Preparation of Bimetallic Pd-Co Nanoparticles on Graphene Support for Use as Methanol Tolerant Oxygen Reduction Electrocatalysts
Abstract
Graphene-supported (40-x) wt% Pd x wt% Co (0≤x≤13.33) alloys/composites have been prepared by a microwave-assisted polyol reduction method and been investigated for their structural and electrocatalytic properties for the oxygen reduction reaction (ORR) in 0.5 M H2SO4 at 298 K. The study demonstrated that the bimetallic Pd-Co composite nanoparticles are, in fact, alloy nanoparticles with fcc crystalline structure. Partial substitution of Pd by Co (from 3.64 to 13.33 wt%) in 40 wt% Pd/graphene decreases the lattice parameter as well as the crystallite size and increases the apparent catalytic activity, the latter, however, being the greatest with 8 wt% Co. The ORR activity of the active 32 wt% Pd 8wt% Co is found to be considerably low when it was deposited on the support multiwall carbon nanotubes under similar conditions. The rotating disk electrode study indicated that the ORR on 32 wt% Pd 8 wt% Co/GNS in 0.5 M H2SO4 follows approximately the four-electron pathway.
Keywords:
graphene-supported composite, oxygen reduction reaction, microwave-assisted polyol reduction method, electrocatalytic propertiesDownloads
References
W. Quian, D. P. Wilkinson, J. Shen, H. Wang, J. Zhang, “Architecture for portable direct liquid fuel cells”, J. Power Sources, Vol. 154, No. 1, pp. 202-213, 2006 DOI: https://doi.org/10.1016/j.jpowsour.2005.12.019
L. Colmenares, Z. Jusys, R. J. Behm, “Activity selectivity and methanol tolerance of Se-modified Ru/C cathode catalysts”, J. Phys. Chem. C, Vol. 111, No. 3, pp. 1273-1283, 2007 DOI: https://doi.org/10.1021/jp0645925
G. Zehl, P. Bogdanoff, I. Dorbandt, S. Fiechter, K. Wippermann, C. Hartnig, “Carbon supported Ru-Se as methanol tolerant catalysts for DMFC cathodes. Part I: Preparation and characterization of catalysts”, J. Appl. Electrochem., Vol. 37, No. 12, pp. 1475-1484, 2007 DOI: https://doi.org/10.1007/s10800-007-9375-4
V. Baglio, A. Di Blasi, C. D`Urso, V. Antonucci, A. S. Arico, R. Ornelas, D. Morales-Acosta, J. Ledesma-Garcia, L. A. Godinez, L. G. Arriaga, L. Alvarez-Contreras, “Development of Pt and Pt-Fe catalysts supported on multiwalled carbon nanotubes for oxygen reduction in direct methanol fuel cell applications”, J. Electrochem. Soc., Vol. 155, No. 8, pp. B829-B833, 2008 DOI: https://doi.org/10.1149/1.2938368
A. S. Arico, S. Srinivasan, V. Antonucci, “DMFCs: from fundamental aspects to technology development”, Fuel Cells, Vol. 1, No. 2, 133-161, 2001 DOI: https://doi.org/10.1002/1615-6854(200107)1:2<133::AID-FUCE133>3.0.CO;2-5
C. Lamy, A. Lima, V. LeRhun, F. Delime, C. Contaceau, J. M. Leger, “Recent advances in the development of direct alcohol fuel cells (DAFC)”, J. Power Sources, Vol. 105, No. 2, pp. 283-296, 2002 DOI: https://doi.org/10.1016/S0378-7753(01)00954-5
J. J. Lingane, “Chronopotentiometry study of oxygen at platinum wire electrode”, J. Electronal. Chem., Vol. 2, No. 4, pp. 296-309, 1961 DOI: https://doi.org/10.1016/0022-0728(61)85003-1
G. F. Alvarez, M. Mamlouk, K. Scott, “An investigation of palladium oxygen reduction catalysts for the direct methanol fuel cell”, Int. J. Electrochem., Article ID 684535, 2011 DOI: https://doi.org/10.4061/2011/684535
F. Kadirgan, S. Beyhan, T. Atilan, “Preparation and characterization of nano-sized Pt-Pd/C catalysts and comparison of their electro-activity toward methanol and ethanol oxidation”, Int. J. Hydrogen Energy, Vol. 34, No. 10, pp. 4312-4320, 2009 DOI: https://doi.org/10.1016/j.ijhydene.2009.03.024
K. Lee, O. Savadogo, A. Ishihara, S. Mitsushima, N. Kamiya, K. I. Ota. “Methanol-tolerant oxygen reduction electrocatalysts based on Pd-3D transition metal alloys for direct methanol fuel cell”, J. Electrochem. Soc. Vol. 153, No.1, pp. A20-A24, 2006 DOI: https://doi.org/10.1149/1.2128101
W. Wang, D. Zheng, C. Du, Z. Zou, X. Zhang, B. Xia, H. Yang, D.L. Akins, “Carbon-supported Pd-Co bimetallic nanoparticles as electrocatalysts for the oxygen reduction reaction”, J. Power Sources, Vol. 167, No. 2, pp. 243-249, 2007 DOI: https://doi.org/10.1016/j.jpowsour.2007.02.013
D. S. Kim, T. J. Kim, J. H. Kim, E. F. Abo Zeid, Y. T. Kim, “Fine structure effect of PdCo electrocatalyst for oxygen reduction reaction activity: based on X-ray absorption spectroscopy studies with synchrotron beam”, J. Electrochem. Sci. and Technol., Vol. 1, No. 1, pp. 31-38, 2010 DOI: https://doi.org/10.33961/JECST.2010.1.1.031
J. L. Fernandez, V. Raghuveer, A. Manthiram, A. J. Bard, “Pd-Ti and Pd-Co-Au electrocatalysts as a replacement for platinum for oxygen reduction in proton exchange membrane fuel cells”, J. Am. Chem. Soc., Vol. 127, No. 38, pp. 13100-13101, 2005 DOI: https://doi.org/10.1021/ja0534710
D. Wang, H. L. Xin, Y. Yu, H. Wang, E. Rus, D. A. Muller, H. D. Abruna, “Pt-decorated PdCo@Pd/C core−shell nanoparticles with enhanced stability and electrocatalytic activity for the oxygen reduction reaction”, J. Am. Chem. Soc., Vol. 132, No. 50, pp. 17664-17666, 2010 DOI: https://doi.org/10.1021/ja107874u
V. D. Noto, E. Negro, S. Lavina, S. Gross, G. Pace, “Pd-Co carbon-nitride electrocatalysts for polymer electrolyte fuel cells”, Electrochim. Acta, Vol. 53, No. 4, pp. 1604-1617, 2007 DOI: https://doi.org/10.1016/j.electacta.2007.05.028
X. Li, Q. Huang, Z. Zou, B. Xia, H. Yang, “Low temperature preparation of carbon-supported Pd-Co alloy electrocatalysts for methanol-tolerant oxygen reduction reaction”, Electrochim. Acta, Vol. 53, No. 22, pp. 6662-6667, 2008 DOI: https://doi.org/10.1016/j.electacta.2008.04.032
D. A. Dikin, S. Stankovich, E. J. Zimney, R. D. Piner, G. H.B. Dommett, G. Evmeneko, S. T. Nguyen, R. S. Ruoff, “Preparation and characterization of graphene oxide paper”, Nature, Vol. 448, pp. 457-460, 2007 DOI: https://doi.org/10.1038/nature06016
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, M. I. Katsnelson, I. V. Grigorieva, S. V. Dubonos, A. A. Firsov, “Two‐dimensional gas of massless Dirac fermions in graphene”, Nature, Vol. 438, pp. 197-200, 2005 DOI: https://doi.org/10.1038/nature04233
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, A. A. Firsov, “Electric field effect in atomically thin carbon films”, Science, Vol. 306, No. 5696, pp. 666-669, 2004 DOI: https://doi.org/10.1126/science.1102896
S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas, E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen, R. S. Ruoff, “Graphene-based composite materials”, Nature, Vol. 442, pp. 282-286, 2006 DOI: https://doi.org/10.1038/nature04969
S. Niyogi, E. Bekyarova, M. E. Itkis, J. L. McWilliams, M. A. Hamon, R. C. Haddon, “Solution properties of graphite and graphene”, J. Am. Chem. Soc., Vol. 128, No. 24, pp. 7720-7721, 2006 DOI: https://doi.org/10.1021/ja060680r
Y. Xu, H. Bai, G. Lu, C. Li, G. Shi, “Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets”, J. Am. Chem. Soc., Vol. 130, No. 18, pp. 5856-5857, 2008 DOI: https://doi.org/10.1021/ja800745y
R. N. Singh, R. Awasthi, “Graphene support for enhanced electrocatalytic activity of Pd for alcohol oxidation”, Catal. Sci. Technol., Vol. 1, pp. 778-783, 2011 DOI: https://doi.org/10.1039/c1cy00021g
R. Kou, Y. Shao, D. Wang, M. H. Engelhard, J. H. Kwak, J. Wang, V. V. Viswanathan, C. Wang, Y. Lin, Y. Wang, I. A. Aksay, J. Liu, “Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction reaction”, Electrochem. Commun., Vol. 11, pp. 954-957, 2009 DOI: https://doi.org/10.1016/j.elecom.2009.02.033
Y. Shao, S. Zhang, C. Wang, Z. Nie, J. Liu, Y. Wang, Y. Lin, “Highly durable graphene nanoplatelets supported Pt nanocatalysts for oxygen reduction”, J. Power Sources, Vol. 195, No. 15, pp. 4600-4605, 2010 DOI: https://doi.org/10.1016/j.jpowsour.2010.02.044
C. V. Rao, A. L. M. Reddy, Y. Ishikawa, P. M. Ajayan, “Synthesis and electrocatalytic oxygen reduction activity of graphene-supported Pt3Co and Pt3Cr alloy nanoparticles”, Carbon, Vol. 49, No. 3, pp. 931-936, 2011 DOI: https://doi.org/10.1016/j.carbon.2010.10.056
W. S. Hummers Jr, R. E. Offeman, “Preparation of Graphitic oxide”, J. Am. Chem. Soc., Vol. 80, No. 6, p. 1339, 1958 DOI: https://doi.org/10.1021/ja01539a017
L. J. Cote, F. Kim, J. Huang, “Langmuir-blodgett assembly of graphite oxide single layers”, J. Am. Chem. Soc. Vol. 131, No. 3, pp. 1043-1049, 2009 DOI: https://doi.org/10.1021/ja806262m
J. Shen, Y. Hu, M. Shi, X. Lu, C. Qin, C. Li, M. Ye, “Fast and facile preparation of graphene oxide and reduced graphene oxide nanoplatelets”, Chem. Mater., Vol. 21, No. 15, pp. 3514-3520, 2009 DOI: https://doi.org/10.1021/cm901247t
R. Awasthi, R. N. Singh, “Optimization of the Pd-Sn-GNS nanocomposite for enhanced electrooxidation of methanol”, Int. J. Hydrogen Energy, Vol. 37, No. 3, pp. 2103-2110, 2012 DOI: https://doi.org/10.1016/j.ijhydene.2011.10.092
R. N. Singh, A. Singh, Anindita, “Electrocatalytic activity of binary and ternary composite films of Pd, MWCNT, and Ni for ethanol electro-oxidation in alkaline solutions”, Carbon, Vol. 47, No. 1, pp. 271-278, 2009 DOI: https://doi.org/10.1016/j.carbon.2008.10.006
R. N. Singh, T. Sharma, A. Singh, Anindita, D. Mishra, S. K. Tiwari, “Perovskite-type La2-xSrxNiO4 (0≤x≤1) as active anode materials for methanol oxidation in alkaline solutions”, Electrochim. Acta, Vol. 53, No. 5, pp. 2322-2330, 2008 DOI: https://doi.org/10.1016/j.electacta.2007.09.047
Y. Zhao, L. Zhan, J. Tian, S. Nie, Z. Ning, “Enhanced electrocatalytic oxidation of methanol on Pd/polypyrrole-graphene in alkaline medium”, Electrochim. Acta, Vol. 56, No. 5, pp. 1967-1972, 2011 DOI: https://doi.org/10.1016/j.electacta.2010.12.005
W. E. Mustain, J. Prakash, “Kinetics and mechanism for the oxygen reduction reaction on polycrystalline cobalt-palladium electrocatalysts in acid media”, J. Power Sources, Vol. 170, No. 1, pp. 28-37, 2007 DOI: https://doi.org/10.1016/j.jpowsour.2007.04.005
S. M. Choi, M. H. Seo, H. J. Kim, W. B. Kim, “Synthesis of surface-functionalized graphene nanosheets with high Pt-loadings and their applications to methanol electrooxidation”, Carbon, Vol. 49, No. 3, pp. 904-909, 2011 DOI: https://doi.org/10.1016/j.carbon.2010.10.055
J. J. Salvador-Pascual, S. Citalan-Cigarroa, O. Solorza-Feria, “Kinetics of oxygen reduction reaction on nanosized Pd electrocatalysts in acid media”, J. Power Sources, Vol. 172, No. 1, pp. 229-234, 2007 DOI: https://doi.org/10.1016/j.jpowsour.2007.05.093
Madhu, R. N. Singh, “Palladium selenides as active methanol tolerant cathode materials for direct methanol fuel cell”, Int. J. Hydrogen Energy, Vol. 36, No. 16, pp. 10006-10012, 2011 DOI: https://doi.org/10.1016/j.ijhydene.2011.05.069
R. Pattabiraman, “Electrochemical investigations on carbon supported palladium catalysts”, Appl. Catal. A, Vol. 153, No. 1, pp. 9-20, 1997 DOI: https://doi.org/10.1016/S0926-860X(96)00327-4
R. N. Singh, A. Singh, Anindita, “Electrocatalytic activity of binary and ternary composite films of Pd, MWCNT and Ni, Part II: methanol electrooxidation in 1 M KOH”, Int. J. Hydrogen Energy, Vol. 34, pp. 2052-2057, 2009 DOI: https://doi.org/10.1016/j.ijhydene.2008.12.047
B. Hammer, J. K. Norskov, “Theoretical surface science and catalyst-calculation concepts”, Adv. Catal. Vol. 45, pp. 71-129, 2000 DOI: https://doi.org/10.1016/S0360-0564(02)45013-4
N. M. Markovic, B. N. Grgur, P. N. Ross, “Temperature-dependent hydrogen electrochemistry on platinum low-index single-crystal surfaces in acid solutions”, J. Phys. Chem. B, Vol. 101, No. 27, pp. 5405-5413, 1997 DOI: https://doi.org/10.1021/jp970930d
J. X. Wang, S. R. Brankovic, Y. Zhu, J. C. Hanson, R. R. Adzic, “Kinetic characterization of PtRu fuel cell anode catalysts made by spontaneous Pt deposition on Ru nanoparticles”, J. Electrochem. Soc. Vol. 150, No. 8, pp. A1108-A1117, 2003 DOI: https://doi.org/10.1149/1.1579481
E. Gileadi, Electrode kinetics for Chemists, Chemical Engineers, and Materials Scientists, Wiley-VCH, 1993
D. Yang, B. Li, H. Zhang, J. Ma, “Kinetics and electrocatalytic activity of IrCo/C catalysts for oxygen reduction reaction in PEMFC”, Int. J. Hydrogen Energy, Vol. 37, No. 3, pp. 2447-2454, 2012 DOI: https://doi.org/10.1016/j.ijhydene.2011.09.154
J. Zhang, Y. Mo, M. B. Vukmirovic, R. Klie, K. Sasaki, R. R. Adzic, “Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on Pd(111) and on carbon-supported Pd nanoparticles”, J. Phys. Chem. B, Vol. 108, No. 30, pp. 10955-10964, 2004 DOI: https://doi.org/10.1021/jp0379953
G. Ramos-Sanchez, O. Solorza-Feria, “Synthesis and characterization of Pd0.5NixSe(0.5-x) electrocatalysts for oxygen reduction reaction in acid media”, Int. J. Hydrogen Energy, Vol. 35, No. 21, pp. 12105-12110, 2010 DOI: https://doi.org/10.1016/j.ijhydene.2009.10.111
R. Rego, M. Cristina Oliveira, F. Alcaide, G. Alvarez, “Development of a carbon paper-supported Pd catalyst for PEMFC application”, Int. J. Hydrogen Energy, Vol. 37, No. 8, pp. 7192-7199, 2012 DOI: https://doi.org/10.1016/j.ijhydene.2011.12.074
K. Jukk, N. Alexeyeva, C. Johans, K. Kontturi, K. Tammeveski, “Oxygen Reduction on Pd nanoparticle/multi-walled carbon nanotube composites”, J. Electronal. Chem. Vol. 666, pp. 67-75, 2012 DOI: https://doi.org/10.1016/j.jelechem.2011.12.003
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