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Research Article

Engineering adjacent Fe3C as proton-feeding centers to single Fe sites enabling boosted oxygen reduction reaction kinetics for robust Zn-air batteries at high current densities

Canhui Zhang, Xingkun Wang( ), Kai Song, Kaiyue Chen, Shuixing Dai, Huanlei Wang, Minghua Huang( )
School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China
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Graphical Abstract

In this work, we deliberately engineer the adjacent Fe3C nanoparticles to single Fe sites on the bubble-wrap-like porous N-doped carbon (Fe3C@FeSA-NC), in which the Fe3C nanoparticles could accelerate the water dissociation and serve as proton-feeding centers for boosting the oxygen reduction reaction (ORR) kinetics of single Fe sites. Benefiting from the synergistic effect of the Fe3C and single Fe sites, the Fe3C@FeSA-NC exhibits an excellent half-wave potential of 0.88 V, and enables the assembled Zn-air batteries with the high peak power density of 164.5 mW·cm−2 and long-term stability of over 200 h at high current densities of 50 mA·cm−2.

Abstract

Oxygen reduction reaction (ORR) plays an important role in the next-generation energy storage technologies, whereas it involves the sluggish and complicated proton-coupled electron transfer (PCET) steps that greatly limit the ORR kinetics. Therefore, it is urgent to construct an efficient catalyst that could simultaneously achieve the rapid oxygen-containing intermediates conversion and fast PCET process but remain challenging. Herein, the adjacent Fe3C nanoparticles coupling with single Fe sites on the bubble-wrap-like porous N-doped carbon (Fe3C@FeSA-NC) were deliberately constructed. Theoretical investigations reveal that the adjacent Fe3C nanoparticles speed up the water dissociation and serve as proton-feeding centers for boosting the ORR kinetics of single Fe sites. Benefiting from the synergistic effect of the Fe3C and single Fe sites, the Fe3C@FeSA-NC affords an excellent half-wave potential of 0.88 V, and enables the assembled Zn-air batteries with the high peak power density of 164.5 mW·cm−2 and long-term stability of over 200 h at high current densities at 50 mA·cm−2. This work clarifies the mechanism for improving ORR kinetics of single atomic sites by engineering the adjacent proton-feeding centers, shedding light on the rational design of cost-effective electrocatalysts for energy conversion and storage technologies.

Keywords

oxygen reduction reactiondischarge stabilitywater dissociationproton-coupled electron transfer

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References

[1]

Qin, X.; Wang, Z.; Han, J. R.; Luo, Y. L.; Xie, F.; Cui, G.; Guo, X.; Sun, X. Fe-doped CoP nanosheet arrays: An efficient bifunctional catalyst for zinc-air batteries. Chem. Commun. 2018, 54, 7693–7696.
Crossref Google Scholar
[2]
Wu, J. B.; Su, J. W.; Wu, J.; Huang, L.; Li, Q.; Luo, Y. X.; Jin, H. R.; Zhou, J.; Zhai, T. Y.; Wang, D. S. et al. Scalable synthesis of 2D Mo2C and thickness-dependent hydrogen evolution on its basal plane and edges. Adv. Mater., in press, https://doi.org/10.1002/adma.202209954.
Crossref
[3]

Li, W. H.; Yang, J. R.; Wang, D. S. Long-range interactions in diatomic catalysts boosting electrocatalysis. Angew. Chem., Int. Ed. 2022, 134, e202213318.
Crossref Google Scholar
[4]

Zhang, E. H.; Tao, L.; An, J. K.; Zhang, J. W.; Meng, L. Z.; Zheng, X. B.; Wang, Y.; Li, N.; Du, S. X.; Zhang, J. T. et al. Engineering the local atomic environments of indium single-atom catalysts for efficient electrochemical production of hydrogen peroxide. Angew. Chem., Int. Ed. 2022, 61, e202117347.
Crossref Google Scholar
[5]

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.
Crossref Google Scholar
[6]

Zhu, X. F.; Hu, C. G.; Amal, R.; Dai, L. M.; Lu, X. Y. Heteroatom-doped carbon catalysts for zinc-air batteries: Progress, mechanism, and opportunities. Energy Environ. Sci. 2020, 13, 4536–4563.
Crossref Google Scholar
[7]

Cui, T. T.; Wang, Y. P.; Ye, T.; Wu, J.; Chen, Z. Q.; Li, J.; Lei, Y. P.; Wang, D. S.; Li, Y. D. Engineering dual single-atom sites on 2D ultrathin N-doped carbon nanosheets attaining ultra-low-temperature zinc-air battery. Angew. Chem., Int. Ed. 2022, 61, e202115219.
Crossref Google Scholar
[8]

Sun, M. Z.; Gong, S. Y.; Zhang, Y. X.; Niu, Z. Q. A perspective on the PGM-free metal-nitrogen-carbon catalysts for PEMFC. J. Energy Chem. 2022, 67, 250–254.
Crossref Google Scholar
[9]

Wang, Z.; Jin, X. Y.; Zhu, C.; Liu, Y. P.; Tan, H.; Ku, R. Q.; Zhang, Y. Q.; Zhou, L. J.; Liu, Z.; Hwang, S. J. et al. Atomically dispersed Co2-N6 and Fe-N4 costructures boost oxygen reduction reaction in both alkaline and acidic media. Adv. Mater. 2021, 33, 2104718.
Crossref Google Scholar
[10]

Han, A.; Wang, X. J.; Tang, K.; Zhang, Z. D.; Ye, C. L.; Kong, K. J.; Hu, H. B.; Zheng, L. R.; Jiang, P.; Zhao, C. X. et al. An adjacent atomic platinum site enables single-atom iron with high oxygen reduction reaction performance. Angew. Chem., Int. Ed. 2021, 60, 19262–19271.
Crossref Google Scholar
[11]

Cao, M. M.; Liu, Y. Y.; Sun, K.; Li, H.; Lin, X. Q.; Zhang, P. X.; Zhou, L. M.; Wang, A.; Mehdi, S.; Wu, X. L. et al. Coupling Fe3C nanoparticles and N-doping on wood-derived carbon to construct reversible cathode for Zn-air batteries. Small 2022, 18, 2202014.
Crossref Google Scholar
[12]

Shang, H. S.; Sun, W. M.; Sui, R.; Pei, J. L.; Zheng, L. R.; Dong, J. C.; Jiang, Z. L.; Zhou, D. N.; Zhuang, Z. B.; Chen, W. X. et al. Engineering isolated Mn-N2C2 atomic interface sites for efficient bifunctional oxygen reduction and evolution reaction. Nano Lett. 2020, 20, 5443–5450.
Crossref Google Scholar
[13]

Li, M.; Zhu, H. Y.; Yuan, Q.; Li, T. Y.; Wang, M. M.; Zhang, P.; Zhao, Y. L.; Qin, D. L.; Guo, W. Y.; Liu, B. et al. Proximity electronic effect of Ni/Co diatomic sites for synergistic promotion of electrocatalytic oxygen reduction and hydrogen evolution. Adv. Funct. Mater. 2023, 33, 2210867.
Crossref Google Scholar
[14]

Wu, J. B.; Xiong, L. K.; Zhao, B. T.; Liu, M. L.; Huang, L. Densely populated single atom catalysts. Small Methods 2020, 4, 1900540.
Crossref Google Scholar
[15]

Liu, Z. H.; Du, Y.; Yu, R. H.; Zheng, M. B.; Hu, R.; Wu, J. S.; Xia, Y. Y.; Zhuang, Z. C.; Wang, D. S. Tuning mass transport in electrocatalysis down to sub-5 nm through nanoscale grade separation. Angew. Chem., Int. Ed. 2023, 62, e202212653.
Crossref Google Scholar
[16]

Zhang, P. X.; Liu, Y. Y.; Wang, S. L.; Zhou, L. M.; Liu, T.; Sun, K.; Cao, H. Q.; Jiang, J. C.; Wu, X. L.; Li, B. J. Wood-derived monolithic catalysts with the ability of activating water molecules for oxygen electrocatalysis. Small 2022, 18, 2202725.
Crossref Google Scholar
[17]

Jiang, R.; Li, Q.; Zheng, X.; Wang, W. Z.; Wang, S. B.; Xu, Z. M.; Wu, J. B. Metal-organic framework-derived Co nanoparticles and single atoms as efficient electrocatalyst for pH universal hydrogen evolution reaction. Nano Res. 2022, 15, 7917–7924.
Crossref Google Scholar
[18]

Liu, S.; Cheng, H.; Xia, J.; Wang, C.; Gui, R. J.; Zhou, T. P.; Liu, H. F.; Peng, J.; Zhang, N.; Wang, W. J. et al. Surface microenvironment optimization-induced robust oxygen reduction for neutral zinc-air batteries. Nat. Sci. 2021, 1, e20210005.
Crossref Google Scholar
[19]

Chen, G. B.; Wang, T.; Liu, P.; Liao, Z. Q.; Zhong, H. X.; Wang, G.; Zhang, P. P.; Yu, M. H.; Zschech, E.; Chen, M. W. et al. Promoted oxygen reduction kinetics on nitrogen-doped hierarchically porous carbon by engineering proton-feeding centers. Energy Environ. Sci. 2020, 13, 2849–2855.
Crossref Google Scholar
[20]

Xiong, Y.; Li, H. C.; Liu, C. W.; Zheng, L. R.; Liu, C.; Wang, J. O.; Liu, S. J.; Han, Y. H.; Gu, L.; Qian, J. S. et al. Single-atom Fe catalysts for Fenton-like reactions: Roles of different N species. Adv. Mater. 2022, 34, 2110653.
Crossref Google Scholar
[21]

Zhu, P.; Xiong, X.; Wang, D. S. Regulations of active moiety in single atom catalysts for electrochemical hydrogen evolution reaction. Nano Res. 2022, 15, 5792–5815.
Crossref Google Scholar
[22]

Li, Z. J.; Ji, S. Q.; Xu, C.; Leng, L. P.; Liu, H. X.; Horton, J. H.; Du, L.; Gao, J. C.; He, C.; Qi, X. Y. et al. Engineering the electronic structure of single-atom iron sites with boosted oxygen bifunctional activity for zinc-air batteries. Adv. Mater. 2022, 2209644.
Crossref Google Scholar
[23]

Wu, J. B.; Zhou, H.; Li, Q.; Chen, M.; Wan, J.; Zhang, N.; Xiong, L. K.; Li, S.; Xia, B. Y.; Feng, G. et al. Densely populated isolated single Co-N site for efficient oxygen electrocatalysis. Adv. Energy Mater. 2019, 9, 1900149.
Crossref Google Scholar
[24]

Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2022, 1, 100013.
Crossref Google Scholar
[25]

Han, A. L.; Zhang, Z. D.; Yang, J. R.; Wang, D. S.; Li, Y. D. Carbon-supported single-atom catalysts for formic acid oxidation and oxygen reduction reactions. Small 2021, 17, 2004500.
Crossref Google Scholar
[26]

Feng, W. T.; Cui, Y. P.; Liu, W.; Wang, H. L.; Zhang, Y.; Du, Y. X.; Liu, S.; Wang, H. L.; Gao, X.; Wang, T. Q. Rigid-flexible coupling carbon skeleton and potassium-carbonate-dominated solid electrolyte interface achieving superior potassium-ion storage. ACS Nano 2020, 14, 4938–4949.
Crossref Google Scholar
[27]

Zhu, Z. J.; Yin, H. J.; Wang, Y.; Chuang, C. H.; Xing, L.; Dong, M. Y.; Lu, Y. R.; Casillas-Garcia, G.; Zheng, Y. L.; Chen, S. et al. Coexisting single-atomic Fe and Ni sites on hierarchically ordered porous carbon as a highly efficient ORR electrocatalyst. Adv. Mater. 2020, 32, 2004670.
Crossref Google Scholar
[28]

Yao, H. X.; Wang, X. K.; Li, K.; Li, C.; Zhang, C. H.; Zhou, J.; Cao, Z. W.; Wang, H. L.; Gu, M.; Huang, M. H. et al. Strong electronic coupling between ruthenium single atoms and ultrafine nanoclusters enables economical and effective hydrogen production. Appl. Catal. B: Environ. 2022, 312, 121378.
Crossref Google Scholar
[29]

Zhou, J. Q.; Qian, T.; Yang, T. Z.; Wang, M. F.; Guo, J.; Yan, C. L. Nanomeshes of highly crystalline nitrogen-doped carbon encapsulated Fe/Fe3C electrodes as ultrafast and stable anodes for Li-ion batteries. J. Mater. Chem. A 2015, 3, 15008–15014.
Crossref Google Scholar
[30]

Wei, X. Q.; Song, S. J.; Wu, N. N.; Luo, X.; Zheng, L. R.; Jiao, L.; Wang, H. J.; Fang, Q.; Hu, L. Y.; Gu, W. L. et al. Synergistically enhanced single-atomic site Fe by Fe3C@C for boosted oxygen reduction in neutral electrolyte. Nano Energy 2021, 84, 105840.
Crossref Google Scholar
[31]

Xu, C. L.; Guo, C. Z.; Liu, J. P.; Hu, B. H.; Dai, J. Y.; Wang, M.; Jin, R.; Luo, Z. L.; Li, H. L.; Chen, C. G. Accelerating the oxygen adsorption kinetics to regulate the oxygen reduction catalysis via Fe3C nanoparticles coupled with single Fe-N4 sites. Energy Storage Mater. 2022, 51, 149–158.
Crossref Google Scholar
[32]

Gao, L.; Zhang, L. L.; Yang, X. L. N,S-codoped porous carbon nanosheets decorated with Fe3C nanoparticles as high-performance anode materials for lithium ion hybrid supercapacitors. Rare Met. 2022, 41, 2517–2526.
Crossref Google Scholar
[33]

Yuan, S.; Cui, L. L.; Dou, Z. Y.; Ge, X.; He, X. Q.; Zhang, W.; Asefa, T. Nonprecious bimetallic sites coordinated on N-doped carbons with efficient and durable catalytic activity for oxygen reduction. Small 2020, 16, 2000742.
Crossref Google Scholar
[34]

Wang, X. K.; Zhou, X. K.; Li, C.; Yao, H. X.; Zhang, C. H.; Zhou, J.; Xu, R.; Chu, L.; Wang, H. L.; Gu, M. et al. Asymmetric Co-N3P1 trifunctional catalyst with tailored electronic structures enabling boosted activities and corrosion resistance in an uninterrupted seawater splitting system. Adv. Mater. 2022, 34, 2204021.
Crossref Google Scholar
[35]

Qiang, F. Q.; Feng, J. G.; Wang, H. L.; Yu, J. H.; Shi, J.; Huang, M. H.; Shi, Z. C.; Liu, S.; Li, P.; Dong, L. F. Oxygen engineering enables N-doped porous carbon nanofibers as oxygen reduction/evolution reaction electrocatalysts for flexible zinc-air batteries. ACS Catal. 2022, 12, 4002–4015.
Crossref Google Scholar
[36]

Zheng, X. B.; Yang, J. R.; Xu, Z. F.; Wang, Q. S.; Wu, J. B.; Zhang, E. H.; Dou, S. X.; Sun, W. P.; Wang, D. S.; Li, Y. D. Ru-Co pair sites catalyst boosts the energetics for the oxygen evolution reaction. Angew. Chem., Int. Ed. 2022, 134, e202205946.
Crossref Google Scholar
[37]

Xiao, M. L.; Chen, Y. T.; Zhu, J. B.; Zhang, H.; Zhao, X.; Gao, L. Q.; Wang, X.; Zhao, J.; Ge, J. J.; Jiang, Z. et al. Climbing the apex of the ORR volcano plot via binuclear site construction: Electronic and geometric engineering. J. Am. Chem. Soc. 2019, 141, 17763–17770.
Crossref Google Scholar
[38]

Zeng, Z. P.; Gan, L. Y.; Bin Yang, H.; Su, X. Z.; Gao, J. J.; Liu, W.; Matsumoto, H.; Gong, J.; Zhang, J. M.; Cai, W. Z. et al. Orbital coupling of hetero-diatomic nickel-iron site for bifunctional electrocatalysis of CO2 reduction and oxygen evolution. Nat. Commun. 2021, 12, 4088.
Crossref Google Scholar
[39]

Cai, S. C.; Cheng, Y. P.; Meng, Z. H.; Li, G. J.; Wu, J. B.; Kan, E. J.; Ouyang, B.; Zhang, H. N.; Tang, H. L. The design of single iron atoms dispersed with nitrogen coordination environment electrocatalyst for zinc-air battery. J. Power Sources 2022, 529, 231174.
Crossref Google Scholar
[40]

Zhao, S. N.; Li, J. K.; Wang, R.; Cai, J. M.; Zang, S. Q. Electronically and geometrically modified single-atom Fe sites by adjacent Fe nanoparticles for enhanced oxygen reduction. Adv. Mater. 2022, 34, 2107291.
Crossref Google Scholar
[41]

Dong, Y.; Wang, Y.; Tian, Z. Q.; Jiang, K. M.; Li, Y. L.; Lin, Y. C.; Oloman, C. W.; Gyenge, E. L.; Su, J. W.; Chen, L. Enhanced catalytic performance of Pt by coupling with carbon defects. Innovation 2021, 2, 100161.
Crossref Google Scholar
[42]

Wang, J. L.; Chen, F. Y.; Jin, Y. C.; Johnston, R. L. Gold-copper aerogels with intriguing surface electronic modulation as highly active and stable electrocatalysts for oxygen reduction and borohydride oxidation. ChemSusChem 2018, 11, 1354–1364.
Crossref Google Scholar
[43]

Sun, S. F.; Zhou, X.; Cong, B. W.; Hong, W. Z.; Chen, G. Tailoring the d-band centers endows (NixFe1−x)2P nanosheets with efficient oxygen evolution catalysis. ACS Catal. 2020, 10, 9086–9097.
Crossref Google Scholar
[44]

Zhou, J.; Han, Z. K.; Wang, X. K.; Gai, H. Y.; Chen, Z. K.; Guo, T.; Hou, X. B.; Xu, L. L.; Hu, X. J.; Huang, M. H. et al. Discovery of quantitative electronic structure-OER activity relationship in metal-organic framework electrocatalysts using an integrated theoretical-experimental approach. Adv. Funct. Mater. 2021, 31, 2102066.
Crossref Google Scholar
[45]

Guo, F. J.; Zhang, M. Y.; Yi, S. C.; Li, X. X.; Xin, R.; Yang, M.; Liu, B.; Chen, H. B.; Li, H. M.; Liu, Y. J. Metal-coordinated porous polydopamine nanospheres derived Fe3N-FeCo encapsulated N-doped carbon as a highly efficient electrocatalyst for oxygen reduction reaction. Nano Res. Energy 2022, 1, 9120027.
Crossref Google Scholar
[46]

Li, C.; Zhao, D. H.; Long, H. L.; Li, M. Recent advances in carbonized non-noble metal-organic frameworks for electrochemical catalyst of oxygen reduction reaction. Rare Met. 2021, 40, 2657–2689.
Crossref Google Scholar
[47]

Gong, S. Y.; Sun, M. Z.; Lee, Y.; Becknell, N.; Zhang, J. W.; Wang, Z. Q.; Zhang, L.; Niu, Z. Q. Bulk-like Pt (100)-oriented ultrathin surface: Combining the merits of single crystals and nanoparticles to boost oxygen reduction reaction. Angew. Chem., Int. Ed. 2023, 62, e202214516.
Crossref Google Scholar
[48]

Zhou, F. L.; Yu, P.; Sun, F. F.; Zhang, G. Y.; Liu, X.; Wang, L. The cooperation of Fe3C nanoparticles with isolated single iron atoms to boost the oxygen reduction reaction for Zn-air batteries. J. Mater. Chem. A 2021, 9, 6831–6840.
Crossref Google Scholar
[49]

Wei, X. Q.; Song, S. J.; Cai, W. W.; Luo, X.; Jiao, L.; Fang, Q.; Wang, X. S.; Wu, N. N.; Luo, Z.; Wang, H. J. et al. Tuning the spin state of Fe single atoms by Pd nanoclusters enables robust oxygen reduction with dissociative pathway. Chem 2023, 9, 181–197.
Crossref Google Scholar
[50]

Wang, X. K.; Chen, Z. K.; Han, Z. K.; Gai, H. Y.; Zhou, J.; Wang, Y. R.; Cui, P. X.; Ge, J. J.; Xing, W.; Zheng, X. S. et al. Manipulation of new married edge-adjacent Fe2N5 catalysts and identification of active species for oxygen reduction in wide pH range. Adv. Funct. Mater. 2022, 32, 2111835.
Crossref Google Scholar
[51]

Shang, H. S.; Zhou, X. Y.; Dong, J. C.; Li, A.; Zhao, X.; Liu, Q. H.; Lin, Y.; Pei, J. J.; Li, Z.; Jiang, Z. L. et al. Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity. Nat. Commun. 2020, 11, 3049.
Crossref Google Scholar
[52]

Wang, X. K.; Zhan, G. M.; Wang, Y. R.; Zhang, Y.; Zhou, J.; Xu, R.; Gai, H. Y.; Wang, H. L.; Jiang, H. Q.; Huang, M. H. Engineering core–shell Co9S8/Co nanoparticles on reduced graphene oxide: Efficient bifunctional Mott–Schottky electrocatalysts in neutral rechargeable Zn-air batteries. J. Energy Chem. 2022, 68, 113–123.
Crossref Google Scholar
[53]

Zhang, S. B.; Wu, Y. F.; Zhang, Y. X.; Niu, Z. Q. Dual-atom catalysts: Controllable synthesis and electrocatalytic applications. Sci. China Chem. 2021, 64, 1908–1922.
Crossref Google Scholar
[54]

Ma, Z. M.; Liu, S. Q.; Tang, N. F.; Song, T.; Motokura, K.; Shen, Z. M.; Yang, Y. Coexistence of Fe nanoclusters boosting Fe single atoms to generate singlet oxygen for efficient aerobic oxidation of primary amines to imines. ACS Catal. 2022, 12, 5595–5604.
Crossref Google Scholar
Nano Research
Volume 16 Issue 7,
July 2023
Pages 9371-9378
DOI: 10.1007/s12274-023-5578-1
Cite this article:
Zhang C, Wang X, Song K, et al. Engineering adjacent Fe3C as proton-feeding centers to single Fe sites enabling boosted oxygen reduction reaction kinetics for robust Zn-air batteries at high current densities. Nano Research, 2023, 16(7): 9371-9378. https://doi.org/10.1007/s12274-023-5578-1
Topics:
Zinc air batteries

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Received: 01 February 2023
Revised: 11 February 2023
Accepted: 13 February 2023
Published: 28 March 2023
© Tsinghua University Press 2023
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