Temperature-dependent oxygen electrochemistry on platinum low-index single crystal surfaces in acid solutions

Temperature-dependent oxygen electrochemistry on platinum low-index single crystal surfaces in acid solutions

Using the rotating ring-disk technique (RRD Pt(hkl) E), the oxygen-reduction reaction (ORR) was studied in sulfuric acid solution over the temperature range 298-333 K At the same temperature, the exchange current density increased in the order, which gives the order of absolute kinetic activities of...

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Veröffentlicht in:Canadian journal of chemistry 1997-11, Vol.75 (11), p.1465-1471
Hauptverfasser: Grgur, B.N, Marković, N.M, Ross, P.N
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Sprache:eng
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Electrochemistry
Oxygen
Platinum
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container_title Canadian journal of chemistry
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creator Grgur, B.N
Marković, N.M
Ross, P.N
description Using the rotating ring-disk technique (RRD Pt(hkl) E), the oxygen-reduction reaction (ORR) was studied in sulfuric acid solution over the temperature range 298-333 K At the same temperature, the exchange current density increased in the order, which gives the order of absolute kinetic activities of Pt(hkl) in 0.05 mol/L H 2 SO 4 : Pt(111) 
doi_str_mv 10.1139/v97-176
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We found that at high current densities every crystal face has an ideally temperature-dependent Tafel slope, i.e., −2 × 2.3(RT/F). The activation energy for the ORR is independent of the surface geometry, . The insensitivity of the activation energy to surface structure implies that the reaction pathway for the ORR is the same on all three single-crystal faces. A "series" pathway for the ORR was proposed, with the first electron transfer being the rate-determining step. The structure sensitivity in the kinetics of the ORR on Pt(hkl) is attributed to the structure-sensitive adsorption of bisulfate and hydroxyl anions and a simple site-blocking effect of these adsorbed anions on the rate of the ORR. 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We found that at high current densities every crystal face has an ideally temperature-dependent Tafel slope, i.e., −2 × 2.3(RT/F). The activation energy for the ORR is independent of the surface geometry, . The insensitivity of the activation energy to surface structure implies that the reaction pathway for the ORR is the same on all three single-crystal faces. A "series" pathway for the ORR was proposed, with the first electron transfer being the rate-determining step. The structure sensitivity in the kinetics of the ORR on Pt(hkl) is attributed to the structure-sensitive adsorption of bisulfate and hydroxyl anions and a simple site-blocking effect of these adsorbed anions on the rate of the ORR. 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subjects Electrochemistry
Oxygen
Platinum
title Temperature-dependent oxygen electrochemistry on platinum low-index single crystal surfaces in acid solutions
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