Nitrogen-Doped Large-Sized Graphene Tubes As an Active Support for a Hybrid Pt Electrocatalyst Towards Oxygen-Reduction
In exploring carbon-based ORR transition metal-nitrogen-carbon (M-N-C) catalysts (M: Fe or Co),(7-11) in situ formation of various carbon nanostructures with nitrogen doping can be realized by catalyzing the decomposition of the nitrogen/carbon precursor at high temperatures (800-1000°C),(12) which was found to result in catalysts with superior activity for the ORR is comparison to other types of nonprecious metal catalysts (NPMCs). Importantly, we can control the formation of different nanostructures (e.g., CNT, onion-like carbon, graphene) during the catalyst synthesis by optimizing the transition metals, nitrogen/carbon precursors and templates.(12) The highly graphitized carbon nanostructures present in the Fe-N-C materials may serve as a matrix for hosting catalytically active nitrogen-metal moieties.(12) The presence of graphitized carbon appears to enhance the stability of the ORR catalysts.(8) In exploring such carbon nanostructure-rich catalysts for ORR, although substantial progress has been achieved in the synthesis and performance improvement, practical resolution regarding its long-term durability and high activity in fuel cells or other energy application is still far from effective.
Herein, we conceive a new method to prepare highly active and stable ORR catalysts by innovatively coupling Pt nanoparticles and highly active Fe-N-C materials in a unique hybrid configuration (Figure 1). In doing so, large-diameter nitrogen-doped graphene tubes (N-GTs) derived from dicyandiamide (DCDA), iron acetate, and metal organic frameworks (MOF), MIL-100(Fe), viaa high temperature method were prepared as novel supports for the development of Pt catalysts. The large size of N-GTs provides a better platform than common carbon nanotubes (with diameters usually less than 30 nm), thus favorably anchoring the deposited metal nanoparticles. While the as-prepared N-GTs were found to show good intrinsic ORR activity and stability in acidic electrolytes, by modification with well-dispersed Pt nanoparticles, the unique Pt/N-GT hybrid materials were found to provide excellent performance that is superior to commercial Pt/C catalyst. The observed enhancements are likely due to the complementary ORR active sites on N-GTs, their highly graphitized structure formed during the high-temeprature heat treatment process, and favourable interactions between the nitrogen dopant species and Pt nanoparticles.
1. Y. H. Bing, H. S. Liu, L. Zhang, D. Ghosh and J. J. Zhang, Chem Soc Rev, 39, 2184 (2010).
2. H. Nakano, W. Z. Li, L. B. Xu, Z. W. Chen, M. Waje, S. Kuwabata and Y. S. Yan, Electrochemistry, 75, 705 (2007).
3. G. Wu, Y.-S. Chen and B.-Q. Xu, Electrochem. Commun., 7, 1237 (2005).
4. G. Wu, D. Li, C. Dai, D. Wang and N. Li, Langmuir, 24, 3566 (2008).
5. G. Wu, C. Dai, D. Wang, D. Li and N. Li, Journal of Materials Chemistry, 20, 3059 (2010).
6. C. Z. Zhu and S. J. Dong, Nanoscale, 5, 1753 (2013).
7. G. Wu, N. H. Mack, W. Gao, S. Ma, R. Zhong, J. Han, J. K. Baldwin and P. Zelenay, ACS Nano, 6, 9764 (2012).
8. G. Wu, K. L. More, P. Xu, H.-L. Wang, M. Ferrandon, A. J. Kropf, D. J. Myers, S. Ma, C. M. Johnston and P. Zelenay, Chem. Commun., 49, 3291 (2013).
9. G. Wu, M. Nelson, S. Ma, H. Meng, G. Cui and P. K. Shen, Carbon, 49, 3972 (2011).
10. G. Wu, M. A. Nelson, N. H. Mack, S. Ma, P. Sekhar, F. H. Garzon and P. Zelenay, Chem. Commun., 46, 7489 (2010).
11. Q. Li, G. Wu, D. A. Cullen, K. L. More, N. H. Mack, H. T. Chung and P. Zelenay, ACS Catalysis, 4, 3193 (2014).