Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells

Nature Catalysis volumeĀ 1,Ā pages 935ā€“945 (2018)Cite this article

Subjects

Abstract

Platinum group metal (PGM)-free catalysts that are also iron free are highly desirable for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells, as they avoid possible Fenton reactions. Here we report an efficient ORR catalyst that consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C). Evidence for the embedding of the atomically dispersed MnN4 moieties within the carbon surface-exposed basal planes was established by X-ray absorption spectroscopy and their dispersion was confirmed by aberration-corrected electron microscopy with atomic resolution. The Mn-N-C catalyst exhibited a half-wave potential of 0.80ā€‰V versus the reversible hydrogen electrode, approaching that of Fe-N-C catalysts, along with significantly enhanced stability in acidic media. The encouraging performance of the Mn-N-C catalyst as a PGM-free cathode was demonstrated in fuel cell tests. First-principles calculations further support the MnN4 sites as the origin of the ORR activity via a 4eāˆ’ pathway in acidic media.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic of atomically dispersed MnN4 site catalyst synthesis.
Fig. 2: Structural characterization by XANES, EXAFS and XPS.
Fig. 3: Morphology and atomic structure of the 20Mn-NC-second catalyst.
Fig. 4: ORR activity studied by using RRDE and fuel cell tests.
Fig. 5: Catalyst stability studied by using potential cycling and constant potentials.
Fig. 6: Fundamental understanding of possible Mn active sites by using DFT calculations.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available from the primary corresponding author (G.Wu) upon reasonable request.

References

  1. LefĆØvre, M., Proietti, E., Jaouen, F. & Dodelet, J.-P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324, 71ā€“74 (2009).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  2. Proietti, E. et al. Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells. Nat. Commun. 2, 416 (2011).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  3. Wu, G. & Zelenay, P. Nanostructured nonprecious metal catalysts for oxygen reduction reaction. Acc. Chem. Res. 46, 1878ā€“1889 (2013).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  4. Gewirth, A. A., Varnell, J. A. & DiAscro, A. M. Nonprecious metal catalysts for oxygen reduction in heterogeneous aqueous systems. Chem. Rev. 118, 2313ā€“2339 (2018).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  5. Chung, H. T. et al. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 357, 479ā€“484 (2017).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  6. Wu, G., More, K. L., Johnston, C. M. & Zelenay, P. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332, 443ā€“447 (2011).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  7. Yan, D. et al. Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions. Adv. Mater. 29, 1606459 (2017).

    ArticleĀ  CASĀ  Google ScholarĀ 

  8. Gong, K., Du, F., Xia, Z., Durstock, M. & Dai, L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760ā€“764 (2009).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  9. Masa, J., Xia, W., Muhler, M. & Schuhmann, W. On the role of metals in nitrogenā€doped carbon electrocatalysts for oxygen reduction. Angew. Chem. Int. Ed. 54, 10102ā€“10120 (2015).

    ArticleĀ  CASĀ  Google ScholarĀ 

  10. Liu, J. et al. High performance platinum single atom electrocatalyst for oxygen reduction reaction. Nat. Commun. 8, 15938 (2017).

    ArticleĀ  CASĀ  PubMedĀ  PubMed CentralĀ  Google ScholarĀ 

  11. Zitolo, A. et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 14, 937ā€“942 (2015).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  12. Jiang, W. J. et al. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe-Nx. J. Am. Chem. Soc. 138, 3570ā€“3578 (2016).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  13. Wu, G. et al. Carbon nanocomposite catalysts for oxygen reduction and evolution reactions: from nitrogen doping to transition-metal addition. Nano Energy 29, 83ā€“110 (2016).

    ArticleĀ  CASĀ  Google ScholarĀ 

  14. Banham, D. et al. A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells. J. Power Sources 285, 334ā€“348 (2015).

    ArticleĀ  CASĀ  Google ScholarĀ 

  15. Ferrandon, M. et al. Stability of iron species in heat-treated polyanilineā€“ironā€“carbon polymer electrolyte fuel cell cathode catalysts. Electrochim. Acta 110, 282ā€“291 (2013).

    ArticleĀ  CASĀ  Google ScholarĀ 

  16. Wu, G. Current challenge and pĆæerspective of PGM-free cathode catalysts for PEM fuel cells. Front. Energy 11, 286ā€“298 (2017).

    ArticleĀ  Google ScholarĀ 

  17. Wu, G. et al. Performance durability of polyaniline-derived non-precious cathode catalysts. ECS Trans. 25, 1299ā€“1311 (2009).

    ArticleĀ  Google ScholarĀ 

  18. Choi, C. H. et al. Stability of Fe-N-C catalysts in acidic medium studied by operando spectroscopy. Angew. Chem. Int. Ed. 54, 12753ā€“12757 (2015).

    ArticleĀ  CASĀ  Google ScholarĀ 

  19. Kramm, U. I., Lefevre, M., Bogdanoff, P., Schmeisser, D. & Dodelet, J. P. Analyzing structural changes of Fe-N-C cathode catalysts in pem fuel cell by mossbauer spectroscopy of complete membrane electrode assemblies. J. Phys. Chem. Lett. 5, 3750ā€“3756 (2014).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  20. Goellner, V. et al. Degradation of Fe/N/C catalysts upon high polarization in acid medium. Phys. Chem. Chem. Phys. 16, 18454ā€“18462 (2014).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  21. Walling, C. Fentonā€™s reagent revisited. Acc. Chem. Res. 8, 125ā€“131 (1975).

    ArticleĀ  CASĀ  Google ScholarĀ 

  22. Wang, X. X. et al. Nitrogen-coordinated single cobalt atom catalysts for oxygen reduction in proton exchange membrane fuel cells. Adv. Mater. 30, 1706758 (2018).

    ArticleĀ  CASĀ  Google ScholarĀ 

  23. Zhong, Y. et al. The constraints of transition metal substitutions (Ti, Cr, Mn, Co and Ni) in magnetite on its catalytic activity in heterogeneous fenton and UV/Fenton reaction: from the perspective of hydroxyl radical generation. Appl. Catal. B 150ā€“151, 612ā€“618 (2014).

    ArticleĀ  CASĀ  Google ScholarĀ 

  24. Wu, G. et al. Synthesisā€“structureā€“performance correlation for polyanilineā€“Meā€“C non-precious metal cathode catalysts for oxygen reduction in fuel cells. J. Mater. Chem. 21, 11392ā€“11405 (2011).

    ArticleĀ  CASĀ  Google ScholarĀ 

  25. Gupta, S. et al. Quaternary FeCoNiMn-based nanocarbon electrocatalysts for bifunctional oxygen reduction and evolution: promotional role of Mn doping in stabilizing carbon. ACS Catal. 7, 8386ā€“8393 (2017).

    ArticleĀ  CASĀ  Google ScholarĀ 

  26. Wang, X. et al. Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction. Nanoscale 7, 20290ā€“20298 (2015).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  27. Zhang, H., Osgood, H., Xie, X., Shao, Y. & Wu, G. Engineering nanostructures of PGM-free oxygen-reduction catalysts using metalā€“organic frameworks. Nano Energy 31, 331ā€“350 (2017).

    ArticleĀ  CASĀ  Google ScholarĀ 

  28. Pan, F. et al. Unveiling active sites of CO2 reduction on nitrogen-coordinated and atomically dispersed iron and cobalt catalysts. ACS Catal. 8, 3116ā€“3122 (2018).

    ArticleĀ  CASĀ  Google ScholarĀ 

  29. Wang, X. X. et al. Ordered Pt3Co intermetallic nanoparticles derived from metalā€“organic frameworks for oxygen reduction. Nano. Lett. 18, 4163ā€“4171 (2018).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  30. Qiao, Z. et al. 3D polymer hydrogel for high-performance atomic iron-rich catalysts for oxygen reduction in acidic media. Appl. Catal. B 219, 629ā€“639 (2017).

    ArticleĀ  CASĀ  Google ScholarĀ 

  31. Gupta, S. et al. Engineering favorable morphology and structure of Fe-N-C oxygen-reduction catalysts through tuning of nitrogen/carbon precursors. ChemSusChem 10, 774ā€“785 (2017).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  32. Wang, H., Zhu, Q.-L., Zou, R. & Xu, Q. Metal-organic frameworks for energy applications. Chem 2, 52ā€“80 (2017).

    ArticleĀ  CASĀ  Google ScholarĀ 

  33. Chen, Y. et al. Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew. Chem. Int. Ed. 56, 6937ā€“6941 (2017).

    ArticleĀ  CASĀ  Google ScholarĀ 

  34. Zhang, H. et al. Single atomic iron catalysts for oxygen reduction in acidic media: particle size control and thermal activation. J. Am. Chem. Soc. 139, 14143ā€“14149 (2017).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  35. Xia, B. Y. et al. A metalā€“organic framework-derived bifunctional oxygen electrocatalyst. Nat. Energy 1, 15006 (2016).

    ArticleĀ  CASĀ  Google ScholarĀ 

  36. Yang, L., Zeng, X., Wang, W. & Cao, D. Recent progress in MOF-derived, heteroatom-doped porous carbons as highly efficient electrocatalysts for oxygen reduction reaction in fuel cells. Adv. Func. Mater. 28, 1704537 (2018).

    ArticleĀ  CASĀ  Google ScholarĀ 

  37. Feng, Z. et al. Atomic-scale cation dynamics in a monolayer VOx/Ī±-Fe2O3 catalyst. RSC Adv. 5, 103834ā€“103840 (2015).

    ArticleĀ  CASĀ  Google ScholarĀ 

  38. Weng, Z. et al. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 9, 415 (2018).

    ArticleĀ  CASĀ  PubMedĀ  PubMed CentralĀ  Google ScholarĀ 

  39. Liu, Z. et al. Tuning the electronic environment of zinc ions with a ligand for dendrite-free zinc deposition in an ionic liquid. Phys. Chem. Chem. Phys. 19, 25989ā€“25995 (2017).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  40. Chen, Y. Z. et al. From bimetallic metalā€“organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis. Adv. Mater. 27, 5010ā€“5016 (2015).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  41. Lai, Q. et al. Metalā€“organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-Nx sites for advanced oxygen reduction in acid media. ACS Catal. 7, 1655ā€“1663 (2017).

    ArticleĀ  CASĀ  Google ScholarĀ 

  42. Wang, Q. et al. Phenylenediamine-based FeNx/C catalyst with high activity for oxygen reduction in acid medium and its active-site probing. J. Am. Chem. Soc. 136, 10882ā€“10885 (2014).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  43. Sahraie, N. R. et al. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts. Nat. Commun. 6, 8618 (2015).

    ArticleĀ  CASĀ  PubMedĀ  PubMed CentralĀ  Google ScholarĀ 

  44. Li, Y. et al. An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nat. Nanotech. 7, 394ā€“400 (2012).

    ArticleĀ  CASĀ  Google ScholarĀ 

  45. Wu, G. et al. Titanium dioxide-supported non-precious metal oxygen reduction electrocatalyst. Chem. Commun. 46, 7489ā€“7491 (2010).

    ArticleĀ  CASĀ  Google ScholarĀ 

  46. Herranz, J. et al. Unveiling N-protonation and anion-binding effects on Fe/N/C-catalysts for O2 reduction in pem fuel cells. J Phys. Chem. C 115, 16087ā€“16097 (2011).

    ArticleĀ  CASĀ  Google ScholarĀ 

  47. Norskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886ā€“17892 (2004).

    ArticleĀ  CASĀ  Google ScholarĀ 

  48. Kulkarni, A., Siahrostami, S., Patel, A. & Norskov, J. K. Understanding catalytic activity trends in the oxygen reduction reaction. Chem. Rev. 118, 2302ā€“2312 (2018).

    ArticleĀ  CASĀ  PubMedĀ  Google ScholarĀ 

  49. Henkelman, G., Uberuaga, B. P. & JĆ³nsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901ā€“9904 (2000).

    ArticleĀ  CASĀ  Google ScholarĀ 

  50. Zhang, C., Zhang, W. & Zheng, W. Pinpointing single metal atom anchoring sites in carbon for oxygen reduction: Doping sites or defects? Chin. J. Catal. 39, 4ā€“7 (2018).

    ArticleĀ  CASĀ  Google ScholarĀ 

Download references

Acknowledgements

G.Wu thanks the Research and Education in eNergy, Environment and Water (RENEW) program at the University at Buffalo, SUNY and National Science Foundation (CBET-1604392, 1804326) for partial financial support. G.Wu, G.Wang and H.X. acknowledge support from the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office (DE-EE0008075). Electron microscopy research was conducted at Oak Ridge National Laboratoryā€™s Center for Nanophase Materials Sciences of (D.A.C. and K.L.M) and the Center for Functional Nanomaterials at Brookhaven National Laboratory (S.H. and D.S., under contract No. DE-SC0012704), which both are US DOE Office of Science User Facilities. XAS measurements were performed at beamline 9-BM at the Advanced Photon Source, a User Facility operated for the US DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 (Z.F. and G.E.S.). Z.W. and J.L. thank the National Natural Science Foundation of China (Grant No. 21273058 and 21673064) for support.

Author information

Author notes

  1. These authors contributed equally: Jiazhan Li, Mengjie Chen

Authors and Affiliations

  1. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China

    Jiazhan LiĀ &Ā Zhenbo Wang

  2. Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, NY, USA

    Jiazhan Li,Ā Mengjie Chen,Ā Hanguang ZhangĀ &Ā Gang Wu

  3. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    David A. Cullen

  4. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

    Sooyeon HwangĀ &Ā Dong Su

  5. School of Chemical Biological, and Environmental Engineering, Oregon State University, Corvallis, OR, USA

    Maoyu Wang,Ā Marcos LuceroĀ &Ā Zhenxing Feng

  6. Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA, USA

    Boyang Li,Ā Kexi LiuĀ &Ā Guofeng Wang

  7. Department of Chemical Engineering, University of South Carolina, Columbia, SC, USA

    Stavros Karakalos

  8. Giner Inc, Newton, MA, USA

    Chao LeiĀ &Ā Hui Xu

  9. Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA

    George E. Sterbinsky

  10. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Karren L. More

Authors
  1. Jiazhan Li
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  2. Mengjie Chen
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  3. David A. Cullen
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  4. Sooyeon Hwang
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  5. Maoyu Wang
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  6. Boyang Li
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  7. Kexi Liu
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  8. Stavros Karakalos
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  9. Marcos Lucero
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  10. Hanguang Zhang
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  11. Chao Lei
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  12. Hui Xu
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  13. George E. Sterbinsky
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  14. Zhenxing Feng
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  15. Dong Su
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  16. Karren L. More
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  17. Guofeng Wang
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  18. Zhenbo Wang
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

  19. Gang Wu
    View author publications

    You can also search for this author in PubMedĀ Google Scholar

Contributions

G.Wu, Z.W. and J. L. designed the experiments, analysed the experimental data, and wrote the manuscript. J.L., M.C. and H.Z. synthesized catalyst samples and carried out electrochemical measurements. D.A.C., K.L.M, S.H. and D.S performed electron microscopy analyses and data interpretation. S.K. conducted XPS analysis. M.W., M.L., G.E.S. and Z.F. recorded and analysed XAS data. C.L. and H.X. carried out fuel cell tests. B.L., K.L. and G.Wang conducted computational studies.

Corresponding authors

Correspondence to Zhenbo Wang or Gang Wu.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisherā€™s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Note 1, Supplementary Figures 1ā€“30, Supplementary Tables 1ā€“13 and Supplementary References

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, J., Chen, M., Cullen, D.A. et al. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat Catal 1, 935ā€“945 (2018). https://doi.org/10.1038/s41929-018-0164-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41929-018-0164-8

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter ā€” what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing