TY - JOUR
T1 - A critical assessment of XH2 O2 as a figure of merit for oxygen reduction electrocatalysts in aqueous electrolytes
AU - Georgescu, Nicholas S.
AU - Jebaraj, Adriel J J
AU - Scherson, Daniel Alberto
PY - 2015/1/1
Y1 - 2015/1/1
N2 - Certain aspects of the interpretation of rotating ring-disk electrode, RRDE, data for the oxygen reduction reaction, ORR, in aqueous electrolytes have been examined. In particular, the classical mechanism proposed by Damjanovic et al. [ J. Chem. Phys. 45, 4057 (1966)] predicts that at a fixed potential, a plot of the ratio of the disk to the ring currents for the ORR vs -Ω-1/2 , where is Ω the rotation rate of the disk, should be linear. According to this analysis, the slope of this line is proportional to k 3 / X H2 O2 , where k3 is the rate constant for the reduction of solution phase hydrogen peroxide, H2 O2 (aq), and X H2 O2 is the fraction of the disk current that generates H2 O2 (aq), the magnitude of which can be determined from the line intercept. Illustrations of this theoretical framework are provided for ORR data reported in the literature for experiments involving Pt-based electrodes and collected in our laboratories for Pt in aqueous acidic solutions. Critically emphasized is the need to perform ring-disk measurements at multiple rotations rates in order to determine reliable values of X H2 O2, which can be used as figures of merit for ranking the efficacy of ORR electrocatalysts.
AB - Certain aspects of the interpretation of rotating ring-disk electrode, RRDE, data for the oxygen reduction reaction, ORR, in aqueous electrolytes have been examined. In particular, the classical mechanism proposed by Damjanovic et al. [ J. Chem. Phys. 45, 4057 (1966)] predicts that at a fixed potential, a plot of the ratio of the disk to the ring currents for the ORR vs -Ω-1/2 , where is Ω the rotation rate of the disk, should be linear. According to this analysis, the slope of this line is proportional to k 3 / X H2 O2 , where k3 is the rate constant for the reduction of solution phase hydrogen peroxide, H2 O2 (aq), and X H2 O2 is the fraction of the disk current that generates H2 O2 (aq), the magnitude of which can be determined from the line intercept. Illustrations of this theoretical framework are provided for ORR data reported in the literature for experiments involving Pt-based electrodes and collected in our laboratories for Pt in aqueous acidic solutions. Critically emphasized is the need to perform ring-disk measurements at multiple rotations rates in order to determine reliable values of X H2 O2, which can be used as figures of merit for ranking the efficacy of ORR electrocatalysts.
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U2 - 10.1149/2.0021506eel
DO - 10.1149/2.0021506eel
M3 - Article
AN - SCOPUS:84928744371
SN - 2162-8726
VL - 4
SP - F39-F42
JO - ECS Electrochemistry Letters
JF - ECS Electrochemistry Letters
IS - 6
ER -