Article

FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes

  • Nature Communications 5, Article number: 5634 (2014)
  • doi:10.1038/ncomms6634
  • Download Citation
Received:
Accepted:
Published online:

Abstract

The catalytic hydrogenation of nitroarenes is an environmentally benign technology for the production of anilines, which are key intermediates for manufacturing agrochemicals, pharmaceuticals and dyes. Most of the precious metal catalysts, however, suffer from low chemoselectivity when one or more reducible groups are present in a nitroarene molecule. Herein we report FeOx-supported platinum single-atom and pseudo-single-atom structures as highly active, chemoselective and reusable catalysts for hydrogenation of a variety of substituted nitroarenes. For hydrogenation of 3-nitrostyrene, the catalyst yields a TOF of ~1,500 h−1, 20-fold higher than the best result reported in literature, and a selectivity to 3-aminostyrene close to 99%, the best ever achieved over platinum group metals. The superior performance can be attributed to the presence of positively charged platinum centres and the absence of Pt–Pt metallic bonding, both of which favour the preferential adsorption of nitro groups.

Additional access options:

Already a subscriber?  Log in  now or  Register  for online access.

References

  1. 1.

    The Nitro Group in Organic Synthesis ed. Feuer H. Wiley-VCH: New York, (2001).

  2. 2.

    , & Aromatic Nitro Compounds: Fine Chemicals Through Heterogeneous Catalysis eds Sheldon R. A., van Bekkum H. Wiley-VCH: Weinheim, (2001).

  3. 3.

    , & Catalytic syntheses of aromatic amines. Catal. Today 37, 121–136 (1997).

  4. 4.

    , , & Chemical Industries (ed. Herkes F. 207–220Marcel Dekker: New York, (1998).

  5. 5.

    , , , & Ag/SiO2: a novel catalyst with high activity and selectivity for hydrogenation of chloronitrobenzenes. Chem. Commun. 5298–5300 (2005).

  6. 6.

    & Chemoselective hydrogenation of nitro compounds with supported gold catalysts. Science 313, 332–334 (2006).

  7. 7.

    , , & Synthesis of chloroanilines: selective hydrogenation of the nitro in chloronitrobenzenes over zirconia-supported gold catalyst. Green Chem. 9, 849–851 (2007).

  8. 8.

    et al. Efficient and selective room-temperature gold-catalyzed reduction of nitro compounds with CO and H2O as the hydrogen source. Angew. Chem. Int. Ed. 48, 9538–9541 (2009).

  9. 9.

    , & Size- and support-dependent silver cluster catalysis for chemoselective hydrogenation of nitroaromatics. J. Catal. 270, 86–94 (2010).

  10. 10.

    et al. Design of a silver-cerium dioxide core-shell nanocomposite catalyst for chemoselective reduction reactions. Angew. Chem. Int. Ed. 51, 136–139 (2012).

  11. 11.

    et al. A molecular mechanism for the chemoselective hydrogenation of substituted nitroaromatics with nanoparticles of gold on TiO2 catalysts: a cooperative effect between gold and the support. J. Am. Chem. Soc. 129, 16230–16237 (2007).

  12. 12.

    , & Exclusive production of chloroaniline from chloronitrobenzene over Au/TiO2 and Au/Al2O3. ChemSusChem 1, 215–221 (2008).

  13. 13.

    , , , & Novel chemoselective hydrogenation of aromatic nitro compounds over ferric hydroxide supported nanocluster gold in the presence of CO and H2O. Chem. Commun. 653–655 (2009).

  14. 14.

    et al. Chemoselective hydrogenation of nitroaromatics by supported gold catalysts: mechanistic reasons of size-and support-dependent activity and selectivity. J. Phys. Chem. C. 113, 17803–17810 (2009).

  15. 15.

    , & Design of highly active and chemoselective bimetallic gold–platinum hydrogenation catalysts through kinetic and isotopic studies. J. Catal. 265, 19–25 (2009).

  16. 16.

    , , & Understanding the synergistic effects of gold bimetallic catalysts. J. Catal. 308, 258–271 (2013).

  17. 17.

    et al. Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes. Nat. Chem. 5, 537–543 (2013).

  18. 18.

    et al. Nanoscale Fe2O3-based catalysts for selective hydrogenation of nitroarenes to anilines. Science 342, 1073–1076 (2013).

  19. 19.

    , & Hydrogenation of nitrobenzene with supported platinum catalysts in supercritical carbon dioxide: effects of pressure, solvent, and metal particle size. J. Catal. 224, 479–483 (2004).

  20. 20.

    , & Transforming nonselective into chemoselective metal catalysts for the hydrogenation of substituted nitroaromatics. J. Am. Chem. Soc. 130, 8748–8753 (2008).

  21. 21.

    et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).

  22. 22.

    et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).

  23. 23.

    et al. CO oxidation on supported single Pt atoms: experimental and ab initio density functional studies of CO interaction with Pt atom on θ-Al2O3(010) surface. J. Am. Chem. Soc. 135, 12634–12645 (2013).

  24. 24.

    , & Active nonmetallic Au and Pt species on ceria-based water-gas shift catalysts. Science 301, 935–938 (2003).

  25. 25.

    et al. Remarkable performance of Ir1/FeOx single-atom catalyst in water gas shift reaction. J. Am. Chem. Soc. 135, 15314–15317 (2013).

  26. 26.

    , & Atomically dispersed Au–(OH)x species bound on titania catalyze the low-temperature water-gas shift reaction. J. Am. Chem. Soc. 135, 3768–3771 (2013).

  27. 27.

    et al. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen. Science 344, 616–619 (2014).

  28. 28.

    , & Heterogeneous catalysis on atomically dispersed supported metals: CO2 reduction on multifunctional Pd catalysts. ACS Catal. 3, 2094–2100 (2013).

  29. 29.

    et al. Catalytically active single-atom niobium in graphitic layers. Nat. Commun. 4, 1924 (2013).

  30. 30.

    et al. Efficient and durable Au alloyed Pd single-atom catalyst for the ullmann reaction of aryl chlorides in water. ACS Catal. 4, 1546–1553 (2014).

  31. 31.

    et al. Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations. Science 335, 1209–1212 (2012).

  32. 32.

    Advanced electron microscopy of metal-support interactions in supported metal catalysts. ChemCatChem 3, 934–948 (2011).

  33. 33.

    et al. Alkali-stabilized Pt-OHx species catalyze low-temperature water-gas shift reactions. Science 329, 1633–1636 (2010).

  34. 34.

    et al. The emergence of nonbulk properties in supported metal clusters: negative thermal expansion and atomic disorder in Pt nanoclusters supported on gamma-Al2O3. J. Am. Chem. Soc. 131, 7040–7054 (2009).

  35. 35.

    , & Tuning the behavior of Au and Pt catalysts for the chemoselective hydrogenation of nitroaromatic compounds. Top. Catal. 54, 439–446 (2011).

Download references

Acknowledgements

We are grateful to the National Science Foundation of China (21176235, 21203182, 21202163, 21303194 and 21373206), the Key Research Program of the Chinese Academy of Sciences, and the Hundred Talents Program of Dalian Institute of Chemical Physics for the financial supports. We also thank Professor Yuying Huang (14W of Shanghai Synchrotron Radiation Facility in China) for his great help in the EXAFS experiment. J.L. acknowledges the start-up fund of the College of Liberal Arts and Sciences of Arizona State University and the use of facilities in the John M. Cowley Center for High Resolution Electron Microscopy at Arizona State University.

Author information

Author notes

    • Haisheng Wei
    •  & Xiaoyan Liu

    These authors contributed equally to this work

Affiliations

  1. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian 116023, China

    • Haisheng Wei
    • , Xiaoyan Liu
    • , Aiqin Wang
    • , Leilei Zhang
    • , Botao Qiao
    • , Xiaofeng Yang
    • , Yanqiang Huang
    • , Shu Miao
    • , Jingyue Liu
    •  & Tao Zhang
  2. University of Chinese Academy of Sciences, Beijing 100049, China

    • Haisheng Wei
  3. Department of Physics, Arizona State University, Tempe, Arizona 85287, USA

    • Botao Qiao
    •  & Jingyue Liu

Authors

  1. Search for Haisheng Wei in:

  2. Search for Xiaoyan Liu in:

  3. Search for Aiqin Wang in:

  4. Search for Leilei Zhang in:

  5. Search for Botao Qiao in:

  6. Search for Xiaofeng Yang in:

  7. Search for Yanqiang Huang in:

  8. Search for Shu Miao in:

  9. Search for Jingyue Liu in:

  10. Search for Tao Zhang in:

Contributions

H.W. performed the catalyst preparation, characterizations and catalytic tests. X.L. and L.Z. performed measurements and data analyses of EXAFS. J.L. and S.M. conducted the STEM examinations and contributed to writing the STEM sections. B.Q., X.Y. and Y.H. helped the catalyst preparation and characterization, and discussed the result. A.W. and T.Z. conceived the idea, designed the study, analysed the data and co-wrote the paper. All the authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Aiqin Wang or Jingyue Liu or Tao Zhang.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    Supplementary Figures 1-14 and Supplementary Tables 1-5

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.