Issue

Vol. 12 (2020)

Secondary-Atom-Doping Enables Robust Fe–N–C Single-Atom Catalysts with Enhanced Oxygen Reduction Reaction

https://doi.org/10.1007/s40820-020-00502-5
Xin Luo
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Xiaoqian Wei
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Hengjia Wang
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Wenling Gu
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Takuma Kaneko
Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182‑8585, Japan
Yusuke Yoshida
Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182‑8585, Japan
Xiao Zhao
Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182‑8585, Japan HIGHLIGHTS • Secondary-atom-doped strategy was proposed to synthesize single-atom electrocatalyst. • The increase in both the density of active sites and their intrinsic activity was achieved simultaneously. • The resultant single-atom catalyst shows outstanding ORR activity in acidic media. ABSTRACT Single-atom catalysts (SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis. However, a large room for improving their activity and durability remains. Herein, we construct atomically dispersed Fe sites in N-doped carbon supports by secondary-atom-doped strategy. Upon the secondary doping, the density and coordination environment of active sites can be efficiently tuned, enabling the simultaneous improvement in the number and reactivity of the active site. Besides, structure optimizations in terms of the enlarged surface area and improved hydrophilicity can be achieved simultaneously. Due to the beneficial microstructure and abundant highly active FeN5 moieties resulting from the secondary doping, the resultant catalyst exhibits an admirable half-wave potential of 0.81 V versus 0.83 V for Pt/C and much better stability than Pt/C in acidic media. This work would offer a general strategy for the design and preparation of highly active SACs for electrochemical energy devices. KEYWORDS Single-atom catalysts; Fe–N–C catalysts; Doping; Porous nanostructures; Oxygen reduction reaction dicyandiamide Fe3+ O2 H2O H2O
Chengzhou Zhu
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China

Corresponding Author: Chengzhou Zhu

czzhu@mail.ccnu.edu.cn

Nano-Micro Letters, Vol. 12 (2020), Article Number: 163

Abstract

Single-atom catalysts (SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis. However, a large room for improving their activity and durability remains. Herein, we construct atomically dispersed Fe sites in N-doped carbon supports by secondary-atom-doped strategy. Upon the secondary doping, the density and coordination environment of active sites can be efficiently tuned, enabling the simultaneous improvement in the number and reactivity of the active site. Besides, structure optimizations in terms of the enlarged surface area and improved hydrophilicity can be achieved simultaneously. Due to the beneficial microstructure and abundant highly active FeN5 moieties resulting from the secondary doping, the resultant catalyst exhibits an admirable half-wave potential of 0.81 V versus 0.83 V for Pt/C and much better stability than Pt/C in acidic media. This work would offer a general strategy for the design and preparation of highly active SACs for electrochemical energy devices.


Highlights:


1 Secondary-atom-doped strategy was proposed to synthesize single-atom electrocatalyst.
2 The increase in both the density of active sites and their intrinsic activity was achieved simultaneously.
3 The resultant single-atom catalyst shows outstanding ORR activity in acidic media.

Keywords

Single-atom catalysts Fe–N–C catalysts Doping Porous nanostructures Oxygen reduction reaction
Luo, Xin, Xiaoqian Wei, Hengjia Wang, Wenling Gu, Takuma Kaneko, Yusuke Yoshida, Xiao Zhao, and Chengzhou Zhu. 2020. “Secondary-Atom-Doping Enables Robust Fe–N–C Single-Atom Catalysts With Enhanced Oxygen Reduction Reaction”. Nano-Micro Letters 12 (August):163. https://doi.org/10.1007/s40820-020-00502-5.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. J. Li, S. Sharma, X. Liu, Y.-T. Pan, J.S. Spendelow et al., Hard-magnet L10-CoPt nanoparticles advance fuel cell catalysis. Joule 3(1), 124–135 (2019). https://doi.org/10.1016/j.joule.2018.09.016
  2. J. Liu, D. Zhu, Y. Zheng, A. Vasileff, S.-Z. Qiao, Self-supported earth-abundant nanoarrays as efficient and robust electrocatalysts for energy-related reactions. ACS Catal. 8(7), 6707–6732 (2018). https://doi.org/10.1021/acscatal.8b01715
  3. W.-J. Liu, H. Jiang, H.-Q. Yu, Emerging applications of biochar-based materials for energy storage and conversion. Energy Environ. Sci. 12(6), 1751–1779 (2019). https://doi.org/10.1039/C9EE00206E
  4. S.K. Singh, K. Takeyasu, J. Nakamura, Active sites and mechanism of oxygen reduction reaction electrocatalysis on nitrogen-doped carbon materials. Adv. Mater. 31, 1804297 (2019). https://doi.org/10.1002/adma.201804297
  5. X. Luo, X. Wei, H. Zhong, H. Wang, Y. Wu et al., Single-atom Ir-anchored 3D amorphous NiFe nanowire@nanosheets for boosted oxygen evolution reaction. ACS Appl. Mater. Interfaces 12(3), 3539–3546 (2020). https://doi.org/10.1021/acsami.9b17476
  6. Y. Guo, T. Park, J. Yi, J. Henzie, J. Kim et al., Nanoarchitectonics for transition-metal-sulfide-based electrocatalysts for water splitting. Adv. Mater. 31(17), 1807134 (2019). https://doi.org/10.1002/adma.201807134
  7. Y. Guo, J. Tang, H. Qian, Z. Wang, Y. Yamauchi, One-pot synthesis of zeolitic imidazolate framework 67-derived hollow Co3S4@MoS2 heterostructures as efficient bifunctional catalysts. Chem. Mater. 29(13), 5566–5573 (2017). https://doi.org/10.1021/acs.chemmater.7b00867
  8. Y. Guo, J. Tang, Z. Wang, Y. Kang, Y. Bando, Y. Yamauchi, Elaborately assembled core-shell structured metal sulfides as a bifunctional catalyst for highly efficient electrochemical overall water splitting. Nano Energy 47, 494–502 (2018). https://doi.org/10.1016/j.nanoen.2018.03.012
  9. X. Luo, X. Wei, H. Wang, Y. Wu, W. Gu, C. Zhu, Hexamine-coordination-framework-derived Co-N-doped carbon nanosheets for robust oxygen reduction reaction. ACS Sustain. Chem. Eng. 8(26), 9721–9730 (2020). https://doi.org/10.1021/acssuschemeng.0c01826
  10. C. Xuan, J. Wang, J. Zhu, D. Wang, Recent progress of metal organic frameworks-based nanomaterials for electrocatalysis Acta Phys. Chim. Sin. 33(1), 149–164 (2017). https://doi.org/10.3866/PKU.WHXB201609143
  11. X. Wei, X. Luo, H. Wang, W. Gu, W. Cai, Y. Lin, C. Zhu, Highly-defective Fe-N-C catalysts towards pH-universal oxygen reduction reaction. Appl. Catal. B: Environ. 263, 118347 (2019). https://doi.org/10.1016/j.apcatb.2019.118347
  12. C. Chen, X. Zhang, Z. Zhou, X. Zhang, S. Sun, Experimental boosting of the oxygen reduction activity of an Fe/N/C Catalyst by sulfur doping and density functional theory calculations. Acta Phys. Chim. Sin. 33(9), 1875–1883 (2017). https://doi.org/10.3866/PKU.WHXB201705088
  13. S. Ahn, X. Yu, A. Manthiram, “Wiring” Fe-Nx-embedded porous carbon framework onto 1D nanotubes for efficient oxygen reduction reaction in alkaline and acidic media. Adv. Mater. 29, 1606534 (2017). https://doi.org/10.1002/adma.201606534
  14. J. Guo, C.-Y. Lin, Z. Xia, Z. Xiang, A pyrolysis-free covalent organic polymer for oxygen reduction, a pyrolysis-free covalent organic polymer for oxygen reduction. Angew. Chem. Int. Ed. 130, 12747–12752 (2018). https://doi.org/10.1002/anie.201808226
  15. J.-I. Jung, M. Risch, S. Park, M.G. Kim, G. Nam et al., Optimizing nanoparticle perovskite for bifunctional oxygen electrocatalysis. Energy Environ. Sci. 9, 176–183 (2016). https://doi.org/10.1039/C5EE03124A
  16. W. Xia, R. Zou, L. An, D. Xia, S. Guo, A metal-organic framework route to in situ encapsulation of Co@Co3O4@C core@bishell nanoparticles into a highly ordered porous carbon matrix for oxygen reduction. Energy Environ. Sci. 8, 568–576 (2015). https://doi.org/10.1039/C4EE02281E
  17. J. Zhang, Z. Zhao, Z. Xia, L. Dai, A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nanotechnol. 10(5), 444–452 (2015). https://doi.org/10.1038/nnano.2015.48
  18. H. Hu, L. Han, M. Yu, Z. Wang, X. Lou, Metal-organic-framework-engaged formation of Co nanoparticle-embedded carbon@ Co9S8 double-shelled nanocages for efficient oxygen reduction. Energy Environ. Sci. 9, 107–111 (2016). https://doi.org/10.1039/C5EE02903A
  19. Y. Wang, Y.J. Tang, K. Zhou, Self-adjusting activity induced by intrinsic reaction intermediate in Fe-N-C single-atom catalysts. J. Am. Chem. Soc. 141(36), 14115–14119 (2019). https://doi.org/10.1021/jacs.9b07712
  20. X. Sun, S. Sun, S. Gu, Z. Liang, J. Zhang et al., High-performance single atom bifunctional oxygen catalysts derived from ZIF-67 superstructures. Nano Energy 61, 245–250 (2019). https://doi.org/10.1016/j.nanoen.2019.04.076
  21. X. Wang, Z. Li, Y. Qu, T. Yuan, W. Wang, Y. Wu, Y. Li, Review of metal catalysts for oxygen reduction reaction: from nanoscale engineering to atomic design. Chem 5(6), 1486–1511 (2019). https://doi.org/10.1016/j.chempr.2019.03.002
  22. L. Hu, X. Zeng, X. Wei, H. Wang, W. Yu et al., Interface engineering for enhancing electrocatalytic oxygen evolution of NiFe LDH/NiTe heterostruces. Appl. Catal. B: Environ. 273(15), 119014 (2020). https://doi.org/10.1016/j.apcatb.2020.119014
  23. Y. Qian, Q. Liu, E. Sarnello, C. Tang, M. Chng et al., MOF-derived carbon networks with atomically dispersed Fe-Nx sites for oxygen reduction reaction catalysis in acidic media. ACS Mater. Lett. 1(1), 37–43 (2019). https://doi.org/10.1021/acsmaterialslett.9b00052
  24. Z. Chen, W. Gong, Z. Liu, S. Cong, Z. Zheng et al., Coordination-controlled single-atom tungsten as a non-3d-metal oxygen reduction reaction electrocatalyst with ultrahigh mass activity. Nano Energy 60, 394–403 (2019). https://doi.org/10.1016/j.nanoen.2019.03.045
  25. Z. Li, H. He, H. Cao, S. Sun, W. Diao et al., Atomic Co/Ni dual sites and Co/Ni alloy nanoparticles in N-doped porous Janus-like carbon frameworks for bifunctional oxygen electrocatalysis. Appl. Catal. B: Environ. 240, 112–121 (2019). https://doi.org/10.1016/j.apcatb.2018.08.074
  26. J. Li, S. Chen, W. Li, R. Wu, S. Ibraheem et al., A eutectic salt-assisted semi-closed pyrolysis route to fabricate high-density active-site hierarchically porous Fe/N/C catalysts for the oxygen reduction reaction. J. Mater. Chem. A 6, 15504–15509 (2018). https://doi.org/10.1039/C8TA05419C
  27. J. Li, S. Chen, N. Yang, M. Deng, S. Ibraheem et al., Ultrahigh-loading zinc single-atom catalyst for highly efficient oxygen reduction in both acidic and alkaline media. Angew. Chem. Int. Ed. 58(21), 7035–7039 (2019). https://doi.org/10.1002/anie.201902109
  28. H. Jiang, Y. Liu, W. Li, J. Li, Co Nanoparticles confined in 3D nitrogen-doped porous carbon foams as bifunctional electrocatalysts for long-life rechargeable zn-air batteries. Small 14(13), 1703739 (2018). https://doi.org/10.1002/smll.201703739
  29. W. Jiao, C. Chen, W. You, J. Zhang, J. Liu, R. Che, Yolk-shell Fe/Fe4N@Pd/C magnetic nanocomposite as an efficient recyclable ORR electrocatalyst and SERS substrate. Small 15(7), 1805032 (2019). https://doi.org/10.1002/smll.201805032
  30. P. Chen, T. Zhou, L. Xing, K. Xu, Y. Tong et al., Atomically dispersed iron-nitrogen species as electrocatalysts for bifunctional oxygen evolution and reduction reactions. Angew. Chem. Int. Ed. 56(2), 610–614 (2017). https://doi.org/10.1002/anie.201610119
  31. K. Yuan, S. Sfaelou, M. Qiu, D. Lützenkirchen-Hecht, X. Zhuang et al., Pyridinic-N-dominated doped defective graphene as a superior oxygen electrocatalyst for ultrahigh-energy-density Zn-air batteries. ACS Energy Lett. 3(5), 252–260 (2018). https://doi.org/10.1021/acsenergylett.8b00303
  32. C. Zhu, S. Fu, Q. Shi, D. Du, Y. Lin, Single-atom electrocatalysts. Angew. Chem. Int. Ed. 56(45), 13944–13960 (2017). https://doi.org/10.1002/anie.201703864
  33. Y. Guo, J. Tang, J. Henzie, B. Jiang, H. Qian et al., Assembly of hollow mesoporous nanoarchitectures composed of ultrafine Mo2C nanoparticles on N-doped carbon nanosheets for efficient electrocatalytic reduction of oxygen. Mater. Horiz. 4, 1171–1177 (2017). https://doi.org/10.1039/C7MH00586E
  34. H. Tan, J. Tang, J. Henzie, Y. Li, X. Xu et al., Assembly of hollow carbon nanospheres on graphene nanosheets and creation of iron-nitrogen-doped porous carbon for oxygen reduction. ACS Nano 12, 5674–5683 (2018). https://doi.org/10.1021/acsnano.8b01502
  35. H. Tan, Y. Li, J. Kim, T. Takei, Z. Wang et al., Sub-50 nm iron-nitrogen-doped hollow carbon sphere-encapsulated iron carbide nanoparticles as efficient oxygen reduction catalysts. Adv. Sci. 5(7), 1800120 (2018). https://doi.org/10.1002/advs.201800120
  36. W. Xia, J. Tang, J. Li, S. Zhang, K. Wu, J. He, Y. Yamauchi, Defect-rich graphene nanomesh produced by thermal exfoliation of metal-organic frameworks for the oxygen reduction reaction. Angew. Chem. Int. Ed. 58(38), 13354–13359 (2019). https://doi.org/10.1002/anie.201906870
  37. R. Jiang, L. Li, T. Sheng, G. Hu, Y. Chen, L. Wang, Edge-site engineering of atomically dispersed Fe-N4 by selective C–N bond cleavage for enhanced oxygen reduction reaction activities. J. Am. Chem. Soc. 140(37), 11594–11598 (2018). https://doi.org/10.1021/jacs.8b07294
  38. Y. Pan, S. Liu, K. Sun, X. Chen, B. Wang et al., A bimetallic Zn/Fe polyphthalocyanine-derived single-atom Fe-N4 catalytic site: a superior trifunctional catalyst for overall water splitting and zn-air batteries. Angew. Chem. Int. Ed. 57(28), 8614–8618 (2018). https://doi.org/10.1002/anie.201804349
  39. Q. Li, W. Chen, H. Xiao, Y. Gong, Z. Li et al., Fe isolated single atoms on S, N codoped carbon by copolymer pyrolysis strategy for highly efficient oxygen reduction reaction. Adv. Mater. 30(25), 1800588 (2018). https://doi.org/10.1002/adma.201800588
  40. E. Luo, H. Zhang, X. Wang, L. Gao, L. Gong et al., Single-atom Cr-N4 sites designed for durable oxygen reduction catalysis in acid media. Angew. Chem. Int. Ed. 58(36), 12469–12475 (2019). https://doi.org/10.1002/anie.201906289
  41. D. Zhao, J.-L. Shui, C. Chen, X. Chen, B.M. Reprogle, D. Wang, D.-J. Liu, Iron imidazolate framework as precursor for electrocatalysts in polymer electrolyte membrane fuel cells. Chem. Sci. 3, 3200–3205 (2012). https://doi.org/10.1039/C2SC20657A
  42. Y. Zhao, X. Li, X. Jia, S. Gao, Why and how to tailor the vertical coordinate of pore size distribution to construct ORR-active carbon materials? Nano Energy 58, 384–391 (2019). https://doi.org/10.1016/j.nanoen.2019.01.057
  43. C. Zhu, Q. Shi, B.Z. Xu, S. Fu, G. Wan et al., Hierarchically porous M-N-C (M = Co and Fe) single-atom electrocatalysts with robust MNx active moieties enable enhanced ORR performance. Adv. Energy Mater. 8(29), 1801956 (2018). https://doi.org/10.1002/aenm.201801956
  44. X. Liu, J. Kang, Y. Dai, C. Dong, X. Guo, X. Jia, Graphene-like nitrogen-doped carbon nanosheet prepared from direct calcination of dopamine confined by g-C3N4 for oxygen reduction. Adv. Mater. Interfaces 5(14), 1800303 (2018). https://doi.org/10.1002/admi.201800303
  45. B.-Q. Li, C.-X. Zhao, S. Chen, J.-N. Liu, X. Chen, L. Song, Q. Zhang, Framework-porphyrin-derived single-atom bifunctional oxygen electrocatalysts and their applications in Zn-air batteries. Adv. Mater. 31(19), 1900592 (2019). https://doi.org/10.1002/adma.201900592
  46. H.-W. Liang, X. Zhuang, S. Brüller, X. Feng, K. Müllen, Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction. Nat. Commun. 5, 4973 (2014). https://doi.org/10.1038/ncomms5973
  47. J. Li, M. Chen, D.A. Cullen, S. Hwang, M. Wang et al., Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat. Catal. 1, 935–945 (2018). https://doi.org/10.1038/s41929-018-0164-8
  48. H. Jiang, J. Gu, X. Zheng, M. Liu, X. Qiu et al., Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER. Energy Environ. Sci. 12, 322–333 (2019). https://doi.org/10.1039/C8EE03276A
  49. J. Wang, G. Yin, Y. Shao, Z. Wang, Y. Gao, Investigation of further improvement of platinum catalyst durability with highly graphitized carbon nanotubes support. J. Phys. Chem. C 112(15), 5784–5789 (2008). https://doi.org/10.1021/jp800186p
  50. Q. Lai, L. Zheng, Y. Liang, J. He, J. Zhao, J. Chen, Metal-organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-Nx sites for advanced oxygen reduction in acid media. ACS Catal. 7(3), 1655–1663 (2017). https://doi.org/10.1021/acscatal.6b02966
  51. X. Ao, W. Zhang, Z. Li, J.-G. Li, L. Soule et al., Markedly enhanced oxygen reduction activity of single-atom Fe catalysts via integration with Fe nanoclusters. ACS Nano 13, 11853–11862 (2019). https://doi.org/10.1021/acsnano.9b05913
  52. Y. Zheng, D.-S. Yang, J.M. Kweun, C. Li, K. Tan et al., Rational design of common transition metal-nitrogen-carbon catalysts for oxygen reduction reaction in fuel cells. Nano Energy 30, 443–449 (2016). https://doi.org/10.1016/j.nanoen.2016.10.037
  53. Y. Chen, S. Ji, S. Zhao, W. Chen, J. Dong et al., Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell. Nat. Commun. 9(1), 5422 (2018). https://doi.org/10.1038/s41467-018-07850-2
  54. Q. Jia, N. Ramaswamy, H. Hafiz, U. Tylus, K. Strickland et al., Experimental observation of redox-induced Fe-N switching behavior as a determinant role for oxygen reduction activity. ACS Nano 9(12), 12496–12505 (2015). https://doi.org/10.1021/acsnano.5b05984
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 5642 Download : 4257

Most read articles by the same author(s)