NDLI: Evaluation of Polycrystalline Platinum and Rhodium Surfaces for the Electro-Oxidation of Aqueous Sulfur Dioxide

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Evaluation of Polycrystalline Platinum and Rhodium Surfaces for the Electro-Oxidation of Aqueous Sulfur Dioxide

Content Provider	Springer Nature Link
Author	Potgieter, M. Parrondo, J. Ramani, V. K. Kriek, R. J.
Copyright Year	2015
Abstract	Polycrystalline Rh and Pt were studied to ascertain their electrocatalytic activity for the electro-oxidation of SO$_{2}$, an important reaction in sulfur dioxide depolarized electrolyzers used to produce hydrogen. Cyclic voltammetry and linear polarization methods were employed to evaluate the catalytic activity of these surfaces. Rh exhibited 25-fold lower catalytic activity than Pt and was more susceptible to poisoning by adsorbed intermediate sulfur species. Koutecky-Levich analysis indicated a two-electron transfer reaction on the Pt surface, which corresponded to the most commonly accepted SO$_{2}$ electro-oxidation reaction mechanism. The Tafel slopes in the low potential region (near the onset potential), in conjunction with an analysis of well-known reaction mechanisms, suggested that the step leading to the oxidation of water to form adsorbed hydroxyl species was the rate-determining step (RDS). This mechanistic model predicts a decrease in Tafel slope with increasing coverage of catalyst active surface sites by adsorbed sulfur species. For Pt, we estimate a surface sulfur coverage of 4 % based on the experimentally measured Tafel slope. In the case of Rh, the sulfur coverage was calculated to be approximately 1 %. The Tafel slopes obtained changed from 106 mV decade$^{−1}$ for Rh and 80 mV decade$^{−1}$ for Pt at potentials below 0.7 V vs. standard hydrogen electrode (SHE) to 210 mV decade$^{−1}$ for Rh and 162 mV decade$^{−1}$ for Pt at potentials above 0.7 V vs. SHE, suggesting a change in the reaction mechanism corresponding to a change in the surface of the electrocatalyst.
Starting Page	50
Ending Page	59
Page Count	10
File Format	PDF
ISSN	18682529
Journal	Electrocatalysis
Volume Number	7
Issue Number	1
e-ISSN	18685994
Language	English
Publisher	Springer US
Publisher Date	2015-09-23
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Platinum Rhodium Polycrystalline SO$_{2}$ electro-oxidation Rotating disk electrode Levich Koutecky-Levich Tafel Electrochemistry Physical Chemistry Catalysis Energy Technology
Content Type	Text
Resource Type	Article
Subject	Electrochemistry

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