Corresponding Author

Zhi-qing ZOU(zouzq@sari.ac.cn);
Hui YANG(yangh@sari.ac.cn)


The development of non-precious metal catalysts for oxygen reduction reaction (ORR) is essential for large-scale application of proton exchange membrane fuel cells. Herein, we present the in situ formed Fe-N doped hollow carbon nanospheres linked by carbon nanotubes composite, synthesized by using ZIF-8 as sacrificed template to form polydopamine (PDA) hollow nanospheres, followed by complexing with FeCl3, high temperature heat-treatment and NH3-etching. ZIF-8 was gradually decomposed simultaneously with PDA coating due to the loss of Zn2+ grabbed by PDA. NH3 etching resulted in the improved surface area, while the reducibility of NH3 resulted in the formation of Fe4N nanoparticles, which benefits the ORR activity of the catalyst. The half-wave potential of the as-prepared of PDA-Fe/N/C-NH3 was 0.79 V, only 60 mV lower than that of commercial Pt/C. The stability and methanol tolerance of PDA-Fe/N/C-NH3 were even superior to that of commercial Pt/C, indicating the good potential of PDA-Fe/N/C-NH3 for the application of fuel cells.

Graphical Abstract


non-precious metal catalyst, oxygen reduction reaction, polydopamine, NH3-etching, carbon nanotubes/hollow nanospheres composite

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[1] Sharma S, Pollet B G. Support materials for PEMFC and DMFC electrocatalysts€”A review[J]. Journal of Power Sources, 2012, 208(Supplement C): 96-119.
[2] Song C J, Zhang J J. Electrocatalytic oxygen reduction reaction[M]. London: Springer, 2008: 89-134.
[3] Chen Z, Higgins D, Yu A, et al. A review on non-precious metal electrocatalysts for PEM fuel cells[J]. Energy & Environmental Science, 2011, 4(9): 3167-3192.
[4] Gasteiger H A, Kocha S S, Sompalli B, et al. Activity benchmarks for Pt, Pt-alloy and non-Pt oxygen reduction catalysts for PEMFCs[J]. Applied Catalysis B-Environmental, 2005, 56(1/2): 9-35.
[5] Wu G, More K L, Johnston C M, et al. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt[J]. Science, 2011, 332(6028): 443-447.
[6] Hu Y, Jensen J O, Zhang W, et al. Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts[J]. Angewandte Chemie International Edition, 2014, 53(14): 3675-3679.
[7] Peng H L, Mo Z Y, Liao S J, et al. High performance Fe- and N-doped carbon catalyst with graphene structure for oxygen reduction[J]. Scientific Reports, 2013, 3(1): 1765.
[8] Zhou D, Yang L P, Yu L H, et al. Fe/N/C hollow nanospheres by Fe(III)-dopamine complexation-assisted one-pot doping as nonprecious-metal electrocatalysts for oxygen reduction[J]. Nanoscale, 2015, 7(4): 1501-1509.
[9] Kitao T, Zhang Y Y, Kitagawa S, et al. Hybridization of MOFs and polymers[J]. Chemical Society Reviews, 2017, 46(11): 3108-3133.
[10] Liang H W, Wei W, Wu Z S, et al. Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction[J]. Journal of the American Chemical Society, 2013, 135(43): 16002-16005.
[11] Xing R H, Zhou T S, Zhou Y, et al. Creation of triple hierarchical micro-meso-macroporous N-doped carbon shells with hollow cores toward the electrocatalytic oxygen reduction reaction[J]. Nano-Micro Letters, 2018, 10(1): 3.
[12] Hu H, Han L, Yu M Z, et al. Metal-organic-framework-engaged formation of Co nanoparticle-embedded carbon@Co9S8 double-shelled nanocages for efficient oxygen reduction[J]. Energy & Environmental Science, 2016, 9(1): 107-111.
[13] Xia W, Qu C, Liang Z B, et al. High-performance energy storage and conversion materials derived from a single metal organic framework/graphene aerogel composite[J]. Nano Letters, 2017, 17(5): 2788-2795.
[14] Liu S H, Wang Z Y, Zhou S, et al. Metal-organic-framework-derived hybrid carbon nanocages as a bifunctional electrocatalyst for oxygen reduction and evolution[J]. Advanced Materials, 2017, 29(31): 1700874.
[15] Zhu C Z, Fu S F, Song J H, et al. Self-assembled Fe-N-doped carbon nanotube aerogels with single-atom catalyst feature as high-efficiency oxygen reduction electrocatalysts[J]. Small, 2017, 13(15): 1603407.
[16] Chen X Q, Yu L, Wang S H, et al. Highly active and stable single iron site confined in graphene nanosheets for oxygen reduction reaction[J]. Nano Energy, 2017, 32: 353-358.
[17] Liang H W, Wu Z Y, Chen L F, et al. Bacterial cellulose derived nitrogen-doped carbon nanofiber aerogel: An efficient metal-free oxygen reduction electrocatalyst for zinc-air battery[J]. Nano Energy, 2015, (11): 366-376.
[18] Zhang C, Wang Y C, An B, et al. Networking pyrolyzed zeolitic imidazolate frameworks by carbon nanotubes improves conductivity and enhances oxygen-reduction performance in polymer-electrolyte-membrane fuel cells[J]. Advanced Material, 2017, 29(4): 1604556.
[19] Guo Y, Yang H J, Zhou X, et al. Electrocatalytic reduction of CO2 to CO with 100% faradaic efficiency by using pyrolyzed zeolitic imidazolate frameworks supported on carbon nanotube networks[J]. Journal of Materials Chemistry A, 2017, 5(47): 24867-24873.
[20] Shultz M D, Reveles J U, Khanna S N, et al. Reactive nature of dopamine as a surface functionalization agent in iron oxide nanoparticles[J]. Journal of the American Chemical Society, 2007, 129(9): 2482-2487.
[21] Ye Z H, Wu S H, Zheng C X, et al. Self-etching of metal-organic framework templates during polydopamine coating: nonspherical polydopamine capsules and potential intracellular trafficking of metal ions[J]. Langmuir, 2017, 33(45): 12952-12959.
[22] Xiang S Y, Wang D D, Zhang K, et al. Chelation competition induced polymerization (CCIP): construction of integrated hollow polydopamine nanocontainers with tailorable functionalities[J]. Chemical Communications, 2016, 52(66): 10155-10158.
[23] Zhang Y K, Lin Y X, Jiang H L, et al. Well-defined cobalt catalyst with N-doped carbon layers enwrapping: the correlation between surface atomic structure and electrocatalytic property[J]. Small, 2018, 14(6): UNSP1702074.
[24] Shultz M D, Reveles J U, Khanna S N, et al. Reactive nature of dopamine as a surface functionalization agent in iron oxide nanoparticles[J]. Journal of the American Chemical Society, 2007, 129(9): 2482-2487.
[25] Rao C V, Cabrera C R, Ishikawa Y. In search of the active site in nitrogen-doped carbon nanotube electrodes for the oxygen reduction reaction[J]. Journal of Physical Chemistry Letters, 2010, 1(18): 2622-2627.
[26] Liang W, Chen J X, Liu Y W, et al. Density-functional-theory calculation analysis of active sites for four-electron reduction of O2 on Fe/N-doped graphene[J]. ACS Catalysis, 2014, 4(11): 4170-4177.
[27] Chen C(陈驰), Lai Y J(赖愉姣), Zhou Z Y(周志有), et al. Thermo-stability and active site structure of Fe/N/C electrocatalyst for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2017, 23(4): 400-408.
[28] Fan X H, Kong F T, Kong A G, et al. Covalent porphyrin framework-derived Fe2P@Fe4N-coupled nanoparticles embedded in N-doped carbons as efficient trifunctional electrocatalysts[J]. ACS Applied Materials & Interfaces, 2017, 9(38): 32840-32850.



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