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Research Article

Single Cu atom dispersed on S,N-codoped nanocarbon derived from shrimp shells for highly-efficient oxygen reduction reaction

Hao Zhang1, Qingdi Sun1, Qian He1, Ying Zhang1, Xiaohui He1, Tao Gan1,2( ), Hongbing Ji1,2,3( )
Fine Chemical Industry Research Institute, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China
School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
School of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming 525000, China
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Graphical Abstract

We propose a ball-milling method to synthesize isolated metal single-atom catalysts (SACs) embedded in S, N-codoped nanocarbon (M-NSDC, M = Cu, Fe, Co, Ni, Mn, Pt, and Pd). In particular, the Cu-NSDC SACs exhibit high electrochemical activity for the oxygen reduction reaction (ORR) with half-wave potential (E1/2) of 0.84 V (vs. reversible hydrogen electrode (RHE), 20 mV higher than Pt/C) in alkaline electrolyte, excellent stability, and electrocatalytic selectivity.

Abstract

Recently, Cu-based single-atom catalysts (SACs) have garnered increasing attention as substitutes for platinum-based catalysts in the oxygen reduction reaction (ORR). Therefore, a facile, economical, and efficient synthetic methodology for the preparation of a high-performance Cu-based SAC electrocatalyst for the ORR is extremely desired, but is also significantly challenging. In this study, we propose a ball-milling method to synthesize isolated metal SACs embedded in S,N-codoped nanocarbon (M-NSDC, M = Cu, Fe, Co, Ni, Mn, Pt, and Pd). In particular, the Cu-NSDC SACs exhibit high electrochemical activity for the ORR with half-wave potential (E1/2) of 0.84 V (vs. reversible hydrogen electrode (RHE), 20 mV higher than Pt/C) in alkaline electrolyte, excellent stability, and electrocatalytic selectivity. Density functional theory (DFT) calculations demonstrated that the desorption of OH* intermediates was the rate-determining step over Cu-NSDC. This study creates a pathway for high-performance ORR single atomic electrocatalysts for fuel cell applications and provides opportunities to convert biowaste materials into commercial opportunities.

Keywords

ball millingoxygen reduction reactionsingle-atom catalysisshrimp shellS,N-codoped nanocarbon

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References

1

Chen, Y. F.; Li, Z. J.; Zhu, Y. B.; Sun, D. M.; Liu, X. E.; Xu, L.; Tang, Y. W. Atomic Fe dispersed on N-doped carbon hollow nanospheres for high-efficiency electrocatalytic oxygen reduction. Adv. Mater. 2019, 31, 1806312.
Crossref Google Scholar
2
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., in press, DOI: 10.1016/j.apmate.2021.10.004.https://doi.org/10.1016/j.apmate.2021.10.004
Crossref
3

Cui, L. T.; Cui, L. R.; Li, Z. J.; Zhang, J.; Wang, H. N.; Lu, S. F.; Xiang, Y. A copper single-atom catalyst towards efficient and durable oxygen reduction for fuel cells. J. Mater. Chem. A 2019, 7, 16690–16695.
Crossref Google Scholar
4

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
5

Xiong, Y.; Yang, Y.; Feng, X. R.; DiSalvo, F. J.; Abruna, H. D. A strategy for increasing the efficiency of the oxygen reduction reaction in Mn-doped cobalt ferrites. J. Am. Chem. Soc. 2019, 141, 4412–4421.
Crossref Google Scholar
6
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., in press, DOI: 10.1002/anie.202115219.https://doi.org/10.1002/anie.202115219
Crossref
7

Xu, Y. S.; Zhu, L. P.; Cui, X. X.; Zhao, M. Y.; Li, Y. L.; Chen, L. L.; Jiang, W. C.; Jiang, T.; Yang, S. G.; Wang, Y. Graphitizing N-doped mesoporous carbon nanospheres via facile single atom iron growth for highly efficient oxygen reduction reaction. Nano Res. 2020, 13, 752–758.
Crossref Google Scholar
8

Guo, Y. C.; Liu, F.; Feng, L.; Wang, X. M.; Zhang, X.; Liang, J. S. Single Co atoms anchored on nitrogen-doped hierarchically ordered porous carbon for selective hydrogenation of quinolines and efficient oxygen reduction. Chem. Eng. J. 2022, 429, 132150.
Crossref Google Scholar
9

Wang, Y. Y.; Kumar, A.; Ma, M.; Jia, Y.; Wang, Y.; Zhang, Y.; Zhang, G. X.; Sun, X. M.; Yan, Z. F. Hierarchical peony-like FeCo-NC with conductive network and highly active sites as efficient electrocatalyst for rechargeable Zn-air battery. Nano Res. 2020, 13, 1090–1099.
Crossref Google Scholar
10

Fei, H. L.; Dong, J. C.; Feng, Y. X.; Allen, C. S.; Wan, C. Z.; Volosskiy, B.; Li, M. F.; Zhao, Z. P.; Wang, Y. L.; Sun, H. T. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 2018, 1, 63–72.
Crossref Google Scholar
11

Bhagi-Damodaran, A.; Michael, M. A.; Zhu, Q. H.; Reed, J.; Sandoval, B. A.; Mirts, E. N.; Chakraborty, S.; Moënne-Loccoz, P.; Zhang, Y.; Lu, Y. Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases. Nat. Chem. 2017, 9, 257–263.
Crossref Google Scholar
12

Wu, H. H.; Li, H. B.; Zhao, X. F.; Liu, Q. F.; Wang, J.; Xiao, J. P.; Xie, S. H.; Si, R.; Yang, F.; Miao, S. et al. Highly doped and exposed Cu(I)-N active sites within graphene towards efficient oxygen reduction for zinc-air batteries. Energy Environ. Sci. 2016, 9, 3736–3745.
Crossref Google Scholar
13

Yuan, K.; Lützenkirchen-Hecht, D.; Li, L. B.; Shuai, L.; Li, Y. Z.; Cao, R.; Qiu, M.; Zhuang, X. D.; Leung, M. K. H.; Chen, Y. W. et al. Boosting oxygen reduction of single iron active sites via geometric and electronic engineering: Nitrogen and phosphorus dual coordination. J. Am. Chem. Soc. 2020, 142, 2404–2412.
Crossref Google Scholar
14

Sun, H.; Wang, M. F.; Du, X. C.; Jiao, Y.; Liu, S. S.; Qian, T.; Yan, Y. C.; Liu, C.; Liao, M.; Zhang, Q. H. et al. Modulating the d-band center of boron doped single-atom sites to boost the oxygen reduction reaction. J. Mater. Chem. A 2019, 7, 20952–20957.
Crossref Google Scholar
15

Jia, C.; Tan, X.; Zhao, Y.; Ren, W. H.; Li, Y. B.; Su, Z.; Smith, S. C.; Zhao, C. Sulfur-dopant-promoted electroreduction of CO2 over coordinatively unsaturated Ni-N2 moieties. Angew. Chem., Int. Ed. 2021, 60, 23342–23348.
Crossref Google Scholar
16

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.
Crossref Google Scholar
17

Chen, D. T.; Zhang, L. H.; Du, J.; Wang, H. H.; Guo, J. Y.; Zhan, J. Y.; Li, F.; Yu, F. S. A tandem strategy for enhancing electrochemical CO2 reduction activity of single-atom Cu-S1N3 catalysts via integration with Cu nanoclusters. Angew. Chem., Int. Ed. 2021, 60, 24022–24027.
Crossref Google Scholar
18

Chen, Z. Y.; Niu, H.; Ding, J.; Liu, H.; Chen, P. H.; Lu, Y. H.; Lu, Y. R.; Zuo, W. B.; Han, L.; Guo, Y. Z. et al. Unraveling the origin of sulfur-doped Fe-N-C single-atom catalyst for enhanced oxygen reduction activity: Effect of iron spin-state tuning. Angew. Chem., Int. Ed. 2021, 60, 25404–25410.
Crossref Google Scholar
19

Zhang, G. X.; Jia, Y.; Zhang, C.; Xiong, X. Y.; Sun, K.; Chen, R. D.; Chen, W. X.; Kuang, Y.; Zheng, L. R.; Tang, H. L. et al. A general route via formamide condensation to prepare atomically dispersed metal-nitrogen-carbon electrocatalysts for energy technologies. Energy Environ. Sci. 2019, 12, 1317–1325.
Crossref Google Scholar
20

Wang, M. F.; Qian, T.; Liu, S. S.; Zhou, J. Q.; Yan, C. L. Unprecedented activity of bifunctional electrocatalyst for high power density aqueous zinc-air batteries. ACS Appl. Mater. Interfaces 2017, 9, 21216–21224.
Crossref Google Scholar
21

Zhang, J. T.; Zhang, M.; Zeng, Y.; Chen, J. S.; Qiu, L. X.; Zhou, H.; Sun, C. J.; Yu, Y.; Zhu, C. Z.; Zhu, Z. H. Single Fe atom on hierarchically porous S,N-codoped nanocarbon derived from porphyra enable boosted oxygen catalysis for rechargeable Zn-air batteries. Small 2019, 15, 1900307.
Crossref Google Scholar
22

Wang, C. Y.; Chen, W. X.; Xia, K. L.; Xie, N. H.; Wang, H. M.; Zhang, Y. Y. Silk-derived 2D porous carbon nanosheets with atomically-dispersed Fe-Nx-C sites for highly efficient oxygen reaction catalysts. Small 2019, 15, 1804966.
Crossref Google Scholar
23

Jiang, W. J.; Hu, W. L.; Zhang, Q. H.; Zhao, T. T.; Luo, H.; Zhang, X.; Gu, L.; Hu, J. S.; Wan, L. J. From biological enzyme to single atomic Fe-N-C electrocatalyst for efficient oxygen reduction. Chem. Commun. 2018, 54, 1307–1310.
Crossref Google Scholar
24

Li, Z. Y.; Gao, Q. M.; Liang, X.; Zhang, H.; Xiao, H.; Xu, P.; Liu, Z. P. Low content of Fe3C anchored on Fe, N, S-codoped graphene-like carbon as bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Carbon 2019, 150, 93–100.
Crossref Google Scholar
25

Li, T. F.; Li, M.; Zhang, M. R.; Li, X.; Liu, K. H.; Zhang, M. Y.; Liu, X. E.; Sun, D. M.; Xu, L.; Zhang, Y. W. et al. Immobilization of Fe3N nanoparticles within N-doped carbon nanosheet frameworks as a high-efficiency electrocatalyst for oxygen reduction reaction in Zn-air batteries. Carbon 2019, 153, 364–371.
Crossref Google Scholar
26

Cheng, Y. J.; Sun, Q. D.; Huang, L. Y.; He, Q.; Zhang, H.; Wang, P. B.; Zhang, Y.; Shi, S. L.; Zhang, X. C.; Gan, T. et al. Protein powder derived nitrogen-doped carbon supported atomically dispersed iron sites for selective oxidation of ethylbenzene. Dalton Trans. 2021, 50, 11711–11715.
Crossref Google Scholar
27

Devi, R.; Dhamodharan, R. Sustainable process for separating chitin and simultaneous synthesis of carbon nanodots from shellfish waste using 2% aqueous urea solution. ACS Sustainable Chem. Eng. 2018, 6, 11313–11325.
Crossref Google Scholar
28

Qu, J. Y.; Geng, C.; Lv, S. Y.; Shao, G. H.; Ma, S. Y.; Wu, M. B. Nitrogen, oxygen and phosphorus decorated porous carbons derived from shrimp shells for supercapacitors. Electrochim. Acta 2015, 176, 982–988.
Crossref Google Scholar
29

Gao, F.; Qu, J. Y.; Geng, C.; Shao, G. H.; Wu, M. B. Self-templating synthesis of nitrogen-decorated hierarchical porous carbon from shrimp shell for supercapacitors. J. Mater. Chem. A 2016, 4, 7445–7452.
Crossref Google Scholar
30

Lu, S. Y.; Jin, M.; Zhang, Y.; Niu, Y. B.; Gao, J. C.; Li, C. M. Chemically exfoliating biomass into a graphene-like porous active carbon with rational pore structure, good conductivity, and large surface area for high-performance supercapacitors. Adv. Energy Mater. 2018, 8, 1702545.
Crossref Google Scholar
31

Huang, L. Y.; Wu, K.; He, Q.; Xiong, C.; Gan, T.; He, X. H.; Ji, H. B. Quasi-continuous synthesis of iron single atom catalysts via a microcapsule pyrolysis strategy. AIChE J. 2021, 67, e17197.
Crossref Google Scholar
32

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
33

He, Q.; Meng, Y. Y.; Zhang, H.; Zhang, Y.; Chen, H. Y.; Xiao, H. J.; He, X. H.; Wu, M. M.; Ji, H. B. Facile synthesis of impurity-free iron single atom catalysts for highly efficient oxygen reduction reaction and active-site identification. Catal. Sci. Technol. 2019, 9, 6556–6560.
Crossref Google Scholar
34

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
Nano Research
Volume 15 Issue 7,
July 2022
Pages 5995-6000
DOI: 10.1007/s12274-022-4289-3
Cite this article:
Zhang H, Sun Q, He Q, et al. Single Cu atom dispersed on S,N-codoped nanocarbon derived from shrimp shells for highly-efficient oxygen reduction reaction. Nano Research, 2022, 15(7): 5995-6000. https://doi.org/10.1007/s12274-022-4289-3
Topics:
Oxygen reduction reaction

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Received: 10 January 2022
Revised: 26 February 2022
Accepted: 03 March 2022
Published: 26 April 2022
© Tsinghua University Press 2022
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