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Redox Chemistry of Heteropolyacid Microemulsions
Author(s) -
Bera Mrinal K.,
Bray Travis H.,
Ellis Ross J.,
Antonio Mark R.
Publication year - 2014
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201402037
Subject(s) - redox , microemulsion , aqueous solution , protonation , chemistry , electrolyte , dissolution , inorganic chemistry , electrochemistry , deprotonation , solvent , organic chemistry , electrode , ion , pulmonary surfactant , biochemistry
Insight from electroanalysis studies of dense fluid phases (known as “third” phases) in the Keggin heteropolyacid tri‐ n ‐butyl phosphate (TBP) system is provided. The differences between the H 3 PW 12 O 40 and H 4 SiW 12 O 40 redox chemistry in the third phases and in bulk aqueous electrolytes reflect the differences in the formal charge of the protonated acid solvates of TBP in the low dielectric organic media and the deprotonated anions in the high dielectric aqueous media. The faradaic W‐based redox activity leading to heteropoly blue entities drives concerted proton transfer across the organic‐analyte–aqueous‐electrolyte phase boundary in both the heteropolyacid microemulsions (formed by solvent extraction) and the molecular liquids (formed by dissolution) to maintain charge neutrality in the organic phases. This study of heteropolyacid third phases complements the emerging field of mesoscale sciences with polyoxometalates and their electrochemical properties.