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Research Article

Accelerated oxygen reduction on Fe/N/C catalysts derived from precisely-designed ZIF precursors

Ergui Luo1,2, Chen Wang1, Yang Li1,2, Xian Wang1,2, Liyuan Gong1,2, Tuo Zhao1,2, Zhao Jin1, Junjie Ge1,2( ), Changpeng Liu1,2( ), Wei Xing1,2,3( )
Laboratory of Advanced Power Sources, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
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Abstract

Fe/N/C material is the most competitive alternative to precious-metal catalysts for oxygen reduction. In view of the present consensus on active centers, further effort is directed at maximizing the density of single Fe atoms. Here, the imperfections in commonly used doping strategy of Fe for the synthesis of zeolitic imidazolateframework (ZIF)-derived Fe/N/C catalysts are revealed. More importantly, a strikingly improved catalyst is obtained by a 'second pyrolysis’ method and delivers a half-wave potential of 0.825 V (vs. RHE) in acidic media. The strong confinement effect of carbonaceous host accounts for the formation of dense single-atom sites and thus the high activity. Our findings will potentially facilitate future improvement of M/N/C catalysts.

Keywords

electrocatalysisfuel cellsoxygen reductionFe/N/Csingle-atom catalysts

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References

[1]
Steele, B. C.; Heinzel, A. Materials for fuel-cell technologies. Nature 2001, 414, 345-352.
Crossref Google Scholar
[2]
Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 2012, 486, 43-51.
Crossref Google Scholar
[3]
Tian, J.; Morozan, A.; Sougrati, M. T.; Lefevre, M.; Chenitz, R.; Dodelet, J. P.; Jones, D.; Jaouen, F. Optimized synthesis of Fe/N/C cathode catalysts for PEM fuel cells: A matter of iron-ligand coordination strength. Angew. Chem., Int. Ed. 2013, 52, 6867-6870.
Crossref Google Scholar
[4]
Xia, W.; Mahmood, A.; Liang, Z. B.; Zou, R. Q.; Guo, S. J. Earth-abundant nanomaterials for oxygen reduction. Angew. Chem., Int. Ed. 2016, 55, 2650-2676.
Crossref Google Scholar
[5]
Chung, H. T.; Cullen, D. A.; Higgins, D.; Sneed, B. T.; Holby, E. F.; More, K. L.; Zelenay, P. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 2017, 357, 479-484.
Crossref Google Scholar
[6]
Martinez, U.; Komini Babu, S.; Holby, E. F.; Chung, H. T.; Yin, X.; Zelenay, P. Progress in the development of Fe-based PGM-free electrocatalysts for the oxygen reduction reaction. Adv. Mater. 2019, 31, 1806545.
Crossref Google Scholar
[7]
Wang, X. X.; Swihart, M. T.; Wu, G. Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation. Nat. Catal. 2019, 2, 578-589.
Crossref Google Scholar
[8]
Chung, H. T.; Won, J. H.; Zelenay, P. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction. Nat. Commun. 2013, 4, 1922.
Crossref Google Scholar
[9]
Wu, G.; More, K. L.; Johnston, C. M.; Zelenay, P. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 2011, 332, 443-447.
Crossref Google Scholar
[10]
Singh, K.; Razmjooei, F.; Yu, J. S. Active sites and factors influencing them for efficient oxygen reduction reaction in metal-N coordinated pyrolyzed and non-pyrolyzed catalysts: A review. J. Mater. Chem. A 2017, 5, 20095-20119.
Crossref Google Scholar
[11]
Jasinski, R. A new fuel cell cathode catalyst. Nature 1964, 201, 1212-1213.
Crossref Google Scholar
[12]
van den Brink, F.; Barendrecht, E.; Visscher, W. The cathodic reduction of oxygen: A review with emphasis on macrocyclic organic metal complexes as electrocatalysts. Recl. Trav. Chim. Pays Bas 1980, 99, 253-262.
Crossref Google Scholar
[13]
Zagal, J. H. Metallophthalocyanines as catalysts in electrochemical reactions. Coord. Chem. Rev. 1992, 119, 89-136.
Crossref Google Scholar
[14]
Vasudevan, P.; Santosh; Mann, N.; Tyagi, S. Transition metal complexes of porphyrins and phthalocyanines as electrocatalysts for dioxygen reduction. Transition Met. Chem. 1990, 15, 81-90.
Crossref Google Scholar
[15]
Li, Z. P.; Liu, B. H. The use of macrocyclic compounds as electrocatalysts in fuel cells. J. Appl. Electrochem. 2010, 40, 475-483.
Crossref Google Scholar
[16]
Bouwkamp-Wijnoltz, A. L.; Visscher, W.; van Veen, J. A. R.; Boellaard, E.; van der Kraan, A. M.; Tang, S. C. On active-site heterogeneity in pyrolyzed carbon-supported iron porphyrin catalysts for the electrochemical reduction of oxygen: An in situ Mössbauer study. J. Phys. Chem. B 2002, 106, 12993-13001.
Crossref Google Scholar
[17]
Lefèvre, M.; Proietti, E.; Jaouen, F.; Dodelet, J. P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 2009, 324, 71-74.
Crossref Google Scholar
[18]
Ramaswamy, N.; Tylus, U.; Jia, Q. Y.; Mukerjee, S. Activity descriptor identification for oxygen reduction on nonprecious electrocatalysts: Linking surface science to coordination chemistry. J. Am. Chem. Soc. 2013, 135, 15443-15449.
Crossref Google Scholar
[19]
Liang, W.; Chen, J. X.; Liu, Y. W.; Chen, S. L. Density-functional-theory calculation analysis of active sites for four-electron reduction of O2 on Fe/N-doped graphene. ACS Catal. 2014, 4, 4170-4177.
Crossref Google Scholar
[20]
Zitolo, A.; Goellner, V.; Armel, V.; Sougrati, M. T.; Mineva, T.; Stievano, L.; Fonda, E.; Jaouen, F. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 2015, 14, 937-942.
Crossref Google Scholar
[21]
Chen, Y. J.; Ji, S. F.; Wang, Y. G.; Dong, J. C; Chen, W. X.; Li, Z.; Shen, R. A.; Zheng, L. R.; Zhuang, Z. B.; Wang, D. S. et al. Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2017, 56, 6937-6941.
Crossref Google Scholar
[22]
Li, J. K.; Ghoshal, S.; Liang, W. T.; Sougrati, M. T.; Jaouen, F.; Halevi, B.; McKinney, S.; McCool, G.; Ma, C. R.; Yuan, X. X. et al. Structural and mechanistic basis for the high activity of Fe-N-C catalysts toward oxygen reduction. Energy Environ. Sci. 2016, 9, 2418-2432.
Crossref Google Scholar
[23]
Jia, Q. Y.; Ramaswamy, N.; Hafiz, H.; Tylus, U.; Strickland, K.; Wu, G.; Barbiellini, B.; Bansil, A.; Holby, E. F.; Zelenay, P. et al. Experimental observation of redox-induced Fe-N switching behavior as a determinant role for oxygen reduction activity. ACS Nano 2015, 9, 12496-12505.
Crossref Google Scholar
[24]
Mun, Y.; Lee, S.; Kim, K.; Kim, S.; Lee, S.; Han, J. W.; Lee, J. Versatile strategy for tuning ORR activity of a single Fe-N4 site by controlling electron-withdrawing/donating properties of a carbon plane. J. Am. Chem. Soc. 2019, 141, 6254-6262.
Crossref Google Scholar
[25]
Wan, X.; Liu, X. F.; Li, Y. C.; Yu, R. H.; Zheng, L. R.; Yan, W. S.; Wang, H.; Xu, M.; Shui, J. L. Fe-N-C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells. Nat. Catal. 2019, 2, 259-268.
Crossref Google Scholar
[26]
Gewirth, A. A.; Varnell, J. A.; DiAscro, A. M. Nonprecious metal catalysts for oxygen reduction in heterogeneous aqueous systems. Chem. Rev. 2018, 118, 2313-2339.
Crossref Google Scholar
[27]
Nie, Y.; Wei, Z. D. Electronic and physical property manipulations: Recent achievements towards heterogeneous carbon-based catalysts for oxygen reduction reaction. ChemCatChem 2019, 11, 5885-5897.
Crossref Google Scholar
[28]
Yin, P. Q.; Yao, T.; Wu, Y.; Zheng, L. R.; Lin, Y.; Liu, W.; Ju, H. X.; Zhu, J. F.; Hong, X.; Deng, Z. X. et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew. Chem., Int. Ed. 2016, 55, 10800-10805.
Crossref Google Scholar
[29]
Wang, J.; Huang, Z. Q.; Liu, W.; Chang, C. R.; Tang, H. L.; Li, Z. J.; Chen, W. X.; Jia, C. J.; Yao, T.; Wei, S. Q. et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc. 2017, 139, 17281-17284.
Crossref Google Scholar
[30]
Xiao, M. L.; Zhu, J. J.; Ma, L.; Jin, Z.; Ge, J. J.; Deng, X.; Hou, Y.; He, Q. G.; Li, J. K.; Jia, Q. Y. et al. Microporous framework induced synthesis of single-atom dispersed Fe-N-C acidic ORR catalyst and its in situ reduced Fe-N4 active site identification revealed by X-ray absorption spectroscopy. ACS Catal. 2018, 8, 2824-2832.
Crossref Google Scholar
[31]
Sun, T. T.; Xu, L. B.; Wang, D. S.; Li, Y. D. Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res. 2019, 12, 2067-2080.
Crossref Google Scholar
[32]
Wang, X. J.; Zhang, H. G.; Lin, H. H.; Gupta, S.; Wang, C.; Tao, Z. X.; Fu, H.; Wang, T.; Zheng, J.; Wu, G. et al. Directly converting Fe-doped metal-organic frameworks into highly active and stable Fe-N-C catalysts for oxygen reduction in acid. Nano Energy 2016, 25, 110-119.
Crossref Google Scholar
[33]
Armel, V.; Hindocha, S.; Salles, F.; Bennett, S.; Jones, D.; Jaouen, F. Structural descriptors of zeolitic-imidazolate frameworks are keys to the activity of Fe-N-C catalysts. J. Am. Chem. Soc. 2017, 139, 453-464.
Crossref Google Scholar
[34]
Ye, Y. F.; Cai, F.; Li, H. B.; Wu, H. H.; Wang, G. X.; Li, Y. S.; Miao, S.; Xie, S. H.; Si, R.; Wang, J. et al. Surface functionalization of ZIF-8 with ammonium ferric citrate toward high exposure of Fe-N active sites for efficient oxygen and carbon dioxide electroreduction. Nano Energy 2017, 38, 281-289.
Crossref Google Scholar
[35]
Lai, Q. X.; Zheng, L. R.; Liang, Y. Y.; He, J. P.; Zhao, J. X.; Chen, J. H. Metal-organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-Nx sites for advanced oxygen reduction in acid media. ACS Catal. 2017, 7, 1655-1663.
Crossref Google Scholar
[36]
Jin, H. H.; Zhou, H.; He, D. P.; Wang, Z. H.; Wu, Q. L.; Liang, Q. R.; Liu, S. L.; Mu, S. C. MOF-derived 3D Fe-N-S co-doped carbon matrix/nanotube nanocomposites with advanced oxygen reduction activity and stability in both acidic and alkaline media. Appl. Catal. B: Environ. 2019, 250, 143-149.
Crossref Google Scholar
[37]
Chen, X. D.; Wang, N.; Shen, K.; Xie, Y. K.; Tan, Y. P.; Li, Y. W. MOF-derived isolated Fe atoms implanted in N-doped 3D hierarchical carbon as an efficient ORR electrocatalyst in both alkaline and acidic media. ACS Appl. Mater. Interfaces 2019, 11, 25976-25985.
Crossref Google Scholar
[38]
Liu, X.; Liu, H.; Chen, C.; Zou, L. L.; Li, Y.; Zhang, Q.; Yang, B.; Zou, Z. Q.; Yang, H. Fe2N nanoparticles boosting FeNx moieties for highly efficient oxygen reduction reaction in Fe-N-C porous catalyst. Nano Res. 2019, 12, 1651-1657.
Crossref Google Scholar
[39]
Li, F.; Ding, X. B.; Cao, Q. C.; Qin, Y. H.; Wang, C. W. A ZIF-derived hierarchically porous Fe-Zn-N-C catalyst synthesized via a two-stage pyrolysis for the highly efficient oxygen reduction reaction in both acidic and alkaline media. Chem. Commun. 2019, 55, 13979-13982.
Crossref Google Scholar
[40]
Qiao, M. F.; Wang, Y.; Wang, Q.; Hu, G. Z.; Mamat, X.; Zhang, S. S.; Wang, S. Y. Hierarchically ordered porous carbon with atomically dispersed FeN4 for ultra-efficient oxygen reduction reaction in proton-exchange membrane fuel cells. Angew. Chem., Int. Ed. 2020, 59, 2688-2694.
Crossref Google Scholar
[41]
Zhang, H. G.; Chung, H. T.; Cullen, D. A.; Wagner, S.; Kramm, U. I.; More, K. L.; Zelenay, P.; Wu, G. High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites. Energy Environ. Sci. 2019, 12, 2548-2558.
Crossref Google Scholar
[42]
Deng, Y. J.; Chi, B.; Li, J.; Wang, G. H.; Zheng, L.; Shi, X. D.; Cui, Z. M.; Du, L.; Liao, S. J.; Zang, K. T. et al. Atomic Fe-doped MOF-derived carbon polyhedrons with high active-center density and ultra-high performance toward PEM fuel cells. Adv. Energy Mater. 2019, 9, 1802856.
Crossref Google Scholar
[43]
Gao, L. Q.; Xiao, M. L.; Jin, Z.; Liu, C. P.; Zhu, J. B.; Ge, J. J.; Xing, W. Correlating Fe source with Fe-N-C active site construction: Guidance for rational design of high-performance ORR catalyst. J. Energy Chem. 2018, 27, 1668-1673.
Crossref Google Scholar
[44]
Garsany, Y.; Baturina, O. A.; Swider-Lyons, K. E.; Kocha, S. S. Experimental methods for quantifying the activity of platinum electrocatalysts for the oxygen reduction reaction. Anal. Chem. 2010, 82, 6321-6328.
Crossref Google Scholar
[45]
Zhu, J. B.; Xiao, M. L.; Liu, C. P.; Ge, J. J.; St-Pierre, J.; Xing, W. Growth mechanism and active site probing of Fe3C@N-doped carbon nanotubes/C catalysts: Guidance for building highly efficient oxygen reduction electrocatalysts. J. Mater. Chem. A 2015, 3, 21451-21459.
Crossref Google Scholar
[46]
Jaouen, F.; Lefèvre, M.; Dodelet, J. P.; Cai, M. Heat-treated Fe/N/C catalysts for O2 electroreduction: are active sites hosted in micropores? J. Phys. Chem. B 2006, 110, 5553-5558.
Crossref Google Scholar
[47]
Westre, T. E.; Kennepohl, P.; DeWitt, J. G.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. A multiplet analysis of Fe K-edge 1s → 3d pre-edge features of iron complexes. J. Am. Chem. Soc. 1997, 119, 6297-6314.
Crossref Google Scholar
Nano Research
Volume 13 Issue 9,
September 2020
Pages 2420-2426
DOI: 10.1007/s12274-020-2868-8
Cite this article:
Luo E, Wang C, Li Y, et al. Accelerated oxygen reduction on Fe/N/C catalysts derived from precisely-designed ZIF precursors. Nano Research, 2020, 13(9): 2420-2426. https://doi.org/10.1007/s12274-020-2868-8
Topics:
Electrolytic reduction Oxygen

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Received: 11 January 2020
Revised: 20 April 2020
Accepted: 10 May 2020
Published: 16 June 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
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