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Exploring the coating of 3D-printed insulating

Cite this: DOI: 10.1039/d2ay00803c
substrates with conductive composites: a simple,
cheap and versatile strategy to prepare customized
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high-performance electrochemical sensors

Fabiano Mendonça de Oliveira,a Maria Zizi Martins Mendonça, a Natália Canhete de
Moraes,b Jacqueline Marques Petroni,b Matheus Meneguel Neves,b Edmar Isaias de
Melo,a Bruno Gabriel Lucca b and Rodrigo Amorim Bezerra da Silva *a

Received 17th May 2022
Accepted 29th July 2022
DOI: 10.1039/d2ay00803c
rsc.li/methods
The development of 3D-printed electrochemical sensors by fused deposition modeling (FDM) has been
increasing exponentially in the last five years. In this context, commercial conductive filaments
composed of a blend of carbon particles (e.g., graphene or carbon black (CB)) and insulating
thermoplastic polymers (e.g., polylactic acid (PLA) or acrylonitrile butadiene styrene (ABS)) have been
widely used for electrode fabrication. However, such materials may be expensive and the electrodes
when used “as-printed” exhibit poor electrochemical performance as a function of the low content of
conductive particles in the composition (
10 to 20 wt%), which requires one or more post-treatment
steps (e.g. polishing, chemical, electrochemical, and photochemical) to reach good electrochemical
performance. In this technical note a less used approach to produce “ready-to-use” electrochemical
platforms based on 3D printing is explored, which consists of the coating of 3D-printed insulating
substrates with homemade conductive composites. To demonstrate the potentiality of this alternative
protocol, 3D-printed ABS insulating substrates at two geometries were coated in a highly loaded
graphite (55 wt%) homemade composite (G–ABS) and evaluated for the detection of the ferri/
ferrocyanide redox probe and model analytes in stationary and hydrodynamic 3D-printed systems (nitrite
in micro-flow injection analysis/mFIA and paracetamol in batch injection analysis/BIA, respectively). The
analytical parameters acquired with the coated electrodes were comparable to those obtained using
conventional electrodes (glassy carbon, boron-doped diamond and carbon screen-printed) and 3D-
printed sensors fabricated with commercial filaments. Moreover, the inclusion of carbon black in the
fluid conductive composite was demonstrated as a perspective to obtain modified coated 3D-printed
surfaces easily for the first time. This alternative “do it yourself” strategy is promising for the large-scale
production of very cheap (US$ 0.08) and high-performance electrodes based on FDM 3D printing.
Moreover, this approach dispenses the acquisition of commercial conductive filaments and the laborious
development of homemade filaments.

due to affordable costs, easy access to open source soware, fast

1 Introduction
3D printing or additive manufacturing (AM) is a versatile and
rapid technology that has been growing exponentially in the last
few years, enabling the prototyping of things in a myriad of
shapes and materials, useful in numerous areas including
engineering, aerospace, medicine, industry and science.
However, fused deposition modeling (FDM) or fused lament
fabrication (FFF) has become the more popular AM technology,
a
Chemistry Institute, Federal University of Uberlândia, Monte Carmelo, MG,
38500-000, Brazil. E-mail: rabsilva@ufu.br; Fax: +55-34-3239-4208; Tel: +55-34-
3810-1099
b
Chemistry Institute, Federal University of Mato Grosso Do Sul, Campo Grande, MS,
79074-460, Brazil
printing speed, and large-scale production.1 In a typical FDM
operation, a semi-molten thermoplastic polymer is reproduc-
ibly extruded on the printing bed layer-by-layer until the crea-
tion of the nal object, according to the standard tessellation
model (.STL le).2
Electroanalytical chemistry has greatly beneted from the
advantages of AM, allowing the development of new and
customized electrochemical cells, accessories, electrodes and
sensors, as summarized in recent review papers.3–7 Considering
the fabrication of sensors, composite materials containing
a blend of conductive material (usually sp2 carbon) and an
insulating polymeric matrix (e.g., polylactic acid, PLA and
acrylonitrile butadiene styrene, ABS) have been used in most

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studies, with the prevalence of two commercially available
laments: Blackmagic® (graphene–PLA) and conductive Proto-
pasta® (carbon black–PLA).3,6 Despite the successful use of
these materials for electrode fabrication, the costs of doped
laments are considerably higher than those of the respective
insulating laments (Blackmagic® z US$ 1000 per kg; Proto-
pasta® z US$ 100 per kg; pure PLA z US$ 20 per kg). Moreover,
the electron-transfer kinetics of these materials in the native
form (“as printed”) is low, as a function of the low ratio of
conductive particles in the composite (e.g., Blackmagic®

8 wt% (ref. 3)). Thus, the excess insulating polymer must be
removed from the surface (enhancing the availability of
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conductive particles) to improve the electrochemical perfor-
mance. For this, some surface post-treatment strategies (alone
or combined) have been reported in the literature through
mechanical polishing,8,9 solvent immersion,10–12 electro-
chemical treatments,10,12–20 photochemical treatment,19
carbonization,21 and reagent-less laser treatment.22
Aiming for cheaper and “ready-to-use” laments, few
research groups have been developing bespoke laments with
higher carbon contents than the commercial ones.3,23–25 For
example, Foster et al.25 developed a composite lament of
nanographite and polylactic acid (NG–PLA), in which the
percentage of NG was varied in the range of 1 to 40 wt%. From
this investigation, the optimized material presented 25 wt% of
NG. However, the development of a new conductive lament is
not a simple task, since an appropriate compromise between
conductivity (to reach a minimal percolation threshold), print-
ability,1 homogeneity and exibility should be achieved. More-
over, this production requires an extruder machine for the
conversion of the polymeric blend into a lament shape and the
optimization of all steps (e.g., ratio among conductive particles,
polymer and solvent to generate the composite powder/pellet
and melting temperature and stirring rate of the extruder24) is
typically a time-consuming and expensive process.26
Another alternative and less explored approach for the
fabrication of sensors based on FDM additive manufacturing
consists of the coating of insulating 3D-printed plastic surfaces
with conductive materials.27–29 Exploring this concept, our
research group recently proposed a simple immersion of an
insulating 3D-printed substrate in a lab-made uid conductive
composite containing a high fraction of conductive particles
(55 wt% of graphite) followed by solvent evaporation.29 Thus,
the electrode does not require complex surface post-treatment
protocols (only polishing), since the surface presents a high
fraction of conductive material. Moreover, this method does not
require the acquisition of commercial conductive laments
(higher-priced than insulating) or extruder machines.
Thus, in this technical note, we aim to demonstrate the great
potential of use and the promising versatility of this approach
(coating of insulator substrates with conductive materials). The
sensors fabricated according to this alternative protocol were
explored for the detection of model analytes in some 3D-printed
electrochemical systems such as stationary cells and hydrody-
namic systems, such as passive microow injection analysis
(mFIA) using a microuidic thread-based electroanalytical
device (mTED) and batch injection analysis (BIA). The analytical
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parameters were compared with those obtained using
commercial electrodes (glassy carbon electrode (GCE), carbon
screen-printed electrode (C-SPE) and boron-doped diamond
electrode (BDDE)) and 3D-printed electrodes produced using
a commercial lament.
2 Materials and methods
2.1. Chemicals, electrodes and solutions
Potassium hexacyanoferrate(II), potassium hexacyanoferrate(III)
and sodium nitrite were ordered from Neon® (Suzano, SP,
Brazil); acetic acid was purchased from Vetec® (Duque de
Caxias, RJ, Brazil); boric acid and acetone were supplied by
Dinâmica (Diadema, SP, Brazil); orthophosphoric acid was ob-
tained from Acros Organics® (Geel, Belgium); graphite powder
(particles < 20 mm) and paracetamol were acquired from Sigma-
Aldrich® (Saint Louis, MO, USA); carbon black powder (Mon-
arch® 430) was acquired from Cabot (São Paulo, SP, Brazil);
acrylonitrile butadiene styrene (ABS) lament (1.75 mm diam-
eter) was provided by 3DFila® (Belo Horizonte, MG, Brazil);
a conductive CB–PLA lament (1.75 mm diameter) was
purchased from Protopasta® (Vancouver, WA, USA); food grade
silicone rubber and its curing agent were supplied by Redelease
(São Paulo, SP, Brazil); UV 405 nm photosensitive resin for
stereolithography/digital light processing (DLP/SLA) 3D printer
was provided by Anycubic® (Shenzhen, Guangdong, China);
a C-SPE was acquired from PalmSens® BV (Houten, The Neth-
erlands) and BDDE with a doping level of 8000 ppm was
acquired from Neocoat® (La Chaux-de-Fonds, Switzerland);
1500 grit sandpaper, M5 screws and y nuts, hydrophilic cotton
bandage gauze and double-sided tape were purchased at local
stores. All the aqueous solutions were prepared using puried
water (resistivity $ 18.2 MU cm) obtained from a Permution
RO0310 reverse osmosis water purier system (Curitiba, PR,
Brazil). Stock solutions of the analytes, buffers and electrolytes
were prepared weekly and stored in the refrigerator. The solu-
tions of the analytes were prepared daily by dilution of the stock
solutions.
2.2. Instrumentation
The electrochemical experiments were performed using an
Autolab PGSTAT128N potentiostat/galvanostat (Ecochemie,
Utrecht, Netherlands) connected to a computer (Metrohm
Autolab® Nova 2.1 soware) and a pocketSTAT potentiostat/
galvanostat/EIS (Ivium®, Eindhoven, Netherlands) controlled
by IviumSo™ soware. The 3D-printed parts were fabricated
using a Creality Ender 3 FDM 3D printer (Creality, Shenzhen,
China) equipped with a 0.4 mm diameter brass extruder nozzle,
a 3D pen from Kuman (Shenzhen, China) and an Anycubic
Photon SLA/DLP 3D printer (Shenzhen, Guangdong, China).
2.3. Fabrication and activation of the G–ABS/ABS electrodes
The graphite–acrylonitrile butadiene styrene (G–ABS) conduc-
tive thermoplastic composite and the electrodes obtained aer
the coating of a 3D-printed ABS substrate (G–ABS/ABS) were
produced according to a protocol recently reported by our
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Fig. 1 3D-printed ABS substrates (strip and round shaped) before (A)
and after (B) coating with the G–ABS composite.
Fig. 2 Images of the evaluated systems coupled to the G–ABS/ABS electrode: (A) 3D-SSE, (B) 3D-MSEC, (C) 3D-mTED and (D) 3D-BIA.
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group.29 Briey, graphite powder and virgin ABS were blended at
a 55 : 45 ratio (w/w) and solubilized using acetone as the
solvent. Aer this, the composite was homogenized by hand-
mixing until the obtention of a viscous and homogeneous ink
(
10 min). Then, the 3D-printed ABS substrates (strip shaped
and round shaped) were quickly immersed (
3 s) in the G–ABS
composite to be coated by the conductive material. The elec-
trodes were then le to dry (evaporation of the solvent) for 72 h.
Using this protocol, the thickness of the conductive layer is 178
(27 mm)29 and the weight of the coated material depends on
the electrode shape (around 40 mg for strip and 50 mg for
round). Aer drying, the electrodes were activated by polishing
with a piece of 1500 grit sandpaper in the presence of ultrapure
water for 30 s, to obtain a homogeneous surface without
scratches. Fig. 1 shows the images of the 3D-printed substrates
before and aer coating with the conductive composite. Lastly,
the parts containing the conductive surface (electrodes) were
cut with a scissor and assembled in the 3D-printed devices for
stationary and hydrodynamic measurements (Sections 2.4 and
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2.5, respectively). Like 3D-printed electrodes, these G–ABS/ABS

electrodes may also be produced on a large scale, since
multiple substrates (printed at once) may be simultaneously
dipped into the uid conductive composite.

2.4. Fabrication and assembly of the stationary

electrochemical cells
2.4.1 3D-printed cell for strip shaped electrodes (3D-SSE).29
The cell covers (bottom and top) and the molds for the silicone
parts were printed in 405 nm photosensitive resin using an SLA/
DLP 3D printer. Aer this, the positive molds were used to cast
the silicone parts of the cell by mixing food grade silicone
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rubber and its curing agent in a 1 : 1 ratio (w/w), degassing the

blend and curing it at 70  C for 12 h. To accommodate the three-
electrode setup, the silicone base contains three channels
(37.5 mm length  3 mm width  1.50 mm depth). The silicone
cover has a 19 mm hole that delimits the area of the electrodes
and prevent leakage in the cell. To assemble the electrochemical
cell, the parts were gathered together by sandwiching the 3D-
printed top cover, the silicone cover, the silicone base and the
3D-printed bottom cover with four M5 screws and their
respective y nuts (Fig. 2A). This cell was also used for the
measurements with the GCE.
2.4.2 3D-printed multi sensor compatible electrochemical
cell (3D-MSEC).17 This cell is composed of three 3D-printed ABS
pieces (stick, cover and solution vessel) easily self-assembled by
screwing (Fig. 2B). The cover contains two 3D-pen-printed CB–
PLA electrodes (counter electrode (CE) and pseudo-reference
electrode (PRE)), and the working electrode (WE: G–ABS/ABS,
CB–G–ABS/ABS or BDDE) is positioned between the stick and
cover, with the area delimited by a rubber o-ring. The cell
requires low electrolyte volumes (0.5–3.0 mL) and is compatible
with several planar working electrodes.
2.5. Fabrication and assembly of the hydrodynamic systems
2.5.1 3D-printed batch injection analysis (3D-BIA) cell.30
This system is composed of a BIA cell printed in ABS (volume

80 mL), an electronic pipette (Eppendorf® Multipette XStream),
Fig. 3 CV curves obtained in the absence (dashed lines) and presence
(solid lines) of 1 : 1 mmol L1 K3Fe(CN)6/K4Fe(CN)6 on different
working electrodes: BDDE (on 3D-MSEC), G–ABS/ABS and GCE (both
on 3D-SSE). Electrolyte: 0.5 mol L1 KCl. n: 50 mV s1.
a lab-made mechanical stirrer and the electrodes (Fig. 2D). The
top cover contains four orices for the assembly of the Pt wire
(CE), Ag/AgCl/KCl (RE), the mechanical stirrer and a support for
accommodation of the pipette Combitip (volume: 10–1000 mL).
This tip is concentric to the WE (G–ABS/ABS or BDDE) placed in
a hole on the bottom of the cell (wall jet mode), between
a rubber o-ring (0.2 cm2) and a steel board (electrical contact).
2.5.2 3D-printed microuidic thread-based electroanalyt-
ical device (3D-mTED).31 This mFIA system is 95 mm length 
60 mm width  122 mm height. It was printed in ABS and
contains two reservoirs, for the inlet and outlet, with a diameter
of 22 mm and a maximum volume of ca. 4 mL each. The outlet
reservoir is xed to the main platform using two M3 screws. The
assembly of the device consisted of placing four hydrophilic
cotton threads (obtained from cotton bandage gauze), which are
used as passive microow channels. These threads were

Table 1 Comparison of reversibility of the ferro/ferricyanide redox probe for 3D-printed electrodes using different commercial filaments and
surface post-treatment protocols

Conductive lament 3D-printed electrode post-treatment DEp (mV) for [Fe(CN)6]3/4 Ref.

Proto-pasta® MPa (120 s) + EAb (+1.4 V/200 s 116–297 14, 15, 17, 18 and 20
followed by 1.0 V/200 s in NaOH
0.5 mol L1)
Proto-pasta® PFc (UV/VIS light for 300 s in a Fe(II)/ 240 19
H2O2 solution) + EAb (+1.8 V for
200 s in an acetic acid solution (pH
2.1))
Proto-pasta® LTd for 50 s (CO2 laser machine) 130 22
Blackmagic® SIe (methanol, ethanol, water, 296 11
acetone, or DMF for 540 s)
Blackmagic® SIe (600 s in DMF) + EAb (2 V for 171 10
150 s in phosphate buffer solution)
G–ABS/ABS MPa for 30 s 110 This work
a b c d e
MP: mechanical polishing. EA: electrochemical activation. PF: photo/Fenton. LT: laser treatment. SI: solvent immersion.

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Fig. 4 Amperograms recorded on mTED system for triplicate injections of NO2 in ascending and descending order (25 to 200 mmol L1) using
(A) G–ABS/ABS and (B) a commercial C-SPE (Palmsens®) as the WE. Insets: respective calibration curves. Conditions: supporting electrolyte:
0.1 mol L1 BR buffer pH ¼ 4.0; PRE and CE: G–ABS/ABS; E ¼ +1.15 V vs. G–ABS/ABS; injection volume: 4.0 mL; height difference between the
inlet and outlet reservoir: 60 mm; number of cotton threads: four in parallel disposition; distance sample injection zone/detection point: 5 mm.

positioned perpendicular to the three G–ABS/ABS electrodes (or
C-SPE) and xed to the reservoirs using double-sided tape
(Fig. 2C).
3 Results and discussion
The rst electrochemical measurements were carried out using
the proposed 3D-printed electrode coated with a conductive
composite (G–ABS/ABS) and stationary cyclic voltammetry (CV)
in the presence of an equimolar mixture (1.0 mmol L1) of
potassium hexacyanoferrate(II) and hexacyanoferrate(III) in
0.5 mol L1 potassium chloride solution (supporting electro-
lyte). These measurements were also performed with commer-
cial electrodes (BDDE and GCE), and the currents of the cyclic
voltammograms were normalized by using the geometric area
(current density, j), for a better comparison of the WEs with

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Fig. 5 BIA amperometric responses after triplicate injections of paracetamol solutions (25 to 200 mmol L1) in increasing and decreasing orders
using G–ABS/ABS (A) and a BDDE (B). Conditions: supporting electrolyte: 0.1 mol L1 phosphate buffer (pH 7.2). Injection volume: 100 mL, stirring
rate: 700 rpm, dispensing rate: 100 mL s1. E ¼ +0.63 V (A) and +0.76 V (B) vs. Ag/AgCl and respective calibration plots (insets). Conditions
optimized according to ref. 16.

different geometries (Fig. 3). As shown, the current density of
the G–ABS/ABS electrode (236.0 mA cm2) was a little better
when compared to the BDDE (225.1 mA cm2) and GCE (175.4
mA cm2). The proposed G–ABS/ABS electrode showed a good
reversibility for the [Fe(CN)6]3/4 redox probe (DEp z 110 mV),
comparable to that obtained for the BDDE and GCE (DEp z
155 mV and 171 mV, respectively). Moreover, the coated elec-
trode (G–ABS/ABS) exhibited similar reversibility (or better) than
those acquired with 3D-printed sensors fabricated using the
most usual conductive commercial laments and post-treated
using different methods, which usually require more toxic or
time-consuming procedures or expensive apparatus (Table 1).
This result may be considered good, since the G–ABS/ABS
electrode uses a fast, so and simple post-treatment (only
mechanical polishing for 30 s), which enhances the exposure of
conductive particles (graphite) through the removal of excess
insulator ABS (surface becomes rougher, more porous and has
more available electroactive sites).29 It is important to empha-
size that good results were achieved with the polished coated
electrode due to the high graphite content present on the

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Table 2 Cost per electrode and analytical characteristics of 3D-printed based and commercial electrodes for the determination of nitrite ions
(NO2) and paracetamol (PA) using the evaluated 3D-printed hydrodynamic systems with amperometric detection
Analyte Platform Electrode Cost (US$)
NO2 mTED G–ABS/ABSa 0.08
NO2 mTED CB–PLAb 0.20
NO2 mTED C-SPE 3.00
PA BIA G–ABS/ABSa 0.08
PA BIA CB–PLAb 0.10
PA BIA BDDE 17.0
a
Insulating 3D-printed substrate coated with a conductive composite.
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surface (55 wt%), unlike 3D-printed electrodes, which have
smaller amounts of conductive particles in the lament (
10 to
20 wt%).
The performance of G–ABS/ABS was also evaluated for the
amperometric detection of nitrite ions in the mFIA–mTED plat-
form and paracetamol in the 3D-BIA cell. Such analyte/systems
were chosen considering previous publications using sensors
3D-printed with a commercial CB–PLA lament,18,31 to enable
a better performance comparison of the proposed G–ABS/ABS
electrode. mFIA–mTED31,32 and BIA33,34 are alternative systems
that are more portable, simpler and cheaper than ow injection
analysis (FIA).35 Both are based on the concepts of continuous
and reproducible analysis, (semi)automation and high sample
throughput. However, unlike FIA that requires complex injec-
tors, tubes and a pumping system, in mFIA–mTED the sample is
inserted (typically by using a usual micropipette) into a carrier
ow (towards the WE) generated spontaneously due to the
capillary forces of hydrophilic threads in contact with the
carrier aqueous solution. In BIA, the injection of a plug of
analyte solution (usually by using an electronic pipette) is per-
formed directly over the WE (wall jet mode) assembled in
a batch cell.33,34
Fig. 4 shows the amperograms for injections of different
concentrations of nitrite ions (25 to 200 mmol L1) on a 3D-
printed mTED platform using G–ABS/ABS and the commercial
C-SPE. The used conditions (see caption of Fig. 4) were chosen
based on an optimization reported before.31 As shown in Fig. 4,
good linear relationships between the nitrite concentration and
current density were obtained using G–ABS/ABS and C-SPE
electrodes (R2 > 0.99). The slope values of the calibration
curves (ascending and descending orders) were similar for both
carbon electrodes, suggesting the absence of memory effects
(without electrode passivation). Moreover, the G–ABS/ABS
electrode presented normalized sensitivity comparable to the
C-SPE (0.34 vs. 0.41 mA cm2/mmol L1). However, the limit of
detection (LOD) of G–ABS/ABS was ten-fold higher than that of
the C-SPE (3.25 vs. 0.30 mmol L1), due to the greatest noise of
the baseline current. The LODs were obtained by 3SDb/S, where
SD is the standard deviation of currents from the baseline (n ¼
5) and S is the slope of the calibration plot. The calculated
theoretical analytical frequency (TAF) (considering the peak
width) for the mTED platform for nitrite analysis was 30 injec-
tions per hour.
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LOD (mmol Linear range
L1) (mmol L1) Ref.
3.25 25–200 This work
2.39 8–200 31
0.30 25–200 This work
0.05 25–200 This work
0.21 1–200 18
0.04 25–200 This work
b
3D-printed using conductive laments.
Fig. 5 shows amperograms for injections of different
concentrations of paracetamol (25–200 mmol L1) on a 3D-
printed BIA system using G–ABS/ABS and a commercial BDDE
and the respective calibration curves. As shown, good linear
dependences between the current density and paracetamol
concentration were obtained using both electrodes (R2 > 0.99).
Moreover, comparing the similar slope values of ascending and
descending calibration plots obtained in each electrode, no (or
minimal) memory effects were noted on both electrode
surfaces. Finally, the normalized sensitivity obtained with G–
ABS/ABS was slightly better than that with the BDDE (0.72 vs.
0.50 mA cm2/mmol L1), with similar LODs (0.05 vs. 0.04 mmol
L1). The calculated TAF for the BIA system during paracetamol
analysis was 600 injections per hour.
Table 2 summarizes some analytical characteristics of the
evaluated 3D-printed hydrodynamic systems coupled with G–
ABS/ABS, commercial electrodes and 3D-printed electrodes
(from the literature) for determination of nitrite and para-
cetamol as well as the unitary electrode costs. The prices of the
fabricated electrodes (coated and 3D-printed) were calculated
only considering the material costs (excluding energy costs). As
can be seen, the analytical performance of the electrode
prepared through coating of a 3D-printed insulating substrate
in a uid conductive composite was comparable with those
obtained using 3D-printed sensors using a commercial
conductive lament (CB–PLA) and usual commercial electrodes
(C-SPE and BDDE). This result is exciting considering that G–
ABS/ABS has a cost considerably lower than commercial elec-
trodes (
0.5% and 3.0% of the cost of the BDDE and C-SPE,
respectively) and may be reused (non-disposable) even if pol-
ished sometimes (as seen in 3D printed electrodes). Thus, based
on what has been reported here, it is clearly demonstrated that
the G–ABS/ABS sensors may be a very interesting option for
electrochemical sensing on different types of analytical plat-
forms, providing great analytical performance with low cost and
simple manufacturing.
An interesting perspective using the coating of 3D-printed
insulating substrates with conductive composites consists of
the incorporation of modiers during composite preparation,
in order to produce modied sensors with improved perfor-
mance. To demonstrate this approach, a modied composite
was prepared by adding carbon black (CB) to the uid matrix,
using a mass proportion of 5 : 50 : 45 (CB : G : ABS). The
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Fig. 6 (A) CV curves in the absence (dashed lines) presence (solid lines) of 200 mmol L1 paracetamol and 100 mmol L1 nitrite on unmodified and
modified composites (G–ABS/ABS and CB–G–ABS/ABS, respectively) assembled in a 3D-MSEC; (B) Nyquist plots, equivalent circuit modeling
(inset 1) and CV curves in 1 : 1 mmol L1 K3Fe(CN)6/K4Fe(CN)6 and 0.1 mol L1 KCl. CV conditions: electrolyte (PA and NO2): 0.1 mol L1
phosphate buffer (pH 4); n: 50 mV s1. EIS: frequency range: 1 Hz to 50.000 Hz, amplitude: 10 mV, points per decade: 10.

electrochemical performance of the electrodes produced using
the modied and unmodied composites (CB–G–ABS/ABS and
G–ABS/ABS, respectively) was assessed by cyclic voltammetry in
the presence of paracetamol and nitrite (Fig. 6A).
As shown (Fig. 6A), the peak currents of both analytes were
better in the modied sensor than those acquired in the
unmodied sensor (1.4-fold higher for paracetamol and 2.2-fold
higher for nitrite). Moreover, a slightly better reversibility for
paracetamol (Fig. 6A) and the ferri/ferrocyanide probe (inset of
Fig. 6B) were acquired in the modied sensor. These results
may be explained by the lower resistance to charge transfer of
the modied sensor in comparison to the unmodied sensor
(RctCB–G–ABS ¼ 120 U; RctG–ABS ¼ 341 U), measured in the EIS study
(Fig. 6B). The better performance of the modied sensor may be
attributed to carbon black, which is an amorphous nanocarbon
form which exhibits better electrical conductivity and higher

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Technical Note
surface area than graphite.36 However, the investigation of the
proportion between the elements of the uid composite (CB, G
and ABS) that generates the sensor with the best electro-
chemical responses is beyond the scope of this technical note,
which demonstrates only a single modication as a perspective.
Thus, the modication of composites with other substances
(e.g. nanomaterials, biomolecules, catalysts, etc.) is a promising
way to create sensors with improved electrochemical perfor-
mance (e.g. more stable, sensitive and/or selective). Further-
more, developing a modied uid conductive composite (to
coat a 3D-printed insulating substrate) is easier, cheaper, and
faster than developing a modied conductive lament (for the
Published on 29 July 2022. Downloaded by RSC Internal on 8/24/2022 1:00:49 PM.
manufactured 3D-printed electrodes).
4 Conclusions
In this technical note a recent alternative approach for the
fabrication of 3D-printed based electrodes was explored in
different electroanalytical systems (stationary and hydrody-
namic), which consists of the spontaneous coating of insulating
3D-printed substrates with a high carbon-loaded conductive
uid composite. This strategy produces a high performance
electrode surface only aer a quick polishing procedure,
different from 3D-printed electrodes using commercial
composite laments which require additional surface post-
treatment steps (e.g., chemical, electrochemical and/or photo-
chemical) to remove the excess insulating polymer. Moreover,
this approach dispenses the development of homemade
conductive laments, which is complicated, time-consuming
and needs the acquisition of an extruder machine.
The results demonstrate that the 3D-printed based electrode
explored here (G–ABS/ABS) presents an analytical performance
comparable to usual commercial electrodes (BDDE and C-SPE)
and a 3D-printed CB–PLA electrode for the determination of
nitrite and paracetamol (coupled to 3D-printed mFIA/mTED and
BIA systems, respectively). These features, combined with the
negligible costs (US$ 0.08 per electrode) and an easy fabrication
procedure, indicate that covering an insulating 3D-printed
substrate with highly conductive composites is a promising
“do it yourself” strategy to produce 3D-printed based electrodes
for use in many electrochemical platforms. Lastly, the simple
incorporation of modiers in the uid polymeric matrix (e.g., to
improve sensitivity and/or selectivity), large-scale electrode
production and the freedom to produce materials in a variety of
shapes and sizes are some exciting possibilities to be explored.
Conflicts of interest
The authors declare that they have no known competing
nancial interests or personal relationships that could have
appeared to inuence this work.
Acknowledgements
The authors would like to thank the nancial support given by
Conselho Nacional de Desenvolvimento Cientı́co e Tec-
nológico (CNPq, processes no. 420526/2018-8 and 407581/2021-
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Analytical Methods
9), FAPEMIG (process APQ-03000-18) and Coordenação de
Aperfeiçoamento de Pessoal de Nı́vel Superior – Brasil (CAPES,
Finance Code 001).
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