Abstract
Shape- and composition-controlled synthesis of platinum-based nanocrystals (NCs) is critical for the development of electrocatalysts that have high activity toward the methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). We report one-pot surfactant-free synthesis of interconnected Pt95Co5 nanowires (NWs) via an oriented attachment process, which has distinct advantages over conventional template- and surfactant-assisted approaches. Enhanced electrochemical activities toward MOR were confirmed through comparison with pure Pt NWs and commercial Pt/C catalyst. Pt95Co5 NWs demonstrated the highest current density during the long-term stability test. These results reveal that the introduction of the 3d-transition metal Co can reduce the catalyst cost and contribute to the improvement of electrochemical performance. The integrated design of interconnected NW structure, bimetallic composition, and clean surfaces in the present system may open a new way to the development of excellent electrocatalysts in DMFCs.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Wang, Y.; Chen, K. S.; Mishler, J.; Cho, S. C.; Adroher, X. C. A review of polymer electrolyte membrane fuel cells: Technology, applications, and needs on fundamental research. Appl. Energy 2011, 88, 981–1007.
Xu, W.; Wu, Z. C.; Tao, S. W. Recent progress in electrocatalysts with mesoporous structures for application in polymer electrolyte membrane fuel cells. J. Mater. Chem. A 2016, 4, 16272–16287.
Peighambardoust, S. J.; Rowshanzamir, S.; Amjadi, M. Review of the proton exchange membranes for fuel cell applications. Int. J. Hydrogen Energy 2010, 35, 9349–9384.
Zhao, X.; Yin, M.; Ma, L.; Liang, L.; Liu, C. P.; Liao, J. H.; Lu, T. H.; Xing, W. Recent advances in catalysts for direct methanol fuel cells. Energy Environ. Sci. 2011, 4, 2736–2753.
Koenigsmann, C.; Wong, S. S. One-dimensional noble metal electrocatalysts: A promising structural paradigm for direct methanol fuel cells. Energy Environ. Sci. 2011, 4, 1161–1176.
Chen, A. C.; Holt-Hindle, P. Platinum-based nanostructured materials: Synthesis, properties, and applications. Chem. Rev. 2010, 110, 3767–3804.
Kakati, N.; Maiti, J.; Lee, S. H.; Viswanathan, B.; Yoon, Y. S. Anode catalysts for direct methanol fuel cells in acidic media: Do we have any alternative for Pt or Pt-Ru? Chem. Rev. 2014, 114, 12397–12429.
Wang, L.; Yamauchi, Y. Block copolymer mediated synthesis of dendritic platinum nanoparticles. J. Am. Chem. Soc. 2009, 131, 9152–9153.
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.
Sun, X. H.; Zhu, X.; Zhang, N.; Guo, J.; Guo, S. J.; Huang, X. Q. Controlling and self assembling of monodisperse platinum nanocubes as efficient methanol oxidation electrocatalysts. Chem. Commun. 2015, 51, 3529–3532.
Liu, H. L.; Nosheen, F.; Wang, X. Noble metal alloy complex nanostructures: Controllable synthesis and their electrochemical property. Chem. Soc. Rev. 2015, 44, 3056–3078.
Gilroy, K. D.; Ruditskiy, A.; Peng, H. C.; Qin, D.; Xia, Y. N. Bimetallic nanocrystals: Syntheses, properties, and applications. Chem. Rev. 2016, 116, 10414–10472.
Wang, D. S.; Li, Y. D. Bimetallic nanocrystals: Liquid-phase synthesis and catalytic applications. Adv. Mater. 2011, 23, 1044–1060.
Jiang, L.-Y.; Huang, X.-Y.; Wang, A.-J.; Li, X.-S.; Yuan, J. H.; Feng, J.-J. Facile solvothermal synthesis of Pt76Co24 nanomyriapods for efficient electrocatalysis. J. Mater. Chem. A 2017, 5, 10554–10560.
Lu, Q. Q.; Wei, C. T.; Sun, L. T.; Alothman, Z. A.; Malgras, V.; Yamauchi, Y.; Wang, H. J.; Wang, L. Smart design of hollow AuPt nanospheres with a porous shell as superior electrocatalysts for ethylene glycol oxidation. RSC Adv. 2016, 6, 19632–19637.
Lu, S. L.; Eid, K.; Ge, D. H.; Guo, J.; Wang, L.; Wang, H. J.; Gu, H. W. One-pot synthesis of PtRu nanodendrites as efficient catalysts for methanol oxidation reaction. Nanoscale 2017, 9, 1033–1039.
Lu, Q. Q.; Wang, H. J.; Eid, K.; Alothman, Z. A.; Malgras, V.; Yamauchi, Y.; Wang, L. Synthesis of hollow platinumpalladium nanospheres with a dendritic shell as efficient electrocatalysts for methanol oxidation. Chem.— Asian. J. 2016, 11, 1939–1944.
Zhu, C. Z.; Shi, Q. R.; Fu, S. F.; Song, J. H.; Xia, H. B.; Du, D.; Lin, Y. H. Efficient synthesis of MCu (M = Pd, Pt, and Au) aerogels with accelerated gelation kinetics and their high electrocatalytic activity. Adv. Mater. 2016, 28, 8779–8783.
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.
Narayanamoorthy, B.; Ramanatha Datta, K. K.; Eswaramoorthy, M.; Balaji, S. Highly active and stable Pt3Rh nanoclusters as supportless electrocatalyst for methanol oxidation in direct methanol fuel cells. ACS Catal. 2014, 4, 3621–3629.
Eid, K.; Ahmad, Y. H.; AlQaradawi, S. Y.; Allam, N. K. Rational design of porous binary Pt-based nanodendrites as efficient catalysts for direct glucose fuel cells over a wide pH range. Catal. Sci. Technol. 2017, 7, 2819–2827.
Xia, B. Y.; Wu, H. B.; Li, N.; Yan, Y.; Lou, X. W.; Wang, X. One-pot synthesis of Pt-Co alloy nanowire assemblies with tunable composition and enhanced electrocatalytic properties. Angew. Chem., Int. Ed. 2015, 54, 3797–3801.
Li, C. L.; Imura, M.; Yamauchi, Y. Displacement plating of a mesoporous Pt skin onto Co nanochains in a lowconcentration surfactant solution. Chem.— Eur. J. 2014, 20, 3277–3282.
Gong, M. X.; Fu, G. T.; Chen, Y.; Tang, Y. W.; Lu, T. H. Autocatalysis and selective oxidative etching induced synthesis of platinum-copper bimetallic alloy nanodendrites electrocatalysts. ACS Appl. Mater. Interfaces 2014, 6, 7301–7308.
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.
Choi, D. S.; Robertson, A. W.; Warner, J. H.; Kim, S. O.; Kim, H. Low-temperature chemical vapor deposition synthesis of Pt-Co alloyed nanoparticles with enhanced oxygen reduction reaction catalysis. Adv. Mater. 2016, 28, 7115–7122.
Bu, L. Z.; Guo, S. J.; Zhang, X.; Shen, X.; Su, D.; Lu, G.; Zhu, X.; Yao, J. L.; Guo, J.; Huang, X. Q. Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis. Nat. Commun. 2016, 7, 11850–11859.
Ma, Z. Z.; Yu, H. C.; Wu, Z. Y.; Wu, Y.; Xiao, F. B. A highly sensitive amperometric glucose biosensor based on a nano-cube Cu2O modified glassy carbon electrode. Chin. J. Anal. Chem. 2016, 44, 822–827.
Zhang, Z. C.; Luo, Z. M.; Chen, B.; Wei, C.; Zhao, J.; Chen, J. Z.; Zhang, X.; Lai, Z. C.; Fan, Z. X.; Tan, C. L. et al. One-pot synthesis of highly anisotropic five-fold-twinned PtCu nanoframes used as a bifunctional electrocatalyst for oxygen reduction and methanol oxidation. Adv. Mater. 2016, 28, 8712–8717.
Nosheen, F.; Zhang, Z. C.; Xiang, G. L.; Xu, B.; Yang, Y.; Saleem, F.; Xu, X. B.; Zhang, J. C.; Wang, X. Threedimensional hierarchical Pt-Cu superstructures. Nano Res. 2015, 8, 832–838.
Wang, W.; Lv, F.; Lei, B.; Wan, S.; Luo, M. C.; Guo, S. J. Tuning nanowires and nanotubes for efficient fuel-cell electrocatalysis. Adv. Mater. 2016, 28, 10117–10141.
Su, Y. K.; Liu, H.; Feng, M.; Yan, Z. L.; Cheng, Z. H.; Tang, J. N.; Yang, H. T. Bimetallic Pt3Co nanowires as electrocatalyst: The effects of thermal treatment on electrocatalytic oxidation of methanol. Electrochim. Acta 2015, 161, 124–128.
Liang, H. W.; Liu, S.; Yu, S. H. Controlled synthesis of one-dimensional inorganic nanostructures using pre-existing one-dimensional nanostructures as templates. Adv. Mater. 2010, 22, 3925–3937.
Zhang, Z. T.; Blom, D. A.; Gai, Z.; Thompson, J. R.; Shen, J.; Dai, S. High-yield solvothermal formation of magnetic CoPt alloy nanowires. J. Am. Chem. Soc. 2003, 125, 7528–7529.
Liu, H. Q.; Adzic, R. R.; Wong, S. S. Multifunctional ultrathin PdxCu1–x and Pt•PdxCu1–x one-dimensional nanowire motifs for various small molecule oxidation reactions. ACS Appl. Mater. Interfaces 2015, 7, 26145–26157.
Hong, W.; Shang, C. S.; Wang, J.; Wang, E. K. Bimetallic PdPt nanowire networks with enhanced electrocatalytic activity for ethylene glycol and glycerol oxidation. Energy Environ. Sci. 2015, 8, 2910–2915.
Zhang, J.; Cullen, D. A.; Forest, R. V.; Wittkopf, J. A.; Zhuang, Z. B.; Sheng, W. C.; Chen, J. G.; Yan, Y. S. Platinum−ruthenium nanotubes and platinum−ruthenium coated copper nanowires as efficient catalysts for electrooxidation of methanol. ACS Catal. 2015, 5, 1468–1474.
Zhao, X.; Zhang, J.; Wang, L. J.; Li, H. X.; Liu, Z. L.; Chen, W. Ultrathin PtPdCu nanowires fused porous architecture with 3D molecular accessibility: An active and durable platform for methanol oxidation. ACS Appl. Mater. Interfaces 2015, 7, 26333–26339.
Xia, B. Y.; Wu, H. B.; Yan, Y.; Lou, X. W.; Wang, X. Ultrathin and ultralong single-crystal platinum nanowire assemblies with highly stable electrocatalytic activity. J. Am. Chem. Soc. 2013, 135, 9480–9485.
Yin, A.-X.; Min, X.-Q.; Zhu, W.; Liu, W.-C.; Zhang, Y.-W.; Yan, C.-H. Pt-Cu and Pt-Pd-Cu concave nanocubes with high-index facets and superior electrocatalytic activity. Chem.—Eur. J. 2012, 18, 777–782.
Liu, L. F.; Pippel, E.; Scholz, R.; Gösele, U. Nanoporous Pt-Co alloy nanowires: Fabrication, characterization, and electrocatalytic properties. Nano Lett. 2009, 9, 4352–4358.
Lai, J. P.; Zhang, L.; Qi, W. J.; Zhao, J. M.; Xu, M.; Gao, W. Y.; Xu, G. B. Facile synthesis of porous PtM (M = Cu, Ni) nanowires and their application as efficient electrocatalysts for methanol electrooxidation. ChemCatChem 2014, 6, 2253–2257.
Chang, F. F.; Yu, G.; Shan, S. Y.; Skeete, Z.; Wu, J. F.; Luo, J.; Ren, Y.; Petkov, V.; Zhong, C.-J. Platinum-nickel nanowire catalysts with composition-tunable alloying and faceting for the oxygen reduction reaction. J. Mater. Chem. A 2017, 5, 12557–12568.
Zhou, Y. Z.; Yang, J.; Zhu, C. Z.; Du, D.; Cheng, X. N.; Yen, C. H.; Wai, C. M.; Lin, Y. H. Newly designed graphene cellular monolith functionalized with hollow Pt-M (M = Ni, Co) nanoparticles as the electrocatalyst for oxygen reduction reaction. ACS Appl. Mater. Interfaces 2016, 8, 25863–25874.
Huang, H. J.; Fan, Y.; Wang, X. Low-defect multi-walled carbon nanotubes supported PtCo alloy nanoparticles with remarkable performance for electrooxidation of methanol. Electrochim. Acta 2012, 80, 118–125.
Xue, Q. M.; Xu, S. B.; Yan, X.; Luo, B. J. Synthesis of worm-like PtCo nanotubes for methanol oxidation. Electrochim. Commun. 2013, 30, 71–74.
Ahmadi, R.; Amini, M. K.; Bennett, J. C. Pt-Co alloy nanoparticles synthesized on sulfur-modified carbon nanotubes as electrocatalysts for methanol electrooxidation reaction. J. Catal. 2012, 292, 81–89.
Liao, Y.; Yu, G.; Zhang, Y.; Guo, T. T.; Chang, F. F.; Zhong, C. J. Composition-tunable PtCu alloy nanowires and electrocatalytic synergy for methanol oxidation reaction. J. Phys. Chem. C 2016, 120, 10476–10484.
Chang, F. F.; Shan, S. Y.; Petkov, V.; Skeete, Z.; Lu, A. L.; Ravid, J.; Wu, J. F.; Luo, J.; Yu, G.; Ren, Y. et al. Composition tunability and (111)-dominant facets of ultrathin platinumgold alloy nanowires toward enhanced electrocatalysis. J. Am. Chem. Soc. 2016, 138, 12166–12175.
Mourdikoudis, S.; Liz-Marzán, L. M. Oleylamine in nanoparticle synthesis. Chem. Mater. 2013, 25, 1465–1476.
Alia, S. M.; Pylypenko, S.; Neyerlin, K. C.; Cullen, D. A.; Kocha, S. S.; Pivovar, B. S. Platinum-coated cobalt nanowires as oxygen reduction reaction electrocatalysts. ACS Catal. 2014, 4, 2680–2686.
Yu, X. F.; Wang, D. S.; Peng, Q.; Li, Y. D. Pt-M (M = Cu, Co, Ni, Fe) nanocrystals: From small nanoparticles to wormlike nanowires by oriented attachment. Chem.—Eur. J. 2013, 19, 233–239.
Wang, Q.; Li, Y. J.; Liu, B. C.; Xu, G. R.; Zhang, G.; Zhao, Q.; Zhang, J. A facile reflux procedure to increase active surface sites form highly active and durable supported palladium@platinum bimetallic nanodendrites. J. Power Sources 2015, 297, 59–67.
Bertin, E.; Garbarino, S.; Ponrouch, A.; Guay, D. Synthesis and characterization of PtCo nanowires for the electrooxidation of methanol. J. Power Sources 2012, 206, 20–28.
Wang, Z. H.; Xie, W. F.; Zhang, F. F.; Xia, J. F.; Gong, S. D.; Xia, Y. Z. Facile synthesis of PtPdPt nanocatalysts for methanol oxidation in alkaline solution. Electrochim. Acta 2016, 192, 400–406.
Xiao, M. L.; Li, S. T.; Zhu, J. B.; Li, K.; Liu, C. P.; Xing, W. Highly active PtAu nanowire networks for formic acid oxidation. ChemPlusChem 2014, 79, 1123–1128.
Zeng, J. H.; Lee, J. Y. Effects of preparation conditions on performance of carbon-supported nanosize Pt-Co catalysts for methanol electro-oxidation under acidic conditions. J. Power Sources 2005, 140, 268–273.
Acknowledgements
The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21435005 and 21627808), the Development Project of Science and Technology of Jilin Province (No. 20170101195JC), and Key Research Program of Frontier Sciences, Chinese Academy of Sciences (No. QYZDY-SSW-SLH019).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
12274_2017_1881_MOESM1_ESM.pdf
One-pot synthesis of interconnected Pt95Co5 nanowires with enhanced electrocatalytic performance for methanol oxidation reaction
Rights and permissions
About this article
Cite this article
Lu, Q., Sun, L., Zhao, X. et al. One-pot synthesis of interconnected Pt95Co5 nanowires with enhanced electrocatalytic performance for methanol oxidation reaction. Nano Res. 11, 2562–2572 (2018). https://doi.org/10.1007/s12274-017-1881-z
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12274-017-1881-z