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org/ac Technical Note

Hard Potato: A Python Library to Control Commercial Potentiostats

and to Automate Electrochemical Experiments
Oliver Rodríguez,* Michael A. Pence, and Joaquín Rodríguez-López*
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ABSTRACT: Here, we develop and show the use of an open-

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source Python library to control commercial potentiostats. It

standardizes the commands for different potentiostat models,
opening the possibility to perform automated experiments
independently of the instrument used. At the time of this writing,
we have included potentiostats from CH Instruments (models
1205B, 1242B, 601E, and 760E) and PalmSens (model Emstat
Pico), although the open-source nature of the library allows for
more to be included in the future. To showcase the general
workflow and implementation of a real experiment, we have
automated the Randles−Š evčı ́k methodology to determine the diffusion coefficient of a redox-active species in solution using cyclic
voltammetry. This was accomplished by writing a Python script that includes data acquisition, data analysis, and simulation. The
total run time was 1 min and 40 s, well below the time it would take even an experienced electrochemist to apply the methodology in
a traditional manner. Our library has potential applications that expand beyond the automation of simple repetitive tasks; for
example, it can interface with peripheral hardware and well-established third-party Python libraries as part of a more complex and
intelligent setup that relies on laboratory automation, advanced optimization, and machine learning.

E lectrochemical experimentation is still mostly done in a

manual way by introducing parameters one by one into the
graphical user interface (GUI) software that comes with the
available and can be directly programmed.5,6 These frameworks,
however, lack consistency between each other; this is expected,
as each instrument has their own implementations and
instrument. For general usage, this is arguably enough; however, requirements. Here, we overcome the lack of consistency
with recent developments in applications such as redox flow between different frameworks by introducing Hardware
batteries1 or electrocatalysis,2 where large amounts of new Potentiostato (or Hard Potato for short), a generalized Python
molecules and materials need to be electrochemically charac- API that internally translates high level functions into the
terized, manual experimentation is cumbersome. Some of the specific commands required by each instrument. The selection
well-known electrochemical instrumentation companies pro- of Python as the programming language for the library responds
vide some sort of automation capabilities for their potentiostats, to its gentle learning curve, its syntax that is easy to understand,
either within their own desktop applications via macros and and the sheer number of third-party libraries available to
block programming or by an application programming interface perform data analysis, instrumental control, and interfacing with
(API) written in a general programming language such as C/C+ the operating system. The flexibility given by Python allows
+, C#, or Python. APIs can be seen as an intermediary users to include electrochemical experimentation onto complex
communication step between the user and the instrument, setups, for example, as part of a high throughput system where
where the user can write simple commands and the API will multiple parameters need to be explored through control of
internally translate them into the set of instructions required by peripheral hardware or when using advanced optimization
the instrument. This simplifies the syntax on the user side, as algorithms and machine learning for autonomous operation.
they do not need to fully understand the specific details of their Furthermore, the open-source nature of the library would allow
potentiostats. APIs are most useful for experienced users, as it the electrochemistry community to be involved in its develop-
allows them to write programs or scripts that include the
experiment and to control other instruments and data analysis
by means of third-party libraries. To the best of our knowledge at Received: November 2, 2022
the time of this writing, only PalmSens and Gamry provide Accepted: February 2, 2023
frameworks to control their devices via a general-use Published: March 8, 2023
programming language like Python.3,4 Other do-it-yourself
potentiostats are also reported in the literature, based mostly on
open hardware microcontrollers with their source code freely
© 2023 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acs.analchem.2c04862
4840 Anal. Chem. 2023, 95, 4840−4845
Analytical Chemistry pubs.acs.org/ac Technical Note

Figure 1. API to control commercial potentiostats. The user writes a script with the high-level functions and the API translates them into the specific
commands expected by the instrument.

ment, for example, to include the control of potentiostat models macro file. Our library uses this to control the potentiostat,
not currently available to the authors. where the user only needs to write the high-level functions; then,
To test our Python API, we demonstrate its application to the internally, the API converts these instructions into macro
Randles−Š evčı ́k methodology7 to determine a diffusion commands that the CHI760E understands. The resulting macro
coefficient (D) for a soluble redox-active species undergoing file also contains instructions to save the data into a .txt and .bin
electron transfer at an electrode using the cyclic voltammetry file, the latter being the format expected by the CHI software. It
(CV) technique. This example is a staple of electrochemical also contains a termination line that closes the software and
studies, but its implementation promptly requires automation returns control to Python to continue with the next instruction
when dealing with large libraries of materials. Furthermore, to line.13 While we have focused on the CHI760E, it is possible to
showcase the flexibility provided by Python, we make use of Soft include more potentiostats into the library as depicted in Figure
Potato,8,9 an open-source library that contains electrochemical 1, where a developer would only need to write its “translator” to
equations and can simulate electrochemical processes assuming match the API’s functions to the instrument of interest. Until
semi-infinite planar diffusion and Butler−Volmer kinetics. January 2023, we have written the translators for the CH

■ EXPERIMENTAL SECTION
API implementation. The API consists of two main
Instrument potentiostats models 1205B, 1242B, 601E, and 760E
and the PalmSens Emstat Pico potentiostat, the latter enabling
the use of a low-cost potentiostat for application in an automated
components: the potentiostat module and a load_data module. electrochemical platform.
The potentiostat module contains high level functions and calls Controlling instruments from different vendors comes with
a “translator” for each commercial potentiostat available in the certain challenges. For example, the CHI760E can perform
library, while the load_data module provides easy data handling automated iR compensation if a resistance value is provided,
(see Figure 1). The potentiostat module provides generalized while this is not possible with the Emstat Pico. Meanwhile, the
functions for typical electrochemical techniques; for example, Emstat Pico has different operation modes (low speed, high
some of the arguments for the potentiostat.CV() function are speed, and maximum potential range) that can be selected. To
the scan rate (sr [V/s]), the first vertex potential (Ev1 [V]), and consider the variability in options for each model, we have
the second vertex potential (Ev2 [V]). The Supporting included optional parameters specific to each instrument. For
Information includes instructions to install the library (Section example, in cyclic voltammetry, a resistance value can be
S1) and script examples for typical experiments as well as the
included if using the CHI760E; this value will be ignored if using
Randles−Š evčı ́k methodology implemented here (Sections S3−
the Emstat Pico. This also allowed us to future-proof the code, as
S8). (See refs 10 and 11 for the latest version of the library and
developers can write the translators for their own instruments
full documentation.)
Figure 1 shows how a common API facilitates communication including the core parameters required by the general library and
between the user and each instrument. The generalized optional parameters only used by their specific instrument. We
functions act as intermediaries between the user and the have also included a validation step to ensure that potential
instrument, where the user does not have to worry about the parameters for each technique and potentiostat model fall within
specific ways on which their commercial software defines the their corresponding range. For more details on the inner
parameters. Internally, these functions are “translated” into workings of the library, see refs 10−12.
specific commands that each instrument understands. In the In the following sections, we use the CH Instruments 760E to
current version of the library (v1.3.11),12 we have included demonstrate how the library can be used to automate data
several CH Instruments potentiostats. For the following, we are acquisition and include data analysis and simulation on the same
using the CHI760E, a highly popular and versatile research script. For this, we have selected the Randles−Š evčı ́k routine, a
grade potentiostat from CH Instruments with the capability to highly used methodology and part of the general electro-
be controlled via internal macro commands, but not directly chemistry toolkit that consists of multiple repetitions and data
with Python. The CHI software allows one to save the analysis that may become tedious. To compare between
instructions as a .mcr text file and to use it as a parameter different potentiostat models and to showcase the flexibility of
when calling the software from the Windows command line. The Hard Potato, we have included the results using the CHI760E,
software then starts and runs the instructions written on the CHI1205B, and Emstat Pico and their respective Python scripts
4841 https://doi.org/10.1021/acs.analchem.2c04862
Anal. Chem. 2023, 95, 4840−4845
Analytical Chemistry pubs.acs.org/ac Technical Note

Figure 2. Results of the automated Randles−Š evčı ́k routine execution. Top: Block diagram of the routine. Bottom: (a) cyclic voltammograms
performed at 0.1, 0.2, 0.3, 0.4, and 0.5 V/s from bottom to top, (b) linear regression following eq 1 to estimate D, and (c) comparison between a cyclic
voltammogram recorded at 0.1 V/s and its simulated response. The solution used consisted of a mixture of 1 mM FcMeOH and 100 mM KNO3. The
simulation was performed assuming planar diffusion and the Butler−Volmer equation with fast electron transfer kinetics; the parameters used were n =
1, k0 = 1 × 108 cm/s, and α = 0.5.

in the Supporting Information, Section S8, and as a Supporting 1/2

i nF D yz
Information zip file. ip = 0.4463nFACjjj zz
k RT { (1)
Chemicals and methods. Hydroxymethylferrocene
(FcMeOH) (Sigma-Aldrich, 97%) and potassium nitrate where ip is the peak current, n is the number of electrons, F is the
(Sigma-Aldrich reagent grade) were used as purchased. A Faraday constant (96,485 C/mol), C is the bulk concentration
three-electrode electrochemical cell was used with a Pt disc (a = of the species, A is the geometrical area of the electrode, D is the
1 mm, CH Instruments) as a working electrode and two Pt wires diffusion coefficient, ν is the scan rate, R is the gas constant, and
used as counter and quasi-reference electrodes. A CH T is the temperature. The repetitive nature of the Randles−
Instruments potentiostat model 760E was used to perform the Š evčı ́k methodology, with the variation of one parameter (ν)
electrochemical experiments. The Python script was run on a and the estimation of another (D), makes it a perfect candidate
MS Windows 8.1 computer with Python version 3.10.6 installed. for automation. Figure 2 shows a block diagram of the
The libraries used were hard potato1.3.11,10 numpy 1.23.1 for implementation. Briefly, the routine consists of four main
data analysis,14 scipy 1.9.0 for linear regression,15 matplotlib parts. In the first part, we declare the variables required by the
setup, which are the potentiostat model, path to the .exe
3.5.2 for plotting the data,16 and softpotato 1.0.18 for the
program in the case of the CHI760E, and the folder where to
electrochemical simulations.8,9 save the data. Then, in the second part, we perform an open

■ RESULTS
Randles−Š evčı ́k is one of the most used electroanalytical
circuit potential (OCP) measurement and use it to estimate the
potential window of the oxidation of FcMeOH; this could be
useful when standard reduction potential of the species (E0) is
methodologies. It allows one to measure the number of unknown, for example, when characterizing new nonaqueous
electrons, the geometrical area of the electrode, or the diffusion redox molecules with unknown redox potentials. The third part
consists of a loop that describes the specific steps during
coefficient of a redox species, provided the rest of the
measurement, one for each scan rate. Here, we also import the
electrochemical parameters are known. It is also one of the
recently acquired data to be used for the analysis later. The
first methodologies taught in introductory electrochemistry fourth part consists of the data analysis and plotting, that is, the
courses.17 It consists of performing CV using a macroelectrode estimation of E0 from the average of the forward and reverse
with a redox active species and analyzing the peak currents as a peak potentials and D from eq 1. Importantly, this step allows us
function of the square root of the scan rate. If the process is to interface with other Python libraries that are useful for
diffusion controlled and displays fast electron transfer kinetics, a electrochemistry. For instance, in our analysis, we used the
linear relationship is observed that is described by the Randles− Randles−Š evčı ́k equation included in the Soft Potato library to
Š evčı ́k equation: fit the experimental peak currents and obtain D. We performed
4842 https://doi.org/10.1021/acs.analchem.2c04862
Anal. Chem. 2023, 95, 4840−4845
Analytical Chemistry pubs.acs.org/ac Technical Note

linear regression to obtain the slope of the ipeak vs ν1/2 curve and of large libraries of redox species.29 The ability to interface with
used the R2 value to ensure our experiments were above a certain third-party libraries for data analysis, plotting, simulations,
threshold, otherwise meaning that the methodology would be machine learning, and even other instruments such as
inappropriate to use due to either experimental artifacts spectrophotometers and (micro)fluidics makes this a very
(resistance, capacitance, noise), the effect of slow kinetics, or powerful tool. For example, here, we used Soft Potato, an open-
the presence of multiple electron transfer steps. Adding controls source Python library that includes typical electrochemical
such as these prevents the need for manual inspection of the equations and can perform simulations assuming semi-infinite
data, which would defeat the purpose of having a fully automated planar diffusion and Butler−Volmer kinetics. Soft Potato makes
system, or when protocols are used by nonexpert electro- the calculation of D from the Randles−Š evčı ́k equation
chemists. We have also used Soft Potato to simulate the cyclic straightforward, as the user does not need to manually code it.
voltammograms once E0 and D were estimated. Using Soft We also used it to simulate the electrochemical response and
Potato in this case helps to confirm the accuracy of the entire compare it to the corresponding experiment, everything on the
approach by plotting the experimental results alongside their same script and immediately after the experiments were
simulations. Figure 2a −c shows the results of the automated performed. Fully integrated, the Potato ecosystem can become
Randles−Š evčı ́k experimentation, data analysis, and comparison a powerful tool to automate electrochemical experimentation
to simulation, promptly displaying the obtained CVs, the linear and data analysis. Furthermore, a script can be shared between
relationship predicted by eq 1, and the comparison between an research groups “as is” to corroborate results or to make changes
experimental and simulated voltammogram. The total time of to the methodology, supporting the philosophy of more open
execution of this script was 1 min and 40 s, well below the total and transparent analytical science. The potential for this
time it would take even an experienced electrochemist to apply approach can be significantly enhanced if companies offer
the full methodology manually. To this point, the first author of compatible Python frameworks and the research community is
this work tested it themselves taking ∼30 min. involved with the development and improvement of the library.

■ DISCUSSION
The use of our API simplifies the execution of straightforward
Specific challenges that can be addressed are the ability to live
stream data to perform operations while the measurement is
being taken, for example, to change current ranges, detect
methods such as CV and enables the automation of electro- oscillations due to iR compensation, and even emergency stops.
chemical experiments. While the execution time in the case We believe that this will be essential in the coming years, since
shown here depends on the scan rates used, performing the full we see automation making its way into the chemistry realm,
methodology in a traditional way is still time consuming as it specifically, synthetic chemistry, where groups around the world
requires changing the scan rate manually for each CV, saving are building fully automated synthesis laboratories.30,31 It is only
data in an appropriate format to be used in commercial data a matter of time until digital electrochemistry becomes the
analysis software, extracting E0 and peak currents (or other norm.
suitable parameters), and performing linear regression against
the square root of the scan rate to obtain D. Additionally, the
user could still invest time in manually inputting parameters to
perform electrochemical simulations, export the simulated data,
■ CONCLUSIONS
Here, we have demonstrated the flexibility of automated
and put it back into the data analysis software to compare it with electrochemical experimentation enabled by our open-source
the experimental data. This methodology is straightforward and Hard Potato Python library. As a use case, we have implemented
can be carried out manually; however, its full implementation a workflow to estimate E0 from voltammograms and D from the
from experiment to data analysis and simulation is tedious and Randles−Š evčı ́k methodology, using these parameters to
time consuming. Our API overcomes practical obstacles not simulate and corroborate the electrochemical response, every-
only by offering automation of all these functions, but also by thing on a single script. The total run time was 1 min and 40 s,
introducing a consistent language that defines commonly used limited only by the scan rates used and the number of
parameters that are independent of the instrument used. experiments performed, as the data analysis and simulation are
The API approach shown here also raises new prospects for virtually instantaneous. The ability to centralize data acquisition,
combining electrochemical methods with a wide variety of analysis, and simulation within a single Python script showcases
Python libraries. While we focused on the Randles−Š evčı ́k how powerful and flexible this tool is. Our primary goal is to
methodology, basically, any other electrochemical routine can automate processes and facilitate the sharing of electrochemical
be easily automated. For example, immediate systematic protocols, as groups can run the same experiments independ-
experiments similar to the one here tested are found in ently of the potentiostat that they possess, provided they have
electrochemical applications such as potential window opening access to the Python script and the potentiostat “translator” is
studies,18 the Koutecky−Levich analysis,19 the implementation included in the library. Overall, we believe that our generalized
of sampled current voltammetry,20−22 the measurement of Hard Potato library can be incorporated into any electro-
electrochemical kinetics with macro23 and microelectrodes,24 chemistry workflow and opens the possibility to perform more
capacitance and solution resistance measurements with interesting problems involving automation, high throughput
voltammetry and electrochemical impedance spectroscopy,25,26 experimentation, and even artificial intelligence for closed-loop
and the electrochemistry part of a homemade scanning experimental design.
electrochemical microscope.27 For example, in our group, we
have recently reported the use of automated tools to estimate
chemical decomposition rates using a set of interdigitated
electrode arrays and an early version of Hard Potato.28 The Hard
■ ASSOCIATED CONTENT
* Supporting Information
sı

Potato library enables researchers to automate these tasks, The Supporting Information is available free of charge at
especially when dealing with repetition and/or characterization https://pubs.acs.org/doi/10.1021/acs.analchem.2c04862.
4843 https://doi.org/10.1021/acs.analchem.2c04862
Anal. Chem. 2023, 95, 4840−4845
Analytical Chemistry pubs.acs.org/ac Technical Note

Instructions on how to install the Hard Potato library, (4) Gamry Instruments Software. https://www.gamry.com/support-2/
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(6) Brown, E. W.; Glasscott, M. W.; Conley, K.; Barr, J.; Ray, J. D.;
ment, linear sweep voltammetry, and the Randles−Š evčı ́k
Moores, L. C.; Netchaev, A. Anal. Chem. 2022, 94 (12), 4906−4912.
methodology performed with a CHI760E, CHI1205B, (7) Bard, A. J.; Faulkner, L. R. Electrochemical Methods. Fundamentals
and Emstat Pico (PDF) and Applications, Second ed.; John Wiley & Sons, Inc.: New York, 2001.
Screen recording of the automation of the Randles− (8) Rodríguez, O. Soft Potato: An Open-Source Electrochemical
Š evčı ́k methodology (MP4) Simulator and Toolkit, ChemRxiv Preprint, 2022. DOI: 10.26434/
Data (ZIP) chemrxiv-2022-4bs3w.
(9) Rodríguez, O. Soft Potato: an open-source electrochemistry toolkit.

■ AUTHOR INFORMATION
Corresponding Authors
https://github.com/oliverrdz/SoftPotato.
(10) Hard Potato GitHub. https://github.com/jrlLAB/hardpotato
(accessed 2022−09−28).
(11) Hard Potato Wiki Page. https://github.com/jrlLAB/hardpotato/
Oliver Rodríguez − Department of Chemistry, University of wiki.
Illinois at Urbana−Champaign, Urbana, Illinois 61801, (12) Hard Potato source code v1.3.11. https://github.com/jrlLAB/
United States; Beckman Institute for Advanced Science and hardpotato/releases/tag/v1.3.11.
Technology, University of Illinois at Urbana−Champaign, (13) The implementation of the termination command in the
Urbana, Illinois 61801, United States; Joint Center for Energy CHI760E requires having the latest firmware and software installed.
Storage Research (JCESR), Argonne National Laboratory, Contact the CH Instruments Support to update them.
Lemont, Illinois 60439, United States; orcid.org/0000- (14) Harris, C. R.; Millman, K. J.; van der Walt, S. J.; Gommers, R.;
0003-2350-1214; Email: [email protected] Virtanen, P.; Cournapeau, D.; Wieser, E.; Taylor, J.; Berg, S.; Smith, N.
Joaquín Rodríguez-López − Department of Chemistry, J.; Kern, R.; Picus, M.; Hoyer, S.; van Kerkwijk, M. H.; Brett, M.;
University of Illinois at Urbana−Champaign, Urbana, Illinois Haldane, A.; del Río, J. F.; Wiebe, M.; Peterson, P.; Gérard-Marchant,
61801, United States; Beckman Institute for Advanced Science P.; Sheppard, K.; Reddy, T.; Weckesser, W.; Abbasi, H.; Gohlke, C.;
Oliphant, T. E. Nature 2020, 585, 357−362.
and Technology, University of Illinois at Urbana−Champaign, (15) Virtanen, P.; Gommers, R.; Oliphant, T. E.; Haberland, M.;
Urbana, Illinois 61801, United States; Joint Center for Energy Reddy, T.; Cournapeau, D.; Burovski, E.; Peterson, P.; Weckesser, W.;
Storage Research (JCESR), Argonne National Laboratory, Bright, J.; van der Walt, S. J.; Brett, M.; Wilson, J.; Millman, K. J.;
Lemont, Illinois 60439, United States; orcid.org/0000- Mayorov, N.; Nelson, A. R. J.; Jones, E.; Kern, R.; Larson, E.; Carey, C.
0003-4346-4668; Email: [email protected] J.; Polat, I.;̇ Feng, Y.; Moore, E. W.; VanderPlas, J.; Laxalde, D.;
Perktold, J.; Cimrman, R.; Henriksen, I.; Quintero, E. A.; Harris, C. R.;
Author Archibald, A. M.; Ribeiro, A. H.; Pedregosa, F.; van Mulbregt, P.;
Michael A. Pence − Department of Chemistry, University of Vijaykumar, A.; Bardelli, A. P.; Rothberg, A.; Hilboll, A.; Kloeckner, A.;
Illinois at Urbana−Champaign, Urbana, Illinois 61801, Scopatz, A.; Lee, A.; Rokem, A.; Woods, C. N.; Fulton, C.; Masson, C.;
United States; Beckman Institute for Advanced Science and Häggström, C.; Fitzgerald, C.; Nicholson, D. A.; Hagen, D. R.;
Technology, University of Illinois at Urbana−Champaign, Pasechnik, D. v.; Olivetti, E.; Martin, E.; Wieser, E.; Silva, F.; Lenders,
Urbana, Illinois 61801, United States; Joint Center for Energy F.; Wilhelm, F.; Young, G.; Price, G. A.; Ingold, G. L.; Allen, G. E.; Lee,
Storage Research (JCESR), Argonne National Laboratory, G. R.; Audren, H.; Probst, I.; Dietrich, J. P.; Silterra, J.; Webber, J. T.;
Lemont, Illinois 60439, United States; orcid.org/0000- Slavič, J.; Nothman, J.; Buchner, J.; Kulick, J.; Schönberger, J. L.; de
0001-5880-9812 Miranda Cardoso, J. V.; Reimer, J.; Harrington, J.; Rodríguez, J. L. C.;
Nunez-Iglesias, J.; Kuczynski, J.; Tritz, K.; Thoma, M.; Newville, M.;
Complete contact information is available at: Kümmerer, M.; Bolingbroke, M.; Tartre, M.; Pak, M.; Smith, N. J.;
https://pubs.acs.org/10.1021/acs.analchem.2c04862 Nowaczyk, N.; Shebanov, N.; Pavlyk, O.; Brodtkorb, P. A.; Lee, P.;
McGibbon, R. T.; Feldbauer, R.; Lewis, S.; Tygier, S.; Sievert, S.; Vigna,
Notes S.; Peterson, S.; More, S.; Pudlik, T.; Oshima, T.; Pingel, T. J.;
The authors declare no competing financial interest. Robitaille, T. P.; Spura, T.; Jones, T. R.; Cera, T.; Leslie, T.; Zito, T.;
Krauss, T.; Upadhyay, U.; Halchenko, Y. O.; Vázquez-Baeza, Y. Nat.

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