Carbon dots-derived carbon nanoflowers decorated with cobalt single atoms and nanoparticles as efficient electrocatalysts for oxygen reduction

doi:10.1016/S1872-2067(22)64146-9

Abstract

Abstract:

The sluggish kinetics of oxygen reduction reaction (ORR) hinders the commercialization of Zn-air batteries (ZABs). Manipulating the electronic structure of electrocatalysts to optimize the adsorption energy of oxygen-containing intermediates during the 4e^- ORR offers a practical route toward improving ORR kinetics. Herein, we designed a novel ORR electrocatalyst containing Co single atoms and nanoparticles supported by carbon dots-derived carbon nanoflowers (Co SAs/NPs CNF). Co SAs/NPs CNF possessed a very high ORR activity (E_1/2 of the Co SAs/NPs CNF catalyst is 0.83 V (vs. RHE)), and outstanding catalytic performance and stability when used as the air-electrode catalyst in rechargeable ZABs (152.32 mW cm^-2, 1000.58 mWh g_Zn^-1, and over 1300 cycles at a current density of 5 mA cm^-2). The Co SAs and Co NPs cooperated to improve electron and proton transfer processes during ORR. Theoretical calculations revealed that the presence of adjacent Co NPs optimized the electronic structure of the isolated Co-N₄ sites, significantly lowering the energy barriers for the rate-determining step in ORR (adsorption of *OOH) and thereby delivering outstanding ORR performance. This work reveals that the combination of supported single-atom sites and metal nanoparticles can be highly beneficial for ORR electrocatalysis, outperforming catalysts containing only Co SAs or Co NPs.

Key words: Carbon dots, Co single atom, Co nanoparticle, Oxygen reduction reaction, Zn-air battery

Yaojia Cheng, Haoqiang Song, Jingkun Yu, Jiangwei Chang, Geoffrey I. N. Waterhouse, Zhiyong Tang, Bai Yang, Siyu Lu. Carbon dots-derived carbon nanoflowers decorated with cobalt single atoms and nanoparticles as efficient electrocatalysts for oxygen reduction[J]. Chinese Journal of Catalysis, 2022, 43(9): 2443-2452.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64146-9

https://www.cjcatal.com/EN/Y2022/V43/I9/2443

Figures/Tables 5

Fig. 1. (a) Schematic diagram showing the synthesis of Co SAs/NPs CNF. (b) SEM images of Co SAs/NPs CNF. (c,d) TEM and HRTEM images of Co SAs/NPs CNF (inset: particle size distribution of Co NPs). (e) HAADF-STEM image of Co SAs/NPs CNF (the bright spots circles in red are atomically dispersed Co atoms and the blue circles are Co NPs). (f) EDS image and elemental (C, N, and Co) mapping analysis of Co SAs/NPs CNF. (g-i) AFM 2D image, AFM height data, and AFM 3D image of Co SAs/NPs CNF. (j) XRD patterns of Co SAs/NPs CNF and Co3O4/C.

Fig. 2. (a) Nitrogen adsorption/desorption isotherms for Co SAs/NPs CNF (inset is the pore-size distribution). High-resolution N 1s XPS spectrum (b) and High-resolution Co 2p XPS spectrum (c) of Co SAs/NPs CNF. Co K-edge XAS spectra (d) and Co K-edge χ(R) EXAFS spectra (e) for Co SAs/NPs CNF, Co Pc, and Co foil. (f) Co K-edge EXAFS fitting curves for Co SAs/NPs CNF. (g-i) WT-EXAFS images for Co foil, Co Pc, and Co SAs/NPs CNF.

Fig. 3. (a) CV curves for Co SAs/NPs CNF and Pt/C in O2-saturated and Ar-saturated 0.1 mol L?1 KOH. LSV polarization curves (b) and Tafel slopes (c) of Co SAs/NPs CNF, Co3O4/C, CM-SH, and commercial Pt/C. (d) The LSV polarization curves of Co SAs/NPs CNF at different rotating speeds and the K-L curves. (e) The n and H2O2 yield between 0.2-0.8 V of Co SAs/NPs CNF and commercial Pt/C. (f) The i-t test results for Co SAs/NPs CNF and Pt/C in O2-saturated 0.1 mol L?1 KOH with and without 1.0 mol L?1 CH3OH. (g) ORR polarization curves for Co SAs/NPs CNF and Pt/C before and after 5000 cycles. (h) The i-t test results for Co SAs/NPs CNF and Pt/C in O2-saturated 0.1 mol L?1 KOH. (i) The i-t curve of the Co SAs/NPs before and after the addition of EDTA or SCN- ions in 0.1 mol L?1 KOH.

Fig. 4. Models of Co SAs/NPs (a), Co SAs (b), Co(111) (c) and the adsorption geometries of the *O2, *OOH, *O, and *OH intermediates. (d,e) The free energy at each reaction step for Co(111), Co SAs, and Co SAs/NPs was U = 0 V and U = 1.23 V. (f) PDOS for Co SAs/NPs, Co SAs, and Co(111).

Fig. 5. (a) Schematic diagram of a ZAB. (b) OCV of a ZAB assembled with Co SAs/NPs CNF (inset is a photograph showing the OCV). (c) Discharge curves and power density curves. (d) Specific capacity curves. (e) Energy-density curves of ZABs assembled with Pt/C and Co SAs/NPs CNF. (f) Comparison of the energy density of the ZAB assembled with Co SAs/NPs CNF and other recently reported results. (g) Stability of ZABs assembled with Co SAs/NPs CNF and Pt/C.

References

[1]	W. Sun, F. Wang, B. Zhang, M. Zhang, V. Küpers, X. Ji, C. Theile, P. Bieker, K. Xu, C. Wang, M. Winter, Science, 2021, 371, 46-51.
[2]	X. Cai, L. Lai, J. Lin, Z. Shen, Mater. Hori., 2017, 4, 945-976.
[3]	J. Fu, Z. P. Cano, M. G. Park, A. Yu, M. Fowler, Z. Chen, Adv. Mater., 2017, 29, 1604685.
[4]	J. Fu, R. Liang, G. Liu, A. Yu, Z. Bai, L. Yang, Z. Chen, Adv. Mater., 2019, 31, 1805230.
[5]	D. Yang, L. Zhang, X. Yan, X. Yao, Small Methods, 2017, 1, 1700209.
[6]	Z. Zhao, X. Fan, J. Ding, W. Hu, C. Zhong, ACS Energy Lett., 2019, 4, 2259-2270.
[7]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[8]	K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai, Science, 2009, 323, 760-764.
[9]	X. Tian, X. Zhao, Y.-Q. Su, L. Wang, H. Wang, D. Dang, B. Chi, H. Liu, E. J. M. Hensen, X. W. Lou, B. Y. Xia, Science, 2019, 366, 850-856.
[10]	C. Chen, Y. Kang, Z. Huo, Z. Zhu, W. Huang, H. L. Xin, J. D. Snyder, D. Li, J. A. Herron, M. Mavrikakis, M. Chi, K. L. More, Y. Li, N. M. Markovic, G. A. Somorjai, P. Yang, V. R. Stamenkovic, Science, 2014, 343, 1339-1343.
[11]	M. Luo, Z. Zhao, Y. Zhang, Y. Sun, Y. Xing, F. Lv, Y. Yang, X. Zhang, S. Hwang, Y. Qin, J.-Y. Ma, F. Lin, D. Su, G. Lu, S. Guo, Nature, 2019, 574, 81-85.
[12]	M. K. Debe, Nature, 2012, 486, 43-51.
[13]	J. Chang, X. Song, C. Yu, J. Yu, Y. Ding, C. Yao, Z. Zhao, J. Qiu, Adv. Funct. Mater., 2020, 30, 2006270.
[14]	Y. Chen, S. Ji, S. Zhao, W. Chen, J. Dong, W.-C. Cheong, R. Shen, X. Wen, L. Zheng, A. I. Rykov, S. Cai, H. Tang, Z. Zhang, C. Chen, Q. Peng, D. Wang, Y. Li, Nat. Commun., 2018, 9, 5422.
[15]	T. Zhou, H. Shan, H. Yu, C. a. Zhong, J. Ge, N. Zhang, W. Chu, W. Yan, Q. Xu, H. a. Wu, C. Wu, Y. Xie, Adv. Mater., 2020, 32, 2003251.
[16]	J. Chang, X. Song, C. Yu, H. Huang, J. Hong, Y. Ding, H. Huang, J. Yu, X. Tan, Z. Zhao, J. Qiu, Nano Energy, 2020, 69, 104377.
[17]	Z. Xu, X. Zhang, X. Wang, J. Fang, Y. Zhang, X. Liu, W. Zhu, Y. Yan, Z. Zhuang, ACS Nano, 2021, 15, 7131-7138.
[18]	S. Liu, Z. Li, C. Wang, W. Tao, M. Huang, M. Zuo, Y. Yang, K. Yang, L. Zhang, S. Chen, P. Xu, Q. Chen, Nat. Commun., 2020, 11, 938.
[19]	J. Jin, J. Yin, H. Liu, P. Xi, Chin. J. Catal., 2019, 40, 43-51.
[20]	J. Yu, H. Song, X. Li, L. Tang, Z. Tang, B. Yang, S. Lu, Adv. Funct. Mater., 2021, 31, 2107196.
[21]	Y. Zhai, B. Zhang, R. Shi, S. Zhang, Y. Liu, B. Wang, K. Zhang, G. I. N. Waterhouse, T. Zhang, S. Lu, Adv. Energy Mater., 2021, 12, 2103426.
[22]	B. Wang, S. Lu, Matter, 2022, 5, 110-149.
[23]	P. Ding, H. Song, J. Chang, S. Lu, Nano Res., 2022, https://doi.org/10.1007/s12274-022-4377-4.
[24]	W. Li, Y. Zhao, Y. Liu, M. Sun, G. I. N. Waterhouse, B. Huang, K. Zhang, T. Zhang, S. Lu, Angew. Chem. Int. Ed., 2021, 60, 3290-3298.
[25]	Y. Liu, N. Chen, W. Li, M. Sun, T. Wu, B. Huang, X. Yong, Q. Zhang, L. Gu, H. Song, R. Bauer, J. S. Tse, S. Zang, B. Yang, S. Lu, SmartMat, 2022, 3, 249-259.
[26]	H. Song, Y. Li, L. Shang, Z. Tang, T. Zhang, S. Lu, Nano Energy, 2020, 72, 104730.
[27]	Y. Liu, Y. Yang, Z. Peng, Z. Liu, Z. Chen, L. Shang, S. Lu, T. Zhang, Nano Energy, 2019, 65, 104023.
[28]	Y. Liu, X. Li, Q. Zhang, W. Li, Y. Xie, H. Liu, L. Shang, Z. Liu, Z. Chen, L. Gu, Z. Tang, T. Zhang, S. Lu, Angew. Chem. Int. Ed., 2020, 59, 1718-1726.
[29]	H. Song, M. Wu, Z. Tang, J. S. Tse, B. Yang, S. Lu, Angew. Chem. Int. Ed., 2021, 60, 7234-7244.
[30]	C. Shao, S. Zhuang, H. Zhang, Q. Jiang, X. Xu, J. Ye, B. Li, X. Wang, Small, 2021, 17, 2006178.
[31]	Z. Sun, Y. Wang, L. Zhang, H. Wu, Y. Jin, Y. Li, Y. Shi, T. Zhu, H. Mao, J. Liu, C. Xiao, S. Ding, Adv. Funct. Mater., 2020, 30, 1910482.
[32]	J. Chang, C. Yu, X. Song, X. Tan, Y. Ding, Z. Zhao, J. Qiu, Angew. Chem. Int. Ed., 2021, 60, 3587-3595.
[33]	P. Yin, T. Yao, Y. Wu, L. Zheng, Y. Lin, W. Liu, H. Ju, J. Zhu, X. Hong, Z. Deng, G. Zhou, S. Wei, Y. Li, Angew. Chem. Int. Ed., 2016, 55, 10800-10805.
[34]	J. Song, Y. Chen, H. Huang, J. Wang, S.-C. Huang, Y.-F. Liao, A. E. Fetohi, F. Hu, H. Li, L. Chen, X. Han, K. M. El-Khatib, S. Peng, Adv. Sci., 2022, 9, 2104522.
[35]	Y. Jiang, Y.-P. Deng, R. Liang, J. Fu, D. Luo, G. Liu, J. Li, Z. Zhang, Y. Hu, Z. Chen, Adv. Energy Mater., 2019, 9, 1900911.
[36]	L. Yang, L. Shi, D. Wang, Y. Lv, D. Cao, Nano Energy, 2018, 50, 691-698.
[37]	C. Chen, Y. Li, D. Cheng, H. He, K. Zhou, ACS Appl. Mater. Interfaces, 2020, 12, 40415-40425.
[38]	X. Xie, L. Peng, H. Yang, G. I. N. Waterhouse, L. Shang, T. Zhang, Adv. Mater., 2021, 33, 2101038.
[39]	C. Tang, B. Wang, H.-F. Wang, Q. Zhang, Adv. Mater., 2017, 29, 1703185.
[40]	Y. Zhao, Q. Lai, J. Zhu, J. Zhong, Z. Tang, Y. Luo, Y. Liang, Small, 2018, 14, 1704207.
[41]	L. Wei, H. E. Karahan, S. Zhai, H. Liu, X. Chen, Z. Zhou, Y. Lei, Z. Liu, Y. Chen, Adv. Mater., 2017, 29, 1701410.
[42]	P. Liu, D. Gao, W. Xiao, L. Ma, K. Sun, P. Xi, D. Xue, J. Wang, Adv. Funct. Mater., 2018, 28, 1706928.
[43]	X. Chen, L. Wei, Y. Wang, S. Zhai, Z. Chen, S. Tan, Z. Zhou, A. K. Ng, X. Liao, Y. Chen, Energy Storage Mater., 2018, 11, 134-143.
[44]	Z. Song, X. Han, Y. Deng, N. Zhao, W. Hu, C. Zhong, ACS Appl. Mater. Interfaces, 2017, 9, 22694-22703.
[45]	Y. Wang, L. Tao, Z. Xiao, R. Chen, Z. Jiang, S. Wang, Adv. Funct. Mater., 2018, 28, 1705356.