Elsevier

Microchemical Journal

Volume 159, December 2020, 105478
Microchemical Journal

Development and surface characterization of a bis(aminotriazoles) derivative based renewable carbon paste electrode for selective potentiometric determination of Cr(III) ion in real water samples

https://doi.org/10.1016/j.microc.2020.105478Get rights and content

Highlights

  • Development of highly selective and sensitive Cr(III) sensor is a challenge.

  • A synthesized bis(aminotriazoles) derivative was applied as Cr(III) selective ionophore.

  • Factors affecting sensor’s response were studied and optimized.

  • The selectivity coefficients were determined by separate solution method (SSM) and fixed interference method (FIM).

  • The sensor was successfully applied for the chromium ion determination in different water samples.

  • It was successfully applied for potentiometric titration of Cr(III) against EDTA.

  • The lipophilicity of the applied ionophore was studied using contact angle measurement technique.

  • The response mechanism and morphology of the prepared sensor was studied.

Abstract

Regarding the Cr(III) importance in the industrial, environmental, and even biological systems, development of highly selective and sensitive Cr(III) sensor is a challenge. In this work, a new carbon paste electrochemical sensor containing a synthesized bis(aminotriazoles) derivative namely 1,3-bis[4-amino-5-benzyl-1,2,4-triazol-3-ylsulfanyl]propane (BABTSP) as the Cr(III) selective ionophore was described. Factors affecting sensor’s response were studied and optimized. The proposed sensor exhibited a Nernstian slope of 20.05 ± 0.35 mV decade−1 covering broad linear range of 1.0 × 10−8−5.0 × 10−2 mol L−1 and detection limit was 8.0 × 10−9 mol L−1 for 3 months over pH range of (2.3–5.2) and fast response time (<10 s). The proposed sensor was selective for Cr(III) ions that was confirmed by separate solution method (SSM) and fixed interference method (FIM) . The sensor was precise and reproducible (RSD% range = 0.8–2.45) and effectively used in potentiometric titration of Cr(III) against EDTA and in diverse water samples analysis with recovery data of 96.08–100.2%. The lipophilicity of the applied ionophore was investigated through contact angle measurement technique and average contact angle was 127.59° that resulted in sensor’s mechanical stability. To study the response mechanism and morphology of the prepared sensor, scanning electron microscope (SEM), energy dispersive X-ray (EDX) and FT-IR spectroscopy were used.

Introduction

The metal ions existence in body can be essential or toxic depending on their concentration levels. The standard concentration of elements in body is beneath the allowable level range that is crucial for the vital body physiological functions [1]. Cr (III) is essential for normal fat and carbohydrate metabolism and its deficiency can result in cardiovascular diseases and diabetes. However, excess amount of Cr(III) can be carcinogenic and can lead to digestive problems and kidney or liver harm [2], [3]. The adequate regular dietary intake for chromium is 50–200 g per day in adults [4]. Chromium ion is essential in industry and environment as well, so the development of a selective, sensitive and quick method for its determination in trace concentrations is a challenging task. Reported analytical techniques have been employed for Cr(III) determination like spectrophotometry [5], [6], [7], fluorimetry [8], atomic absorption spectroscopy [9], [10], high performance liquid chromatography (HPLC) [11], ion chromatography [12], etc., but there are disadvantageous in terms of cost and routine analysis. The continuous growing in ion selective electrode (ISE) field is due to its relatively low cost and maintenance. Moreover, the potentiometric measurements using ISEs are non-destructive and are characterized by high selectivity and sensitivity, speed, portability, no sample pretreatment and ease of preparation [13], [14], [15], [16], [17], [18], [19]. Carbon paste electrode (CPE) is heterogeneous carbon electrode of composite nature made of graphite powder as an electrical conductor embedded in a suitable binder providing the mechanical stability of the paste [20], [21], [22], [23]. CPEs are characterized by low background current, ease of fabrication and its surface renewability [24], [25], [26], [27], [28], [29].

Different types of ionophores have been introduced for the fabrication of cation selective electrodes for example, crown ethers, porphyrins, calixarenes, Schiff’s bases, macrocyclic compounds, metal chelates and ligands which are a category of supramolecular receptors with rigid cavities that can complex with a large variety of cations and the used ionophore efficiency depends on the high mobility, flexibility and lipophilicity of it [30]. Many ionophores were used in fabrication of Cr(III) ion selective electrode as reported [30], [31], [32], [33], [34], but triazoles exhibited

a large number of functions such as catalysts and inclusion compounds [30]. In addition, many reported papers have utilized triazole derivatives as a sensing material or ionophores for determination of metal ions due to their selective complexation ability, lipophilicity and conformational flexibility [30], [35], [36], [37].

In this research work, a novel, highly selective and sensitive carbon paste based sensor modified with two triazole rings derivative namely 1,3-bis[4-amino-5-benzyl-1,2,4-triazol-3-ylsulfanyl]propane, as an electroactive material, was fabricated for the determination of chromium(III) ions. Selectivity and experimental conditions affecting the sensor response were studied and optimized. The proposed synrhesized sensor was applied in analysis of Cr(III) in variant real water samples.

Section snippets

Reagents and samples

Analytical grade reagents were used in this work. A stock solution of 0.1 mol L−1 Cr(III) was prepared from a sufficient quantity of CrCl3·6H2O (Purity ≥98.0%) supplied from Sigma-Aldrich, in bidistilled water and buffered at pH = 4.5. The diluted solutions were prepared day by day via appropriate dilution from stock solution. In interference studies, the used metal solutions were made from analytical category chloride salts acquired from El Nasr Company. Graphite powder (synthetic 1–2 μm,

The effect of carbon paste composition on the sensor’s response

The nature and amount of electroactive material and plasticizer determine the selectivity and accuracy of carbon paste electrode. The target ion-ionophore interaction can be selective for several causes: the analyte ion size may fit the ionophore cavity, or the functional polar groups of the ionophore may form a complex with the target ion specifically, etc. This complexation selectivity and stability of the formed complex between ion and ionophore translates into the electrode’s potentiometric

Conclusion

A novel Cr(III) ion carbon paste electrode was developed by application of 1,3-bis(4-amino-5-benzyl-1,2,4-triazol-3-ylsulfanyl)propane as a neutral carrier. The results showed that this sensor is a good addition to the existing list of Cr(III) potentiometric sensors as it showed an enhancement in selectivity and sensitivity. This effortless, inexpensive and renewable Cr(III) sensor can be served as an indicator electrode in potentiometric titration of Cr(III) against EDTA and can also be

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

The authors would like to thank all persons, Cairo University and institutions that participated in production of this work either by advice or by technical helpful.

References (64)

  • N. Altunay et al.

    Food Chem.

    (2018)
  • Y. Zhao et al.

    Talanta

    (1994)
  • M. Guzinski et al.

    Anal. Chim. Acta

    (2013)
  • Z. Lu et al.

    Electrochim. Acta

    (2019)
  • J. Ping et al.

    Electrochem. Comm.

    (2011)
  • C. Jiang et al.

    Actuators B Chem.

    (2019)
  • Y. Yao et al.

    Biosens. Bioelectron.

    (2019)
  • H. Karimi-Maleh et al.

    J. Mol. Liq.

    (2020)
  • H. Karimi-Maleh et al.

    Mater. Chem. Phys.

    (2020)
  • H. Karimi-Maleh et al.

    J. Collid. Interface Sci.

    (2020)
  • H. Karimi-Maleh et al.

    J. Collid. Interface Sci.

    (2019)
  • M. Miraki et al.

    J. Mol. Liq.

    (2019)
  • M. Ghaedi et al.

    J. Hazard. Mater.

    (2010)
  • H.A. Zamani et al.

    Desalination

    (2009)
  • A.K. Singh et al.

    Anal. Chim. Acta

    (2007)
  • T. Puthiyedath et al.

    Actuators B Chem.

    (2018)
  • T.A. Ali et al.

    Int. J. Electrochem. Sci.

    (2015)
  • H.M. Abu Shawish et al.

    Actuators B Chem.

    (2016)
  • A.M. Othman et al.

    Anal. Chim. Acta

    (2004)
  • H. Khani et al.

    J. Hazard Mater.

    (2010)
  • T.A. Ali et al.

    J. Ind. Eng. Chem.

    (2017)
  • A.K. Jain et al.

    Electrochim. Acta

    (2006)
  • V.K. Gupta et al.

    J. Mol. Liq.

    (2013)
  • R.K. Mahajan et al.

    Int. J. Electrochem. Sci.

    (2007)
  • M.A. Deshmukh et al.

    Electrochim. Acta

    (2018)
  • W.H. Mahmoud et al.

    J. Mol. Str.

    (2015)
  • V.K. Gupta et al.

    J. Mol. Liq.

    (2012)
  • S.Y. Kazemi et al.

    Talanta

    (2010)
  • M. Shirani et al.

    Microchem. J.

    (2020)
  • D.E. Kimbrough et al.

    Crit. Rev. Environ. Sci. Tech.

    (1999)
  • National Research Council

    Recommended Dietary Allowance

    (1989)
  • L.V. Tan et al.

    J. Anal. Methods Chem.

    (2015)
  • Cited by (0)

    View full text