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Diamond & Related Materials
journal homepage: www.elsevier.com/locate/diamond
Nitrogen-doped carbon nanotubes towards electrochemical sensing: Efect
of synthesis temperature
Marines Steinmetz
a,1
, Dhésmon Lima
a,1
, Raíssa Ribeiro Lima Machado
b
,
Uttandaraman Sundararaj
c
, Mohammad Arjmand
d
, Aline Bruna da Silva
b
, João Paulo Santos
b
,
Christiana Andrade Pessôa
a
, Karen Wohnrath
a,
⁎
a
Department of Chemistry, Universidade Estadual de Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, Paraná, Brazil
b
Department of Materials Engineering, Centro Federal de Educação Tecnológica de Minas Gerais, Av. Amazonas, 5253, 30421-169 Belo Horizonte, Minas Gerais, Brazil
c
Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Dr N.W., T2N 1N4 Calgary, Alberta, Canada
d
School of Engineering, University of British Columbia, 1137 Alumni Avenue, V1V 1V7 Kelowna, British Columbia, Canada
ARTICLE INFO
Keywords:
Nitrogen-doped carbon nanotube
Chemical vapor deposition
Electrochemical sensing
Dopamine
Epinephrine
ABSTRACT
Nitrogen-doped carbon nanotubes (N-CNTs) were synthesized at various temperatures ranging from 650 to
950 °C, at 100 °C intervals, by chemical vapor deposition technique (CVD). The synthesized N-CNTs were em-
ployed as modifers of glassy carbon paste electrodes (GCPE), which were further used as electrochemical
sensors for the determination of dopamine (DA) and epinephrine (EP), two important catecholamines that
display biological roles as neurotransmitters and hormones. The results revealed that electrodes modifed with
the N-CNTs synthesized at 650 °C (GCPE/N-CNT
650
) and 950 °C (GCPE/N-CNT
950
) presented better electro-
catalytic activities and sensing capabilities than the others (GCPE/N-CNT
750
and GCPE/N-CNT
850
). N-CNT
950
had the highest graphitization and the highest powder conductivity, whereas N-CNT
650
had the lowest gra-
phitization and the lowest powder conductivity. However, both N-CNT
950
and N-CNT
650
had the highest ni-
trogen contents, 3.5 and 3.8 at.%, respectively, which probably enhanced their number of electroactive sites to
interact with DA and EP molecules. This result is of high signifcance, because the use of the lowest temperature
(650 °C) in the CVD process, yielded N-CNTs with improved electrocatalytic activity and less energy con-
sumption during CVD.
1. Introduction
Carbon nanotubes (CNTs) have been recognized as good candidates
to improve the performance of electrochemical sensors due to their
exceptional electrical, physical, and chemical properties [1–4]. CNTs
exhibit large surface area, high thermal conductivity, chemical stabi-
lity, and rapid electron transfer capability, which are responsible for
their widespread use as electrode materials aiming biomolecule detec-
tion [3,5,6]. Such properties of CNTs are associated with their unique
tubular and porous structure, presence of defect sites (such as hepta-
gons, pentagons, and Stone-Wales defects), active sites at end-caps, and
carbon bonding type [4,6]. Despite their remarkable properties, CNTs
exhibit very low dispersibility and high tendency to agglomerate in
usual polar and non-polar solvents [7,8]. Strategies to overcome this
issue include chemical functionalization of CNT with polymers, in-
corporation in composite matrices, and doping with foreign atoms
[8–10].
The latter strategy has been widely employed not only to increase
CNT dispersibility, but also to enhance their sensing capability [11] and
conductivity [12]. Among the several techniques for heteroatom in-
sertion into CNTs, nitrogen doping stands out due to the close atomic
radius between nitrogen and carbon atoms [13,14]. Several types of
nitrogen bonding can be formed during the doping process, e.g., pyr-
idinic, pyrrolic, and graphitic [15,16]. Nitrogen has fve valence elec-
trons; thus, its insertion into carbon-based structures creates drastic
changes in the energy band arrangements. This leads to creation of
additional energy levels [17,18], besides the formation of chemically
active sites [10,19]. Nitrogen doping introduces a substantial amount of
defects into CNT structure, providing more reactive sites on their sur-
face, which infuences their electrochemical properties [11,19,20]. For
instance, nitrogen-doped CNTs (N-CNTs) generally exhibit enhanced
electrical transfer properties, increased surface reactivity, and
https://doi.org/10.1016/j.diamond.2020.108093
Received 8 July 2020; Received in revised form 19 August 2020; Accepted 11 September 2020
⁎
Corresponding author.
E-mail address: karen.woh@gmail.com (K. Wohnrath).
1
Marines Steinmetz and Dhésmon Lima made equal contributions to this work.
Diamond & Related Materials 110 (2020) 108093
Available online 18 September 2020
0925-9635/ © 2020 Elsevier B.V. All rights reserved.
T