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Flagship Article

Modulating the electronic spin state by constructing dual-metal atomic pairs for activating the dynamic site of oxygen reduction reaction

Shenghua Ye1,3,§, Shuhua Xie1,§, Yaqi Lei1,§, Xiuyuan Yang1, Jing Hu1, Lirong Zheng4, Zhida Chen1, Yonghuan Fu1, Xiangzhong Ren1, Yongliang Li1, Xiaoping Ouyang5, Qianling Zhang1( ), Jianhong Liu1,3( ), Xueliang Sun2( )
College of Chemistry and Environmental Engineering, Graphene Composite Research Center, Shenzhen University, Shenzhen 518060, China
Department of Mechanical and Materials Engineering, University of Western Ontario, London, Ontario N6A 5B9, Canada
Shenzhen Eigen-Equation Graphene Technology Co. Ltd., Shenzhen 518000, China
Institute of High Energy Physics Chinese Academy of Sciences, Beijing 100049, China
School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105, China

§ Shenghua Ye, Shuhua Xie, and Yaqi Lei contributed equally to this work.

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Graphical Abstract

The binuclear MnFeN8 moiety anchored onto a graphite-like structure (GLS) (Mn-Fe BNSs/GLS) was constructed by pyrolysis for oxygen reduction reaction (ORR). Unique short-range electronic interaction between Mn and Fe sites renders Fe sites transform from intermediate to a high spin state facilitates the cleavage of O–O and endows Mn-Fe BNSs/GLS with excellent ORR activity.

Abstract

In this study, dual-metal atomic pairs of manganese (Mn)-iron (Fe) binuclear sites (BNSs) with two conjoint MnN4 and FeN4 moieties (MnFeN8) anchored onto a graphite-like structure (GLS) (Mn-Fe BNSs/GLS) were constructed. The binuclear MnFeN8 structure was verified experimentally and theoretically. Magnetic measurements and Gaussian calculations reveal that this unique Mn-Fe BNSs exhibit strong short-range electronic interaction between Mn and Fe sites, which decouples two paired d electrons in Fe sites, thereby transforming Fe sites from an intermediate to a high spin state. The optimal electronic configuration of Fe sites and their binuclear structure facilitate an oxygen reduction reaction (ORR) thermodynamically and dynamically, respectively, endowing Mn-Fe BNSs with improved ORR performance.

Keywords

manganese (Mn)-iron (Fe) binuclear sitessynergistic effectspin stateoxygen reduction reaction

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References

[1]

Guo, D. H.; Shibuya, R.; Akiba, C.; Saji, S.; Kondo, T.; Nakamura, J. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 2016, 351, 361–365.
Crossref Google Scholar
[2]

Chen, K. J.; Liu, K.; An, P. D.; Li, H. J. W.; Lin, Y. Y.; Hu, J. H.; Jia, C. K.; Fu, J. W.; Li, H. M.; Liu, H. et al. Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction. Nat. Commun. 2020, 11, 4173.
Crossref Google Scholar
[3]

Li, Y. G.; Dai, H. J. Recent advances in zinc-air batteries. Chem. Soc. Rev. 2014, 43, 5257–5275.
Crossref Google Scholar
[4]

Zhao, C. X.; Liu, J. N.; Wang, J.; Ren, D.; Li, B. Q.; Zhang, Q. Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts. Chem. Soc. Rev. 2021, 50, 7745–7778.
Crossref Google Scholar
[5]

Liu, Z. Y.; Zhao, Z. P.; Peng, B. S.; Duan, X. F.; Huang, Y. Beyond extended surfaces: Understanding the oxygen reduction reaction on nanocatalysts. J. Am. Chem. Soc. 2020, 142, 17812–17827.
Crossref Google Scholar
[6]

Chattot, R.; Le Bacq, O.; Beermann, V.; Kühl, S.; Herranz, J.; Henning, S.; Kühn, L.; Asset, T.; Guétaz, L.; Renou, G. et al. Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Nat. Mater. 2018, 17, 827–833.
Crossref Google Scholar
[7]

Ma, Q. L.; Jin, H. H.; Zhu, J. W.; Li, Z. L.; Xu, H. W.; Liu, B. S.; Zhang, Z. W.; Ma, J. J.; Mu, S. C. Stabilizing Fe-N-C catalysts as model for oxygen reduction reaction. Adv. Sci. 2021, 8, 2102209.
Crossref Google Scholar
[8]

Gao, R. J.; Wang, J.; Huang, Z. F.; Zhang, R. R.; Wang, W.; Pan, L.; Zhang, J. F.; Zhu, W. K.; Zhang, X. W.; Shi, C. X. et al. Pt/Fe2O3 with Pt-Fe pair sites as a catalyst for oxygen reduction with ultralow Pt loading. Nat. Energy 2021, 6, 614–623.
Crossref Google Scholar
[9]

Song, Z. X.; Zhang, L.; Doyle-Davis, K.; Fu, X. Z.; Luo, J. L.; Sun, X. L. Recent advances in MOF-derived single atom catalysts for electrochemical applications. Adv. Energy Mater. 2020, 10, 2001561.
Crossref Google Scholar
[10]

Wan, C. Z.; Duan, X. F.; Huang, Y. Molecular design of single-atom catalysts for oxygen reduction reaction. Adv. Energy Mater. 2020, 10, 1903815.
Crossref Google Scholar
[11]

Yu, Y.; Zhang, J. N. Optimizing configuration engineering of edge-hosted Fe-Nx active sites for oxygen reduction reaction. Chem. Catal. 2021, 1, 1155–1157.
Crossref Google Scholar
[12]

Han, Y. H.; Wang, Y. G.; Xu, R. R.; Chen, W. X.; Zheng, L. R.; Han, A. J.; Zhu, Y. Q.; Zhang, J.; Zhang, H. B.; Luo, J. et al. Electronic structure engineering to boost oxygen reduction activity by controlling the coordination of the central metal. Energy Environ. Sci. 2018, 11, 2348–2352.
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]

Li, J. Z.; Zhang, H. G.; Samarakoon, W.; Shan, W. T.; Cullen, D. A.; Karakalos, S.; Chen, M. J.; Gu, D. M.; More, K. L.; Wang, G. F. et al. Thermally driven structure and performance evolution of atomically dispersed FeN4 sites for oxygen reduction. Angew. Chem., Int. Ed. 2019, 58, 18971–18980.
Crossref Google Scholar
[15]

Zhang, Y.; Huang, B. L.; Luo, G.; Sun, T.; Feng, Y. G.; Wang, Y. C.; Ma, Y. H.; Shao, Q.; Li, Y. F.; Zhou, Z. Y. et al. Atomically deviated Pd-Te nanoplates boost methanol-tolerant fuel cells. Sci. Adv. 2020, 6, eaba9731.
Crossref Google Scholar
[16]

Lyu, X.; Jia, Y.; Mao, X.; Li, D. H.; Li, G.; Zhuang, L. Z.; Wang, X.; Yang, D. J.; Wang, Q.; Du, A. J. et al. Gradient-concentration design of stable core–shell nanostructure for acidic oxygen reduction electrocatalysis. Adv. Mater. 2020, 32, 2003493.
Crossref Google Scholar
[17]

Li, H. G.; Di, S. L.; Niu, P.; Wang, S. L.; Wang, J.; Li, L. A durable half-metallic diatomic catalyst for efficient oxygen reduction. Energy Environ. Sci. 2022, 15, 1601–1610.
Crossref Google Scholar
[18]

Alkhalifah, M. A.; Howchen, B.; Staddon, J.; Celorrio, V.; Tiwari, D.; Fermin, D. J. Correlating orbital composition and activity of LaMnxNi1–xO3 nanostructures toward oxygen electrocatalysis. J. Am. Chem. Soc. 2022, 144, 4439–4447.
Crossref Google Scholar
[19]

Zhu, G. H.; Yang, H. Y.; Jiang, Y.; Sun, Z. Q.; Li, X. P.; Yang, J. P.; Wang, H. F.; Zou, R. J.; Jiang, W.; Qiu, P. P. et al. Modulating the electronic structure of FeCo nanoparticles in N-doped mesoporous carbon for efficient oxygen reduction reaction. Adv. Sci. 2022, 9, 2200394.
Crossref Google Scholar
[20]

Li, R. Z.; Wang, D. S. Understanding the structure–performance relationship of active sites at atomic scale. Nano Res. 2022, 15, 6888–6923.
Crossref Google Scholar
[21]

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. 2022, 61, e202115219.
Google Scholar
[22]

Zheng, X. B.; Li, B. B.; Wang, Q. S.; Wang, D. S.; Li, Y. D. Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis. Nano Res. 2022, 15, 7806–7839.
Crossref Google Scholar
[23]

Chao, G. J.; An, X. Y.; Zhang, L. S.; Tian, J.; Fan, W.; Liu, T. X. Electron-rich platinum electrocatalysts supported onto tin oxides for efficient oxygen reduction. Compos. Commun. 2021, 24, 100603.
Crossref Google Scholar
[24]

Zhu, T. Y.; Feng, Q. C.; Liu, S. L.; Zhang, C. Metallogel-derived 3D porous carbon nanosheet composites as an electrocatalyst for oxygen reduction reaction. Compos. Commun. 2020, 20, 100376.
Crossref Google Scholar
[25]

Hu, J.; Cao, L. J.; Wang, Z.; Liu, J. L.; Zhang, J. J.; Cao, Y. L.; Lu, Z. G.; Cheng, H. Hollow high-entropy metal organic framework derived nanocomposite as efficient electrocatalyst for oxygen reduction reaction. Compos. Commun. 2021, 27, 100866.
Crossref Google Scholar
[26]

Zhang, L.; Si, R. R.; Liu, H. S.; Chen, N.; Wang, Q.; Adair, K.; Wang, Z. Q.; Chen, J. T.; Song, Z. X.; Li, J. J. et al. Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction. Nat. Commun. 2019, 10, 4936.
Crossref Google Scholar
[27]

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.
Crossref Google Scholar
[28]

Wang, J.; Huang, Z. Q.; Liu, W.; Chang, C. R.; Tang, H. L.; Li, Z. J.; Chen, W. X.; Jia, C. J.; Yao, T.; Wei, S. Q. et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc. 2017, 139, 17281–17284.
Crossref Google Scholar
[29]

Lu, Z. Y.; Wang, B.; Hu, Y. F.; Liu, W.; Zhao, Y. F.; Yang, R. O.; Li, Z. P.; Luo, J.; Chi, B.; Jiang, Z. et al. An isolated zinc-cobalt atomic pair for highly active and durable oxygen reduction. Angew. Chem., Int. Ed. 2019, 58, 2622–2626.
Crossref Google Scholar
[30]

Zhu, W. J.; Zhang, L.; Liu, S. H.; Li, A.; Yuan, X. T.; Hu, C. L.; Zhang, G.; Deng, W. Y.; Zang, K. T.; Luo, J. et al. Enhanced CO2 electroreduction on neighboring Zn/Co monomers by electronic effect. Angew. Chem., Int. Ed. 2020, 59, 12664–12668.
Crossref Google Scholar
[31]

Deng, D. J.; Qian, J. C.; Liu, X. Z.; Li, H. P.; Su, D.; Li, H. N.; Li, H. M.; Xu, L. Non-covalent interaction of atomically dispersed Cu and Zn pair sites for efficient oxygen reduction reaction. Adv. Funct. Mater. 2022, 32, 2203471.
Crossref Google Scholar
[32]

Bai, L. C.; Hsu, C. S.; Alexander, D. T. L.; Chen, H. M.; Hu, X. L. A cobalt-iron double-atom catalyst for the oxygen evolution reaction. J. Am. Chem. Soc. 2019, 141, 14190–14199.
Crossref Google Scholar
[33]

Yin, S. H.; Yang, J.; Han, Y.; Li, G.; Wan, L. Y.; Chen, Y. H.; Chen, C.; Qu, X. M.; Jiang, Y. X.; Sun, S. G. Construction of highly active metal-containing nanoparticles and FeCo-N4 composite sites for the acidic oxygen reduction reaction. Angew. Chem., Int. Ed. 2020, 59, 21976–21979.
Crossref Google Scholar
[34]

He, Y. T.; Yang, X. X.; Li, Y. S.; Liu, L. T.; Guo, S. W.; Shu, C. Y.; Liu, F.; Liu, Y. N.; Tan, Q.; Wu, G. Atomically dispersed Fe-Co dual metal sites as bifunctional oxygen electrocatalysts for rechargeable and flexible Zn-air batteries. ACS Catal. 2022, 12, 1216–1227.
Crossref Google Scholar
[35]

Chen, J. Y.; Li, H.; Fan, C.; Meng, Q. W.; Tang, Y. W.; Qiu, X. Y.; Fu, G. T.; Ma, T. Y. Dual single-atomic Ni-N4 and Fe-N4 sites constructing janus hollow graphene for selective oxygen electrocatalysis. Adv. Mater. 2020, 32, 2003134.
Crossref Google Scholar
[36]

Wan, W. C.; Zhao, Y. G.; Wei, S. Q.; Triana, C. A.; Li, J. G.; Arcifa, A.; Allen, C. S.; Cao, R.; Patzke, G. R. Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts. Nat. Commun. 2021, 12, 5589.
Crossref Google Scholar
[37]

Chang, Y. Q.; Hong, F.; He, C. X.; Zhang, Q. L.; Liu, J. H. Nitrogen and sulfur dual-doped non-noble catalyst using fluidic acrylonitrile telomer as precursor for efficient oxygen reduction. Adv. Mater. 2013, 25, 4794–4799.
Crossref Google Scholar
[38]

Mi, H. W.; Li, Y. L.; Zhu, P. Y.; Chai, X. Y.; Sun, L. N.; Zhuo, H. T.; Zhang, Q. L.; He, C. X.; Liu, J. H. In situ coating of nitrogen-doped graphene-like nanosheets on silicon as a stable anode for high-performance lithium-ion batteries. J. Mater. Chem. A 2014, 2, 11254–11260.
Google Scholar
[39]

Rahaman, M. S. A.; Ismail, A. F.; Mustafa, A. A review of heat treatment on polyacrylonitrile fiber. Polym. Degrad. Stab. 2007, 92, 1421–1432.
Crossref Google Scholar
[40]

Yan, H. J.; Xie, Y.; Jiao, Y. Q.; Wu, A. P.; Tian, C. G.; Zhang, X. M.; Wang, L.; Fu, H. G. Holey reduced graphene oxide coupled with an Mo2N-Mo2C heterojunction for efficient hydrogen evolution. Adv. Mater. 2018, 30, 1704156.
Crossref Google Scholar
[41]

Ye, S. H.; Luo, F. Y.; Xu, T. T.; Zhang, P. Y.; Shi, H. D.; Qin, S. Q.; Wu, J. P.; He, C. X.; Ouyang, X. P.; Zhang, Q. L. et al. Boosting the alkaline hydrogen evolution of Ru nanoclusters anchored on B/N-doped graphene by accelerating water dissociation. Nano Energy 2020, 68, 104301.
Crossref Google Scholar
[42]

Fei, H. L.; Dong, J. C.; Feng, Y. X.; Allen, C. S.; Wan, C. Z.; Volosskiy, B.; Li, F. M.; 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
[43]

Shen, G. Q.; Zhang, R. R.; Pan, L.; Hou, F.; Zhao, Y. J.; Shen, Z. Y.; Mi, W. B.; Shi, C. X.; Wang, Q. F.; Zhang, X. W. et al. Regulating the spin state of FeIII by atomically anchoring on ultrathin titanium dioxide for efficient oxygen evolution electrocatalysis. Angew. Chem., Int. Ed. 2020, 59, 2313–2317.
Crossref Google Scholar
[44]

Li, J. Z.; Chen, M. J.; Cullen, D. A.; Hwang, S.; Wang, M. Y.; Li, B. Y.; Liu, K. X.; Karakalos, S.; Lucero, M.; Zhang, H. G. et al. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat. Catal. 2018, 1, 935–945.
Crossref Google Scholar
[45]

Kramm, U. I.; Herranz, J.; Larouche, N.; Arruda, T. M.; Lefèvre, M.; Jaouen, F.; Bogdanoff, P.; Fiechter, S.; Abs-Wurmbach, I.; Mukerjee, S. et al. Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells. Phys. Chem. Chem. Phys. 2012, 14, 11673–11688.
Crossref Google Scholar
[46]

Lu, Y.; Li, L.; Zhang, Q.; Niu, Z. Q.; Chen, J. Electrolyte and interface engineering for solid-state sodium batteries. Joule 2018, 2, 1747–1770.
Crossref Google Scholar
[47]

Sun, Y. M.; Sun, S. N.; Yang, H. T.; Xi, S. B.; Gracia, J.; Xu, Z. J. Spin-related electron transfer and orbital interactions in oxygen electrocatalysis. Adv. Mater. 2020, 32, 2003297.
Crossref Google Scholar
Nano Research
Volume 16 Issue 2,
February 2023
Pages 1869-1877
DOI: 10.1007/s12274-022-4979-x
Cite this article:
Ye S, Xie S, Lei Y, et al. Modulating the electronic spin state by constructing dual-metal atomic pairs for activating the dynamic site of oxygen reduction reaction. Nano Research, 2023, 16(2): 1869-1877. https://doi.org/10.1007/s12274-022-4979-x
Topics:
Oxygen reduction reaction

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Received: 05 August 2022
Revised: 26 August 2022
Accepted: 27 August 2022
Published: 04 November 2022
© Tsinghua University Press 2022
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