Skip to main content
SpringerLink
Log in

Pt nanoparticles supported on non-carbon titanium chromium nitride nanotubes with high activity and durability for methanol oxidation reaction

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

A hybrid titanium chromium nitride nanotube (Ti0.95Cr0.05N NT) support was prepared by a facile synthesis procedure and further used as support for Pt nanoparticles (Pt/Ti0.95Cr0.05N NTs). The catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and nitrogen absorption/desorption, which show that the Pt/Ti0.95Cr0.05N NTs are formed with homogeneous cohesively attached nitride nanotube crystals. The X-ray photoelectron spectroscopy (XPS) reveals that the interaction between Ti0.95Cr0.05N NTs and Pt nanoparticles is enhanced due to the Cr element doping. Furthermore, the electrochemical experiments demonstrate that Ti0.95Cr0.05N NT-supported Pt catalyst exhibits enhanced catalytic activity and durability for methanol electrooxidation compared with traditional Pt/C catalyst. The experimental dates indicate that the excellent stability and durability of Pt/Ti0.95Cr0.05N NTs toward methanol electrochemical oxidation might be mainly ascribed to the synergistic effect introduced by Cr doping and the tubular nanostructures. The above results indicate that Ti0.95Cr0.05N NTs as support have a promising future in direct methanol fuel cells.

Robust non-carbon Ti0.95Cr0.05N nanotubes with tubular structure used as Pt support are synthesized by a facile method, and the Pt/Ti0.95Cr0.05N NT catalyst exhibits much higher activity and stability than conventional JM Pt/C and Pt/TiN NT catalysts for methanol electrooxidation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Zheng J, Cullen DA, Forest RV, Wittkopf JA, Zhuang Z, Sheng W, Chen JG, Yan Y (2015) Platinum–ruthenium nanotubes and platinum–ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol. ACS Catal 5(3):1468–1474

    Article  CAS  Google Scholar 

  2. Hsin YL, Hwang KC, Yeh C-T (2007) Poly (vinylpyrrolidone)-modified graphite carbon nanofibers as promising supports for PtRu catalysts in direct methanol fuel cells. J Am Chem Soc 129(32):9999–10010

    Article  CAS  PubMed  Google Scholar 

  3. Yu F, Xie Y, Tang H, Yang N, Meng X, Wang X, Tian XL, Yang X (2018) Platinum decorated hierarchical porous structures composed of ultrathin titanium nitride nanoflakes for efficient methanol oxidation reaction. Electrochim Acta 264:216–224

    Article  CAS  Google Scholar 

  4. Zheng Y, Zhan H, Tang H, Luo J, Dang D, Shu T, Ren J, Tian X, Liao S (2017) Atomic platinum layer coated titanium copper nitride supported on carbon nanotubes for the methanol oxidation reaction. Electrochim Acta 248:349–355

    Article  CAS  Google Scholar 

  5. Akyıldırım O, Yüksek H, Saral H, Ermiş İ, Eren T, Yola ML (2016) Platinum nanoparticles supported on nitrogen and sulfur-doped reduced graphene oxide nanomaterial as highly active electrocatalysts for methanol oxidation. J Mater Sci Mater Electron 27:8559–8566

    Article  CAS  Google Scholar 

  6. Liu B, Huo L, Zhang G, Zhang J (2016) Ternary hollow mesoporous TiN/N-graphene/Pt hybrid results in enhanced electrocatalytic performance for methanol oxidation and oxygen reduction reaction. Electrochim Acta 213:771–782

    Article  CAS  Google Scholar 

  7. Tian XL, Wang L, Deng P, Chen Y, Xia BY (2017) Research advances in unsupported Pt-based catalysts for electrochemical methanol oxidation. J Energy Chen 26(6):1067–1076

    Article  Google Scholar 

  8. Li L, Hu L, Li J, Wei Z (2015) Enhanced stability of Pt nanoparticle electrocatalysts for fuel cells. Nano Res 8(2):418–440

    Article  CAS  Google Scholar 

  9. Zhang L-M, Sui X-L, Zhao L, Zhang J-J, Gu D-M, Wang Z-B (2016) Nitrogen-doped carbon nanotubes for high-performance platinum-based catalysts in methanol oxidation reaction. Carbon 108:561–567

    Article  CAS  Google Scholar 

  10. Avasarala B, Haldar P (2013) Durability and degradation mechanism of titanium nitride based electrocatalysts for PEM (proton exchange membrane) fuel cell applications. Energy 57:545–553

    Article  CAS  Google Scholar 

  11. Lamy C, Guenot B, Cretin M, Pourcelly G (2015) Kinetics analysis of the electrocatalytic oxidation of methanol inside a DMFC working as a PEM electrolysis cell (PEMEC) to generate clean hydrogen. Electrochim Acta 177:352–358

    Article  CAS  Google Scholar 

  12. Suntivich J, Xu Z, Carlton CE, Kim J, Han B, Lee SW, Bonnet N, Marzari N, Allard LF, Gasteiger HA, Hamad-Schifferli K, Shao-Horn Y (2013) Surface composition tuning of Au-Pt bimetallic nanoparticles for enhanced carbon monoxide and methanol electro-oxidation. J Am Chem Soc 135(21):7985–7991

    Article  CAS  PubMed  Google Scholar 

  13. Tian X, Tang H, Luo J, Nan H, Shu T, Du L, Zeng J, Liao S, Adzic RR (2017) High-performance core-shell catalyst with nitride nanoparticles as a core: well-defined titanium copper nitride coated with an atomic Pt layer for the oxygen reduction reaction. ACS Catal 7(6):3810–3817

    Article  CAS  Google Scholar 

  14. Yu F, Xie Y, Wang L, Yang N, Meng X, Wang X, Tian XL, Yang X (2018) Platinum supported on multifunctional titanium cobalt oxide nanosheets assembles for efficient oxygen reduction reaction. Electrochim Acta 265:364–371

    Article  CAS  Google Scholar 

  15. Tian X, Luo J, Nan H, Zou H, Chen R, Shu T, Li X, Li Y, Song H, Liao S, Adzic RR (2016) Transition metal nitride coated with atomic layers of Pt as a low-cost, highly stable electrocatalyst for the oxygen reduction reaction. J Am Chem Soc 138(5):1575–1583

    Article  CAS  PubMed  Google Scholar 

  16. Yang M, Allen AJ, Nguyen MT, Ralston WT, MacLeod MJ, DiSalvo FJ (2013) Corrosion behavior of mesoporous transition metal nitrides. J Solid State Chem 205:49–56

    Article  CAS  Google Scholar 

  17. Avasarala B, Murray T, Li W, Haldar P (2009) Titanium nitride nanoparticles based electrocatalysts for proton exchange membrane fuel cells. J Mater Chem 19(13):1803

    Article  Google Scholar 

  18. Nan H, Dang D, Tian XL (2018) Structural engineering of robust titanium nitride as effective platinum support for the oxygen reduction reaction. J Mater Chen A 6(14):6065–6073

    Article  CAS  Google Scholar 

  19. Tian X, Luo J, Nan H, Fu Z, Zeng J, Liao S (2015) Binary transition metal nitrides with enhanced activity and durability for the oxygen reduction reaction. J Mater Chem A 3(32):16801–16809

    Article  CAS  Google Scholar 

  20. Zheng Y, Zhang J, Zhan H, Sun D, Dang D, Tian XL (2018) Porous and three dimensional titanium nitride supported platinum as an electrocatalyst for oxygen reduction reaction. Electrochem Commun 91:31–35

    Article  CAS  Google Scholar 

  21. Yang M, Guarecuco R, DiSalvo FJ (2013) Mesoporous chromium nitride as high performance catalyst support for methanol electrooxidation. Chem Mater 25(9):1783–1787

    Article  CAS  Google Scholar 

  22. Zhao L, Wang L, Yu P, Zhao D, Tian C, Feng H, Ma J, Fu H (2015) A chromium nitride/carbon nitride containing graphitic carbon nanocapsule hybrid as a Pt-free electrocatalyst for oxygen reduction. ChemComm 51:12399–12402

    CAS  Google Scholar 

  23. Zhao W, DiSalvo FJ (2015) Direct access to macroporous chromium nitride and chromium titanium nitride with inverse opal structure. ChemComm 51:4876–4879

    CAS  Google Scholar 

  24. Zhan G, Fu Z, Sun D, Pan Z, Xiao C, Wu S, Chen C, Hu G, Wei Z (2016) Platinum nanoparticles decorated robust binary transition metal nitride–carbon nanotubes hybrid as an efficient electrocatalyst for the methanol oxidation reaction. J Power Sources 326:84–92

    Article  CAS  Google Scholar 

  25. Yang M, Cui Z, DiSalvo FJ (2013) Mesoporous titanium nitride supported Pt nanoparticles as high performance catalysts for methanol electrooxidation. Phys Chem Chem Phys 15(4):1088–1092

    Article  PubMed  Google Scholar 

  26. Peng H, Liu F, Liu X, Liao S, You C, Tian X, Nan H, Luo F, Song H, Fu Z, Huang P (2014) Effect of transition metals on the structure and performance of the doped carbon catalysts derived from polyaniline and melamine for ORR application. ACS Catal 4(10):3797–3805

    Article  CAS  Google Scholar 

  27. Sun D, Lang J, Yan X, Hu L, Xue Q (2011) Fabrication of TiN nanorods by electrospinning and their electrochemical properties. J Solid State Chem 184(5):1333–1338

    Article  CAS  Google Scholar 

  28. Yang M, Cui Z, DiSalvo FJ (2012) Mesoporous vanadium nitride as a high performance catalyst support for formic acid electrooxidation. ChemComm 48:10502–10504

    CAS  Google Scholar 

  29. Liu G, Pan Z, Zhang B, Xiao J, Xia G, Zhao Q, Shi S, Hu G, Xiao C, Wei Z, Xu Y (2017) A novel TiN coated CNTs nanocomposite CNTs@TiN supported Pt electrocatalyst with enhanced catalytic activity and durability for methanol oxidation reaction. Int J Hydrog Energy 42(17):12467–12476

    Article  CAS  Google Scholar 

  30. Roca-Ayats M, García G, Galante JL, Peña MA, Martínez-Huerta MV (2013) TiC, TiCN, and TiN supported Pt electrocatalysts for CO and methanol oxidation in acidic and alkaline media. J Phys Chem C 117(40):20769–20777

    Article  CAS  Google Scholar 

  31. Yang H, Alonso-Vante N, Lamy C, Akins DL (2005) High methanol tolerance of carbon-supported Pt-Cr alloy nanoparticle electrocatalysts for oxygen reduction. J Electrochem Soc 152(4):A704

    Article  CAS  Google Scholar 

  32. Ocampo-Restrepo VK, Calderón-Cárdenas A, Lizcano-Valbuena WH (2017) Catalytic activity of Pt-based nanoparticles with Ni and Co for ethanol and acetaldehyde electrooxidation in alkaline medium. Electrochim Acta 246:475–483

    Article  CAS  Google Scholar 

  33. Huang H, Wang H, Hu W, Lv W, Ye W (2017) Exploring the role of nickel in the formation of amorphous Pt-based metallic alloys for methanol electro-oxidation with significant enhancement. Electrochem Commun 82:107–111

    Article  CAS  Google Scholar 

  34. Huang W, Wang H, Zhou J, Wang J, Duchesne PN, Muir D, Zhang P, Han N, Zhao F, Zeng M, Zhong J, Jin C, Li Y, Lee ST, Dai H (2015) Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum-nickel hydroxide-graphene. Nat Commun 6(1):10035

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  35. Shimizu K, Francis Cheng I, Wai CM (2009) Aqueous treatment of single-walled carbon nanotubes for preparation of Pt–Fe core–shell alloy using galvanic exchange reaction: selective catalytic activity towards oxygen reduction over methanol oxidation. Electrochem Commun 11(3):691–694

    Article  CAS  Google Scholar 

  36. Peng Z, Yang H (2009) Designer platinum nanoparticles: control of shape, composition in alloy, nanostructure and electrocatalytic property. Nano Today 4(2):143–164

    Article  CAS  Google Scholar 

  37. Gan L, Heggen M, O'Malley R, Theobald B, Strasser P (2013) Understanding and controlling nanoporosity formation for improving the stability of bimetallic fuel cell catalysts. Nano Lett 13(3):1131–1138

    Article  CAS  PubMed  Google Scholar 

  38. Seifitokaldani A, Savadogo O (2015) Electrochemically stable titanium oxy-nitride support for platinum electro-catalyst for PEM fuel cell applications. Electrochim Acta 167:237–245

    Article  CAS  Google Scholar 

  39. Luo J, Tian X, Zeng J, Li Y, Song H, Liao S (2016) Limitations and improvement strategies for early-transition-metal nitrides as competitive catalysts toward the oxygen reduction reaction. ACS Catal 6(9):6165–6174

    Article  CAS  Google Scholar 

  40. Xiao Y, Zhan G, Fu Z, Pan Z, Xiao C, Wu S, Chen C, Hu G, Wei Z (2015) Titanium cobalt nitride supported platinum catalyst with high activity and stability for oxygen reduction reaction. J Power Sources 284:296–304

    Article  CAS  Google Scholar 

  41. Kwon JA, Kim M-S, Shin DY, Kim JY, Lim D-H (2017) First-principles understanding of durable titanium nitride (TiN) electrocatalyst supports. J Ind Eng Chem 49:69–75

    Article  CAS  Google Scholar 

  42. Patel PP, Datta MK, Jampani PH, Hong D, Poston JA, Manivannan A, Kumta PN (2015) High performance and durable nanostructured TiN supported Pt 50 –Ru 50 anode catalyst for direct methanol fuel cell (DMFC). J Power Sources 293:437–446

    Article  CAS  Google Scholar 

  43. Xiao Y, Fu Z, Zhan G, Pan Z, Xiao C, Wu S, Chen C, Hu G, Wei Z (2015) Increasing Pt methanol oxidation reaction activity and durability with a titanium molybdenum nitride catalyst support. J Power Sources 273:33–40

    Article  CAS  Google Scholar 

  44. Avasarala B, Haldar P (2010) Electrochemical oxidation behavior of titanium nitride based electrocatalysts under PEM fuel cell conditions. Electrochim Acta 55(28):9024–9034

    Article  CAS  Google Scholar 

  45. Hu C, Cao Y, Yang L, Bai Z, Guo Y, Wang K, Xu P, zhou J (2011) Preparation of highly dispersed Pt-SnOx nanoparticles supported on multi-walled carbon nanotubes for methanol oxidation. Appl Surf Sci 257(18):7968–7974

    Article  CAS  Google Scholar 

  46. Jehng J-M, Liu W-J, Pan T-C, Dai Y-M (2013) Preparation of Pt nanoparticles on different carbonaceous structure and their applications to methanol electro-oxidation. Appl Surf Sci 268:425–431

    Article  CAS  Google Scholar 

Download references

Funding

This work was financially supported by the Natural Science Foundation of Guangdong Province, China (No. 2016A030313704) and Science and Technology Planning Project of Guangdong Province, China (No. 2016A010103035, No. 2016B020240003).

Author information

Authors and Affiliations

  1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, 510006, Guangdong, China

    Xiaoxiang Chen, Zhanchang Pan, Qiuman Zhou, Zhaojie Huang, Yanbin Xu & Guanghui Hu

  2. Huizhou King Brother Electronic Technology Co., Ltd, Huizhou, 516083, China

    Shoukun Wu, Chun Chen, LuHua Lin & Yingsheng Lin

Authors
  1. Xiaoxiang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhanchang Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qiuman Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhaojie Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yanbin Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Guanghui Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Shoukun Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Chun Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. LuHua Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Yingsheng Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Zhanchang Pan or Yanbin Xu.

Additional information

Highlights

• Non-carbon Ti0.95Cr0.05N NTs hybrid support was successfully synthesized by a facile process.

• Ti0.95Cr0.05N NTs with hollow tubular structure and high surface area are prepared.

• The chromium doping significantly enhanced the MOR activity.

• The novel catalyst shows significantly enhanced MOR activity and durability.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, X., Pan, Z., Zhou, Q. et al. Pt nanoparticles supported on non-carbon titanium chromium nitride nanotubes with high activity and durability for methanol oxidation reaction. J Solid State Electrochem 23, 315–324 (2019). https://doi.org/10.1007/s10008-018-4135-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-018-4135-4

Keywords

Search

Navigation