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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.
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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 purication. 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-modied electrode
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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
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-modied 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 veried 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-modied GCE CPM-900-A3-modied 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 modied 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-modied
modied 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-modied 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-modied GCE is Next, we studied the effects of pH in the buffer solution on
much lower than that over other carbon modied electrodes, electro-oxidation of DA over CPM-modied GCE. This was
such as carbon nanotube (CNT)-modied ionic liquid gel carried out by varying the pH (3.0–11.0) of N2-saturated PBS
(ILG),57 graphene,58 or thionine-naon 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-modied GCE tends to shi toward
A3-modied GCE also exhibited a well-dened 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
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4. Conclusions
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