Journal: The Journal of Physical Chemistry C,  2020

Authors: Elise Duquesne, Stephanie Betelu, Cyrille Bazin, Alain Seron,Ioannis Ignatiadis, Hubert Perrot, Ozlem Sel, Catherine Debiemme-Chouvy

Abstract: Pseudo-capacitive properties and the mixed cation-/anion-exchanger nature of layered double hydroxides (LDHs) were highlighted via in situ electrochemical and physicochemical analyses conducted in a KOH solution (1 mol/L) on a nano-Ni/Fe-LDH. The reversible Ni(II)/Ni(III) oxidation/reduction reaction was monitored using an electrochemical quartz crystal microbalance (EQCM). The coupling of powerful electrochemical methods, EQCM and ac-electrogravimetry, and physicochemical techniques, EDX, XPS and in situ XRD, provided results clarifying the corre-sponding mass transfer mechanisms. Ac-electrogravimetry identified the nature, in terms of molar mass, kinetics and concentration variation of all reversibly transferred species associated with the redox reactions involving Ni and water molecules. This methodology demonstrated a reversible anion intercalation/de-intercalation into/from the interlayer spacing, in agreement with the redox reactions leading to modulate the electric charge of the layers. This phenomenon was also identified by in situ XRD. In addition, the variation of the pH at the LDH/electrolyte interface via a catalysed oxygen evolution reaction (OER) leads to cation electro-adsorption/desorption onto/from the external LDH surfaces.