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In situ development of highly concave and composition-confined PtNi octahedra with high oxygen reduction reaction activity and durability

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Abstract

Controlled syntheses of PtNi metal nanocrystals with unique structures for catalyzing oxygen reduction reactions (ORRs) have attracted great interest. Here, we report the one-step synthesis of single-crystal PtNi octahedra with in situ-developed highly concave features and self-confined composition that are optimal for ORR. Detailed studies revealed that the Pt-rich seeding, subsequent Pt/Ni co-reduction, and Pt–Ni interfusion resulted in uniform single-crystal PtNi octahedra, and that the combination of Ni facet segregation and oxygen etching of a Ni-rich surface led to the concavity and confined Ni content. The concave PtNi nanocrystals exhibited much higher ORR performance than the commercially available Pt/C catalyst in terms of both specific activity (29.1 times higher) and mass activity (12.9 times higher) at 0.9 V (vs. reversible hydrogen electrode (RHE)). The performance was also higher than that of PtNi octahedra without concavity, confirming that the higher activity was closely related to its morphology. Moreover, the concave octahedra also exhibited remarkable stability in ORR (93% mass activity remained after 10,000 cycles between 0.6 and 1.1 V vs. RHE) owing to the passivation of the unstable sites.

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References

  1. Bing, Y. H.; Liu, H. S.; Zhang, L.; Ghosh, D.; Zhang, J. J. Nanostructured Pt-alloy electrocatalysts for PEM fuel cell oxygen reduction reaction. Chem. Soc. Rev. 2010, 39, 2184–2202.

    Article  Google Scholar 

  2. Su, D. S.; Sun, G. Q. Nonprecious-metal catalysts for low-cost fuel cells. Angew. Chem., Int. Ed. 2011, 50, 11570–11572.

    Article  Google Scholar 

  3. Chen, Z. W.; Higgins, D.; Yu, A. P.; Zhang, L.; Zhang, J. J. A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Environ. Sci. 2011, 4, 3167–3192.

    Google Scholar 

  4. Chen, J. Y.; Lim, B.; Lee, E. P.; Xia, Y. N. Shape-controlled synthesis of platinum nanocrystals for catalytic and electrocatalytic applications. Nano Today 2009, 4, 81–95.

    Article  Google Scholar 

  5. Wu, J. B.; Yang, H. Platinum-based oxygen reduction electrocatalysts. Acc. Chem. Res. 2013, 46, 1848–1857.

    Article  Google Scholar 

  6. Porter, N. S.; Wu, H., Quan, Z. W.; Fang, J. Y. Shapecontrol and electrocatalytic activity-enhancement of Pt-based bimetallic nanocrystals. Acc. Chem. Res. 2013, 46, 1867–1877.

    Article  Google Scholar 

  7. Morozan, A.; Jousselme, B.; Palacin, S. Low-platinum and platinum-free catalysts for the oxygen reduction reaction at fuel cell cathodes. Energy Environ. Sci. 2011, 4, 1238–1254.

    Article  Google Scholar 

  8. Gasteiger, H. A.; Kocha, S. S.; Sompalli, B.; Wagner, F. T. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal., B 2005, 56, 9–35.

    Article  Google Scholar 

  9. De Bruijn, F. A.; Dam, V. A. T.; Janssen, G. J. M. Review: Durability and degradation issues of PEM fuel cell components. Fuel Cells 2008, 8, 3–22.

    Article  Google Scholar 

  10. Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T. P.; Hansen, H. A.; Jaramillo, T. F.; Rossmeisl, J.; Chorkendorff, I.; Nørskov, J. K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 2009, 1, 552–556.

    Article  Google Scholar 

  11. Gasteiger, H. A.; Markovic, N. M. Just a dream-or future reality? Science 2009, 324, 48–49.

    Article  Google Scholar 

  12. Nørskov, J. K.; Bligaard, T.; Rossmeisl, J.; Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 2009, 1, 37–46.

    Article  Google Scholar 

  13. Lee, I.; Zhang, Q.; Ge, J. P.; Yin, Y. D.; Zaera, F. Encapsulation of supported Pt nanoparticles with mesoporous silica for increased catalyst stability. Nano Res. 2011, 4, 115–123.

    Article  Google Scholar 

  14. Li, Y. J.; Li, Y. J.; Zhu, E. B.; McLouth, T.; Chiu, C. Y.; Huang, X. Q.; Huang, Y. Stabilization of high-performance oxygen reduction reaction Pt electrocatalyst supported on reduced graphene oxide/carbon black composite. J. Am. Chem. Soc. 2012, 134, 12326–12329.

    Article  Google Scholar 

  15. Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G. F.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 2007, 6, 241–247.

    Article  Google Scholar 

  16. Wu, J. B.; Gross, A.; Yang, H. Shape and compositioncontrolled platinum alloy nanocrystals using carbon monoxide as reducing agent. Nano Lett. 2011, 11, 798–802.

    Article  Google Scholar 

  17. Zhang, J.; Fang, J. Y. A general strategy for preparation of Pt 3d-transition metal (Co, Fe, Ni) nanocubes. J. Am. Chem. Soc. 2009, 131, 18543–18547.

    Article  Google Scholar 

  18. Chen, G. X.; Zhao, Y.; Fu, G.; Duchesne, P. N.; Gu, L.; Zheng, Y. P.; Weng, X. F.; Chen, M. S.; Zhang, P.; Pao, C.-W. et al. Interfacial effects in iron–nickel hydroxide- platinum nanoparticles enhance catalytic oxidation. Science 2014, 344, 495–499.

    Google Scholar 

  19. Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G. F.; Ross, P. N.; Lucas, C. A.; Markovic, N. M. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 2007, 315, 493–497.

    Article  Google Scholar 

  20. Aricò, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J. M.; Van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 2005, 4, 366–377.

    Article  Google Scholar 

  21. Guo, S. J.; Zhang, S.; Sun, S. H. Tuning nanoparticle catalysis for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2013, 52, 8526–8544.

    Article  Google Scholar 

  22. Huang, X.; Zhao, Z.; Cao, L.; Chen, Y.; Zhu, E.; Lin, Z.; Li, M.; Yan, A.; Zettl, A.; Wang, Y. M. et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 2015, 348, 1230–1234.

    Google Scholar 

  23. Choi, S. I.; Xie, S. F.; Shao, M. H.; Odell, J. H.; Lu, N.; Peng, H. C.; Protsailo, L.; Guerrero, S.; Park, J.; Xia, X. H. 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. 2013, 13, 3420–3425.

    Google Scholar 

  24. Zhang, J.; Yang, H. Z.; Fang, J. Y.; Zou, S. Z. Synthesis and oxygen reduction activity of shape-controlled Pt3Ni nanopolyhedra. Nano Lett. 2010, 10, 638–644.

    Article  Google Scholar 

  25. Huang, X. Q.; Zhu, E. B.; Chen, Y.; Li, Y. J.; Chiu, C. Y.; Xu, Y. X.; Lin, Z. Y.; Duan, X. F.; Huang, Y. A facile strategy to Pt3Ni nanocrystals with highly porous features as an enhanced oxygen reduction reaction catalyst. Adv. Mater. 2013, 25, 2974–2979.

    Google Scholar 

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

    Article  Google Scholar 

  27. Carpenter, M. K.; Moylan, T. E.; Kukreja, R. S.; Atwan, M. H.; Tessema, M. M. Solvothermal synthesis of platinum alloy nanoparticles for oxygen reduction electrocatalysis. J. Am. Chem. Soc. 2012, 134, 8535–8542.

    Article  Google Scholar 

  28. Wang, X.; Choi, S. I.; Roling, L. T.; Luo, M.; Ma, C.; Zhang, L.; Chi, M. F.; Liu, J. Y.; Xie, Z. X.; Herron, J. A. et al. Palladium–platinum core–shell icosahedra with substantially enhanced activity and durability towards oxygen reduction. Nat. Commun. 2015, 6, 7594.

    Google Scholar 

  29. Zhang, L.; Roling, L. T.; Wang, X.; Vara, M.; Chi, M. F.; Liu, J. Y.; Choi, S.; Park, J.; Herron, J. A.; Xie, Z. X. et al. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets. Science 2015, 349, 412–416.

    Google Scholar 

  30. Li, Y. J.; Quan, F. X.; Zhu, E. B.; Chen, L.; Huang, Y.; Chen, C. F. PtxCuy nanocrystals with hexa-pod morphology and their electrocatalytic performances towards oxygen reduction reaction. Nano Res. 2015, 8, 3342–3352.

    Article  Google Scholar 

  31. Liu, X.; Wang, W.; Li, H.; Li, L.; Zhou, G.; Yu, R.; Wang, D.; Li, Y. One-pot protocol for bimetallic Pt/Cu hexapod concave nanocrystals with enhanced electrocatalytic activity. Sci. Rep. 2013, 3, 1404.

    Google Scholar 

  32. Chen, C.; Kang, Y.; Huo, Z.; Zhu, Z.; Huang, W.; Xin, H. L.; Synder, J. D.; Li, D.; Herron, J. A.; Mavrikakis, M. et al. Highly crystalline multimetallic nanoframes with threedimensional electrocatalytic surfaces. Science 2014, 343, 1339–1343.

    Google Scholar 

  33. Li, Y. J.; Quan, F. X.; Chen, L.; Zhang, W. J.; Yu, H. B.; Chen, C. F. Synthesis of Fe-doped octahedral Pt3Ni nanocrystals with high electro-catalytic activity and stability towards oxygen reduction reaction. RSC Adv. 2014, 4, 1895–1899.

    Article  Google Scholar 

  34. Colón-Mercado, H. R.; Popov, B. N. Stability of platinum based alloy cathode catalysts in PEM fuel cells. J. Power Sources 2006, 155, 253–263.

    Article  Google Scholar 

  35. Kang, Y. J.; Murray, C. B. Synthesis and electrocatalytic properties of cubic Mn–Pt nanocrystals (nanocubes). J. Am. Chem. Soc. 2010, 132, 7568–7569.

    Article  Google Scholar 

  36. Wu, Y. E.; Cai, S. F.; Wang, D. S.; He, W.; Li, Y. D. Syntheses of water-soluble octahedral, truncated octahedral, and cubic Pt–Ni nanocrystals and their structure-activity study in model hydrogenation reactions. J. Am. Chem. Soc. 2012, 134, 8975–8981.

    Article  Google Scholar 

  37. Wang, D.; Xin, H. L.; Hovden, R.; Wang, H.; Yu, Y.; Muller, D. A.; Di Salvo, F. J.; Abruña, H. D. Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat. Mater. 2013, 12, 81–87.

    Article  Google Scholar 

  38. Wu, J. B.; Zhang, J. L.; Peng, Z. M.; Yang, S. C.; Wagner, F. T.; Yang, H. Truncated octahedral Pt3Ni oxygen reduction reaction electrocatalysts. J. Am. Chem. Soc. 2010, 132, 4984–4985.

    Article  Google Scholar 

  39. Wu, Y. E.; Wang, D. S.; Niu, Z. Q.; Chen, P. C.; Zhou, G.; Li, Y. D. A strategy for designing a concave Pt–Ni alloy through controllable chemical etching. Angew. Chem., Int. Ed. 2012, 51, 12524–12528.

    Google Scholar 

  40. Cui, C. H.; Gan, L.; Li, H. H.; Yu, S. H.; Heggen, M.; Strasser, P. Octahedral PtNi nanoparticle catalysts: Exceptional oxygen reduction activity by tuning the alloy particle surface composition. Nano Lett. 2012, 12, 5885–5889.

    Article  Google Scholar 

  41. Yang, H.; Vogel, W.; Lamy, C.; Alonso-Vante, N. Structure and electrocatalytic activity of carbon-supported Pt–Ni alloy nanoparticles toward the oxygen reduction reaction. J. Phys. Chem. B 2004, 108, 11024–11034.

    Article  Google Scholar 

  42. Fortunelli, A.; Goddard III, W. A.; Sementa, L.; Barcaro, G.; Negreiros, F. R.; Jaramillo-Botero, A. The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts. Chem. Sci. 2015, 6, 3915–3925.

    Article  Google Scholar 

  43. Vitos, L.; Ruban, A. V.; Skriver, H. L.; Kollár, J. The surface energy of metals. Surf. Sci. 1998, 411, 186–202.

    Article  Google Scholar 

  44. Gan, L.; Cui, C. H.; Heggen, M.; Dionigi, F.; Rudi, S.; Strasser, P. Element-specific anisotropic growth of shaped platinum alloy nanocrystals. Science 2014, 346, 1502–1506.

    Article  Google Scholar 

  45. Speight, J. G. Lange's Handbook of Chemistry; McGraw-Hill: New York, 2005.

    Google Scholar 

  46. Walker, R. A.; Darby, J. B. Jr. Thermodynamic properties of solid nickel–platinum alloys. Acta Metall. 1970, 18, 1261–1266.

    Article  Google Scholar 

  47. Wiley, B.; Sun, Y. G.; Xia, Y. N. Synthesis of silver nanostructures with controlled shapes and properties. Acc. Chem. Res. 2007, 40, 1067–1076.

    Article  Google Scholar 

  48. Lu, Z. W.; Wei, S. H.; Zunger, A. Long-range order in binary late-transition-metal alloys. Phys. Rev. Lett. 1991, 66, 1753–1756.

    Article  Google Scholar 

  49. Shang, S. L.; Wang, Y.; Kim, D. E.; Zacherl, C. L.; Du, Y.; Liu, Z. K. Structural, vibrational, and thermodynamic properties of ordered and disordered Ni1-xPtx alloys from first-principles calculations. Phys. Rev. B 2011, 83, 144204.

    Article  Google Scholar 

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

    Article  Google Scholar 

  51. Jin, M. S.; Zhang, H.; Xie, Z. X.; Xia, Y. N. Palladium concave nanocubes with high-index facets and their enhanced catalytic properties. Angew. Chem., Int. Ed. 2011, 50, 7850–7854.

    Article  Google Scholar 

  52. Zhang, L.; Zhang, J. W.; Kuang, Q.; Xie, S. F.; Jiang, Z. Y.; Xie, Z. X.; Zheng, L. S. Cu2+-assisted synthesis of hexoctahedral Au–Pd alloy nanocrystals with high-index facets. J. Am. Chem. Soc. 2011, 133, 17114–17117.

    Article  Google Scholar 

  53. Zhang, H.; Jin, M. S.; Xia, Y. N. Noble-metal nanocrystals with concave surfaces: Synthesis and applications. Angew. Chem., Int. Ed. 2012, 51, 7656–7673.

    Article  Google Scholar 

  54. Zhang, J.; Langille, M. R.; Personick, M. L.; Zhang, K.; Li, S. Y.; Mirkin, C. A. Concave cubic gold nanocrystals with high-index facets. J. Am. Chem. Soc. 2012, 132, 14012–14014.

    Article  Google Scholar 

  55. Huang, X. Q.; Zhao, Z. P.; Fan, J. M.; Tan, Y. M.; Zheng, N. F. Amine-assisted synthesis of concave polyhedral platinum nanocrystals having {411} high-index facets. J. Am. Chem. Soc. 2011, 133, 4718–4721.

    Article  Google Scholar 

  56. Yu, T.; Kim, D. Y.; Zhang, H.; Xia, Y. N. Platinum concave nanocubes with high-index facets and their enhanced activity for oxygen reduction reaction. Angew. Chem., Int. Ed. 2011, 50, 2773–2777.

    Article  Google Scholar 

  57. Xu, X. L.; Zhang, X.; Sun, H.; Yang, Y.; Dai, X. P.; Gao, J. S.; Li, X. Y.; Zhang, P. F.; Wang, H. H.; Yu, N. F. et al. Synthesis of Pt–Ni alloy nanocrystals with high-index facets and enhanced electrocatalytic properties. Angew. Chem. 2014, 126, 12730–12735.

    Google Scholar 

  58. Snyder, J.; Erlebacher, J. Kinetics of crystal etching limited by terrace dissolution. J. Electrochem. Soc. 2010, 157, C125–C130.

    Article  Google Scholar 

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Zhu, E., Li, Y., Chiu, CY. et al. In situ development of highly concave and composition-confined PtNi octahedra with high oxygen reduction reaction activity and durability. Nano Res. 9, 149–157 (2016). https://doi.org/10.1007/s12274-015-0927-3

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