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Electrodeposition of Gold on Fluorine-Doped Tin Oxide: Characterization and

Application for Catalytic Oxidation of Nitrite

Article in Bulletin- Korean Chemical Society · June 2014

DOI: 10.5012/bkcs.2014.35.7.XXX

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Electrodeposition of Gold on Fluorine-Doped Tin Oxide Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 1
http://dx.doi.org/10.5012/bkcs.2014.35.7.XXX

Electrodeposition of Gold on Fluorine-Doped Tin Oxide:

Characterization and Application for Catalytic Oxidation of Nitrite
Md. Mahbubur Rahman, Xiao-Bo Li, Nasrin Siraj Lopa, and Jae-Joon Lee*

Nanotechnology Research Center & Department of Applied Life Science, College of Biomedical and Health Science,
Konkuk University, Chungju 380-701, Korea. *E-mail: [email protected]
Received January 7, 2014, Accepted March 17, 2014

Sub-micrometer size gold particles were electrodeposited on a transparent fluorine-doped tin oxide (FTO) from
acetonitrile solution containing AuCl4− and tetramethylammonium tetraflouroborate (TMATFB) for detecting
NO2−. A series of two-electron (2e−) and one-electron (1e−) reductions of the AuCl4−-AuCl2−-Au redox systems
were observed at FTO and a highly stable and homogeneous distribution of Au on FTO (Au/FTO) was obtained
by stepping the potential from 0 to −0.55 V (vs. Ag/Ag+). The Au/FTO electrode exhibited sufficiently high
catalytic activity toward the oxidation of NO2− with a detection limit (S/N = 3) and sensitivity of 2.95 µM and
223.4 μA·cm−2·mM−1, respectively, under optimal conditions. It exhibited an interference-free signal for NO2−
detection with excellent recoveries from real samples.
Key Words : Gold, Fluorine-doped tin oxide, Electrodeposition, Cyclic voltammetry, Nitrite oxidation

Introduction stabilities are required. Sheridan et al. directly electrodeposited

Au nanoparticles on FTO and 3-aminopropyldimethylmeth-
Electrodes modified with gold nanostructures have attracted oxysilane (ADMMS)-modified FTO in an aqueous phase
much interest because of their stability and high surface area with an emphasis on the control of nucleation mechanism,20
along with an excellent catalytic activity toward many analytes while the potential application to sensing devices were left
including CO and nitrite (NO2−).1-3 They are particularly for further study.
suitable for many electrochemical sensor applications such This work reports a similar binder-free approach for the
as the quantitative detection of NO2− level in many foods electrochemical deposition of sub-micrometer size Au particles
and human blood stream to facilitate compliance with the on FTO at room temperature from acetonitrile solution to
maximum contaminant level of NO2− (MCL; 1 ppm, 21.7 investigate the catalytic oxidation of NO2−. It was found that
μM, as defined by the Environmental Protection Agency the Au/FTO electrode prepared in this study performed a
(EPA)).4-7 strong catalytic oxidation of NO2− within a reasonable detec-
Although the electrochemical detection method is simple tion range without any serious interference from many
and cost-effective,8-10 it often requires undesirably high over- common ions.
voltage for voltammetric oxidation/reduction of NO2−, which
in turn causes significant interference by other readily oxidized Experimental
compounds (e.g., Ca2+, Zn2+, Cl−, SO42−, NO3−, etc.).11
Therefore, the preparation of electrodes modified by Au Chemicals. Double-distilled water obtained from a Milli-
would be a promising strategy to decrease the oxidation/ Q water-purifying system (18 MΩ·cm) was used in all experi-
reduction overpotential12 for many applications that require ments. Chloroauric acid (HAuCl4), acetonitrile, tetramethyl-
high catalytic activities at electrodes; it would also be very ammonium tetraflouroborate (TMATFB), disodium hydro-
useful when thin and transparent conducting oxides (TCOs) gen phosphate (Na2HPO4), sodium dihydrogen phosphate
are used as substrates for electrode preparation. TCOs such (NaH2PO4), sodium nitrite (NaNO2), calcium chloride (CaCl2),
as indium tin oxide (ITO) and fluorine-doped tin oxide magnesium sulfate (MgSO4), zinc chloride (ZnCl2), zinc
(FTO) are already used in a wide variety of applications for nitrate (Zn(NO3)2), and sodium carbonate (Na2CO3) were
biosensors, display devices, and many solar energy conver- used as received from Sigma-Aldrich. Phosphate buffer saline
sion systems.13-15 Although various self-assembly approaches (PBS) solution was prepared by mixing 0.1 M Na2HPO4
have been applied to the deposition of gold nanostructures with 0.1 M NaH2PO4.
on TCOs, they usually require special organic binders such Instrumentation. A CHI430A electrochemical workstation
as (aminopropyl)siloxane, (mercaptopropyl)siloxane,16 which (CH instruments, Inc. USA) was used for electrochemical
often deteriorate the catalytic activity and conductivity of Au measurements. An FTO electrode (8 Ω/Sq. TEC8, Pilkington),
deposits. Meanwhile there were many reports on the electro- a platinum wire, and a Ag/Ag+ or Ag/AgCl (aq, saturated
deposition of Au directly on ITO in an aqueous phase,17-19 it KCl) electrode were used as working, counter, and reference
was hardly found on FTO even though the latter is more electrodes, respectively. Differential pulse voltammograms
useful in many cases where higher thermal and chemical (DPVs) were obtained by scanning the potential from 0.6 to
2 Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 Md. Mahbubur Rahman et al.

1.0 V with the pulse amplitude of 100 mV·s−1, pulse width of AuCl2− + e− ↔ Au + 2Cl− (2)
2 ms, and pulse period of 100 ms. Electrochemical impedance
Similar voltammetric behavior of AuCl4− was observed at a
spectra (EIS) were obtained at +0.30 V in the frequency
glassy carbon electrode (GCE) (Inset, Fig. 1) and is essentially
range of 105-0.1 Hz with an AC amplitude of 5 mV (IM6ex,
consistent with the voltammetric responses of AuCl4− at
Zahner-Elektrik GmbH & Co. KG). Simulation of EIS
GCE in ionic liquid systems such as 1-methyl-3-ethylimid-
spectra with the equivalent circuit model was performed by
azolium chloride (EMIC) and 1-ethyl-3-methylimidazolium
using Z-view software (version 3.1, Scribner Associates
tetrafluoroborate (EMIBF4).21,22
Inc., USA). Field emission scanning electron microscopy
FE-SEM and EDS Characterization of Gold Deposits.
(FE-SEM, JSM-6700F, JEOL) and energy dispersive X-ray
Figures 2(a)-(c) shows the typical FE-SEM images of the Au
spectroscopy (EDS, INCAx-sight7421, Oxford Instruments)
deposited on FTO for 25, 50, or 100 s. The average size of
were used to characterize the surface morphology and
Au deposits increased with deposition time (τ) (ca. 300, 500,
elements, respectively.
and 1000 nm, respectively), and they were homogeneously
Deposition of Gold on FTO. A sheet of FTO (15 × 30
distributed. The EDS spectrum confirmed the formation of
mm2) was cleaned by sonication in Triton X-100 aqueous
pure Au by electrochemical deposition (Fig. 2(d)).
solution and washed with ethanol and acetone followed by
Voltammetric and EIS Characterization of Au/FTO
drying under nitrogen purging. For the electrochemical de-
Electrodes. The CVs of the Au/FTO electrodes in PBS (pH
position of Au, the FTO sheet was placed into a Teflon cell
7.0) over a potential range from 0.0 to 1.4 V clearly indicate
containing acetonitrile with 0.5 mM HAuCl4 and 0.25 mM
the formation of gold oxide (AuOx) on Au deposit, peaked at
TMATFB. The cell had an exposed area of ca. 0.32 cm2
ca. 1.0 V by positive polarization,23 which reduced back at
defined by O-ring. Au/FTO was prepared by stepping the
ca. 0.4 V during the reverse scan (Fig. 3(a)). It was seen that
potential from 0 to −0.55 V for 25, 50, or 100 s.
both peaks reach a maximum current at the deposition time
(τ) of 50 s, and thereafter decrease with τ. The latter behavior
Results and Discussion
is attributable to a decrease in the net surface area of Au on
FTO as the electrochemical deposition process continued. It
Redox Behavior of AuCl4− at FTO. In Figure 1, two
is consistent with the monotonic increase in the size of Au
cathodic waves are observed at ca. −0.30 (I) and −0.65 V (II)
nanostructures with increasing τ while the density decreased,
in the cyclic voltammograms (CVs) of AuCl4− at FTO
as shown in the SEM images. This strongly suggested that
during a negative potential scan from 2.0 to −0.75 V along
the electrochemical deposition of Au on FTO was done by
with the corresponding anodic waves that peak at ca. 1.5 (I')
instantaneous nucleation process followed by the growth
and 0.67 V (II') in the reverse scan. They are attributed to the
and coalescence of the existing nuclei without the formation
reduction of AuCl4− to AuCl2−, and of AuCl2− to Au (i.e., the
of additional nuclei as suggested in the previous litera-
forward reactions of 1 and 2), respectively, while the two
tures.20,24,25 Both CVs and EIS spectra in Figures 3(b) and
corresponding anodic peaks are assigned to I' and II' (i.e., the
3(c) showed that the peak-to-peak separation (∆Ep) and the
backward reactions of 1 and 2), respectively.21
charge transfer resistance (Rct) were smallest at τ = 50 s. It
AuCl4− + 2e− ↔ AuCl2− + 2Cl− (1) indicated the highest electrochemical catalytic reactivities
for Au/FTO prepared at τ = 50 s (Table 1), which was con-

Figure 1. Cyclic voltammograms (CVs) obtained at an FTO

electrode in an acetonitrile solution containing 0.5 mM HAuCl4
and 0.25 mM TMATFB. Potential scan range: 2.0 to −0.75 V
(solid line); 2.0 to −0.40 V (dot line). Inset shows CVs obtained at Figure 2. FE-SEM images of sub-micrometer size Au deposited
GCE in the same solution. Potential scan range: 2.0 to −0.75 V on FTO for 25 s (a), 50 s (b), 100 s (c), and an EDS spectrum of the
(solid line); 2.0 to −0.40 V (dash line). Scan rate: 100 mV·s−1. Au/FTO electrode deposited for 50 s (d).
Electrodeposition of Gold on Fluorine-Doped Tin Oxide Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 3

Figure 3. (a) Cyclic voltammograms (CVs) of FTO and different Au/FTO electrodes in PBS (pH 7.0): scan rate 100 mV·s−1. CVs (b) and
electrochemical impedance spectra (EIS) (c) of FTO and different Au/FTO electrodes in 5 mM [Fe(CN)6]3−/4− (in PBS, pH 7.0); scan rate
100 mV·s−1. (d) CVs of the Au/FTO electrode in 1 mM NO2− and PBS (pH 7.0), and FTO electrode in 1 mM NO2−; scan rate 100 mV·s−1. (e)
CVs of the Au/FTO electrode in 1 mM NO2− at different scan rates (a-f: 20, 50, 100, 150, 200, 300 mV·s−1). Inset show the plot of Jpeak vs.
ν1/2 and Epa vs. logν. (f) Calibration plot of Jpeak vs. [NO2−] (0.01, 0.025, 0.050, 0.075, 0.1, 0.25, 0.5 and 0.75 mM) obtained from differential
pulse voltammetric responses at Au/FTO sensor.

sidered as the optimum condition hereafter, due to the 0.13 cm2, equivalent to ca. 40.6% of the geometric area of
maximized net surface area of Au under this deposition time. FTO, under optimum deposition time (50 s) as shown in
The net surface area of Au nanostructure on FTO was Figure 3(a) (Table 1). The apparent standard heterogeneous
calculated from the net charge of the gold oxide (AuOx) rate constant (kapp) at the electrodes, calculated from EIS in
reduction with respect to that of the AuOx monolayer (ca. Figure 3(c), also consistent with the trend observed in
400 μC·cm−2).27,28 It reached to the maximum value up to ca. voltammograms and Rct (Table 1).
4 Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 Md. Mahbubur Rahman et al.

Table 1. Electrochemical properties of FTO and Au/FTO electrodes

Average Surface area Apparent standard heterogeneous
Electrodes τ/s Rct /Ω
particle size/nm /cm2 rate constant (kapp)a/cm·s−1
FTO - - - 110.15 4.4 × 10−9
Au/FTO 25 ~300 0.03 55.25 8.8 × 10−9
Au/FTO 50 ~500 0.13 35.55 1.4 × 10−8
Au/FTO 100 ~1000 0.07 162.85 3.0 × 10−9
a
kapp values were measured according to the previously reported method.26

Electrochemical Behavior of Nitrite at Au/FTO. Under including orange juice, grape juice, and local tap water
the optimized condition, the Au/FTO electrode showed a (Table 2). The detection of NO2− at concentrations of up to 1
well-defined oxidation wave in CV at ca. 0.89 V for 1 mM mM by this electrode was not affected by most of the
NO2− in PBS (pH 7.0), while there is no significant electro- common interfering species such as Cl−, SO42−, NO3−, CO3−,
chemical reactivity of NO2− at the bare FTO electrode (Fig. Ca2+, Mg2+, Zn2+, and Na+.
3(d)). The linear relationship between the NO2− oxidation
peak current density and the square root of the scan rate (ν1/2) Conclusions
indicates that the NO2− oxidation is a diffusion-controlled
process (Inset, Fig. 3(e)). The transfer coefficient (α) for Homogeneous distributions of sub-micrometer size Au
NO2− oxidation is estimated to be 0.58 by assuming that the deposits on FTO (Au/FTO) were prepared by potential-step
number of electrons (na) involved with the rate-limiting methods for detecting NO2−. It was found that the electro-
process is one, as obtained from the linear relationship chemical deposition of Au on FTO occurred by instantane-
between Epa vs. log ν (Inset, Fig. 3(e)), which is evidenced ous nucleation followed by the growth and coalescence of
by Eq. (1)5, where T, R, and F are the temperature, gas, and the existing nuclei. The Au/FTO electrode showed an
Faraday constant, respectively. improved electrocatalytic activity toward the oxidation of
NO2− under the optimal conditions, with detection limit and
2.3RT
Epa = ------------------------------ log ν + K (1) sensitivity of 2.95 μM and 223.4 μA·cm−2·mM−1, respec-
2( 1 – α )na F tively. There was a significant recovery ratio from real
samples, and no significant interference was observed from
The value of α, bigger than 0.5 in this case, implied that the common interfering ions. Based on the electrochemical
the relatively high catalytic oxidation rate of NO2− to NO2 on analysis, it was found that a relatively high rate of catalytic
Au was followed by the disproportionation reaction of NO2, oxidation of NO2− to NO2 occurred at Au surface and was
as shown in reactions (3) and (4), respectively.29,30 followed by a disproportionation reaction of NO2 to NO2−
NO2− → NO2 + e− (3) and NO3−.
2NO2 + H2O ↔ NO2− + NO3− + 2H +
(4) Acknowledgments. This research was supported by Basic
Analytical Performance of the Au/FTO Sensor. The Science Research Program through the National Research
sensitivity and the detection limit (S/N = 3) are estimated to Foundation of Korea (NRF) funded by the Ministry of
be ca. 223.4 µA·cm−2·mM−1 and 2.95 µM, respectively. They Education (2013R1A1A4A01013236) and by the New &
were calculated from the linear relationship between NO2− Renewable Energy Core Technology Program of the Korea
oxidation peak current densities (Jpeak’s), obtained from Institute of Energy Technology Evaluation and Planning
differential pulse voltammetric (DPV) responses vs. [NO2−] (KETEP) granted financial resource from the Ministry of Trade,
in the range 10.0–7.5 × 102 µM (Fig. 3(f)). Thus, this elec- Industry & Energy, Republic of Korea (No. 20133030000140).
trode is highly reliable and appropriate for the real-time
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