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:

Reaction-driven restructuring of defective PtSe2 into ultrastable catalyst for the oxygen reduction reaction

Nature Materials volume 23, pages 1704–1711 (2024)Cite this article

Subjects

Abstract

PtM (M = S, Se, Te) dichalcogenides are promising two-dimensional materials for electronics, optoelectronics and gas sensors due to their high air stability, tunable bandgap and high carrier mobility. However, their potential as electrocatalysts for the oxygen reduction reaction (ORR) is often underestimated due to their semiconducting properties and limited surface area from van der Waals stacking. Here we show an approach for synthesizing a highly efficient and stable ORR catalyst by restructuring defective platinum diselenide (DEF-PtSe2) through electrochemical cycling in an O2-saturated electrolyte. After 42,000 cycles, DEF-PtSe2 exhibited 1.3 times higher specific activity and 2.6 times higher mass activity compared with a commercial Pt/C electrocatalyst. Even after 126,000 cycles, it maintained superior ORR performance with minimal decay. Quantum mechanical calculations using hybrid density functional theory reveal that the improved performance is due to the synergistic contributions from Pt nanoparticles and the apical active sites on the DEF-PtSe2 surface. This work highlights the potential of DEF-PtSe2 as a durable electrocatalyst for ORR, offering insights into PtM dichalcogenide electrochemistry and the design of advanced catalysts.

Access through your institution
Buy or subscribe

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

Access options

Access through your institution

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

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

Fig. 1: Structure and composition of DEF-PtSe2.
Fig. 2: Structure and composition of DEF-PtSe2 (42,000).
Fig. 3: Electrochemical properties of different electrodes.
Fig. 4: Formation mechanism of DEF-PtSe2 (42,000).
Fig. 5: Anti-poisoning tests for Pt/C and DEF-PtSe2 (42,000).
Fig. 6: Electronic property calculations and free energy diagram.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available in the Supplementary Information.

References

  1. Shao, M., Chang, Q., Dodelet, J. P. & Chenitz, R. Recent advances in electrocatalysts for oxygen reduction reaction. Chem. Rev. 116, 3594–3657 (2016).

    Article  PubMed  Google Scholar 

  2. Dey, S. et al. Molecular electrocatalysts for the oxygen reduction reaction. Nat. Rev. Chem. 1, 0098 (2017).

    Article  CAS  Google Scholar 

  3. Kulkarni, A., Siahrostami, S., Patel, A. & Nørskov, J. K. Understanding catalytic activity trends in the oxygen reduction reaction. Chem. Rev. 118, 2302–2312 (2018).

    Article  CAS  PubMed  Google Scholar 

  4. Bu, L. et al. PtPb/PtNi intermetallic core/atomic layer shell octahedra for efficient oxygen reduction electrocatalysis. J. Am. Chem. Soc. 139, 9576–9582 (2017).

    Article  CAS  PubMed  Google Scholar 

  5. Strasser, P. & Kühl, S. Dealloyed Pt-based core-shell oxygen reduction electrocatalysts. Nano Energy 29, 166–177 (2016).

    Article  CAS  Google Scholar 

  6. Wang, X. et al. Review of metal catalysts for oxygen reduction reaction: from nanoscale engineering to atomic design. Chem 5, 1486–1511 (2019).

    Article  CAS  Google Scholar 

  7. Lin, R. et al. High-performance graphene/β-Ga2O3 heterojunction deep-ultraviolet photodetector with hot-electron excited carrier multiplication. ACS Appl. Mater. Interfaces 10, 22419–22426 (2018).

    Article  CAS  PubMed  Google Scholar 

  8. Luo, M. et al. Stable high‐index faceted Pt skin on zigzag‐like PtFe nanowires enhances oxygen reduction catalysis. Adv. Mater. 30, 1705515 (2018).

    Article  Google Scholar 

  9. Jiang, K. et al. Efficient oxygen reduction catalysis by subnanometer Pt alloy nanowires. Sci. Adv. 3, e1601705 (2017).

    Article  PubMed  PubMed Central  Google Scholar 

  10. Najam, T. et al. An efficient anti‐poisoning catalyst against SOx, NOx, and POx: P, N‐doped carbon for oxygen reduction in acidic media. Angew. Chem. Int. Ed. 130, 15321–15326 (2018).

    Article  Google Scholar 

  11. Wang, Y. et al. Monolayer PtSe2, a new semiconducting transition-metal-dichalcogenide, epitaxially grown by direct selenization of Pt. Nano Lett. 15, 4013–4018 (2015).

    Article  CAS  PubMed  Google Scholar 

  12. Wagner, S. et al. Highly sensitive electromechanical piezoresistive pressure sensors based on large-area layered PtSe2 films. Nano Lett. 18, 3738–3745 (2018).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Hu, D. et al. Unveiling the layer‐dependent catalytic activity of PtSe2 atomic crystals for the hydrogen evolution reaction. Angew. Chem. Int. Ed. 131, 7051–7055 (2019).

    Article  Google Scholar 

  14. Wang, Y., Li, Y. & Heine, T. PtTe monolayer: two-dimensional electrocatalyst with high basal plane activity toward oxygen reduction reaction. J. Am. Chem. Soc. 140, 12732–12735 (2018).

    Article  CAS  PubMed  Google Scholar 

  15. Lin, S. et al. Tunable active edge sites in PtSe2 films towards hydrogen evolution reaction. Nano Energy 42, 26–33 (2017).

    Article  CAS  Google Scholar 

  16. Chia, X. et al. Layered platinum dichalcogenides (PtS2, PtSe2, and PtTe2) electrocatalysis: monotonic dependence on the chalcogen size. Adv. Funct. Mater. 26, 4306–4318 (2016).

    Article  CAS  Google Scholar 

  17. Wang, Z. et al. A noble metal dichalcogenide for high‐performance field‐effect transistors and broadband photodetectors. Adv. Funct. Mater. 30, 1907945 (2020).

    Article  CAS  Google Scholar 

  18. Cao, K. et al. Nanofence stabilized platinum nanoparticles catalyst via facet‐selective atomic layer deposition. Small 13, 1700648 (2017).

    Article  Google Scholar 

  19. Durst, J. et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 7, 2255–2260 (2014).

    Article  CAS  Google Scholar 

  20. Lucas, C. A., Markovic, N. M. & Ross, P. N. Underpotential deposition of Cu on Pt (001): interface structure and the influence of adsorbed bromide. Phys. Rev. B 57, 13184 (1998).

    Article  CAS  Google Scholar 

  21. Green, C. L. & Kucernak, A. Determination of the platinum and ruthenium surface areas in platinum–ruthenium alloy electrocatalysts by underpotential deposition of copper. I. Unsupported catalysts. J. Phys. Chem. B 106, 1036–1047 (2002).

    Article  CAS  Google Scholar 

  22. Liu, P., Ge, X., Wang, R., Ma, H. & Ding, Y. Facile fabrication of ultrathin Pt overlayers onto nanoporous metal membranes via repeated Cu UPD and in situ redox replacement reaction. Langmuir 25, 561–567 (2009).

    Article  PubMed  Google Scholar 

  23. Becke, A. D. A new mixing of Hartree-Fock and local density-functional theories. J. Chem. Phys. 98, 1372–1377 (1993).

    Article  Google Scholar 

  24. Heyd, J., Peralta, J. E., Scuseria, G. E. & Martin, R. L. Energy band gaps and lattice parameters evaluated with the Heyd-Scuseria-Ernzerhof screened hybrid functional. J. Chem. Phys. 123, 174101 (2005).

    Article  PubMed  Google Scholar 

  25. Lei, Y. et al. Low-temperature synthesis of heterostructures of transition metal dichalcogenide alloys (WxMo1–xS2) and graphene with superior catalytic performance for hydrogen evolution. ACS Nano 11, 5103 (2017).

    Article  CAS  PubMed  Google Scholar 

  26. Parac, M., Etinski, M., Peric, M. & Grimme, S. A theoretical investigation of the geometries and binding energies of molecular tweezer and clip host−guest systems. J. Chem. Theory Comput. 1, 1110–1118 (2005).

    Article  CAS  PubMed  Google Scholar 

  27. Han, S. S. et al. Horizontal-to-vertical transition of 2D layer orientation in low-temperature chemical vapor deposition-grown PtSe2 and its influences on electrical properties and device applications. ACS Appl. Mater. Interfaces 11, 13598–13607 (2019).

    Article  CAS  PubMed  Google Scholar 

  28. Dong, J. C. et al. In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces. Nat. Energy 4, 60–67 (2019).

    Article  CAS  Google Scholar 

  29. Niu, W. et al. Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction. J. Am. Chem. Soc. 137, 5555–5562 (2015).

    Article  CAS  PubMed  Google Scholar 

  30. Bai, G. et al. Atomic carbon layers supported Pt nanoparticles for minimized CO poisoning and maximized methanol oxidation. Small 15, 1902951 (2019).

    Article  Google Scholar 

  31. Wang, P. et al. Ternary Pt9RhFex nanoscale alloys as highly efficient catalysts with enhanced activity and excellent CO-poisoning tolerance for ethanol oxidation. ACS Appl. Mater. Interfaces 9, 9584–9591 (2017).

    Article  CAS  PubMed  Google Scholar 

  32. Hersbach, T. J., Ye, C., Garcia, A. C. & Koper, M. T. Tailoring the electrocatalytic activity and selectivity of Pt (111) through cathodic corrosion. ACS Catal. 10, 15104–15113 (2020).

    Article  CAS  Google Scholar 

  33. Li, K. et al. The oxygen reduction reaction on Pt (111) and Pt (100) surfaces substituted by subsurface Cu: a theoretical perspective. J. Mater. Chem. A 3, 11444–11452 (2015).

    Article  CAS  Google Scholar 

  34. Liu, S., White, M. G. & Liu, P. Mechanism of oxygen reduction reaction on Pt (111) in alkaline solution: importance of chemisorbed water on surface. J. Phys. Chem. C 120, 15288–15298 (2016).

    Article  CAS  Google Scholar 

  35. Viswanathan, V., Hansen, H. A., Rossmeisl, J. & Nørskov, J. K. Unifying the 2e– and 4e– reduction of oxygen on metal surfaces. J. Phys. Chem. Lett. 3, 2948–2951 (2012).

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

B.E.K. and W.N. were financially supported by the National Science Foundation (NSF) under grant no. CHE-1800376. B.E.K. and W.N. also acknowledge the use of Princeton’s Imaging and Analysis Center, which is partially supported through the Princeton Center for Complex Materials (PCCM), an NSF-MRSEC program (DMR-2011750). F.Z. acknowledges financial support from the Simons Foundation (no. 377485) and John Templeton Foundation (no. 58851). S.P. acknowledges financial support from the Science and Engineering Research Board, under the schemes Core Research Grant (no. CRG/2021/000572); ECRA (no. ECR/2018/000255); and Council of Scientific & Industrial Research (no. 22/0883/23/EMR-II). B.E.K. and W.N. thank M. R. Smith for his helpful comments and careful proofreading of the manuscript. J.L.M.-C. acknowledges startup funds from Michigan State University. The computational and theoretical calculations presented in this work were supported in part through computational resources and services provided by the Institute for Cyber-Enabled Research at Michigan State University.

Author information

Author notes

  1. These authors contributed equally: Wenhan Niu, Srimanta Pakhira.

Authors and Affiliations

  1. Department of Chemical & Biological Engineering, Princeton University, Princeton, NJ, USA

    Wenhan Niu & Bruce E. Koel

  2. Department of Physics and Centre for Advanced Electronics (CAE), Indian Institute of Technology Indore, Indore, India

    Srimanta Pakhira

  3. Princeton Materials Institute (PMI), Princeton University, Princeton, NJ, USA

    Guangming Cheng & Nan Yao

  4. Department of Physics, Princeton University, Princeton, NJ, USA

    Fang Zhao

  5. Department of Physics & Astronomy, Michigan State University, East Lansing, MI, USA

    Jose L. Mendoza-Cortes

  6. Department of Chemical Engineering & Materials Science, Michigan State University, East Lansing, MI, USA

    Jose L. Mendoza-Cortes

Authors
  1. Wenhan Niu
    View author publications

    Search author on:PubMed Google Scholar

  2. Srimanta Pakhira
    View author publications

    Search author on:PubMed Google Scholar

  3. Guangming Cheng
    View author publications

    Search author on:PubMed Google Scholar

  4. Fang Zhao
    View author publications

    Search author on:PubMed Google Scholar

  5. Nan Yao
    View author publications

    Search author on:PubMed Google Scholar

  6. Jose L. Mendoza-Cortes
    View author publications

    Search author on:PubMed Google Scholar

  7. Bruce E. Koel
    View author publications

    Search author on:PubMed Google Scholar

Contributions

The manuscript was written through contributions of all authors. W.N., S.P., J.L.M.-C. and B.E.K. developed the ideas and directed the experiments and theoretical calculations. W.N. and F.Z. synthesized the materials. G.C. and N.Y. conducted the STEM measurements for this work. J.L.M.-C. designed and directed the theoretical calculations. S.P. carried out most of the DFT calculations. J.L.M.-C. led the submission and resubmission efforts, coordinated responses from all authors throughout the review process, and is acknowledged for shouldering this important task with perseverance over the course of this multi-year project.

Corresponding authors

Correspondence to Jose L. Mendoza-Cortes or Bruce E. Koel.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Materials thanks Fernando Soto and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–16, Tables 1–5 and discussion.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Niu, W., Pakhira, S., Cheng, G. et al. Reaction-driven restructuring of defective PtSe2 into ultrastable catalyst for the oxygen reduction reaction. Nat. Mater. 23, 1704–1711 (2024). https://doi.org/10.1038/s41563-024-02020-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41563-024-02020-w

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — 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