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Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional electrocatalysis

Nature Catalysis volume 2, pages 495–503 (2019)Cite this article

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Abstract

Platinum-based nanocatalysts play a crucial role in various electrocatalytic systems that are important for renewable, clean energy conversion, storage and utilization. However, the scarcity and high cost of Pt seriously limit the practical application of these catalysts. Decorating Pt catalysts with other transition metals offers an effective pathway to tailor their catalytic properties, but often at the sacrifice of the electrochemical active surface area (ECSA). Here we report a single-atom tailoring strategy to boost the activity of Pt nanocatalysts with minimal loss in surface active sites. By starting with PtNi alloy nanowires and using a partial electrochemical dealloying approach, we create single-nickel-atom-modified Pt nanowires with an optimum combination of specific activity and ECSA for the hydrogen evolution, methanol oxidation and ethanol oxidation reactions. The single-atom tailoring approach offers an effective strategy to optimize the activity of surface Pt atoms and enhance the mass activity for diverse reactions, opening a general pathway to the design of highly efficient and durable precious metal-based catalysts.

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Fig. 1: Schematic diagram for SANi-PtNWs.
Fig. 2: Structural characterization of the SANi-PtNWs.
Fig. 3: Electrocatalytic performance of the SANi-PtNWs for HER compared against Pt/C and pure-PtNWs in 1 M KOH electrolyte.
Fig. 4: DFT calculations of the active sites.
Fig. 5: MOR and EOR electrocatalytic activities of the SANi-PtNWs, pure-PtNWs and Pt/C in 1 M KOH electrolyte.

Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request.

References

  1. Yin, H. et al. Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity. Nat. Commun. 6, 6430 (2015).

    Article  CAS  Google Scholar 

  2. Wang, P. et al. Precise tuning in platinum–nickel/nickel sulfide interface nanowires for synergistic hydrogen evolution catalysis. Nat. Commun. 8, 14580 (2017).

    Article  CAS  Google Scholar 

  3. Cao, Z. et al. Platinum–nickel alloy excavated nano-multipods with hexagonal close-packed structure and superior activity towards hydrogen evolution reaction. Nat. Commun. 8, 15131 (2017).

    Article  Google Scholar 

  4. Huang, W. et al. Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum–nickel hydroxide–graphene. Nat. Commun. 6, 10035 (2015).

    Article  CAS  Google Scholar 

  5. Ren, F. et al. One-pot synthesis of a RGO-supported ultrafine ternary PtAuRu catalyst with high electrocatalytic activity towards methanol oxidation in alkaline medium. J. Mater. Chem. A 1, 7255–7261 (2013).

    Article  CAS  Google Scholar 

  6. Feng, Y.-Y., Bi, L.-X., Liu, Z.-H., Kong, D.-S. & Yu, Z.-Y. Significantly enhanced electrocatalytic activity for methanol electro-oxidation on Ag oxide-promoted PtAg/C catalysts in alkaline electrolyte. J. Catal. 290, 18–25 (2012).

    Article  CAS  Google Scholar 

  7. Wu, H., Li, H., Zhai, Y., Xu, X. & Jin, Y. Facile synthesis of free‐standing Pd‐based nanomembranes with enhanced catalytic performance for methanol/ethanol oxidation. Adv. Mater. 24, 1594–1597 (2012).

    Article  CAS  Google Scholar 

  8. Ren, F. et al. Clean method for the synthesis of reduced graphene oxide-supported PtPd alloys with high electrocatalytic activity for ethanol oxidation in alkaline medium. ACS Appl. Mater. Interfaces 6, 3607–3614 (2014).

    Article  CAS  Google Scholar 

  9. Danilovic, N. et al. Enhancing the alkaline hydrogen evolution reaction activity through the bifunctionality of Ni(OH)2/metal catalysts. Angew. Chem. Int. Ed. 124, 12663–12666 (2012).

    Article  Google Scholar 

  10. Li, M. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 354, 1414–1419 (2016).

    Article  CAS  Google Scholar 

  11. Chen, C. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science 343, 1339–1343 (2014).

    Article  CAS  Google Scholar 

  12. Choi, S.-I. et al. Synthesis and characterization of 9 nm Pt–Ni octahedra with a record high activity of 3.3 A/mgPt for the oxygen reduction reaction. Nano Lett. 13, 3420–3425 (2013).

    Article  CAS  Google Scholar 

  13. Zhang, Z. et al. Crystal phase and architecture engineering of lotus–thalamus‐shaped Pt–Ni anisotropic superstructures for highly efficient electrochemical hydrogen evolution. Adv. Mater. 30, 1801741 (2018).

    Article  Google Scholar 

  14. Zhang, Z. et al. One‐pot synthesis of highly anisotropic five‐fold‐twinned PtCu nanoframes used as a bifunctional electrocatalyst for oxygen reduction and methanol oxidation. Adv. Mater. 28, 8712–8717 (2016).

    Article  CAS  Google Scholar 

  15. Zhang, L. et al. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets. Science 349, 412–416 (2015).

    Article  CAS  Google Scholar 

  16. van der Vliet, D. F. et al. Unique electrochemical adsorption properties of Pt-skin surfaces. Angew. Chem. Int. Ed. 124, 3193–3196 (2012).

    Article  Google Scholar 

  17. Cui, C., Gan, L., Heggen, M., Rudi, S. & Strasser, P. Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. Nat. Mater. 12, 765–771 (2013).

    Article  CAS  Google Scholar 

  18. Zhang, J. et al. Platinum monolayer on nonnoble metal–noble metal core–shell nanoparticle electrocatalysts for O2 reduction. J. Phys. Chem. B 109, 22701–22704 (2005).

    Article  CAS  Google Scholar 

  19. Fu, X.-Z., Liang, Y., Chen, S.-P., Lin, J.-D. & Liao, D.-W. Pt-rich shell coated Ni nanoparticles as catalysts for methanol electro-oxidation in alkaline media. Catal. Commun. 10, 1893–1897 (2009).

    Article  CAS  Google Scholar 

  20. Calle-Vallejo, F. et al. Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors. Science 350, 185–189 (2015).

    Article  CAS  Google Scholar 

  21. Calle-Vallejo, F. et al. Why conclusions from platinum model surfaces do not necessarily lead to enhanced nanoparticle catalysts for the oxygen reduction reaction. Chem. Sci. 8, 2283–2289 (2017).

    Article  CAS  Google Scholar 

  22. Huang, X. et al. High-performance transition metal–doped Pt3Ni octahedra for oxygen reduction reaction. Science 348, 1230–1234 (2015).

    Article  CAS  Google Scholar 

  23. Strasser, P. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2, 454–460 (2010).

    Article  CAS  Google Scholar 

  24. Cui, C. et al. Octahedral PtNi nanoparticle catalysts: exceptional oxygen reduction activity by tuning the alloy particle surface composition. Nano Lett. 12, 5885–5889 (2012).

    Article  CAS  Google Scholar 

  25. Subbaraman, R. et al. Trends in activity for the water electrolyser reactions on 3D M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550–557 (2012).

    Article  CAS  Google Scholar 

  26. Jiang, Q., Jiang, L., Wang, S., Qi, J. & Sun, G. A highly active PtNi/C electrocatalyst for methanol electro-oxidation in alkaline media. Catal. Commun. 12, 67–70 (2010).

    Article  CAS  Google Scholar 

  27. Subbaraman, R. et al. Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni(OH)2–Pt interfaces. Science 334, 1256–1260 (2011).

    Article  CAS  Google Scholar 

  28. Zhao, Z. et al. Surface-engineered PtNi-O nanostructure with record-high performance for electrocatalytic hydrogen evolution reaction. J. Am. Chem. Soc. 140, 9046–9050 (2018).

    Article  CAS  Google Scholar 

  29. Pearson, D., Ahn, C. & Fultz, B. White lines and d-electron occupancies for the 3d and 4d transition metals. Phys. Rev. B 47, 8471–8478 (1993).

    Article  CAS  Google Scholar 

  30. Becknell, N. et al. Atomic structure of Pt3Ni nanoframe electrocatalysts by in situ X-ray absorption spectroscopy. J. Am. Chem. Soc. 137, 15817–15824 (2015).

    Article  CAS  Google Scholar 

  31. Burke, M. S., Enman, L. J., Batchellor, A. S., Zou, S. & Boettcher, S. W. Oxygen evolution reaction electrocatalysis on transition metal oxides and (oxy)hydroxides: activity trends and design principles. Chem. Mater. 27, 7549–7558 (2015).

    Article  CAS  Google Scholar 

  32. Bates, M. K., Jia, Q., Doan, H., Liang, W. & Mukerjee, S. Charge-transfer effects in Ni–Fe and Ni–Fe–Co mixed-metal oxides for the alkaline oxygen evolution reaction. ACS Catal. 6, 155–161 (2015).

    Article  Google Scholar 

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

    Article  Google Scholar 

  34. Le Bacq, O. et al. Effect of atomic vacancies on the structure and the electrocatalytic activity of Pt‐rich/C nanoparticles: a combined experimental and density functional theory study. ChemCatChem 9, 2324–2338 (2017).

    Article  Google Scholar 

  35. Chattot, Rl et al. Beyond strain and ligand effects: microstrain-induced enhancement of the oxygen reduction reaction kinetics on various PtNi/C nanostructures. ACS Catal. 7, 398–408 (2016).

    Article  Google Scholar 

  36. Chattot, R. et al. Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Nat. Mater. 17, 827–834 (2018).

    Article  CAS  Google Scholar 

  37. Fei, H. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 1, 63–72 (2018).

    Article  Google Scholar 

  38. Marcinkowski, M. D. et al. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation. Nat. Chem. 10, 325–332 (2018).

    Article  CAS  Google Scholar 

  39. Back, S., Lim, J., Kim, N.-Y., Kim, Y.-H. & Jung, Y. Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements. Chem. Sci. 8, 1090–1096 (2017).

    Article  CAS  Google Scholar 

  40. Zhang, H., Liu, G., Shi, L. & Ye, J. Single‐atom catalysts: emerging multifunctional materials in heterogeneous catalysis. Adv. Energy Mater. 8, 1701343 (2018).

    Article  Google Scholar 

  41. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  CAS  Google Scholar 

  42. Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  44. Hansen, M. H., Jin, C., Thygesen, K. S. & Rossmeisl, J. Finite bias calculations to model interface dipoles in electrochemical cells at the atomic scale. J. Phys. Chem. C 120, 13485–13491 (2016).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Y.H. acknowledges support from the Office of Naval Research (grant no. N000141812155). X.D. acknowledges financial support from the National Science Foundation (grant no. 1800580). T.C. was supported by the Collaborative Innovation Center of Suzhou Nano Science & Technology, the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) and the 111 Project. W.A.G. was supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under award no. DE‐SC0004993. This work used the Extreme Science and Engineering Discovery Environment (XSEDE) which is supported by National Science Foundation grant no. ACI‐1053575. J.L. acknowledges the National Key R&D Program of China (2017YFA0700104) and National Natural Science Foundation of China (51761165012). STEM experiments were conducted using the facilities in the Irvine Materials Research Institute (IMRI) at the University of California-Irvine. The authors thank S. Fakra for technical support for the EXAFS experiment. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DEAC02-05CH11231. R.Y. acknowledges the National Natural Science Foundation of China (51525102, 51390475). Use of resources of the National Center for Electron Microscopy in Beijing is acknowledged. The calculations were performed on the Hoffman2 cluster at UCLA Institute for Digital Research and Education (IDRE) and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (grant no. ACI‐1053575).

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Author notes

  1. These authors contributed equally: Mufan Li, Kaining Duanmu, Chengzhang Wan, Tao Cheng.

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA

    Mufan Li, Chengzhang Wan, Peng Li, Huilong Fei, Zhaoyang Lin, Hongtao Sun, Philippe Sautet & Xiangfeng Duan

  2. Department of Materials Science and Engineering, University of California, Los Angeles, CA, USA

    Mufan Li, Zipeng Zhao, Mengning Ding, Jin Huang & Yu Huang

  3. Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA, USA

    Kaining Duanmu & Philippe Sautet

  4. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA

    Tao Cheng & William A. Goddard III

  5. Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Joint International Research Laboratory of Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, Jiangsu, China

    Tao Cheng

  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Liang Zhang & Jinghua Guo

  7. Department of Materials Science and Engineering, University of California Irvine, Irvine, CA, USA

    Sheng Dai & Xiaoqing Pan

  8. Department of Chemistry, Tsinghua University, Beijing, China

    Wenxin Chen

  9. National Center for Electron Microscopy in Beijing, School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Yuanming Zhu & Rong Yu

  10. Center for Electron Microscopy in Tianjin University of Technology, Tianjin, China

    Jun Luo & Ketao Zang

  11. Irvine Materials Research Institute (IMRI), University of California Irvine, Irvine, CA, USA

    Xiaoqing Pan

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Contributions

X.D., Y.H. and P.S. supervised the project and designed the research. X.D., Y.H. and M.L. conceived the idea. M.L. and C.W. performed the synthesis, electrochemical tests and characterizations. K.D. and P.S. conceived and performed the DFT calculations. T.C. and W.G. performed the model simulations. L.Z. and W.C. performed XAS measurements and analysis. J.G. and W.C. provided expertise for XAS analysis. S.D. and X.P. performed the EELS and HAADF-STEM measurements. Z.Z., Y.Z., R.Y., J.L., K.Z. and Z.L. assisted with material characterizations. Z.Z., P.L., H.F., M.D., J.H. and H.S. assisted with catalytic measurements. M.L., K.D., C.W., P.S., Y.H. and X.D. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Philippe Sautet, Yu Huang or Xiangfeng Duan.

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Supplementary information

Supplementary Figs. 1–11 and Supplementary Tables 1–4.

Supplementary Data

Atomic coordinates of the optimized computational models.

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Li, M., Duanmu, K., Wan, C. et al. Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional electrocatalysis. Nat Catal 2, 495–503 (2019). https://doi.org/10.1038/s41929-019-0279-6

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