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231224s2013 xx |||||o 00| ||eng c |
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|a 10.1021/la305141q
|2 doi
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|a pubmed24n0747.xml
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|a (DE-627)NLM224101722
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|a (NLM)23311730
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|a DE-627
|b ger
|c DE-627
|e rakwb
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| 041 |
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|a eng
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|a Yang, Yao-Yue
|e verfasserin
|4 aut
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|a Infrared spectroelectrochemical study of dissociation and oxidation of methanol at a palladium electrode in alkaline solution
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|c 2013
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
|b c
|2 rdamedia
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|a ƒa Online-Ressource
|b cr
|2 rdacarrier
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|a Date Completed 29.07.2013
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|a Date Revised 21.11.2013
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|a published: Print-Electronic
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|a Citation Status MEDLINE
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|a The dissociative adsorption and electrooxidation of CH(3)OH at a Pd electrode in alkaline solution are investigated by using in situ infrared spectroscopy with both internal and external reflection modes. The former (ATR-SEIRAS) has a higher sensitivity of detecting surface species, and the latter (IRAS) can easily detect dissolved species trapped in a thin-layer-structured electrolyte. Real-time ATR-SEIRAS measurement indicates that CH(3)OH dissociates to CO(ad) species at a Pd electrode accompanied by a "dip" at open circuit potential, whereas deuterium-replaced CH(3)OH doesn't, suggesting that the breaking of the C-H bond is the rate-limiting step for the dissociative adsorption of CH(3)OH. Potential-dependent ATR-SEIRAS and IRAS measurements indicate that CH(3)OH is electrooxidized to formate and/or (bi)carbonate, the relative concentrations of which depend on the potential applied. Specifically, at potentials negative of ca. -0.15 V (vs Ag/AgCl), formate is the predominant product and (bi)carbonate (or CO(2) in the thin-layer structure of IRAS) is more favorable at potentials from -0.15 to 0.10 V. Further oxidation of the CO(ad) intermediate species arising from CH(3)OH dissociation is involved in forming (bi)carbonate at potentials above -0.15 V. Although the partial transformation from interfacial formate to (bi)carbonate may be justified, no bridge-bonded formate species can be detected over the potential range under investigation
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a Solutions
|2 NLM
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|a Sodium Hydroxide
|2 NLM
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|a 55X04QC32I
|2 NLM
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|a Palladium
|2 NLM
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|a 5TWQ1V240M
|2 NLM
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|a Methanol
|2 NLM
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|a Y4S76JWI15
|2 NLM
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| 700 |
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|a Ren, Jie
|e verfasserin
|4 aut
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|a Zhang, Han-Xuan
|e verfasserin
|4 aut
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| 700 |
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|a Zhou, Zhi-You
|e verfasserin
|4 aut
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|a Sun, Shi-Gang
|e verfasserin
|4 aut
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| 700 |
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|a Cai, Wen-Bin
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Langmuir : the ACS journal of surfaces and colloids
|d 1992
|g 29(2013), 5 vom: 05. Feb., Seite 1709-16
|w (DE-627)NLM098181009
|x 1520-5827
|7 nnns
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| 773 |
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|g volume:29
|g year:2013
|g number:5
|g day:05
|g month:02
|g pages:1709-16
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|u http://dx.doi.org/10.1021/la305141q
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