Golden single-atomic-site platinum electrocatalysts

Abstract

Bimetallic nanoparticles with tailored structures constitute a desirable model system for catalysts, as crucial factors such as geometric and electronic effects can be readily controlled by tailoring the structure and alloy bonding of the catalytic site. Here we report a facile colloidal method to prepare a series of platinum–gold (PtAu) nanoparticles with tailored surface structures and particle diameters on the order of 7 nm. Samples with low Pt content, particularly Pt4Au96, exhibited unprecedented electrocatalytic activity for the oxidation of formic acid. A high forward current density of 3.77 A mgPt−1 was observed for Pt4Au96, a value two orders of magnitude greater than those observed for core–shell structured Pt78Au22 and a commercial Pt nanocatalyst. Extensive structural characterization and theoretical density functional theory simulations of the best-performing catalysts revealed densely packed single-atom Pt surface sites surrounded by Au atoms, which suggests that their superior catalytic activity and selectivity could be attributed to the unique structural and alloy-bonding properties of these single-atomic-site catalysts.

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Fig. 1: Synthesis, reactivity and EXAFS of catalysts.
Fig. 2: HAADF-STEM images and structural models.
Fig. 3: Further electrochemical analysis.
Fig. 4: DFT-calculated binding of CO at PtAu surfaces.
Fig. 5: Calculated and experimental DOS.

Data availability

The data supporting the results of this work are available from the authors on reasonable request.

References

  1. 1.

    Chen, A. & Holt-Hindle, P. Platinum-based nanostructured materials: synthesis, properties, and applications. Chem. Rev. 110, 3767–3804 (2010).

    CAS  Article  Google Scholar 

  2. 2.

    Hunt, S. T. et al. Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts. Science 352, 974–978 (2016).

    CAS  Article  Google Scholar 

  3. 3.

    Yu, Y., Wang, X. & Lim, K. H. A DFT study on the adsorption of formic acid and its oxidized intermediates on (100) facets of Pt, Au, monolayer and decorated Pt@Au surfaces. Catal. Lett. 141, 1872–1882 (2011).

    CAS  Article  Google Scholar 

  4. 4.

    Wang, X., He, B., Hu, Z., Zeng, Z. & Han, S. Current advances in precious metal core–shell catalyst design. Sci. Technol. Adv. Mater. 15, 043502 (2014).

    Article  Google Scholar 

  5. 5.

    Liu, X., Wang, D. & Li, Y. Synthesis and catalytic properties of bimetallic nanomaterials with various architectures. Nano Today 7, 448–466 (2012).

    CAS  Article  Google Scholar 

  6. 6.

    Liu, X., Wang, D. & Li, Y. Bimetallic nanocrystals: liquid-phase synthesis and catalytic applications. Adv. Mater. 23, 1044–1060 (2011).

    Article  Google Scholar 

  7. 7.

    Jiang, K., Zhang, H.-X., Zou, S. & Cai, W.-B. Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications. Phys. Chem. Chem. Phys. 16, 20360–20376 (2014).

    CAS  Article  Google Scholar 

  8. 8.

    Liu, J. et al. Tackling CO poisoning with single atom alloy catalysts. J. Am. Chem. Soc. 138, 6396–6399 (2016).

    CAS  Article  Google Scholar 

  9. 9.

    Yuge, K., Koyama, Y., Kuwabara, A. & Tanaka, I. Surface design of alloy protection against CO-poisoning from first principles. J. Phys. Condens. Matter. 26, 355006 (2014).

    Article  Google Scholar 

  10. 10.

    Habrioux, A. et al. Structural and electrochemical studies of Au–Pt nanoalloys. Phys. Chem. Chem. Phys. 11, 3573–3579 (2009).

    CAS  Article  Google Scholar 

  11. 11.

    Ji, X. et al. Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat. Chem. 2, 286–293 (2010).

    CAS  Article  Google Scholar 

  12. 12.

    Zhang, H., Watanabe, T., Okumura, M., Haruta, M. & Toshima, N. Catalytically highly active top gold atom on palladium nanocluster. Nat. Mater. 11, 49–52 (2012).

    Article  Google Scholar 

  13. 13.

    Guo, S. et al. Nanocatalyst superior to Pt for oxygen reduction reactions: the case of core/shell Ag(Au)/CuPd nanoparticles. J. Am. Chem. Soc. 136, 15026–15033 (2014).

    CAS  Article  Google Scholar 

  14. 14.

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

    CAS  Article  Google Scholar 

  15. 15.

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

    CAS  Article  Google Scholar 

  16. 16.

    Chen, G. et al. Interfacial effects in iron-nickel hydroxide–platinum nanoparticles enhance catalytic oxidation. Science 344, 495–499 (2014).

    CAS  Article  Google Scholar 

  17. 17.

    Roy, A. et al. Enhanced catalytic activity of Ag/Rh bimetallic nanomaterial: evidence of an ensemble effect. J. Phys. Chem. C 120, 5457–5467 (2016).

    CAS  Article  Google Scholar 

  18. 18.

    Prinz, J. et al. Ensemble effect evidenced by CO adsorption on the 3-fold PdGa surfaces. J. Phys. Chem. C 118, 12260–12265 (2014).

    CAS  Article  Google Scholar 

  19. 19.

    Zaera, F., Gellman, J. A. & Somorjai, G. A. Surface science studies of catalysis: classification of reactions. Acc. Chem. Res. 19, 24–31 (1986).

    CAS  Article  Google Scholar 

  20. 20.

    Ruff, M., Takehiro, N., Liu, P., Nørskov, J. K. & Behm, R. J. Size-specific chemistry on bimetallic surfaces: a combined experimental and theoretical study. ChemPhysChem 8, 2068–2071 (2007).

    CAS  Article  Google Scholar 

  21. 21.

    Sachtler, W. M. H. Chemisorption complexes on alloy surfaces. Catal. Rev. Sci. Eng. 14, 193–210 (1976).

    CAS  Article  Google Scholar 

  22. 22.

    Stevanović, S. et al. Insight into the effect of Sn on CO and formic acid oxidation at PtSn catalysts. J. Phys. Chem. C 118, 278–289 (2014).

    Article  Google Scholar 

  23. 23.

    Duchesne, P. N. & Zhang, P. Element-specific analysis of the growth mechanism, local structure, and electronic properties of Pt clusters formed on Ag nanoparticle surfaces. J. Phys. Chem. C 118, 21714–21721 (2014).

    CAS  Article  Google Scholar 

  24. 24.

    Yu, Y., Hu, Y., Liu, X., Deng, W. & Wang, X. The study of Pt@Au electrocatalyst based on Cu underpotential deposition and Pt redox replacement. Electrochim. Acta 54, 3092–3097 (2009).

    CAS  Article  Google Scholar 

  25. 25.

    Kim, J., Jung, C., Rhee, C. K. & Lim, T. Electrocatalytic oxidation of formic acid and methanol on Pt deposits on Au(111). Langmuir 23, 10831–10836 (2007).

    CAS  Article  Google Scholar 

  26. 26.

    Luo, J. et al. Phase properties of carbon-supported gold–platinum nanoparticles with different bimetallic compositions. Chem. Mater. 17, 3086–3091 (2005).

    CAS  Article  Google Scholar 

  27. 27.

    Atkins, P. & de Paula, J. Atkins' Physical Chemistry 8th edn, 1005–1006 (W.H. Freeman and Company, New York, 2006).

  28. 28.

    Wu, B. & Zheng, N. Surface and interface control of noble metal nanocrystals for catalytic and electrocatalytic applications. Nano Today 8, 168–197 (2013).

    Article  Google Scholar 

  29. 29.

    Bligaard, T. et al. The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis. J. Catal. 224, 206–217 (2004).

    CAS  Article  Google Scholar 

  30. 30.

    Zhong, W. & Zhang, D. New insight into the CO formation mechanism during formic acid oxidation on Pt(111). Catal. Commun. 29, 82–86 (2012).

    CAS  Article  Google Scholar 

  31. 31.

    Neurock, M., Janik, M. & Wieckowski, A. A first principles comparison of the mechanism and site requirements for the electrocatalytic oxidation of methanol and formic acid over Pt. Faraday Discuss. 140, 363–378 (2009).

    Article  Google Scholar 

  32. 32.

    Cuesta, A., Escudero, M., Lanova, B. & Baltruschat, H. Cyclic voltammetry, FTIRS, and DEMS study of the electrooxidation of carbon monoxide, formic acid, and methanol on cyanide-modified Pt(111) electrodes. Langmuir 25, 6500–6507 (2009).

    CAS  Article  Google Scholar 

  33. 33.

    Mason, M. Electronic structure of supported small metal clusters. Phys. Rev. B 27, 748–762 (1983).

    CAS  Article  Google Scholar 

  34. 34.

    Schneider, C. A., Rasband, W. S. & Eliceiri, K. W. NIH Image to ImageJ: 25 years of image analysis. Nat. Methods 9, 671–675 (2012).

    CAS  Article  Google Scholar 

  35. 35.

    Kraft, S., Stümpel, J., Becker, P. & Kuetgens, U. High resolution X-ray absorption spectroscopy with absolute energy calibration for the determination of absorption edge energies. Rev. Sci. Instrum. 67, 681–687 (1996).

    CAS  Article  Google Scholar 

  36. 36.

    Bearden, J. A. X-ray wavelengths. Rev. Mod. Phys. 39, 78–124 (1967).

    CAS  Article  Google Scholar 

  37. 37.

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

    CAS  Article  Google Scholar 

  38. 38.

    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).

    CAS  Article  Google Scholar 

  39. 39.

    Wagner, C. D. in Practical Surface Analysis (eds Briggs, D. & Seah, M. P.) 635–638 (Wiley, Hoboken, 1990).

  40. 40.

    Naumkin, A. V., Kraut-Vass, A., Gaarenstroom, S. W. & Powell, C. J. NIST X-ray Photoelectron Spectroscopy Database (NIST, 2012); http://srdata.nist.gov/xps/

  41. 41.

    Luo, S., Zhao, Y. & Truhlar, D. G. Improved CO adsorption energies, site preferences, and surface formation energies from a meta-generalized gradient approximation exchange–correlation functional, M06-L. J. Phys. Chem. Lett. 3, 2975–2979 (2012).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

P.Z. acknowledges financial support from the NSERC Canada Discovery Grant and P.N.D. was funded by an NSERC CGS scholarship. Financial supports from European COST Action MP0903 ‘Nanoalloy’ (Z.Y.L.) and the US National Science Foundation DMR-1409396 (S.C.) are acknowledged. A.A. and Z.A. acknowledge the financial support by Deanship of Scientific Research, King Saud University. Part of this work was supported by a PCOSS Open Project Grant (Xiamen University) awarded to P.Z. and hosted by N.Z. DFT calculations were sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division and used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC02-05CH11231. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the US DOE under contract no. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. The Canadian Light Source is supported by the CFI, NSERC, NRC, CIHR, the University of Saskatchewan, the Government of Saskatchewan and Western Economic Diversification Canada. We are also grateful for the assistance of Z. Finfrock (CLS@APS) and Y. Hu (SXRMB@CLS) for synchrotron technical support, and L. Leonardo for the collection of additional EDX mapping in the JEOL-York Nanocenter using JEM-2200FS Cs-corrected (S)TEM operating at 200 keV.

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P.N.D. synthesized all the samples, conducted the XAS experiments and analysis, performed some of the electrochemical and TEM studies, and wrote the manuscript. P.Z. designed the project, coordinated the process of the work and supervised P.N.D. to conduct this research. Z.Y.L. and J.Y. performed the HAADF-STEM measurements and image analysis. C.P.D. performed the electrochemical experiments under the supervision of S.C. V.F. conducted the DFT calculations under the supervision of D.J. X.Z. contributed to the TEM measurements under the supervision of N.Z. A.A. and Z.A. also contributed to part of the TEM measurements. T.R. performed some of the XPS measurements at the Canadian Light Source.

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Correspondence to Peng Zhang.

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Duchesne, P.N., Li, Z.Y., Deming, C.P. et al. Golden single-atomic-site platinum electrocatalysts. Nature Mater 17, 1033–1039 (2018). https://doi.org/10.1038/s41563-018-0167-5

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