NDLI: Reversibility of electrosurface transfer through eutectic interfaces of MeWO$_{4}$|WO$

Content Provider	Springer Nature Link
Author	Pestereva, N. N. Neiman, A. Ya.
Copyright Year	2012
Abstract	It is found that electrosurface transition (EST) through eutectic interfaces of (−/+)WO$_{3}$\|MeWO$_{4}$(+/−) induced by electric field is a reversible process. In the case of the (−/+) polarity, nominally, in the “direct experiment”, macro amounts of WO$_{3}$ from a W 3 (−) brick are drawn in the (+) direction onto the inner surface of MeWO$_{4}$ forming a two-phase {ie1070-1} composite. Simultaneously, nonequivalent countertransport of Me $^{2+}$ within the W 3 (−) brick occurs, which changes the color of W 3 (−) from the natural hue to dark-green. Intercalation of Me $^{2+}$ into W 3 (−) is proved by several spectroscopic methods. The key role in the EST phenomenon belongs to a nonautonomous electrolytic phase of MeW-s formed on the contact interface with WO$_{3}$\|MeWO$_{4}$. The composition of MeW-s is close to W/Me ≈ 2. As a result of EST, the cell acquires a more complicated structure: {fx1070-1} where \|///\| are interface regions occupied by the MeW-s phase. At the cathodic boundary of subcell {fx1070-2} the following process occurs: {fx1070-3}, The process at the anodic boundary is: {fx1070-4}. Ultimately, WO$_{3}$ is transported in the (+) direction (into the composite) and Me $^{2+}$ penetrates under the effect of the gradient in chemical potential into W 3 (−) forming a dark-green Me $_{ x }$WO$_{3}$ phase with its front reaching the (−) Pt electrode. After the end of the “direct experiment”, the cell polarity was changed to (+/−) and the “reverse experiment” was carried out. Now, on the cathodic boundary \|$_{ 4 }$ of subcell {fx1070-5} anions (WO$_{4}$)$^{2−}$ are generated that are discharged on boundary $_{ 3 }$\| to oxide WO$_{3}$ that is intercalated into the right boundary of MeWO$_{4 − (3)}$, where the rightmost composite region {ie1070-2} is formed. Thus, the mass of W 3 (−) decreases; it becomes dark-green (see above) and the mass of the MeWO$_{4}$ disk continues growing and now its structure is as follows {ie1070-3}. It is important that the left W 3 (+) disk that was dark-green after the “direct experiment” gradually becomes lighter in the “reverse experiment” up to its natural pale green color, i.e., Me $^{2+}$ is deintercalated from it: Me $^{2+}$: Me $_{ x }$WO$_{3}$ + 1/2O$_{2}$ → xMe $^{2+}$ + 2e + WO$_{3}$. It is found that dependences of variations of disk masses Δm(Q) practically coincide for the “direct” and “reverse” experiments.
Starting Page	1070
Ending Page	1078
Page Count	9
File Format	PDF
ISSN	10231935
Journal	Russian Journal of Electrochemistry
Volume Number	48
Issue Number	11
e-ISSN	16083342
Language	English
Publisher	SP MAIK Nauka/Interperiodica
Publisher Date	2012-11-17
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	reversibility of electrosurface transfer eutectic interfaces transfer of multiatomic anions intercalation of cations Physical Chemistry Electrochemistry
Content Type	Text
Resource Type	Article
Subject	Electrochemistry

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