Here we present the synthesis of porous platinum–palladium macrobeams templated from high aspect ratio Magnus’ salt needle derivatives. The combination of [PtCl4]2− and/or [PdCl4]2− with [Pt(NH3)4]2+ ions results in salt needles ranging from 15 to 300 µm in length. Electrochemical reduction of the salt templates results in porous macrobeams with a square cross-section. Porous side wall texture and elemental composition was controlled with initial platinum to palladium salt ratio. Macrobeam free-standing films exhibited a specific capacitance up to 11.73 F/g and a solvent accessible surface area of 26.6 m2/g. These salt-templated porous platinum–palladium macrobeams offer a promising material for fuel cell catalysis.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
B. Jiang, K. Kani, M. Iqbal, H. Abe, T. Kimura, M.S.A. Hossain, O. Anjaneyulu, J. Henzie, and Y. Yamauchi: Mesoporous bimetallic RhCu alloy nanospheres using a sophisticated soft-templating strategy. Chem. Mater. 30, 428 (2018).
X. Qiu, Y. Dai, X. Zhu, H. Zhang, P. Wu, Y. Tang, and S. Wei: Template-engaged synthesis of hollow porous platinum–palladium alloy nanospheres for efficient methanol electro-oxidation. J. Power Sources 302, 195 (2016).
L. Liu, E. Pippel, R. Scholz, and U. Gösele: Nanoporous Pt-Co alloy nanowires: fabrication, characterization, and electrocatalytic properties. Nano Lett. 9, 4352 (2009).
C. Xu, Y. Zhang, L. Wang, L. Xu, X. Bian, H. Ma, and Y. Ding: Nanotubular mesoporous PdCu bimetallic electrocatalysts toward oxygen reduction reaction. Chem. Mater. 21, 3110 (2009).
Y. Yamauchi, A. Tonegawa, M. Komatsu, H. Wang, L. Wang, Y. Nemoto, N. Suzuki, and K. Kuroda: Electrochemical synthesis of mesoporous Pt–Au binary alloys with tunable compositions for enhancement of electrochemical performance. J. Am. Chem. Soc. 134, 5100 (2012).
M. Victor, A.E. Hamed, W. Hongjing, J. Bo, L. Cuiling, W.K.C.W., K.J. Ho, and Y. Yusuke: Nanoarchitectures for mesoporous metals. Adv. Mater. 28, 993 (2016).
Z. Peng and H. Yang: Designer platinum nanoparticles: Control of shape, composition in alloy, nanostructure and electrocatalytic property. Nano. Today. 4, 143 (2009).
V.R. Stamenkovic, B. Fowler, B.S. Mun, G. Wang, P.N. Ross, C.A. Lucas, and N.M. Markovic: Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315, 493 (2007).
F.J. Burpo, E.A. Nagelli, L.A. Morris, J.P. McClure, M.Y. Ryu, and J.L. Palmer: Direct solution-based reduction synthesis of Au, Pd, and Pt aerogels. J. Mater. Res. 32, 4153 (2017).
L.X. Ding, A.L. Wang, G.R. Li, Z.Q. Liu, W.X. Zhao, C.Y. Su, and Y.X. Tong: Porous Pt-Ni-P composite nanotube arrays: highly electroactive and durable catalysts for methanol electrooxidation. J. Am. Chem. Soc. 134, 5730 (2012).
K. Eid, H. Wang, P. He, K. Wang, T. Ahamad, S.M. Alshehri, Y. Yamauchi, and L. Wang: One-step synthesis of porous bimetallic PtCu nanocrystals with high electrocatalytic activity for methanol oxidation reaction. Nanoscale 7, 16860 (2015).
Z.Y. Shih, C.W. Wang, G. Xu, and H.T. Chang: Porous palladium copper nanoparticles for the electrocatalytic oxidation of methanol in direct methanol fuel cells. J. Mater. Chem. A 1, 4773 (2013).
H. Zhang, M. Jin, and Y. Xia: Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd. Chem. Soc. Rev. 41, 8035 (2012).
J. Wu, P. Li, Y.T. Pan, S. Warren, X. Yin, and H. Yang: Surface lattice-engineered bimetallic nanoparticles and their catalytic properties. Chem. Soc. Rev. 41, 8066 (2012).
C. Zhongwei, W. Mahesh, L. Wenzhen, and Y. Yushan: Supportless Pt and PtPd nanotubes as electrocatalysts for oxygen-reduction reactions. Angew. Chem. Int. Ed. 46, 4060 (2007).
S.S. Li, J.N. Zheng, A.J. Wang, F.L. Tao, J.J. Feng, J.R. Chen, and H. Yu: Branched platinum-on-palladium bimetallic heteronanostructures supported on reduced graphene oxide for highly efficient oxygen reduction reaction. J. Power Sources 272, 1078 (2014).
O. Winjobi, Z. Zhang, C. Liang, and W. Li: Carbon nanotube supported platinum–palladium nanoparticles for formic acid oxidation. Electrochim. Acta 55, 4217 (2010).
N.L. Vauquelin: Memoire sur le palladium et le rhodium. Ann. Chim. 88, 167 (1813).
F.J. Burpo, E.A. Nagelli, S.J. Winter, J.P. McClure, S.F. Bartolucci, A.R. Burns, S.F. O’Brien, and D.D. Chu: Salt-templated hierarchically porous platinum macrotube synthesis. Chem. Select. 3, 4542 (2018).
X. Xiao, H. Song, S. Lin, Y. Zhou, X. Zhan, Z. Hu, Q. Zhang, J. Sun, B. Yang, T. Li, L. Jiao, J. Zhou, J. Tang, and Y. Gogotsi: Scalable salt-templated synthesis of two-dimensional transition metal oxides. Nat. Commun. 7, 11296 (2016).
X. Xiao, H. Yu, H. Jin, M. Wu, Y. Fang, J. Sun, Z. Hu, T. Li, J. Wu, L. Huang, Y. Gogotsi, and J. Zhou: Salt-templated synthesis of 2D metallic MoN and other nitrides. ACS Nano 11, 2180 (2017).
G. Magnus: Ueber einige Verbindungen des Platinchlorürs. Ann. Phys. 90, 239 (1828).
C.A. Schneider, W.S. Rasband, and K.W. Eliceiri: NIH Image to ImageJ: 25 years of image analysis. Nat. Methods 9, 671 (2012).
J. Bremi, D. Brovelli, W. Caseri, G. Hähner, P. Smith, and T. Tervoort: From Vauquelin’s and Magnus’ salts to gels, uniaxially oriented films, and fibers: synthesis, characterization, and properties of tetrakis(1-aminoalkane)metal(II) tetrachlorometalates(II). Chem. Mater. 11, 977 (1999).
W.P. Zhou, A. Lewera, R. Larsen, R.I. Masel, P.S. Bagus, and A. Wieckowski: Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid. J. Phys. Chem. B 110, 13393 (2006).
R. de Levie: On porous electrodes in electrolyte solutions—IV. Electrochim. Acta 9, 1231 (1964).
M. Lukaszewski: Electrochemical methods of real surface area determination of noble metal electrodes––an overview. Int. J. Electrochem. Sci. 11, 4442 (2016).
T. Biegler, D.A.J. Rand, and R. Woods: Limiting oxygen coverage on platinized platinum; relevance to determination of real platinum area by hydrogen adsorption. J. Electroanal. Chem. 29, 269 (1971).
G. Fu, K. Wu, J. Lin, Y. Tang, Y. Chen, Y. Zhou, and T. Lu: 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 117, 9826 (2013).
H.V. Hien, T.D. Thanh, N.D. Chuong, D. Hui, N.H. Kim, and J.H. Lee: Hierarchical porous framework of ultrasmall PtPd alloy-integrated graphene as active and stable catalyst for ethanol oxidation. Composites Part B 143, 96 (2018).
This work was funded by a United States Military Academy Faculty Development Research Fund grant. We appreciate the assistance with polarized optical microscopy from Lance Richardson from the Department of Chemistry and Life Science at the United States Military Academy.
These authors contributed equally.
Electronic supplementary material
The supplementary material for this article can be found at https://doi.org/10.1557/mrc.2018.217
About this article
Cite this article
Burpo, F.J., Nagelli, E.A., Mitropoulos, A.N. et al. Salt-templated platinum–palladium porous macrobeam synthesis. MRS Communications 9, 280–287 (2019). https://doi.org/10.1557/mrc.2018.217