ArticlePublisher preview available

3D-printed carbon black/polylactic acid electrode modified with silver particles: a powerful alternative and cost-effective sensor for nitrate sensing in real water samples

Authors:
Anderson O. Alves
Anderson O. Alves
Anderson O. Alves
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Lucas V. de Faria
Lucas V. de Faria
Lucas V. de Faria
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Natalia Caldas at Fluminense Federal University
Natalia Caldas
Amanda G. Batista
Amanda G. Batista
Amanda G. Batista
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Show all 12 authorsHide
Read publisher preview
Download citation
To read the full-text of this research, you can request a copy directly from the authors.

Abstract and Figures

Monitoring nitrate in aquatic systems is of fundamental importance since its presence at high levels can result in adverse effects on human health. Thus, in this work, manufactured carbon black (CB)/polylactic acid (PLA)-based 3D-printed electrochemical sensors modified with electrodeposited silver particles (AgPs) for nitrate analysis in real water samples. Raman and FT-IR spectra, scanning electron microscopy images, and analysis by energy-dispersive spectroscopy confirmed the presence of AgPs on the porous carbonaceous surface. The preliminary electrochemical studies showed that using the modified electrode (CB-PLA/AgPs) an incredible increase in the electrochemical response (around 16.5-fold in terms of current density) was obtained for the electroreduction of nitrate at around − 1.08 V vs. Ag|AgCl|KCl(sat.) compared to the unmodified electrode (CB-PLA). The linear sweep voltammetry technique was employed whose instrumental parameters have been carefully optimized. Under optimized conditions, a linear range between 5 and 80 mg L⁻¹ (R² > 0.99) was achieved, with a detection limit of 2.7 mg L⁻¹, which is below the maximum level permitted (50 mg L⁻¹) by the World Health Organization (WHO). Repeatability (intra-electrode, n = 8) and reproducibility (inter-electrode, n = 3) studies were performed, and RSDs < 2.1% were found, demonstrating good precision of the analysis and reproducible manufacturing process of the sensors. Moreover, the proposed sensor proved to be selective in the presence of other inorganic compounds frequently found in environmental waters. Importantly, in the recovery tests, percentage values between 91 and 117% confirmed the accuracy and reliability of the analyses. Thus, the developed strategy can be useful for nitrate sensing in real water samples in remote locations.
Figures - available from: Journal of Solid State Electrochemistry
This content is subject to copyright. Terms and conditions apply.
A preview of this full-text is provided by Springer Nature.
Learn more
Content available from Journal of Solid State Electrochemistry
This content is subject to copyright. Terms and conditions apply.
Vol.:(0123456789)
Journal of Solid State Electrochemistry (2025) 29:1217–1225
https://doi.org/10.1007/s10008-024-05919-1
ORIGINAL PAPER
3D‑printed carbon black/polylactic acid electrode modified withsilver
particles: apowerful alternative andcost‑effective sensor fornitrate
sensing inreal water samples
AndersonO.Alves1,2· LucasV.deFaria1 · NataliaM.Caldas1· AmandaG.Batista1· SuéllenF.L.doNascimento1·
BrennoE.Danho2· DiegoA.Peixoto3· EdsonNossol3· DiegoP.Rocha4· FelipeS.Semaan1· WagnerF.Pacheco1·
RafaelM.Dornellas1
Received: 7 February 2024 / Revised: 24 April 2024 / Accepted: 29 April 2024 / Published online: 13 May 2024
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2024
Abstract
Monitoring nitrate in aquatic systems is of fundamental importance since its presence at high levels can result in adverse
effects on human health. Thus, in this work, manufactured carbon black (CB)/polylactic acid (PLA)-based 3D-printed electro-
chemical sensors modified with electrodeposited silver particles (AgPs) for nitrate analysis in real water samples. Raman and
FT-IR spectra, scanning electron microscopy images, and analysis by energy-dispersive spectroscopy confirmed the presence
of AgPs on the porous carbonaceous surface. The preliminary electrochemical studies showed that using the modified elec-
trode (CB-PLA/AgPs) an incredible increase in the electrochemical response (around 16.5-fold in terms of current density)
was obtained for the electroreduction of nitrate at around − 1.08V vs. Ag|AgCl|KCl(sat.) compared to the unmodified electrode
(CB-PLA). The linear sweep voltammetry technique was employed whose instrumental parameters have been carefully
optimized. Under optimized conditions, a linear range between 5 and 80mg L−1 (R2 > 0.99) was achieved, with a detection
limit of 2.7mg L−1, which is below the maximum level permitted (50mg L−1) by the World Health Organization (WHO).
Repeatability (intra-electrode, n = 8) and reproducibility (inter-electrode, n = 3) studies were performed, and RSDs < 2.1%
were found, demonstrating good precision of the analysis and reproducible manufacturing process of the sensors. Moreover,
the proposed sensor proved to be selective in the presence of other inorganic compounds frequently found in environmental
waters. Importantly, in the recovery tests, percentage values between 91 and 117% confirmed the accuracy and reliability
of the analyses. Thus, the developed strategy can be useful for nitrate sensing in real water samples in remote locations.
Keywords Water analysis· 3D printing· Disposable sensors· Portable methods· Point-of-need sensor
Introduction
Nitrate ions (NO3−), in addition to being naturally present
in the environment, are also part of the physiological sys-
tems of living organisms [1]. Furthermore, such ions are
still present in industry, where they are used in various pro-
cesses, such as in the fireworks’ manufacture, in the ferti-
lizer, and food industries (where they are used as additives).
Such anthropogenic uses can lead to several environmental
contamination problems, especially in aquatic environments
(ground and surface waters), leading to an anormal increase
in the proliferation of plants, algal blooms, and microorgan-
isms, resulting in the eutrophication of these ecosystems,
harming the survival, growth, and reproduction of aquatic
animals [1]. Moreover, excess NO3− in food or water for
* Lucas V. de Faria
viniciuslucas82@yahoo.com.br
* Rafael M. Dornellas
rafaeldornellas@id.uff.br
1 Departamento de Química Analítica, Instituto de Química,
Universidade Federal Fluminense, Niterói, RJ24020-141,
Brazil
2 Moniport Ambidados Ltda, RiodeJaneiro, RJ20040-009,
Brazil
3 Instituto de Química, Universidade Federal de Uberlândia,
Uberlândia, MG38408-100, Brazil
4 Departamento de Química, Instituto Federal Do Paraná,
Pitanga, PR85200-000, Brazil
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
ResearchGate has not been able to resolve any citations for this publication.
Epoxy/Graphite Composite Electrode Modified with Recycled Silver Nanoparticles: An Eco-Friendly Strategy to Improve Lead Detection
Article
Full-text available
  • May 2023
  • J BRAZIL CHEM SOC
In this work, silver nanoparticles (AgNPs) obtained from photographic waste were synthesized and electrodeposited via cyclic voltammetry using epoxy-graphite composite as an electrochemical substrate. Both electrodes, unmodified (Epoxy/C) and modified (Epoxy/C/AgNPs), were characterized electrochemically by electrochemical impedance spectroscopy (EIS), charge transfer constant (K 0), and electroactive area. The modified electrode provided lower charge transfer resistance (275 Ω), more kinetically favored electron transfer (K 0 = 1.15 × 10-3 cm s-1), and a 1.7-fold increase in the active area compared to the unmodified electrode. Additional characterizations by scanning electron microscopy (SEM) and Raman spectroscopy confirmed the presence of AgNPs structures on the carbonaceous surface. As a proof of concept, Pb 2+ was used as a model analyte, and a square wave anodic stripping voltammetry (SWASV) method was developed to evaluate the analytical performance of both electrodes. A wider linear range (4.0 to 40.0 µg L-1), the appropriate limit of detection (1.2 µg L-1), and a 6-fold increase in sensitivity were found using the modified electrode, suggesting that the AgNPs significantly contributed to the performance of the electrode. The proposed method was applied to three real water samples, where the Pb 2+ levels varied from 11.3 to 19.5 µg L-1. The proposed protocol (reuse of silver waste) has proven to be a powerful tool for improving the detection of Pb 2+ , which can be helpful for other electrochemical sensing applications in locations with minimal infrastructure.
View
Calcium and magnesium in drinking water and risk of myocardial infarction and stroke – a population-based cohort study
Article
Full-text available
  • Jul 2022
Background The implication of calcium and magnesium in drinking water for cardiovascular disease is unclear. Objectives To assess the association of the concentration of calcium and magnesium in drinking water with incidence of myocardial infarction and stroke, accounting for dietary mineral intake. Methods We linked drinking water monitoring data to residential information of 26,733 women from the population-based Swedish Mammography Cohort, who completed a 96-item food frequency questionnaire at baseline. Drinking water was categorized into low (magnesium <10 mg/L and calcium <50 mg/L) or high (magnesium ≥10 mg/L or calcium ≥50 mg/L) mineral concentration. Incident cases of myocardial infarction and stroke types were ascertained 1998–2019 using the National Patient Register. Results Calcium and magnesium in drinking water was mean (± SD) 29 (±7) and 5 (±1) mg/L in the low and 52 (±20) and 10 (±3) mg/L in the high exposed areas, respectively. During 16 years of follow-up, we ascertained 2,023, 2,279 and 452 cases of myocardial infarction, ischemic and hemorrhagic stroke, respectively. High drinking water calcium and magnesium was associated with lower risk of ischemic and hemorrhagic stroke hazard ratios (HRs) 0.87 (95% confidence interval; CI: 0.80, 0.95) and 0.78 (95% CI: 0.65, 0.95), while the HR for myocardial infarction was 0.93 (95% CI: 0.85, 1.02). In separate analyses, only drinking water magnesium, not calcium, remained associated with ischemic stroke (HR: 0.69; 95% CI: 0.54, 0.88). Conclusion Drinking water with a high concentration of calcium and magnesium, particularly magnesium, may lower the risk of stroke in postmenopausal women.
View
Electrochemical Detection of Nitrate, Nitrite and Ammonium for On-site Water Quality Monitoring
Article
Full-text available
  • Dec 2021
This review examines the most recent electrochemical developments for nitrate, nitrite and ammonium detection for on-site water monitoring. There remains a high demand for effective field-based detection of the dissolved inorganic nitrogen (DIN) analytes to aid in mitigating nitrogen loading. Electrochemical approaches show increasing potential to fill this role as advancements in nanotechnology continually improve analytical performance and on-site applicability. However, translating these improvements into the field still faces the resonating challenges of reaching analytical proficiency (selectivity, sensitivity, robustness, stability), practical end-user functionality, minimal matrix interferences and cost effectiveness. Herein, we elaborate on these challenges via a critical evaluation of current studies and examine how realistic the prospects of on-site nitrate, nitrite and ammonium are. We also present recommendations in addressing these gaps to conclude the review.
View
View
Trace manganese detection via differential pulse cathodic stripping voltammetry using disposable electrodes: additively manufactured nanographite electrochemical sensing platforms
Article
  • Mar 2020
  • Analyst
Additive manufacturing is a promising technology for the rapid and economical fabrication of portable electroanalytical devices. In this paper we seek to determine how our bespoke additive manufacturing feedstocks act as the basis of an electrochemical sensing platform towards the sensing of manganese(II) via differential pulse cathodic stripping voltammetry (DPCSV), despite the electrode comprising only 25 wt% nanographite and 75 wt% plastic (polylactic acid). The Additive Manufactured electrodes (AM-electrodes) are also critically compared to graphite screen-printed macroelectrodes (SPEs) and both are explored in model and real tap-water samples. Using optimized DPCSV conditions at pH 6.0, the analytical outputs using the AM-electrodes are as follows: limit of detection, 1.6 × 10−9 mol L−1 (0.09 μg L−1); analytical sensitivity, 3.4 μA V μmol−1 L; linear range, 9.1 × 10−9 mol L−1 to 2.7 × 10−6 mol L−1 (R2 = 0.998); and RSD 4.9% (N = 10 for 1 μmol L−1). These results are compared to screen-printed macroelectrodes (SPEs) giving comparable results providing confidence that AM-electrodes can provide the basis for useful electrochemical sensing platforms. The proposed electroanalytical method (both AM-electrodes and SPEs) is shown to be successfully applied for the determination of manganese(II) in tap water samples and in the analysis of a certified material (drinking water). The proposed method is feasible to be applied for in-loco analyses due to the portability of sensing; in addition, the use of AM-printed electrodes is attractive due to their low cost.
View
Carbon black/acrylonitrile‐butadiene‐styrene composite material incorporated with silver nanoparticles: A new sensitive and cost‐effective electrochemical platform for trace lead detection in seawater samples
Article
  • Dec 2023
A novel composite material based on acrylonitrile‐butadiene‐styrene (ABS) and carbon black (CB) was proposed here. Different ratios between CB and ABS (40 : 60–60 : 40 %, w/w) were studied to obtain a substrate with improved electrochemical properties. These materials were characterized by techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), Raman and Fourier transform infrared (FT‐IR) spectroscopies and scanning electron microscopy (SEM). Under the CB/ABS substrate (50 : 50 %, w/w), a lower charge transfer resistance (854 Ω) and a higher heterogeneous electron transfer constant (K ⁰ =1.551×10 ⁻³ cm s ⁻¹ ) were found, indicating a kinetically more favorable reaction. To improve the electroanalytical performance of the CB/ABS electrode (50 : 50 %, w/w), silver nanoparticles (AgNPs) were electrodeposited using recycled silver from photographic waste, whose presence was confirmed by SEM imaging and Raman spectra. A method using square wave anodic stripping voltammetry (SWASV) and Pb ²⁺ as model species was developed, where a wider linear working range (4.0 to 40.0 μg L ⁻¹ ) and lower detection limit (0.4 μg L ⁻¹ ) were achieved for the modified electrode. The electrode modification process was highly reproducible (RSD=9.7 %, n=9, inter‐electrode), with precise electrochemical responses (RSD=3.6 %, n=9, intra‐electrode). The applicability was demonstrated in two seawater samples, where recovery levels between 94 and 106 %, as well as statistically similar results to those obtained by atomic absorption spectroscopy, attested to the reliability of the analysis. Furthermore, it is noteworthy that an appropriate selectivity was achieved even in the presence of other metallic species. The proposed composite material is low‐cost, robust, versatile, and can be a promising tool for additive manufacturing of electrochemical sensors.
View
View
Electrochemical determination of nitrate on Ag nanoparticles‐decorated poly (direct blue 15) electrodes
Article
  • Apr 2023
In this study, for the first time, the electro‐polymerization of Direct blue15 (DB15), an azo dye, was carried out on the surface of ITO. Furthermore, the poly(DB15) surface was electrochemically decorated with Ag nanoparticles (AgNPs), and the fabricated AgNPs/PDB15 electrodes were examined as nitrate sensors. Compared to unmodified ITO electrode, the AgNPs/PDB15 electrode had greatly improved electrochemical response to nitrate reduction. The nitrate determination in a linear range from 1.0×10 ⁻⁵ mol L ⁻¹ to 2.27×10 ⁻³ mol L ⁻¹ was performed with a detection limit of 9.66 μM. The synthesized electrode is a promising sensor for the electrochemical detection of nitrate pollutants in water.
View
Nanoporous gold microelectrode arrays using microchips: A highly sensitive and cost-effective platform for electroanalytical applications
Article
  • Oct 2022
  • J ELECTROANAL CHEM
In this paper, we investigate the effect of electrochemical treatment on the surface of low-cost and disposable devices (microchips) containing gold microelectrode arrays (Au-µE). This procedure consisted of electrode anodization to generate nanoporous gold structures (NPAu-μE), which contributed to 4.4-fold increase in the electroactive area and decrease in the resistance to charge transfer. Energy-dispersive X-ray spectra revealed the formation of gold oxide nanostructures. The electrochemical response of these sensors was properly investigated using dipyrone (DIP), cysteine (CyS) and lead(II) as target species, and for all the analytes, enhanced analytical performances were obtained using the treated surface. NPAu-μE was combined with a batch-injection analysis (BIA) cell for the amperometric determination of DIP and CyS, which resulted in detection limits lower than 1.2 µmol L⁻¹, adequate precision (RSD < 4.0 %), wide linear ranges (1.0 – 200.0 and 5.0 – 150.0 µmol L⁻¹), and high sample throughput (148 and 185 analysis per hour) for DIP and CyS, respectively. Moreover, the NPAu-µE sensor proved to be suitable for Pb²⁺ detection by square-wave anodic stripping voltammetry (SWASV), with a detection limit of 2.0 nmol L⁻¹, linear ranges from 24 to 240 nmol L-1, and 289 to 531 nmol L⁻¹, and good precision (RSD = 4.3 %), which enabled a good recovery of Pb²⁺ added to drinking water at the level corresponding to the WHO allowed threshold limit (48.2 nmol L⁻¹ or 10 µg L⁻¹). In summary, we demonstrate that NPAu-μE device can be applied for either organic or inorganic species with satisfactory sensing properties.
View
Electrochemical (Bio)Sensors Enabled by Fused Deposition Modeling-Based 3D Printing: A Guide to Selecting Designs, Printing Parameters, and Post-Treatment Protocols
Article
  • Mar 2022
The 3D printing (or additive manufacturing, AM) technology is capable to provide a quick and easy production of objects with freedom of design, reducing waste generation. Among the AM techniques, fused deposition modeling (FDM) has been highlighted due to its affordability, scalability, and possibility of processing an extensive range of materials (thermoplastics, composites, biobased materials, etc.). The possibility of obtaining electrochemical cells, arrays, pieces, and more recently, electrodes, exactly according to the demand, in varied shapes and sizes, and employing the desired materials has made from 3D printing technology an indispensable tool in electroanalysis. In this regard, the obtention of an FDM 3D printer has great advantages for electroanalytical laboratories, and its use is relatively simple. Some care has to be taken to aid the user to take advantage of the great potential of this technology, avoiding problems such as solution leakages, very common in 3D printed cells, providing well-sealed objects, with high quality. In this sense, herein, we present a complete protocol regarding the use of FDM 3D printers for the fabrication of complete electrochemical systems, including (bio)sensors, and how to improve the quality of the obtained systems. A guide from the initial printing stages, regarding the design and structure obtention, to the final application, including the improvement of obtained 3D printed electrodes for different purposes, is provided here. Thus, this protocol can provide great perspectives and alternatives for 3D printing in electroanalysis and aid the user to understand and solve several problems with the use of this technology in this field.
View