Electrochimica Acta 47 (2002) 3509
/3513

www.elsevier.com/locate/electacta

Electrochemical oxidation of benzoic acid at boron-doped diamond

electrodes
F. Montilla a, P.A. Michaud b, E. Morallón a,1,*, J.L. Vázquez a,2, Ch. Comninellis b,3
a
Departamento de Quı́mica Fı́sica, Universidad de Alicante, Apartado 99, 03080 Alicante, Spain
b
Institute of Chemical Engineering, Swiss Federal Institute of Technologie, CH-1015 Lausanne, Switzerland

Received 19 March 2002; received in revised form 14 May 2002

Abstract

The electrochemical oxidation of benzoic acid (BA) has been studied on boron-doped diamond electrodes on acid medium by
cyclic voltammetry and bulk electrolysis. The results showed that in the potential region where the supporting electrolyte is stable,
reactions occur, resulting in the loss of activity due to electrode fouling. Electrolysis at high anodic potentials in the region of
electrolyte decomposition causes complex oxidation reactions that lead to incineration of BA. There is no indication of electrode
fouling. Salicylic acid, 2,5-hydroxybenzoic acid and hydroquinone have been detected at trace level by HPLC as soluble products
during the electrolysis of BA. # 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Electrolysis; Anodic oxidation; Cyclic voltammetry; Wastewater treatment; Hydroxyl radical

1. Introduction high thermal stability, hardness, good electrical con-

Aromatic compounds present in wastewater are
highly hazardous pollutants produced in many indus-
trial processes. The electrochemical oxidation of these
pollutants is a promising technique for wastewater
treatment. Several model aromatic compounds, such
as phenolic compounds, polyaromatic hydrocarbons,
anilines and other benzene derivatives have been used
for test the performance of different anode material like
platinum, porous carbon felts, Ti/PbO2, Pb/PbO2, Ti/
SnO2 and other DSA type electrodes [1
/7]. However,
the main problem in this process is the low current
efficiency and the low anode stability.
Boron doped diamond thin-films electrodes are emer-
ging as excellent material for several applications, such
as electrosynthesis, energy accumulation devices, elec-
troanalysis, etc. [8,9]. These electrodes present some
useful properties including high resistance to corrosion,
* Corresponding author. Tel.: /34-9-6590-9590; fax: /34-9-6590-
3537
E-mail address: morallon@ua.es (E. Morallón).
1
ISE member.
2
ISE member.
3
ISE member.
0013-4686/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 2 ) 0 0 3 1 8 - 3
ductivity, etc. The electrochemical behaviour of dia-
mond thin films deposited on p -silicon substrates (p -Si/
BDD) has been studied for its use on electrochemical
oxidation of organic wastes [10
/13].
This work deals to the electrochemical behaviour of
benzoic acid (BA) using p -Si/BDD electrodes in per-
chloric acid solutions. Cyclic voltammetry and bulk
electrolysis have been used in order to study the
performance of this electrode in the elimination of this
organic compound.
2. Mathematical model
A theoretical model that permits the prediction of the
chemical oxygen demand (COD) and instantaneous
current efficiency (ICE) during the electrochemical
oxidation of organic pollutants on p -Si/BDD electrodes
in a batch recirculation system under galvanostatic
conditions has been described previously [13].
The model supposes that the electrochemical incin-
eration of an organic compound is complete to CO2, in
this case BA, with electrogenerated active intermediates
formed by water discharge (OH radicals) and/or direct
electron transfer. This is a fast reaction (Eq. (1)) and is
3510 F. Montilla et al. / Electrochimica Acta 47 (2002) 3509
/3513
controlled by the mass transport of the organic com-
pound (BA) towards the anode.
C7 H6 O2 12H2 O 0 7CO2 18H 18e (1)
Under these conditions, the limiting current density
for the electrochemical incineration of BA is given by
the relation (Eq. (2)), and it is related to the COD of the
electrolyte during electrolysis [14]:
jlim (t)4Fkm COD(t) (2)
where jlim(t) is the limiting current density (A m 2) at a
given time t , F is the Faraday constant (C mol 1), km is
the average mass transport coefficient in the electro-
chemical reactor (m s 1) and COD(t) is the COD in the
electrolyte at a given time t.
This equation is valid for the electrocombustion of
any organics and even when the solution contains more
than one compounds [14].
Depending on the applied current density, two
different operating regimes are identified:
a) jappl. B/jlim: the electrolysis is under current control,
current efficiency is 100% and COD decreases
linearly with time,
b) jappl. /jlim: the electrolysis is under mass transport
control and secondary reactions (such as oxygen
evolution) start, resulting in a decrease of ICE. In
this regime, COD removal due to mass transport
limitation follows an exponential trend.
The equations that describe the temporal trends of
COD and ICE in both regimes are summarised in Table
1.
3. Experimental
The boron-doped diamond (Si/BDD) electrodes were
provided and synthesised by the Swiss Center for
Electronics and Microtechnology SA, Neuchâtel-Swit-
zerland using the hot filament chemical vapour deposi-
tion technique (HF-CVD) on conducting p -Si. The
obtained diamond film thickness was about 1 mm.
Table 1
Equations that describe ICE and COD during BA oxidation at Si/BDD electrode
Instantaneous current efficiency ICE
Under current limited control japplied B jlimit / ICE(t)1/
Ak 1a
Under mass transport control japplied  jlimit / ICE(t)expð m 
VR
The test solution employed during the experiments
were 0.5 M HClO4 prepared from Riedel-de Haën 70%
analytical reagent, and the BA was Fluka p.a.
Voltammetric measurements were obtained with an
EG&G potentiostat/galvanostat model 273 controlled
by software ECHEM M270. Working electrode were Si/
BDD plates of 1 cm2 of geometric area. Current
densities are calculated with respect to that area.
Counter electrode was a platinum wire. Reference
electrode was a Hg/HgSO4/K2SO4 (sat) (ESS). Cyclic
voltammograms were obtained at a constant sweep rate
of 100 mV s 1.
Bulk anodic oxidation of BA was carried out using an
undivided electrochemical flow cell. The anode were
disk of p-Si/BDD and the cathode was a zirconium
plate, respectively. The geometric area of both electro-
des was 50 cm2, with an inter-electrode gap of 10 mm.
The electrolyte was stored in a thermo-regulated glass
tank and circulated through the electrolytic cell by a
centrifugal pump. The electrochemical reactor volume
was VE /50 cm3 and the reservoir volume VR /500
cm3. The value of the mass-transfer coefficient in the cell
(determined using the ferri/ferrocyanide couple) was
1.5 /105 m s 1.
The electrolyses were performed in galvanostatic
mode. COD was determined by a HACH DR200
analyser. Total Organic Carbon of the solution were
determined by a TOC-5050 Shimadzu apparatus. The
formation of several organic compounds coming from
the electrochemical treatment of BA was followed by
means of a HPLC apparatus Lichrosper† 100 RP-18
equipped with a photodiode array detector.
The ICE during electrolysis has been calculated by
means of the relation [15]:
[(COD)t  (COD)tDt ]
ICE  4FV
IDt
where (COD)t and (COD)tDt are the CODs at times t
and t/Dt (in molO2 dm 3), respectively, I is the
current (A), F is the Faraday constant (96 487 C
mol 1) and V is the volume of electrolyte (dm3).
Chemical oxygen demand COD (molO2 m 3)
aAkm
/COD(t)COD(0)ð1 tÞ/
VR
Ak 1a
Þ/ /COD(t)aCOD(0)expð m t Þ/
a VR a
 F. Montilla et al. / Electrochimica Acta 47 (2002) 3509
/3513 3511

the degree of deactivation is only the 11%, instead of the

Fig. 1. Cyclic voltammograms for a Si/BDD electrode in 0.5 M
HClO4/0.013 M BA solution. Scan rate 100 mV s 1. Filled line first
scan. Dashed line second scan. Doted line fifth scan.
4. Results and discussion
4.1. Cyclic voltammetry of benzoic acid on p -Si/BDD
Fig. 1 shows consecutive cyclic voltammograms
obtained with a p-Si/BDD electrode in 0.5 M
HClO4/0.013 M BA solution. During the first scan
an oxidation peak is obtained at 1.78 V/ESS, which
increase linearly with the BA concentration and is
shifted to more positive potentials by increasing BA
concentration.
Fig. 1 shows also that in the second scan a remarkable
decrease of the current peak is observed, indicating a
loss of electrode activity. After five cycles, the voltam-
mogram is stabilised. Table 2 shows the current densities
of the oxidation peak in the first and the fifth cycle for
the oxidation of BA, the degree of deactivation is also
presented. This deactivation is dependent on the con-
centration of BA in solution and of the anodic potential
limit of the scan. For a concentration of BA ranging
between 1.6 and 13 mM, the degree of deactivation
change from 20 to 61% in the fifth voltammetric cycle. If
we change the anodic limit of the scan to more positive
potentials, a lower deactivation on the electrode surface
is observed. In such manner, for a concentration of BA
of 13 mM, if we scan up to 2.55 V, after the fifth cycle,
61% achieved with cycling up to 2.1 V.
This deactivation of the surface could be due to the
formation of polymeric product coming from the BA
oxidation on the electrode surface. After the oxidation
at 2.1 V a product adhered to the electrode surface with
a yellowish colour was observed, on the electrode
surface exposed to the electrolytic solution. The elec-
trode remains in the same deactivated form although we
rinsed the electrode with either water or iso -propanol.
However, its initial activity can be restored by treatment
at high anodic potential. In fact the initial voltammo-
gram in the BA solution is again obtained after an
anodic polarisation of the electrode during 10 min at 10
mA cm2 (2.1 V).
Fig. 2 (filled line) shows the amplified voltammo-
grams obtained for a solution containing 13 mM of BA,
which shows the appearance of a reduction peak around
/1.0 V, after the first scan up to 2.1 V, in the following
negative-going scan. The corresponding oxidation peak
at around 0.9 V is also observed. This redox couple
seems to be related to products coming from the
oxidation of the BA because it does not appear when
the voltammogram is performed between /1.1 and 1.5
V (before BA oxidation). If the electrode is polarised at
2.1 V during 5 or 10 min and following the voltammo-
gram is recorded between 2.1 and /1.1 V, an increase of
the current associated with this redox couple is ob-
served.
In order to determine the nature of the compounds
responsible of the redox couple and thinking the
possibility of quinones formation from BA oxidation,
the behaviour of p -Si/BDD electrodes in presence of
some amount of p -benzoquinone in the solution has
been studied. Fig. 2 (dashed line) shows the voltamo-
gram obtained in a solution 0.5 M HClO4/8 mM of
para -benzoquinone, which a couple of redox peaks
appear due to the reduction and oxidation of that redox
system, however, the potential of these peaks are

Table 2
Peak potential, current density in the first and in the fifth scan and
percentage of deactivation of the oxidation peak of BA, measured in
the voltammogram of different solutions of BA in 0.5 M HClO4 for an
anodic potential limit of 2.1 V

C Epeak Current density Deactivation

(mM) (V vs. ESS) (mA cm 2) (%)

First scan Fifth scan

1.6 1.78 3.06 2.46 20 Fig. 2. Solid line, amplification of zone between /0.6 and /0.6 mA
3 1.80 5.60 3.67 34 cm 2 of the voltammogram for a Si/BDD electrode during the fifth
7 1.89 10.03 5.18 52 stabilised scan between 2.15 V for a 0.5 M HClO4/0.013 M BA
13 1.91 13.73 5.36 61 solution. Dashed line, 5th stabilised voltammogram between /1.05
and 2.15 V for a Si/BDD electrode in a 0.5 M HClO4/0.008 M para -
Working electrode, Si/BDD; scan rate, 100 mV s 1. benzoquinone solution. Scan rate 100 mV s 1.
3512 F. Montilla et al. / Electrochimica Acta 47 (2002) 3509
/3513

different from the products coming from the oxidation manner of the mathematical model proposed and after
of BA. Then, the redox couple could be due to the the COD decays exponentially from a critical value of
contribution of a mixing of substituted quinines in charge. At current densities higher than limiting current,
solution. COD decays exponentially from the beginning of the
electrolysis.
From the ratio between COD and TOC it is possible
4.2. Bulk electrolysis to calculate the value of the average Oxidation State
(OS) of the organic carbon in solution as follows:
In a series of experiments, we realised the electrolyses
of BA solutions in 0.5 M HClO4 under galvanostatic Oxidation State 4(TOCCOD)=TOC
conditions (I/1.5 A). Different initial BA concentra-
where COD and TOC are in molar units.
tion have been used (2.11, 4.76 and 8.86 mM). The COD
This parameter can be followed during the electro-
values of these solutions have been calculated. This can
lysis, analysing the effect of the applied current density
allow to change the initial value of the limiting current
on the amount of intermediate products formed. The
using Eq. (2). For example for the electrolyte containing
calculated initial value of OS for a solution of pure BA is
initially 2.11 mM (258 ppm) of BA, the initial limiting
OS //0.3. If during the electrolysis, benzoic is oxidised
current calculated by Eq. (2) was 0.85 A.
to CO2, without formation of any intermediate in
Fig. 3 shows the evolution with time of COD and ICE
solution, this value of OS will remain unchanged.
during the electrochemical oxidation of different solu-
However, if the average OS in the solution increases
tions of BA at constant current of 1.5 A. In the same
during electrolysis, this will indicates that intermediate
figure the theoretical value of COD and current
products coming from the oxidation of BA are formed
efficiency trends calculated from the model (Table 1)
in solution. Fig. 4 shows the evolution with time of the
are reported. As predicted from the model, at the
average OS of carbon during the electrolyses of BA in a
beginning of the electrolysis and at high BA concentra-
concentration of 2.9 mM. It can be observed that this
tion (8.86 mM, COD/2500 ppm), the reaction is under
parameter changes during the electrolysis indicating the
current limiting control (j B/jlim) This result in an ICE of
formation of soluble intermediate compounds from the
almost 100% and in a linear decrease of COD with the
oxidation of BA. Moreover, at this concentration the
specific charge passed. After some time of electrolysis,
the COD in the solution decreased until a critical value,
COD(tC) is achieved after this value both ICE and COD
decrease exponentially with the specific charge passed as
predicted by the model.
In a second series of experiments the oxidation of BA
was performed at different current densities (from 5, 11,
22 to 32 mA cm 2), under and over the calculated
limiting current. In all cases, the model predicted
reasonably well the evolution with time of COD and
ICE. At current densities lower than the limiting
current, at the beginning of the electrolysis, COD
decreases linearly with the specific charge, in the same

Fig. 3. Evolution of the COD and ICE (inset) during electrolysis of
BA in 0.5 M HClO4. Initial concentration of BA, ( ) 8.86 mM, (j)
4.76 mM, (m) 2.11 mM. Anode: boron-doped diamond electrode. Zr
plate as cathode. T /25 8C. j/24 mA cm2. The solid lines
represent the model prediction.
Fig. 4. Evolution of the average OS during the electrolysis of the BA
(initial concentration 2.9 mM) in 0.5 M HClO4 with diamond
electrodes. The abscissa axis represents the decrease of TOC during
the electrolysis run. (a) Current densities (j) 5 mA cm2, (m) 11 mA
cm 2 (b) Current densities (m) 22 mA cm2, (") 32 mA cm2.
 F. Montilla et al. / Electrochimica Acta 47 (2002) 3509
/3513
initial limiting current density calculated from equation
5 is 16 mA cm 2. Then, the electrolysis was performed
at different current densities below and over this
calculated value in order to analyse the effect of the
current density in the OS parameter. At the lowest
applied current density (5 mA cm 2, Fig. 4a), the
average OS of carbon increase rapidly from /0.3 to
/1.8. When the applied current density increases up to
11 mA cm 2 the final value of OS reaches a value of /
1.3, however, when the current density is 32 mA cm 2
the OSs increases to /0.4 (Fig. 4b), a lower value than
in the other cases. These results show that high current
densities are adequate for complete combustion of
organics with the formation of lower amounts of
intermediate compounds in solution. However, the
ICE of the process is lower than 100% (mass transport
control, jappl. /jlim). Under these conditions, the oxygen
evolution reaction, which is an undesired parallel
reaction, is yielded in higher extent, producing a
decrease in the value ICE for the oxidation of the
organic compound.
In order to determine the nature of the intermediates
formed during electrolysis of BA, a preparative electro-
lysis was performed at 20 mA cm 2 of a 0.012 M BA
solution in 0.5 M HClO4 and the main intermediates
were detected by HPLC. The main detected aromatic
intermediate (at trace level) were salicylic acid, 2,5-
hydroxybenzoic acid and hydroquinone.
5. Conclusions
Cyclic voltammetry measurements in the potential
region of water/supporting electrolyte stability showed
that BA is oxidised, resulting in electrode deactivation
due to fouling.
Bulk electrolysis of BA in the potential region of
water/supporting electrolyte decomposition results in
the incineration of BA with electrogenerated active
intermediates. Good agreement between the experimen-
tal data and the theoretical model, based on the
assumption that the anodic oxidation of BA is diffu-
3513
sion-controlled, confirmed that the reaction of BA with
electrogenerated intermediates (hydroxyl radicals) on
BDD is a fast reaction.
Acknowledgements
Financial support of the Ministerio de Ciencia y
Tecnologı́a and Feder funds (MAT2001-1007) and
Generalitat Valenciana (GV01-313) are gratefully ac-
knowledged. F. Montilla thanks Generalitat Valenciana
for a grant for his stay in the Institute of Chemical
Engineering (Laussane).
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