Scanning Electrochemical Cell Microscopy (SECCM) in Aprotic Solvents: Practical Considerations and Applications
Cameron L. Bentley, Minkyung Kang, Patrick R. Unwin
Abstract
process (Fc = ferrocene) as a model system, high boiling point (low vapor pressure) solvents give rise to highly robust and reproducible electrochemistry, whereas volatile (low boiling point) solvents need to be mixed with suitable low melting point supporting electrolytes (e.g., ionic liquids) or high boiling point solvents to avoid complications associated with salt precipitation/crystallization on the scanning (minutes to hours) time scale. When applied to perform microfabrication-specifically the electrosynthesis of the conductive polymer, polypyrrole-the optimized SECCM set up produces highly reproducible arrays of synthesized (electrodeposited) material on a commensurate scale to the employed pipet probe. Applying SECCM to map electrocatalytic activity-specifically the electro-oxidation of iodide at polycrystalline platinum-reveals unique (i.e., structure-dependent) patterns of surface activity, with grains of specific crystallographic orientation, grain boundaries and areas of high local surface misorientation identified as potential electrocatalytic "hot spots". The work herein further cements SECCM as a premier technique for structure-function-activity studies in (electro)materials science and will open up exciting new possibilities through the use of aprotic solvents for rational analysis/design in electrosynthesis, microfabrication, electrochemical energy storage/conversion, and beyond.