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A B S T R A C T
Indium tin oxide-coated glass substrates were modied with tris (2,2-bipyridyl) ruthenium (II) dichloride
hexahydrate [Ru(bpy)3]2 +/Naon solution via dip-coating. The Naon[Ru(bpy)3]2 + ratio was varied to
optimize the sensitivity of the modied electrodes in detecting lead (Pb2 +) and cadmium (Cd2 +). The surface
morphology of the deposited thin lm was characterized by scanning electron microscopy (SEM). The lowest
concentration detected was 0.007 M (0.001 g/mL) and 4.91 M (0.552 g/mL) for lead and cadmium, re-
spectively. The optimum Naon volume concentration in the lm was 0.4% which gave an average lm
thickness of 217.90 nm.
Corresponding author at: Technological University of the Philippines, Ermita, Manila, Philippines.
E-mail address: toni_lopez@dlsu.edu.ph (T.B.G. Lopez).
http://dx.doi.org/10.1016/j.sbsr.2017.07.001
Received 15 May 2017; Received in revised form 18 July 2017; Accepted 19 July 2017
2214-1804/ 2017 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/BY-NC-ND/4.0/).
T.B.G. Lopez et al. Sensing and Bio-Sensing Research 15 (2017) 3440
Laboratory grade lead II chloride was purchased from Techno software to perform the electrochemical measurements. The three
Pharmachem, India and cadmium chloride was from Sigma Aldrich as electrode system consisted of a platinum wire as counter electrode,
well. saturated calomel electrode (SCE) as reference electrode, and the
modied electrode as the working electrode. During the cleaning and
2.2. Apparatus deposition stages of the anodic stripping voltammetry, a high purity
nitrogen gas was used for sparging while a ceramic magnetic stirrer was
BST8-stat Potentiostat/Galvanostat (ALV Technologies) along with used for stirring. The surface morphology of the modied electrode was
voltammetric cell and the three electrode system (Pine Research investigated using the JEOL Model 5310 Scanning Electron Microscope
Instrument) was interfaced to a computer with installed BST8-stat (SEM).
Fig. 1. Modied electrodes with varying Naon concentrations at (A) 0.1%, (B) 0.2%, (C) 0.3%, (D) 0.4%, and (E) 0.5% volume concentration. SEM micrographs at 15000 mag-
nication.
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T.B.G. Lopez et al. Sensing and Bio-Sensing Research 15 (2017) 3440
0.10% 74.60 121.20 97.90 2.3.2. Second optimization: varying [Ru(bpy)3]2 + concentrations
0.20% 102.80 140.20 121.50 The Naon volume concentration that obtained the highest anodic
0.30% 117.20 195.00 156.10 current for the rst optimization was held constant in this optimization.
0.40% 135.00 300.80 217.90
The mass of the mediator per unit volume of Naon in the coating
0.50% 155.20 323.60 239.40
solution was varied at 1 mg/mL, 5 mg/mL, 10 mg/mL [8], 20 mg/mL,
and 40 mg/mL. The same dip coating and ASV parameters from the rst
2.3. Procedure optimization were applied.
Fig. 4. Modied electrodes with varying Naon concentrations at (A) 1 mg/mL (B) 5 mg/mL, (C) 10 mg/mL, (D) 20 mg/mL, (D) 20 mg/mL, and (E) 40 mg/mL [Ru(bpy)3]2 + mediator
concentration. SEM micrographs at 15000 magnication.
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T.B.G. Lopez et al. Sensing and Bio-Sensing Research 15 (2017) 3440
2.3.3. Calibration curve The plots of the reduction current versus the mediator concentration
The optimized modied electrode was used to determine increasing (Figs. 5 and 6) show that the reduction current increased as the med-
concentrations of lead and cadmium in an electrolyte solution. The iator concentration was increased from 1 mg/mL to 5 mg/mL and de-
same parameters from the rst and second optimizations were applied creased when the mediator concentration was increased from 10 mg/
in the ASV tests. The minimum detection concentration was identied mL to 40 mg/mL. The optimum concentration was therefore 5 mg of
by getting a series of voltammograms until a at line (zero current) or [Ru(bpy)3]2 + for every 1 mL of 10% Naon.
noise was registered. The highest anodic current was plotted against the
heavy metal concentration. The Pearson coecient (R2) and the slope
were then determined. 3.3. Calibration curve
3. Results and discussion The optimized dip coated modied electrode was used as the
working electrode in ASV to detect dierent concentrations of lead and
3.1. First optimization cadmium. The voltammograms obtained in the ASV tests were overlaid
(Fig. 7-A and Fig. 8-A) and the peak current was plotted against the
Fig. 1 showed dierent micrographs of the deposited thin lm on heavy metal concentration (Fig. 7-B and Fig. 8-B).
ITO surface. The smoothness of the surface became more evident as the From the gures shown, the peak current increases as the heavy
Naon volume concentration was increased. The thicknesses of the metal concentration was increased, both for lead chloride and cadmium
lm deposited from the upper (near the clip) and lower (other end) chloride. The concentrations of the heavy metal ions were calculated
regions of a 2.5 cm 1.0 cm dip coated substrate were measured by (cf. Table 2) since the chlorine component of the compound dissociated
scraping the center of the sample, then the SEM stage was lowered during the ASV tests. The lowest concentrations of lead and cadmium
maintaining a working distance of 14 mm and tilted to an angle 75. that the optimized electrode has detected are 0.007 M (0.001 g/mL)
Table 1 showed the direct relationship of the Naon volume con- and 4.91 M (0.552 g/mL), respectively. Triplicate ASV runs were
centration to the thickness of the deposited lm. The dierence in the performed to determine the detection limit of the electrode.
upper and lower regions was attributed to gravity since the substrate
was dip coated into the solution and allowed the remaining solution to
drip o the substrate. As expected, the upper regions have thinner lm
than the lower regions.
As the fabricated electrodes were used in ASV, a noticeable increase
in the peak current as the Naon volume concentration was increased.
The Naon concentration that maximized the eectivity of the mod-
ied electrode was 0.4%. This means the resulting lm was not too
thick enabling the incorporated redox mediators to facilitate electron
transfer relatively faster compared to other concentrations [25,2729].
At greater concentrations, the polymeric thickness was thicker than the
diusion layer thus preventing the eective detection of the heavy
metals (cf. Figs. 2 and 3).
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Fig. 10. Peak Current vs. Cycle Number graph showing relatively constant peak current values as the number of cycle is increased.
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