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Improving Pd–N–C fuel cell electrocatalysts through fluorination-driven rearrangements of local coordination environment

Nature Energy volume 6, pages 1144–1153 (2021)Cite this article

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Abstract

The local coordination environment around catalytically active sites plays a vital role in tuning the activity of electrocatalysts made of carbon-supported metal nanoparticles. However, the rational design of electrocatalysts with improved performance by controlling this environment is hampered by synthetic limitations and insufficient mechanistic understanding of how the catalytic phase forms. Here we show that introducing F atoms into Pd/N–C catalysts modifies the environment around the Pd and improves both activity and durability for the ethanol oxidation reaction and the oxygen reduction reaction. Our data suggest that F atom introduction creates a more N-rich Pd surface, which is favourable for catalysis. Durability is enhanced by inhibition of Pd migration and decreased carbon corrosion. A direct ethanol fuel cell that uses the Pd/N–C catalyst with F atoms introduced for both the ethanol oxidation reaction and oxygen reduction reaction achieves a maximum power density of 0.57 W cm−2 and more than 5,900 hours of operation. Pd/C catalysts containing other heteroatoms (P, S, B) can also be improved through the addition of F atoms.

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Fig. 1: Schematic illustration of the fluorination-driven rearrangement of the LCE.
Fig. 2: Structural characterization by Fourier-transform infrared spectra, Raman spectra, electrical conductivity and ultraviolet photoelectron spectroscopy (UPS).
Fig. 3: Morphology and atomic structure of Pd/X–F catalysts.
Fig. 4: Spectroscopic analyses by XAS.
Fig. 5: Electrochemical ORR and EOR performance.
Fig. 6: Direct ethanol fuel cell tests and stability.
Fig. 7: DFT calculations.

Data availability

The authors declare that all data supporting the findings of this study are available within the paper and Supplementary Information files. Source data are provided with this paper.

References

  1. Li, X., Rong, H., Zhang, J., Wang, D. & Li, Y. Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance. Nano Res. 13, 1842–1855 (2020).

    Article  Google Scholar 

  2. Zhang, J. et al. Tuning the coordination environment in single-atom catalysts to achieve highly efficient oxygen reduction reactions. J. Am. Chem. Soc. 141, 20118–20126 (2019).

    Article  Google Scholar 

  3. Bianchini, C. & Shen, P. K. Palladium-based electrocatalysts for alcohol oxidation in half cells and in direct alcohol fuel cells. Chem. Rev. 109, 4183–4206 (2009).

    Article  Google Scholar 

  4. Ramaswamy, N. & Mukerjee, S. Alkaline anion-exchange membrane fuel cells: challenges in electrocatalysis and interfacial charge transfer. Chem. Rev. 119, 11945–11979 (2019).

    Article  Google Scholar 

  5. Wang, G., Chang, J., Koul, S., Kushima, A. & Yang, Y. CO2 bubble-assisted Pt exposure in PtFeNi porous film for high-performance zinc-air battery. J. Am. Chem. Soc. 143, 11595–11601 (2021).

    Article  Google Scholar 

  6. Li, Z. et al. Stabilizing atomic Pt with trapped interstitial F in alloyed PtCo nanosheets for high-performance zinc-air batteries. Energy Environ. Sci. 13, 884–895 (2020).

    Article  Google Scholar 

  7. Wang, G., Yang, Z., Du, Y. & Yang, Y. Programmable exposure of Pt active facets for efficient oxygen reduction. Angew. Chem. Int. Ed. 58, 15848–15854 (2019).

    Article  Google Scholar 

  8. Niu, W. et al. Surface-modified porous carbon nitride composites as highly efficient electrocatalyst for Zn-air batteries. Adv. Energy Mater. 8, 1701642 (2018).

    Article  Google Scholar 

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

    Article  Google Scholar 

  10. Sun, T. et al. Design of local atomic environments in single-atom electrocatalysts for renewable energy conversions. Adv. Mater. 33, 2003075 (2021).

    Article  Google Scholar 

  11. Yuan, K. et al. Boosting oxygen reduction of single iron active sites via geometric and electronic engineering: nitrogen and phosphorus dual coordination. J. Am. Chem. Soc. 142, 2404–2412 (2020).

    Article  Google Scholar 

  12. Zhang, J. & Dai, L. Nitrogen, phosphorus, and fluorine tri-doped graphene as a multifunctional catalyst for self-powered electrochemical water splitting. Angew. Chem. Int. Ed. 55, 13296–13300 (2016).

    Article  Google Scholar 

  13. Wang, Y. et al. Advanced electrocatalysts with single-metal-atom active sites. Chem. Rev. 120, 12217–12314 (2020).

    Article  Google Scholar 

  14. Kowal, A. et al. Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2. Nat. Mater. 8, 325–330 (2009).

    Article  Google Scholar 

  15. Liang, Z. et al. Direct 12-electron oxidation of ethanol on a ternary Au(core)-PtIr(shell) electrocatalyst. J. Am. Chem. Soc. 141, 9629–9636 (2019).

    Article  Google Scholar 

  16. Kim, I. et al. Catalytic reactions in direct ethanol fuel cells. Angew. Chem. Int. Ed. 50, 2270–2274 (2011).

    Article  Google Scholar 

  17. Kavanagh, R., Cao, X. M., Lin, W. F., Hardacre, C. & Hu, P. Origin of low CO2 selectivity on platinum in the direct ethanol fuel cell. Angew. Chem. Int. Ed. 51, 1572–1575 (2012).

    Article  Google Scholar 

  18. Wang, X. X., Swihart, M. T. & Wu, G. Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation. Nat. Catal. 2, 578–589 (2019).

    Article  Google Scholar 

  19. Shao, Y., Dodelet, J. P., Wu, G. & Zelenay, P. PGM-free cathode catalysts for PEM fuel cells: a mini-review on stability challenges. Adv. Mater. 31, 1807615 (2019).

    Article  Google Scholar 

  20. Zhou, Y. et al. A universal method to produce low–work function electrodes for organic electronics. Science 336, 327–332 (2012).

    Article  Google Scholar 

  21. Vayenas, C. G., Bebelis, S. & Ladas, S. Dependence of catalytic rates on catalyst work function. Nature 343, 625–627 (1990).

    Article  Google Scholar 

  22. Tian, N., Zhou, Z. Y., Sun, S. G., Ding, Y. & Wang, Z. L. Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science 316, 732–735 (2007).

    Article  Google Scholar 

  23. Chong, L. et al. Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks. Science 362, 1276–1281 (2018).

  24. Luo, M. et al. PdMo bimetallene for oxygen reduction catalysis. Nature 574, 81–85 (2019).

    Article  Google Scholar 

  25. Lim, B. et al. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction. Science 324, 1302–1305 (2009).

    Article  Google Scholar 

  26. Wang, M., Árnadóttir, L., Xu, Z. J. & Feng, Z. In situ X-ray absorption spectroscopy studies of nanoscale electrocatalysts. Nano Micro Lett. 11, 47 (2019).

    Article  Google Scholar 

  27. Wang, Y., Sun, D., Wang, M., Feng, Z. & Hall, A. S. Oxygen reduction electrocatalysis on ordered intermetallic Pd–Bi electrodes is enhanced by a low coverage of spectator species. J. Phys. Chem. C 124, 5220–5224 (2020).

    Article  Google Scholar 

  28. Liao, H. et al. A multisite strategy for enhancing the hydrogen evolution reaction on a nano-Pd surface in alkaline media. Adv. Energy Mater. 7, 1701129 (2017).

    Article  Google Scholar 

  29. Funke, H., Scheinost, A. C. & Chukalina, M. Wavelet analysis of extended X-ray absorption fine structure data. Phys. Rev. B 71, 094110 (2005).

    Article  Google Scholar 

  30. Funke, H., Chukalina, M. & Scheinost, A. C. A new FEFF-based wavelet for EXAFS data analysis. J. Synchrotron Radiat. 14, 426–432 (2007).

    Article  Google Scholar 

  31. Liu, Y. et al. A highly efficient metal-free electrocatalyst of F-doped porous carbon toward N2 electroreduction. Adv. Mater. 32, 1907690 (2020).

    Article  Google Scholar 

  32. Li, M. et al. Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional electrocatalysis. Nat. Catal. 2, 495–503 (2019).

    Article  Google Scholar 

  33. Jin, H. et al. Improved electrocatalytic activity for ethanol oxidation by Pd@N-doped carbon from biomass. Chem. Commun. 50, 12637–12640 (2014).

    Article  Google Scholar 

  34. Tian, X. et al. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 366, 850–856 (2019).

    Article  Google Scholar 

  35. Chang, J., Feng, L., Liu, C., Xing, W. & Hu, X. Ni2P enhances the activity and durability of the Pt anode catalyst in direct methanol fuel cells. Energy Environ. Sci. 7, 1628–1632 (2014).

    Article  Google Scholar 

  36. von Weber, A. et al. Size-dependent electronic structure controls activity for ethanol electro-oxidation at Ptn/indium tin oxide (n = 1 to 14). Phys. Chem. Chem. Phys. 17, 17601–17610 (2015).

    Article  Google Scholar 

  37. Li, Z. et al. Iridium single-atom catalyst on nitrogen-doped carbon for formic acid oxidation synthesized using a general host–guest strategy. Nat. Chem. 12, 764–772 (2020).

    Article  Google Scholar 

  38. Brushett, F. R., Naughton, M. S., Ng, J. W. D., Yin, L. & Kenis, P. J. A. Analysis of Pt/C electrode performance in a flowing-electrolyte alkaline fuel cell. Int. J. Hydrog. Energy 37, 2559–2570 (2012).

    Article  Google Scholar 

  39. Kaserer, S., Rakousky, C., Melke, J. & Roth, C. Design of a reference electrode for high-temperature PEM fuel cells. J. Appl. Electrochem. 43, 1069–1078 (2013).

    Article  Google Scholar 

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

    Article  Google Scholar 

  41. Chang, J., Wang, G. & Yang, Y. Recent advances in electrode design for rechargeable zinc–air batteries. Small Science 1, 2100044 (2021).

  42. Greeley, J. et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 1, 552–556 (2009).

    Article  Google Scholar 

  43. Guo, Y. et al. Potential-dependent mechanistic study of ethanol electro-oxidation on palladium. ACS Appl. Mater. Interfaces 13, 16602–16610 (2021).

    Article  Google Scholar 

  44. Cheng, Y., Tian, Y., Fan, X., Liu, J. & Yan, C. Boron doped multi-walled carbon nanotubes as catalysts for oxygen reduction reaction and oxygen evolution reaction in alkaline media. Electrochim. Acta 143, 291–296 (2014).

    Article  Google Scholar 

  45. Chang, J., Feng, L., Liu, C., Xing, W. & Hu, X. An effective Pd-Ni2P/C anode catalyst for direct formic acid fuel cells. Angew. Chem. Int. Ed. 53, 122–126 (2014).

    Article  Google Scholar 

  46. Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. B 136, B864–B871 (1964).

    Article  MathSciNet  Google Scholar 

  47. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).

    Article  MathSciNet  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  51. Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  52. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  Google Scholar 

  53. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

    Article  MathSciNet  Google Scholar 

Download references

Acknowledgements

This work was supported by a start-up grant from the University of Central Florida. J.C. acknowledges financial support from the Preeminent Postdoctoral Program (P3) at the University of Central Florida. The XPS test was supported by the US National Science Foundation (Division of Electrical, Communications and Cyber Systems, no. 1726636), hosted in the Materials Characterization Facility and Advanced Materials Processing and Analysis Center, Department of Materials Science and Engineering, College of Engineering and Computer Science, University of Central Florida. Z.F. acknowledges support from the US National Science Foundation (National Nanotechnology Coordinated Infrastructure, no. 2025489). Guofeng Wang and B.L. acknowledge support from the US National Science Foundation (Division of Chemical, Bioengineering, Environmental and Transport Systems, no. 1804534). Computational resources were provided by the University of Pittsburgh Center for Research Computing as well as the Extreme Science and Engineering Discovery Environment, which is supported by National Science Foundation grant no. ACI-1053575. The use of the Advanced Photon Source at Argonne National Laboratory for XAS measurements at beamlines 5-BM and 12-BM was supported by the US Department of Energy under contract no. DE-AC02-06CH11357. DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) is supported through E. I. duPont de Nemours and Company, Northwestern University and the Dow Chemical Company. M.G. acknowledges support from the Guangdong Innovative and Entrepreneurial Research Team Program (grant no. 2019ZT08C044) and the Peacook Team Program supported by the Science, Technology and Innovation Commission of Shenzhen Municipality (KQTD20190929173815000).

Author information

Authors and Affiliations

  1. NanoScience Technology Center, University of Central Florida, Orlando, FL, USA

    Jinfa Chang, Guanzhi Wang, Wei Zhang & Yang Yang

  2. Department of Materials Science and Engineering, University of Central Florida, Orlando, FL, USA

    Guanzhi Wang, Wei Zhang & Yang Yang

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

    Maoyu Wang & Zhenxing Feng

  4. Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, China

    Qi Wang, Yuanmin Zhu & Meng Gu

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

    Boyang Li & Guofeng Wang

  6. X-ray Science Division, Argonne National Laboratory, Lemont, IL, USA

    Hua Zhou

  7. Department of Mechanical and Aerospace Engineering, University of Central Florida, Orlando, FL, USA

    Mahmoud Omer & Nina Orlovskaya

  8. Renewable Energy and Chemical Transformation Cluster, University of Central Florida, Orlando, FL, USA

    Mahmoud Omer, Nina Orlovskaya & Yang Yang

  9. DND-CAT, Synchrotron Research Center, Advanced Photon Source, Lemont, IL, USA

    Qing Ma

  10. Department of Chemistry, University of Central Florida, Orlando, FL, USA

    Yang Yang

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  1. Jinfa Chang
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Contributions

Y.Y. led the project and proposed the concept. J.C. designed and performed most of the experiments and analysed most of the data. Guanzhi Wang performed the X-ray diffraction, XPS and UPS characterizations. W.Z. performed the NMR test. Q.W., Y.Z. and M.G. carried out the electron microscopy analysis. M.O. and N.O. performed the Raman tests. M.W., Q.M., H.Z. and Z.F. collected and analysed the XAS data. B.L. and Guofeng Wang performed the DFT calculations. J.C. and Y.Y. wrote the paper. All authors discussed the results and revised the paper together.

Corresponding authors

Correspondence to Meng Gu, Zhenxing Feng, Guofeng Wang or Yang Yang.

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Competing interests

The fluorinated fuel cell catalysts disclosed in this work have been filed as US Provisional Patent Application (Serial No. 63/260,768) with Y.Y. and J.C. as inventors. The status of the patent application is pending.

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Peer review information Nature Energy thanks Wenzhen Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–63, Tables 1–8, Notes 1–5 and references.

Supplementary Data 1

Source data for Supplementary Figs. 36a–c, 44d, 49, 50e, 51d, 55, 58j and 59c.

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Chang, J., Wang, G., Wang, M. et al. Improving Pd–N–C fuel cell electrocatalysts through fluorination-driven rearrangements of local coordination environment. Nat Energy 6, 1144–1153 (2021). https://doi.org/10.1038/s41560-021-00940-4

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