Catalysis Letters

, Volume 142, Issue 8, pp 975–983 | Cite as

Low Pt Loading High Catalytic Performance of PtFeNi/Carbon Nanotubes Catalysts for CO Preferential Oxidation in Excess Hydrogen I: Promotion Effects of Fe and/or Ni

  • Limin ChenEmail author
  • Ding Ma
  • Zhen Zhang
  • Yuanyuan Guo
  • Daiqi Ye
  • Bichun Huang


The commercial carbon nanotubes (CNTs-o) and purified carbon nanotubes (CNTs-p) have been utilized to prepare Pt(FeNi)/CNTs catalysts for CO preferential oxidation (PROX) in H2 rich stream. The 3 wt%Pt0.41 %Fe 0.35 %Ni/CNTs-p catalyst after activation at 500 °C in H2 can almost completely remove CO at 6 °C in feed gas containing 1 % CO, 0.5 % O2 (volume ratio) and H2 balance. CNTs-o supported 3 wt% Pt can also remove CO almost completely at room temperature, after activation at 500 °C in the feed gas. And this catalyst can keep high activity, high selectivity and high stability for PROX of CO at room temperature. These catalysts are the most effective catalysts for PROX of CO with much lower Pt loading until so far. H-TPR, XRD, HRTEM and reaction results indicate that the Fe and/or Ni precursors have been reduced to metallic state after activation in H2 which can be oxidized to coordinatively unsaturated FeOx and/or NiOx active species after exposure to feed gas. XPS data point out that over oxidation of Fe and Pt species will deactivate the catalysts seriously. The high catalytic performance is mainly due to the promotion effects of in situ formed coordinatively unsaturated FeOx and/or NiOx species and the unique properties of CNTs.

Graphical Abstract


Low Pt loading Fe/Ni promoted Pt catalysts Carbon nanotubes CO preferential oxidation (PROX) 



The authors gratefully thank Dr. Xinhe Bao and Dr. Xiulian Pan at Dalian Institute of Chemical Physics, Chinese Academy of Sciences, for their enthusiastic supervision and helpful discussions. This work is financially supported by the Natural Science Foundation of Guangdong Province, China (Grant No. S2011010000737), the Doctoral Fund of Ministry of Education of China (20110172120017), the Fundamental Research Funds for the Central Universities (Grant No. 2011zm 0048), and the Key Laboratory of Renewable Energy and Gas Hydrate, Chinese Academy of Sciences (No. Y007K1).

Supplementary material

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Supplementary material 1 (DOC 67 kb)


  1. 1.
    Bing YH, Liu HS, Zhang L, Ghosh D, Zhang JJ (2010) Nanostructured Pt-alloy electrocatalysts for PEM fuel cell oxygen reduction reaction. Chem Soc Rev 39:2184–2202CrossRefGoogle Scholar
  2. 2.
    Devanathan R (2008) Recent developments in proton exchange membranes for fuel cells. Energy Environ Sci 1:101–119CrossRefGoogle Scholar
  3. 3.
    Antolini E (2009) Carbon supports for low-temperature fuel cell catalysts. Appl Catal B 88:1–24CrossRefGoogle Scholar
  4. 4.
    Shao YY, Sui JH, Yin GP, Gao YZ (2008) Nitrogen-doped carbon nanostructures and their composites as catalytic materials for proton exchange membrane fuel cell. Appl Catal B 79:89–99CrossRefGoogle Scholar
  5. 5.
    Park ED, Lee D, Lee HC (2009) Recent progress in selective CO removal in a H2-rich stream. Catal Today 139:280–290CrossRefGoogle Scholar
  6. 6.
    Bion N, Epron F, Moreno M, Marino F, Duprez D (2008) Preferential oxidation of carbon monoxide in the presence of hydrogen (PROX) over noble metals and transition metal oxides: advantages and drawbacks. Top Catal 51:76–88CrossRefGoogle Scholar
  7. 7.
    Bulushev DA, Yuranov I, Suvorova EI, Buffat PA, Kiwi-Minsker L (2004) Highly dispersed gold on activated carbon fibers for low-temperature CO oxidation. J Catal 224:8–17CrossRefGoogle Scholar
  8. 8.
    Siani A, Alexeev OS, Lafaye G, Amiridis MD (2011) The effect of Fe on SiO2-supported Pt catalysts: structure, chemisorptive, and catalytic properties. J Catal 266:26–38CrossRefGoogle Scholar
  9. 9.
    Kotobuki M, Watanabe A, Uchida H, Yamashita H, Watanabe M (2005) Reaction mechanism of preferential oxidation of carbon monoxide on Pt, Fe, and Pt–Fe/mordenite catalysts. J Catal 236:262–269CrossRefGoogle Scholar
  10. 10.
    Siani A, Captain B, Alexeev OS, Stafyla E, Hungria AB, Midgley PA et al (2006) Improved CO oxidation activity in the presence and absence of hydrogen over cluster-derived PtFe/SiO2 catalysts. Langmuir 22:5160–5167CrossRefGoogle Scholar
  11. 11.
    Fu Q, Li WX, Yao YX, Liu HY, Su HY, Ma D et al (2010) Interface-confined ferrous centers for catalytic oxidation. Science 328:1141–1144CrossRefGoogle Scholar
  12. 12.
    Wang C, Li B, Lin HQ, Yuan YZ (2012) Carbon nanotube-supported Pt-Co bimetallic catalysts for preferential oxidation of CO in a H2-rich stream with CO2 and H2O vapor. J Power Sources 202:200–208CrossRefGoogle Scholar
  13. 13.
    Ko EK, Park ED, Lee HC, Lee D, Kim S (2007) Supported Pt-Co catalysts for selective CO oxidation in a hydrogen-rich stream. Angew Chem Int Ed 46:734–737CrossRefGoogle Scholar
  14. 14.
    Ding ZX, Yang HY, Liu JF, Dai WX, Chen X, Wang XX, Fu XZ (2011) Promoted CO oxidation activity in the presence and absence of hydrogen over the TiO2-supported Pt/Co-B bicomponent catalyst. Appl Catal B 101:326–332CrossRefGoogle Scholar
  15. 15.
    Mu RT, Fu Q, Xu H, Zhang H, Huang YY, Jiang Z, Zhang S, Tan DL, Bao XH (2011) Synergetic effect of surface and subsurface Ni species at Pt-Ni bimetallic catalysts for CO oxidation. J Am Chem Soc 133:1978–1986CrossRefGoogle Scholar
  16. 16.
    Ko EY, Park ED, Seo KW, Lee HC, Lee D, Kim S (2006) Pt–Ni/γ-Al2O3 catalyst for the preferential CO oxidation in the hydrogen stream. Catal Lett 110:275–279CrossRefGoogle Scholar
  17. 17.
    Şimşek E, Özkara S, Aksoylu AE, Önsan ZI (2007) Preferential CO oxidation over activated carbon supported catalysts in H2-rich gas streams containing CO2 and H2O. Appl Catal A 316:169–174CrossRefGoogle Scholar
  18. 18.
    Gorke O, Pfeifer P (2011) Preferential CO oxidation over a platinum ceria alumina catalyst in a microchannel reactor. Int J Hydrogen Energy 36:4673–4681CrossRefGoogle Scholar
  19. 19.
    Ayastuy JL, González-Marcos MP, González-Velasco JR, Gutiérrez-Ortiz MA (2007) MnOx/Pt/Al2O3 catalysts for CO oxidation in H2-rich streams. Appl Catal B 70:532–541CrossRefGoogle Scholar
  20. 20.
    Tanaka H, Kuriyama M, Ishida Y, Ito SI, Tomishige K, Kunimori K (2008) Preferential CO oxidation in hydrogen-rich stream over Pt catalysts modified with alkali metals: part I. Catalytic performance. Appl Catal A 343:117–124CrossRefGoogle Scholar
  21. 21.
    Pedrero C, Waku T, Iglesia E (2005) Oxidation of CO in H2–CO mixtures catalyzed by platinum: alkali effects on rates and selectivity. J Catal 233:242–255CrossRefGoogle Scholar
  22. 22.
    Kuriyama M, Tanaka H, Ito SI, Kubota T, Miyao T, Naito S et al (2007) Promoting mechanism of potassium in preferential CO oxidation on Pt/Al2O3. J Catal 252:39–48CrossRefGoogle Scholar
  23. 23.
    Chen LM, Ma D, Bao XH (2007) Hydrogen treatment-induced surface reconstruction: formation of superoxide species on activated carbon over Ag/activated carbon catalysts for selective oxidation of CO in H2-rich gases. J Phys Chem C 111:2229–2234CrossRefGoogle Scholar
  24. 24.
    Chen LM, Ma D, Li XY, Bao XH (2006) Silver catalysts supported over activated carbons for the selective oxidation of CO in excess hydrogen: effects of different treatments on the supports. Catal Lett 111:133–139CrossRefGoogle Scholar
  25. 25.
    Zhang J, Liu X, Blume R, Zhang AH, Schlögl R, Su DS (2008) Surface-modified carbon nanotubes catalyze oxidative dehydrogenation of n-butane. Science 322:73–77CrossRefGoogle Scholar
  26. 26.
    Zhang J, Comotti M, Schüth F, Schlögl R, Su DS (2007) Commercial Fe- or Co-containing carbon nanotubes as catalysts for NH3 decomposition. Chem Commun 19:1916–1918CrossRefGoogle Scholar
  27. 27.
    Guo SJ, Pan XL, Gao HL, Yang ZQ, Zhao JJ, Bao XH (2010) Probing the electronic effect of carbon nanotubes in catalysis: NH3 synthesis with Ru nanoparticles. Chem Eur J 16:5379–5384Google Scholar
  28. 28.
    Rodriguez NM, Kim MS, Baker RTK (1994) Carbon nanofibers: a unique catalyst support medium. J Phys Chem 98:13108–13111CrossRefGoogle Scholar
  29. 29.
    Hung V, Gonçalves F, Philippe R, Lamouroux E, Kihn MCY, Plee D et al (2006) Bimetallic catalysis on carbon nanotubes for the selective hydrogenation of cinnamaldehyde. J Catal 240:18–22CrossRefGoogle Scholar
  30. 30.
    Hofmann S, Blume R, Wirth CT, Cantoro M, Sharma R, Ducati C et al (2009) State of transition metal catalysts during carbon nanotube growth. J Phys Chem C 113:1648–1656CrossRefGoogle Scholar
  31. 31.
    Qu ZP, Cheng MJ, Shi C, Bao XH (2002) Effects of silver loading and pretreatment with reaction gas on CO selective oxidation in H2 over silver catalyst. Chin J Catal 23:460–464Google Scholar
  32. 32.
    Abbaslou RMM, Tavasoli A, Dalai AK (2009) Effect of pre-treatment on physico- chemical properties and stability of carbon nanotubes supported iron Fischer–Tropsch catalysts. Appl Catal A 355:33–41CrossRefGoogle Scholar
  33. 33.
    Silva LMS, Órfão JJM, Figueiredo JL (2001) Formation of two metal phases in the preparation of activated carbon-supported nickel catalysts. Appl Catal A 209:145–154CrossRefGoogle Scholar
  34. 34.
    Fraga MA, Jordão E, Mendes MJ, Freitas MMA, Faria JL, Figueiredo JL (2002) Properties of carbon-supported platinum catalysts: role of carbon surface sites. J Catal 209:355–364CrossRefGoogle Scholar
  35. 35.
    Mahata N, Gonçalves F, Pereira MFR, Figueiredo JL (2008) Selective hydrogenation of cinnamaldehyde to cinnamyl alcohol over mesoporous carbon supported Fe and Zn promoted Pt catalyst. Appl Catal A 339:159–168CrossRefGoogle Scholar
  36. 36.
    Chen W, Pan XL, Bao XH (2007) Tuning of redox properties of iron and iron oxides via encapsulation within carbon nanotubes. J Am Chem Soc 129:7421–7426CrossRefGoogle Scholar
  37. 37.
    Menning CA, Hwu HH, Chen JG (2006) Experimental and theoretical investigation of the stability of Pt-3d-Pt(111) bimetallic surfaces under oxygen environment. J Phys Chem B 110:15471–15477CrossRefGoogle Scholar
  38. 38.
    Ma T, Fu Q, Cui Y, Zhang Z, Wang Z, Tan DL, Bao XH et al (2010) Controlled transformation of the structures of surface Fe (FeO) and subsurface Fe on Pt(111). Chin J Catal 31:24–32CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Limin Chen
    • 1
    • 2
    Email author
  • Ding Ma
    • 2
    • 3
  • Zhen Zhang
    • 2
  • Yuanyuan Guo
    • 1
  • Daiqi Ye
    • 1
  • Bichun Huang
    • 1
  1. 1.Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, College of Environmental Science and EngineeringSouth China University of TechnologyGuangzhouChina
  2. 2.State Key Laboratory of Catalysis, Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalianChina
  3. 3.College of Chemistry and Molecular EngineeringPeking UniversityBeijingChina

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