Towards a comprehensive understanding of FeCo coated with N-doped carbon as a stable bi-functional catalyst in acidic media
Source abstract
Abstract
The identification and development of efficient catalysts made of non-precious materials for oxygen reduction reaction (ORR) are essential for the successful operation of a wide range of energy devices. This study provides evidence that earth-abundant nanoparticles of transition metals encapsulated in a nitrogen-doped carbon shell (M@N–C, M=Fe, Co, Ni, Cu or Fe alloys) are promising catalysts in acidic solutions. By density functional theory calculations and experimental validations, we quantitatively propose a method of tuning the ORR activity of M@N–C by controlling the nitrogen-doping level, the thickness of the N–C shells and binary alloying. FeCo@N–C/KB was chosen as the best ORR catalyst because of its onset and half-wave potentials of 0.92 and 0.74 V vs a reversible hydrogen electrode (RHE), respectively, and its excellent durability. Furthermore, FeCo@N–C/KB possesses a high activity for the hydrogen evolution reaction (HER; −0.24 V vs RHE at −10 mA cm−2), thus demonstrating that it is a good bi-functional ORR and HER catalyst in acidic media. Transition metals encapsulated in a nitrogen-doped carbon shell show high activity as bi-functional catalysts in acidic solutions. Platinum catalysts currently used for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) — both crucial processes in fuel-cells — are expensive and often unstable in acidic media. Now, Takeo Ohsaka and colleagues in Japan and Korea investigate the performance of transition metals and their alloys as the core component of core-shell catalysts for ORR and HER from both theoretical and experimental perspectives. Iron-core catalysts are more active in ORR than copper, cobalt or nickel equivalents. Iron-cobalt (FeCo) alloys coated in the nitrogen-doped carbon shell are highly active for ORR and HER and show high durability in acidic solutions. In general, a thin carbon shell and the presence of graphitic nitrogen sites are advantageous for high catalytic performance. FeCo@N—C nanoparticle as a bi-functional catalyst in both oxygen reduction reaction and hydrogen evolution reaction.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Electrocatalysts for Energy Conversion · Fuel Cells and Related Materials · Advanced battery technologies research
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (54)
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1. Shao, M. Electrocatalysis in Fuel Cells, (Springer, 2013).10.1007/978-1-4471-4911-8 ↗
2. Doyle, M., Rajendran, G., Vielstich, W., Gasteiger, H. A. & Lamm, A. Handbook of Fuel Cells Fundamentals, Technology and Applications Vol. 3, (Wiley, 2003).
3. Seo, M. H., Park, H. W., Lee, D. U., Park, M. G. & Chen, Z. Design of highly active perovskite oxides for oxygen evolution reaction by combining experimental and ab initio studies. ACS Catal. 5, 4337–4344 (2015).10.1021/acscatal.5b00114 ↗
4. Strasser, P., Koh, S., Anniyev, T., Greeley, J., More, K., Yu, C., Liu, Z., Kaya, S., Nordlund, D., Ogasawara, H., Toney, M. F. & Nilsson, A. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2, 454–460 (2010).10.1038/nchem.623 ↗
5. Stamenkovic, V. R., Mun, B. S., Arenz, M., Mayrhofer, K. J., Lucas, C. A., Wang, G., Ross, P. N. & Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 6, 241–247 (2007).10.1038/nmat1840 ↗
6. Seo, M. H., Choi, S. M., Lim, E. J., Kwon, I. H., Seo, J. K., Noh, S. H., Kim, W. B. & Han, B. Toward new fuel cell support materials: a theoretical and experimental study of nitrogen‐doped graphene. ChemSusChem 7, 2609–2620 (2014).10.1002/cssc.201402258 ↗
7. Liang, Y., Li, Y., Wang, H., Zhou, J., Wang, J., Regier, T. & Dai, H. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 10, 780–786 (2011).10.1038/nmat3087 ↗
8. Wu, G., More, K. L., Johnston, C. M. & Zelenay, P. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332, 443–447 (2011).10.1126/science.1200832 ↗
9. Gong, K., Du, F., Xia, Z., Durstock, M. & Dai, L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760–764 (2009).10.1126/science.1168049 ↗
10. Geng, D., Chen, Y., Chen, Y., Li, Y., Li, R., Sun, X., Ye, S. & Knights, S. High oxygen-reduction activity and durability of nitrogen-doped graphene. Energy Environ. Sci. 4, 760–764 (2011).10.1039/c0ee00326c ↗
11. Yan, X.-H. & Xu, B.-Q. Mesoporous carbon material co-doped with nitrogen and iron (Fe–N–C): high-performance cathode catalyst for oxygen reduction reaction in alkaline electrolyte. J. Mater. Chem. A 2, 8617–8622 (2014).10.1039/C3TA15300B ↗
12. Wang, M.-Q., Yang, W.-H., Wang, H.-H., Chen, C., Zhou, Z.-Y. & Sun, S.-G. Pyrolyzed Fe–N–C composite as an efficient non-precious metal catalyst for oxygen reduction reaction in acidic medium. ACS Catal. 4, 3928–3936 (2014).10.1021/cs500673k ↗
13. Menezes, P. W., Indra, A., Gonzaález-Flores, D., Sahraie, N. R., Zaharieva, I., Schwarze, M., Strasser, P., Dau, H. & Driess, M. High-performance oxygen redox catalysis with multifunctional cobalt oxide nanochains: morphology-dependent activity. ACS Catal. 5, 2017–2027 (2015).10.1021/cs501724v ↗
14. Liang, Y., Wang, H., Zhou, J., Li, Y., Wang, J., Regier, T. & Dai, H. Covalent hybrid of spinel manganese–cobalt oxide and graphene as advanced oxygen reduction electrocatalysts. J. Am. Chem. Soc. 134, 3517–3523 (2012).10.1021/ja210924t ↗
15. Artyushkova, K., Kiefer, B., Halevi, B., Knop-Gericke, A., Schlogl, R. & Atanassov, P. Density functional theory calculations of XPS binding energy shift for nitrogen-containing graphene-like structures. Chem. Commun. 49, 2539–2541 (2013).10.1039/c3cc40324f ↗
16. Kattel, S., Atanassov, P. & Kiefer, B. Catalytic activity of Co-Nx/C electrocatalysts for oxygen reduction reaction: a density functional theory study. Phys. Chem. Chem. Phys. 15, 148–153 (2013).10.1039/C2CP42609A ↗
17. Kattel, S. & Wang, G. Reaction pathway for oxygen reduction on FeN4 embedded graphene. J. Phys. Chem. Lett. 5, 452–456 (2014).10.1021/jz402717r ↗
18. Orellana, W. Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: a theoretical study. Chem. Phys. Lett. 541, 81–84 (2012).10.1016/j.cplett.2012.05.048 ↗
19. Deng, D., Yu, L., Chen, X., Wang, G., Jin, L., Pan, X., Deng, J., Sun, G. & Bao, X. Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. Angew. Chem. Int. Ed. 52, 371–375 (2013).10.1002/anie.201204958 ↗
20. Chung, H. T., Won, J. H. & Zelenay, P. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction. Nat. Commun. 4, 1922 (2013).10.1038/ncomms2944 ↗
21. Hou, Y., Huang, T., Wen, Z., Mao, S., Cui, S. & Chen, J. Metal− organic framework‐derived nitrogen‐doped core‐shell‐structured porous Fe/Fe3C@ C nanoboxes supported on graphene sheets for efficient oxygen reduction reactions. Adv. Energy Mater. 4, 1400337 (2014).10.1002/aenm.201400337 ↗
22. Hu, Y., Jensen, J. O., Zhang, W., Cleemann, L. N., Xing, W., Bjerrum, N. J. & Li, Q. Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts. Angew. Chem. Int. Ed. 53, 3675–3679 (2014).10.1002/anie.201400358 ↗
23. Prasai, D., Tuberquia, J. C., Harl, R. R., Jennings, G. K. & Bolotin, K. I. Graphene: corrosion-inhibiting coating. ACS Nano 6, 1102–1108 (2012).10.1021/nn203507y ↗
24. Noh, S. H., Kwak, D. H., Seo, M. H., Ohsaka, T. & Han, B. First principles study of oxygen reduction reaction mechanisms on N-doped graphene with a transition metal support. Electrochim. Acta 140, 225–231 (2014).10.1016/j.electacta.2014.03.076 ↗
25. Noh, S. H., Seo, M. H., Ye, X., Makinose, Y., Okajima, T., Matsushita, N., Han, B. & Ohsaka, T. Design of an active and durable catalyst for oxygen reduction reactions using encapsulated Cu with N-doped carbon shells (Cu@N-C) activated by CO2 treatment. J. Mater. Chem. A 3, 22031–22034 (2015).10.1039/C5TA06108C ↗
26. Chen, T. C., Zhao, M. Q., Zhang, Q., Tian, G. L., Huang, J. Q. & Wei, F. In situ monitoring the role of working metal catalyst nanoparticles for ultrahigh purity single‐walled carbon nanotubes. Adv. Funct. Mater. 23, 5066–5073 (2013).10.1002/adfm.201300614 ↗
27. Deng, J., Yu, L., Deng, D., Chen, X., Yang, F. & Bao, X. Highly active reduction of oxygen on a FeCo alloy catalyst encapsulated in pod-like carbon nanotubes with fewer walls. J. Mater. Chem. A 1, 14868–14873 (2013).10.1039/c3ta13759g ↗
28. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).10.1103/PhysRevB.54.11169 ↗
29. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994).10.1103/PhysRevB.50.17953 ↗
30. Tan, T. L., Wang, L.-L., Johnson, D. D. & Bai, K. A comprehensive search for stable Pt–Pd nanoalloy configurations and their use as tunable catalysts. Nano Lett. 12, 4875–4880 (2012).10.1021/nl302405k ↗
31. Zheng, Y., Jiao, Y., Zhu, Y., Li, L. H., Han, Y., Chen, Y., Du, A., Jaroniec, M. & Qiao, S. Z. Hydrogen evolution by a metal-free electrocatalyst. Nat. Commun. 5, 3783 (2014).10.1038/ncomms4783 ↗
32. Kumar, B., Asadi, M., Pisasale, D., Sinha-Ray, S., Rosen, B. A., Haasch, R., Abiade, J., Yarin, A. L. & Salehi-Khojin, A. Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction. Nat. Commun. 4, 2819 (2013).10.1038/ncomms3819 ↗
33. Chen, Z., Dodelet, J.-P. & Zhang, J. Non-Noble Metal Fuel Cell Catalysts, (John Wiley & Sons, 2014).10.1002/9783527664900 ↗
34. Kwak, D., Khetan, A., Noh, S., Pitsch, H. & Han, B. First principles study of morphology, doping level, and water solvation effects on the catalytic mechanism of nitrogen‐doped graphene in the oxygen reduction reaction. ChemCatChem 6, 2662–2670 (2014).10.1002/cctc.201402248 ↗
35. Lv, R., Li, Q., Botello-Méndez, A. R., Hayashi, T., Wang, B., Berkdemir, A., Hao, Q., Elías, A. L., Cruz-Silva, R. & Gutiérrez, H. R. Nitrogen-doped graphene: beyond single substitution and enhanced molecular sensing. Sci. Rep. 2, 586 (2012).10.1038/srep00586 ↗
36. Fujimoto, Y. & Saito, S. Formation, stabilities, and electronic properties of nitrogen defects in graphene. Phys. Rev. B 84, 245446 (2011).10.1103/PhysRevB.84.245446 ↗
37. Hammer, B. & Nørskov, J. K. Theoretical surface science and catalysis—calculations and concepts. Adv. Catal. 45, 71–129 (2000).10.1016/S0360-0564(02)45013-4 ↗
38. Nørskov, J. K., Rossmeisl, J., Logadottir, A., Lindqvist, L., Kitchin, J. R., Bligaard, T. & Jonsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).10.1021/jp047349j ↗
39. Greeley, J., Stephens, I., Bondarenko, A., Johansson, T. P., Hansen, H. A., Jaramillo, T., Rossmeisl, J., Chorkendorff, I. & Nørskov, J. K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 1, 552–556 (2009).10.1038/nchem.367 ↗
40. Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).10.1038/nchem.121 ↗
41. Stephens, I. E., Bondarenko, A. S., Grønbjerg, U., Rossmeisl, J. & Chorkendorff, I. Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. Energy Environ. Sci. 5, 6744–6762 (2012).10.1039/c2ee03590a ↗
42. Bligaard, T. & Nørskov, J. K. Ligand effects in heterogeneous catalysis and electrochemistry. Electrochim. Acta 52, 5512–5516 (2007).10.1016/j.electacta.2007.02.041 ↗
43. Kim, H., Lee, K., Woo, S. I. & Jung, Y. On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbons. Phys. Chem. Chem. Phys. 13, 17505–17510 (2011).10.1039/c1cp21665a ↗
44. Cui, X., Ren, P., Deng, D., Deng, J. & Bao, X. Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation. Energy Environ. Sci. 9, 123–129 (2016).10.1039/C5EE03316K ↗
45. Tavakkoli, M., Kallio, T., Reynaud, O., Nasibulin, A. G., Johans, C., Sainio, J., Jiang, H., Kauppinen, E. I. & Laasonen, K. Single-shell carbon-encapsulated iron nanoparticles: synthesis and high electrocatalytic activity for hydrogen evolution reaction. Angew. Chem. Int. Ed. 54, 4535–4538 (2015).10.1002/anie.201411450 ↗
46. Noh, S. H., Han, B. & Ohsaka, T. First-principles computational study of highly stable and active ternary PtCuNi nanocatalyst for oxygen reduction reaction. Nano Res 8, 3394–3403 (2015).10.1007/s12274-015-0839-2 ↗
47. Noh, S. H., Seo, M. H., Seo, J. K., Fischer, P. & Han, B. First principles computational study on the electrochemical stability of Pt–Co nanocatalysts. Nanoscale 5, 8625–8633 (2013).10.1039/c3nr02611f ↗
48. Nam, G., Park, J., Choi, M., Oh, P., Park, S., Kim, M. G., Park, N., Cho, J. & Lee, J.-S. Carbon-Coated Core–Shell Fe–Cu Nanoparticles as Highly Active and Durable Electrocatalysts for a Zn–Air Battery. ACS Nano 9, 6493–6501 (2015).10.1021/acsnano.5b02266 ↗
49. Ramírez-Caballero, G. E., Ma, Y., Callejas-Tovar, R. & Balbuena, P. B. Surface segregation and stability of core–shell alloy catalysts for oxygen reduction in acid medium. Phys. Chem. Chem. Phys. 12, 2209–2218 (2010).10.1039/b917899f ↗
50. Ma, Y. & Balbuena, P. B. Surface segregation in bimetallic Pt3M (M= Fe, Co, Ni) alloys with adsorbed oxygen. Surf. Sci. 603, 349–353 (2009).10.1016/j.susc.2008.11.036 ↗
51. Vitos, L., Ruban, A., Skriver, H. L. & Kollar, J. The surface energy of metals. Surf. Sci. 411, 186–202 (1998).10.1016/S0039-6028(98)00363-X ↗
52. Nørskov, J. K., Bligaard, T., Logadottir, A., Kitchin, J., Chen, J., Pandelov, S. & Stimming, U. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).10.1149/1.1856988 ↗
53. Deng, J., Ren, P., Deng, D., Yu, L., Yang, F. & Bao, X. Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction. Energy Environ. Sci. 7, 1919–1923 (2014).10.1039/C4EE00370E ↗
54. Deng, J., Ren, P., Deng, D. & Bao, X. Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction. Angew. Chem. Int. Ed. 54, 2100–2104 (2015).10.1002/anie.201409524 ↗