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Research Article

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

Enbo Zhu1, Yongjia Li1, Chin-Yi Chiu1, Xiaoqing Huang1, Mufan Li2, Zipeng Zhao1, Yuan Liu1, Xiangfeng Duan2,3, Yu Huang1,3( )
Department of Materials Science and EngineeringUniversity of CaliforniaLos AngelesCA90095USA
Department of Chemistry and BiochemistryUniversity of CaliforniaLos AngelesCA90095USA
California NanoSystems InstituteUniversity of CaliforniaLos AngelesCA90095USA
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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.

Keywords

PtNi alloyconcaveoxygen reduction reaction

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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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref Google Scholar
5

Wu, J. B.; Yang, H. Platinum-based oxygen reduction electrocatalysts. Acc. Chem. Res. 2013, 46, 1848-1857.
Crossref Google Scholar
6

Porter, N. S.; Wu, H., Quan, Z. W.; Fang, J. Y. Shape- control and electrocatalytic activity-enhancement of Pt-based bimetallic nanocrystals. Acc. Chem. Res. 2013, 46, 1867-1877.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref Google Scholar
11

Gasteiger, H. A.; Marković, N. M. Just a dream-or future reality? Science 2009, 324, 48-49.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref Google Scholar
16

Wu, J. B.; Gross, A.; Yang, H. Shape and composition- controlled platinum alloy nanocrystals using carbon monoxide as reducing agent. Nano Lett. 2011, 11, 798-802.
Crossref 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.
Crossref 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.
Crossref Google Scholar
19

Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G. F.; Ross, P. N.; Lucas, C. A.; Marković, N. M. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 2007, 315, 493-497.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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 three- dimensional electrocatalytic surfaces. Science 2014, 343, 1339-1343.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref Google Scholar
37

Wang, D.; Xin, H. L.; Hovden, R.; Wang, H.; Yu, Y.; Muller, D. A.; DiSalvo, 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref Google Scholar
43

Vitos, L.; Ruban, A. V.; Skriver, H. L.; Kollár, J. The surface energy of metals. Surf. Sci. 1998, 411, 186-202.
Crossref 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.
Crossref Google Scholar
45

Speight, J. G. Lange's Handbook of Chemistry; McGraw-Hill: New York, 2005.
46

Walker, R. A.; Darby, J. B. Jr. Thermodynamic properties of solid nickel-platinum alloys. Acta Metall. 1970, 18, 1261- 1266.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref Google Scholar
50

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 2007, 316, 732-735.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref 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.
Crossref Google Scholar
58

Snyder, J.; Erlebacher, J. Kinetics of crystal etching limited by terrace dissolution. J. Electrochem. Soc. 2010, 157, C125-C130.
Crossref Google Scholar
Nano Research
Volume 9 Issue 1,
January 2016
Pages 149-157
DOI: 10.1007/s12274-015-0927-3
Cite this article:
Zhu E, Li Y, Chiu C-Y, et al. In situ development of highly concave and composition-confined PtNi octahedra with high oxygen reduction reaction activity and durability. Nano Research, 2016, 9(1): 149-157. https://doi.org/10.1007/s12274-015-0927-3
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Received: 25 August 2015
Revised: 21 October 2015
Accepted: 25 October 2015
Published: 25 November 2015
© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2015
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