Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Nitrogen-doped graphene (NG) was successfully synthesized by a novel, facile, and scalable bottom-up method. The annealed NG (NG-A) possessed high specific surface area and a hierarchical porous texture, and exhibited remarkably improved electrocatalytic activity in the oxygen reduction reaction in both alkaline and acidic media. Ab initio molecular dynamic simulations indicated that rapid H transfer and the thermodynamic stability of six-membered N structures promoted the transformation of N-containing species from pyrrolic to pyridinic at 600 ℃. In O2-staturated 0.1 M KOH solution, the half-wave potential (E1/2) of NG-A was only 62 mV lower than that of a commercial Pt/C catalyst, and the limiting current density of NG-A was 0.5 mA·cm–2 larger than that of Pt/C. Koutecky–Levich (K–L) plots and rotating ring-disk electrode measurement indicated a four-electron-transfer pathway in NG-A, which could be ascribed to its high content of pyridinic N.
Bonaccorso, F.; Colombo, L.; Yu, G. H.; Stoller, M.; Tozzini, V.; Ferrari, A. C.; Ruoff, R. S.; Pellegrini, V. Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage. Science 2015, 347, 1246501.
Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J. M. Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 2011, 11, 19–29.
Park, S.; Shao, Y. Y.; Liu, J.; Wang, Y. Oxygen electrocatalysts for water electrolyzers and reversible fuel cells: Status and perspective. Energy Environ. Sci. 2012, 5, 9331–9344.
Faber, M. S.; Jin, S. Earth-abundant inorganic electrocatalysts and their nanostructures for energy conversion applications. Energy Environ. Sci. 2014, 7, 3519–3542.
Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T. P.; Hansen, H. A.; Jaramillo, T. F.; Rossmeisl, J.; Chorkendorff, I.; Nørskov, J. K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 2009, 1, 552–556.
Lee, D. U.; Kim, B. J.; Chen, Z. W. One-pot synthesis of a mesoporous NiCo2O4 nanoplatelet and graphene hybrid and its oxygen reduction and evolution activities as an efficient bi-functional electrocatalyst. J. Mater. Chem. A 2013, 1, 4754–4762.
Ge, X. M.; Liu, Y. Y.; Goh, F. W. T.; Hor, T. S. A.; Zong, Y.; Xiao, P.; Zhang, Z.; Lim, S. H.; Li, B.; Wang, X. et al. Dual-phase spinel MnCo2O4 and spinel MnCo2O4/nanocarbon hybrids for electrocatalytic oxygen reduction and evolution. ACS Appl. Mater. Interfaces 2014, 6, 12684–12691.
Liu, Q.; Jin, J. T.; Zhang, J. Y. NiCo2S4@graphene as a bifunctional electrocatalyst for oxygen reduction and evolution reactions. ACS Appl. Mater. Interfaces 2013, 5, 5002–5008.
Ganesan, P.; Prabu, M.; Sanetuntikul, J.; Shanmugam, S. Cobalt sulfide nanoparticles grown on nitrogen and sulfur codoped graphene oxide: An efficient electrocatalyst for oxygen reduction and evolution reactions. ACS Catal. 2015, 5, 3625–3637.
Wang, X. W.; Sun, G. Z.; Routh, P.; Kim, D. -H.; Huang, W.; Chen, P. Heteroatom-doped graphene materials: Syntheses, properties and applications. Chem. Soc. Rev. 2014, 43, 7067–7098.
Xia, B. Y.; Yan, Y.; Wang, X.; Lou, X. W. Recent progress on graphene-based hybrid electrocatalysts. Mater. Horiz. 2014, 1, 379–399.
Wu, Z. -S.; Ren, W. C.; Gao, L. B.; Liu, B. L.; Zhao, J. P.; Cheng, H. -M. Efficient synthesis of graphene nanoribbons sonochemically cut from graphene sheets. Nano Res. 2010, 3, 16–22.
Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Origin of the electrocatalytic oxygen reduction activity of graphene-based catalysts: A roadmap to achieve the best performance. J. Am. Chem. Soc. 2014, 136, 4394–4403.
Wang, H. B.; Maiyalagan, T.; Wang, X. Review on recent progress in nitrogen-doped graphene: Synthesis, characterization, and its potential applications. ACS Catal. 2012, 2, 781–794.
Zheng, B.; Wang, J.; Wang, F. -B.; Xia, X. -H. Synthesis of nitrogen doped graphene with high electrocatalytic activity toward oxygen reduction reaction. Electrochem. Commun. 2013, 28, 24–26.
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.
Sheng, Z. -H.; Shao, L.; Chen, J. -J.; Bao, W. -J.; Wang, F. -B.; Xia, X. -H. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano 2011, 5, 4350–4358.
Lin, Z. Y.; Waller, G. H.; Liu, Y.; Liu, M. L.; Wong, C. P. 3D nitrogen-doped graphene prepared by pyrolysis of graphene oxide with polypyrrole for electrocatalysis of oxygen reduction reaction. Nano Energy 2013, 2, 241–248.
Favaro, M.; Ferrighi, L.; Fazio, G.; Colazzo, L.; Di Valentin, C.; Durante, C.; Sedona, F.; Gennaro, A.; Agnoli, S.; Granozzi, G. Single and multiple doping in graphene quantum dots: Unraveling the origin of selectivity in the oxygen reduction reaction. ACS Catal. 2015, 5, 129–144.
Ito, Y.; Qiu, H. J.; Fujita, T.; Tanabe, Y.; Tanigaki, K.; Chen, M. W. Bicontinuous nanoporous N-doped graphene for the oxygen reduction reaction. Adv. Mater. 2014, 26, 4145–4150.
Liu, Z. Y.; Zhang, G. X.; Lu, Z. Y.; Jin, X. Y.; Chang, Z.; Sun, X. M. One-step scalable preparation of N-doped nanoporous carbon as a high-performance electrocatalyst for the oxygen reduction reaction. Nano Res. 2013, 6, 293–301.
Xing, T.; Zheng, Y.; Li, L. H.; Cowie, B. C. C.; Gunzelmann, D.; Qiao, S. Z.; Huang, S. M.; Chen, Y. Observation of active sites for oxygen reduction reaction on nitrogen-doped multilayer graphene. ACS Nano 2014, 8, 6856–6862.
Lai, L. F.; Potts, J. R.; Zhan, D.; Wang, L.; Poh, C. K.; Tang, C. H.; Gong, H.; Shen, Z. X.; Lin, J. Y.; Ruoff, R. S. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ. Sci. 2012, 5, 7936–7942.
Subramanian, N. P.; Li, X. G.; Nallathambi, V.; Kumaraguru, S. P.; Colon-Mercado, H.; Wu, G.; Lee, J. -W.; Popov, B. N. Nitrogen-modified carbon-based catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells. J. Power Sources 2009, 188, 38–44.
Nosé, S. A molecular dynamics method for simulations in the canonical ensemble. Mol. Phys. 1984, 52, 255–268.
Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane- wave basis set. Comp. Mater. Sci. 1996, 6, 15–50.
Lin, T. Q.; Huang, F. Q.; Liang, J.; Wang, Y. X. A facile preparation route for boron-doped graphene, and its CdTe solar cell application. Energy Environ. Sci. 2011, 4, 862–865.
Deng, D. H.; Pan, X. L.; Yu, L.; Cui, Y.; Jiang, Y. P.; Qi, J.; Li, W. -X.; Fu, Q.; Ma, X. C.; Xue, Q. K. et al. Toward N- doped graphene via solvothermal synthesis. Chem. Mater. 2011, 23, 1188–1193.
Wei, D. C.; Liu, Y. Q.; Wang, Y.; Zhang, H. L.; Huang, L. P.; Yu, G. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett. 2009, 9, 1752–1758.
Lin, Z. Y.; Waller, G. H.; Liu, Y.; Liu, M. L.; Wong, C. P. Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions. Carbon 2013, 53, 130–136.
Yang, H. M.; Cui, X. J.; Deng, Y. Q.; Shi, F. Ionic liquid templated preparation of carbon aerogels based on resorcinol- formaldehyde: Properties and catalytic performance. J. Mater. Chem. 2012, 22, 21852–21856.
Hong, X.; Zhang, L. D.; Zhang, T. C.; Qi, F. An experimental and theoretical study of pyrrole pyrolysis with tunable synchrotron VUV photoionization and molecular-beam mass spectrometry. J. Phys. Chem. A 2009, 113, 5397–5405.
Ma, T. Y.; Dai, S.; Jaroniec, M.; Qiao, S. Z. Graphitic carbon nitride nanosheet–carbon nanotube three-dimensional porous composites as high-performance oxygen evolution electrocatalysts. Angew. Chem., Int. Ed. 2014, 53, 7281–7285.
Ferrari, A. C.; Meyer, J. C.; Scardaci, V.; Casiraghi, C.; Lazzeri, M.; Mauri, F.; Piscanec, S.; Jiang, D.; Novoselov, K. S.; Roth, S. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 2006, 97, 187401.
Lin, Z. Y.; Waller, G.; Liu, Y.; Liu, M. L.; Wong, C. -P. Facile synthesis of nitrogen-doped graphene via pyrolysis of graphene oxide and urea, and its electrocatalytic activity toward the oxygen-reduction reaction. Adv. Energy Mater. 2012, 2, 884–888.
Shao, Y. Y.; Zhang, S.; Engelhard, M. H.; Li, G. S.; Shao, G. C.; Wang, Y.; Liu, J.; Aksay, I. A.; Lin, Y. H. Nitrogen- doped graphene and its electrochemical applications. J. Mater. Chem. 2010, 20, 7491–7496.
Ni, Z. H.; Wang, H. M.; Kasim, J.; Fan, H. M.; Yu, T.; Wu, Y. H.; Feng, Y. P.; Shen, Z. X. Graphene thickness determination using reflection and contrast spectroscopy. Nano Lett. 2007, 7, 2758–2763.
Saidi, W. A. Oxygen reduction electrocatalysis using N-doped graphene quantum-dots. J. Phys. Chem. Lett. 2013, 4, 4160–4165.
Bao, X. G.; Nie, X. W.; von Deak, D.; Biddinger, E. J.; Luo, W. J.; Asthagiri, A.; Ozkan, U. S.; Hadad, C. M. A first- principles study of the role of quaternary-N doping on the oxygen reduction reaction activity and selectivity of graphene edge sites. Top Catal. 2013, 56, 1623–1633.
Pels, J. R.; Kapteijn, F.; Moulijn, J. A.; Zhu, Q.; Thomas, K. M. Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis. Carbon 1995, 33, 1641–1653.
Jeon, I. -Y.; Choi, H. -J.; Choi, M.; Seo, J. -M.; Jung, S. -M.; Kim, M. -J.; Zhang, S.; Zhang, L. P.; Xia, Z. H.; Dai, L. M. et al. Facile, scalable synthesis of edge-halogenated graphene nanoplatelets as efficient metal-free eletrocatalysts for oxygen reduction reaction. Sci. Rep. 2013, 3, 1810.
Tian, G. -L.; Zhao, M. -Q.; Yu, D. S.; Kong, X. -Y.; Huang, J. -Q.; Zhang, Q.; Wei, F. Nitrogen-doped graphene/carbon nanotube hybrids: In situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction. Small 2014, 10, 2251–2259.
Zheng, Y.; Jiao, Y.; Ge, L.; Jaroniec, M.; Qiao, S. Z. Two- step boron and nitrogen doping in graphene for enhanced synergistic catalysis. Angew. Chem., Int. Ed. 2013, 52, 3110–3116.
Wang, J.; Wang, H. -S.; Wang, K.; Wang, F. -B.; Xia, X. -H. Ice crystals growth driving assembly of porous nitrogen-doped graphene for catalyzing oxygen reduction probed by in situ fluorescence electrochemistry. Sci. Rep. 2014, 4, 6723.
Hancock, C. A.; Ong, A. L.; Slater, P. R.; Varcoe, J. R. Development of CaMn1−xRuxO3−y (x = 0 and 0.15) oxygen reduction catalysts for use in low temperature electrochemical devices containing alkaline electrolytes: Ex situ testing using the rotating ring-disk electrode voltammetry method. J. Mater. Chem. A 2014, 2, 3047–3056.
Chen, P.; Wang, L. -K.; Wang, G.; Gao, M. -R.; Ge, J.; Yuan, W. -J.; Shen, Y. -H.; Xie, A. -J.; Yu, S. -H. Nitrogen-doped nanoporous carbon nanosheets derived from plant biomass: An efficient catalyst for oxygen reduction reaction. Energy Environ. Sci. 2014, 7, 4095–4103.
Yu, D. S.; Zhang, Q.; Dai, L. M. Highly efficient metal-free growth of nitrogen-doped single-walled carbon nanotubes on plasma-etched substrates for oxygen reduction. J. Am. Chem. Soc. 2010, 132, 15127–15129.
Zhang, L. P.; Xia, Z. H. Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J. Phys. Chem. C 2011, 115, 11170–11176.