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PolArStat: An Arduino Based Potentiostat for

Low-Power Electrochemical Applications

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T. Tichtera,∗, M. Gernhardb , P. C. K. Vesborga
a Technical University of Denmark, Fysikvej 307, 2800 Kgs Lyngby, Denmark
b Universität Bayreuth, Universitätsstr. 30, 95447 Bayreuth, Germany

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Abstract

A potentiostatic circuit for low-power applications in the range of ±3.3 V and

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±13.75 mA is developed. The device achieves a full-scale resolution of ≈ 1.6 mV
and ≈ 1 µA — sufficient for a wide range of electroanalytical experiments.

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For controlling the potentiostat a Python-based graphical user interface (GUI)
is developed and implemented in our open-source electrochemistry software
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Polarographica. This allows to conductenables electroanalytical experiments
such as cyclic voltammetry (CV) and chronoamperometry (CA) in a live-graphing
environment at an operational convenience similar to commercial devices, com-
bined with a powerful tool for subsequent data analysis. The performance of
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our potentiostat is validated by the excellent agreement of CV and CA data

acquired with five different in-house built devices and a commericalcommercial
Gamry Reference 620. Finally, we provide a printed circuit board (PCB) design
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of our device as an Arduino shield that requires only a minimum of additional

components. This powerful open-source tool is suitable for customized electro-
chemical experiments at material costs of less than 1540 €.
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Keywords: Microcontroller Based Potentiostat for Low Power Applications;

Graphical User Interface; ADS1115; MCP4725; Arduino-Uno Shield;
Electrochemical Analysis Software; Cyclic Voltammetry; Chronoamperometry
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∗ Corresponding author: [email protected]

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Preprint submitted to Electrochimica Acta March 9, 2023

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
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1. Introduction

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The instrumentation for controlling the bias of a working electrode with
respect to a fixed reference potential in a three-electrode configuration was
invented by Hickling in 1942 [1] and referred to as potentiostat. Nowadays,
5 these devices are indispensible in any electrochemical laboratory. Distributed as
blackboxes encapsulating the electronics, experimentalists do not have to worry

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about the internal circuit and the working principle of the machine. Instead,
users are usually provided with a device which offers a multitude of specialized
applications in a dynamic range of operating potentials and a neat software for

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10 interfacing and displaying the aquired data in a pre-processed form. However,
in many cases only a very few of these built-in routines are frequently used.

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Consequently, commercial potentiostats are oftentimes severly overpowered —
and hence overpriced — especially if only simple electroanalytical applications
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like stepping or sweeping potentials at moderate rates are needed. Moreover,
15 if measurement routines differing from the build-in functions are required, a
re-programming of the devices’ internal software is a cumbersome task or even
made impossible. Finally, since commercial potentiostats are designed for plug-
and-play applications and supposed to be particularly not opened for warranty
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purposes, the electrochemists’ technical understanding of these devices becomes

20 deliberately limited to common textbook-representations.
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To mitigate the burden of costly equipment and to open the potentiostatic

blackbox , various potentiostat projects have been reported in the past decade.
An overview of the capabilities of the respective devices is given in table 1.
Starting with the CheapStat project by Rowe [2] a potentiostat at costs
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25 of less than 80 € was introduced in 2011. Operating in a potential range of

±0.99 V, the output capabilities of this device are, however, rather limited.These
issues have been solved with the DStat — a potentiostat developed in 2015 by
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Dryden [3]. Employing an ATXmega 256 microcontroller in combination with

analog-to-digital converters (ADC) and digital-to-analog converters (DAC), the
30 device achieves a remarkable accuracy in a voltage range of ±1.5 V at a cost
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
 ed
less than 120 €1 Equiped with a Python-based graphical user interface (GUI)

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the DStat provides a convenient freeware solution and became thus a standard
in the area of do-it-yourself (DIY) potentiostat solutions.
A way of mitigating the burden of costly equipment and opening the
35 potentiostatic blackbox for experimental electrochemists
In 2016, Aremo [4] presented a DIY potentiostat based on the. Utilizing

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the PIC18F452 microcontroller in combination with a R-2R resistor ladder as
a 10-bit digital to analog converter (DAC). The device the authors propose a
potentiostat which achieves a resolution of 5 mV and 50 µA on a full scale of

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40 ± 2.5 V and ± 25 mA. Though the devices’ performance is checked by investi-
gating the Ni/Ni2+ -redox reaction a comparison to commercial potentiostats is

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not provided. Furthermore, since subsequent data analysis for the strictly irre-
versible Ni-redox system is performed in terms of the reversible Randles-Ševčı́k
equation the performance of the device remains unknown.
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45 In the same year, an educational paper on an Arduino-based potentiostat
at a cost of about than 19 €1 was published by Meloni [5]. The device uses
an RC-low-pass filter as DAC for the 8-bit pulse-width modulation (PWM) of
an Arduino Uno and a few amplifiers to create the triangular ramp required
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for measuring cyclic voltammetry. This introduces a lot of noise and achieves
50 a full-scale resolution of only 20 mV — sufficient for educational, but not for
analytical purposes. Furthermore, it is important to note that working and
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counter electrode are flipped in this design. Since data is sendsent through the
serial interface of the Arduino and is meant to be recieved by a serial monitor,
it can only be displayed subsequently to measuerments.
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55 Another potentiostatic circuit using the LMP91000 sensing chip and an Ar-
duino Uno for communication with the PC was proposed in 2017 [6]. Reference
measurements, comparing the device with a commercial Autolab PGSTAT show
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1 Original literature reports the values in US-dollar. These have been converted to Euro ac-
cording to the mean exchange rate of the year 2022 (1.053 $/€) to achieve a better comparison
among different references.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
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a rather poor agreement (i.e. presented CV traces deviate by more than 100 mV

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and possess several kinks when compared to the commercial device).
60 In 2018, an Arduino based potentiostat was proposed by Li [7]. Though still
limited to the 8-bit PWM of the Arduino in combination with an RC-filter,
the authors provide a graphical user interface written in proprietarily licensed
LabView which results in an improved operational convenience. Two additional

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publications from 2018 are presented in refs [8, 9], where ref. [8] is essentially a
65 copy of the design by Meloni. Ref. [9] on the other hand uses a Raspberry Pi
computer as replacement for the Arduino and equippesequips the device with

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a touch pad for portable applications. By using external 12-bit DAC and ADC
modules an operational range of ±4 V and ±20 mA with a resolution of 2.4 mV

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is achieved. Though not compared to commercial devices, the data presented
in this paper looks very clean.Though not compared to commercial devices,
the data presented in ref. [9] exhibits very little noise. This might essentially
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result from the authors effort in removing ripple from the voltage supply rails
by including low-dropout voltage regulators in the circuit.
In 2019, the ABE-Stat — a wireless potentiostat based on the ESP8266 mi-
75 crocontroller — was developed by Jenkins et.al. Their device utilizes a 16-bit
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DAC and a 24-bit ADC and is capable of performing CA, CV and fundamen-
tal electrochemical impedance spectroscopy (EIS) measurements. The perfor-
mance of the potentiostat shows a very good agreement with data acquired with
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commercial devices. However, the circuit is already rather complex and with
80 approximately 99 €1 for material costs at least five times as expensive as the
Arduino based devices.
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In 2020, a six-channel potentiostat for monitoring the glucose concentration

during fermentation processes was published in ref. [10]. The device is based on
an ATmega 2560 microcontroller in combination with a 16-bit DAC (AD5752)
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1 Original literature reports the values in US-dollar. These have been converted to Euro ac-
cording to the mean exchange rate of the year 2022 (1.053 $/€) to achieve a better comparison
among different references.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
 ed
85 and a 16-bit ADC (AD7656). The performance is compared to a commercially

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available PalmSens3 potentiostat and shows a very good agreement for CV.
Furthermore, the authors provide a LabView based GUI for interfacing with
the device. A second potentiostatic circuit, which was proposed in 2020 can
be found in ref. [11]. Aiming to minimize the size of the circuit to fit onto
90 a micropipett for on-site electrochemical characterizations, the authors utilize

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an Arduino Nano, a 12-bit DAC (MCP4921) and a 12-bit ADC (MCP3202).
Controlling the device is realized via smartphone over bluetooth. Two additional
potentiostat projects reported in the same year can be found in refs. [12, 13],

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where [12] is formally identical with the design of Meloni, apart from using a
95 Node MCU ESP32 microcontroller instead of an Arduino Uno and ref. [13], as

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a two electrode device, is not too practical.
In 2021, a series of home-built potentiostats have been published [14–20]
among which, regarding the hardware, the MYSTAT project from Irving [18]
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is probably the most advanced DIY potentiostat to date. Using a PIC16F1459
100 microcontroller, a 20-bit DAC (DAC1220) and a 22-bit ADC (MCP3550-60)
and implementing four current ranges, the device covers remarkable ±200 mA
at ±12 V and is, regarding the operational range, comparable with commercial
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potentiostats. Furthermore, it can be operated as either a potentiostat or a

galvanostat. In this context it is, however, worth to note that soleyly the Texas
105 Instruments DAC1220 costs as much as the entire potentiostat of ref. [5] and
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that the 15SPS conversion rate of the 22-bit ADC is very slow. The latter
drawback becomes limiting for experiments using higher potential sweep rates.
Consequently, the device might be optimized by using an ADC with a lower
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resolution and a higher sampling speed (e.g. the ADS1115 or ADS1015).

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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
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110 Apart from the potentiostat/galvanostat function of the MYSTAT, the devive

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device presented by Matsubara [19] features the additional capability of mea-
suring electrochemical impedance spectroscopy (EIS). At a cost of 410 €1 this
open source device can be thus a powerful addition to the laboratory. The de-
vice presented in ref. [17] can be considered as an imporvedimproved version
115 of the design by Meloni [5]. Using an Arduino Mega in combination with an

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external 12-bit DAC (MCP4725) and an additional 12-bit ADC (ADS1015), the
potentiostat avoids the drawbacks of combining the 8-bit PWM of the Arduino
with an RC low-pfoot ass filter. Regarding the circuit, the operational ranges

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are limited to ±5 V and ±200 µA.
120 Recently, two different potentiostat projects have been presented. The ACE-

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stat [21] is based on the ADuCM355-microchip, specifically designed for chem-
ical sensing purposes. Implementing CA, CV and EIS, the emphasis of this
project is to unlock the capabilities of recent integrated circuit (IC) poten-
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tiostats such as the EMstat-Pico and to allow for miniaturization of potentio-
125 stat projects. The PassStat [22] is basically an assembly of four different open-
source potentiostats for computer or smartphone controlled measurements. Im-
plementing the Teensy 3.6 USB microcontroller or the Analog Discovery 2 USB
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oscilloscope, the devices’ costs (and capabilities) range from 10 € to 300 €.

Interfacing with the potentiostats is performed with either Android Studio, a
130 combined Android/Python software or, in case of the USB oscilloscope solution,
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via Waveforms from Digilent.

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1 Original literature reports the values in US-dollar. These have been converted to Euro ac-
cording to the mean exchange rate of the year 2022 (1.053 $/€) to achieve a better comparison
among different references.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
 ed
1.1. Novelty of the Recent Work

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Summarizing the aforementioned publications,and consulting table 1 it is
seen that none of the projects combines the neatprovides an integration of the
135 hardware with a software tool specifically designed for subsequent analysis of
voltammetric data electroanalytical purposes. Solving this demand is hence the
emphasis of the present paper. Herein, we propose a potentiostat — the Po-

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lArStat —ic circuit which is designed as an open-source PCB shield for the
Arduino Uno which is interfaced through the live-graphing, Python based, GUI
140 of our open-source software Polarographica [23]. In this manner, we provide a

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powerfulstandalone tool for the acquisition, simulation and fitting of voltammet-
ric data is provided., suitable for educational and scientific purposes. The hard-

145
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ware is inspired by and builds upon the work of Meloni [5] and Farhan [17] and
is designed as an open-source PCB shield for the Arduino Uno. The firmware
for our potentiostatthe PolArStat is written in C++ and contains pre-built
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functions for CV, CA and a calibration routine. Equiped with an external 12-
bit DAC (MCP4725) and a 16-bit ADC (ADS1115), the potentiostatPolArStat
can operate at ±3.3 V and ±13.75 mA at a full-scale resolution of ≈ 1.6 mV
and ≈1 µA. In this manner,This results in an excellent agreement of electro-
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150 chemical data acquired with PolArStat and a commercial potentiostat solution.
from five of our in-house built potentiostats with a commercial Gamry Ref. 620
is achieved. The firmware for our potentiostat is written in C++ and contains
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pre-built functions for CV, CA and a calibration. Subsequently to uploading the

firmware via the Arduino IDE to the ATmega328P, the device can be interfaced
155 in a live-graphing Python based GUI which is implemented in our open-source
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software Polarographica [23]. In this manner, we provide a powerful tool for the
acquisition, simulation and fitting of voltammetric data, suitable for educational
and scientific purposes.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
 ed
Table 1: Overview on different DIY potentiostat projects of the last decade. It can be seen

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that non of the projects provides the potentiostat with a software for analysis of voltammetric
data such as CV or CA.

E-range I-range bit-ADC/DAC Cost GUI Ana.-softw. Ref.

±0.99 V ±50 µA N/A 80 € yes no [2]

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±2.5 V ±0.5 mA N/A 50 € no no [24]
±0.5 V ±0.5 µA 16/16 N/A yes no [25]
±1.5 V N/A 24/16 120 € yes no [3]

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±2.5 V ±25 mA 10/10 N/A no no [4]
±2.5 V ±0.2 mA 10/8 30 € no no [5]
±0.6 V
±2.5 V
±4 V
±60 µA
±10 mA
±20 mA
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10/8
12/12
N/A
40 €
100 €
no
yes
no
no
no
no
[6]
[7]
[9]
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±1 V ±1 mA 10/8 N/A no no [8]
±1.65 V ±10 mA 24/16 100 € yes no [26]
±5 V ±50 mA 16/16 N/A yes no [10]
±0.5 V −50 to +30 µA 10/8 60 € yes no [12]
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±1.65 V ±10 µA 12/12 N/A yes no [11]

±1.5 V ±15 µA 16/12 55 € yes no [13]
−1 to +2 V ±1 mA 12/8 N/A yes no [14]
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±1.5 V ±10 mA 16/12 50 € yes no [15]

±4 V ±5 mA 16/12 70 € yes no [16]
±5 V ±0.2 mA 12/12 N/A yes no [17]
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±12 V ±200 mA 22/20 220 € yes no [18]

±12 V ±100 mA 14/x 375 € yes no [19]
±2 V ±0.2 mA 10/8 30 € no no [20]
60 €
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±3.1 V ±3 mA 18/12 yes no [21]

±2.4 V flex. 12/12 39-300 € yes no [22]
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
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2. Circuit Design

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160 The potentiostatic circuit developed in this project is depicted in figure 1.
It involves 8 operational amplifiers, 15 resistors, external integrated circuit (IC)
DAC and ADC chips, a cell-switching Reed-relay, a protective zener diode and
a cell on/off LED. The specifications and costs of these components are sum-
marized in table 2.

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165 Apart from them, the circuit does only require an Arduino Uno and a sym-
metrical dual-rail power supply (which can be composed of two 9 V batteries2
or salvaged from an old PC) to be a fully functional potentiostat.

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2 Considering the battery-based solution with a capacity of about 260 mAh per 9 V block

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and the measured quiescent current of 3.5 mA, the power supply lasts for approximately 74
hours.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
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Figure 1: Potentiostatic circuit developed in this work. All amplifiers are LM324N. Remaining
components of the circuit are specified in table 2.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
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Table 2: Pricing (october 2022) and specifications of the individual components of the PolAr-

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Stat bought/ordered from a) RS components, b) amazon, c) mouser electronics d) JLCPCB

Component Label Specification Quant.×price

Resistance I) R1–R6, R9–R13 1 kΩ±1%, a) 12×0.05 €
Resistance II) R7, R8, R15 5.6 kΩ±1%, a) 2×0.07 €
1×0.07 €

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Resistance III) R14 120 Ω±1%, a)
Amplifier O1, O2 LM324N, a) 2×0.36 €
DAC 12-bit MCP4725 MCP4725, b) 1×5.50 €
ADC 16-bit ADS1115 ADS1115 b) 1×3.10 €

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Z–diode, 3.3 V D1 1N4728A a) 1×0.10 €
5V LED green LED1 TLCPG5100 c) 1×0.14 €
Reed-relay
PCB shield
K1
—
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Custom, d)
1×2.10 €
1×1.50 €
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Arduino-Uno — — b) 1×21.99 €
Alligator clips — — b) 3×0.14 €
Total 36.38 €
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2.1. Building Blocks of the Circuit

The usual textbook representation of a potentiostat involves blocks E), D)
170 and F) of the circuit depicted in figure 1. For discussing this feedback system, as
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well as the remaining components, a fundamental understanding of operational

amplifiers is required.
An operational amplifier is basically an active electronic component which
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is used to magnify minor potential differences between its two high impedance
175 input terminals at a low impedance output. Generally, these devices output
whatever voltage (within the capabilities of the power supply) required to com-
pensate the potential difference between the input terminals. This features that
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operational amplifiers can be connected in certain configurations of which I)

buffering, II) inflecting and III) summing potentials are important for building
180 a potentiostat.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4401435
 ed
Regarding figure 1 it can be seen that blocks B), D) and H) are functionally

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identical. By tying back the output to the inverting input (negative) termi-
nal, the operational amplifier will output the same potential w.r.t the circuit´s
ground as connected to the high-impedance path of the non-inverting (positive)
185 input. Consequently, these amlifiers are used for an almost current free buffer-
ing of the input signals from A) the digital to analog converter, D) the reference

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electrode and H) the signal obtained from block G). Especially regarding block
D), this represents the high impedance path of the reference electrode required
for a potentiostat to function.

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190 Block A) in figure 1 is configured as an inverting operational amplifier which
is used to create a negative voltage rail, symmetrical to the positive reference

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voltage of 3.3 V. By connecting the non-inverting input of this amplifier to the
circuits ground this amplifier will output whatever voltage required to drive the
inverting input to zero (the concept of a virtual ground). By using a symmetrical
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195 voltage divider consisting of R1 = R2 = 1 kΩ, this can only be achieved, if the
output potential equals the negative of the input potential — thus −3.3 V. By
exploiting this configuration we a) avoid the use of an additional linear voltage
regulator like in the circuit proposed in ref [5], b) provide a negative voltage
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rail which is always symmetrical to the positive reference voltage and c) do not
200 leave any terminal of the two LM324N packages unused.
Block F) in figure 1 is used as a current-to-voltage converter. By connecting
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its non-inverting input to the circuits ground, the lead of the working electrode
will be kept at virtual ground. According to Ohms law, the potential at the
output block F) has to be adjusted to Eout,F = −I ·R14 for shunting any current
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205 across R14. This potential is then fed into block G) — a summing–inverting
amplifier — being functionally identical with block C).
The configuration of a summing–inverting amplifier is based on the same
voltage-divider principle as was used in block A). By grounding the non-inverting
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input terminal, the inverting input is kept at virtual ground. Using block C)
as example, this entails the current flowing through resistors R3, R4 and R5
towards the amplifier has to be shunted across resistor R6, since the inverting
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 ed
input has an ideally infinite input impedance. Noting that R3 = R4 = R5 =

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R6 = 1 kΩ this results in
 
Eout,B Eout,A
Eout,C = −1 kΩ · + = − [2 Eout,B + Eout,A ] , (1)
500 Ω 1 kΩ
which allows for a weighted summation of the negative reference voltage and
the inputs from Block B) or Block F), respectively.

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2.2. Working Principle of the Potentiostatic Circuit
210 The potentiostatic circuit uses a 3.3 V architecture, supplied by the re-
spective reference voltage of the Arduino Uno. Consequently, the MCP4725,

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as a 12-bit DAC, can output 4096 different potential values at a stepsize of
3300 mV /212 = 0.81 mV. TheseThis variable input signal is buffered in block

215
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B) and, together with the negative reference voltage generated in block A),
fed into the summing–inverting amplifier of block C). The input potentials are
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monitored at the output of block B) by connecting it to pin 3 of the ADS1115
ADC-chip. The outputs of block C), depending on the voltage provided by the
DAC, are displayed in table 3. It can be seen that the full potential span is
6.6 V which corresponds to a full-scale writing resolution of about 1.6 mV.
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Table 3: Input and output voltages of blocks A), B) and C) of figure 1 depending on the
bit-index (IDX) of the DAC.
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In A) Out A) IDX-MCP4725 In B) Out B) Out C)

3.3 V -3.3 V 0 0V 0V 3.3 V
3.3 V -3.3 V 2047 1.65 V 1.65 V 0V
3.3 V -3.3 V 4095 3.3 V 3.3 V -3.3 V
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220 Since R7 = R8, the output of block C) is symmetrically summed with the
buffered potential of the reference electrode in block E). Note that this amplifier
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is not in an open loop configuration (if the cell switch K1 is conductive) — the
feedback path is provided through the connection along the reference electrode
and block D). Since the inverting input of the amplifier in block E) is held at
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 ed
225 virtual ground, this component will source or sink whatever current along the

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path between counter electrode and working electrode, to drive the potential at
the reference electrode (which is buffered in block D) ) to be the negative of
the input voltage. Since the working electrode is kept at virtual ground, this
introduces the desired behaviour, that the WE is always at the input potential
230 w.r.t. the RE, whereas the CE imposes whatever current required to do so. This

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current is converted into a voltage in block F) by shunting it across resistor R14.
Since currents can be positive or negative (depending on the WE being the sink
or source), these voltages can be positive or negative either. To generate positive

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potentials only, the output of block F) is passed through the summing–inverting
235 amplifier in block G). Considering that R14 = 120 Ω, this gives the following
current ranges and resolutions.
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Table 4: Input and output voltages of blocks F), G) and H) of figure 1, as well as the bit-index
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of the ADS1115-ADC, depending on the current flowing across the CE-WE path.

ICE−WE Out F) Out G) Out H) IDX ADS1115)

13.75 mA -1.65 V 3.3 V 3.3 V 26400
0 mA 0V 1.65 V 1.65 V 13200
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-13.75 mA 1.65 V 0V 0V 0
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Regarding table 4, the maximum absolute current is 13.75 mA. This is a

result of using R14 = 120 Ω in the current to voltage converter of block F in
combiation with a 3.3 V zener diode (D1) for protection of the circuit. In prin-
240 ciple, the LM324N could source and sink a continuous current up to ±20 mA.
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However, at absolute currents larger than 13.75 mA, D1 will shunt the output
and clipping of the measured signal will occur. The bit-indices given in table 4
result from the fact that the ADS1115 (as a 16-bit ADC) achieves an effective
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15-bit resolution (so 215 = 32768 points) in single-ended mode. Setting its
245 internal programmable gain amplifier (PGA) to the range of 4.096 V (closest to
the 3.3 V architecture used in this work) 26400 indices can be used effectively.
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Hence, a resolution of 26400 discrete points along the range of ±13.75 mA is
achieved which corresponds to a resolution of 1.04 µA and is sufficient for a

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multitude of experimentally relevant scenarios.

250 3. Hardware Design

Designing the potentiostat as a printed circuit board (PCB) fitting an Ar-

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duino UNO R3 as a shield was done by using the software tool KiCAD. Figure 2
depicts the a) frontside, b) backside, c) CAD model and d) photograph of the
assembled device. Respective Gerber-files for ordering the PCB-shield from an

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255 external manufacturer can be found in the supporting information or at GitHub
along with our open-source software Polarographica. Providing the components

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listed in table 2 are accessible, assembling the potentiostat takes approximately
40 minutes. A detailed guide on how to assemble the PolArStat can be found
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in the supporting information.
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Figure 2: Panel a) frontside, b) backside and c) CAD model of the PCB shield for the
potentiostatic circuit developed in this work. Panel d) photograph of the assembled device.
ot

260 4. Software Development

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The software required for controlling the potentiostat is divided into I) a

firmware script which is uploaded to the microcontroller for receiving commands
from and sending data to the computer and II) a software script which is running
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on the computer for sending commands and receiving data.

265 The firmware for the device is written in C++ using the Arduino IDE. It
can be downloaded as open-source code from our GitHub project Polarographica
ep

and is attached as supplementary file as well.

The software for controlling the potentiostat is a Python script with a graph-
ical user interface. The communication is facilitated over USB connection using
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 ed
270 serial interfacing accessible through the pySerial module. Implemented in our

iew
open-source electroanalytical software Polarographica users are provided with a
powerful platform for conducting voltammetric experiments at an operational
convenience similar to commercial potentiostats. As an example, figure 3 shows
the cyclic-voltammetry function in our software.
275 Subsequently to choosing a serial port (in case multiple PolArStats are con-

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nected to the computer) and starting the serial connection, CV can be measured.
A similarly straighforward GUI is accessible for chronoamperometry as well as
for a calibration of the device.

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Figure 3: Graphical user interface (GUI) for measuring cyclic voltammetry with the PolArStat.
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 ed
5. Experimental Benchmarking

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280 Validating the experimental performance of the potentiostat is performed in
a two-step procedure. First, a 1 kΩ precision resistor (±1%) is used as a dummy
in a linear-sweep-voltammetry (LSV) experiment spanning the full scale of po-
tentials (i.e. ±3.3 V). For this purpose, the device was set up in a two electrode
configuration (i.e. in the connection RE/CE—WE). The result of this checkup

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285 is depicted in figure 4.

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Figure 4: Linear-sweep-voltammetry of a 1 kΩ precision resistor (±1%) acquired with a PolAr-

Stat (black dotted line) as well as a simulation of an Ohmic resistor of exactly 1 kΩ (red line).
The grey curve, scaling on the secondary ordinate, depicts the residuals between measurement
tn

and simulation. It can be seen that the absolute error isless than 3 µA at any potential. In a
linear fitting a resistance of 999.8 Ω was found, which is in the range of error tolerance of the
precision resistor.
rin

In another experiment, the performance of the PolArStat is thoroughly val-

idated in a true electrochemical system by measuring cyclic voltammetry and
chronoamperometry for five different devices and by comparing the results with
ep

a commercial Gamry Ref. 620. As reference system, the electrochemical redox

290 reaction of ferro/ferricyanide was studied at a 7 mm glassy carbon disc elec-
trode. Electrolyte solutions were 1 M NaCl (Sigma Aldrich, BioXtra > 99.5%)
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 ed
containing 50 mM analytical grade K4 [Fe(CN)6 ] (Merck). During the experi-

iew
ments, an Ag/AgCl electrode (Sigma Aldrich, Z113085, sat. NaCl) was used as
reference (RE) and a platinum wire as counter electrode. Before each individual
295 measurement, the working electrode was polished with alumina paste (MicroP-
olish, 0.3 µm, Buehler) and thoroughly rinsed with ultrapure water (MilliPore,
18.2 MΩcm). Figure 5 shows a) 30 chronoamperometry measurements and b)

ev
30 cyclic voltammetry measurements (five for each PolArStat (grey traces) and
five for the Gamry Ref.620 (red traces) ) to the conditions given in the cap-
300 tion. It can be seen that an excellent agreement between the acquired data is

r
achieved.
To investigate the performance of our device at different potential sweep-

305
er
rates, a Randles-Ševčı́k experiment has been conducted for five different PolAr-
Stat and a the commercial Gamry Ref. 620. In this experiment, only one CV
has been acquired per device and sweep-rate. The data is shown in figure 6,
pe
where experimental parameters are given in the caption. It can be seen that
also at larger potential sweep rates an excellent agreement of the data acquired
with the PolArStat and the commercial device is achieved.
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 ed
iew
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Figure 5: Panel a): Chronoamperometry measurements stepping the potential from -0.05 V

er
vs. RE to 0.55 V vs. RE after a conditioning period of 10 s. Panel b) Cyclic voltammetry
measurements at 20 mV/s between -0.05 V vs. RE to 0.55 V vs. RE after a conditioning
at -0.05 V vs. RE for 5 s. Experiments were conducted in 1 M NaCl, containing 50 mM
ferrocyanide as analyte. Electrodes were WE: mirror-polished glassy carbon, d = 7mm, CE:
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Pt-wire, RE: Ag/AgCl sat. NaCl. The initial scanning direction was positive.
ot
tn
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Figure 6: Randles-Ševčı́k experiment at sweep-rates of 100, 80, 60, 40 and 20 mV/s for five
ep

PolArStat (grey) and one Gamry Ref.620 potentiostat. Plotting the peak current w.r.t. the
potential sweep rate yields straight lines in all cases. Experiments were conducted in the same
system as for figure 5.
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 ed
5.1. CV-Analysis with Polarographica

iew
310 Subsequently to performing voltammetric experiments with the PolArStat,
the acquired data can be analyzed directly in the environment of Polarograph-
ica [23] which is one of the major advantages of this project. Using the CV-
fitting function3 for planar semi-infinite diffusion on one of the CV-datasets in
figure 5, a good agreement between simulated and experimentally acquired data

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315 is achieved (cf. 8).

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Figure 7: CV data acquired for the electrochemical oxidation of ferrocyanide with a PolArStat
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(black trace) fitted with the planar semi-infinite diffusion model in Polarographica (red
trace). Minor discrepancies between experiment and simulation arise from the fact that the
computation in Polarographica does not account for Ohmic drop effects in the electrolyte and
the PolArStat does not offer an operando resistance correction like positive feedback (PF).
rin

3 For details on the CV-fitting process with Polarographica see[27].

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 ed
iew
r ev
er
Figure 8: CV data acquired for the electrochemical oxidation of ferrocyanide with a PolAr-
Stat (black trace) fitted with the planar semi-infinite diffusion model in Polarographica (red
pe
trace). Minor discrepancies between experiment and simulation arise from the fact that the
computation in Polarographica does not account for Ohmic drop effects in the electrolyte and
the PolArStat does not offer an operando resistance correction like positive feedback (PF).

The estimated diffusion coefficient for ferrocyanide of D = 7.5 cm2 /s

ot

D = 7.2 cm2 /s is also in line with the literature value [28] of D = 7.26 cm2 /s
which underlines that the PolArStat performes accurately at a quantitaive scale.
tn

However — and even more important — it demonstrates that the combination

320 of the PolArStat and Polarographica provides a powerful open-souce solution
for performing electroanalytical experiments and analyzing voltammetric data.
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6. Summary and Conclusions

In this work a potentiostatic circuit was developed in the form of a printed

circuit board fitting on top of a classical Arduino UNO in the form of a shield.
ep

325 Using only a very few standard operational ampliefiers, resistors, an external
digital-to-analog and analog-to-digital converter the material costs of the project
are less than 15 €. An open-source firmware for receiving and sending data from
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 ed
and to the computer, for performing cyclic voltammetry (CV) and chronoam-

iew
perometry (CA) or for calibrating the device is provided as a classical Arduino
330 sketch which can be readily uploaded to the microcontroller, using the Arduino
integrated development environment (IDE). A graphical user interface with a
live-updating console is provided as a Python script. This allows to perform CV
and CA measurements with our device similar to commercial potentiostats.This

ev
allows the instrument to perform CV and CA measurements in a manner similar
335 to commercially available potentiostats. Finally, this function is implemented in
our open-source electroanalytical tool Polarographica which provides users with

r
a standalone software for measuring, simulating and evaluating voltammetric
experiments without the need of commercial software or hardware.

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 ed
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