RESEARCH ARTICLE | MAY 02 2023

Electrochemical performance of graphene paste electrode

modified TiO2-Calix[4]Arene (G@TC) as a Cd2+ Ion detection
Nasriadi Dali; Deriatman Deriatman; Zul Arham; ... et. al

AIP Conference Proceedings 2719, 030011 (2023)

https://doi.org/10.1063/5.0133281

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 Electrochemical Performance of Graphene Paste Electrode
Modified TiO2-Calix[4]Arene (G@TC) as a Cd2+ Ion
Detection
Nasriadi Dali1, Deriatman Deriatman1, Zul Arham2, Irwan Irwan1, Faisal Mustapa3,
Maulidiyah Maulidiyah1 and Muhammad Nurdin1,a)

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1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Halu Oleo, Kendari,
Indonesia
2
Department of Mathematics and Natural Science, Institut Agama Islam Negeri (IAIN) Kendari, Kendari, Indonesia
3
Department of Aquaqulture, Faculty of Sciences and Technology, Institut Teknologi dan Kesehatan Avicenna,
Kendari, Indonesia
a)
Corresponding author: mnurdin06@yahoo.com

Abstract. Synthesis of graphene electrodes modified TiO2-Calix[4]Arene (G@TC) has been successfully carried out using
a mechanical homogenization method. Electrodes were characterized using Scanning Electron Microscope (SEM) and
detection of Cu2+ ion using cyclic voltammetry. Based on SEM analysis, results show that the G@TC electrodes are
composed of rough surfaces with different grain sizes and have a dense structure with small pores. G@TC electrodes
showed good voltammetric performance in the measurement of Cd2+ ions. In this case it occurs at optimum conditions,
including the use of Calix[4]Arene of 0.015 g and citrate buffer with pH = 5. During the measurement, a reversible reaction
occurs with both an oxidation potential (Epa) and a reduction potential (Epc) for the Cd2+ ion are 0.19 V and 0.25 V,
respectively.

INTRODUCTION

Cadmium is a non-essential heavy metal that is toxic and is more easily accumulated in aquatic environments [1,2].
In addition, Cadmium is often found to accumulate in living things compared to other types of heavy metals [3].
Several analytical approaches have been applied to determine the amount of cadmium in aquatic environments,
including spectroscopic methods such as FAAS [4,5], ICPOES [6,7], GFAAS [8,9]. However, this method is quite
complicated to be applied in the determination of Cd2+ ions, as well as expensive analysis costs.
In addition to spectroscopic techniques, voltammetry techniques in the last year were reported as one of the good
techniques to be applied in the determination of heavy metals [10,11]. Some of the advantages of this technique such
as high selectivity of measurement, low detection limits, low cost of analysis, and the use and preparation of simple
samples [12–16]. In its application, the performance of this technique is strongly influenced by the working electrode
and modifier [17–20]. Several studies have reported work electrode modifications including Mesoporous Silica
Nanoparticles modified Bismuth Film Electrode [21], modified carbon paste electrode with carbon
nanotubes/Fe3O4/eggshell composites [3], multiwalled carbon nanotubes, bismuth particles, TiO2 Photoelectrode
Nanostructures [22] and polypyrrole [11], and carbon fiber rod [23]. The addition of modified TiO2 to CPE has
succeeded in showing a good electron transfer rate on the surface of the working electrode. TiO 2 has a relatively good
thermal stability, large surface area, high adsorption properties, and has abundant adsorption sites [24–27].
In this work, we report the performance of Graphene electrodes Modified TiO 2-Calix[4] Arene (G@TC) in the
determination of Cd2+ ions. Graphene is reported to have a wider potential window and lower residual current than
carbon electrodes or precious metal electrodes [28,29]. The use of TiO2 and Calix[4]Arene has a different function.
The use of TiO2 can significantly increase the flow and transfer of electrons on the electrode surface [29–32]. Whereas
the use of Calix[4]Arene is expected to improve the selectivity of metal ions

The 3rd International Seminar on Science and Technology 2021

AIP Conf. Proc. 2719, 030011-1–030011-6; https://doi.org/10.1063/5.0133281
Published by AIP Publishing. 978-0-7354-4519-2/$30.00

030011-1
 MATERIAL AND METHODS

Synthesis of calix[4]arene

Calix[4] Arene was made using a process described by [12]. In summary, as much as 0.0019 moles of material
mixed with 0.0089 moles of potassium hydroxide, then dissolved in 100 mL 96% ethanol. The mixture was refluxed
for 24 hours using a temperature of 78 oC, cooled at room temperature, and acidified using 1.0 M HCl. The formed
white precipitate was filtered and washed with 1.0 M HCl and distilled water, respectively. The precipitate is then
dried in a desiccator and recrystallized..

Synthesis of graphene electrodes modified TiO2-Calix[4]arene

Synthesis of Graphene electrodes modified TiO2-Calix[4]Arene (G@TC) is carried out by mixing graphene, TiO2
anatase, and Calix[4]Arene using paraffin oil. Mixing is done mechanically using a magnetic stirrer with a mixing
temperature of 80oC. The obtained paste is placed in a 3 mm diameter glass tube that has been connected with copper

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wire. For comparison, electrodes used graphene electrode modified TiO 2 (G@T). Where the preparation process is
the same as preparing G@TC electrodes. After that, G@TC electrodes were characterized using SEM and
electrochemical properties test using voltammetry technique.

Analytical procedure

Detection of Cd(II) with G@TC electrode was evaluated by cyclic voltammetry (CV). Cd 2+ solution with
concentration 1 ppm entered into an electrochemical cell containing NaNO3 0,1 M solution (as supporting electrolyte)
and citrate buffer 5 mL solution. After that, we measured the current at a potential of -0.2 V to 0.8 V at a scan rate of
0.5 V/s.

RESULTS AND DISCUSSION

Morphology of Graphene Electrodes modified TiO2-Calix[4]Arene

Figure 1 shows the results of SEM analysis regarding the surface morphology of the G@TC composite electrode.
Based on this image, the electrodes are composed of beads of different sizes, which cause the surface to become rough.
In addition, electrodes have a tight structure with small pores. The difference in grain size comes from mixing
Graphene and TiO2. Our previous studies showed that Graphene and TiO2 have rough surface morphology.

FIGURE 1. SEM analysis of the graphene electrode modified TiO2-Calix[4]Arene

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 Voltammetric performance of electrodes

Figure 2 shows a cyclic voltammogram of a G@TC electrode in a solution containing Cd 2+ ions. Based on the
voltammogram, we can see the peak of both the oxide and the reduction. The appearance of the two peaks indicates
that the Cd2+ ion has a reversible reaction found by the G@TC electrode, with potential values of both oxidation (Ep a)
and reduction (Epc), respectively, 0.19 V and 0.25 V.

Current (μA)

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(a)
(b)

(c)

Potential (V)

FIGURE 2. Cyclic voltammogram of the G@TC electrode in Cd2+ ion solution: (a) with addition of Calix[4]Arene 0.005 g; (b)
0.010 g; and (c) 0.015 g.

In addition to obtaining the potential redox value from Cd 2+, Figure 2 also shows that the mass of Calix[4]Arene
influences the increase in the measurement current, either oxidation (Ipa) or reduction (Ipc). Where the measurement
current increases linearly as the mass of Calix[4]Arene rises. The current values of both oxidation and reduction when
using a different mass of Calix[4]Arene are shown in Table 1.

TABLE 1. Effect of mass of calix[4]Arene on the current value of the Cd 2+ measurement

Calix[4]Arene Ipa Ipc
(g) (µA) (µA)
0.005 48.6 -43.2
0.010 59.5 -51.4
0.015 65.4 -58.4

Like the mass of Calix[4]Arene, the difference in the pH value of the supporting electrolyte also affects the current
measurement value of the Cd2+ ion, both the oxidation current and the reduction current. Figure 3A depicts the
influence of the pH of the supporting electrolyte on the observed current value of the Cd 2+ ion. Where citrate buffer
was selected as a supporting electrolyte used in this study. The use of supporting electrolytes with high pH gradually
causes a decrease in the current value and changes in the potential value. Based on the plot results, the relationship
between pH and oxidation current shows that pH = 5 is the optimum pH for the supporting electrolyte (Figure 3B). In
acidic pH conditions, Cd2+ ions in the form of free ions in large quantities so that many will be trapped on the surface
of the working electrode and provide a high peak current response and a reduction in H + ions that compete with Cd2+
ions to bind with Calix [4]Arene so that the complexes formed stronger. In addition, high pH will provide a low peak
current response. This is because, in a high pH state, very little Cd 2+ ions are adsorbed on the surface of the electrode
by the presence of OH- ions. At high pH, the metal ions will bind more to OH- ions. At that pH metal, ions will form
hydroxides and precipitate which will produce Cd(OH) 2.

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 pH = 3
A pH = 4
pH = 5
pH = 6

Current (μA)

Potential (V)

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B
Current (μA)

FIGURE 3. (A) Cyclic voltammogram influences the pH of the supporting electrolyte (buffer citrate) on the measurement
current of the Cd2+ ion; (B) Plot the relationship of pH to the oxidation current of Cd 2+ ions.

The stability of the G@TC electrode was also studied in this study, where the stability test was carried out by
repeated measurements of one working electrode. Figure 4 shows that after 21 repetitions, the measured current value
of Cd2+ ions is relatively stable with the resulting relative standard deviation (% RSD) of 1.56%.

FIGURE 4. Histogram of stability of G@TC electrode in Cd2 +

ion measurement

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 CONCLUSION

In this study, the performance of the G@TC electrodes in the determination of Cd 2+ ions based voltammetry was
successfully investigated. The results of the investigation generally explained that the use of Calix[4]Arene as an
electrode modifier had a significant effect on the increase in the current measurement of Cd 2+ ions. In addition, the
combination of TiO2 with Calix[4]Arene showed excellent performance in facilitating the process of electron transfer
on the electrode surface. For the investigation's findings, it is known that the Cd2+ ion undergoes a reversible reaction
on the surface of the electrode with the resulting oxidation and potential reduction values, respectively, of 0.19 V and
0.25 V.

ACKNOWLEDGMENTS

We acknowledge the financial support from the Ministry of Education and Culture of the Republic of Indonesia

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under the Applied Research award grant no 270/E4.1/AK.04.PT/2021 and Ministry of Education, Culture, Research
and Technology of the Republic of Indonesia under the World Class Professor award grant no
2817/E4.1/KK.04.05/2021.

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