Apart from the current flow between the electrode and the analyte in solution as a result of electron transfer (faradaic current), there is also a possibility of current flow without such transfer of electron [102]. This occurs as a result of the formation of a double layer capacitance between the electrolyte solution and the electrode. This relationship generates a charging current (non-faradaic current) that limits the faradaic current recorded in cyclic voltammetry because the total current output is a summation of the duo [103]. Pulse voltammetry has greatly reduced this charging current by progressively applying short pulses over time. These pulses are assigned within a potential step such that the current before the end of a pulse (I1) and just before the application of a pulse (I2) is subtracted to obtain the current output in a pulse (Figure 5A) [104]. The cumulative current over a certain potential range is plotted against the potential to obtain a differential pulse voltammogram (Figure 5B) [104]. The magnitude of the charging current, in this case, is so small that the DPV gives a better result in terms of sensitivity compared to CV. This improved sensitivity is the reason DPV is mostly used for selectivity test in electrochemical sensors. The outstanding sensitivity makes discrimination of analytes feasible.
Differential pulse voltammetry showing (A) Potential against time; and (B) Current against potential (Adapted from [104] copyright Elsevier, 2017).
As a result of this proven sensitivity of DPV, more than 90% of the carbon-based QD-modified electrochemical sensors have been used for analytical determination of monoamine neurotransmitters via DPV. Additionally, the real sample determination and selectivity tests have been mostly carried out with the help of DPV which makes signal detection in the presence of interferents much easier. Only a few publications have attempted the use of other techniques for the analytical application of the fabricated electrodes.
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