For
electrochemical experiments involving biological buffers, pH values,
ions, and electrode materials play major roles in the electrochemical
readout of the measurements. When conducting electrochemical experiments,
background signals are sometimes mixed with true signals, easily leading
to a wrong interpretation of the data. These background signals are
easily induced by the reactions between buffers and electrode materials.
However, these background signals have rarely been studied systematically.
In response to rapid developments in the field and application of
bioelectrodes, we conducted a much-needed systematic study of these
background signals and the electrochemical windows in buffersspecifically,
of the electrochemical windows gold, glassy carbon, and platinum in
three most commonly used biological buffers, namely, Tris, HEPES,
and phosphate. We examined the pH effect using HCl, H2SO4, and NaOH to modulate the pH values from 6.0 to 9.0 in the
three buffers. Furthermore, through comparison of HCl and H2SO4, we were able to illustrate the reaction between Cl– ions and the metallic electrode. This reaction also
led to clear redox peaks as background signals in cyclic voltammograms.
When a high potential was applied, the formation of hydroxide was
evident on the metallic electrode, which led to a clear reduction
peak in cyclic voltammograms. In addition, we used an atomic force
microscope to monitor the morphology of the electrode surface when
a cyclic potential was applied. All tests were conducted in the presence
of 100 mM LiClO4, which was used as the electrolytes. These
characterization results yield critical insights into electrode surface
reactions, insights which are crucial for precisely interpreting electrochemical
results measured in biological buffers. This fundamental study provides
comprehensive information, which is especially helpful for the development
of bioelectrode materials and bioelectronics applications.