Abstract
Bimetallic core-shell nanostructures with porous surfaces have drawn considerable attention due to their promising applications in various fields, including catalysis and electronics. In this work, Au@Pd core-shell nanothorns (CSNTs) with rough and porous surfaces were synthesized for the first time through a facile co-chemical reduction method in the presence of polyallylamine hydrochloride (PAH) and ethylene glycol (EG) at room temperature. The size, morphology, and composition of Au@Pd CSNTs were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDX), EDX mapping, and X-ray photoelectron spectroscopy (XPS). The electrochemical properties of as-synthesized Au@Pd CSNTs were also studied by various electrochemical techniques. Au@Pd CSNTs exhibited remarkably high electrocatalytic activity and durability for the oxygen reduction reaction (ORR) in the alkaline media, owing to the unique porous structure and the synergistic effect between the Au core and Pd shell.
Similar content being viewed by others
References
Lim, B.; Jiang, M. J.; Camargo, P. H. C.; Cho, E. C.; Tao, J.; Lu, X. M.; Zhu, Y. M.; Xia, Y. N. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction. Science 2009, 324, 1302–1305.
Peng, Z. M.; Yang, H. Synthesis and oxygen reduction electrocatalytic property of Pt-on-Pd bimetallic heteronanostructures. J. Am. Chem. Soc. 2009, 131, 7542–7543.
Peng, Z. M.; Yang, H. PtAu bimetallic heteronanostructures made by post-synthesis modification of Pt-on-Au nanoparticles. Nano Res. 2009, 2, 406–415.
Hong, J. W.; Kim, M.; Kim, Y.; Han, S. W. Trisoctahedral Au-Pd alloy nanocrystals with high-index facets and their excellent catalytic performance. Chem. Eur. J. 2012, 18, 16626–16630.
Lee, Y. W.; Kim, M.; Kim, Y.; Kang, S. W.; Lee, J.-H.; Han, S. W. Synthesis and electrocatalytic activity of Au-Pd alloy nanodendrites for ethanol oxidation. J. Phys. Chem. C 2010, 114, 7689–7693.
Lim, B.; Jiang, M. J.; Yu, T.; Camargo, P. H. C.; Xia, Y. N. Nucleation and growth mechanisms for Pd-Pt bimetallic nanodendrites and their electrocatalytic properties. Nano Res. 2010, 3, 69–80.
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.
Wang, W. J.; Zhang, J.; Yang, S. C.; Ding, B. J.; Song, X. P. Au@Pd core-shell nanobricks with concave structures and their catalysis of ethanol oxidation. ChemSusChem 2013, 6, 1945–1951.
Balcha, T.; Strobl, J. R.; Fowler, C.; Dash, P.; Scott, R. W. J. Selective aerobic oxidation of crotyl alcohol using AuPd core-shell nanoparticles. ACS Catal. 2011, 1, 425–436.
Lim, B.; Jiang, M. J.; Yu, T.; Camargo, P. H. C.; Xia, Y. N. Nucleation and growth mechanisms for Pd-Pt bimetallic nanodendrites and their electrocatalytic properties. Nano Res. 2010, 3, 69–80.
Li, W. Z.; Kuai, L.; Qin, Q.; Geng, B. Ag-Au bimetallic nanostructures: Co-reduction synthesis and their component-dependent performance for enzyme-free H2O2 sensing. J. Mater. Chem. A 2013, 1, 7111–7117.
Chen, L.; Kuai, L.; Yu, X.; Li, W.; Geng, B. Advanced catalytic performance of Au-Pt double-walled nanotubes and their fabrication through galvanic replacement reaction. Chem. Eur. J. 2013, 19, 11753–11758.
Kim, D. Y.; Kang, S. W.; Choi, K. W.; Choi, S. W.; Han, S. W.; Im, S. H.; Park, O. O. Au@Pd nanostructures with tunable morphologies and sizes and their enhanced electrocatalytic activity. CrystEngComm 2013, 15, 7113–7120.
Xu, J. G.; Wilson, A. R.; Rathmell, A. R.; Howe, J.; Chi, M. F.; Wiley, B. J. Synthesis and catalytic properties of Au-Pd nanoflowers. ACS Nano 2011, 5, 6119–6127.
Kim, D. Y.; Choi, K. W.; Zhong, X.-L.; Li, Z.-Y.; Im, S. H.; Park, O. O. Au@Pd core-shell nanocubes with finely-controlled sizes. CrystEngComm 2013, 15, 3385–3391.
Lee, Y. W.; Kim, M.; Kim, Z. H.; Han, S. W. One-step synthesis of Au@Pd core-shell nanooctahedron. J. Am. Chem. Soc. 2009, 131, 17036–17037.
Li, J.; Zheng, Y. Q.; Zeng, J.; Xia, Y. N. Controlling the size and morphology of Au@Pd core-shell nanocrystals by manipulating the kinetics of seeded growth. Chem. Eur. J. 2012, 18, 8150–8156.
Song, H. M.; Anjum, D. H.; Sougrat, R.; Hedhili, M. N.; Khashab, N. M. Hollow Au@Pd and Au@Pt core-shell nanoparticles as electrocatalysts for ethanol oxidation reactions. J. Mater. Chem. 2012, 22, 25003–25010.
Kuai, L.; Geng, B. Y.; Wang, S. Z.; Sang, Y. A general and high-yield galvanic displacement approach to Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells and enhanced electrocatalytic performances. Chem. Eur. J. 2012, 18, 9423–9429.
Fu, G. T.; Wu, K.; Lin, J.; Tang, Y.; Chen, Y.; Zhou, Y. M.; Lu, T. H. One-pot water-based synthesis of Pt-Pd alloy nanoflowers and their superior electrocatalytic activity for the oxygen reduction reaction and remarkable methanol-tolerant ability in acid media. J. Phys. Chem. C 2013, 117, 9826–9834.
Fu, G.; Wu, K.; Jiang, X.; Tao, L.; Chen, Y.; Lin, J.; Zhou, Y.; Wei, S.; Tang, Y.; Lu, T.; et al. Polyallylamine-directed green synthesis of platinum nanocubes. Shape and electronic effect codependent enhanced electrocatalytic activity. Phys. Chem. Chem. Phys. 2013, 15, 3793–3802.
Garsany, Y.; Baturina, O. A.; Swider-Lyons, K. E.; Kocha, S. S. Experimental methods for quantifying the activity of platinum electrocatalysts for the oxygen reduction reaction. Anal. Chem. 2010, 82, 6321–6328.
Awaludin, Z.; Suzuki, M.; Masud, J.; Okajima, T.; Ohsaka, T. Enhanced electrocatalysis of oxygen reduction on Pt/TaOx/GC. J. Phys. Chem. C 2011, 115, 25557–25567.
Stamenković, V.; Schmidt, T. J.; Ross, P. N.; Marković, N. M. Surface composition effects in electrocatalysis: Kinetics of oxygen reduction on well-defined Pt3Ni and Pt3Co alloy surfaces. J. Phys. Chem. B 2002, 106, 11970–11979.
Takai, A.; Ataee-Esfahani, H.; Doi, Y.; Fuziwara, M.; Yamauchi, Y.; Kuroda, K. Pt nanoworms: Creation of a bumpy surface on one-dimensional (1D) Pt nanowires with the assistance of surfactants embedded in mesochannels. Chem. Commun. 2011, 47, 7701–7703.
Lim, B.; Lu, X.; Jiang, M.; Camargo, P. H.; Cho, E. C.; Lee, E. P.; Xia, Y. Facile synthesis of highly faceted multioctahedral Pt nanocrystals through controlled overgrowth. Nano Lett. 2008, 8, 4043–4047.
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.
Zhou, W. J.; Lee, J. Y. Highly active core-shell Au@Pd catalyst for formic acid electrooxidation. Electrochem. Commun. 2007, 9, 1725–1729.
Tan, Q.; Du, C. Y.; Yin, G. P.; Zuo, P. J.; Cheng, X. Q.; Chen, M. Highly efficient and stable nonplatinum anode catalyst with Au@Pd core-shell nanostructures for methanol electrooxidation. J. Catal. 2012, 295, 217–222.
Fu, G. T.; Jiang, X.; Ding, L. F.; Tao, L.; Chen, Y.; Tang, Y. W.; Zhou, Y. M.; Wei, S. H.; Lin, J.; Lu, T. H. Green synthesis and catalytic properties of polyallylamine functionalized tetrahedral palladium nanocrystals. Appl. Catal. B: Environ. 2013, 138–139, 167–174.
Fu, G. T.; Han, W.; Yao, L. F.; Lin, J.; Wei, S. H.; Chen, Y.; Tang, Y. W.; Zhou, Y.; Lu, T. H.; Xia, X. H. One-step synthesis and catalytic properties of porous palladium nanospheres. J. Mater. Chem. 2012, 22, 17604–17611.
Fu, G. T.; Jiang, X.; Tao, L.; Chen, Y.; Lin, J.; Zhou, Y. M.; Tang, Y. W.; Lu, T. H. Polyallylamine functionalized palladium icosahedra: One-pot water-based synthesis and their superior electrocatalytic activity and ethanol tolerant ability in alkaline media. Langmuir 2013, 29, 4413–4420.
Jeong, G. H.; Choi, D.; Kang, M.; Shin, J.; Kang, J. G.; Kim, S. W. One-pot synthesis of Au@ Pd/graphene nanostructures: Electrocatalytic ethanol oxidation for direct alcohol fuel cells (DAFCs). RSC Adv. 2013, 3, 8864–8870.
Zhang, L.-F.; Zhang, C.-Y. Dodecahedral Au@Pd nanocrystals with high-index facets and excellent electrocatalytic activity and highly efficient surface-enhanced Raman scattering enhancement. Nanoscale 2013, 5, 6074–6080.
Lee, Y. W.; Kim, N. H.; Lee, K. Y.; Kwon, K.; Kim, M.; Han, S. W. Synthesis and characterization of flower-shaped porous Au-Pd alloy nanoparticles. J. Phys. Chem. C 2008, 112, 6717–6722.
Li, Z. H.; Li, R.; Mu, T. C.; Luan, Y. X. Ionic liquid assisted synthesis of Au-Pd bimetallic particles with enhanced electrocatalytic activity. Chem. Eur. J. 2013, 19, 6005–6013.
Heo, J.; Kim, D.-S.; Kim, Z. H.; Lee, Y. W.; Kim, D.; Kim, M.; Kwon, K.; Park, H. J.; Yun, W. S.; Han, S. W. Controlled synthesis and characterization of the enhanced local field of octahedral Au nanocrystals. Chem. Commun. 2008, 6120–6122.
Tian, Z.-Q.; Ren, B.; Li, J.-F.; Yang, Z.-L. Expanding generality of surface-enhanced Raman spectroscopy with borrowing SERS activity strategy. Chem. Commun. 2007, 3514–3534.
Peng, Z. M.; Yang, H. Designer platinum nanoparticles: Control of shape, composition in alloy, nanostructure and electrocatalytic property. Nano Today 2009, 4, 143–164.
Zhang, J.; Mo, Y.; Vukmirovic, M.; B. Klie, R.; Sasaki, K.; Adzic, R. R. Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on Pd (111) and on carbon-supported Pd nanoparticles. J. Phys. Chem. B 2004, 108, 10955–10964.
Sun, S. H.; Zhang, G. X.; Geng, D. S.; Chen, Y. G.; Li, R. Y.; Cai, M.; Sun, X. L. A highly durable platinum nanocatalyst for proton exchange membrane fuel cells: Multiarmed starlike nanowire single crystal. Angew. Chem. Int. Ed. 2011, 50, 422–426.
Xia, B. Y.; Ng, W. T.; Wu, H. B.; Wang, X.; Lou, X. W. Self-supported interconnected Pt nanoassemblies as highly stable electrocatalysts for low-temperature fuel cells. Angew. Chem. Int. Ed. 2012, 51, 7213–7216.
Kuai, L.; Yu, X.; Wang, S. Z.; Sang, Y.; Geng, B. Y. Au-Pd alloy and core-shell nanostructures: One-pot coreduction preparation, formation mechanism, and electrochemical properties. Langmuir 2012, 28, 7168–7173.
Lee, C.-L.; Chao, Y.-J.; Chen, C.-H.; Chiou, H.-P.; Syu, C. C. Graphite-nanofiber-supported porous Pt-Ag nanosponges: Synthesis and oxygen reduction electrocatalysis. Int. J. Hydrogen Energ. 2011, 36, 15045–15051.
Lima, F. H. B.; de Castro, J. F. R.; Ticianelli, E. A. Silver-cobalt bimetallic particles for oxygen reduction in alkaline media. J. Power Sources 2006, 161, 806–812.
Zhang, G. J.; Zhang, L.; Shen, L. P.; Chen, Y.; Zhou, Y. M.; Tang, Y. W.; Lu, T. H. Synthesis and electrocatalytic properties of palladium network nanostructures. ChemPlusChem 2012, 77, 936–940.
Tan, Y. M.; Fan, J. M.; Chen, G. X.; Zheng, N. F.; Xie, Q. J. Au/Pt and Au/Pt3Ni nanowires as self-supported electrocatalysts with high activity and durability for oxygen reduction. Chem. Commun. 2011, 47, 11624–11626.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Fu, G., Liu, Z., Chen, Y. et al. Synthesis and electrocatalytic activity of Au@Pd core-shell nanothorns for the oxygen reduction reaction. Nano Res. 7, 1205–1214 (2014). https://doi.org/10.1007/s12274-014-0483-2
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12274-014-0483-2