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Title: Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions

Abstract

We determined, by the rotating disk electrode technique, the kinetics of the oxygen-reduction reaction (ORR) on the surfaces of single crystals of Au(111), Ag(111), Pd(111), Rh(111), Ir(111), and Ru(0001), on Pt monolayers deposited on their surfaces, and also on nanoparticles of these metals dispersed on high-surface-area carbon. Plotting the correlation between the experimentally determined activities of these three types of electrocatalysts with the calculated metal d-band center energies,{var_epsilon}{sub d}, revealed a volcano-type dependence. In all cases, the electronic properties of the metal electrocatalysts, represented by the {var_epsilon}{sub d} value, were used for elucidating the metal-dependent catalytic activities, and establishing their electronic properties-the ORR kinetics relationship. Pt(111), Pt/C, and Pt/Pd(111) were found to top their corresponding volcano plots. Pd in alkaline solutions showed particularly high activity, suggesting it may offer potential replacement for Pt in fuel cells.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930305
Report Number(s):
BNL-81015-2008-JA
TRN: US200822%%1460
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry C; Journal Volume: 111; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; CARBON; CORRELATIONS; ELECTROCATALYSTS; ELECTRODES; FUEL CELLS; KINETICS; METALS; MONOCRYSTALS; PLATINUM; REDUCTION; SOLUTIONS; SURFACES; TRIOCTYLPHOSPHINE SULFIDE; national synchrotron light source

Citation Formats

Lima,F., Zhang, J., Shao, M., Sasaki, K., Vukmirovic, M., Ticianelli, E., and Adzic, R. Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions. United States: N. p., 2007. Web. doi:10.1021/jp065181r.
Lima,F., Zhang, J., Shao, M., Sasaki, K., Vukmirovic, M., Ticianelli, E., & Adzic, R. Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions. United States. doi:10.1021/jp065181r.
Lima,F., Zhang, J., Shao, M., Sasaki, K., Vukmirovic, M., Ticianelli, E., and Adzic, R. Mon . "Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions". United States. doi:10.1021/jp065181r.
@article{osti_930305,
title = {Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions},
author = {Lima,F. and Zhang, J. and Shao, M. and Sasaki, K. and Vukmirovic, M. and Ticianelli, E. and Adzic, R.},
abstractNote = {We determined, by the rotating disk electrode technique, the kinetics of the oxygen-reduction reaction (ORR) on the surfaces of single crystals of Au(111), Ag(111), Pd(111), Rh(111), Ir(111), and Ru(0001), on Pt monolayers deposited on their surfaces, and also on nanoparticles of these metals dispersed on high-surface-area carbon. Plotting the correlation between the experimentally determined activities of these three types of electrocatalysts with the calculated metal d-band center energies,{var_epsilon}{sub d}, revealed a volcano-type dependence. In all cases, the electronic properties of the metal electrocatalysts, represented by the {var_epsilon}{sub d} value, were used for elucidating the metal-dependent catalytic activities, and establishing their electronic properties-the ORR kinetics relationship. Pt(111), Pt/C, and Pt/Pd(111) were found to top their corresponding volcano plots. Pd in alkaline solutions showed particularly high activity, suggesting it may offer potential replacement for Pt in fuel cells.},
doi = {10.1021/jp065181r},
journal = {Journal of Physical Chemistry C},
number = 1,
volume = 111,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
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