DOI: 10.1002/elan.201900194
Pulsed Deposited Manganese and Vanadium Oxide Film
Modified with Carbon Nanotube and Gold Nanoparticle:
Chitosan and Ionic Liquid-based Biosensor
Seçil Akoğulları,
[a]
Seda Çιnar,
[a]
Kemal Volkan Özdokur,
[b]
Tülin Aydemir,
[a]
Fatma Nil Ertaş,
[c]
and
Süleyman Koçak*
[a]
Abstract: Present study describes the synthesis of mixed
oxide films of manganese and vanadium by electro-
chemical pulsed deposition technique on a glassy carbon
electrode (GCE) modified with multiwall carbon nano-
tubes (MWCNT). The film was further decorated with
gold nanoparticles to enhance the reduction signal of
dissolved oxygen in pH 5.17 acetate buffer solution. All of
the electrochemical synthesized modified electrodes have
been characterized with Scanning electron microscopy
(SEM), High-resolution transmission electron microscopy
(HRTEM), X-Ray photoelectron spectroscopy (XPS), X-
Ray diffraction (XRD) techniques. The electrode ob-
tained (AuNPs/MnOx À VOx/CNT/GCE) was utilized as a
platform for glucose biosensor where the glucose oxidase
enzyme was immobilized on the composite film with the
aid of chitosan and an ionic liquid. The electrochemical
performance of the biosensor was investigated by cyclic
voltammetry and the relative parameters have been
optimized by amperometric measurements in pH 5.17
acetate buffer solution. The developed biosensor exhib-
ited a linear range for glucose between 0.1–1.0 mM and
the limit of detection was calculated as 0.02 mM.
Keywords: Gold nanoparticles · manganese and vanadium oxide · pulsed deposition · oxygen · glucose
1 Introduction
Transition metal oxides, molybdenum [1–3], manganese
[4,5] and vanadium [6] oxides in particular, and their
binary and ternary combinations have received much
attention recently owing to their remarkable electro-
catalytic and electrochromic properties. It was also
reported that these properties largely depend on the
synthesis procedure and among these techniques; electro-
deposition offers an economic and practical way for
producing uniform and thin oxide films on the electrode
surface [6,7]. Repetitive cycling of the potential of a
carbon based [8] or indium À tin oxide (ITO) electrodes [3]
dipped into a cell containing a transition metal ions results
in a mixed-valent metal oxide (MeO
x
) formation which is
most probably responsible from the catalytic activity of
the oxide film [9]. Besides the cycling the potential,
electrochemical pulsed deposition (PD) has become
popular in the last decade, and it was revealed that the
pattern of applied potential determines the compositions
and morphologies of MeOx deposits [9,10].
The main goal of electrocatalysis is to minimize the
overpotential, particularly for gas evolving or consuming
electrode reactions including hydrogen evolution reaction
(HER) and oxygen reduction reaction (ORR). The
mechanism of the latter reaction on a carbon based
electrode modified with transition metal oxides has
revealed that the different oxidation states of the
transition metal was responsible from the reaction with
dissolved oxygen adsorbed on carbon electrode [3,8,9].
Electrocatalytic activity of the electrode can be further
enhanced by decorating the oxide film with noble metal
nanoparticles and resulting combination of hypo- hyper-d
electronic transition metal À metal oxides has displayed
pronounced synergetic effect for both anode and cathode
reactions [1,4,11]. This effect has been shown to improve
by using binary or ternary oxide films decorated with
metallic nanoparticles. As indicated in recent reviews, the
electrode surfaces modified with carbon based nano-
materials including carbon nanotubes (CNT), graphene
etc., and ionic liquids have been mostly exploited in
pursue of the synergic effect for ORR [1,4,5,11–13].
Electrochemical sensors developed by this means can
also be applied for sensitive and selective detection of a
variety of analytes. Gold nanoparticles have been greatly
exploited in biosensor technologies [14,15] while transi-
tion metal oxides have also been employed to construct
[a] S. Akoğulları, S. Çιnar, T. Aydemir, S. Koçak
Manisa Celal Bayar University, Faculty of Science and Art,
Department of Chemistry, 45040 Manisa, Turkey
Tel.: + 902362013162
Fax: + 902362412158
E-mail: suleyman.kocak@cbu.edu.tr
[b] K. V. Özdokur
Erzincan Binali Yıldırım University, Faculty of Science and
Art, Department of Chemistry, Turkey
[c] F. N. Ertaş
Ege University, Faculty of Science, Department of Chemistry,
İzmir, 35100, Turkey
Supporting information for this article is available on the
WWW under https://doi.org/10.1002/elan.201900194
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