The role of adsorbed ions during electrocatalysis in ionic liquids

The effects of electrode–adsorbate interactions on electrocatalysis at Pt in ionic liquids are described. The ionic liquids are diethylmethylammonium trifluoromethanesulfonate, [dema][TfO], dimethylethylammonium trifluoromethanesulfonate, [dmea][TfO], and diethylmethylammonium bis(trifluoromethanesulfonyl)imide, [dema][Tf2N]. Electrochemical analysis indicates that a monolayer of hydrogen adsorbs onto Pt during potential cycling in [dema][[TfO] and [dmea][TfO]. In addition, a prepeak is observed at lower potentials than that of the main oxidation peak during CO oxidation in the [TfO]−-based liquids. In contrast, hydrogen does not adsorb onto Pt during potential cycling in [dema][Tf2N] and no prepeak is observed during CO oxidation. By displacing adsorbed ions on Pt surfaces with CO at a range of potentials, and measuring the charge passed during ion displacement, the potentials of zero total charge of Pt in [dema][TfO] and [dmea][TfO] were measured as 271 ± 9 and 289 ± 10 mV vs RHE, respectively. CO displacement experiments also indicate that the [Tf2N]− ion is bound to the Pt surface at potentials above −0.2 V and the implications of ion adsorption on electrocatalysis of the CO oxidation reaction and O2 reduction reaction in the protic ionic liquids are discussed

Highly decoupled ionic and protonic solid electrolyte systems, in relation to other relaxing systems and their energy landscapes

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Parallel developments in aprotic and protic ionic liquids : physical chemistry and applications

This Account covers research dating from the early 1960s in the field of low-melting molten salts and hydrates,which has recently become popular under the rubric of &ldquo;ionic liquids&rdquo;. It covers understanding gained in the principal author&rsquo;s laboratories (initially in Australia, but mostly in the U.S.A.) from spectroscopic, dynamic, and thermodynamic studies and includes recent applications of this understanding in the fields of energy conversion and biopreservation. Both protic and aprotic varieties of ionic liquids are included, but recent studies have focused on the protic class because of the special applications made possible by the highly variable proton activities available in these liquids.<br /