Sains Malaysiana 53(1)(2024): 149-162

http://doi.org/10.17576/jsm-2024-5301-12

Nonenzymatic Sensor Based on Polythiophene/Titanium Dioxide (PTh/TiO₂) Composite for the Determination of Malathion in Water

(Penderia Nonenzim Berdasarkan Komposit Politiofen/Titanium Dioksida (PTh/TiO₂) untuk Penentuan Malation dalam Air)

SONGÜL ŞEN GÜRSOY^1,* & DERYA KAHRAMAN²

¹Burdur Mehmet Akif Ersoy University, Faculty of Arts and Sciences, Department of Chemistry, TR-15030 Burdur, Turkey

²Burdur Mehmet Akif Ersoy University, Institute of Applied and Natural Sciences, Department of Chemistry, TR-15030 Burdur, Turkey

Received: 7 April 2023/Accepted: 29 December 2023

Abstract

This study presents a novel nonenzymatic pesticide sensor utilizing a polythiophene/TiO₂ (PTh/TiO₂) film deposited on a glassy carbon (GC) electrode as the working electrode. The thiophene monomer was polymerized onto TiO₂ by cyclic voltammetric method in the range of 0.0-2.5 V with 15 cycles at room temperature. The prepared electrode was used for the sensitive and selective detection of malathion thus providing the basis for facile electrochemical quantification. The surface morphology and crystal structure of the (PTh/TiO₂) film were studied by SEM and XRD. FTIR was used for the structural analysis of (PTh/TiO₂) film. FTIR results indicated that the PTh/TiO₂composite structure was formed. The smooth surface morphology of PTh/TiO₂ was supported by SEM results. XRD analysis verified that PTh is covered on TiO₂ particles. The crystal phase of TiO₂ was changed to amorph state after PTh modification. Additionally, the electrochemical characterization of polymer film and its response to malathion was examined by the CV method. Under optimized operational conditions, the response of the pesticide sensor was measured by CV in the range of -1 to 2.3 V versus the Ag/AgCl reference electrode due to the electrooxidation of malathion. The analysis focused on current values at -0.73 V, where the reduction of the PTh/TiO2 system occurred upon the addition of known amounts of malathion. The PTh/TiO₂ composite film was sensitive to malathion in a linear range from 9.9 ppm to 436 ppm. The sensitivity was calculated as 57.5 μA/ µM cm² whereas the detection limit was calculated as 7.45 µM.  The maximum reaction rate was estimated as 767 μA. The developed sensor also showed good selectivity and reproducibility. The nonenzymatic pesticide sensor was successfully applied to detect malathion in tap water with at least 90% recovery.

Keywords: Conducting polymer; pesticide; polythiophene; TiO₂; sensor

Abstrak

Kajian ini membentangkan penderia racun perosak nonenzimatik baru yang menggunakan filem politiofen/TiO₂ (PTh/TiO₂) yang dimendapkan pada elektrod karbon berkaca (GC) sebagai elektrod kerja. Monomer tiofen telah dipolimerkan ke TiO₂ melalui kaedah voltametri kitaran dalam julat 0.0-2.5 V dengan 15 kitaran pada suhu bilik. Elektrod yang disediakan telah digunakan untuk pengesanan sensitif dan memilih malation sekali gus menyediakan asas untuk pengkuantitian elektrokimia yang mudah. Morfologi permukaan dan struktur hablur filem (PTh/TiO₂) telah dikaji oleh SEM dan XRD. FTIR digunakan untuk analisis struktur filem (PTh/TiO₂). Keputusan FTIR menunjukkan bahawa struktur komposit PTh/TiO₂ telah terbentuk. Morfologi permukaan licin PTh/TiO₂ disokong oleh keputusan SEM. Analisis XRD mengesahkan bahawa PTh diliputi pada zarah TiO₂. Fasa kristal TiO₂ telah ditukar kepada keadaan amorf selepas pengubahsuaian PTh. Selain itu, pencirian elektrokimia filem polimer dan tindak balasnya terhadap malation telah diperiksa dengan kaedah CV. Di bawah keadaan operasi yang dioptimumkan, tindak balas penderia racun perosak diukur oleh CV dalam julat -1 hingga 2.3 V berbanding elektrod rujukan Ag/AgCl disebabkan oleh elektrooksidasi malation. Analisis tertumpu pada nilai semasa pada -0.73 V dengan pengurangan sistem PTh/TiO₂ berlaku apabila penambahan jumlah malation yang diketahui. Filem komposit PTh/TiO₂ adalah sensitif kepada malation dalam julat linear dari 9.9 ppm hingga 436 ppm. Kepekaan dihitung sebagai 57.5 μA/µM cm² manakala had pengesanan dihitung sebagai 7.45 µM. Kadar tindak balas maksimum dianggarkan sebagai 767 μA. Sensor yang dibangunkan juga menunjukkan keterpilihan dan kebolehulangan yang baik. Penderia racun perosak nonenzim telah berjaya digunakan untuk mengesan malation dalam air paip dengan sekurang-kurangnya 90% pemulihan.

Kata kunci: Penderia; polimer pengalir; politiofen; racun perosak; TiO₂

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*Corresponding author; email: ssen@mehmetakif.edu.tr