21. Midland M.M. and Lee P.E. (1985). Efficient asymmetric reduction of acyl cyanides with B-3-pinanyl 9-BBN (Alpine-borane). J. Org. Chem. 50: 3237–3242CrossRefGoogle Scholar
  22. Nitta Y., Okamoto Y., Imanaka T. and Teranishi S. (1980). Surface state and catalytic activity and selectivity of nickel catalysts in hydrogenation reactions III electronic and catalytic properties of nickel catalysts. J. Catal. 64: 397–408CrossRefGoogle Scholar
  23. Okamoto Y., Fukino K. and Imanaka T. (1982). Surface state and catalytic activity and selectivity of nickel catalysts in hydrogenation reactions IV. Electronic effects on the selectivity in the hydrogenation of 1,3-butadiene. J. Catal. 74: 173–180CrossRefGoogle Scholar
  24. Okamoto Y., Nitta Y., Imanaka T. and Teranishi S. (1979). Surface characterisation of nickel boride and nickel phosphide catalysts by X-ray photoelectron spectroscopy. J. Chem. Soc. Faraday Trans. I 75: 2027–2038CrossRefGoogle Scholar
  25. Okamoto Y., Nitta Y., Imanaka T. and Teranishi S. (1980). Surface state, catalytic activity and selectivity of nickel catalysts in hydrogenation reactions. J. Chem. Soc. Faraday Trans. I 76: 998–1002CrossRefGoogle Scholar
  26. Osby J.O., Heinzman S.W. and Ganem B. (1986). Studies on the mechanism of transition-metal-assisted sodium borohydride and lithium aluminum hydride reductions. J. Am. Chem. Soc. 108: 67–72CrossRefGoogle Scholar
  27. Paul R., Buisson P. and Joseph N. (1952). Catalytic activity of nickel borides. Ind. Eng. Chem. 44: 1006–1012CrossRefGoogle Scholar
  28. Pelavin M., Hendrickson D.N., Hollander J.M. and Jolly W.L. (1970). Phosphorus 2p electron binding energies correlation with extended huckel charges. J. Phys. Chem. 74: 1116CrossRefGoogle Scholar
  29. Rajadhyaksha R.A. and Karwa S.L. (1986). Solvent effects in catalytic hydrogenation. Chem. Eng. Sci. 41: 1765–1770CrossRefGoogle Scholar
  30. Ramachandran P.A. and Chaudhari R.V. (1983). Three Phase Catalytic Reactors. Gordon and Breach Science Publishers, New York, 15Google Scholar
  31. Rei M.H., Sheu L.L. and Chen Y.Z. (1986). Nickel boride catalysts in organic synthesis. Appl. Catal. 23: 281–290CrossRefGoogle Scholar
  32. Schlesinger H.I. and Brown H.C. (1953). New developments in the chemistry of diborane and borohydrides, I. General summary. J. Am. Chem. Soc. 75: 186–192CrossRefGoogle Scholar
  33. Seo G. and Chon H. (1981). Hydrogenation of furfural over copper-containning catalysts. J. Catal. 67: 424–430CrossRefGoogle Scholar
  34. Shen J., Hu Z., Zhang Q., Zhang L. and Chen Y. (1992). Investigation of Ni–P–B ultrafine amorphous alloy particles produced by chemical reduction. J. Appl. Phys. 71: 5217–5221CrossRefGoogle Scholar
  35. Tijani A., Coq B. and Figueras F. (1991). Hydrogenation of para-chloronitrobenzene over supported ruthenium-based catalysts. Appl. Catal. 76: 255–266CrossRefGoogle Scholar
  36. Weisz P.B. and Prater D.C. (1954). Interpretation of Measurements in Experimental Catalysis. In Advances in Catalysis . New York, Academic Press, 143Google Scholar
  37. Wheeler A. (1951). Reaction Rates and Selectivity in Catalyst Pores. In Advances in Catalysis. New York, Academic Press, 249Google Scholar
  38. Yan X., Liu M., Liu H. and Liew K.Y. (2001). Role of boron species in the hydrogenation of o-chloronitrobenzene over polymer-stabilized ruthenium colloidal catalysts. J. Mol. Catal. A: Chem. 169: 225–233CrossRefGoogle Scholar
  39. Yao H.C. and Emmett P.H. (1962). Kinetics of liquid phase hydrogenation. IV. Hydrogenation of nitrocompounds over Raney nickel and nickel powder catalysts. J. Am. Chem. Soc. 84: 1086–1094CrossRefGoogle Scholar
  40. Yu Z.B., Qiao M.H., Li H.X. and Deng J.F. (1997). Preparation of amorphous Ni–Co–B alloys and the effect of cobalt on their hydrogenation activity. Appl. Catal. A 163: 1–13CrossRefGoogle Scholar
  41. Zhou R., Han X., Zheng X. and Jiang H. (2003). Effect of rare earths on the hydrogenation properties of p-chloronitrobenzene over polymer-anchored platinum catalysts. J. Mol. Catal. A: Chem. 193: 103–108CrossRefGoogle Scholar

Copyright information

© Springer 2006

Authors and Affiliations

  1. 1.Department of Chemical and Materials Engineering, Nanocatalysis Research CenterNational Central UniversityChung-LiTaiwan

Personalised recommendations