Atomically Dispersed Co Atoms Stabilized by Nitrogen Species in Carbon Skeleton for Efficient Oxygen Reduction and Zn-air Batteries
Rongrong Liu （ College of Science, Hebei Agricultural University, Baoding 071001, China. ）
Jizheng Feng （ College of Science, Hebei Agricultural University, Baoding 071001, China. ）
Tao Meng （ College of Science, Hebei Agricultural University, Baoding 071001, China. ）
https://doi.org/10.37155/2717-526X-0501-2Abstract
Atomically dispersed and nitrogen-coordinated single metal atom implanted into the carbon substrate holds great promise as Pt-liked catalysts for oxygen reduction reaction (ORR). However, the complicated synthetic procedures of single atomic catalysts heavily limit their widespread applications. Herein, the atomically dispersed Co stabilized by nitrogen species in carbon skeleton (Co-SAs/NC) is prepared by a controllable pyrolysis of the nano-confined Co-precursor, and further employed as alkaline ORR catalyst. The atomic configuration and electronic structure of Co-SAs/NC are systematic investigated by a wide range of advanced techniques, such as electron microscopic and X-ray absorption spectroscopy. As expected, Co-SAs/NC exhibites excellent ORR activity with a large onset and half-wave potentials, as well as good selectivity and favorable stability. More importantly, the outstanding ORR performances of Co-SAs/NC enable the assembled Zn-air battery to deliver a large specific capacity of 788.4 mAh•gZn-1, a maximum power density of 233.6 mW•cm-2, and a long cycle life.
Keywords
Atomically dispersed Co sites; Oxygen evolution reaction; Zn-air batteryFull Text
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[3] Li Y, Cui M, Yin Z, et al. Metal-organic framework based bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries: current progress and prospects. Chemical Science, 2020;11(43):11646-11671. https://doi.org/10.1039/D0SC04684A
[4] Lin X, Shi L, Liu F, et al. Large-scale production of holey carbon nanosheets implanted with atomically dispersed Fe sites for boosting oxygen reduction electrocatalysis. Nano Research, 2022;15:1926-1933. https://doi.org/10.1007/s12274-021-3816-y
[5] Yu P, Wang L, Sun F, et al. Co Nanoislands rooted on Co-N-C nanosheets as efficient oxygen electrocatalyst for Zn-air batteries. Advanced Materials, 2019;31(30):1901666. https://doi.org/10.1002/adma.201901666
[6] Holby EF, Wang G and Zelenay P. Acid stability and demetalation of PGM-free ORR electrocatalyst structures from density functional theory: a model for “single-atom catalyst” dissolution. ACS Catalysis, 2020;10:14527-14539. https://doi.org/10.1021/acscatal.0c02856
[7] Liu M, Zhao Z, Duan X, et al. Nanoscale structure design for high-performance Pt-based ORR catalysts. Advanced Materials, 2019;31(6):1802234. https://doi.org/10.1002/adma.201802234
[8] Wu ZP, Lu XF, Zang SQ, et al. Non-noble-metal-based electrocatalysts toward the oxygen evolution reaction. Advanced Functional Materials, 2020;30(15):1910274. https://doi.org/10.1002/adfm.201910274
[9] Hu C and Dai L. Carbon-based metal-free catalysts for electrocatalysis beyond the ORR. Angewandte Chemie International Edition, 2016;55(39):11736-11758. https://doi.org/10.1002/anie.201509982
[10] Greeley J, Stephens IEL, Bondarenko AS, et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nature Chemistry, 2009;1(7):552-556. https://doi.org/10.1038/nchem.367
[11] Chen Z, Higgins D, Yu A, et al. A review on non-precious metal electrocatalysts for PEM fuel cells. Energy & Environmental Science, 2011;4(9):3167-3192. https://doi.org/10.1039/C0EE00558D
[12] Artyushkova K, Matanovic I, Halevi B, et al. Oxygen binding to active sites of Fe-N-C ORR electrocatalysts observed by ambient-pressure XPS. The Journal of Physical Chemistry C, 2017;121(5):2836-2843. https://doi.org/10.1021/acs.jpcc.6b11721
[13] Wang R, Zhang P, Wang Y, et al. ZIF-derived Co-N-C ORR catalyst with high performance in proton exchange membrane fuel cells. Progress in Natural Science: Materials International, 2020;30(6):855-860. https://doi.org/10.1016/j.pnsc.2020.09.010
[14] Wang X, Chen Z, Han Z, et al. Manipulation of new married edge-adjacent Fe2N5 catalysts and identification of active species for oxygen reduction in wide pH range. Advanced Functional Materials, 2022;32(18):2111835. https://doi.org/10.1002/adfm.202111835
[15] Kong F, Huang Y, Chen M, et al. Creation of densely exposed and cavity-edged single Fe active sites for enhanced oxygen electroreduction. Applied Catalysis B: Environmental, 2022;317:121768. https://doi.org/10.1016/j.apcatb.2022.121768
[16] Chen Y, Ji S, Chen C, et al. Single-atom catalysts: synthetic strategies and electrochemical applications. Joule, 2018;2(7):1242-1264. https://doi.org/10.1016/j.joule.2018.06.019
[17] Wang A, Li J and Zhang T. Heterogeneous single-atom catalysis. Nature Reviews Chemistry, 2018;2(6):65-81. https://doi.org/10.1038/s41570-018-0010-1
[18] Qiu X, Yan X, Pang H, et al. Isolated Fe single atomic sites anchored on highly steady hollow graphene nanospheres as an efficient electrocatalyst for the oxygen reduction reaction. Advanced Science, 2019;6(2):1801103. https://doi.org/10.1002/advs.201801103
[19] Han X, Ling X, Wang Y, et al. Generation of nanoparticle, atomic-cluster, and single-atom cobalt catalysts from zeolitic imidazole frameworks by spatial isolation and their use in zinc-air batteries. Angewandte Chemie, 2019;131(16):5413-5418. https://doi.org/10.1002/ange.201901109
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[21] Sun T, Zhao S, Chen W, et al. Single-atomic cobalt sites embedded in hierarchically ordered porous nitrogen-doped carbon as a superior bifunctional electrocatalyst. Proceedings of the National Academy of Sciences, 2018;115(50):12692-12697. https://doi.org/10.1073/pnas.1813605115
[22] Zang W, Sumboja A, Ma Y, et al. Single Co atoms anchored in porous N-doped carbon for efficient zinc-air battery cathodes. Acs Catalysis, 2018;8(10):8961-8969. https://doi.org/10.1021/acscatal.8b02556
[23] Zhou L, Zhou P, Zhang Y, et al. 3D star-like atypical hybrid MOF derived single-atom catalyst boosts oxygen reduction catalysis. Journal of Energy Chemistry, 2021;55:355-360. https://doi.org/10.1016/j.jechem.2020.06.059
[24] Meng T, Qin J, Wang S, et al. In situ coupling of Co 0.85 Se and N-doped carbon via one-step selenization of metal-organic frameworks as a trifunctional catalyst for overall water splitting and Zn-air batteries. Journal of Materials Chemistry A, 2017;5(15):7001-7014. https://doi.org/10.1039/C7TA01453H
[25] He J, Li N, Li ZG, et al. Strategic defect engineering of metal-organic frameworks for optimizing the fabrication of single-atom catalysts. Advanced Functional Materials, 2021;31(41):2103597. https://doi.org/10.1002/adfm.202103597
[26] Feng J, Tang R, Liu G, et al. Regulating d-orbital electronic character and HER free energy of VN electrocatalyst by anchoring single atom. Chemical Engineering Journal, 2023;452:139131. https://doi.org/10.1016/j.cej.2022.139131
[27] Zhou B, Liu Y, Wu X, et al. Wood-derived integrated air electrode with Co-N sites for rechargeable zinc-air batteries. Nano Research, 2022;15(2):1415-1423. https://doi.org/10.1007/s12274-021-3678-3
[28] Cheng Q, Han S, Mao K, et al. Co nanoparticle embedded in atomically-dispersed Co-NC nanofibers for oxygen reduction with high activity and remarkable durability. Nano Energy, 2018;52:485-493. https://doi.org/10.1016/j.nanoen.2018.08.005
[29] Wang Y, Tao L, Xiao Z, et al. 3d carbon electrocatalysts in situ constructed by defect-rich nanosheets and polyhedrons from NaCl-sealed zeolitic imidazolate frameworks. Advanced Functional Materials, 2018;28(11):1705356. https://doi.org/10.1002/adfm.201705356
[30] Yuan E, Zhou M, Shi G, et al. Ultralow-loading single-atom cobalt on graphitic carbon nitrogen with robust Co-N pairs for aerobic cyclohexane oxidation. Nano Research, 2022;15(10):8791-8803. https://doi.org/10.1007/s12274-022-4556-3
[31] Wang Z, Jin X, Zhu C, et al. Atomically dispersed Co2-N6 and Fe-N4 costructures boost oxygen reduction reaction in both alkaline and acidic media. Advanced Materials, 2021;33(49):2104718. https://doi.org/10.1002/adma.202104718
[32] Zhu X, Tan X, Wu KH, et al. Intrinsic ORR activity enhancement of Pt atomic sites by engineering the d-band center via local coordination tuning. Angewandte Chemie International Edition, 2021;60(40):21911-21917. https://doi.org/10.1002/anie.202107790
[33] Zhong W, Qiu Y, Shen H, et al. Electronic spin moment as a catalytic descriptor for Fe single-atom catalysts supported on C2N. Journal of the American Chemical Society, 2021;143(11):4405-4413. https://doi.org/10.1021/jacs.1c00889
[34] Chai L, Hu Z, Wang X, et al. Fe7C3 nanoparticles with in situ grown CNT on nitrogen doped hollow carbon cube with greatly enhanced conductivity and ORR performance for alkaline fuel cell. Carbon, 2021;174:531-539. https://doi.org/10.1016/j.carbon.2020.12.070
[35] Feng J, Tang R, Wang X, et al. Biomass-derived activated carbon sheets with tunable oxygen functional groups and pore volume for high-performance oxygen reduction and Zn-air batteries. ACS Applied Energy Materials, 2021;4(5):5230-5236. https://doi.org/10.1021/acsaem.1c00755
Copyright © 2023 Rongrong Liu, Jizheng Feng, Tao Meng
Publishing time:2023-03-10
This work is licensed under a Creative Commons Attribution 4.0 International License
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