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 platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution

Nature Energy volume 4, pages 512–518 (2019)Cite this article

Subjects

Abstract

Dispersing catalytically active metals as single atoms on supports represents the ultimate in metal utilization efficiency and is increasingly being used as a strategy to design hydrogen evolution reaction (HER) electrocatalysts. Although platinum (Pt) is highly active for HER, given its high cost it is desirable to find ways to improve performance further while minimizing the Pt loading. Here, we use onion-like nanospheres of carbon (OLC) to anchor stable atomically dispersed Pt to act as a catalyst (Pt1/OLC) for the HER. In acidic media, the performance of the Pt1/OLC catalyst (0.27 wt% Pt) in terms of a low overpotential (38 mV at 10 mA cm−2) and high turnover frequencies (40.78 H2 s−1 at 100 mV) is better than that of a graphene-supported single-atom catalyst with a similar Pt loading, and comparable to a commercial Pt/C catalyst with 20 wt% Pt. First-principle calculations suggest that a tip-enhanced local electric field at the Pt site on the curved support promotes the reaction kinetics for hydrogen evolution.

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: Rational design of the Pt1/OLC catalyst via reducing the dimensions and introducing curvature.
Fig. 2: Structural identification of Pt single atom in Pt1/OLC catalyst.
Fig. 3: Hydrogen evolution performance of the Pt1/OLC catalyst.
Fig. 4: Theoretical investigation of the HER using the Pt1/OLC catalyst.

Similar content being viewed by others

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request

References

  1. Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).

    Article  Google Scholar 

  2. Greeley, J., Jaramillo, T. F., Bonde, J., Chorkendorff, I. B. & Norskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 5, 909–913 (2006).

    Article  Google Scholar 

  3. Deng, D. et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotechnol. 11, 218–230 (2016).

    Article  Google Scholar 

  4. Nilsson, A. et al. The electronic structure effect in heterogeneous catalysis. Catal. Lett. 100, 111–114 (2005).

    Article  Google Scholar 

  5. Yin, Y. 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. 138, 7965–7972 (2016).

    Article  Google Scholar 

  6. Jiao, Y., Zheng, Y., Davey, K. & Qiao, S. Z. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nat. Energy 1, 16130 (2016).

    Article  Google Scholar 

  7. Liu, P. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 352, 797–801 (2016).

    Article  Google Scholar 

  8. Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).

    Article  Google Scholar 

  9. Yan, H. et al. Single-atom Pd1/graphene catalyst achieved by atomic layer deposition: remarkable performance in selective hydrogenation of 1,3-butadiene. J. Am. Chem. Soc. 137, 10484–10487 (2015).

    Article  Google Scholar 

  10. Liu, G. et al. MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction. Nat. Chem. 9, 810–816 (2017).

    Article  Google Scholar 

  11. Thomas, J. M. Catalysis: tens of thousands of atoms replaced by one. Nature 525, 325–326 (2015).

    Article  Google Scholar 

  12. Yang, X. F. et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).

    Article  Google Scholar 

  13. Bayatsarmadi, B., Zheng, Y., Vasileff, A. & Qiao, S. Z. Recent advances in atomic metal doping of carbon-based nanomaterials for energy conversion. Small 13, 1700191 (2017).

    Article  Google Scholar 

  14. Mahmood, J. et al. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. Nat. Nanotechnol. 12, 441–446 (2017).

    Article  Google Scholar 

  15. Cheng, N. et al. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nat. Commun. 7, 13638 (2016).

    Article  Google Scholar 

  16. Tiwari, J. N. et al. Multicomponent electrocatalyst with ultralow Pt loading and high hydrogen evolution activity. Nat. Energy 3, 773–782 (2018).

    Article  Google Scholar 

  17. Yin, X. P. et al. Engineering the coordination environment of single-atom platinum anchored on graphdiyne for optimizing electrocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 57, 9382–9386 (2018).

    Article  Google Scholar 

  18. Kwak, J. H. et al. Coordinatively unsaturated Al3+ centers as binding sites for active catalyst phases of platinum on γ-Al2O3. Science 325, 1670–1673 (2009).

    Article  Google Scholar 

  19. Yang, M. et al. A common single-site Pt(ii)–O(OH)x-species stabilized by sodium on ‘active’ and ‘inert’ supports catalyzes the water–gas shift reaction. J. Am. Chem. Soc. 137, 3470–3473 (2015).

    Article  Google Scholar 

  20. Zeiger, M., Jäckel, N., Mochalin, V. N. & Presser, V. Review: carbon onions for electrochemical energy storage. J. Mater. Chem. A 4, 3172–3196 (2016).

    Article  Google Scholar 

  21. Pech, D. et al. Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. Nat. Nanotechnol. 5, 651–654 (2010).

    Article  Google Scholar 

  22. Ganguly, A., Sharma, S., Papakonstantinou, P. & Hamilton, J. Probing the thermal deoxygenation of graphene oxide using high-resolution in situ X-ray-based spectroscopies. J. Phys. Chem. C 115, 17009–17019 (2011).

    Article  Google Scholar 

  23. Sun, Z., Liu, Q., Yao, T., Yan, W. & Wei, S. X-ray absorption fine structure spectroscopy in nanomaterials. Sci. China Mater. 58, 313–341 (2015).

    Article  Google Scholar 

  24. Ressler, T. WinXAS: a program for X-ray absorption spectroscopy data analysis under MS-windows. J. Synchrotron Radiat. 5, 118–122 (1998).

    Article  Google Scholar 

  25. Yoshida, H., Nonoyama, S., Yazawa, Y. & Hattori, T. Quantitative determination of platinum oxidation state by XANES analysis. Phys. Scr. T115, 813–815 (2005).

    Article  Google Scholar 

  26. Li, Y. et al. Implementing metal-to-ligand charge transfer in organic semiconductor for improved visible-near-infrared photocatalysis. Adv. Mater. 28, 6959–6965 (2016).

    Article  Google Scholar 

  27. Rennie, A. J., Sanchez-Ramirez, N., Torresi, R. M. & Hall, P. J. Ether-bond-containing ionic liquids as supercapacitor electrolytes. J. Phys. Chem. Lett. 4, 2970–2974 (2013).

    Article  Google Scholar 

  28. Fei, H. et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat. Commun. 6, 8668 (2015).

    Article  Google Scholar 

  29. Zhang, L. et al. Graphene defects trap atomic Ni species for hydrogen and oxygen evolution reactions. Chem 4, 285–297 (2018).

    Article  Google Scholar 

  30. Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).

    Article  Google Scholar 

  31. Sundararaman, R., Goddard, W. A. & Arias, T. A. Grand canonical electronic density-functional theory: algorithms and applications to electrochemistry. J. Chem. Phys. 146, 114104 (2017).

    Article  Google Scholar 

  32. Sundararaman, R. et al. JDFTx: software for joint density-functional theory. SoftwareX 6, 278–284 (2017).

    Article  Google Scholar 

  33. Kim, D., Shi, J. & Liu, Y. Substantial impact of charge on electrochemical reactions of two-dimensional materials. J. Am. Chem. Soc. 140, 9127–9131 (2018).

    Article  Google Scholar 

  34. Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016).

    Article  Google Scholar 

  35. Jiang, H., Hou, Z. & Luo, Y. Unraveling the mechanism for the sharp-tip enhanced electrocatalytic carbon dioxide reduction: the kinetics decide. Angew. Chem. Int. Ed. 56, 15617–15621 (2017).

    Article  Google Scholar 

  36. Oldham, K. B. A Gouy–Chapman–Stern model of the double layer at a (metal)/(ionic liquid) interface. J. Electroanal. Chem. 613, 131–138 (2008).

    Article  Google Scholar 

  37. Haleem, Y. A. et al. Surface functionalization and structure characterizations of nanodiamond and its epoxy based nanocomposites. Composites B 78, 480–487 (2015).

    Article  Google Scholar 

  38. Marcano, D. C. et al. Improved synthesis of graphene oxide. ACS Nano 4, 4806–4814 (2010).

    Article  Google Scholar 

  39. Ankudinov, A. L., Ravel, B., Rehr, J. J. & Conradson, S. D. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure. Phys. Rev. B 58, 7565–7576 (1998).

    Article  Google Scholar 

  40. Li, Y. et al. An oxygen reduction electrocatalyst based on carbon nanotube–graphene complexes. Nat. Nanotechnol. 7, 394–400 (2012).

    Article  Google Scholar 

  41. Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  Google Scholar 

  42. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  43. Sundararaman, R. & Goddard, W. A. The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model. J. Chem. Phys. 142, 064107 (2015).

    Article  Google Scholar 

  44. Hinnemann, B. et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 127, 5308–5309 (2005).

    Article  Google Scholar 

Download references

Acknowledgements

This study was financially supported in part by the MOST (nos 2017YFA0303500 and 2018YFA0208603), the NSFC (nos 11574280, 11375198, U1532112, 91127042, 21790350, 21633006 and 21473166), the Recruitment Program of Global Experts and the CAS Hundred Talent Program and the Anhui Initiative in Quantum Information Technologies (AHY090200 and AHY090000). We thank the SSRF (14W1), the BSRF (1W1B and soft X-ray), the NSRL (photoemission, MCD and catalysis/surface science) and the USTC Center for Micro and Nanoscale Research and Fabrication for help with the characterization. We also thank Y. Liu and J. Shi for helpful discussions.

Author information

Author notes

  1. These authors contributed equally: Daobin Liu, Xiyu Li.

Authors and Affiliations

  1. National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, China

    Daobin Liu, Shuangming Chen, Changda Wang, Chuanqiang Wu, Yasir A. Haleem & Li Song

  2. Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, China

    Xiyu Li, Huan Yan, Junling Lu, Yi Luo & Jun Jiang

  3. Department of Theoretical Chemistry and Biology School of Engineering Sciences in Chemistry, Biotechnology and Health, Royal Institute of Technology, Stockholm, Sweden

    Sai Duan

  4. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Binghui Ge

  5. Department of Materials Science and Nano Engineering, Rice University, Houston, TX, USA

    Pulickel M. Ajayan

Authors
  1. Daobin Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiyu Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Shuangming Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Huan Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Changda Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chuanqiang Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yasir A. Haleem
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Sai Duan
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Junling Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Binghui Ge
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Pulickel M. Ajayan
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Yi Luo
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Jun Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Li Song
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

L.S. and J.J. conceived the research and designed the project. D.L. performed most of the experiments. X.L., S.D. and J.J. performed the simulations. S.C. contributed to the XAS measurements. H.Y. and J.L. contributed to the ALD preparation. B.G. contributed to the STEM characterizations. C. Wang, C. Wu and Y.A.H. partially contributed to experimental data. D.L., X.L., P.M.A., Y.L., J.J. and L.S. analysed the data and co-wrote the paper. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Jun Jiang or Li Song.

Ethics declarations

Competing interests

The authors declare no competing interests.

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. 1–18, Supplementary Tables 1 and 2, and Supplementary references.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, D., Li, X., Chen, S. et al. Atomically dispersed platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution. Nat Energy 4, 512–518 (2019). https://doi.org/10.1038/s41560-019-0402-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-019-0402-6

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