Citation: Yanhui Yu, Peng Rao, Suyang Feng, Min Chen, Peilin Deng, Jing Li, Zhengpei Miao, Zhenye Kang, Yijun Shen, Xinlong Tian. Atomic Co Clusters for Efficient Oxygen Reduction Reaction[J]. Acta Physico-Chimica Sinica, ;2023, 39(8): 221003. doi: 10.3866/PKU.WHXB202210039 shu

Atomic Co Clusters for Efficient Oxygen Reduction Reaction

State Key Laboratory of Marine Resource Utilization in South China Sea, Hainan Provincial Key Lab of Fine Chemistry, School of Chemical Engineering and Technology, Hainan University, Haikou 570228, China

Corresponding author: Peilin Deng, dengpeilin@hainanu.edu.cn Zhengpei Miao, zpmiao92@hainanu.edu.cn Xinlong Tian, tianxl@hainanu.edu.cn

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Received Date: 27 October 2022
Revised Date: 12 November 2022
Accepted Date: 14 November 2022
Available Online: 21 November 2022
Fund Project: the Hainan Provincial Natural Science Foundation of China 222RC548the National Natural Science Foundation of China 22109034the National Natural Science Foundation of China 22109035the National Natural Science Foundation of China 52164028the National Natural Science Foundation of China 62105083the Postdoctoral Science Foundation of Hainan Province RZ2100007123the Foundation of State Key Laboratory of Marine Resource Utilization in South China Sea 海南大学the Foundation of State Key Laboratory of Marine Resource Utilization in South China Sea MRUKF2021029the Start-up Research Foundation of Hainan University KYQD(ZR)-20008the Start-up Research Foundation of Hainan University 20082the Start-up Research Foundation of Hainan University 20083the Start-up Research Foundation of Hainan University 20084the Start-up Research Foundation of Hainan University 21065the Start-up Research Foundation of Hainan University 21124the Start-up Research Foundation of Hainan University 21125

Environment-friendly energy storage and conversion technologies, such as metal–air batteries and fuel cells, are considered promising approaches to address growing environmental concerns. The oxygen reduction reaction (ORR) is the core of renewable energy conversion technology and plays an irreplaceable role in this fundamental issue. However, the complex multi-reaction process of the ORR presents a bottleneck that limits efforts to accelerate its kinetics. Traditionally, Pt and Pt-based catalysts are regarded as a good choice to improve the sluggish kinetics of the ORR. However, because Pt-based catalysts are expensive and have low durability, their use to resolve the energy crisis and current environmental challenges is impractical. Hence, exploring low-cost, highly active, and durable ORR catalysts as potential alternatives to commercial Pt/C is an urgent undertaking. Atomic cluster catalysts (ACCs) may be suitable alternatives to commercial Pt/C catalysts owing to their ultra-high atomic utilization efficiency, unique electronic structure, and stable nanostructures. However, despite the significant progress achieved in recent years, ACCs remain unusable for practical applications. In this study, a facile plasma bombing method combined with an acid washing strategy is proposed to fabricate an atomic Co cluster-decorated porous carbon supports catalyst (Co_AC/NC) showing improved ORR performance. The typical atomic cluster features of the resultant Co_AC/NC catalyst are confirmed using comprehensive characterization techniques. The Co_AC/NC catalyst exhibits considerable ORR activity with a half-wave potential of as high as 0.887 V (versus a reversible hydrogen electrode (RHE)), which is much higher than that of a commercial Pt/C catalyst. More importantly, the Co_AC/NC catalyst displays excellent battery performance when applied to a Zn-air battery, showing a peak power density of 181.5 mW∙cm⁻² and long discharge ability (over 67 h at a discharge current density of 5 mA∙cm⁻²). The desirable ORR performance of the fabricated Co_AC/NC catalyst could be mainly attributed to the high atom utilization efficiency and stable active sites endowed by the unique Co atomic clusters, as well as synergistic effects between the neighboring Co atoms of these clusters. Moreover, the high specific surface area and wide pore distribution of the catalyst offer abundant accessible active sites for the ORR. This work not only provides an outstanding alternative to commercial Pt catalysts for the ORR but also offers new insights into the rational design and practical application of ACCs.
- Atomic cluster catalyst,
- Electrocatalyst,
- Plasma bombing,
- Co cluster,
- Oxygen reduction reaction
1. [1]
  Tian, X.; Zhao, X.; Su, Y. Q.; Wang, L.; Wang, H.; Dang, D.; Chi, B.; Liu, H.; Hensen, E. J. M.; Lou, X. W. Science 2019, 366, 850. doi: 10.1126/science.aaw7493 doi: 10.1126/science.aaw7493
2. [2]
  Tian, X.; Lu, X. F.; Xia, B. Y.; Lou, X. W. Joule 2020, 4, 45. doi: 10.1016/j.joule.2019.12.014 doi: 10.1016/j.joule.2019.12.014
3. [3]
  Li, L.; Shen, S.; Wei, G.; Zhang, J. Acta Phys. -Chim. Sin. 2021, 37, 1911011. doi: 10.3866/PKU.WHXB201911011
4. [4]
  Ding, L.; Tang, T.; Hu, J. -S. Acta Phys. -Chim. Sin. 2021, 37, 2010048. doi: 10.3866/PKU.WHXB202010048
5. [5]
  Lin, Z.; Xiao, B.; Huang, M.; Yan, L.; Wang, Z.; Huang, Y.; Shen, S.; Zhang, Q.; Gu, L.; Zhong, W. Adv. Energy Mater. 2022, 12, 2200855. doi: 10.1002/aenm.202200855 doi: 10.1002/aenm.202200855
6. [6]
  Nan, H.; Su, Y. Q.; Tang, C.; Cao, R.; Li, D.; Yu, J.; Liu, Q.; Deng, Y.; Tian, X. Sci. Bull. 2020, 65, 1396. doi: 10.1016/j.scib.2020.04.015 doi: 10.1016/j.scib.2020.04.015
7. [7]
  Gu, J.; Zhao, Y.; Lin, S.; Huang, J.; Cabrera, C. R.; Sumpter, B. G.; Chen, Z. J. Energy Chem. 2021, 63, 285. doi: 10.1016/j.jechem.2021.08.004 doi: 10.1016/j.jechem.2021.08.004
8. [8]
  Huang, B.; Hou, K.; Liu, Y.; Hu, R.; Guan, L. J. Energy Chem. 2021, 63, 521. doi: 10.1016/j.jechem.2021.08.024 doi: 10.1016/j.jechem.2021.08.024
9. [9]
  Li, J.; Wang, Y.; Yin, Z.; He, R.; Wang, Y.; Qiao, J. J. Energy Chem. 2022, 66, 348. doi: 10.1016/j.jechem.2021.08.007 doi: 10.1016/j.jechem.2021.08.007
10. [10]
  Liu, M.; Yang, M.; Shu, X.; Zhang, J. Acta Phys. -Chim. Sin. 2021, 37, 2007072. doi: 10.3866/PKU.WHXB202007072
11. [11]
  Yang, H.; Gao, S.; Rao, D.; Yan, X. Energy Storage Mater. 2022, 46, 553. doi: 10.1016/j.ensm.2022.01.040 doi: 10.1016/j.ensm.2022.01.040
12. [12]
  Deng, Y.; Luo, J.; Chi, B.; Tang, H.; Li, J.; Qiao, X.; Shen, Y.; Yang, Y.; Jia, C.; Rao, P.; Tian, X. Adv. Energy Mater. 2021, 11, 2101222. doi: 10.1002/aenm.202101222 doi: 10.1002/aenm.202101222
13. [13]
  Yang, Y.; Wu, D.; Li, R.; Rao, P.; Li, J.; Deng, P.; Luo, J.; Huang, W.; Chen, Q.; Kang, Z.; Tian, X. Appl. Catal. B: Environ. 2022, 317, 121796. doi: 10.1016/j.apcatb.2022.121796 doi: 10.1016/j.apcatb.2022.121796
14. [14]
  Lou, Y.; Liu, J.; Liu, M.; Wang, F. ACS Catal. 2020, 10, 2443. doi: 10.1021/acscatal.9b03716 doi: 10.1021/acscatal.9b03716
15. [15]
  Wang, Y.; Li, Z.; Zhang, P.; Pan, Y.; Zhang, Y.; Cai, Q.; Silva, S. R. P.; Liu, J.; Zhang, G.; Sun, X.; et al. Nano Energy 2021, 87, 106147. doi: 10.1016/j.nanoen.2021.106147 doi: 10.1016/j.nanoen.2021.106147
16. [16]
  Xiao, Y.; Pei, Y.; Hu, Y.; Ma, R.; Wang, D.; Wang, J. Acta Phys. -Chim. Sin. 2021, 37, 2009051. doi: 10.3866/PKU.WHXB202009051
17. [17]
  Li, Y.; Zang, K.; Duan, X.; Luo, J.; Chen, D. J. Energy Chem. 2021, 55, 572. doi: 10.1016/j.jechem.2020.07.041 doi: 10.1016/j.jechem.2020.07.041
18. [18]
  Xie, X.; He, C.; Li, B.; He, Y.; Cullen, D. A.; Wegener, E. C.; Kropf, A. J.; Martinez, U.; Cheng, Y.; Engelhard, M. H. Nat. Catal. 2020, 3, 1044. doi: 10.1038/s41929-020-00546-1 doi: 10.1038/s41929-020-00546-1
19. [19]
  Rao, P.; Deng, Y.; Fan, W.; Luo, J.; Deng, P.; Li, J.; Shen, Y.; Tian, X. Nat. Commun. 2022, 13, 5071. doi: 10.1038/s41467-022-32850-8 doi: 10.1038/s41467-022-32850-8
20. [20]
  Wang, H. Y.; Weng, C. C.; Yuan, Z. Y. J. Energy Chem. 2021, 56, 470. doi: 10.1016/j.jechem.2020.08.030 doi: 10.1016/j.jechem.2020.08.030
21. [21]
  Yang, J.; Liu, W.; Xu, M.; Liu, X.; Qi, H.; Zhang, L.; Yang, X.; Niu, S.; Zhou, D.; Liu, Y. J. Am. Chem. Soc. 2021, 143, 14530. doi: 10.1021/jacs.1c03788 doi: 10.1021/jacs.1c03788
22. [22]
  Kumar, A.; Bui, V. Q.; Lee, J.; Wang, L.; Jadhav, A. R.; Liu, X.; Shao, X.; Liu, Y.; Yu, J.; Hwang, Y. Nat. Commun. 2021, 12, 6766. doi: 10.1038/s41467-021-27145-3 doi: 10.1038/s41467-021-27145-3
23. [23]
  Lei, Z.; Cai, W.; Rao, Y.; Wang, K.; Jiang, Y.; Liu, Y.; Jin, X.; Li, J.; Lv, Z.; Jiao, S. Nat. Commun. 2022, 13, 24. doi: 10.1038/s41467-021-27664-z doi: 10.1038/s41467-021-27664-z
24. [24]
  Zhang, M.; Zhang, J.; Ran, S.; Qiu, L.; Sun, W.; Yu, Y.; Chen, J.; Zhu, Z. Nano Res. 2020, 14, 1175. doi: 10.1007/s12274-020-3168-z doi: 10.1007/s12274-020-3168-z
25. [25]
  Lei, Z.; Tan, Y.; Zhang, Z.; Wu, W.; Cheng, N.; Chen, R.; Mu, S.; Sun, X. Nano Res. 2020, 14, 868. doi: 10.1007/s12274-020-3127-8 doi: 10.1007/s12274-020-3127-8
26. [26]
  Yang, J.; Qi, H.; Li, A.; Liu, X.; Yang, X.; Zhang, S.; Zhao, Q.; Jiang, Q.; Su, Y.; Zhang, L. J. Am. Chem. Soc. 2022, 144, 12062. doi: 10.1021/jacs.2c02262 doi: 10.1021/jacs.2c02262
27. [27]
  Xing, G.; Tong, M.; Yu, P.; Wang, L.; Zhang, G.; Tian, C.; Fu, H. Angew. Chem. Int. Ed. 2022, 61, e202211098. doi: 10.1002/anie.202211098 doi: 10.1002/anie.202211098
28. [28]
  Bai, X.; Zhao, X.; Zhang, Y.; Ling, C.; Zhou, Y.; Wang, J.; Liu, Y. J. Am. Chem. Soc. 2022, 144, 17140. doi: 10.1021/jacs.2c07178 doi: 10.1021/jacs.2c07178
29. [29]
  Shen, S.; Hu, Z.; Zhang, H.; Song, K.; Wang, Z.; Lin, Z.; Zhang, Q.; Gu, L.; Zhong, W. Angew. Chem. Int. Ed. 2022, 61, e202206460. doi: 10.1002/anie.202206460 doi: 10.1002/anie.202206460
30. [30]
  Liu, J. C.; Ma, X. L.; Li, Y.; Wang, Y. G.; Xiao, H.; Li, J. Nat. Commun. 2018, 9, 1610. doi: 10.1038/s41467-018-03795-8 doi: 10.1038/s41467-018-03795-8
31. [31]
  Huang, H.; Yu, D.; Hu, F.; Huang, S. C.; Song, J.; Chen, H. Y.; Li, L. L.; Peng, S. Angew. Chem. Int. Ed. 2022, 61, e202116068. doi: 10.1002/anie.202116068 doi: 10.1002/anie.202116068
32. [32]
  Wang, Q.; Huang, X.; Zhao, Z. L.; Wang, M.; Xiang, B.; Li, J.; Feng, Z.; Xu, H.; Gu, M. J. Am. Chem. Soc. 2020, 142, 7425. doi: 10.1021/jacs.9b12642 doi: 10.1021/jacs.9b12642
33. [33]
  Cai, C.; Wang, M.; Han, S.; Wang, Q.; Zhang, Q.; Zhu, Y.; Yang, X.; Wu, D.; Zu, X.; Sterbinsky, G. E. ACS Catal. 2020, 11, 123. doi: 10.1021/acscatal.0c04656 doi: 10.1021/acscatal.0c04656
34. [34]
  Chen, Z. W.; Yan, J. M.; Jiang, Q. Small Methods 2018, 3, 1800291. doi: 10.1002/smtd.201800291 doi: 10.1002/smtd.201800291
35. [35]
  Zhang, X.; Chen, A.; Zhang, Z.; Zhou, Z. J. Mater. Chem. A 2018, 6, 18599. doi: 10.1039/c8ta07683a doi: 10.1039/c8ta07683a
36. [36]
  Yu, P.; Wang, L.; Sun, F.; Xie, Y.; Liu, X.; Ma, J.; Wang, X.; Tian, C.; Li, J.; Fu, H. Adv. Mater. 2019, 31, e1901666. doi: 10.1002/adma.201901666 doi: 10.1002/adma.201901666
37. [37]
  Yang, Z.; Zhao, C.; Qu, Y.; Zhou, H.; Zhou, F.; Wang, J.; Wu, Y.; Li, Y. Adv. Mater. 2019, 31, e1808043. doi: 10.1002/adma.201808043 doi: 10.1002/adma.201808043
38. [38]
  Han, X.; Ling, X.; Yu, D.; Xie, D.; Li, L.; Peng, S.; Zhong, C.; Zhao, N.; Deng, Y.; Hu, W. Adv. Mater. 2019, 31, e1905622. doi: 10.1002/adma.201905622 doi: 10.1002/adma.201905622
39. [39]
  Rao, P.; Wu, D.; Wang, T. -J.; Li, J.; Deng, P.; Chen, Q.; Shen, Y.; Chen, Y.; Tian, X. eScience 2022, 2, 399. doi: 10.1016/j.esci.2022.05.004 doi: 10.1016/j.esci.2022.05.004
40. [40]
  Gao, J.; Hu, Y.; Wang, Y.; Lin, X.; Hu, K.; Lin, X.; Xie, G.; Liu, X.; Reddy, K. M.; Yuan, Q. Small 2021, 17, e2104684. doi: 10.1002/smll.202104684 doi: 10.1002/smll.202104684
41. [41]
  Yang, Z.; Chen, B.; Chen, W.; Qu, Y.; Zhou, F.; Zhao, C.; Xu, Q.; Zhang, Q.; Duan, X.; Wu, Y. Nat. Commun. 2019, 10, 3734. doi: 10.1038/s41467-019-11796-4 doi: 10.1038/s41467-019-11796-4
42. [42]
  Zhong, H.; Shi, C.; Li, J.; Yu, R.; Yu, Q.; Liu, H.; Yao, Y.; Wu, J.; Zhou, L.; Mai, L. Chem. Commun. 2020, 56, 4488. doi: 10.1039/c9cc10036a doi: 10.1039/c9cc10036a
43. [43]
  Ren, W.; Tan, X.; Yang, W.; Jia, C.; Xu, S.; Wang, K.; Smith, S. C.; Zhao, C. Angew. Chem. Int. Ed. 2019, 58, 6972. doi: 10.1002/anie.201901575 doi: 10.1002/anie.201901575
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