Electrochimica Acta 295 (2019) 157e163

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Enhancement of the electron transfer rate in carbon nanotube flexible

electrochemical sensors by surface functionalization
Keita Nishimura a, Takuya Ushiyama a, Nguyen Xuan Viet a, 1, Masafumi Inaba b,
Shigeru Kishimoto a, Yutaka Ohno a, b, *
a
Department of Electronics, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan
b
Institute of Materials and Systems for Sustainability, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Thin films of single-walled carbon nanotubes (SWNTs) possess high potential for use in flexible elec-
Received 11 July 2018 trochemical sensors in wearable medical devices. However, the electrochemical activity of such materials
Received in revised form is not yet fully understood. We studied the enhancement in electrochemical activity of SWNT-based
30 September 2018
flexible electrochemical sensors. To exclude the effect of surface contaminations from the fabrication
Accepted 23 October 2018
Available online 25 October 2018
processes on the electrochemical activity, we introduced the dry process for high-quality and clean
SWNT film formation and the clean device fabrication process with a protective layer. So-fabricated
SWNT electrodes exhibited a low electron transfer rate. Electrochemical functionalization with an
Keywords:
Flexible electronics
H2SO4 solution successfully enhanced the electrochemical activity of the SWNT electrode for the inner
Electrochemical biosensor sphere probes such as [Fe(CN)6]4
/3
. This method is quite gentle and controllable, but also effective at
Single-walled carbon nanotube increasing the electron transfer rate without either degrading the potential window. We found out that
Electron transfer rate there was a correlation between the electron transfer rate and the amount of defects evaluated from
Functionalization Raman scattering spectroscopy. XPS analysis showed that the functionalization process introduced CeO
and C]O species, suggesting that these species constituted active sites for inner sphere probes. The
electrochemical functionalization was also effective for enhancing the limit of detection in dopamine
detection with the flexible SWNT electrode. The limit of detection was ~100 nM for functionalized
electrode whereas it was ~1 mM for as-fabricated electrodes.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction based sensors and peripheral circuits on plastic films.

Flexible electronics are attracting much attention for their po-
tential use in wearable health monitoring devices [1]. Carbon
nanotube thin films, and especially single-walled carbon nanotube
(SWNT) thin films, are promising material for flexible electronics
applications because of their remarkable electrical [2,3] and me-
chanical properties [4,5], as well as the simplicity of film manu-
facture using solution [6e9] and transfer processes [10,11].
Electrochemical sensors can also be constructed on flexible plastic
films using carbon nanotube thin film [12e15], enabling the pro-
duction of ultrathin wearable devices involving SWNT thin film-
* Corresponding author. Institute of Materials and Systems for Sustainability,
Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan.
E-mail address: yohno@nagoya-u.jp (Y. Ohno).
1
Present address: Department of Physical Chemistry, Faculty of Chemistry, VNU
University of Science, Hanoi, 19 Le Thanh Tong, Hoan Kiem, Hanoi, Vietnam.
Despite its potential of SWNTs as flexible sensor material, the
origin of electrochemical activity has not fully been understood yet.
The electrochemical activity of carbon materials, such as graphite,
carbon nanotubes, and graphene, have been a focus of research for
many years. In the case of graphite, electrochemical reactions are
thought to occur mainly at the edge of graphene, instead of at the
surface basal plane [16,17]. Similarly, in the case of multi-walled
carbon nanotubes (MWNTs), the edges of the MWNTs and defects
likely are related to the electrochemical reactions [16,17]. The
SWNT sidewall has been generally considered electrochemically
inert [18,19]; however, Heller et al. and Dumitrescu et al. reported
that sidewalls of SWNTs grown via chemical-vapor deposition
exhibited more electrochemical activity than previously observed
[20,21].
More recently, the electrochemical activities of graphite and
SWNTs have been revealed using novel scanning probe micros-
copies such as scanning electrochemical microscopy [22] and

https://doi.org/10.1016/j.electacta.2018.10.147
0013-4686/© 2018 Elsevier Ltd. All rights reserved.
158 K. Nishimura et al. / Electrochimica Acta 295 (2019) 157e163
scanning electrochemical cell microscopy [23], which have shown
the graphite basal plane and SWNT sidewall to be as electro-
chemically active as Pt [22,23]; however, high electron transfer
rates were obtained only when the surfaces were free from
airborne contaminants and impurities in the sample electrolyte
solution [23]. The graphite electron transfer rate is degraded by a
few orders of magnitude due to surface contamination within a few
minutes of cleavage by airborne hydrocarbons [24]. During prac-
tical nanocarbon-based electrochemical sensor applications, this
surface contamination is unavoidable and surface functionalization
would be essential in enhancing the electron transfer kinetics
[19,25] to obtain sufficient detection sensitivity.
In this work, we studied the electrochemical activity of flexible
SWNT thin-film sensors fabricated on a plastic film. To avoid con-
taminations of SWNT surface during the sensor fabrication, we
introduced clean processes such as the dry transfer process for
SWNT thin film formation and the sensor fabrication process with a
surface protective layer. The surface functionalization with elec-
trochemical method and the effect on the structure of SWNTs and
the electron transfer kinetics were studied, using cyclic voltam-
metry, Raman scattering spectroscopy, and X-ray photoelectron
spectroscopy (XPS). Finally, we demonstrated an enhancement in
sensitivity in dopamine (DA) detection by the functionalization
with flexible SWNT sensors.
2. Materials and methods
2.1. Materials
The SWNT thin film was formed using a dry transfer process
based on floating-catalyst chemical vapor deposition (FC CVD)
[10,26]. SWNTs were grown by an ambient-pressure FC CVD tech-
nique with CO as the carbon source, wherein catalyst nanoparticles
were produced by the decomposition of ferrocene vapors. CO (200
sccm) was passed through a cartridge containing ferrocene powder.
Additional CO (200 sccm) and CO2 (3 sccm) were introduced into
the furnace. The SWNTs were grown at 850  C, then discharged
from the CVD furnace and collected by a membrane filter. Then, the
SWNT film was transferred from the membrane filter onto a poly-
ethylenenaphthalate (PEN) film (Teijin, Teonex Q65HA). The SWNT
film was densified by immersion in isopropanol and subsequent air
drying. The SWNT thin film was ~30 nm thick. The absorption
Fig. 1. Flexible electrochemical sensor based on SWNT thin film. (a) Structural schematic; (b) photograph of the fabricated sample, including an electrode micrograph and an SEM
image of the SWNT thin film. (c) Experimental setup.
spectrum of the SWNT thin film indicated that the grown SWNTs
had an average diameter of 1.7 nm, and that the abundance of
semiconducting SWNTs [27] was ~70%.
This simple dry-transfer film formation method is advantageous
in terms of electrical conductivity and film cleanliness compared to
solution processes, in which SWNTs are generally damaged by
ultrasonication and contaminated by the surfactants used to enable
stable dispersion in water. Moreover, the dry-transfer method also
offers the excellent uniformity of carbon nanotube thin film [3], as
compared to the solution-based film formation process used in
previous carbon nanotube-based flexible sensors [12e15]. In the
solution process, the aggregation of carbon nanotubes often occurs
due to the surface tension of liquid, resulting in a formation of voids
in the film. For sensor applications, surface cleanliness and uni-
formity are essential to sensor characteristic reproducibility and
high electrochemical activity.
2.2. Device fabrication
Fig. 1(a) shows a structural schematic of the SWNT-based flex-
ible electrochemical sensor fabricated in this work. The sensor
device consisted of a SWNT thin film, Ti/Au metal wires (10/
100 nm), SiO2 (70 nm) and Polymethylmethacrylate (PMMA)
(700 nm) protective layers, and PEN film. It is known that the
polymers such as photoresist are hard to remove from the SWNT
surface once they are attached [28]. The SiO2 layer was deposited
just after the SWNT thin film formation to prevent the SWNT sur-
face from being contaminated by the photoresist and PMMA used
in the device fabrication process. The PMMA top layer, along with
the SiO2 layer, avoided the short circuit between the electrolyte
solution and metal wires so that only the SWNT thin film served as
an electrochemical electrode, unlike previous devices [29,30]. An
array of 72 electrodes was fabricated on the PEN film, as shown in
Fig. 1(b). Each SWNT electrode measured 0.2  1 mm2. The unifor-
mity of the SWNT thin film can be confirmed by the SEM image.
After the wiring was produced on the PEN film via photoli-
thography, electron-beam (EB) evaporation, and a lift-off process,
the SWNT thin film was transferred using above-mentioned dry
transfer process. The SiO2 layer was deposited via EB evaporation
over the entire sample surface. The SiO2 layer and SWNT thin film
were patterned using photolithography and reactive ion etching
(RIE), which was performed with CF4 for SiO2 and with O2 for
 K. Nishimura et al. / Electrochimica Acta 295 (2019) 157e163
SWNT, to electrically separate each sensor. After spin-coating the
PMMA layer, the electrode windows were created by etching the
PMMA via RIE with O2 and SiO2 with a buffered HF solution.
2.3. Setup for electrochemical experiments
Fig. 1(c) shows a photograph of the setup for the electrochemical
experiments. During the electrochemical functionalization process
and successive electrochemical measurements, the sample was set
on the probe station stage and the SWNT working electrode (WE)
was electrically contacted via the probe needle. Then, 20 ml of
electrolyte solution was placed onto the sample, where the elec-
trolyte was repelled somewhat by the hydrophobic PMMA top layer
so as to form a droplet on the sample surface. An Ag/AgCl reference
electrode (RE) of 2 mm in diameter (World Precision Instruments,
DRIRFE-2) and Pt counter electrode (CE) of 0.5 mm in diameter
(Bio-Logic Science Instruments, A-002222) were inserted into the
electrolyte droplet. A potentiostat (Metrohm, Autolab) was used for
electrochemical functionalization and subsequent measurements.
All the electrochemical experiments were performed in the
ambient air.
2.4. Surface functionalization
Surface functionalization was performed to improve the SWNT
electron transfer rate. There are several methods for nanocarbon
material functionalization, including gas-phase oxidation [31],
strong acid treatment [32,33], and electrochemical oxidation [17].
The gas-phase oxidation and the acid treatments are not applicable
for flexible sensors because they require high temperature treat-
ment at about 750  C and chemically violate the plastic substrate,
respectively. Only electrochemical oxidation, which features a
moderate and controllable oxidation rate at room temperature, is
appropriate for the SWNT thin-film electrodes on plastic film.
Functionalization was performed by the application of a constant
potential of 1.6e2.2 V (vs. Ag/AgCl) to the SWNT electrodes for 10 s
in a 2 M H2SO4 solution.
2.5. Characterization
The electrochemical characteristics of the SWNT electrodes
were evaluated by measuring the cyclic voltammetry of the redox
reaction involving [Fe(CN)6]4
/3
(100 mM) in a 0.1 M KCl solution.
The scan range and scan rate were
0.3e0.8 V (vs. Ag/AgCl) and
Fig. 2. (a) Oxidation and reduction potentials (Eox and Ered) and the Fermi level (EF) of SWNTs with a diameter of 1.7 nm, along with the standard electrode potential E0 of
[Fe(CN)6]3
/4
; (b) cyclic voltammograms of [Fe(CN)6]3
/4
measured for as-fabricated (blue curve) and functionalized (red curve) SWNT materials. Peak separation (DEp) values are
denoted by bars. (c) (upper graph) DEp and (lower graph) k0 as functions of functionalization potential. (For interpretation of the references to colour in this figure legend, the reader
is referred to the Web version of this article.)
159
25 mV/s, respectively. The potential window was also measured via
cyclic voltammetry in PBS 1 at a scan rate of 25 mV/s. Note that
[Fe(CN)6]4
/3
is known as inner sphere probe, and it is useful to
investigate the functionalization effect on electron transfer rate of
inner sphere molecules such as DA and other neurotransmitters.
We also investigated the functionalization effect for [Ru(NH3)6]2þ/
3þ
known as outer sphere probe. The experimental method was
same as that for [Fe(CN)6]4
/3
.
Raman scattering spectroscopy and XPS were used to investi-
gate the structural and chemical modifications arising from func-
tionalization. For Raman and XPS, SWNT samples were prepared on
a Si substrate with a 100-nm-thick thermally-grown oxide film to
avoid interference from the PEN film. The Raman measurement was
carried out the micro-Raman spectrometer (Renishaw, inVia™)
equipped with an excitation laser of wavelength of 532 nm. XPS
measurements were performed with an Al Ka X-ray source (VG
Systems, ESCALAB250).
2.6. Detection of DA
DA sensing experiments were performed with the same elec-
trochemical setup described previously. DA (100 nM-10 mM) cyclic
voltammetry was performed in PBS 1  with a scan rage of
0.3 V
to 1.0 V and a scan rate of 25 mV/s.
3. Results and discussion
3.1. Effect of electrochemical functionalization
Fig. 2(a) shows the oxidation and reduction potentials (Eox and
Ered) and Fermi level (EF) of a semiconducting SWNT with a diam-
eter of 1.7 nm and the standard potential (E0) of [Fe(CN)6]3
/4
. The
E0 of [Fe(CN)6]3
/4
is located in the forbidden band of the semi-
conducting SWNTs. Hence, the density of states is zero near the E0
of [Fe(CN)6]3-/4-, and, thus, the semiconducting SWNTs are
considered to be hardly active in the electrochemical reaction [23].
Previous studies have shown that defect states are formed in the
middle of the forbidden band in semiconducting SWNTs [34e37],
and defect states may enhance electrochemical activity. In addition,
for the case of inner sphere electron transfer probes such as
[Fe(CN)6]3
/4
and DA, the electron transfer rate is sensitive to the
surface condition. Because 70% of the SWNTs herein are semi-
conductive, as described in the previous section, the electro-
chemical functionalization would be essential to the high electron
160 K. Nishimura et al. / Electrochimica Acta 295 (2019) 157e163
transfer rates and sensitivity obtained herein through the defect
formation and/or the modification of the surface condition.
Fig. 2(b) shows cyclic voltammograms of [Fe(CN)6]3
/4
for the
as-fabricated SWNT electrodes and an electrode functionalized at
2.2 V. The electron transfer rate can be evaluated using the peak
separation (DEp), which is represented by the potential difference
between the oxidation and reduction peaks in the cyclic voltam-
mogram. The DEp decreased from 415 to 119 mV after functionali-
zation, indicating an enhancement in electrochemical activity. The
standard rate constant k0 was evaluated from the DEp value by
Nicholson's method (See Supplementary Information, 1. Evaluation
of rate constant k0, for the detail) [38]. It should be noted that this
method was not suitable for the inner sphere redox probes, how-
ever, it was employed in this work for comparison with previous
literatures [17,39e41]. DEp and k0 are summarized in Fig. 2(c) as
functions of functionalization potential. With increasing function-
alization potential, DEp (k0) monotonically decreases (increases) in
this potential regime. Further increases in functionalization po-
tential resulted in bubble generation at the SWNT surface. The k0
values are 3.6  10
5 cm/s for the as-grown SWNT and
1.7  10
3 cm/s for the electrode functionalized at 2.2 V. The func-
tionalized SWNT value is comparable to previously reported values
for carbon materials such as screen-printed carbon electrodes
[18,39e42] and SWNTs on a gold surface [43], but they are not
flexible. This indicates that the electrochemical functionalization
can effectively activate SWNT electrodes fabricated on a flexible
plastic film to a usable level.
We also carried out the cyclic voltammetry of [Ru(NH3)6]2þ/3þ
which is outer sphere probe. In this case, DEp was not varied by the
functionalization as shown in Supplementary information (Fig. S2).
The surface functionalization was effective for the inner sphere
probes to enhance electron transfer rate, but not for the outer
sphere probes. Therefore, the enhancement of electron transfer rate
for [Fe(CN)6]3
/4
probably resulted from the modification of
interaction between [Fe(CN)6]3
/4
and the SWNT surface via the
functional groups formed on the SWNT surface. The contribution of
the defect states in the forbidden band was not confirmed in this
study.
We investigated the structural modifications caused by elec-
trochemical functionalization using Raman and XPS. Fig. 3(a) shows
Raman spectra of as-fabricated SNWTs and SNWTs functionalized
at potentials of 1.6e2.2 V. The Raman spectra contain two major
peaks, namely a G-band at ~1590 cm
1 and a D-band at ~1350 cm
1.
The G-band is the inherent vibration mode of the graphite layer in
the in-plane direction, where intensity is proportional to the
Fig. 3. (a) Raman scattering spectra of as-fabricated and functionalized SWNT thin films, (b) G/D ratio as a function of functionalization potential, and (c) k0 versus the G/D ratio.
amount of material and also dependent on the crystallinity of the
graphite layer [44]. The D-band is a defect-induced Raman feature
and thus cannot be seen in highly crystalline SWNTs. The ratio of
the G-band intensity to the D-band intensity (G/D ratio) is used to
characterize the quantity of defects (including functional groups) in
the SWNTs. The as-fabricated SWNTs exhibit G/D ratios as high as
88, indicating high crystallinity and material purity. The D-band
intensity increases with surface functionalization, as seen in the
spectra. The G/D ratio decreases from 88 to 4.5 with increasing
functionalization potential, as shown in Fig. 3(b), implying that it is
possible to control defect formation using the electrochemical
functionalization method herein. It was found out that there was a
strong correlation between G/D ratio and k0 as shown in Fig. 3(c).
This suggests that the introduced defects including functional
groups are the dominant active electrochemical reaction sites in the
functionalized SWNTs. It should be noted that G/D ratio at func-
tionalization potential of 2.2 V was slightly higher than that at 2.0 V.
We observed small bubbles on the surface of SWNT electrode at
2.2 V probably due to the electrolysis of water, and this became
significant at 2.4 V. The small bubbles might impede the function-
alization of SWNTs at 2.2 V.
We used XPS analysis to investigate the types of functional
groups introduced by electrochemical functionalization. Fig. 4(a)
shows C1s XPS spectra of as-grown SWNTs and SWNTs function-
alized at 2.2 V. An asymmetrical peak is observed at 284.5 eV for
both samples. The difference between the as-fabricated and func-
tionalized SWNTs is small, unlike those in previous studies con-
cerning functionalized MWNTs [17,45] and UV-ozone treated
SWNTs [43]. This implies that the electrochemical functionalization
method used herein effectively enhances the electrochemical ac-
tivity of SWNTs despite its mildness.
For clarity, the difference between the as-fabricated SWNT XPS
spectrum and the functionalized SWNT spectrum is plotted in
Fig. 4(b); this difference increases in intensity from 286 to 289 eV.
Here, we ignored the differences caused by spectral broadening of
the main peak due to sp2 CeC bonds. According to the literature,
XPS peaks at 286.2, 287.5, and 288.9 eV arise from carbon atoms
involved in one (CeO), two (C]O), or three (COO) bonds with ox-
ygen atoms, respectively. The difference spectrum suggests that
CeO (e.g., alcohols and ethers) and C]O (ketones and aldehydes)
species were increased by functionalization. This is in contrast to
other functionalization methods, such as acid oxidation (using
mixtures of HNO3 and H2SO4), high-temperature air oxidation [45],
H2O2 oxidation [46], and electrochemical functionalization in PBS
[17], which increase COO species (carboxylic acids and esters) as
 K. Nishimura et al. / Electrochimica Acta 295 (2019) 157e163 161

Fig. 4. (a) C1S XPS spectra of as-fabricated and functionalized SWNT thin films; (b) the
Fig. 5. Cyclic voltammograms used to evaluate potential windows of various materials.
difference spectrum (i.e., the functionalized SWNT spectrum minus the as-fabricated
From the top, data are shown for functionalized SWNTs, as-fabricated SWNTs,
spectrum).
monolayer graphene, and Au.

well as CeO and/or C]O species. Further study is necessary to

understand the mechanism how these functional groups contrib-
utes to the enhancement of the electrochemical interactions be-
tween inner sphere probes and SWNTs.
We carried out the bending test to demonstrate flexibility of the
present SWNT electrode fabricated on plastic film. Even after
bending 1000 times on a cylinder of 37 mm in diameter, we
observed neither open circuit of the wires nor short circuit between
the wire and electrolyte after the bending test. Please see Fig. S3 in
Supplementary Information.

3.2. Potential window

The potential window is an important facet of electrochemical

electrode materials used in sensor applications. Fig. 5 shows cyclic
voltammograms measured in PBS 1 for as-fabricated and func-
tionalized (at 2.2 V) SWNTs, with monolayer graphene and Au for
comparison. Even though the background current slightly
increased, the functionalization causes no significant decreases in
potential. The values of potential window were 0.75 V for Au, 1.80 V
for graphene, 1.68 V for as-fabricated SWNT, and 1.63 V for func-
tionalized SWNT. Here, the potential window was defined at the
threshold current of 0.1 mA. The potential window was much wider
than that of Au and comparable to that of monolayer graphene.
3.3. DA detection
DA, a neurotransmitter, is both a stress marker and a biomarker
of Parkinson's disease and schizophrenia. In this work, DA was used
to demonstrate the detection sensitivity enhancement in the flex-
ible SWNT electrodes due to electrochemical functionalization.
Fig. 6(a) shows the DA redox reaction scheme; DA transforms
reversibly to o-dopamine quinone via a redox reaction. Measured
cyclic voltammograms are shown in Fig. 6(b) for as-fabricated and
functionalized (at 2.2 V) SWNT electrodes and three DA concen-
trations: 10 mM, 1 mM, and 100 nM. In comparison with the as-
fabricated SWNTs, the functionalized SWNTs feature increased DA
signal current and the appearance of a sharp peak. Despite
Fig. 6. (a) DA redox reaction; (b) cyclic voltammograms of DA measured with as-
fabricated and functionalized SWNTs under DA concentrations of (left) 10 mМ, (mid-
dle) 1 mМ, and (right) 100 nM.
concurrent increases in background current due to functionaliza-
tion, the signal-to-noise ratio was also increased, probably due to
the enhanced electron transfer rate. As a result, the DA detection
limit was improved from ~1 mM to ~100 nM by functionalization.
DA is an inner sphere redox probe as [Fe(CN)6]3-/4- is. From the
previous discussions on the mechanism of the enhancement of
electron transfer rate by the surface functionalization, it was ex-
pected that the surface functionalization enhanced the interaction
between the inner sphere redox species and SWNT surface. T. Pal-
om€aki et al. proposed a complicated DA redox reaction consisting of
adsorption and following chemical steps at the surface of carbon
nanotubes [47,48]. Our result agrees with their redox reaction
model including the adsorption step.
We tested the stability in detection of DA by measuring cyclic
162 K. Nishimura et al. / Electrochimica Acta 295 (2019) 157e163
voltammetry repeatedly at high DA concentration as 100 mM.
Neither significant degradation of signal current nor DEp was
observed (see Fig. S4 in Supplementary information).
The selectivity in detection is the key issue for sensor applica-
tion in the practical specimen. For DA sensors, ascorbic acid (AA)
and uric acid (UA) dominantly interfere in the detection signal of
DA. We tested the selectivity of the SWNT electrode in the detection
of DA in the presence of AA and UA. The results are shown in Fig. S5
in Supplementary Information. With as-fabricated SWNT elec-
trodes, each specie exhibited broad oxidation signals at an oxida-
tion potential similar to each other, so that, it was hard to
selectively detect each specie in the mixture sample. The func-
tionalized SWNT, on the other hand, exhibited clear shoulder and
peak structures corresponding to DA, AA, and UA in the mixture
sample, showing a possibility of selective detections. Interestingly,
this selectivity arose not only from peak narrowing, but also from
the shift of oxidation potentials. The oxidation potential decreased
(increased) for DA (UA) as compared to as-fabricated SWNT cases.
Similar behavior was observed with the hybrid nanocarbon mate-
rial reported in the recent literature by T. Lauria et al. [48].
4. Conclusions
We investigated a method for enhancing the activity of flexible
SWNT thin film electrochemical sensors fabricated on a plastic film.
The high-quality SWNT thin film was prepared using a dry transfer
process based on FC CVD. The flexible SWNT thin-film electrodes
were subjected to electrochemical functionalization with a H2SO4
solution. This method gently, controllably, and, most importantly,
effectively enhanced the electrochemical activity of the SWNT thin
film without significant degradation of the potential window. It was
found that the surface functionalization enhanced the electron
transfer rate for inner sphere probes such as [Fe(CN)6]3
/4
and DA,
but not for outer sphere probes such as [Ru(NH3)6]2þ/3þ. We also
found that there was a strong correlation between the electron
transfer rate and the amount of defects introduced by the electro-
chemical functionalization. XPS analysis revealed the formation of
CeO and C]O species through functionalization. There results
suggested that these species played a role in the enhanced elec-
trochemical activity via an enhancement in the interaction be-
tween the inner sphere probes and the SWNT surface. The
sensitivity in DA detection with the flexible SWNT electrode was
also improved from ~1 mM to ~100 nM by the functionalization.
Acknowledgments
This work was partially supported by JST/CREST (JPMJCR 16Q2)
and MEXT KAKENHI Grant Numbers JP15H05867 and JP26107521.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2018.10.147.
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