Infrared spectroelectrochemical study of dissociation and oxidation of methanol at a palladium electrode in alkaline solution

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	Infrared spectroelectrochemical study of dissociation and oxidation of methanol at a palladium electrode in alkaline solution
	Yang, Yao-Yue ; Ren, Jie ; Zhang, Han-Xuan ; Zhou, Zhi-You ; Sun, Shi-Gang ; Cai, Wen-Bin ; Zhou ZY(周志有) ; Sun SG(孙世刚)
刊名	http://dx.doi.org/10.1021/la305141q
	2013-02-05
关键词	Adsorption Carbon dioxide Carbonation Deuterium Electrooxidation Infrared spectroscopy Methanol Reaction intermediates Spectroelectrochemistry
英文摘要	The dissociative adsorption and electrooxidation of CH3OH 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 CH3OH dissociates to COad species at a Pd electrode accompanied by a "dip" at open circuit potential, whereas deuterium-replaced CH3OH doesn't, suggesting that the breaking of the C-H bond is the rate-limiting step for the dissociative adsorption of CH 3OH. Potential-dependent ATR-SEIRAS and IRAS measurements indicate that CH3OH 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 CO2 in the thin-layer structure of IRAS) is more favorable at potentials from -0.15 to 0.10 V. Further oxidation of the COad intermediate species arising from CH3OH 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. ? 2013 American Chemical Society.
语种	英语
出版者	American Chemical Society
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89115]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Yang, Yao-Yue,Ren, Jie,Zhang, Han-Xuan,et al. Infrared spectroelectrochemical study of dissociation and oxidation of methanol at a palladium electrode in alkaline solution[J]. http://dx.doi.org/10.1021/la305141q,2013.
APA	Yang, Yao-Yue.,Ren, Jie.,Zhang, Han-Xuan.,Zhou, Zhi-You.,Sun, Shi-Gang.,...&孙世刚.(2013).Infrared spectroelectrochemical study of dissociation and oxidation of methanol at a palladium electrode in alkaline solution.http://dx.doi.org/10.1021/la305141q.
MLA	Yang, Yao-Yue,et al."Infrared spectroelectrochemical study of dissociation and oxidation of methanol at a palladium electrode in alkaline solution".http://dx.doi.org/10.1021/la305141q (2013).