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Research Papers

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

[+] Author and Article Information
Katarzyna Morawa Eblagon

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

Lúcia Brandão

LEPABE,
Faculdade de Engenharia da
Universidade do Porto,
Rua Dr. Roberto Frias,
Porto 4200-465, Portugal;
BioMark/CINTESIS–ISEP,
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.

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Figures

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%).

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