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Thin‐Layer Spectroelectrochemistry on an Aqueous Microdrop
Author(s) -
Schroll Cynthia A.,
Chatterjee Sayandev,
Heineman William R.,
Bryan Samuel A.
Publication year - 2012
Publication title -
electroanalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.574
H-Index - 128
eISSN - 1521-4109
pISSN - 1040-0397
DOI - 10.1002/elan.201100711
Subject(s) - aqueous solution , diffusion , analytical chemistry (journal) , ionic bonding , electrolysis , chemistry , diffusion layer , absorption (acoustics) , analyte , electrochemistry , layer (electronics) , thin film , cyclic voltammetry , materials science , ion , electrode , chromatography , nanotechnology , electrolyte , organic chemistry , thermodynamics , physics , composite material
Here we report a technique to perform thin layer spectroelectrochemistry using an aqueous microdrop. The chemical systems used to demonstrate the aqueous microdrop technique were an absorption based ionic probe [Fe(CN) 6 ] 3−/4− and an emission based ionic probe [Ru(bpy) 3 ] 3+/2+ . The ability of the technique to perform semi‐infinite linear diffusion spectroelectrochemistry on an aqueous microdrop has been previously demonstrated; in this work we were able to demonstrate spectroelectrochemical behavior consistent with the restricted diffusion in a thin layer cell by reducing the analyte volume and the optical path length. The thin‐layer diffusion behavior was illustrated by substantial reduction in peak‐to‐peak separations of the cyclic voltammograms and the significant decrease in electrolysis time compared to the semi‐infinite linear diffusion behavior.