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Small-sized tungsten nitride anchoring into a 3D CNT-rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions

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Abstract

The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanoparticles (NPs), of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework (CNT-rGO) using an assembly route. After depositing Pt, the contacted and strongly coupled Pt–WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt–WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA·mgPt –1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C(JM) catalysts, respectively. The catalyst also exhibited a more positive onset potential (1.03 V), higher mass activity (151.3 mA·mgPt –1), and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt–WN can enhance the catalytic activity and CO-tolerance of Pt. Pt–WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.

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References

  1. Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 2012, 486, 43–51.

    Article  Google Scholar 

  2. Long, N. V.; Yang, Y.; Thi, C. M.; van Minh, N.; Cao, Y. Q.; Nogami, M. The development of mixture, alloy, and core–shell nanocatalysts with nanomaterial supports for energy conversion in low-temperature fuel cells. Nano Energy 2013, 2, 636–676.

    Article  Google Scholar 

  3. Tong, Y. Y.; Kim, H. S.; Babu, P. K.; Waszczuk, P.; Wieckowski, A.; Oldfield, E. An NMR investigation of CO tolerance in a Pt/Ru fuel cell catalyst. J. Am. Chem. Soc. 2002, 124, 468–473.

    Article  Google Scholar 

  4. Fang, B. Z.; Chaudhari, N. K.; Kim, M. S.; Kim, J. H.; Yu, J. S. Homogeneous deposition of platinum nanoparticles on carbon black for proton exchange membrane fuel cell. J. Am. Chem. Soc. 2009, 131, 15330–15338.

    Article  Google Scholar 

  5. Liu, M. M.; Zhang, R. Z.; Chen, W. Graphene-supported nanoelectrocatalysts for fuel cells: Synthesis, properties, and applications. Chem. Rev. 2014, 114, 5117–5160.

    Article  Google Scholar 

  6. Chen, X. M.; Wu, G. H.; Chen, J. M.; Chen, X.; Xie, Z. X.; Wang, X. R. Synthesis of “clean” and well-dispersive Pd nanoparticles with excellent electrocatalytic property on graphene oxide. J. Am. Chem. Soc. 2011, 133, 3693–3695.

    Article  Google Scholar 

  7. Guo, S. J.; Dong, S. J.; Wang, E. K. Three-dimensional Pt-on-Pd bimetallic nanodendrites supported on graphene nanosheet: Facile synthesis and used as an advanced nanoelectrocatalyst for methanol oxidation. ACS Nano 2010, 4, 547–555.

    Article  Google Scholar 

  8. Cui, Z. M.; Chen, H.; Zhao, M. T.; Marshall, D.; Yu, Y. C.; Abruña, H.; DiSalvo, F. J. Synthesis of structurally ordered Pt3Ti and Pt3V nanoparticles as methanol oxidation catalysts. J. Am. Chem. Soc. 2014, 136, 10206–10209.

    Article  Google Scholar 

  9. Xia, B. Y.; Wu, H. B.; Li, N.; Yan, Y.; Lou, X. W.; Wang, X. One-pot synthesis of Pt–Co alloy nanowire assemblies with tunable composition and enhanced electrocatalytic properties. Angew. Chem., Int. Ed. 2015, 54, 3797–3801.

    Article  Google Scholar 

  10. Saleem, F.; Zhang, Z. C.; Xu, B.; Xu, X. B.; He, P. L.; Wang, X. Ultrathin Pt–Cu nanosheets and nanocones. J. Am. Chem. Soc. 2013, 135, 18304–18307.

    Article  Google Scholar 

  11. Scofield, M. E.; Koenigsmann, C.; Wang, L.; Liu, H. Q.; Wong, S. S. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction. Energy Environ. Sci, 2015, 8, 350–363.

    Article  Google Scholar 

  12. Wang, C.; Daimon, H.; Onodera, T.; Koda, T.; Sun, S. H. A general approach to the size- and shape-controlled synthesis of platinum nanoparticles and their catalytic reduction of oxygen. Angew. Chem., Int. Ed. 2008, 47, 3588–3591.

    Article  Google Scholar 

  13. Wu, J. B.; Yang, H. Synthesis and electrocatalytic oxygen reduction properties of truncated octahedral Pt3Ni nanoparticles. Nano Res. 2011, 4, 72–82.

    Article  Google Scholar 

  14. Qu, L. T.; Liu, Y.; Baek, J. B.; Dai, L. M. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 2010, 4, 1321–1326.

    Article  Google Scholar 

  15. Zhang, W.; Wu, Z. Y.; Jiang, H. L.; Yu, S. H. Nanowiredirected templating synthesis of metal–organic framework nanofibers and their derived porous doped carbon nanofibers for enhanced electrocatalysis. J. Am. Chem. Soc. 2014, 136, 14385–14388.

    Article  Google Scholar 

  16. Yang, Z.; Yao, Z.; Li, G. F.; Fang, G. Y.; Nie, H. G.; Liu, Z.; Zhou, X. M.; Chen, X. A.; Huang, S. M. Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano 2012, 6, 205–211.

    Article  Google Scholar 

  17. Zheng, Y.; Jiao, Y.; Chen, J.; Liu, J.; Liang, J.; Du, A. J.; Zhang, W. M.; Zhu, Z. H.; Smith, S. C.; Jaroniec, M. et al. Nanoporous graphitic-C3N4@carbon metal-free electrocatalysts for highly efficient oxygen reduction. J. Am. Chem. Soc. 2011, 133, 20116–20119.

    Article  Google Scholar 

  18. Lee, K. C.; Zhang, L.; Lui, H. S.; Hui, R.; Shi, Z.; Zhang, J. J. Oxygen reduction reaction (ORR) catalyzed by carbonsupported cobalt polypyrrole (Co-PPy/C) electrocatalysts. Electrochim. Acta 2009, 54, 4704–4711.

    Article  Google Scholar 

  19. Zhu, Y. S.; Zhang, B. S.; Liu, X.; Wang, D. W.; Su, D. S. Unravelling the structure of electrocatalytically active Fe–N complexes in carbon for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2014, 53, 10673–10677.

    Article  Google Scholar 

  20. Chen, S.; Bi, J. Y.; Zhao, Y.; Yang, L. J.; Zhang, C.; Ma, Y. W.; Wu, Q.; Wang, X. Z.; Hu, Z. Nitrogen-doped carbon nanocages as efficient metal-free electrocatalysts for oxygen reduction reaction. Adv. Mater. 2012, 24, 5593–5597.

    Article  Google Scholar 

  21. Shen, A. L.; Zou, Y. Q.; Wang, Q.; Dryfe, R. A. W.; Huang, X. B.; Dou, S.; Dai, L. M.; Wang, S. Y. Oxygen reduction reaction in a droplet on graphite: Direct evidence that the edge is more active than the basal plane. Angew. Chem., Int. Ed. 2014, 53, 10804–10808.

    Article  Google Scholar 

  22. Houchins, C.; Kleen, G. J.; Spendelow, J. S.; Kopasz, J.; Peterson, D.; Garland, N. L.; Ho, D. L.; Marcinkoski, J.; Martin, K. E.; Tyler, R. et al. U. S. DOE progress towards developing low-cost, high performance, durable polymer electrolyte membranes for fuel cell applications. Membranes 2012, 2, 855–878.

    Article  Google Scholar 

  23. Chen, J. G. Carbide and nitride overlayers on early transition metal surfaces: Preparation, characterization, and reactivities. Chem. Rev. 1996, 96, 1477–1498.

    Article  Google Scholar 

  24. Liang, C. H.; Ding, L.; Li, C.; Pang, M.; Su, D. S.; Li, W. Z.; Wang, Y. M. Nanostructured WCx/CNTs as highly efficient support of electrocatalysts with low Pt loading for oxygen reduction reaction. Energy Environ. Sci. 2010, 3, 1121–1127.

    Article  Google Scholar 

  25. Cui, Z. M.; Gong, C.; Guo, C. X.; Li, C. M. Mo2C/CNTs supported Pd nanoparticles for highly efficient catalyst towards formic acid electrooxidation. J. Mater. Chem. A 2013, 1, 1179–1184.

    Article  Google Scholar 

  26. Yin, J.; Wang, L.; Tian, C. G.; Tan, T. X.; Mu, G.; Zhao, L.; Fu, H. G. Low-Pt loaded on a vanadium nitride/graphitic carbon composite as an efficient electrocatalyst for the oxygen reduction reaction. Chem. Eur. J. 2013, 19, 13979–13986.

    Article  Google Scholar 

  27. Yan, H. J.; Tian, C. G.; Sun, L.; Wang, B.; Wang, L.; Yin, J.; Wu, A. P.; Fu, H. G. Small-sized and high-dispersed WN from [SiO4(W3O9)4]4-clusters loading on GO-derived graphene as promising carriers for methanol electro-oxidation. Energy Environ. Sci. 2014, 7, 1939–1949.

    Article  Google Scholar 

  28. Whitby, R. L. D. Chemical control of graphene architecture: Tailoring shape and properties. ACS Nano 2014, 8, 9733–9754.

    Article  Google Scholar 

  29. Lee, S. H.; Sridhar, V.; Jung, J. H.; Karthikeyan, K.; Lee, Y. S.; Mukherjee, R.; Koratkar, N.; Oh, I. K. Graphenenanotube- iron hierarchical nanostructure as lithium ion battery anode. ACS Nano 2013, 7, 4242–4251.

    Article  Google Scholar 

  30. Li, S. S.; Luo, Y. H.; Lv, W.; Yu, W. J.; Wu, S. D.; Hou, P. X.; Yang, Q. H.; Meng, Q. B.; Liu, C.; Cheng, H. M. Vertically aligned carbon nanotubes grown on graphene paper as electrodes in lithium-ion batteries and dye-sensitized solar cells. Adv. Energy Mater. 2011, 1, 486–490.

    Article  Google Scholar 

  31. Youn, D. H.; Han, S.; Kim, J. Y.; Kim, J. Y.; Park, H.; Choi, S. H.; Lee, J. S. Highly active and stable hydrogen evolution electrocatalysts based on molybdenum compounds on carbon nanotube–graphene hybrid support. ACS Nano 2014, 8, 5164–5173.

    Article  Google Scholar 

  32. Duan, J. J.; Chen, S.; Chambers, B. A.; Andersson, G. G.; Qiao, S. Z. 3D WS2 nanolayers@heteroatom-doped graphene films as hydrogen evolution catalyst electrodes. Adv. Mater. 2015, 27, 4234–4241.

    Article  Google Scholar 

  33. Zhang, L. M.; Lu, Z. X.; Zhao, Q. H.; Huang, J.; Shen, H.; Zhang, Z. J. Enhanced chemotherapy efficacy by sequential delivery of siRNA and anticancer drugs using PEI-grafted graphene oxide. Small 2011, 7, 460–464.

    Article  Google Scholar 

  34. Li, J.; Tang, W. J.; Huang, J. W.; Jin, J.; Ma, J. T. Polyethyleneimine decorated graphene oxide-supported Ni1-x Fex bimetallic nanoparticles as efficient and robust electrocatalysts for hydrazine fuel cells. Catal. Sci. Technol. 2013, 3, 3155–3162.

    Article  Google Scholar 

  35. Hu, X. G.; Wang, T.; Qu, X. H.; Dong, S. J. In situ synthesis and characterization of multiwalled carbon nanotube/Au nanoparticle composite materials. J. Phys. Chem. B 2006, 110, 853–857.

    Article  Google Scholar 

  36. Cao, X. Y.; Chen, J. J.; Wen, S. H.; Peng, C.; Shen, M. W.; Shi X. Y. Effect of surface charge of polyethyleneiminemodified multiwalled carbon nanotubes on the improvement of polymerase chain reaction. Nanoscale 2011, 3, 1741–1747.

    Article  Google Scholar 

  37. Yu, D. S.; Dai, L. M. Self-assembled graphene/carbon nanotube hybrid films for supercapacitors. J. Phys. Chem. Lett. 2010, 1, 467–470.

    Article  Google Scholar 

  38. Ferrari, A. C. Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun. 2007, 143, 47–57.

    Article  Google Scholar 

  39. Stankovich, S.; Dikin, D. A.; Piner, R. D.; Kohlhaas, K. A.; Kleinhammes, A.; Jia, Y. Y.; Wu, Y.; Nguyen, S. T.; Ruo, R. S. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 2007, 45, 1558–1565.

    Article  Google Scholar 

  40. Zhang, C. H.; Fu, L.; Liu, N.; Liu, M. H.; Wang, Y. Y.; Liu, Z. F. Synthesis of nitrogen-doped graphene using embedded carbon and nitrogen sources. Adv. Mater. 2011, 23, 1020–1024.

    Article  Google Scholar 

  41. Fernandes, D. M.; Brett, C. M. A.; Cavaleiro, A. M. V. Layer-by-layer self-assembly and electrocatalytic properties of poly(ethylenimine)-silicotungstate multilayer composite films. J Solid State Electrochem. 2011, 15, 811–819.

    Article  Google Scholar 

  42. Patil, A. J.; Vickery, J. L.; Scott, T. B.; Mann, S. Aqueous stabilization and self-assembly of graphene sheets into layered bio-nanocomposites using DNA. Adv. Mater. 2009, 21, 3159–3164.

    Article  Google Scholar 

  43. Wu, Z. S.; Yang, S. B.; Sun, Y.; Parvez, K.; Feng, X. L.; Müllen, K. 3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction. J. Am. Chem. Soc. 2012, 134, 9082–9085.

    Article  Google Scholar 

  44. Liu, R. L.; Wu, D. Q.; Feng, X. L.; Müllen, K. Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew. Chem., Int. Ed. 2010, 122, 2619–2623.

    Article  Google Scholar 

  45. Tian, G. L.; Zhang, Q.; Zhang, B. S.; Jin, Y. G.; Huang, J. Q.; Su, D. S.; Wei, F. Toward full exposure of “active sites”: nanocarbon electrocatalyst with surface enriched nitrogen for superior oxygen reduction and evolution reactivity. Adv. Funct. Mater. 2014, 24, 5956–5961.

    Article  Google Scholar 

  46. Sun, L.; Tian, C. G.; Fu, Y.; Yang, Y.; Yin, J.; Wang, L.; Fu, H. G. Nitrogen-doped porous graphitic carbon as an excellent electrode material for advanced supercapacitors. Chem. Eur. J. 2014, 20, 564–574.

    Article  Google Scholar 

  47. He, C. Y.; Meng, H.; Yao, X. Y.; Shen, P. K. Rapid formation of nanoscale tungsten carbide on graphitized carbon for electrocatalysis. Int. J. Hydrogen Energy 2012, 37, 8154–8166.

    Article  Google Scholar 

  48. Wang, R. H.; Yang, J.; Shi, K. Y.; Wang, B.; Wang, L.; Tian, G. H; Bateer, B.; Tian, C. G.; Shen, P. K.; Fu, H. G. Single-step pyrolytic preparation of Mo2C/graphitic carbon nanocomposite as catalyst carrier for the direct liquid-feed fuel cells. RSC Adv. 2013, 3, 4771–4777.

    Article  Google Scholar 

  49. Sun, S. H.; Zhang, G. X.; Gauquelin, N.; Chen, N.; Zhou, J. G.; Yang, S. L.; Chen, W. F.; Meng, X. B.; Geng, D. S.; Banis, M. N. et al. Single-atom catalysis using Pt/graphene achieved through atomic layer deposition. Sci. Rep. 2013, 3, 1775.

    Google Scholar 

  50. Wang, D. L.; Lu, S. F.; Xiang, Y.; Jiang, S. P. Self- assembly of HPW on Pt/C nanoparticles with enhanced electrocatalysis activity for fuel cell applications. Appl. Catal. B: Environ. 2011, 103, 311–317.

    Article  Google Scholar 

  51. Cui, G. F.; Shen, P. K.; Meng, H.; Zhao, J.; Wu, G. Tungsten carbide as supports for Pt electrocatalysts with improved CO tolerance in methanol oxidation. J Power Sources 2011, 196, 6125–6130.

    Article  Google Scholar 

  52. Su, F. B.; Tian, Z. Q.; Poh, C. K.; Wang, Z.; Lim, S. H.; Liu, Z. L.; Lin, J. Y. Pt nanoparticles supported on nitrogendoped porous carbon nanospheres as an electrocatalyst for fuel cells. Chem. Mater. 2010, 22, 832–839.

    Article  Google Scholar 

  53. Zhao, S. L.; Yin, H. J.; Du, L.; He, L. C.; Zhao, K.; Chang, L.; Yin, G. P.; Zhao, H. J.; Liu, S. Q.; Tang, Z. Y.; Carbonized nanoscale metal–organic frameworks as high performance electrocatalyst for oxygen reduction reaction. ACS Nano 2014, 8, 12660–12668.

    Article  Google Scholar 

  54. Kongkanand, A.; Kuwabata, S.; Girishkumar, G.; Kamat, P. Single-wall carbon nanotubes supported platinum nanoparticles with improved electrocatalytic activity for oxygen reduction reaction. Langmuir 2006, 22, 2392–2396.

    Article  Google Scholar 

  55. Selvarani, G.; Selvaganesh, S. V.; Krishnamurthy, S.; Kiruthika, G. V. M.; Sridhar, P.; Pitchumani, S.; Shukla, A. K. A methanol-tolerant carbon-supported Pt–Au alloy cathode catalyst for direct methanol fuel cells and its evaluation by DFT. J. Phys. Chem. C 2009, 113, 7461–7468.

    Article  Google Scholar 

  56. Cho, Y. H.; Kim, O. H.; Chung, D. Y.; Choe, H.; Cho, Y. H.; Sung, Y. E. PtPdCo ternary electrocatalyst for methanol tolerant oxygen reduction reaction in direct methanol fuel cell. Appl. Catal. B: Environ. 2014, 154–155, 309–315.

    Article  Google Scholar 

  57. Jeon, M. K.; Lee, K. R.; Lee, W. S.; Daimon, H.; Nakahara, A.; Woo, S. I. Investigation of Pt/WC/C catalyst for methanol electro-oxidation and oxygen electro-reduction. J. Power Sources 2008, 185, 927–931.

    Article  Google Scholar 

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Authors and Affiliations

  1. Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People’s Republic of China, Heilongjiang University, Harbin, 150080, China

    Haijing Yan, Meichen Meng, Lei Wang, Aiping Wu, Chungui Tian, Lu Zhao & Honggang Fu

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  1. Haijing Yan
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  2. Meichen Meng
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  3. Lei Wang
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  7. Honggang Fu
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Correspondence to Chungui Tian or Honggang Fu.

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Yan, H., Meng, M., Wang, L. et al. Small-sized tungsten nitride anchoring into a 3D CNT-rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions. Nano Res. 9, 329–343 (2016). https://doi.org/10.1007/s12274-015-0912-x

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