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231223s2006 xx ||||| 00| ||eng c |
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|a pubmed25n0556.xml
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|a (NLM)17129008
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|a DE-627
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|c DE-627
|e rakwb
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|a eng
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|a Chen, Y-X
|e verfasserin
|4 aut
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|a Bridge-bonded formate
|b active intermediate or spectator species in formic acid oxidation on a Pt film electrode?
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|c 2006
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|a Text
|b txt
|2 rdacontent
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|a ohne Hilfsmittel zu benutzen
|b n
|2 rdamedia
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|a Band
|b nc
|2 rdacarrier
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|a Date Completed 19.01.2007
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|a Date Revised 24.11.2016
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|a published: Print
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|a Citation Status MEDLINE
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|a We present and discuss the results of an in situ IR study on the mechanism and kinetics of formic acid oxidation on a Pt film/Si electrode, performed in an attenuated total reflection (ATR) flow cell configuration under controlled mass transport conditions, which specifically aimed at elucidating the role of the adsorbed bridge-bonded formates in this reaction. Potentiodynamic measurements show a complex interplay between formation and desorption/oxidation of COad and formate species and the total Faradaic current. The notably faster increase of the Faradaic current compared to the coverage of bridge-bonded formate in transient measurements at constant potential, but with different formic acid concentrations, reveals that adsorbed formate decomposition is not rate-limiting in the dominant reaction pathway. If being reactive intermediate at all, the contribution of formate adsorption/decomposition to the reaction current decreases with increasing formic acid concentration, accounting for at most 15% for 0.2 M DCOOH at 0.7 VRHE. The rapid build-up/removal of the formate adlayer and its similarity with acetate or (bi-)sulfate adsorption/desorption indicate that the formate adlayer coverage is dominated by a fast dynamic adsorption-desorption equilibrium with the electrolyte, and that formate desorption is much faster than its decomposition. The results corroborate the proposal of a triple pathway reaction mechanism including an indirect pathway, a formate pathway, and a dominant direct pathway, as presented previously (Chen, Y. X.; et al. Angew. Chem. Int. Ed. 2006, 45, 981), in which adsorbed formates act as a site-blocking spectator in the dominant pathway rather than as an active intermediate
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|a Comparative Study
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a Formates
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|a Membranes, Artificial
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|a formic acid
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|a 0YIW783RG1
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|a Platinum
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|a 49DFR088MY
|2 NLM
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|a Silicon
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|a Z4152N8IUI
|2 NLM
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|a Heinen, M
|e verfasserin
|4 aut
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|a Jusys, Z
|e verfasserin
|4 aut
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|a Behm, R J
|e verfasserin
|4 aut
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|i Enthalten in
|t Langmuir : the ACS journal of surfaces and colloids
|d 1991
|g 22(2006), 25 vom: 05. Dez., Seite 10399-408
|w (DE-627)NLM098181009
|x 0743-7463
|7 nnns
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| 773 |
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|g volume:22
|g year:2006
|g number:25
|g day:05
|g month:12
|g pages:10399-408
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|d 22
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|h 10399-408
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