Article

pubs.acs.org/ac

Direct Determination of Chemical Oxygen Demand by Anodic

Decomposition of Organic Compounds at a Diamond Electrode
Takeshi Kondo,*,†,‡ Yusuke Tamura,† Masaki Hoshino,† Takeshi Watanabe,§ Tatsuo Aikawa,†,‡
Makoto Yuasa,†,‡ and Yasuaki Einaga*,§,∥
†
Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki,
Noda, Chiba 278-8510, Japan
‡
Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
§
Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Yokohama 223-8522, Japan
∥
JST-CREST, 3-14-1 Hiyoshi, Yokohama 223-8522, Japan

ABSTRACT: Chemical oxygen demand (COD) was measured directly with a simple electrochemical method using a boron-
doped diamond (BDD) electrode. By applying a highly positive potential (+2.5 V vs Ag/AgCl) to an aqueous electrolyte
containing potassium hydrogen phthalate, glucose, and lactic acid or sodium dodecylbenzenesulfonate using a BDD electrode, an
anodic current corresponding to the electrolytic decomposition of these organic compounds was observed. No such current was
seen on glassy carbon or platinum electrodes due to a significant background current caused by the oxygen evolution reaction.
The electric charge for the anodic current observed at the BDD electrode was found to be consistent with the theoretical charge
required for the electrolytic decomposition of the organic compounds to CO2 and was used to calculate COD. This analysis was
performed by a simple I−t measurement at constant potential using a BDD electrode, and no calibration was needed. This new
simple indicator, “ECOD” (electrochemical oxygen demand), will be useful for continuous monitoring of industrial wastewater
with low protein concentrations and on-site instant analysis of natural water with a BDD electrode-based portable ECOD meter.

M easurement of the amount of organic compounds in

water (e.g., river/lake water and industrial wastewater) is
undoubtedly important for management of pollution levels.
Chemical oxygen demand (COD) is widely used as an
indication of water pollution by organic compounds.1 In
many countries, potassium dichromate (K2Cr2O7) is employed
as an oxidizer for the COD test. Dichromate contains
poisonous hexavalent chromium, and the wastewater produced
by the COD test has to be strictly managed until it is treated.
Potassium permanganate (KMnO4) can also be employed as an
oxidizer for the COD test. Although it is less toxic than
dichromate, it is a weaker oxidant and most organic compounds
can only be partially oxidized. The COD test consists of several
steps, including sampling, addition of the oxidizer, heating, and
optical measurement, and thus is not suitable for a simple
automatic system. Total organic carbon (TOC) measurement
is also an important method for evaluating the pollution level of
water. The TOC measurement involves complete combustion
of the sample and infrared absorption measurement, which
enables precise evaluation of the organic content of the sample.
The TOC measurement often requires a relatively large and
expensive analyzer. If the precise, inexpensive, and rapid
evaluation of water pollution levels can be achieved with a
lightweight and simple system, it will be a powerful tool for
managing water pollution levels (e.g., by continuous monitor-
ing of industrial wastewater and on-site analysis of natural
water).
Electrochemical techniques show promise for COD measure-
ment, and therefore, various electrode materials have been
investigated.2−10 Yu et al. reported COD measurements
through amperometric analysis of anodic decomposition of
organic compounds at boron-doped diamond (BDD) electro-
des.11,12 The BDD electrode is one of the most stable electrode
Received: March 12, 2014
Accepted: July 23, 2014
Published: July 23, 2014

© 2014 American Chemical Society 8066 dx.doi.org/10.1021/ac500919k | Anal. Chem. 2014, 86, 8066−8072
Analytical Chemistry
Figure 1. (a) CV for 3 mM glucose in 0.1 M Na2SO4 using a BDD electrode, at a potential sweep rate of 100 mV s−1. (b−d) Anodic current
response to injection of glucose samples in stirred 0.1 M Na2SO4 with a BDD electrode. Initial solution volume was 2.7 mL, and a 0.3 mL sample
aliquot containing 150 nmol glucose was injected at each step indicated by an arrow. The constant potentials were (b) 2.4, (c) 2.5, and (d) 2.6 V vs
Ag/AgCl.
materials for electrolytic experiments, and its wide potential
window or large overpotential for the oxygen evolution reaction
of water decomposition is also favorable for efficient
decomposition of organic compounds.13−15 However, it is
difficult to make amperometric measurements in practical COD
tests. First, the use of a reaction current as the signal for COD
estimation requires a calibration curve. Furthermore, the
amperometric current does not always reflect the COD value.
Basically, only when the sample contains a single species can
the COD value be estimated from the calibration curve. Lastly,
calculating the number of electrons transferred during oxidation
is not simple, especially for real sample solutions containing
many chemical species. This is because the particulars of the
oxidation reaction depend on the type of compounds present.
A direct method for determining COD based on the
complete oxidation of organic compounds in water with a
photocatalytic technique has been investigated.16,17 This should
be useful because COD can be calculated directly, without
calibration, from the charge required for photoelectrolytic
decomposition of organic compounds. For the photoelec-
trochemical measurement, a UV light source is necessary for
excitation and this may limit the miniaturization of the
measurement system.
In this work, we investigated the direct determination of
COD from the anodic charge of electrolytic decomposition of
organic compounds at highly positive potentials using a BDD
electrode. In principle, organic compounds in an aqueous
electrolyte can be oxidized completely to carbon dioxide by
electrochemical oxidation at a highly positive potential:
CaHbNcOd + {(x − b)/2}H 2O
→ aCO2 + c NO2 + x H+ + x e−
Article
On the other hand, complete oxidation of organic compounds
by reaction with oxygen can be expressed as follows:
CaHbNcOd + yO2 → aCO2 + (b/2)H 2O + c NO2 (2)
From eqs 1 and 2, the relationship x = 4y (= 4a + b + 4c − 2d)
can be obtained. Thus, the total charge for the electro-oxidation
can be used to calculate COD (denoted here as electrochemical
oxygen demand, ECOD). Practically, however, estimation of
the charge is often difficult because the highly positive electrode
potential causes water decomposition, resulting in a significant
anodic current by the oxygen evolution reaction (OER). The
OER current at a highly positive potential often fluctuates
significantly due to bubble formation on the electrode surface
making it difficult to separate the current due to the
decomposition of organic compounds from the total current.
In addition, application of a highly positive potential may cause
reaction/decomposition of the electrode material itself.
BDD thin films have been known to be one of the most
stable electrode materials with respect to electrochemical
polarization at large overpotentials for water decomposition.
Thus, we expected the BDD electrode to be suitable for the
electrochemical estimation of COD. In addition, it has been
reported that hydroxyl radicals (•OH) can be generated at the
BDD electrode during anodic water decomposition with high
current efficiency:18−22
H 2O → •OH + H+ + e− (3)
The hydroxyl radical is a strong oxidant capable of oxidizing
organic compounds to carbon dioxide:
CaHbNcOd + z • OH
(1) → aCO2 + {(b + z)/2}H 2O + c NO2 (4)
8067 dx.doi.org/10.1021/ac500919k | Anal. Chem. 2014, 86, 8066−8072
Analytical Chemistry Article

In this study, we discovered that the electric charge for anodic
decomposition of certain organic compounds at +2.5 V versus
Ag/AgCl can be evaluated by the use of a BDD electrode. The
amount of charge was found to correspond to the theoretical
value, enabling direct determination of COD.
AgCl for the electrolysis processes examined in this study, since
the response current was large and stable at this potential.
2. ECOD Measurements on Organic Compounds at
+2.5 V vs Ag/AgCl Using a BDD Electrode. Figure 2a

■ EXPERIMENTAL SECTION
BDD electrodes were prepared by microwave plasma-assisted
chemical vapor deposition (MPCVD) of a polycrystalline BDD
thin film on a conductive silicon wafer substrate using a
microwave power of 5000 W, a hydrogen gas flow rate of 540
sccm, a total pressure of 120 Torr, and a deposition time of 8 h.
The carbon/boron source was a mixture of acetone/methanol
(9:1, v/v) containing trimethoxyborane at a total atomic B/C
ratio of 0.5%. Detailed MPCVD conditions are described
elsewhere.23 For ECOD measurements, potassium hydrogen
phthalate (KC8H5O4, KHP), glucose (C6H12O6), lactic acid
(C3H6O3, LA), and sodium dodecylbenzenesulfonate (Na-
C18H29O3S, SDBS) were used as model organic pollutants. The
BDD electrode was placed at the bottom of an electrochemical
cell, contacting the electrolyte solution with an O-ring (11 mm
in diameter). A magnetic stirrer was put on the bottom of the
cell, parallel to the electrode, with a 4 mm thick spacer. A
platinum wire and an Ag/AgCl electrode in 3 M NaCl were
used as the counter and reference electrodes, respectively. A
Figure 2. (a) I−t curve for anodic decomposition of 200 nmol KHP in
potential of +2.5 V vs Ag/AgCl was applied to 4 mL of 0.1 M 0.1 M Na2SO4 at a BDD electrode. The constant potential was +2.5 V
Na2SO4 in the cell with stirring, and 0.3 mL of 0.1 M Na2SO4 vs Ag/AgCl. The KHP sample was injected at 1000 s. The shaded area
containing the organic compound was added to the solution was integrated to calculate ECOD. (b) Q−t curve created from the
after the background current became stable. The charge data of (a).
transferred during the anodic decomposition was calculated
from the area under the I−t curve after subtraction of the
shows the I−t curve for the electrochemical decomposition of
background. The area was calculated by integration of current
200 nmol of KHP (12.0 mg O2 L−1) in 4 mL of 0.1 M Na2SO4
with a sampling interval of 1 s. In this study, the background
at +2.5 V vs Ag/AgCl. After a stable background current was
current was determined as a linear line passing through the
obtained with the blank solution (0.1 M Na2SO4), a sample
current value just before addition of the sample and that after
solution containing KHP was added to the solution, resulting in
8000 s from the sample addition. A simple COD meter
an increase of the anodic current. The current then decreased
(photoLab 6100, WTW) and a TOC analyzer (TOC-L,
gradually to the initial background level within 10000 s. The
Shimadzu) were employed to estimate the COD and TOC,
background current was attributed to the anodic decomposition
respectively, of the model solutions for comparison. For a
of water and was basically constant over the course of each
standard addition study using a real sample, water was collected
electrolysis experiment. The increase in current upon addition
from the Tone canal, Nagareyama, Japan.

■
RESULTS AND DISCUSSION
1. Optimization of Electrode Potential. In general, BDD
electrodes exhibit large overpotentials for the anodic decom-
position of organic compounds due to their poor surface
adsorption (or catalytic effect). Figure 1a shows a cyclic
voltammogram (CV) of 3 mM glucose in 0.1 M Na2SO4 at the
BDD electrode. From the CVs, it was determined that the
onset of the OER current was at around +1.8 V vs Ag/AgCl,
and no obvious anodic current for glucose oxidation was
observed at less positive potentials. Next, we investigated the
operating potential for glucose oxidation at more positive
potentials. At a constant electrode potential below +2.3 V vs
Ag/AgCl with stirring, no obvious current response was
observed after addition of the glucose solution (150 nmol).
At potentials from +2.4 to 2.6 V vs Ag/AgCl, however, a clear
current response was observed upon addition of the glucose
sample (Figure 1, panels b−d). At potentials higher than +2.6 V
vs Ag/AgCl, the current was not stable due to a significant
increase in the background (OER) current. We ultimately
decided on an optimal electrode potential of +2.5 V vs Ag/
of the KHP sample solution was thus due to the anodic
decomposition of KHP. As the electrolysis continued, this
current decreased as the KHP concentration in the cell
dropped. The electric charge transferred during KHP
decomposition, estimated by integrating the background-
subtracted anodic reaction current, was 580 mC (Figure 2b).
The overall electrochemical oxidation reaction of the hydrogen
phthalate ion is expressed as follows:
C8H5O4 − + 12H 2O → 8CO2 + 29H+ + 30e− (5)
In accordance with Faraday’s law, using the Faraday constant
(96485 C mol−1), the total number of moles of electrons
required for KHP decomposition resulting from 580 mC of
charge passing through the cell was calculated to be 6.01 μmol.
The amount of KHP reacted was then estimated from eq 5 to
be 200 nmol, identical to the actual value. This confirmed that
the reaction current was based on the total decomposition of
KHP. The anodic charge Q [C] could be converted to ECOD
[mg O2 L−1] from the following relationship derived from eqs 1
and 2:
ECOD[mg O2 L−1] = (8 × 106 /Fv)Q (6)

8068 dx.doi.org/10.1021/ac500919k | Anal. Chem. 2014, 86, 8066−8072

Analytical Chemistry Article

Figure 3. (a) Estimated ECOD for KHP, glucose (G), LA, and SDBS as a function of the number of moles of each compound. (b) Experimental
ECOD (ECODexp) vs theoretical ECOD (ECODtheor) for KHP, glucose (G), LA, SDBS, and an equimolar mixture of KHP and glucose. The solid
lines indicate theoretical values.

where F is the Faraday constant and v is the solution volume in

milliliters. The fluctuation of the current in the I−t curve
(Figure 2a) due to stirring of the solution and O2 gas evolution
was ±0.008 mA, leading to a variation of the charge to be ±64
mC. This corresponds to a variation of the estimated ECOD
value to be ±1.3 mg O2 L−1. When limit of detection is defined
as three times this value, it can be estimated to be 3.9 mg O2
L−1, which is in the range of those reported for other
electrochemical methods.11,12 Reproducibility of the ECOD for
200 nmol of KHP was confirmed to be 11.6 ± 1.6 mg O2 L−1
(n = 5).
For various concentrations of KHP, glucose, LA, and SDBS,
the ECOD values obtained from the I−t curves were found to
be close to the respective theoretical values (Figure 3a).
Similarly, the ECOD values for glucose, LA, and SDBS
obtained at +2.5 V versus Ag/AgCl were consistent with the
theoretical values. The experimental ECOD values for KHP,
glucose, LA, SDBS, and mixtures of KHP and glucose were also
found to be identical to the corresponding theoretical values
(Figure 3b). From the results above, it was evident that the
anodic decomposition of organic compounds at highly positive
potentials at a BDD electrode is useful for the direct
determination of COD. COD may be estimated from the
Figure 4. SEM images of (a and b) BDD and (c and d) GC electrode
anodic current by the use of a calibration curve. By referring to surfaces. (a) Before and (b) after application of +2.5 V vs Ag/AgCl for
the electric charge passed, on the other hand, COD could be 150 h; (c) before and (d) after application of +2.5 V vs Ag/AgCl for 3
calculated rather simply, obviating the measurement of h.
calibration curves.
3. Necessity of Using a BDD electrode. Figure 4 shows
scanning electron microscopy (SEM) images of BDD and than +1.5 V vs Ag/AgCl). The foregoing results demonstrated
glassy carbon (GC) electrode surfaces before and after that BDD was the most suitable electrode material of the three
application of a potential at +2.5 V versus Ag/AgCl in 0.1 M examined for ECOD measurements involving anodic decom-
Na2SO4 for 150 h (BDD) or 3 h (GC). No obvious change in position of organic compounds at highly positive potentials,
morphology was observed in the BDD electrode surface even based on its high dimensional stability and low background
after applying such a high potential for such a long time. The current (OER current).
surface morphology of the GC electrode, however, was changed Another advantage of the BDD electrode for electrolysis at
greatly by corrosion, indicating that GC was too unstable to be highly positive potentials is the efficient generation of hydroxyl
used as an electrode material for ECOD measurements. In the radicals (•OH).15,20−22,24−26 It is known that this radical can be
I−t curves for the anodic decomposition of 300 nmol of KHP generated by the anodic decomposition of water (eq 3). For
at +2.5 V vs Ag/AgCl at GC and platinum electrodes, the example, anodic water decomposition at an active electrode
current for the anodic decomposition of KHP could not be such as Pt or RuO2 generates oxygen species that are chemically
recognized due to the large background current (Figure 5, adsorbed on the electrode surface, and these species can oxidize
panels a and b). As can be seen in the CV curves (Figure 5c), organic compounds in the electrolyte. On the other hand, at an
GC and platinum electrodes exhibited smaller overpotentials inactive electrode material with poor adsorption of the oxygen
for water decomposition (i.e., narrower potential windows) species, such as PbO2 or BDD, the hydroxyl radical can be
than the BDD electrode, leading to the large background generated efficiently.19,27 This radical is a strong oxidant and
currents observed at highly positive potentials (more positive can oxidize low molecular weight organic compounds
8069 dx.doi.org/10.1021/ac500919k | Anal. Chem. 2014, 86, 8066−8072
Analytical Chemistry Article

Figure 5. Anodic decomposition of 300 nmol KHP at +2.5 V vs Ag/AgCl at (a) GC and (b) Pt electrodes. The KHP sample was injected at 1000 s
(arrows). (c) CVs in 0.1 M Na2SO4 using BDD, GC, and Pt electrodes at a potential sweep rate of 100 mV s−1.

Figure 6. (a) COD values measured with a commercial COD meter and (b) TOC values measured with a commercial TOC analyzer, and the
corresponding values calculated from the anodic charge, along with theoretical values, for a KHP solution. Solid lines indicate the theoretical values.

completely to CO2 during anodic decomposition.28 Direct
anodic oxidation of 1 mol of glucose to carbon dioxide requires
24 mol of electrons:
xC6H12O6 + 6x H 2O → 6xCO2 + 24x H+ + 24x e−
On the other hand, in hydroxyl radical-mediated anodic
oxidation (indirect oxidation), we have
24(1 − x)H 2O → 24(1 − x)• OH + 24(1 − x)H+
+ 24(1 − x)e−
(1 − x)C6H12O6 + 24(1 − x)• OH
→ 6(1 − x)CO2 + 18(1 − x)H 2O
Thus, the overall reaction from eqs 8 and 9 is
(1 − x)C6H12O6 + 6(1 − x)H 2O
→ 6(1 − x)CO2 + 24(1 − x)H+ + 24(1 − x)e−
The sum of eqs 7 and 10 gives
C6H12O6 + 6H 2O → 6CO2 + 24H+ + 24e−
Even when direct and indirect oxidation occur in any
proportion x (0 ≤ x ≤ 1), 24 mol of electrons are transferred
per mol of glucose. Thus, the number of electrons transferred,
and hence the electric charge, can be directly used to calculate
COD. In this regard, this method is fundamentally different
from the electrochemical estimation of COD based on the
(7)
measurement of amperometric current, which requires an
experimental calibration curve.
4. Comparison with Results from a Commercial COD
Meter and TOC Analyzer. The ECOD value obtained with a
BDD electrode was compared to COD data measured with a
(8) COD meter. Figure 6a shows the experimentally measured
COD versus the theoretical value for a KHP solution. The
values obtained with the COD meter were somewhat smaller
than the theoretical values. The conventional COD test
(9) includes multiple steps, namely, addition of reagent (potassium
dichromate), heating (for the oxidation reaction to occur), and
an absorbance measurement, thus requiring considerable time
and often resulting in data scattering. On the other hand, the
electrochemical method proposed in this study is more precise,
can be performed more easily and is suitable for automation
(10) with a simple instrument. Figure 6b shows the experimental
TOC value obtained with a commercial TOC analyzer and by
calculation from the anodic charge. When the chemical
(11)
composition of the sample is known, TOC can be calculated
from the charge transferred using eq 1. TOC measurements,
based on the complete combustion of organic compounds in
8070 dx.doi.org/10.1021/ac500919k | Anal. Chem. 2014, 86, 8066−8072
Analytical Chemistry
the sample solution, are known to be precise. The TOC values
calculated from the charge, however, were found to be closer to
the corresponding theoretical values than those obtained by a
TOC analyzer. This indicated that the ECOD values found
using a BDD electrode could be useful as a reliable indication of
organic water pollution, measurable with a simple instrument.
5. Interference and Standard Addition Studies. Effect
of the presence of proteins in the sample solution to ECOD
measurement was investigated as an interference study. When a
sample aliquot containing 200 nmol KHP and bovine serum
albumin (BSA, 1 wt % in the sample aliquot or 0.025 wt % in
the electrochemical cell) was injected in the stirred 0.1 M
Na2SO4, at +2.5 V vs Ag/AgCl, the current suddenly decreased
and minor current increase by electrolysis was observed (result
not shown). On the other hand, in the case of lower BSA
concentrations (0.001 and 0.01 wt % in the sample aliquot), no
current decrease by the injection and current increase for the
electrolysis of KHP was observed. However, the anodic charge
was found to be smaller (7.8 and 5.4 mg O2 L−1 for 0.001 and
0.01 wt % BSA, respectively) than the theoretical one (12.0 mg
O2 L−1). These results should be because of adsorption of the
protein to the electrode surface, which can disturb the
background current (oxygen evolution reaction current) and
hydroxyl radical generation, even though the BDD surface may
not adsorb proteins strongly.29,30
In addition, we have demonstrated a standard addition study
using a canal water sample. 100, 200, and 300 nmol of KHP
were added in the water sample, and the ECOD was estimated.
When the blank canal water sample (without KHP) was
injected to the electrolyte, no obvious increase of current was
observed. However, in the case of KHP-containing canal water,
the current increased as the sample was injected, and the
ECOD calculated from the anodic charge was close to the
theoretical one (Figure 7). Thus, this method should be useful
for estimation of organic pollution of environmental waters
with low protein concentrations.
Figure 7. Estimated ECOD for KHP-containing canal water samples
as a function of the number of moles of KHP added. The solid line
indicates theoretical values.
■
CONCLUSIONS
By applying a high positive potential (+2.5 V vs Ag/AgCl) at a
BDD electrode, KHP, glucose, LA, and mixtures thereof, were
completely decomposed in the aqueous electrolyte solution.
The electric charge required for the decomposition was found
to be consistent with the charge required for electrochemical
oxidation of the organic compounds to CO2. In this study, we
used an electrochemical cell with a solution volume of 4 mL for
the experiment, requiring a long measurement time for
8071
Article
complete electrolytic decomposition. This measurement time
could be reduced by using an electrochemical cell with a thin
electrolyte layer in order to increase the electrode area relative
to the electrolyte solution volume, and this investigation will be
done in a future study. Since the ECOD measurement can be
performed fairly simply (I−t measurement at a constant
potential) and no calibration is needed, this method should
be useful for continuous monitoring of industrial wastewater
with low protein concentrations and on-site instant analysis of
natural water with a portable ECOD meter.
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: t-kondo@rs.noda.tus.ac.jp.
*E-mail: einaga@chem.keio.ac.jp.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by DKK-TOA Corporation (Saitama,
Japan).
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