Research Papers

RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

[+] Author and Article Information
Katarzyna Morawa Eblagon

Faculdade de Engenharia da
Universidade do Porto,
Rua Dr. Roberto Frias,
Porto 4200-465, Portugal;
Faculdade de Engenharia da
Universidade do Porto,
Rua Dr. Roberto Frias,
Porto 4200-465, Portugal

Lúcia Brandão

Faculdade de Engenharia da
Universidade do Porto,
Rua Dr. Roberto Frias,
Porto 4200-465, Portugal;
Rua Dr. António Bernardino de Almeida, 431,
Porto 4200-072, Portugal
e-mail: lbrandao@fe.up.pt

1Corresponding author.

Contributed by the Advanced Energy Systems Division of ASME for publication in the JOURNAL OF FUEL CELL SCIENCE AND TECHNOLOGY. Manuscript received October 8, 2013; final manuscript received December 15, 2014; published online January 13, 2015. Assoc. Editor: Abel Hernandez-Guerrero.

J. Fuel Cell Sci. Technol 12(2), 021006 (Apr 01, 2015) (8 pages) Paper No: FC-13-1095; doi: 10.1115/1.4029422 History: Received October 08, 2013; Revised December 15, 2014; Online January 13, 2015

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

Copyright © 2015 by ASME
Your Session has timed out. Please sign back in to continue.


Wang, X., Li, W., Chen, Z., Waje, M., and Yan, Y., 2006, “Durability Investigation of Carbon Nanotube as Catalyst Support for Proton Exchange Membrane Fuel Cell,” J. Power Sources, 158(1), pp. 154–159. [CrossRef]
Neburchilov, V., Martin, J., Wang, H., and Zhang, J., 2007, “A Review of Polymer Electrolyte Membranes for Direct Methanol Fuel Cells,” J. Power Sources, 169(2), pp. 221–238. [CrossRef]
Ricea, C., Haa, S., and Masela, R. I., 2003, “Catalysts for Direct Formic Acid Fuel Cells,” J. Power Sources, 115(2), pp. 229–235. [CrossRef]
Sa, S., Silva, H., Brandao, L., Sousa, J. M., and Mendes, A., 2010, “Catalysts for Methanol Steam Reforming—A Review,” Appl. Catal. B, 99(1–2), pp. 43–57. [CrossRef]
Song, S. Q., Zhou, W. J., Li, W. Z., Sun, G., Xin, Q., Kontou, S., and Tsiakaras, P., 2004, “Direct Methanol Fuel Cells: Methanol Crossover and Its Influence on Single DMFC Performance,” Ionics, 10(5–6), pp. 458–462. [CrossRef]
Kamarudina, S. K., Achmada, F., and Dauda, W. R. W., 2009, “Overview on the Application of Direct Methanol Fuel Cell (DMFC) for Portable Electronic Devices,” Int. J. Hydrogen Energy, 34(16), pp. 6902–6916. [CrossRef]
Ahmed, M., and Dincer, I., 2011, “A Review on Methanol Crossover in Direct Methanol Fuel Cells: Challenges and Achievements,” Int. J. Energy Res., 35(14), pp. 1213–1228. [CrossRef]
Wang, Y., Chen, K. S., Mishler, J., Cho, S. C., and Adroher, X. C., 2011, “A Review of Polymer Electrolyte Membrane Fuel Cells: Technology, Applications, and Needs on Fundamental Research,” Appl. Energy, 88(4), pp. 981–1007. [CrossRef]
Haile, S. M., 2003, “Fuel Cell Materials and Components,” Acta Mater., 51(19), pp. 5981–6000. [CrossRef]
Arbizzani, C., Righi, S., Soavi, F., and Mastragostino, M., 2011, “Graphene and Carbon Nanotube Structures Supported on Mesoporous Xerogel Carbon as Catalysts for Oxygen Reduction Reaction in Proton-Exchange-Membrane Fuel Cells,” Int. J. Hydrogen Energy, 36(8), pp. 5038–5046. [CrossRef]
Jeon, I.-Y., Choi, H.-J., Choi, M., Seo, J.-M., Jung, S.-M., Kim, M.-J., Zhang, S., Zhang, L., Xia, Z., Dai, L., Park, N., and Baek, J.-B., 2013, “Facile, Scalable Synthesis of Edge-Halogenated Graphene Nanoplatelets as Efficient Metal-Free Eletrocatalysts for Oxygen Reduction Reaction,” Sci. Rep., 3, p. 1810. [CrossRef]
Feng, Y. J., Gago, A., Timperman, L., and Alonso-Vante, N., 2011, “Chalcogenide Metal Centers for Oxygen Reduction Reaction: Activity and Tolerance,” Electrochim. Acta, 56(3), pp. 1009–1022. [CrossRef]
Johnston, C. M., Cao, D. X., Choi, J. H., Babu, P. K., Garzon, F., and Zelenay, P., 2011, “Se-Modified Ru Nanoparticles as ORR Catalysts—Part 1: Synthesis and Analysis by RRDE and in PEFCs,” J. Electroanal. Chem., 662(1), pp. 257–266. [CrossRef]
Hara, Y., Minami, N., and Itagaki, H., 2008, “Electrocatalytic Properties of Ruthenium Modified With Te Metal for the Oxygen Reduction Reaction,” Appl. Catal., A, 340(1), pp. 59–66. [CrossRef]
Colmenares, L., Jusys, Z., and Behm, R. J., 2007, “Activity, Selectivity, and Methanol Tolerance of Se-Modified Ru/C Cathode Catalysts,” J. Phys. Chem. C, 111(3), pp. 1273–1283. [CrossRef]
Neergat, M., Gunasekar, V., and Singh, R. K., 2011, “Oxygen Reduction Reaction and Peroxide Generation on Ir, Rh, and Their Selenides—A Comparison With Pt and RuSe,” J. Electrochem. Soc., 158(9), pp. B1060–B1066. [CrossRef]
Ezeta-Mejía, A., Solorza-Feria, O., Dorantes-Rosales, H. J., López, J. M. H., and Arce-Estrada, E. M., 2012, “Electrocatalytic Properties of Bimetallic Surfaces for the Oxygen Reduction Reaction,” Int. J. Electrochem. Sci., 7, pp. 8940–8957. http://www.electrochemsci.org/papers/vol7/7098940.pdf
González-Huerta, R. G., Chávez-Carvayar, J. A., and Solorza-Feria, O., 2006, “Electrocatalysis of Oxygen Reduction on Carbon Supported Ru-Based Catalysts in a Polymer Electrolyte Fuel Cell,” J. Power Sources, 153(1), pp. 11–17. [CrossRef]
Cheng, H., Yuan, W., and Scott, K., 2007, “Influence of Thermal Treatment on RuSe Cathode Materials for Direct Methanol Fuel Cells,” Fuel Cells, 7(1), pp. 16–20. [CrossRef]
Babu, P. K., Lewera, A., Chung, J. H., Hunger, R., Jaegermann, W., Alonso-Vante, N., Wieckowski, A., and Oldfield, E., 2007, “Selenium Becomes Metallic in Ru-Se Fuel Cell Catalysts: An EC-NMR and XPS Investigation,” J. Am. Chem. Soc., 129(49), pp. 15140–15141. [CrossRef] [PubMed]
Tritsaris, G. A., Nørskov, J. K., and Rossmeisl, J., 2011, “Trends in Oxygen Reduction and Methanol Activation on Transition Metal Chalcogenides,” Electrochim. Acta, 56(27), pp. 9783–9788. [CrossRef]
Matsumoto, T., Komatsu, T., Nakano, H., Arai, K., Nagashima, Y., Yoo, E., Yamazaki, T., Kijima, M., Shimizu, H., Takasawa, Y., and Nakamura, J., 2004, “Efficient Usage of Highly Dispersed Pt on Carbon Nanotubes for Electrode Catalysts of Polymer Electrolyte Fuel Cells,” Catal. Today, 90(3–4), pp. 277–281. [CrossRef]
Andersen, S. M., Borghei, M., Lund, P., Elina, Y. R., Pasanen, A., Kauppinen, E., Ruiz, V., Kauranen, P., and Skou, E. M., 2013, “Durability of Carbon Nanofiber (CNF) & Carbon Nanotube (CNT) as Catalyst Support for Proton Exchange Membrane Fuel Cells,” Solid State Ionics, 231, pp. 94–101. [CrossRef]
Brandão, L., Passeira, C., Mirabile Gattia, D., and Mendes, A., 2011, “Use of Single Wall Carbon Nanohorns in Polymeric Electrolyte Fuel Cells,” J. Mater. Sci., 46(22), pp. 7198–7205. [CrossRef]
Brandão, L., Boaventura, M., Passeira, C., Gattia, D. M., Marazzi, R., Antisari, M. V., and Mendes, A., 2011, “An Electrochemical Impedance Spectroscopy Study of Polymer Electrolyte Membrane Fuel Cells Electrocatalyst Single Wall Carbon Nanohorns-Supported,” J. Nanosci. Nanotechnol., 11(10), pp. 9016–9024. [CrossRef] [PubMed]
Brandao, L., Boaventura, M., and Ribeirinha, P., 2012, “Single Wall Nanohorns as Electrocatalyst Support for Vapour Phase High Temperature DMFC,” Int. J. Hydrogen Energy, 37(24), pp. 19073–19081. [CrossRef]
Boaventura, M., Brandão, L., and Mendes, A., 2011, “Single-Wall Nanohorns as Electrocatalyst Support for High Temperature PEM Fuel Cells,” J. Electrochem. Soc., 158(4), pp. B394–B401. [CrossRef]
Oh, H. S., Lim, K. H., Roh, B., Hwang, I., and Kim, H., 2009, “Corrosion Resistance and Sintering Effect of Carbon Supports in Polymer Electrolyte Membrane Fuel Cells,” Electrochim. Acta, 54(26), pp. 6515–6521. [CrossRef]
Zaikovskii, V. I., Nagabhushana, K. S., Kriventsov, V. V., Loponov, K. N., Cherepanova, S. V., Kvon, R. I., Bonnemann, H., Kochubey, D. I., and Savinova, E. R., 2006, “Synthesis and Structural Characterization of Se-Modified Carbon-Supported Ru Nanoparticles for the Oxygen Reduction Reaction,” J. Phys. Chem., 110(13), pp. 6881–6890. [CrossRef]
Shen, M. Y., Chiao, S. P., Tsai, D. S., Wilkinson, D. P., and Jiang, J. C., 2009, “Preparation and Oxygen Reduction Activity of Stable RuSex/C Catalyst With Pyrite Structure,” Electrochim. Acta, 54(18), pp. 4297–4304. [CrossRef]
Li, L., and Xing, Y., 2006, “Electrochemical Durability of Carbon Nanotubes in Noncatalyzed and Catalyzed Oxidations,” J. Electrochem. Soc., 153(10), pp. A1823–A1828. [CrossRef]
Shao, Y., Yin, G., Zhang, J., and Gao, Y., 2006, “Comparative Investigation of the Resistance to Electrochemical Oxidation of Carbon Black and Carbon Nanotubes in Aqueous Sulfuric Acid Solution,” Electrochim. Acta, 51(26), pp. 5853–5857. [CrossRef]
Hung, C. C., Lim, P. Y., Chen, J. R., and Shih, H. C., 2011, “Corrosion of Carbon Support for PEM Fuel Cells by Electrochemical Quartz Crystal Microbalance,” J. Power Sources, 196(1), pp. 140–146. [CrossRef]
Zhang, M. F., Yamaguchi, T., Iijima, S., and Yudasaka, M., 2009, “Individual Single-Wall Carbon Nanohorns Separated From Aggregates,” J. Phys. Chem. C, 113(26), pp. 11184–11186. [CrossRef]
Li, L., and Xing, Y., 2008, “Electrochemical Durability of Carbon Nanotubes at 80 °C,” J. Power Sources, 178(1), pp. 75–79. [CrossRef]


Grahic Jump Location
Fig. 1

HRTEM for Ru/C_N_1 sample reduced by NaHB4

Grahic Jump Location
Fig. 2

Particle size distribution (left) and XRD pattern (right) for the Ru/C_N_1 sample

Grahic Jump Location
Fig. 3

HRTEM pictures (top) and particle size distribution (bottom) for ruthenium samples reduced by H2; Ru/C_H_1 (left) and Ru/C_H_2 (right)

Grahic Jump Location
Fig. 4

XRD patterns of unmodified Ru/C and RuSe/C prepared with various ratios and calcination temperatures. For comparison purposes, the diffraction lines for crystalline ruthenium (red line) and RuSe2 (pyrite) (blue line) are also included.

Grahic Jump Location
Fig. 5

SEM pictures and EDAX diagrams for RuSe/C samples (Ru:Se = 1:0.7); (RuSe/C_0.7_NC (top) and RuSe/C_0.7_250 (bottom))

Grahic Jump Location
Fig. 6

Preliminary ORR activity for some selected RuSe/C based electrodes and the Pt/C commercial electrode

Grahic Jump Location
Fig. 7

ACT; (♦) carbon black, (◊) commercial electrode, (◣) SWNH

Grahic Jump Location
Fig. 8

Voltammograms obtained for the different electrodes before (solid line) and after (dashed line) ACT. %ESA after ACT: carbon black (65%), commercial (35%), SWNH (30%).



Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In