Abstract
The development of an efficient syntheses method to produce multimetallic nanocomposites with an appropriate structure is required to study the structure–composition–property relationship of the synthesized nanocomposites and to investigate, evaluate their possible technological applications. In this work, a fine hetero-structured Au and Pt containing multi-metallic nanocomposites (Au/Pt/Ag and Au/Pd/Pt colloidal nanocomposites) were synthesized through a microwave irradiation method with the use of trisodium citrate as a reducing agent and it has been coated on the glassy carbon electrode. It is characterized by high-resolution transmission electron microscopy, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopic techniques to elucidate structure, surface morphology, bulk-composition and metallic state of the resulting Au/Pt/Ag and Au/Pd/Pt colloidal nanocomposites respectively. The colloidal nanocomposites were also characterized by zeta potential and dynamic light scattering studies. The electrochemical techniques (cyclic voltammetry and chronoamperometry) have been employed to investigate the electrochemical parameters related to the electro-oxidation of methanol which in turn will be useful for conventional fuel cell applications. In addition to that, the density functional theoretical optimized minimum-energy structures of Pt n (n = 3–6) were studied as they are forming shell and thus involved in catalysis. Electronic density of state plots of the optimized Pt n and Pd n clusters using B3LYP/Lanl2DZ level of theory was made. The multi-metallic nanocomposites of these metals are proposed as a promising new class of catalyst for the electro-oxidation reaction of methanol particularly in fuel-cell applications. The formation of hetero-structure is discussed as the desirable condition to obtain a better electrocatalytic activity. It is also found that, the electrocatalytic activity and stability of the resultant Au/Pt/Ag colloidal nanocomposites modified glassy carbon electrode is much better catalyst towards methanol electrooxidation in acid medium.
Similar content being viewed by others
References
C. Shang, W. Hong, J. Wang, and E. Wang (2015). Carbon Supported Trimetallic Nickel–Palladium–Gold Hollow Nanoparticles with Superior Catalytic Activity for Methanol Electrooxidation. J. Power Sources 285, 12.
C. Li and Y. Yamauchi (2013). Facile Solution Synthesis of Ag@Pt Core-Shell Nanoparticles with Dendritic Pt Shells. Phys. Chem. Chem. Phys. 15, 3490.
R. Wang, C. Wang, W. B. Cai, and Y. Ding (2010). Ultralow-Platinum-Loading High-Performance Nanoporous Electrocatalysts with Nanoengineered Surface Structures. Adv. Mater. 22, 1845.
L. X. Ding, G. R. Li, Z. L. Wang, Z. Q. Liu, H. Liu, and Y. X. Tong (2012). Porous Ni@Pt Core-Shell Nanotube Array Electrocatalyst with High Activity and Stability for Methanol Oxidation. Chem. Eur. J. 18, 8386.
M. M. Liu, Y. Z. Lu, and W. Chen (2013). PdAg Nanorings Supported on Graphene Nanosheets: Highly Methanol-Tolerant Cathode Electrocatalyst for Alkaline Fuel Cells. Adv. Funct. Mater. 23, 1289.
Z. Yin, M. F. Chi, Q. J. Zhu, D. Ma, J. M. Sun, and X. H. Bao (2013). Supported Bimetallic PdAu Nanoparticles with Superior Electrocatalytic Activity Towards Methanol Oxidation. J. Mater. Chem. A 1, 9157.
J. N. Tiwari, R. N. Tiwari, G. Singh, and K. S. Kim (2013). Recent Progress in the Development of Anode and Cathode Catalysts for Direct Methanol Fuel Cells. Nano Energy 2, 553.
Y. Zhang, G. Chang, S. Liu, J. Tian, L. Wang, W. Lu, X. Qin, and X. Sun (2011). Microwave-assisted, Environmentally Friendly, One-pot Preparation of Pd Nanoparticles/Graphene Nanocomposites and Their Application in Electrocatalytic Oxidation of Methanol. Catal. Sci. Technol. 1, 1636.
S. Link and M. A. El-Sayed (2000). Shape and Size Dependence of Radiative, Non-radiative and Photothermal Properties of Gold Nanocrystals. Int. Rev. Phys. Chem. 19, 409.
A. I. Ryasnyanskiy, B. Palpant, S. Debrus, U. Pal, and A. L. Stepanov (2007). Optical Non-linearities of Au Nanoparticles Embedded in a Zinc Oxide Matrix. Opt. Commun. 273, 538.
G. Schmid and B. Corain Nanoparticulated Gold: Syntheses, Structures, Electronics, and Reactivities (Eur J, Inorg. Chem., 2003), p. 3081.
B. Karthikeyan and M. Murugavelu (2012). Nano Bimetallic Ag/Pt System as Efficient Opto and Electrochemical Sensing Platform towards Adenine. Sens. Actuators B 163, 216.
W. Zhao, M. A. Brook, and Y. Li (2008). Design of Gold Nanoparticle-Based Colorimetric Biosensing Assays. Chem. Bio. Chem. 9, 2363.
K. Saha, S. S. Agasti, C. Kim, X. Li, and V. M. Rotello (2012). Gold Nanoparticles in Chemical and Biological Sensing. Chem. Rev. 112, 2739.
T. K. Sau, A. L. Rogach, F. Jackel, T. A. Klar, and J. Feldmann (2010). Properties and Applications of Colloidal Non-Spherical Noble Metal Nanoparticles. Adv. Mater. 22, 1805.
M. B. Cortie and A. M. Mc-Donagh (2011). Synthesis and Optical Properties of Hybrid and Alloy Plasmonic Nanoparticles. Chem. Rev. 111, 3713.
M. Kim, Y. W. Lee, D. Kim, S. Lee, S. R. Ryoo, D. H. Min, S. B. Lee, and S. W. Han (2012). Reshaping Nanocrystals for Tunable Plasmonic Substrates. ACS Appl. Mater. Interfaces 4, 5038.
M. Rycenga, C. M. Cobley, J. Zeng, W. Li, C. H. Moran, Q. Zhang, D. Qin, and Y. Xia (2011). Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications. Chem. Rev. 111, 3669.
M. Y. Haik, A. I. Ayesh, T. Abdulrehman, and Y. Haik (2014). Novel Organic Memory Devices Using Au-Pt-Ag Nanoparticles as Charge Storage Elements. Mater. Lett. 124, 67.
B. Karthikeyan and B. Loganathan (2012). Strategic Green Synthesis and Characterization of Au/Pt/Ag Trimetallic Nanocomposites. Mater. Lett. 85, 53.
B. Karthikeyan and B. Loganathan (2013). A Close Look of Au/Pt/Ag Nanocomposites using SERS Assisted with Optical, Electrochemical. Spect. Theor. Methods Phys. E 49, 105.
B. Loganathan and B. Karthikeyan (2013). Au Core Pd/Pt Shell in Trimetallic Au/Pd/Pt Colloidal Nanocomposites-Physicochemical Characterization Study. Colloids Surf. A 436, 944.
T. T. B. Quyen, W. N. Su, C. H. Chen, J. Rick, J. Y. Liu, and B. J. Hwang (2014). Novel Ag/Au/Pt Trimetallic Nanocages used with Surface-Enhanced Raman Scattering for Trace Fluorescent Dye Detection. J. Mater. Chem. B 2, 5550.
H. Jang, S. R. Ryoo, K. Kostarelos, S. W. Han, and D. H. Min (2013). The Effective Nuclear Delivery of Doxorubicin from Dextran-Coated Gold Nanoparticles Larger than Nuclear Pores. Biomater 34, 3503.
X. H. N. Xu, J. Chen, R. B. Jeffers, and S. Kyriacou (2002). Direct Measurement of Sizes and Dynamics of Single Living Membrane Transporters using Nanooptics. Nano Lett. 2, 175.
J. Gu, W. C. Liu, Z. Q. Zhao, G. X. Lan, W. Zhu, and Y. W. Zhang (2014). Pt/Ru/C Nanocomposites for Methanol Electrooxidation: How Ru Nanocrystals’ Surface Structure Affects Catalytic Performance of Deposited Pt Particles. Inorg. Chem. Front. 1, 109.
Q. Luo, M. Peng, X. Sun, and A. M. Asiri (2015). In Situ Growth of Nickel Selenide Nanowire Arrays on Nickel Foil for Methanol Electro-oxidation in Alkaline Media. RSC Adv. 5, 87051.
G. R. Zhang, J. Wu, and B. Q. Xu (2012). Syntheses of Sub-30 nm Au@Pd Concave Nanocubes and Pt-on-(Au@Pd) Trimetallic Nanostructures as Highly Efficient Catalysts for Ethanol Oxidation. J. Phys. Chem. C 116, 20839.
Q. Luo, M. Peng, X. Sun, and A. M. Asiri (2016). Hierarchical Nickel Oxide Nanosheet@nanowire Arrays on Nickel Foam: An Efficient 3D Electrode for Methanol Electro-oxidation. Catal. Sci. Technol. 6, 1157.
A. Dutta and J. Datta (2012). Outstanding Catalyst Performance of PdAuNi Nanoparticles for the Anodic Reaction in an Alkaline Direct Ethanol (with Anion-Exchange Membrane) Fuel Cell. J. Phys. Chem. C 116, 25677.
H. Li, G. Chang, Y. Zhang, J. Tian, S. Liu, Y. Luo, A. M. Asiri, A. O. Al-Youbi, and X. Sun (2012). Photocatalytic Synthesis of Highly Dispersed Pd Nanoparticles on Reduced Graphene Oxide and Their Application in Methanol Electro-oxidation. Catal. Sci. Technol. 2, 1153.
C. Zhu, S. Guo, and S. Dong (2012). Facile Synthesis of Trimetallic AuPtPd Alloy Nanowires and their Catalysis for Ethanol Electrooxidation. J. Mater. Chem. 22, 14851.
L. Wang, Y. Zhang, and Z. Li (2013). Chemical Reduced Graphene Oxide/AuPtPd Nanocomposite for Enhanced Electrocatalytic Ability. Mater. Lett. 94, 179.
S. Zhang, S. Guo, H. Zhu, D. Su, and S. Sun (2012). Structure-Induced Enhancement in Electrooxidation of Trimetallic FePtAu Nanoparticles. J. Am. Chem. Soc. 134, 5060.
S. Duan, Y. F. Ji, P. P. Fang, Y. X. Chen, X. Xu, Y. Luo, and Z. Q. Tian (2013). Density Functional Theory Study on the Adsorption and Decomposition of the Formic Acid Catalyzed by Highly Active Mushroom-Like Au@Pd@Pt Tri-Metallic Nanoparticles. Phys. Chem. Chem. Phys. 15, 4625.
Y. Song and S. Chen (2013). Trimetallic Ag@AuPt Neapolitan Nanoparticles. Nanoscale 5, 7284.
Y. Wu, D. Wang, G. Zhou, R. Yu, C. Chen, and Y. Li (2014). Sophisticated Construction of Au Islands on Pt–Ni: An Ideal Trimetallic Nanoframe Catalyst. J. Am. Chem. Soc. 136, 11594.
S. Guo, S. Zhang, D. Su, and S. Sun (2013). Seed-Mediated Synthesis of Core/Shell FePtM/FePt (M = Pd, Au) Nanowires and Their Electrocatalysis for Oxygen Reduction Reaction. J. Am. Chem. Soc. 135, 13879.
V. R. Stamenkovic, B. Fowler, B. S. Mun, G. Wang, P. N. Ross, C. A. Lucas, and N. M. Markovic (2007). Improved Oxygen Reduction Activities on Pt3Ni(111) via Increased Surface Site Availability. Science 315, 493.
L. Chen, J. M. Chabu, and Y. Liu (2013). Bimetallic AgM (M = Pt, Pd, Au) Nanostructures: Synthesis and Applications for Surface-Enhanced Raman Scattering. RSC Adv. 3, 4391.
H. Mao, L. Zhou, T. Huang, and A. Yu (2014). Surface Platinum-Rich CuPt Bimetallic Nanoparticles Supported by Partially Unzipped Vapor Grown Carbon Fibers and their Electrocatalytic Activities. RSC Adv. 4, 29429.
G. R. Zhang, D. Zhao, Y. Y. Feng, B. Zhang, D. S. Su, G. Liu, and B. Q. Xu (2012). Catalytic Pt-on-Au Nanostructures: Why Pt Becomes More Active on Smaller Au Particles. ACS Nano 3, 2226.
V. Selvaraj, M. Vinoba, and M. Alagar (2008). Electrocatalytic Oxidation of Ethylene Glycol on Pt and Pt–Ru Nanoparticles Modified Multi-Walled Carbon Nanotubes. J. Colloid Interface Sci. 322, 537.
M. Sakthivel, A. Schlange, U. Kunz, and T. Turek (2010). Microwave Assisted Synthesis of Surfactant Stabilized Platinum/Carbon Nanotube Electrocatalysts for Direct Methanol Fuel Cell Applications. J. Power Sources 195, 7083.
M. Zhiani, B. Rezaei, and J. Jalili (2010). Methanol Electro-Oxidation on Pt/C Modified by Polyaniline Nanofibers for DMFC Applications. Int. J. Hydrogen Energy 35, 9298.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery-Jr, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, and J. A. Pople Gaussian 03, Revision B.05 (Gaussian Inc., Pittsburgh, PA, 2003).
A. D. Becke (1993). Density Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys. 98, 5648.
C. Lee, W. Yang, and R. G. Parr (1988). Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Phys. Rev. B Condens. Matter. 37, 785.
T. H. Dunning Jr., and P. J. Hay, in Modern Theoretical Chemistry, ed. by H. F. Schaefer III (Plenum, New York, 1976), pp. 1–28.
B. V. Christ Hand Book of Monochromatic XPS Spectra (Wiley, Newyork, 2000).
N. Toshima and T. Yonezawa (1998). Bimetallic Nanoparticles-Novel Materials for Chemical and Physical Applications. New J. Chem. 22, 1179.
B. Loganathan, V. L. Chandraboss, S. Senthilvelan, and B. Karthikeyan (2015). Surface Enhanced Vibrational Spectroscopy and First-Principles Study of l-cysteine Adsorption on Noble Trimetallic Au/Pt@Rh Clusters. Phys. Chem. Chem. Phys. 17, 21268.
B. N. Wanjala, J. Luo, B. Fang, D. Mott, and C. J. Zhong (2011). Gold-Platinum Nanoparticles: Alloying and Phase Segregation. J. Mater. Chem. 21, 4012.
L. O. Paz-Borbon, R. L. Johnston, G. Barcaro, and A. Fortunelli (2008). Structural Motifs, Mixing, and Segregation Effects in 38-Atom Binary Clusters. J. Chem. Phys. 128, 134517.
B. Loganathan, V. L. Chandraboss, S. Senthilvelan, and B. Karthikeyan (2016). Tailored Rh Surface Facilitates, Enhancement of Raman Scattering in Trimetallic AuPt Core/Rh Shell Composites: Experimental and Theoretical Evidences. Physica E, 75, 223.
S. Liu, L. Wang, J. Tian, W. Lu, Y. Zhang, X. Wang, and X. Sun (2011). Microwave-Assisted Rapid Synthesis of Pt/Graphene Nanosheet Composites and Their Application for Methanol Oxidation. J. Nanopart. Res. 13, 4731.
H. A. Gasteiger, N. Markovic, P. N. Ross-Jr, and E. J. Cairns (1993). Methanol Electrooxidation on Well-Characterized Platinum Ruthenium Bulk Alloys. J. Phys. Chem. 97, 12020.
Acknowledgements
FE-SEM images/elemental color mapping were recorded at Department of Nanoscience and Nanotechnology, Bharathiar University, Coimbatore. The authors are highly thankful to Avinash Balakrishnan, Assistant Professor, Amrita Center for Nanoscience, Kerala-India, for XPS data. Zeta Potential and DLS studies were carried out at Department of Nanoscience, Karunya University, Coimbatore. G. Mariappan and V. L. Chandraboss are acknowledged for helpful discussions on electronic density of states (DOS) plot. Author B. L wishes to acknowledge the University Grants Commission (UGC)-Basic Sciences Research (BSR)-Special Assistant Programme (SAP) Fellowship from the UGC, New Delhi, India. Finally we thank the editor and referees for their constructive comments.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing financial interest.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Loganathan, B., Karthikeyan, B. Tailored Au and Pt Containing Multi-metallic Nanocomposites for a Promising Fuel Cell Reaction. J Clust Sci 28, 1463–1487 (2017). https://doi.org/10.1007/s10876-017-1157-5
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10876-017-1157-5