Investigation of Noise at a Microelectrode during a Faradaic Reaction.

Measurement of small currents is often impeded by a suboptimal signal-to-noise ratio, largely due to background noise. This background noise significantly constrains the range of catalysts accessible for interrogation via micro- and nanoscale electrochemistry. In response, this work reveals how background noise scales in the presence of induced Faradaic reactions. We measured noise under a series of electrochemical conditions and discovered that the induced noise from a Faradaic reaction scales directly with current. Complementary electrochemical impedance spectroscopy measurements demonstrated that diffusional resistance dictates the noise of Faradaic reactions, independent of the electrochemical mechanism. The noise source is thermal in origin and propagates in a predictable trend, which is inversely proportional to the equivalent diffusional resistance of the analyte. The universality of the observed phenomenon allows for better deconvolution of measured charge from background noise, thus assisting in achieving higher resolution and measurement precision, which is a key in micro- and nanoscale electrochemical measurements.