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Porous carbon modified electrodes as highly


selective and sensitive sensors for detection of
dopamine

Article in The Analyst · July 2014


DOI: 10.1039/C4AN01083C

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Porous carbon-modified electrodes as highly


selective and sensitive sensors for detection of
Cite this: Analyst, 2014, 139, 4994
dopamine†
Pitchaimani Veerakumar,‡a Rajesh Madhu,‡b Shen-Ming Chen,*b Chin-Te Hung,a
Pi-Hsi Tang,ac Chen-Bin Wangc and Shang-Bin Liu*ad

Carbon porous materials (CPMs) with high surface areas up to 2660 m2 g1, directly fabricated by a facile
microwave-assisted route, were applied to the electrochemical detection of dopamine (DA). The CPM-
Received 16th June 2014
Accepted 16th July 2014
modified electrodes exhibited excellent selectivity, a desirable detection limit (2.9 nM), and extraordinary
sensitivity (2.56 mA mM1 cm2) for detection of DA, even in the presence of large amounts of foreign
DOI: 10.1039/c4an01083c
species, such as ascorbic acid (AA) and uric acid (UA), making feasible the practical applications of these
www.rsc.org/analyst electrodes as DA sensors.

supports for electrodes in fuel cells.18–22 CPMs have also been


1. Introduction widely utilized as electrodes for disposable electrochemical
Carbon porous materials (CPMs) possess numerous unique sensors, owing to their high surface area, excellent conductivity,
physicochemical properties, such as high surface areas, tailor- chemical inertness, bio-compatibility, and low cost.5,23–28 It has
able pore size, good electrical conductivity, biocompatibility, also been shown that CPMs readily provide favourable sites for
and desirable thermal, mechanical, and electrical properties, electron transfer in biomolecules; hence, CPMs can greatly
and they have attracted considerable R&D attention.1 It is these improve the sensitivity of electrochemical detection.23–26
unique properties that make CPMs promising supports for Dopamine (DA), one of the major catecholamines, plays
electrodes and/or for electrode materials themselves in many many critical roles in the human central nervous and cardio-
important applications, such as in adsorption/separation, vascular systems.29,30 For instance, dopaminergic neurotrans-
purication, catalysis, fuel cells, supercapacitors, sensors, and mission is found to be closely related to diseases such as
bioanalysis.2–9 Numerous methods have been developed for the Parkinson's and schizophrenia.31 In recent decades, many
synthesis of CPMs by various hard or so templates.1,10–15 For techniques have been developed for sensitive detection of DA,
example, it has been shown that ordered mesoporous carbons including uorimetry,32 spectrophotometry,33 and electro-
may be fabricated via a facile self-assembly route using low-cost chemical methods.34,35 Among them, electrochemical detection
phenolic resin and commercial surfactants, followed by a of DA was found to be the most simple, cost-effective, and user-
carbonization treatment.16 Compared to conventional methods, friendly method. The electrochemical method also exhibits the
CPM fabrication via microwave-assisted heating has drawn desirable sensitivity and selectivity. However, scant reports on
considerable R&D attention owing to its advantages, such as the selective detection of DA and/or simultaneous detection of
facile control of porosity and surface area, increased product DA, ascorbic acid (AA), and uric acid (UA) based on CPM-
yield and purity, reduced reaction time and operation cost, and modied electrodes are available.36–40 In this study, we report a
feasibility for mass production.17 In fact, CPMs prepared under facile microwave-assisted synthesis route for fabricating CPMs
microwave irradiation have been extensively exploited as with high surface area and pore volume. The CPMs so prepared
were utilized for electrochemical detection of DA. It is shown
a
that such CPM-modied, glassy carbon electrodes (GCEs)
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
E-mail: sbliu@sinica.edu.tw exhibit excellent sensitivity and selectivity and should be highly
b
Department of Chemical Engineering and Biotechnology, National Taipei University of feasible as practical and cost-effective DA sensors.
Technology, Taipei 10608, Taiwan. E-mail: smchen78@ms15.hinet.net
c
Department of Chemical and Materials Engineering, Chung Cheng Institute of
Technology, National Defense University, Taoyuan 33449, Taiwan 2. Experimental
d
Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan 2.1 Chemicals and solutions
† Electronic supplementary information (ESI) available: Schemes,
electrochemical oxidation mechanism, calculation details, Raman, SEM, TEM, Resorcinol (ACS, 99.98%, Acros), formaldehyde (37% in water,
pore size distribution, CV and DPV results. See DOI: 10.1039/c4an01083c Acros), anhydrous sodium carbonate (ACS, Fisher), triblock
‡ These authors contributed equally. copolymer Pluronic F-127 (EO106PO70EO106, Mw ¼ 12 600,

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Sigma-Aldrich), ethanol (C2H5OH, 99%), and dopamine hydro- (900 or 1000  C), and then being kept for 1–2 h before it was
chloride (Sigma-Aldrich) were obtained commercially and used eventually brought down to RT under a N2 gas ow. These CPMs
without further purication. The phosphate buffer solution activated with CO2 at 900  C for 1 h, 1000  C for 1 h, and 1000  C
(PBS) at pH 7.0 was prepared by using 0.05 M Na2HPO4 and for 2 h are denoted as CPM-x-A1, CPM-x-A2, and CPM-x-A3,
NaH2PO4 solutions. The pH of the solutions was adjusted with respectively, where x represents the original carbonization
0.5 M H2SO4 and 2.0 M NaOH. All other chemicals used were temperature.
analytical grade and all solutions were prepared using ultrapure
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water (Millipore).
2.4 Fabrication of CPM-modied electrode

2.2 Instrumentation To prepare carbon electrodes for electrochemical sensors,


typically 5.0 mg CPM was rst dispersed in 1.0 mL water and
All powdered X-ray diffraction (XRD) patterns were recorded on
sonicated for 2 h; then 6.0 mL of the substrate was withdrawn
a PANalytical (X'Pert PRO) diffractometer using CuKa radiation
and placed onto the pre-cleaned GCE. The CPM-modied elec-
(wavelength l ¼ 0.1541 nm). Textural properties of CPMs,
trode was allowed to dry in air at 30  C for 2 h, followed by gently
including Brunauer–Emmett–Teller (BET)-specic surface
rinsing with doubly distilled water several times to remove the
areas, pore volumes, and pore sizes were analyzed by nitrogen
loosely bound carbon prior to further electrochemical
adsorption/desorption isotherm data measured on a Quan-
measurements, which were carried out at RT under inert (N2)
tachrome Autosorb-1 apparatus (at 77 K). The pore size distri-
atmosphere.
bution of each CPM was derived from the adsorption branch of
the isotherm using the Barrett–Joyner–Halanda (BJH) method.
The morphology of various samples was monitored by eld 3. Results and discussion
emission-transmission electron microscopy (FE-TEM; JEOL
3.1 Structural and textural properties of CPMs
JEM-2100F). All Raman spectra were recorded at ambient
temperature on a WITeck CRM200 confocal microscopy system Fig. 1 shows the large-angle powdered XRD patterns of assorted
equipped with a laser (l ¼ 488 nm). Cyclic voltammetry (CV) and pristine and activated CPM samples. Regardless of the post-
differential pulse voltammetry (DPV) studies were performed on synthesis activation treatment, all CPMs exhibit two main
an electrochemical analyzer (CH instruments; CHI 900). characteristic peaks associated with turbostratic carbons with
graphitized structures.46–48 More specically, the diffraction
2.3 Material synthesis peaks at 23.5 and 43.5 may be attributed to (002) and (100)
index planes, respectively. The degree of graphitization of
CPMs were synthesized under conditions based on procedures
various CPMs was also examined by Raman spectroscopy.
reported previously.41–44 Typically, 0.0056 g of Na2CO3 was rst
Raman spectra obtained from CPMs revealed two characteristic
dissolved in carbon precursors consisting of formaldehyde
peaks centering at ca. 1360 (D-band) and 1600 (G-band) cm1,
(1.13 g) solution (37 wt%) and resorcinol (1.10 g) at RT for 1 h in
which may be attributed to disorder or defects located at the
a stirring water bath (see Step I, Scheme S1 in the ESI†). The
edges of graphite platelets and sp2-bonded graphitized carbons,
resultant polymeric RF resol (light brown) was then mixed with
respectively (Fig. S1; ESI†).49,50 Accordingly, the D- to G-band
a solvent mixture (ethanol–water ¼ 7 : 2) together with the
amphiphilic Pluronic F-127 surfactant polyol (0.8 g; as the
structural directing agent or so template). To this solution, 1.0
mL of 2.0 M HCl were added dropwise under continuous stir-
ring. Subsequently, the precipitated mixture was then subjected
to microwave irradiation (typically for 1–2 h), followed by curing
(at 100  C overnight), washing and drying of the polymeric gel
(Step II, Scheme S1; ESI†). Finally, the dried sample was sub-
jected to a carbonization procedure in a tube furnace under a
continuous ow of N2 gas. Typically, the carbonization proce-
dure was carried out by slowly ramping from RT to 350  C with
a rate 1  C min1, then, by further liing the temperature to
600–900  C at a rate of 2  C min1, and kept at the nal
temperature for 5 h before being cooled to RT (Step III, Scheme
S1; ESI†). The samples so prepared are denoted as CPM-x, where
x denotes the carbonization temperature (Tc). Additional acti-
vation of CPMs with CO2 were also performed.45 This was done
by loading the pristine CPM (1 g) in a quartz tube placed
inside the furnace. Subsequently, the substrate was rst heated
under a N2 environment at a rate 10  C min1 until reaching a Fig. 1 Large-angle XRD patterns of (a) CPM-350, (b) CPM-600, (c)
temperature of 900  C, followed by switching to a CO2 gas CPM-900, (d) CPM-900-A1, (e) CPM-900-A2, and (f) CPM-900-A3
stream (ow rate 30 cm3 min1) at a designated temperature materials.

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peak intensity ratio (ID/IG) deduced for the CPM-900 sample is


1.1, revealing the presence of graphitized carbon structure.
Based on SEM results, the as-synthesized CPMs exhibited
morphology of micron-size crystalline aggregates with irregular
shapes (see Fig. S2; ESI†). Additional TEM studies revealed that
the pristine CPMs thus fabricated via the microwave-assisted
synthesis procedure showed mesosopic pores with short-range
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ordering (Fig. 2a and S3; ESI†), indicating the presence of


multidimensional wormhole-like pore structure,51,52 which is
consistent with the results obtained from N2 adsorption/
desorption isotherm measurements. As displayed in Fig. 3A, Fig. 3 N2 adsorption/desorption (77 K) isotherms of various CPMs (A)
the isotherms obtained from pristine CPM-x (x ¼ 350, 600, and before and (B) after activation treatment by CO2. (a) CPM-350, (b)
CPM-600, (c) CPM-900, (d) CPM-900-A1, (e) CPM-900-A2, (f) CPM-
900  C) samples exhibit typical Type-IV curves with indicated 900-A3.
capillary condensation steps at P/P0  0.4–0.7 and well-dened
H1-type hysteresis loop anticipated for mesoporous materials.53
The sharp increase of the isotherm curve at P/P0 < 0.05 also
obtained from TEM (Fig. 2a and S3; ESI†) and isotherm
reveals the presence of microporosity in these CPMs. Moreover,
measurements (Fig. 3A). The presence of microporosity was
a notable increase in BET surface area (SBET) and total pore
further analyzed by using the t-plot method. The results of the
volume (Vo) with increasing carbonization temperature (Tc) may
microporous surface area and pore volume derived from t-plot
be inferred for the pristine CPMs. As shown in Table 1, the SBET
analyses are given in Table 1.
observed for CPMs prepared with Tc from 350 to 900  C
Upon activation with CO2, notable increases in structural
increased from 243 to 744 m2 g1, while the corresponding Vo
and absorptive properties were observed for the activated CPMs
also increased from 0.20 to 0.53 cm3 g1. On the other hand, a
as compared to the as-synthesized CPM-900 sample. This may
consistent decrease in average pore size (dBJH) with Tc was
be readily seen by the variations in TEM proles (Fig. 2) and
observed for these CPMs, as revealed by results deduced from
isotherm curves (Fig. 3B). As a result, substantial increases in
their BJH pore-size distributions (Table 1 and Fig. S4; ESI†). For
SBET and Vo were also found. This phenomenon, which became
example, a notable decrease in pore size was observed for the
more pronounced with increasing severity of the activation
CPM-900 sample (dBJH ¼ 5.9 nm) compared to CPM-600 (dBJH ¼
treatment, was accompanied by simultaneous increase in
6.9 nm). It is noteworthy that a narrower pore-size distribution
microporosity as well as a decrease in dBJH (Table 1). For
prole was observed for CPMs graphitized at higher Tc, indi-
example, upon activation of the pristine CPM-900 at 1000  C for
cating that carbon framework shrinkage is accompanied by
2 h under the CO2 environment, signicant increases in SBET
improved structural ordering, which coincides with results
(from 744 to 2661 cm2 g1) and Vo (from 0.53 to 2.05 cm3 g1)
were observed for the resultant CPM-900-A3 (Table 1). Mean-
while, the corresponding microporous surface area and pore
volume were also found to increase from 411 to 510 cm2 g1 and
0.18 to 0.28 cm3 g1, respectively, while dBJH decreased from
5.9 to 5.4 nm. However, a slight degradation of mesostructure
was observed for carbon samples subjected to prolonged treat-
ment at elevated activation temperature (Ta $ 1000  C), as evi-
denced by the broadening of characteristic diffraction peaks
(Fig. 1). Nonetheless, a similar ID/IG ratio (1.1) was deduced for
CPM-900 sample before and aer activation treatment (Fig. S1;
ESI†). Similar behaviours were also found for CO2-activated
mesoporous carbons prepared from phenol–formaldehyde
resol.54

3.2 Electrochemical oxidation of DA


We applied cyclic voltammetry (CV) technique to assess the
performance of electrochemical oxidation of DA over the CPM-
modied glassy carbon electrode (GCE). Over the unmodied
GCE, the DA oxidation peak recorded in the presence of N2-
saturated phosphate buffer solution (PBS) with 2.0 mM DA was
found to locate at 0.453 V (Fig. S5a; ESI†). Moreover, as a blank
Fig. 2 TEM images of (a) as-synthesized CPM-900, (b) CPM-900-A1,
test, no peak was observed for the bare CPM-900-A3-modied
(c) CPM-900-A2 and (d) CPM-900-A3 obtained after various CO2- GCE in PBS without the presence of DA (Fig. S5b; ESI†). On the
activation treatments (see text). other hand, an enhanced DA oxidation peak at 0.209 V was

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Table 1 Textural properties of as-synthesized and activated CPM samples, electrochemical activities, and relevant kinetic parameters obtained
from corresponding CPM-modified GCE during DA detectiona

CO2 activation SBET (m2 g1) Vo (cm3 g1)

Sample Tc ( C) Ta ( C) Time (h) Total Micropore Total Micropore dBJH (nm) Ipab (mA) Dc (cm2 s1) Kad (cm s1)

CPM-350 350 — — 243 120 0.20 0.31 7.9 2.3 0.007 0.01
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CPM-600 600 — — 541 381 0.37 0.15 6.9 4.7 0.031 0.04
CPM-900 900 — — 744 411 0.53 0.18 5.9 8.9 0.110 0.59
CPM-900-A1 900 900 1.0 1116 449 0.69 0.19 5.8 2.7 0.010 0.66
CPM-900-A2 900 1000 1.0 1349 486 0.84 0.22 5.9 2.8 0.011 0.69
CPM-900-A3 900 1000 2.0 2661 510 2.05 0.28 5.4 27.0 1.012 0.88
a
SBET ¼ BET surface area; Vo ¼ pore volume; dBJH ¼ BJH pore size; Ipa ¼ anodic peak current; D ¼ diffusion coefficient; Ka ¼ apparent electron
transfer rate constants. b Determined with a scan rate of 50 mV s1. c Calculated from Randles–Sevcik equation (ESI). d Derived from Laviron
equation (ESI).

observed over the CPM-900-A3-modied GCE at a scan rate of electrode surface.61 These results reveal that CPM-900-A3 pores
50 mV s1 (Fig. S5c; ESI†). Interestingly, the corresponding peak act as reservoirs, which effectively reduce the diffusion length of
current increased 27-fold compared to that of the pristine GCE; ions from the electrolyte. This was further veried by varying the
this may be attributed to the faster diffusion and electron scan rate of CV measurement, as illustrated in Fig. 4a for the
transfer rate observed for the CPM-900-A3-modied GCE CPM-900-A3-modied GCE in N2-saturated PBS with 2 mM DA.
compared to the other CPMs (Table 1; more details in ESI†).55,56 The fact that the oxidation peak current (Ipa) showing a linear
For comparison, CV curves recorded from various modied dependence with the scan rate between 50 and 500 mV s1
electrodes are also depicted (Fig. S6; ESI†). Evidently, electrodes (Fig. 4b) indicates that oxidation of DA at the CPM-modied
modied with CPM-900-A3 exhibited the best electrochemical electrode is indeed a surface-controlled process.62 A mechanism
performance towards the detection of DA. This may be attrib- invoking the reversible electron transfer between DA and
uted to the enriched porosities and higher surface possessed by dopamine-o-quninone over the CPM-modied electrode is
CPM-900-A3 (vide supra). It is also noteworthy that the DA illustrated in Scheme S2 (ESI†).
oxidation potential so observed over the CPM-modied GCE is Next, we studied the effects of pH in the buffer solution on
much lower than that over other carbon modied electrodes, electro-oxidation of DA over CPM-modied GCE. This was
such as carbon nanotube (CNT)-modied ionic liquid gel carried out by varying the pH (3.0–11.0) of N2-saturated PBS
(ILG),57 graphene,58 or thionine-naon supported on multi-wall containing 2.0 mM DA. The CV curves recorded with a scan rate
carbon nanotubes (MWCNTs),59 as summarized in Table 2. This of 50 mV s1 under varied buffer solution pH are displayed in
is attributed to the excellent conductivity and high surface areas Fig. 5. Upon increasing pH of the buffer solution containing DA,
possessed by the CO2-activated CPM.60 Moreover, the CPM-900- the CV curve of CPM-900-A3-modied GCE tends to shi toward
A3-modied GCE also exhibited a well-dened oxidation peak of more negative anodic and cathodic peak potentials, and vice
DA with peak to peak separation (DEp) of 41 mV. Such a small versa for descending pH. On the basis of linear correlation
DEp value is favourable for fast electron transfer of DA at the between the anodic peak potential and pH of the buffer

Table 2 Types of modified electrodes and performance as DA sensors

DA detection Sensitivity Oxidation


Modied electrodesa limit (mM) (mA mM1 cm2) Detection methoda potential (V) Reference

MWCNT/GONR 0.08 3.14 Amperometry 0.20 33


MPEG polymer 0.05 198.4 DPV 0.25 34
Degraded dopamine 0.04 1.20 SWV 0.19 35
CCINPs-CS 0.83 2.20 DPV 0.24 36
GNPs/graphene 0.04 2.27 DPV 0.27 37
Pt/carbon 0.12 — CV 0.21 38
CNTs-ILG 0.10 — DPV 0.27 57
Graphene — — DPV 0.25 58
Thionine-naon/MWNT 0.20 — DPV 0.52 59
Calix[4]arene crown-4 ether 3.40 — CV 0.44 63
CPM 0.002 2560 DPV 0.17 This work
a
Abbreviations: MWCNT ¼ multi-wall carbon nanotube; GONR ¼ graphene oxide nanoribbon; MPEG ¼ methoxypolyethylene glycol; CCINPs-CS ¼
carbon-coated iron nanoparticles-chitosan; GNPs ¼ gold nanoparticles; ILG ¼ ionic liquid gel; CPM ¼ carbon porous material; DPV ¼ differential
pulse voltammetry; SWV ¼ square-wave voltammetry; CV ¼ cyclic voltammetry.

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Fig. 6 (a) DPV curves of CPM-900-A3-modified GCE in N2-saturated


PBS with varied concentrations of DA (9.0 nm–0.3 mM). Inset (b):
Fig. 4 (a) Cyclic voltammogram of CPM-900-A3-modified GCE in correlation of peak current with DA concentration.
N2-saturated PBS with 2.0 mM DA recorded at different potential scan
rates (50500 mV s1). Inset (b): Ipa and Ipc vs. scan rate.

peak at 0.172 V was observed for DA, a linear correlation


between the peak current and DA concentration was also
solution, a slope of Epa (V) 45.9 mV pH1 was derived from the observed, as shown in Fig. 6b. The linear correlation may be
regression tting equation shown in Fig. 5b (inset). This value is expressed as Ipa ¼ 202.37 (0.36) [DA] + 0.6529 (0.054), with an
very close to the theoretical value of 59 mV pH1 at 25  C for excellent regression coefficient of R2 ¼ 0.9929. Accordingly, an
the transport process with an equal number of protons (H+) and excellent DA detection limit of 2.9 nM. An extraordinary sensi-
electrons (e).63 Thus, we may conclude that electro-oxidation of tivity of 2.56 mA mM1 cm2 may be derived, which surpasses
DA over the CPM-modied GCE invokes an equal number of other modied electrode materials previously reported for
protons and electrons during the electrochemical transfer electrochemical detection of DA (Table 2). The superior
process. Moreover, from the variation of anodic peak current performance is attributed to the large surface area, good elec-
(Ipa) with pH, a maximum peak current at pH ¼ 7.0 may be trical conductivity, higher energy adsorption sites of the CO2-
inferred for the presence of DA. activated CPM, and the lower over-potential and the enormous
anodic peak current observed for the proposed DA sensor using
3.3 Electrocatalytic performance of CPM-modied electrode the CPM-modied electrode. Thus, the unique CPM-modied
electrode report herein is highly desirable for sensitive detec-
Fig. 6a shows the typical differential pulse voltammetry (DPV)
tion of DA.
curves for electrooxidation of DA over CPM-900-A3-modied
GCE in N2-saturated PBS (pH ¼ 7.0) with different DA concen-
3.4 Stability, reproducibility and selectivity in DA detection
trations (from 9.0 nM to 0.3 mM). While a maximum oxidation
The stability of the CPM-900-A3-modied GCE was investigated
by monitoring the variation of CV curve over a period of 10 days.
Again, modied electrodes in 0.1 M PBS containing 2.0 mM DA
were employed to record the CV curve daily for 10 days. The 10
CV curves so collected readily overlapped on top of each other,
as shown in Fig. 7a. The anodic peak response current declined
only slightly over the 10 day period (Fig. 7b; inset), revealing a
satisfactory stability for the detection of DA. Moreover, the
reproducibility of the CPM-modied GCE during DA detection
was accessed by performing CV measurement consecutively for
10 cycles. The resultant CV curves nearly overlapped on top of
one another (Fig. 7c; inset). Thus, our device offers excellent
reproducibility as a DA sensor.
To examine the relative reactivity and selectivity of the CPM-
900-A3-modied electrode toward detection of DA, DPV curves
were performed with varied concentrations of DA while in the
presence of two other electroactive biomolecules, namely
Fig. 5 (a) CV curves of CPM-900-A3-modified GCE in N2-saturated
ascorbic acid (AA) and uric acid (UA). Since AA and UA have
PBS of varied pH (3–11) with 2.0 mM DA recorded at a scan rate of 50 rather similar electrochemical properties with DA (see Scheme
mV s1. Insets: (b) E0 vs. pH, and (c) Ipa vs. pH plots. 3; ESI†), they tend to oxidize at nearly the same potential over

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may be inferred, indicating the excellent electrocatalytic


performances of the CPM-modied GCE for sensitive and
selective detection of DA, even in the presence of high
concentrations of foreign species.

4. Conclusions
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Carbon porous materials (CPMs) were successfully synthesized


by a microwave irradiation route and were characterized by
XRD, N2 adsorption/desorption isotherm measurements, SEM,
FE-TEM, and Raman spectroscopy. These CPMs possess a high
surface area (up to 2660 m2 g1) aer activation treatment by
CO2. We assessed their electrocatalytic performances via cyclic
voltammetry (CV) and differential pulse voltammetry (DPV). The
CPM-modied sensor exhibits a linear correlation between peak
Fig. 7 (a) Ten overlapped CV curves of CPM-900-A3-modified GCE in current and DA concentration (9.0 nM–0.3 mM), with an excel-
N2-saturated PBS with 2.0 mM DA recorded (scan rate of 50 mV s1) lent detection limit of 2.9 nM and ultrahigh sensitivity of 2.56
daily over a period of 10 days. Insets: (b) variation of response peak
mA mM1 cm2 for detecting DA, surpassing the conventional
current with time, and (c) CV curves recorded over 10 consecutive
cycles. GCE and other modied electrodes. Moreover, we report supe-
rior stability, reproducibility, and selectivity of the new CPM-
modied electrode, which should have important practical
application as a DA sensor in biological sample systems, even in
most conventional electrodes.64 Thus, it is highly desirable to
the presence of foreign species.
develop sensitive and selective methods for detection of DA in
the presence of UA and AA.65,66 Interestingly, linear dependence
of the observed peak current with DA concentration was also Acknowledgements
observed over a wide range (0.05–0.45 mM) in the presence of
Financial support for this work by the Ministry of Science and
large quantities of AA (10 mM) and UA (1 mM), as shown in
Technology, Taiwan (NSC101-2113-M-001-020-MY3 to SBL) is
Fig. 8. The linear correlation may be expressed as Ipa ¼ 175.35
gratefully acknowledged. The authors thank Prof. Tom T. S. Lin
[DA] + 4.157, with R2 ¼ 0.9963. Accordingly, the calculated value
for helpful discussions.
of the detection limit and sensitivity were determined as 3.2 nM
and 2.21 mA mM1 cm2, respectively. Similar conclusions may
be drawn based on results obtained from separate experiments Notes and references
carried out with even higher concentrations of AA (20 mM), and
1 Y. Deng, J. Wei, Z. Sun and D. Zhao, Chem. Soc. Rev., 2013, 42,
UA (2 mM), as shown in Fig. S7 (ESI†). In this case, a detection
4054–4070.
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