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Staircase Voltammetry (SCV)

Last Updated: 1/18/22 by Neil Spinner

ARTICLE TAGS
  • current vs. potential,
  • AfterMath SCV,
  • SCV,
  • staircase voltammetry,
  • step voltamemtry
Article Contents/Section Navigation
  1. Technique Overview
  2. Fundamental Equations
  3. Experimental Setup in AfterMath
    1. Basic Tab
    2. Advanced Tab
    3. Ranges, Filters, and Post Experiment Conditions Tab
  4. Typical Result
  5. Example Applications
  6. References

1Technique Overview

Staircase Voltammetry (SCV) is a potentiostatic method that offers some advantages to common techniques like Cyclic Voltammetry (CV). SCV involves sweeping the potential of the working electrode linearly with time at rates faster than CV, typically between 10 V/s and 100 V/s.  The current is plotted as a function of potential to yield a voltammogram.  The difference between SCV and CV is that you choose the size and duration of each potential step.

Though there are similarities between SCV, Cyclic Voltammetry (CV), Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV), Linear Sweep Voltammetry (LSV) SCV allows more control of the waveform that is applied to the working electrode.  CV and LSV waveforms are optimized to take full advantage of the resolution of the potentiostat's digital-to-analog converter, while the waveform in SCV is designed for much higher sweep rates than typically encountered in CV or LSV.
 
As with many other methods, users can initially sweep positively (towards an anodic limit) or negatively (toward a cathodic limit) initially.  Below, typical NPV waveforms are shown for illustration, using only an increasing positive pulse sequence.

INFO:  Initial sweep direction can be positive-increasing or negative increasing.  Not all possibilities have been provided as examples in this article.  Users must tailor their parameters to suit their specific electrochemistry.  Contact us with any questions or additional assistance.

In the simplest case, when Segments (SN) = 1 (see Figure 1), potential steps, in time by period and in potential by amplitude, from an initial to final potential, sampling current at the specified width (time prior to next step) (see Figure 7).
 
Staircase Voltammetry (SCV) One Segment Waveform

Figure 1. Staircase Voltammetry (SCV) One Segment Waveform

 
In the simplest case, when Segments (SN) = 2 (see Figure 2), potential steps, in time by period and in potential by amplitude, from an initial potential to vertex potential to final potential, sampling current at the specified width (time prior to next step) (see Figure 7).
 
Staircase Voltammetry (SCV) with Two Segments

Figure 2. Staircase Voltammetry (SCV) Two Segment Waveform

 
When Segments (SN) = 3 (see Figure 3), potential steps, in time by period and in potential by amplitude, from an initial potential to vertex potential to upper potential to lower potential and to final potential, sampling current at the specified width (time prior to next step) (see Figure 7).
 
Staircase Voltammetry (SCV) Three Segment Waveform

Figure 3. Staircase Voltammetry (SCV) Three Segment Waveform

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2Fundamental Equations

One of the best ways to understand the fundamentals of SCV will be to compare it to the more common Cyclic Voltammetry (CV).  Bard and Faulkner Bard, A. J.; Faulkner, L. A.  Electrochemical Methods: Fundamentals and Applications, 2nd ed. Wiley-Interscience: New York, 2000. provides a more exhaustive theoretical background and readers should consult this text for additional detail.
 
Unlike CV, where users specify a sweep rate (dE/dT, \upsilon), the equivalent sweep rate in SCV is determined by the ratio of step amplitude and period (see Table 1 and Figure 7) as,
 
\displaystyle dE/DT  = \frac{E_A,\; SCV}{T_P,\; SCV}=\upsilon =\frac{\Delta E}{\tau}
 
Under ideal conditions or conditions where uncompensated resistance is negligible, SCV should produce results identical to CV.  At very high sweep rates, which is effectively possible with SCV as compared to CV, it is possible that kinetic effects can be masked as uncompensated resistance.  A plot of  {\Delta} E_p \; vs \; {\nu}^{1/2} should extrapolate to  RT/nF when a large  {\Delta}E_p is caused only by uncompensated resistance.
 
Both CV and SCV utilize staircase waveforms (as opposed to truly linear waveforms generated in analog instruments); however, CV is optimized to take full advantage of the resolution of the potentiostat digital-to-analog converter (DAC).  SCV gives you the ability to control the step height and duration enabling sweep rates greater than 10 V/s.  Both methods provide some user control over current sampling.  With CV, the parameter Alpha determines when the current is sampled, Cyclic Voltammetry (CV) where value of \alpha =0 means that the current is sampled immediately after the potential step whereas when \alpha =100 means that the current is sampled immediately prior to the next potential step.  In SCV, the parameter Sampling Control Width (defined in Table 1 and Figure 7, TW, SCV) determines the point (in time) along the potential step at which current is sampled before the next potential step; therefore, when TW, SCV = 5 ms and the Step period (defined in Table 1 and Figure 7, TS, SCV) = 10 ms in SCV, this corresponds to an Alpha of 50% in CV.   Theoretically, it is ideal to sample at 1/4 of the sample window (\alpha =75 in CV in the case of SCV,
 
\displaystyle i_{sample}=\frac{1}{4}\left({T_{P,\; SCV}}\right)
 
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3Experimental Setup in AfterMath

To perform a staircase voltammetry experiment in AfterMath, choose Staircase Voltammetry (SCV) from the Experiments menu (see Figure 4).
 
Staircase Voltammetry (SCV) Experiment Menu Selection in AfterMath

Figure 4. Staircase Voltammetry (SCV) Experiment Menu Selection in AfterMath

 
Doing so creates an entry within the archive, called SCV Parameters. In the right pane of the AfterMath application, several tabs will be shown (see Figure 5).
 
Staircase Voltammetry (SCV) Experiment Basic Tab

Figure 5. Staircase Voltammetry (SCV) Experiment Basic Tab

 
The experiment sequence is
 
Induction Period → Staircase → Relaxation Period → Post-Experiment Idle Conditions
 
Continue reading for detailed information about the fields on each unique tab.
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3.1Basic Tab

TIP:  Click the AutoFill button ("I Feel Lucky" prior to May 2019) on the top bar in AfterMath to automatically fill all required parameters with reasonable starting values.  While the values provided may not be appropriate for your specific system, they are reasonable parameters with which to start your experiment, especially if you are new to the method.

 
The basic tab contains fields for the fundamental parameters necessary to perform an SCV experiment.  AfterMath shades fields with yellow when a required entry is blank and shades fields pink when the entry is invalid (see Figure 6).
 
Staircase Voltammetry (SCV) Basic tab in AfterMath

Figure 6. Staircase Voltammetry (SCV) Basic tab in AfterMath

 
During the induction period, Induction Period a set of initial conditions are applied to the electrochemical cell and the cell equilibrates at these conditions.  Data are not collected during the induction period, nor are they shown on the plot during this period.  Users will define induction period parameters on the Advanced Tab.
 
After the induction period, the potential of the working electrode is stepped through a series of increasing steps from the Initial potential to the Final potential at a specified period (TP, SCV).  The potential is incremented with each successive pulse according to the Pulse amplitude (EA, SCV).  Current is measured at the time defined by Pulse width (TW, SCV), which is the time before the next step.   In a typical experiment, Segments = 1 and there is a single series of increasing steps.  Some may want to reverse the pulses (move in the opposite direction), accomplished by adjusting the number of segments to be > 1.  Refer to Figures 1, 2, and 3 for examples of such SCV waveforms that vary based on the number of segments.
 
The parameter settings for step-type experiments are often not as clear as with something more simple like Cyclic Voltammetry (a sweep method ).  Refer to Figure 2 above when understanding each parameter of the NPV pulse.  Further, clicking "AutoFill" ("I Feel Lucky" in older versions of AfterMath) provides reasonable starting parameters if you are unsure of typical values used in these experiments.  Most often, research journal articles describe the NPV pulse sequence used, which can be replicated using AfterMath.
 
The experiment concludes with a relaxation period.  Relaxation Period  During the relaxation period, a set of final conditions (specified on the Advanced tab) are applied to the electrochemical cell and the cell equilibrates at these conditions (set on the Advanced Tab).  Data are not collected during the induction period, nor are they shown on the plot during this period.
 
At the end of the relaxation period, the post-experiment idle conditions are applied to the cell and the instrument returns to the idle state.
 
A plot of the typical experiment sequence, containing labels of the fields on the Basic tab, helps to illustrate the sequence of events in an NPV experiment (see Table 1 and Figure 7).

The table below lists the group and field names and symbols for each parameter associated with this experiment (see Table 1).

Group Name Field Name Symbol
Sweep (Sweep limits) Segments S_N
Sweep (Sweep limits) Initial Potential E_I
Sweep (Sweep limits) Initial Direction DIR_I
Sweep (Sweep limits) Upper Potential E_U
Sweep (Sweep limits) Vertex Potential E_V
Sweep (Sweep limits) Lower Potential E_{LOW}
Sweep (Sweep limits) Final Potential E_F
Normal Pulse
(Pulse parameters)
Baseline E_{B, \;NP}
Normal Pulse
(Pulse parameters)
Width T_{W, \;NP}
Normal Pulse
(Pulse parameters)
Period T_{P, \;NP}
Normal Pulse
(Pulse parameters)
Increment E_{I, \;NP}
Normal Pulse
(Pulse parameters)
Sampling Width T_{S, \;NP}
Table 1.  Basic Tab Group Names, Field Names, and Symbols.
 
Normal Pulse Voltammetry (NPV) Pulse Parameter Field Diagram

Figure 7. Normal Pulse Voltammetry (NPV) Pulse Parameter Field Diagram

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3.2Advanced Tab

3.3Ranges, Filters, and Post Experiment Conditions Tab

4Typical Result

Typical results for a 1.5 mM solution of Ferrocene in 0.1 M Bu4NClO4/MeCN are shown below. Two different sweep rates have been shown along with different Sample windows.
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5Example Applications

The first example uses staircase voltammetry to generate sweep rates as high as 200 V/s.  Baur et al.  Baur, J. E.; Kristensen, E. W.; May, L. J.; Wiedemann, D. J.; Wightman, R. M.  Fast-scan voltammetry of biogenic amines.  Anal. Chem., 1988, 60(13), 1268-1272. used staircase voltammetry to detect biogenic amines.  These high sweep rates have three advantages:
 
  1. High sweep rates allow for the detection of these species while preventing the formation of an insulating layer.
  2. High sweep rates allow extracellular detection of these amines in the brain
  3. High sweep rates discriminate against chemical events after the initial electron transfer.
 
In another example, Heering et al. Heering, H. A.; Mondal, M. S.; Armstrong, F. A.  Using the Pulsed Nature of Staircase Cyclic Voltammetry To Determine Interfacial Electron-Transfer Rates of Adsorbed Species.  Anal. Chem., 1999, 71(1), 174-182. used SCV to measure electron transfer rates of an adsorbed species. The researchers showed that SCV becomes independent of step amplitude and similar to CV at high sweep rates ( {\upsilon} > 10 \; k_0\times E_{step} ) if the current is sampled at 1/2 of the step period. The researchers determined the rate constant (ko) and n for adsorbed yeast cytochrome c peroxidase.  Values obtained from SCV were comparable to more traditional methods such as chronoamperometry (CA). Chronoamperometry (CA)
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6References

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