Elsevier

Sensors and Actuators B: Chemical

Volume 252, November 2017, Pages 165-174
Sensors and Actuators B: Chemical

Printex 6L Carbon Nanoballs used in Electrochemical Sensors for Simultaneous Detection of Emerging Pollutants Hydroquinone and Paracetamol

https://doi.org/10.1016/j.snb.2017.05.121Get rights and content

Highlights

Abstract

We report the use of Printex 6L Carbon nanoballs (CNB) as electrode material for electrochemical detection of hydroquinone (HQ) and paracetamol (PARA). Nanoballs with diameters between 20 and 25 nm are amorphous, impurity-free according to energy-dispersive X-ray spectroscopy, and formed homogeneous films on glassy carbon (GC) electrodes. Their conductive behavior was confirmed with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), which could be exploited in differential pulse voltammetry (DPV) to detect HQ and PARA at low overpotential (67 and 341 mV vs. Ag/AgCl for HQ and PARA, respectively) between 8.0 × 10−8 and 2.3 × 10−4 mol L−1. The limit of detection for these GC/CNB sensors was 13.0 and 8.0 × 10−9 mol L−1 for HQ and PARA, respectively, being competitive with other devices made with carbonaceous materials. In spite of their simplicity, the sensors were also stable, reproducible and robust against typical interferents in biological fluids such as nitrite, sulfite, the antibiotic amoxicillin, sodium dodecyl sulfate (SDS) and humic substances. Experiments with natural waters from a creek indicated that electrochemical sensing of HQ and PARA with GC/CNB is as efficient as standard chromatography. Because CNB are much simpler and cheaper to produce than other carbon materials, e.g. graphene and nanotubes, their use may be advantageous in other electroanalytical applications.

Section snippets

INTRODUCTION

Carbonaceous nanomaterials including carbon black, carbon nanofibers, nanotubes, nanoparticles, graphene, fullerenes and foams have been used extensively in sensors [1], [2], [3] and biosensors [4], [5], [6], [7]. Carbon black (CB), in particular, is investigated because it is one of the most inexpensive. It is normally constituted of small fine particles with low amounts of organic and inorganic surface compounds [6], and employed in screen printed electrodes for electronalysis of a variety of

Reagents and solutions

All chemicals were of analytical grade and used without further purification. Hydroquinone of high purity (99%) was obtained from Merck (Darmstadt, Germany), while paracetamol and N,N-dimethylformamide (DMF) were acquired from Sigma–Aldrich (St. Louis, MO, USA). Printex L6 Carbon was purchased from Degussa (Essen, North Rhine-Westphalia, Germany). High-purity water (resistivity > 18  cm) was taken from a Nanopure Ultrapurification System (Barnstead Inc., Waltham, MA, USA). The 0.1 mol L−1

Morphological and structural properties

CNB are made of amorphous carbon, according to the powder XRD pattern in Fig. 2A, with well-defined peaks of the hexagonal phase at 2θ = 24.52° and 43.63°, corresponding to the (002) and (100) planes, respectively (JCPDF 73-2096 [22]). The XPS survey spectrum in Fig. 2B indicates that the sensing material contains 94% carbon and 6% oxygen. The HR-TEM images of CNB on copper grids in Fig. 2(C–E) reveal multiple nanoball-shaped particles with a narrow size distribution of ca. ∼20–25 nm.

CONCLUSIONS

We have shown that carbon nanoballs (CNB) with 20–25 nm diameter can be deposited on glassy carbon (GC) electrodes and promote oxidation of HQ and PARA at lower potentials than bare GC, also yielding higher currents. The GC/CNB sensor was then tested for detecting HQ and PARA, and exhibited the best performance in terms of sensitivity and detection limit among carbon-based electrochemical sensors we could find in the literature. Furthermore, with GC/CNB it was possible to detect HQ and PARA

Competing financial interest

The authors declare no competing financial interest.

ACKNOWLEDGMENTS

This work was supported by São Paulo Research Foundation (FAPESP, (2012/17689-9, 2014/05197-0, 2016/01919-6, 2016/12759-0 and 2013/14262-7), CNPq and CAPES. The authors are grateful to Ms. Marcio de Paula and CAQI/IQSC/USP are specially acknowledged for SEM facilities and to Prof. Marcos R. V. Lanza for the generous donation of Printex L6 Carbon. The authors thank the Brazilian Nanotechnology National Laboratory/Center for Research in Energy and Materials (LNNano/ CNPEM) and Structural

Paulo Augusto Raymundo-Pereira received his BSc. degree in Chemistry from Univ. Estadual Paulista, Brazil, in 2008, and his MSc. degree in 2011 and Ph.D. in 2016 in Analytical Chemistry from Institute of Chemistry of São Carlos, Brazil. He has experience in Analytical Chemistry, with emphasis on electroanalysis, acting on the following topics: electro-analysis, electrochemical sensor and biosensor, modified electrode, nanomaterials and hybrid materials. Now, he is a Post-doc at Institute of

References (47)

  • F. Arduini et al.

    High performance electrochemical sensor based on modified screen-printed electrodes with cost-effective dispersion of nanostructured carbon black

    Electrochem. Commun.

    (2010)
  • F.C. Vicentini et al.

    Nanostructured carbon black for simultaneous sensing in biological fluids

    Sens. Actuators B-Chem.

    (2016)
  • M.H.M.T. Assumpcao et al.

    A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

    Carbon

    (2011)
  • B.C. Janegitz et al.

    Direct electrochemistry of tyrosinase and biosensing for phenol based on gold nanoparticles electrodeposited on a boron-doped diamond electrode

    Diam. Relat. Mater.

    (2012)
  • M. Murugananthan et al.

    Mineralization of bisphenol A (BPA) by anodic oxidation with boron-doped diamond (BDD) electrode

    J. Hazard. Mater.

    (2008)
  • S.H. Lee et al.

    Determination of acetaminophen using functional paper-based electrochemical devices

    Sensors and Actuators B: Chemical

    (2016)
  • P.A. Raymundo-Pereira et al.

    Synergy between Printex nano-carbons and silver nanoparticles for sensitive estimation of antioxidant activity

    Analytica Chimica Acta

    (2016)
  • P.A. Raymundo-Pereira et al.

    A Nanostructured Bifunctional platform for Sensing of Glucose Biomarker in Artificial Saliva: Synergy in hybrid Pt/Au surfaces

    Biosensors and Bioelectronics

    (2016)
  • T.C. Canevari et al.

    Sol-gel thin-film based mesoporous silica and carbon nanotubes for the determination of dopamine, uric acid and paracetamol in urine

    Talanta

    (2013)
  • A. Klimek-Turek et al.

    Frontally eluted components procedure with thin layer chromatography as a mode of sample preparation for high performance liquid chromatography quantitation of acetaminophen in biological matrix

    J. Chromatogr. A

    (2016)
  • E.A. Abdelaleem et al.

    HPTLC and RP-HPLC methods for simultaneous determination of Paracetamol and Pamabrom in presence of their potential impurities

    J. Pharm. Biomed.

    (2015)
  • P.K. Kalambate et al.

    Simultaneous voltammetric determination of paracetamol and domperidone based on a graphene/platinum nanoparticles/nafion composite modified glassy carbon electrode

    Sens. Actuators B-Chem.

    (2015)
  • P.K. Kalambate et al.

    Simultaneous voltammetric determination of paracetamol, cetirizine and phenylephrine using a multiwalled carbon nanotube-platinum nanoparticles nanocomposite modified carbon paste electrode

    Sensors and Actuators B: Chemical

    (2016)
  • Cited by (53)

    • Emerging electrochemical portable methodologies on carbon-based electrocatalyst for the determination of pharmaceutical and pest control pollutants: State of the art

      2023, Journal of Environmental Chemical Engineering
      Citation Excerpt :

      The developed sensor showed enhanced performance when compared to CNT and graphene. As a result of CNB preparation procedures, cheaper materials can be obtained, as well as the amount/number of reagents and residues consumed can be reduced [77]. An interesting study was done using a gold modified electrode (CNF@AuNPs) as the working electrode for fabricating the electrochemical sensors for the detection of antibiotic metronidazole.

    • Electrochemical sensors for hydroquinone and catechol based on nano-flake graphite and activated carbon sensitive materials

      2022, Synthetic Metals
      Citation Excerpt :

      Carbon materials including graphite, carbon nanotube, graphene and activated carbon have aroused increasing attention in the past several years [7–10]. For instance, Raymundo-Pereira and his group reported many carbon-based sensors about carbon screen-printed electrodes (SPEs), electrochemical treatment-SPEs, Ag/SiO2/MWCNT and Printex 6 L Carbon nanoballs (CNB) used to determine simultaneously the presence of HQ, CC and other emerging pollutants [11–14]. Huang synthesized a graphene sheets embedded carbon (GSEC) film that was electrochemically activated in KOH solution for high sensitivity simultaneous determination of HQ and CC [4].

    View all citing articles on Scopus

    Paulo Augusto Raymundo-Pereira received his BSc. degree in Chemistry from Univ. Estadual Paulista, Brazil, in 2008, and his MSc. degree in 2011 and Ph.D. in 2016 in Analytical Chemistry from Institute of Chemistry of São Carlos, Brazil. He has experience in Analytical Chemistry, with emphasis on electroanalysis, acting on the following topics: electro-analysis, electrochemical sensor and biosensor, modified electrode, nanomaterials and hybrid materials. Now, he is a Post-doc at Institute of Physics of São Carlos (IFSC), University of São Paulo. His research interests include electrochemical sensors, biosensors, hybrid surfaces, nanostructured materials, polymers, ultrathin films and enzymes for recognition molecular and detection of endocrine disruptors, neurotransmiters on environmental and clinical samples.

    Anderson Massahiro de Campos received his BSc. degree in Chemistry from Sao Paulo University, Brazil, in 2016. He has experience in analytical chemistry, with emphasis on electroanalysis, acting on the following topics: electroanalysis, electrochemical sensors and modified electrodes, nanomaterials and hybrid materials.

    Camila Domingues Mendonça received his BSc. degree in Chemistry from Federal University of Maranhão in 2011 and her MSc. degree in Analytical Chemistry from University of São Paulo in 2015. Her research interests are sensors and biosensors, pesticides, hormones and chromatographic methods.

    Marcelo Luiz Calegaro received his BSc. degree in Chemistry from Chemistry Institute of São Carlos in 1990. He received his MSc. degree in 1995 and PhD. in 2000 from Chemistry Institute of São Carlos, University of São Paulo, Brazil. He is an electrochemist working on the following subjects: metal oxide catalysts, ethanol anodic oxidation, direct ethanol fuel cell, oxygen reduction reactions and sol-gel.

    Sergio Antonio Spinola Machado received his BSc. degree in Chemistry from Federal University of São Carlos, in 1980. He received his MSc. degree in 1984 and PhD in 1989 from University of São Paulo. He is an associate professor at the Institute of Chemisty of São Carlos, University of São Paulo. He is an electrochemist working on electroanalysis, biosensors, analysis of pesticides, modifications of electrodes surfaces with self-assembled monolayers and carbon nanotubes. He is a member of the International Society of Electrochemistry (ISE), and the Sociedad Iberoamericana de Electroquímica (SIBAE).

    Osvaldo N. Oliveira Jr received his BSc. in 1982 and MSc in 1984 from the University of São Paulo. He received PhD in 1990 from the University of Wales, Bangor, UK. He is a professor at the São Carlos Institute of Physics, University of São Paulo. His main areas of activity are in nanostructured organic films, topic of condensed matter physics, and processing of natural languages. He is a member of the Academy of Sciences of the State of São Paulo, associate editor of the Journal of Nanoscience and Nanotechnology and Display and Imaging. He was awarded the 2006 Scopus Award, by Elsevier and Capes.

    View full text