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Nano Research 2022, 15(5): 3913-3919 https://doi.org/10.1007/s12274-021-4046-z
Research Article | Issue | Published: 31 December 2021

Ultrafast Joule heating synthesis of hierarchically porous graphene-based Co-N-C single-atom monoliths

Show Author's Information Lingli Xing,  Rui Liu,  Zhichao Gong,  Jingjing Liu,  Jianbin Liu,  Haisheng Gong,  Kang Huang,  Huilong Fei ( )
Advanced Catalytic Engineering Research Center of the Ministry of Education, State Key Laboratory for Chemo/Biosensing and Chemometrics, and College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
Keywords:
hydrogen evolution reaction, hierarchically porous structure, single atom catalysts, Joule heating, self-supporting film
Topics:
Synthesis
Cite this article:
Xing L, Liu R, Gong Z, et al. Ultrafast Joule heating synthesis of hierarchically porous graphene-based Co-N-C single-atom monoliths. Nano Research, 2022, 15(5): 3913-3919. https://doi.org/10.1007/s12274-021-4046-z
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Abstract Full text Electronic supplementary material About this article

Herein, we develop a transient heating-quenching strategy triggered by Joule heating for the synthesis of single-atom cobalt- and nitrogen-doped graphene materials with three-dimensional porous monolithic architecture (denoted as CoNG-JH). The ultrafast Joule heating procedure simultaneously enables the reduction of graphene oxide and the incorporation of metal and nitrogen atoms into the graphene matrix within 2-second period. Meanwhile, the transient quenching avoids the extended heating-induced atom aggregation, ensuring the rapid and stable dispersion of atomic-scale CoNx active sites in graphene. Additionally, the interconnected macropores and nanopores formed by the self-assembly of graphene sheets facilitate the unimpeded ion and gas transport during the catalytic process. When used as an electrode for the hydrogen evolution reaction (HER), the fabricated free-standing CoNG-JH exhibits high catalytic activity and durability with a low overpotential of 106 mV at 10 mA·cm−2 and a small Tafel slope of 66 mV·dec−1 in 0.5 M H2SO4 electrolyte. The presented synthesis and design strategy open up a rapid and facile route for the manufacturing of single atom catalysts.


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About this article

Ultrafast Joule heating synthesis of hierarchically porous graphene-based Co-N-C single-atom monoliths

Show Author's information Lingli Xing, Rui Liu, Zhichao Gong, Jingjing Liu, Jianbin Liu, Haisheng Gong, Kang Huang, Huilong Fei ( )
Advanced Catalytic Engineering Research Center of the Ministry of Education, State Key Laboratory for Chemo/Biosensing and Chemometrics, and College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China

Abstract

Herein, we develop a transient heating-quenching strategy triggered by Joule heating for the synthesis of single-atom cobalt- and nitrogen-doped graphene materials with three-dimensional porous monolithic architecture (denoted as CoNG-JH). The ultrafast Joule heating procedure simultaneously enables the reduction of graphene oxide and the incorporation of metal and nitrogen atoms into the graphene matrix within 2-second period. Meanwhile, the transient quenching avoids the extended heating-induced atom aggregation, ensuring the rapid and stable dispersion of atomic-scale CoNx active sites in graphene. Additionally, the interconnected macropores and nanopores formed by the self-assembly of graphene sheets facilitate the unimpeded ion and gas transport during the catalytic process. When used as an electrode for the hydrogen evolution reaction (HER), the fabricated free-standing CoNG-JH exhibits high catalytic activity and durability with a low overpotential of 106 mV at 10 mA·cm−2 and a small Tafel slope of 66 mV·dec−1 in 0.5 M H2SO4 electrolyte. The presented synthesis and design strategy open up a rapid and facile route for the manufacturing of single atom catalysts.

Keywords: hydrogen evolution reaction, hierarchically porous structure, single atom catalysts, Joule heating, self-supporting film

References(57)

1

Yang, X. F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y.; Zhang, T. Single-atom catalysts: A new frontier in heterogeneous catalysis. Acc. Chem. Res. 2013, 46, 1740–1748.
DOI Google Scholar
2

Chen, Y. J.; Ji, S. F.; Sun, W. M.; Lei, Y. P.; Wang, Q. C.; Li, A.; Chen, W. X.; Zhou, G.; Zhang, Z. D.; Wang, Y. et al. Engineering the atomic interface with single platinum atoms for enhanced photocatalytic hydrogen production. Angew. Chem. 2020, 132, 1311–1317.
DOI Google Scholar
3

Yang, J. R.; Li, W. H.; Wang, D. S.; Li, Y. D. Single-atom materials: Small structures determine macroproperties. Small Struct. 2021, 2, 2000051.
DOI Google Scholar
4

Chen, Y. J.; Ji, S. F.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Single-atom catalysts: Synthetic strategies and electrochemical applications. Joule 2018, 2, 1242–1264.
DOI Google Scholar
5

Han, A. L.; 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.
DOI Google Scholar
6

Lei, Y. P.; Wang, Y. C.; Liu, Y.; Song, C. Y.; Li, Q.; Wang, D. S.; Li, Y. D. Designing atomic active centers for hydrogen evolution electrocatalysts. Angew. Chem., Int. Ed. 2020, 59, 20794–20812.
DOI Google Scholar
7

Yang, J. R.; Li, W. H.; Tan, S. D.; Xu, K. N.; Wang, Y.; Wang, D. S.; Li, Y. D. The electronic metal-support interaction directing the design of single atomic site catalysts: Achieving high efficiency towards hydrogen evolution. Angew. Chem. 2021, 133, 19233–19239.
DOI Google Scholar
8

Baby, A.; Trovato, L.; Di Valentin, C. Single atom catalysts (SAC) trapped in defective and nitrogen-doped graphene supported on metal substrates. Carbon 2021, 174, 772–788.
DOI Google Scholar
9

Bie, C. B.; Yu, H. G.; Cheng, B.; Ho, W. K.; Fan, J. J.; Yu, J. G. Design, fabrication, and mechanism of nitrogen-doped graphene-based photocatalyst. Adv. Mater. 2021, 33, 2003521.
DOI Google Scholar
10
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.
11

Fei, H. L.; Dong, J. C.; Chen, D. L.; Hu, T. D.; Duan, X. D.; Shakir, I.; Huang, Y.; Duan, X. F. Single atom electrocatalysts supported on graphene or graphene-like carbons. Chem. Soc. Rev. 2019, 48, 5207–5241.
DOI Google Scholar
12

He, Y. H.; Liu, S. W.; Priest, C.; Shi, Q. R.; Wu, G. Atomically dispersed metal-nitrogen-carbon catalysts for fuel cells: Advances in catalyst design, electrode performance, and durability improvement. Chem. Soc. Rev. 2020, 49, 3484–3524.
DOI Google Scholar
13

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.
DOI Google Scholar
14

Pan, Y.; Chen, Y. J.; Wu, K. L.; Chen, Z.; Liu, S. J.; Cao, X.; Cheong, W. C.; Meng, T.; Luo, J.; Zheng, L. R. et al. Regulating the coordination structure of single-atom Fe-NxCy catalytic sites for benzene oxidation. Nat. Commun. 2019, 10, 4290.
DOI Google Scholar
15

Guan, J. Q.; Duan, Z. Y.; Zhang, F. X.; Kelly, S. D.; Si, R.; Dupuis, M.; Huang, Q. G.; Chen, J. Q.; Tang, C. H.; Li, C. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nat. Catal. 2018, 1, 870–877.
DOI Google Scholar
16

Du, Z. Z.; Chen, X. J.; Hu, W.; Chuang, C. H.; Xie, S.; Hu, A. J.; Yan, W. S.; Kong, X. H.; Wu, X. J.; Ji, H. X. et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries. J. Am. Chem. Soc. 2019, 141, 3977–3985.
DOI Google Scholar
17

Fei, H. L.; Dong, J. C.; Wan, C. Z.; Zhao, Z. P.; Xu, X.; Lin, Z. Y.; Wang, Y. L.; Liu, H. T.; Zang, K. T.; Luo, J. et al. Microwave-assisted rapid synthesis of graphene-supported single atomic metals. Adv. Mater. 2018, 30, 1802146.
DOI Google Scholar
18

Lacey, S. D.; Dong, Q.; Huang, Z. N.; Luo, J. R.; Xie, H.; Lin, Z. W.; Kirsch, D. J.; Vattipalli, V.; Povinelli, C.; Fan, W. et al. Stable multimetallic nanoparticles for oxygen electrocatalysis. Nano Lett. 2019, 19, 5149–5158.
DOI Google Scholar
19

Xie, P. F.; Yao, Y. G.; Huang, Z. N.; Liu, Z. Y.; Zhang, J. L.; Li, T. Y.; Wang, G. F.; Shahbazian-Yassar, R.; Hu, L. B.; Wang, C. Highly efficient decomposition of ammonia using high-entropy alloy catalysts. Nat. Commun. 2019, 10, 4011.
DOI Google Scholar
20

Yao, Y. G.; Huang, Z. N.; Xie, P. F.; Lacey, S. D.; Jacob, R. J.; Xie, H.; Chen, F. J.; Nie, A. M.; Pu, T. C.; Rehwoldt, M. et al. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science 2018, 359, 1489–1494.
DOI Google Scholar
21

Yao, Y. G.; Huang, Z. N.; Xie, P. F.; Li, T. Y.; Lacey, S. D.; Jiao, M. L.; Xie, H.; Fu, K. K.; Jacob, R. J.; Kline, D. J. et al. Ultrafast, controllable synthesis of sub-nano metallic clusters through defect engineering. ACS Appl. Mater. Interfaces 2019, 11, 29773–29779.
DOI Google Scholar
22

Yao, Y. G.; Huang, Z. N.; Xie, P. F.; Wu, L. P.; Ma, L.; Li, T. Y.; Pang, Z. Q.; Jiao, M. L.; Liang, Z. Q.; Gao, J. L. et al. High temperature shockwave stabilized single atoms. Nat. Nanotechnol. 2019, 14, 851–857.
DOI Google Scholar
23

Jin, Q. Y.; Ren, B. W.; Cui, H.; Wang, C. X. Nitrogen and cobalt co-doped carbon nanotube films as binder-free trifunctional electrode for flexible zinc-air battery and self-powered overall water splitting. Appl. Catal. B: Environ. 2021, 283, 119643.
DOI Google Scholar
24

Ma, T. Y.; Dai, S.; Qiao, S. Z. Self-supported electrocatalysts for advanced energy conversion processes. Mater. Today 2016, 19, 265–273.
DOI Google Scholar
25

Cai, G. R.; Zhang, W.; Jiao, L.; Yu, S. H.; Jiang, H. L. Template-directed growth of well-aligned MOF arrays and derived self-supporting electrodes for water splitting. Chem 2017, 2, 791–802.
DOI Google Scholar
26

Son, H. J.; Kim, M. J.; Ahn, S. H. Monolithic Co-N-C membrane integrating Co atoms and clusters as a self-supporting multi-functional electrode for solid-state zinc-air batteries and self-powered water splitting. Chem. Eng. J. 2021, 414, 128739.
DOI Google Scholar
27

Wang, Y. Q.; Zou, Y. Q.; Tao, L.; Wang, Y. Y.; Huang, G.; Du, S. Q.; Wang, S. Y. Rational design of three-phase interfaces for electrocatalysis. Nano Res. 2019, 12, 2055–2066.
DOI Google Scholar
28

Xie, W. F.; Song, Y. K.; Li, S. J.; Li, J. B.; Yang, Y. S.; Liu, W.; Shao, M. F.; Wei, M. Single-atomic-Co electrocatalysts with self-supported architecture toward oxygen-involved reaction. Adv. Funct. Mater. 2019, 29, 1906477.
DOI Google Scholar
29

Pan, Z. Y.; Tang, Z.; Zhan, Y. Z.; Sun, D. Three-dimensional porous CoNiO2@reduced graphene oxide nanosheet arrays/nickel foam as a highly efficient bifunctional electrocatalyst for overall water splitting. Tungsten 2020, 2, 390–402.
DOI Google Scholar
30

Lv, Z. P.; Ma, W. S.; Wang, M.; Dang, J.; Jian, K. L.; Liu, D.; Huang, D. J. Co-constructing interfaces of multiheterostructure on MXene (Ti3C2Tx)-modified 3D self-supporting electrode for ultraefficient electrocatalytic HER in alkaline media. Adv. Funct. Mater. 2021, 31, 2102576.
DOI Google Scholar
31

Zhang, L. L.; Wang, Y. J.; Niu, Z. Q.; Chen, J. Single atoms on graphene for energy storage and conversion. Small Methods 2019, 3, 1800443.
DOI Google Scholar
32

Voiry, D.; Yang, J.; Kupferberg, J.; Fullon, R.; Lee, C.; Jeong, H. Y.; Shin, H. S.; Chhowalla, M. High-quality graphene via microwave reduction of solution-exfoliated graphene oxide. Science 2016, 353, 1413–1416.
DOI Google Scholar
33

Liang, J.; Jiao, Y.; Jaroniec, M.; Qiao, S. Z. Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angew. Chem., Int. Ed. 2012, 51, 11496–11500.
DOI Google Scholar
34

Xia, W.; Tang, J.; Li, J. J.; Zhang, S. H.; Wu, K. C. W.; He, J. P.; Yamauchi, Y. Defect-rich graphene nanomesh produced by thermal exfoliation of metal-organic frameworks for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2019, 58, 13354–13359.
DOI Google Scholar
35

Zhao, X. J.; Pachfule, P.; Li, S.; Langenhahn, T.; Ye, M. Y.; Schlesiger, C.; Praetz, S.; Schmidt, J.; Thomas, A. Macro/microporous covalent organic frameworks for efficient electrocatalysis. J. Am. Chem. Soc. 2019, 141, 6623–6630.
DOI Google Scholar
36

Liu, J. J.; Gong, Z. C.; Allen, C.; Ge, W.; Gong, H. S.; Liao, J. W.; Liu, J. B.; Huang, K.; Yan, M. M.; Liu, R. et al. Edge-hosted Fe-N3 sites on a multiscale porous carbon framework combining high intrinsic activity with efficient mass transport for oxygen reduction. Chem Catal. 2021, 1, 1291–1307.
DOI Google Scholar
37

Ma, Y. F.; Chen, M.; Geng, H. B.; Dong, H. F.; Wu, P.; Li, X. M.; Guan, G. Q.; Wang, T. J. Synergistically tuning electronic structure of porous β-Mo2C spheres by Co doping and Mo-vacancies defect engineering for optimizing hydrogen evolution reaction activity. Adv. Funct. Mater. 2020, 30, 2000561.
DOI Google Scholar
38

Yang, L.; Lv, Y. L.; Cao, D. P. Co, N-codoped nanotube/graphene 1D/2D heterostructure for efficient oxygen reduction and hydrogen evolution reactions. J. Mater. Chem. A 2018, 6, 3926–3932.
DOI Google Scholar
39

Jia, Y.; Zhang, L. Z.; Zhuang, L. Z.; Liu, H. L.; Yan, X. C.; Wang, X.; Liu, J. D.; Wang, J. C.; Zheng, Y. R.; Xiao, Z. H. et al. Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen doping. Nat. Catal. 2019, 2, 688–695.
DOI Google Scholar
40

Tavakkoli, M.; Flahaut, E.; Peljo, P.; Sainio, J.; Davodi, F.; Lobiak, E. V.; Mustonen, K.; Kauppinen, E. I. Mesoporous single-atom-doped graphene-carbon nanotube hybrid: Synthesis and tunable electrocatalytic activity for oxygen evolution and reduction reactions. ACS Catal. 2020, 10, 4647–4658.
DOI Google Scholar
41

Lu, Q.; Wu, H.; Zheng, X. R.; Chen, Y. N.; Rogach, A. L.; Han, X. P.; Deng, Y. D.; Hu, W. B. Encapsulating cobalt nanoparticles in interconnected N-doped hollow carbon nanofibers with enriched Co-N-C moiety for enhanced oxygen electrocatalysis in Zn-air batteries. Adv. Sci. 2021, 8, 2101438.
DOI Google Scholar
42

Fei, H. L.; Dong, J. C.; Arellano-Jiménez, M. J.; Ye, G. L.; Kim, N. D.; Samuel, E. L. G.; Peng, Z. W.; Zhu, Z.; Qin, F.; Bao, J. M. et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat. Commun. 2015, 6, 8668.
DOI Google Scholar
43

Liu, R.; Gong, Z. C.; Liu, J. B.; Dong, J. C.; Liao, J. W.; Liu, H.; Huang, H. K.; Liu, J. J.; Yan, M. M.; Huang, K. et al. Design of aligned porous carbon films with single-atom Co-N-C sites for high-current-density hydrogen generation. Adv. Mater. 2021, 33, e2103533.
DOI Google Scholar
44

Wang, X. Q.; Chen, Z.; Zhao, X. Y.; Yao, T.; Chen, W. X.; You, R.; Zhao, C. M.; Wu, G.; Wang, J.; Huang, W. X. et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO2. Angew. Chem., Int. Ed. 2018, 57, 1944–1948.
DOI Google Scholar
45

Faber, M. S.; Dziedzic, R.; Lukowski, M. A.; Kaiser, N. S.; Ding, Q.; Jin, S. High-performance electrocatalysis using metallic cobalt pyrite (CoS2) micro- and nanostructures. J. Am. Chem. Soc. 2014, 136, 10053–10061.
DOI Google Scholar
46

Cao, L. L.; Luo, Q. Q.; Liu, W.; Lin, Y.; Liu, X. K.; Cao, Y. J.; Zhang, W.; Wu, Y. E.; Yang, J. L.; Yao, T. et al. Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution. Nat. Catal. 2019, 2, 134–141.
DOI Google Scholar
47

Liang, H. W.; Brüller, S.; Dong, R. H.; Zhang, J.; Feng, X. L.; Müllen, K. Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution. Nat. Commun. 2015, 6, 7992.
DOI Google Scholar
48

Yi, J. D.; Xu, R.; Chai, G. L.; Zhang, T.; Zang, K. T.; Nan, B.; Lin, H.; Liang, Y. L.; Lv, J. Q.; Luo, J. et al. Cobalt single-atoms anchored on porphyrinic triazine-based frameworks as bifunctional electrocatalysts for oxygen reduction and hydrogen evolution reactions. J. Mater. Chem. A 2019, 7, 1252–1259.
DOI Google Scholar
49

Wan, J. W.; Zhao, Z. H.; Shang, H. S.; Peng, B.; Chen, W. X.; Pei, J. J.; Zheng, L. R.; Dong, J. C.; Cao, R.; Sarangi, R. et al. In situ phosphatizing of triphenylphosphine encapsulated within metal-organic frameworks to design atomic Co1-P1N3 interfacial structure for promoting catalytic performance. J. Am. Chem. Soc. 2020, 142, 8431–8439.
DOI Google Scholar
50

Wan, G.; Yang, C.; Zhao, W. P.; Li, Q. R.; Wang, N.; Li, T.; Zhou, H.; Chen, H. R.; Shi, J. L. Anion-regulated selective generation of cobalt sites in carbon: Toward superior bifunctional electrocatalysis. Adv. Mater. 2017, 29, 1703436.
DOI Google Scholar
51

Sun, T. T.; Zhao, S.; Chen, W. X.; Zhai, D.; Dong, J. C.; Wang, Y.; Zhang, S. L.; Han, A. J.; Gu, L.; Yu, R. et al. Single-atomic cobalt sites embedded in hierarchically ordered porous nitrogen-doped carbon as a superior bifunctional electrocatalyst. Proc. Natl. Acad. Sci. USA 2018, 115, 12692–12697.
DOI Google Scholar
52

Zhang, Y. J.; Li, W. F.; Lu, L. H.; Song, W. G.; Wang, C. R.; Zhou, L. S.; Liu, J. H.; Chen, Y.; Jin, H. Y.; Zhang, Y. G. Tuning active sites on cobalt/nitrogen doped graphene for electrocatalytic hydrogen and oxygen evolution. Electrochim. Acta 2018, 265, 497–506.
DOI Google Scholar
53

Popczun, E. J.; Read, C. G.; Roske, C. W.; Lewis, N. S.; Schaak, R. E. Highly active electrocatalysis of the hydrogen evolution reaction by cobalt phosphide nanoparticles. Angew. Chem., Int. Ed. 2014, 53, 5427–5430.
DOI Google Scholar
54

Kibsgaard, J.; Jaramillo, T. F. Molybdenum phosphosulfide: An active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2014, 53, 14433–14437.
DOI Google Scholar
55

Chen, W. X.; Pei, J. J.; He, C. T.; Wan, J. W.; Ren, H. L.; Zhu, Y. Q.; Wang, Y.; Dong, J. C.; Tian, S. B.; Cheong, W. C. et al. Rational design of single molybdenum atoms anchored on N-doped carbon for effective hydrogen evolution reaction. Angew. Chem., Int. Ed. 2017, 56, 16086–16090.
DOI Google Scholar
56

Yin, Y.; Han, J. C.; Zhang, Y. M.; Zhang, X. H.; Xu, P.; Yuan, Q.; Samad, L.; Wang, X. J.; Wang, Y.; Zhang, Z. H. et al. Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets. J. Am. Chem. Soc. 2016, 138, 7965–7972.
DOI Google Scholar
57

Marcano, D. C.; Kosynkin, D. V.; Berlin, J. M.; Sinitskii, A.; Sun, Z. Z.; Slesarev, A.; Alemany, L. B.; Lu, W.; Tour, J. M. Improved synthesis of graphene oxide. ACS Nano 2010, 4, 4806–4814.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 06 November 2021
Revised: 02 December 2021
Accepted: 04 December 2021
Published: 31 December 2021
Issue date: May 2022

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

H. L. F. acknowledges financial support from the National Natural Science Foundation of China (No. 51902099), Hunan high-level talent gathering project (No. 2019RS1021), Fundamental Research Funds for the Central Universities (No. 531119200087).

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