Chemosphere 89 (2012) 1195–1201

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Degradation of paracetamol by advance oxidation processes using modified

reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3
H.C. Arredondo Valdez a, G. García Jiménez a,⇑, S. Gutiérrez Granados a, C. Ponce de León b
a
Universidad de Guanajuato, Departamento de Química, Cerro de la Venada S/N, Pueblito de Rocha, CP 36040 Guanajuato, Gto., Mexico
b
Electrochemical Engineering Laboratory, Energy Technology Research Group, Engineering Sciences, University of Southampton, Highfield, Southampton SO17 1BJ, United Kingdom

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" Photochemical, electrochemical and Electrochemical cell used for the degradation of paracetamol in the presence of hydrogen peroxide using
photoelectrochemical degradation of photochemical, electrolysis and photoelectrolysis processes with modified reticulated vitreous carbon
paracetamol. (RVC) electrodes with TiO2. The degradations followed a pseudo first order reaction kinetics with high
" Low cost modified reticulated percentage of TOC removal (80–99%), current efficiencies of 32–68% and energy consumption of
vitreous carbon electrodes coated 3.3–11.0 kW h L1.
with TiO2.
" 95% Paracetamol degradation at 68% Input (O2)
Output
current efficiency was achieved.
" Performance parameters are
comparable with more expensive
electrodes.
Reference
Electrode
Working
Electrode

Auxiliary
UV Lamp Electrode

a r t i c l e i n f o a b s t r a c t

Article history: The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out
Received 25 April 2012 by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitre-
Received in revised form 10 July 2012 ous carbon electrodes. The electrodes were coated with catalysts such as TiO2 and CuO/TiO2/Al2O3 by elec-
Accepted 12 July 2012
trophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon
Available online 26 August 2012
electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates
such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrol-
Keywords:
ysis was carried out with the modified electrodes such as TiO2/RVC, 90% degradation was achieved in 2 h
Advanced Oxidation Processes (AOPs)
Electrocatalysis
while with CuO/TiO2/Al2O3/RVC, 98% degradation took only 1 h. The degradation was also carried out in the
Paracetamol presence of UV reaching 95% degradation with TiO2/RVC/UV and 99% with CuO/TiO2/Al2O3/RVC/UV in 1 h.
Photocatalysis The reactions were followed by spectroscopy UV–Vis, HPLC and total organic carbon analysis. These studies
Photoelectrocatalysis show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.
Reticulated vitreous carbon Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction

The electrochemical Advanced Oxidation Processes (AOPs) de-

⇑ Corresponding author. grade pollutants contained in water effectively and rely on highly
E-mail address: mggj@ugto.mx (G. García Jiménez). oxidant species such as the hydroxyl radical HO which has an

0045-6535/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2012.07.020
1196 H.C. Arredondo Valdez et al. / Chemosphere 89 (2012) 1195–1201
oxidation potential of +2.8 V vs. SHE (Huang et al., 1993; Jüttner
et al., 2000; Brillas et al., 2009; Panizza and Cerisola, 2009; Sirés
and Brillas, 2012). This radical can be generated chemically, photo-
chemically or electrochemically. If hydrogen peroxide is present in
the same solution, the oxidation power would be even higher mak-
ing the complete mineralisation of organic compounds faster and
more effective being environmentally accepted (Wang et al., 2001).
The high oxidation powers of the AOPs has been used in a wide
range of applications including: contaminated soil (Wang et al.,
2001), sludge (Galindo et al., 2000), residual water (Scott and Ollis,
1995) and air (Xiao et al., 2002). In combination with other meth-
ods such as H2O2 and UV light, the efficiency of the oxidation de-
pends on the concentration of hydrogen peroxide, the time of the
photolysis and the frequency and wavelength of the incident light.
The treatment of contaminated water containing pharmaceutical
products in particular, the degradation of paracetamol, has been
widely studied. Paracetamol has been found at concentrations up
to 65 lg L1 in waste waters and can be reduced to less than
10 lg L1 after conventional waste water treatments (Roberts
and Thomas, 2006). The environmental regulations in Mexico
states that the effluents should comply with pH within 6–7, chem-
ical oxygen demand (COD) of 100–120 mg L1, biochemical oxygen
demand (BOD) of 200–250 mg L1, grease 20–30 mg L1 and total
suspended solids (TSS) 150–180 mg L1 (INE, 1995), however,
there are no specific regulation for the disposal of particular phar-
maceutical compounds.
AOPs such as H2O2/UV, O3-based processes and photo-Fenton
have been used to degrade several pharmaceuticals such as: met-
ronidazole (Shemer et al., 2006), carbamazepine (Vogna et al.,
2004a), diclofenac (Ravina et al., 2002; Vogna et al., 2004b), na-
proxen (Pereira et al., 2007) and penicillin (Arslan-Alaton et al.,
2004), amoxicillin (Andreozzi et al., 2005), carbamazepine (Ikehata
et al., 2006), sulphonamide (Huber et al., 2005), penicillium (Ar-
slan-Alaton and Dogruel, 2004), metromidazol (Shemer et al.,
2006) and paracetamol (Sirés et al., 2006; Waterston et al., 2006;
Klavarioti et al., 2009). In these studies the degradation can be be-
tween 30% up to 98% (Adams et al., 2002; Vogna et al., 2004a).
Partial degradation of paracetamol is commonly reported in the
literature, e.g., Vogna et al. (2002) reported that using H2O2/UV,
they obtained 2-hidroxi-4-(4-N acetyl) aminophenol, acetamide
and oxamic acids as intermediates, while Andreozzi et al. (2003)
reported 30% and 40% degradation using O3 and H2O2/UV at pH
2.0 and 7.0, respectively. The oxidation with ozone produces
hydrogen peroxide as well as intermediate species such as hydro-
quinone, 1,2,4-trihydroxibenzene and 2-hydroxi-4-(N-acetyl) ami-
nophenol and glycoxilic, oxalic and formic aliphatic acids
(Andreozzi et al., 2003).
In a detailed study of the photocatalytic degradation of paracet-
amol using TiO2 in suspension, UV-light and H2O2, (Yang et al.,
2009) it was shown that the hydroxyl radical (OH) caused the
highest degradation of paracetamol compared with other species
such as HO2 , O2 and H2O2 and follows a second-order rate con-
stant with paracetamol. The degradation of paracetamol on boron
doped diamond (BDD) electrodes decreased the total organic car-
bon (TOC) by more than 98% (Brillas et al., 2005). BDD electrodes
are the preferred anode material due to their ability to operate at
high positive potentials with minimum degradation and high effi-
ciency. However, they are still expensive and other cheaper more
available methodologies have been investigated. Some of these in-
clude the electrolytic process using titanium anodes modified with
TiO2 and with mixtures of RuO2–IrO2 to degrade phenolic acid
(Rajkumar and Palanivelu, 2004), clofibric acid (Sirés et al., 2007)
and piroxicam (Torriero et al., 2006).
The catalytic properties of low cost catalyst such as CuO sup-
ported on alumina, modified with a monolayer of TiO2, (CuO/
TiO2/Al2O3) have been studied for the cyclopropanation of styrene
(Liu et al., 2003). Higher activity and selectivity has been obtained
by supporting the CuO catalyst on TiO2/Al2O3 rather than on sepa-
rated TiO2 or Al2O3, indicating the relationship between the cata-
lyst support and the activity. The authors suggested that the
highly dispersed CuO and the monolayer of dispersed TiO2 interact
with on Al2O3 and propose that Cu(II) in the cupric oxide gets re-
duced during the cyclopropanation reaction (Fraile et al., 1997;
Liu et al., 2003).
The objective of this work is to determine the degradation route
of paracetamol in the presence of TiO2 and CuO/TiO2/Al2O3 modi-
fied electrodes supported on reticulated vitreous carbon (RVC)
(Friedrich et al., 2004; Recio et al., 2011). The importance of these
electrodes is their low cost and their potential to be employed in a
scale-up water treatment process for large volumes containing or-
ganic waste material.
2. Experimental
Three different processes to degrade paracetamol were studied;
each comprises several methodologies which are listed in Table 1
and described in the following sections.
2.1. Synthesis of TiO2 using titanium mesh
The TiO2 used to prepare the modified electrodes and in the
photochemical process was prepared by dissolving a titanium
mesh in concentrated HCl (36.5–38%, J.T. Baker) heated at 80 °C
while stirring for 3 h in order to form TiCl4 (Esquivel et al.,
2011). The solution was neutralised with ammonium hydroxide
to form TiO2 followed by the addition of 10% HNO3 (J.T. Baker) to
complete the oxidation of Ti0 to Ti4+, according to the following
equations:
0
Ti þ 6HCl þ 2H2 O ! TiCl4 þ 2HCl þ 2H2 O ð1Þ
TiCl4 þ 2NH4 OH ! TiO2 þ 2HCl þ 2NH4 Cl ð2Þ
The TiO2 formed was characterised by EDAX, SEM and X-ray
diffraction.
2.2. Preparation of the RVC modified electrodes
Two 100 pores per inch (ppi) RVC electrodes of 1  3  0.05 cm
dimensions were used as anode and cathode to prepare the modi-
fied electrodes by electrophoresis. The electrodes were glued to a
graphite rod with carbon cement and were completely immersed
in a solution of 0.5 M Na2SO4 at pH 5 contained in a BAS cell of
50 cm3 capacity. The graphite rod was kept out of solution and
the distance between the electrodes was 3 cm. One gram of each
catalyst TiO2 and CuO/TiO2/Al2O3, prepared by the method Sol–
Gel, was suspended in separated experiments in 20 cm3 of ethanol
and deposited on the anode by applying 4 V across the RVC elec-
trodes during 60 s via a Bioelec model FR500-125 power supply.
After the electrodeposition, the anodes were submitted to a heat
treatment process for 3.5 h at 550 °C in a furnace (Fisher-Scientific
Isotemp) in nitrogen atmosphere. The deposits were characterised
by a Scanning Electron Microscope (SEM) JEOL6060LV coupled
with a microprobe OXSOR and with an Energy-Dispersive X-ray
analysis (EDAX). The XRD analysis confirmed the presence of the
photochemically-active phase anatase of TiO2.
2.3. Photochemical process I (photolysis and photocatalysis)
A cell with 0.150 dm3 capacity shown in Fig. 1 containing
96 mg L1 of paracetamol and 0.01 M of H2O2 in deionised water
was used. The experiments lasted 6 h using TiO2 and CuO/TiO2/
 H.C. Arredondo Valdez et al. / Chemosphere 89 (2012) 1195–1201 1197

Al2O3 powders as catalysts while the solution was stirred with a

Summary of the degradation methods used to oxidise 96 mg L1 of paracetamol in the presence of 0.01 M H2O2, 0.05 M Na2SO4 at pH 5.0. The Table shows the composition of the electrolyte solutions after 1 and 2 h of reaction as well as

magnetic follower. A mercury lamp with 350 nm maximum wave-

length was used as a source of photons and the development of the
Energy consumption

solution was followed by taking aliquots of 1  103 dm3 every

15 min.
(kW h m3)

2.4. Electrochemical process II (electrolysis and electrocatalysis)

11.0
4.5

6.5

3.3
–

–
The electrolyses were carried out in a typical three-electrode cell
containing 96 mg L1 of paracetamol and 0.01 M of H2O2, with
(%)
CE

43

53

68

32
–

0.5 M Na2SO4 as a supporting electrolyte. A 100 ppi bare RVC elec-

trode and the two modified RVC electrodes were used as anodes
TOC
(%)

35

98

95

99
60
20

40
30
80
80
90
while the cathode and reference electrodes were a platinised tita-
2
4

nium mesh and a saturated calomel electrode (SCE), respectively.

An electrode potential of 1.3 V vs. SCE was applied to the anodes
Benzoquinone

based on earlier studies that show that at this potential the oxida-
(mg L1)

tion of paracetamol occurred preferentially on the electrodes used

in this study. The modified working electrodes were TiO2/RVC and
No
No
No
No
No

No

No

No

No
<7
<3
<3

CuO/TiO2/Al2O3/RVC prepared as explained in Section 2.2. The

development of the reaction was followed by analysing
1  103 dm3 aliquot of the electrolyte every 15 min during 6 h. A
Hydroquinone

Princeton Applied Research bi-potentiostat Model 366 was used

(mg L1)

for the electrochemical measurements.

<10

<10

<10
No
No
No

No

No
No
No

No

No

2.5. Photoelectrochemical process III

Oxalic + Oxamic acids

Similar electrochemical cell system with the modified elec-

trodes as described in the previous section was used. In addition
the system was irradiated with UV light from an Hg lamp at
350 nm wavelength maintaining the potential of the working elec-
(mg L1)

trode at 1.3 V vs. SCE (Fig. 1). The reaction was carried out over
<25
<15
<10
No
No
No

No

No

No

No

No
<7

60 min and the degradation of paracetamol was followed by taking

aliquots of 1  103 dm3 every 10 min.
Paracetamol

2.6. Analytical methods

(mg L1)
the percentage of TOC removal (degradation of paracetamol), current efficiency and energy consumption.

94
92
62
39
77

58
67
19
19
<10
<2

<5

<1

The reaction intermediates were analysed using an HPLC CC5,

Solvent Deliver System PM80, fitted with UV–Vis detector 116A
and temperature control LC-22C. The mobile phase was a 30/70%
Reaction (h)

(v/v) mixture of methanol/phosphate buffer adjusted to pH 2.6 at

0.8  103 dm3 min1 flow rate. The concentration of the phos-
Time of

phate buffer was 1  103 M and the column was an Alltima

1
2
1
2
1

2
1
2
1
2
1

2
1

2
1

HPC18 of 5l with 4.6 mm ID and 150 mm length. The retention

times of the carboxylic acids intermediates such as oxalic
CuO/TiO2/Al2O3/

CuO/TiO2/Al2O3/

CuO/TiO2/Al2O3/

(2.18 min) and oxamic acid (2.6 min) as well as those of hydroqui-
TiO2/RVC/UV

none (2.6 min), benzoquinone (3.7 min) and paracetamol (3.2 min)
TiO2/RVC
Notation

TiO2/UV

were compared with standards purchased from Merck. The inter-

RVC/UV

mediates were chosen based on the literature reports of the degra-

RVC

RVC
UV

UV

dation of paracetamol. Typically, 20 lL of a solution containing one

standard at the time was injected into the chromatographic col-
Photoelectrocatalysis

Photoelectrocatalysis
(5) Electrocatalysis

(6) Electrocatalysis

umn. The concentration of the standards varied between 12.00

(2) Photocatalysis

(3) Photocatalysis

and 15.00 mg L1. Before injecting the samples from the oxidation
(4) Electrolysis
(1) Photolysis

process into the HPLC, the samples were analysed by an UV–Vis

spectrophotometer Cary 50 Probe to confirm the presence or the
Method

absence of organic compounds. The total organic carbon (TOC)

(7)

(8)

was determined at 680 °C with a TOC analyser SHIMADZU. An acid

digestion method was used to prepare the samples before the TOC
analysis.
III. Photoelectrochemical
II. Electrochemical

3. Results and discussion

I. Photochemical

3.1. Photochemical process I (photolysis and photocatalysis)

Process
Table 1

Fig. 2 shows the concentration decay of 96 mg L1 of paraceta-

mol, determined by HPLC, vs. time for the photochemical process
1198 H.C. Arredondo Valdez et al. / Chemosphere 89 (2012) 1195–1201

I comprising three different methods (see Table 1). Curve (1) repre-
sents the paracetamol degradation during the photolysis process
using only UV light (method 1) and shows that the concentration
decreased <20% down to 76.8 mg L1 after 6 h. In the presence of
TiO2/UV (method 2) represented by curve (2), the degradation
reached 80% down to 19.2 mg L1 after 6 h. When CuO/TiO2/
Al2O3/UV was used (method 3) curve (3), the concentration after
6 h was 38.6 mg L1, indicating 60% degradation. The degradation
of paracetamol in these systems follows the order: TiO2/UV > -
CuO/TiO2/Al2O3/UV > UV. The catalytic activity of the p-type semi-
conductor TiO2 is higher due to its intrinsic ability to generate
electron–holes pairs under UV radiation. The adsorption of photons
creates an electronic distribution on the TiO2 surface that favours
the formation of free radicals (Lai et al., 2006; Peralta-Hernández
et al., 2007).
In the case of CuO/TiO2/Al2O3/UV, the presence of a semicon-
ductor n-type such as CuO is considered as an impurity and a syn-
ergetic effect between TiO2 and CuO is assumed, causing an
increase in the band gap and therefore more resistance to the elec-
tron transfer. This is the reason why in the method represented by
the curve (3), the degradation process is not effective.
3.2. Kinetic study
The inset in Fig. 2b shows the logarithm of the normalised con-
centration of paracetamol ct/c0 as a function of time for methods 1,
2 and 3. If the degradation of paracetamol follows a pseudo-first
order kinetics reaction the concentration decay can be expressed
in terms of the apparent rate constant, kapp. The figure shows that
the data for the three systems: UV, TiO2/UV and CuO/TiO2/Al2O3/
UV (see Section 3.1) are linear with an apparent rate constant of
0.4  103, 1.5  103 and 1.2  103 s1, respectively indicating
a pseudo-first order kinetic reaction. The experiment with TiO2/
UV shows higher percentage of degradation than when the exper-
iment was carried out with UV and CuO/TiO2/Al2O3/UV. Fig. 3
Photocatalysis cell
Input (O2)
Output
shows the chromatograms of the solution at the beginning (solid
line) and after 360 min (dash line) of the degradation process as
well as the standards of paracetamol, carboxylic acids and hydro-
quinone, found as intermediates. The curve after 360 min reaction
shows that the amount of paracetamol concentration decreased
80%. The curves (solid line) and (dash line) show the signal of the
paracetamol at an elution time of 3.2 min and two additional sig-
nals, at 2.1–2.3 and 2.6–2.7 min corresponding to the carboxylic
acids and hydroquinone, respectively. The degradation of paracet-
amol occurs via the formation of oxalic and oxamic carboxylic
acids therefore a standard of oxalic acid was used to follow the for-
mation of by-products. The presence of these intermediates was
confirmed by UV–Vis spectroscopy.
3.3. Electrochemical process II (electrolysis and electrocatalysis)
Fig. 4 shows the normalised concentration change of paraceta-
mol as a function of time with the three electrochemical systems
(methods 4, 5 and 6). The solution contained 96 mg L1 of paracet-
amol and 0.5 M Na2SO4 at pH 5 and the electrode potential was
held at 1.3 V vs. SCE. The electrolysis using RVC (curve 1) shows
90% degradation in 4 h while the electrolysis with the modified
electrode TiO2/RVC (curve 2) shows 90% in 2 h reaction. When
CuO/TiO2/Al2O3/RVC was used (curve 3), 98% degradation was
achieved in only 1 h. These reactions follow a pseudo-first order ki-
netic behaviour as the inset in the figure shows. The apparent rate
constants (kapp) for these systems are 4.3  103, 16.6  103 and
18.1  103 s1 for the systems: RVC, TiO2/RVC and CuO/TiO2/
Al2O3/RVC, respectively.
3.4. Photoelectrochemical process III
Fig. 5 shows the normalised concentration decay of paracetamol
when the initial concentration was 96 mg L1 in 0.5 M Na2SO4 at
pH 5. After 1 h reaction with TiO2/RVC/UV (method 7) (curve 1)
at 1.3 V vs. SCE the concentration decreased to 4.8 mg L1, repre-
senting 95% degradation. When CuO/TiO2/Al2O3/RVC/UV (method
8) was used the concentration decay of paracetamol (curve 2)
was 0.96 mg L1 (99% degradation) after less than 1 h reaction.
1.0
Normalised concentration of paracetamol, ct/c0

(1)
0.8 (a)
0.6
(3)
Reference Time,t / s
0.4
Electrode 0 5000 10000 15000 20000
Working 1
0.9 (2)
Electrode 0.2 (1) 0.8
0.7

(b)
0.6
(3) 0.5
0.0 0.4
Log ct/c0

0.3
(2)
Auxiliary -0.2 0.2
UV Lamp Electrode
-0.4
0.1

0 5000 10000 15000 20000

Time, t / s

Fig. 2. (a) Development of the normalised concentration of paracetamol vs. time

Fig. 1. Diagram of the quartz cell used for the photochemical and photoelectro-
catalytic batch operations. When the photochemical processes were carried out the
mercury lamp inserted in the middle of the cell as shown in the drawing.
under the photochemical process I showing the three systems used: (1) UV, (2)
TiO2/UV, (3) CuO/TiO2/Al2O3/UV. (b) Semi-logarithmic plot log (ct/c0) vs. time
during the degradation of paracetamol in the systems described above. The solution
contained 96 mg L1 of paracetamol in 0.5 M Na2SO4, 0.01 M H2O2 at pH 5 and the
reactions were carried out under stirring conditions and UV light at 350 nm.
 H.C. Arredondo Valdez et al. / Chemosphere 89 (2012) 1195–1201 1199

The kinetic rate constants calculated from the slopes of the curves
shown in the inset of the figure of the systems described above
were 13.8  103 s (curve 1) and 15.1  103 s1 (curve 2).
3.5. Percentages of paracetamol decay
Table 1 shows the concentration of different intermediates spe-
cies found in solution after 1 and 2 h degradation of 96 mg L1 of
paracetamol for the different systems described above. In the UV
system the concentration of paracetamol only decreased 2% and
4% during the 1st and 2nd h, respectively without any detectable
concentration of intermediates. When the degradation was carried
out using the photocatalytic system, TiO2/UV (method 2) small
amounts of oxalic acid and benzoquinone were detected at very
poor percentages of degradation. Similarly, very low concentra-
tions of intermediates were detected when the system CuO/TiO2/
Al2O3/UV (method 3) was used. The electrolysis with RVC (method
4) produced larger amounts of carboxylic acids and benzoquinone
with a degradation of 80% of paracetamol in 2 h. However, the elec-
trolysis with the modified electrode TiO2/RVC (method 5) 90% deg-
radation without formation of intermediates was achieved also in
2 h. When the modified electrode CuO/TiO2/Al2O3/RVC (method
6) was used, the degradation reached 98% without intermediates
in 1 h. The other systems tested were: incident UV light on TiO2/
CVR/UV (method 7) which achieved 95% degradation in 1 h, while
the system CuO/TiO2/Al2O3/RVC/UV (method 8) showed 99% in the
same period of time, indicating that the use of UV significantly in-
creases the oxidation rate.
3.6. Determination of the total organic carbon (TOC) during
degradation of paracetamol
Fig. 6 shows the development of the total organic carbon (TOC)
values during the degradation of paracetamol over 1 h reaction of
the photochemical processes I, II and III for all methods employed
except method 1, listed in Table 1. Curves (2) and (3) correspond
to the experiments carried out with powdery catalyst in a stirred
solution; TiO2/UV (method 2) and CuO/TiO2/Al2O3/UV (method 3).
Curves (7) and (8) represent the development of TOC when a pho-
toelectrochemical process was carried out with the modified RVC
electrodes and with UV incident light, method 7 (TiO2/RVC/UV)
and method 8 (CuO/TiO2/Al2O3/RVC/UV) listed in Table 1. The pho-
tochemical processes (curves 2 and 3) show that the TOC values de-
crease to 30 and 60 mg dm3, respectively after 1 h confirming that
there is still organic matter in solution. In the case of the photo elec-
trochemical processes (curves 7 and 8) the depletion of the TOC is
significantly more important, 90 and 100 mg dm3, respectively.
This demonstrates the complete demineralisation of the drug after
1 h reaction using process III.
The Fig. 6 also shows that in the electrochemical processes II in
the absence of UV light, the values of TOC during the electrolysis
with an RVC electrode (curve 4) are still high after 1 h, indicating
poor mineralisation. The curves (5) and (6) represent the develop-
ment of the TOC values during the electrolysis with the modified
electrodes TiO2/RVC and CuO/TiO2/Al2O3/RVC, respectively. The
TOC decreases considerably, especially for the system containing
CuO and indicates that the system represented by curve (6) is
the most efficient system to degrade paracetamol.
3.7. Current efficiency for the mineralisation process
In this study the systems that yielded the highest percentage of
mineralisation of paracetamol were considered to calculate the
current efficiency and the energy consumption. These include the
electrochemical and photoelectrochemical processes II and III
respectively which comprise the methods numbered 5, 6, 7 and
8. Less efficient methods such as 1, 2, 3 and 4 present higher energy
consumption due to their lower percentage of TOC and were not
calculated as they are not attractive to scale-up the process. The
global mineralisation of paracetamol oxidation can be written as
(Brillas et al., 2005):
HOC6 H4  NHCOCH3 þ 14H2 O ! 8CO2 þ NHþ4 þ 33Hþ þ 34e ð3Þ
The current efficiency at time t can be calculated by the follow-
ing equation (Brillas et al., 2005):
Current efficiency ¼ u ¼ ½DðTOCÞexp =DðTOCÞtheory   100 ð4Þ
where D(TOC)exp and D(TOC)theory are the experimental values of
TOC at time t and the theoretical calculation of TOC assuming that
Eq. (3) is the only one occurring during the electrolysis process
1.0 0
Normalised concentration of paracetamol, ct/c0

10

1.0 (a) (b)

Standards
Starting time 0.8
Paracetamol -1
10 (1)
After 6 h
Log ct/c0

0.8
-2
10
Hydroquinone 0.6 (2)
(3)
Arbitrary units

0.6
-3
10
0 5000 10000 15000 20000 25000
0.4
Time, t / s
0.4
(1)
Carboxylic acid 0.2
(3)
0.2 Benzoquinone (2)
0.0
0 5000 10000 15000 20000 25000
0.0 Time, t / s
1 2 3 4
Time, t / min Fig. 4. (a) Normalised concentration change of paracetamol vs. time during the
electrolysis at 1.3 V vs. SCE carried out using the electrochemical process II in a
Fig. 3. Chromatograms of the degradation of paracetamol via photocatalysis using solution containing 96 mg L1 of paracetamol and 0.5 M Na2SO4, 0.01 M H2O2 at pH
TiO2/UV, solid line (—) starting time, dash line (- - -) after 6 h reaction. The dotted 5. The electrodes were: (1) RVC, (2) modified TiO2/RVC, and (3) CuO/TiO2/Al2O3/
line corresponds to the HPLC standards of the compounds showed in the graph. The RVC. (b) Semi-logarithmic plot of the normalised concentration vs. time of the three
volumetric flow rate was 0.8  103 dm3 min1. systems mentioned above.
1200 H.C. Arredondo Valdez et al. / Chemosphere 89 (2012) 1195–1201

1.0 100
100 2) TiO2/UV
Normalised concentration of paracetamol, ct/c0

(a) (b) 3) CuO/TiO2/Al2O3/UV

4) RVC

Total organic carbon, TOC / mg dm-3

5) TiO 2/RVC
0.8 (1) 80
6) CuO/TiO2/Al2O3/RVC

Log ct/c0
(1) 10-1 7) TiO2/RVC/UV
(2) 8) CuO/TiO2/Al2O3/RVC/UV

0.6 60

(2) 10-2
0 1000 2000 3000 4000
0.4 40
Time, t / s

0.2 20

0.0 0
0 1000 2000 3000 4000 5000 0 1000 2000 3000 4000
Time, t / s Time, t / s

Fig. 5. a) Normalised concentration decay of paracetamol with time during the Fig. 6. Development of the total organic carbon vs. time during the degradation of
photoelectrochemical process III with the modified electrodes (1) (d) TiO2/RVC/UV 96 mg L1 paracetamol in 0.5 M Na2SO4, 0.01 M H2O2 at pH 5 under different
and (2) (s) CuO/TiO2/Al2O3/RVC/UV. The process was carried out at 1.3 V vs. SCE in degradation processes: photochemical, electrochemical, and photo-
the presence of UV light at 350 nm in a solution containing 96 mg L1 of electrochemical.
paracetamol and 0.5 M Na2SO4, 0.01 M H2O2 at pH 5. (b) Semi-logarithmic plot of
the normalised concentration vs. time.
The energy consumption during the degradation of paracetamol
without considering the energy used by the UV lamp is reported in
(Brillas et al., 2005), respectively. The TOC values can be calculated
Table 1 for the most effective methods. This parameter is not often
according to the following equation (Comninellis, 1994):
reported in the literature for paracetamol but comparisons can be
made with other systems such as the degradation of b-blockers and
TOC ¼ 12  TOC ð5Þ
the removal of heavy metals ions. The energy consumption re-
where TOC is the number of moles of carbon per unit volume (M) ported in this work lies between 3.3 and 11.0 kW h m3 while for
while TOC is the weight of carbon per unit volume (g L1). The cal- the degradation of 15 mg L1 b-blockers was higher (36 kW h m3)
culation of the total organic carbon during the degradation of para- (Sirés et al., 2010). The comparison with the recovery of heavy
cetamol using Eq. (5) suggested by Comninellis (1994) resulted in metals shows that the values in this paper are within the same or-
0.631 g L1 TOC. The equation used to calculate the specific energy der of magnitude: 500 mg L1 of Pd2+ (1.04–2.8 kW h m3) (Terra-
consumption Es, is expressed as (Terrazas-Rodríguez et al., 2011a): zas-Rodríguez et al., 2011b), 922 mg L1 of Cu2+ (4–7 kW h m3)
(Rivera et al., 2008), 1187 mg L1 of Sn4+ (2–10 kW h m3) (Gar-
zFEcell DTOC cía-Gabaldón et al., 2005) and 55 mg L1 of Cd2+ (1–2.5 kW h m3)
Es ¼ ð6Þ (Grau and Bisang, 2001) in divided and undivided rotating cylinder
3:6  103 uM
electrodes (RCEs).
where z is the number of electrons, F is the Faraday constant, M is
the molar mass, Ecell is the cell potential, DTOC is the change of total 4. Conclusions
organic carbon during degradation process and u is the cumulative
efficiency. Using a photochemical degradation process, the effective miner-
The changes of TOC, current efficiency and energy consumption alisation of paracetamol in different systems occurs in the following
are shown in Table 1 for those methods that offered the highest re- order during 6 h period: TiO2/UV > CuO/TiO2/Al2O3/UV > UV. When
moval percentage of TOC. The modified electrodes, arranged from an electrocatalysis process was used the degradation of paraceta-
the most efficient mineralisation systems follow the order: CuO/ mol can be achieved quicker after 1 and 2 h of reaction with up to
TiO2/Al2O3/RVC/UV (method 8) > CuO/TiO2/Al2O3/RVC (method 90% and 98% degradation, respectively with the modified elec-
6) > TiO2/RVC/UV (method 7) > TiO2/RVC (method 5) with 99%, trodes: CuO/TiO2/Al2O3/RVC > TiO2/RVC > RVC. The photoelectro-
98%, 95% and 80% of TOC, respectively. The current efficiencies catalytic process also degrades paracetamol up to 95% and 99%,
are higher in the systems containing the modified electrodes with and the TOC removal indicates complete mineralisation in 60 min
TiO2 and not CuO. However, the presence of CuO in the modified in the following order: CuO/TiO2/Al2O3/RVC//UV > TiO2/RVC/UV.
electrodes allows the highest percentage of mineralisation with The electrolysis with reticulated vitreous carbon shows the
high energy consumption. The values of current efficiency for the presence of intermediates such as carboxylic acids, hydroquinone
mineralisation of paracetamol found in this work are higher than and benzoquinone in considerable amounts resulting in a poor per-
those reported by (Brillas et al., 2005) who achieved between centage of degradations which was confirmed by the values of TOC.
9.7% and 18% current efficiency at temperatures between 25 °C The kinetic study shows that in all cases the degradation of par-
and 45 °C during the degradation of 157 mg L1 of paracetamol acetamol follows a pseudo-first order reaction. The CuO/TiO2/
in 0.05 M Na2SO4 at pH 3 using a boron-doped diamond (BDD) an- Al2O3/RVC/UV system shows the largest pseudo kinetic constant
ode. This could be due to the lower concentration of paracetamol indicating rapid conversion of paracetamol directly to CO2.
used in this paper and the larger electrochemical active area of The system with the highest degradation efficiency was the
the modified electrodes but also shows that these electrodes can photoelectrocatalysis (method 7) using TiO2/RVC/UV modified
be an efficient lower cost alternative to the high cost BDD electrode which shows 95% degradation at 68% current efficiency.
electrodes. The efficiency values are in the same order of magnitude as those
 H.C. Arredondo Valdez et al. / Chemosphere 89 (2012) 1195–1201
reported in the literature for paracetamol while the energy con-
sumption compares with that reported for heavy metal recovery
in different electrochemical reactors.
Acknowledgements
The authors are grateful to ‘‘Consejo Nacional de Ciencia y Tec-
nología’’ (CONACYT) Mexico, for the scholarship for H.C. Arredondo
Valdez and the financial support for C. Ponce de León (consolida-
tion visitor) and to CIDETEQ, Mexico, for allowing the use of their
equipment.
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