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Facile cation electro-insertion into layer-by-layer assembled iron phytate films
Authors:Charles Y Cummings  Alistair H Roweth  Andrew KZ Ching  A Toby A Jenkins  John M Mitchels  Sara Shariki  Soon Yee Liew  Wim Thielemans  Darren A Walsh  Frank Marken
Institution:1. Department of Chemistry, University of Bath, Bath BA2 7AY, UK;2. School of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK;3. Faculty of Engineering, Process & Environmental Research Division, University of Nottingham, Nottingham NG7 2RD, UK
Abstract:Molecular layer-by-layer assembly from pre-saturated aqueous solutions of Fe3+ and phytate is employed to build up iron phytate deposits on tin-doped indium oxide (ITO) electrodes. Globular films with approximately 1 nm growth per layer are observed by AFM imaging and sectioning. In electrochemical experiments the iron phytate films show well-defined voltammetric responses consistent with an immobilised Fe(III/II) redox system in aqueous (LiClO4, NaClO4, KClO4, phosphate buffer) and in ethanolic (LiClO4, NaClO4, NBu4ClO4) electrolyte solutions. The Fe(III/II) redox system is reversible and cation insertion/expulsion occurs fast on the timescale of voltammetric experiments even for more bulky NBu4+ cations and in ethanolic solution. Peak shape analysis and scan rate dependent midpoint potentials suggest structural changes accompanying the redox process and limiting propagation. Iron phytate is proposed as a versatile and essentially colourless cation electro-insertion material and as a potential energy storage material.
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