Buletinul tiinific al Universitii Politehnica din Timisoara, ROMNIA

Seria CHIMIE I INGINERIA MEDIULUI

Chem. Bull. "POLITEHNICA" Univ. (Timioara) Volume 54(68), 1, 2009

46
Electrochemical Degradation of Aromatic Compounds at Modified
SnO
2
Anodes

M. Iho
*
, F. Manea**, A. Iovi**


*National Research and Development Institute for Industrial EcologyECOIND, P-ta Victoriei nr.2, 300006 Timisoara, Romania,
Phone/Fax: ++40256220369, E-Mail: [email protected]

**
Politehnica University of Timisoara, Faculty of Industrial Chemistry and Environmental Engineering, P-ta Victoriei nr.2, 300006
Timisoara, Romania, Phone/Fax: ++40256403070, E-Mail: [email protected]


Abstract. The purpose of this study was the electrochemical degradation of a mixture of Reactive Black 5 (RB5) azo dye
and nonylphenol ethoxylate with 9 ethoxy units (NP9EO) at modified SnO
2
anodes. Ti/RuO
2
/SnO
2
-Sb
2
O
5
-RuO
2
and
Ti/RuO
2
/SnO
2
-Sb
2
O
5
-Bi
2
O
3
anodes were prepared by thermal decomposition of appropriate precursors. Both NP9EO and
RB5 concentrations were 0.1 g/L in 0.1 M Na
2
SO
4
as supporting electrolyte. The electrolysis were conducted under
galvanostatic regime at applied current densities of 50, 75 and 100 A/m
2
and electrolysis time of 30, 60 and 120 minutes.
The electrolysed solutions were characterised by UV-VIS spectroscopy. The spectral data revealed the aromatic ring
opening and they were also used to assess the colour removal efficiency. Based on the spectral data, it was assessed the
colour efficiency and some aspects of oxidation process were discussed.

Keywords: aromatic compounds, electrochemical degradation, modified SnO
2
anodes


1. Introduction

Textile wastewaters contain aromatic compounds like
dyes and nonionic surfactants. Usually, dyes are not
treatable by biological organisms. Nonylphenol
ethoxylates, which are nonionic surfactants, require a very
long time to be broken down by bacteria. Consequently,
their release in the environment is undesirable.
Electrochemical methods are promising concerning
the treatment of wastewaters containing dyes and
nonylphenol ethoxylates. Researches have been conducted
by using dimensionally stable anodes (DSA) to degrade
organic pollutants [1-3].
An appropriate choice of anode material can allow
complete elimination of total organic carbon with high
current efficiency. One of these materials could be DSA
having electrocatalytic layer of modified SnO
2
. Studies
have been reported the use of modified SnO
2
anodes for the
electrochemical oxidation of organic compounds [4, 5].
The aim of this paper was electrochemical
degradation of a mixture of RB5 and NP9EO
at modified SnO
2
anodes, Ti/RuO
2
/SnO
2
-Sb
2
O
5
-RuO
2
and
Ti/RuO
2
/SnO
2
-Sb
2
O
5
-Bi
2
O
3
.

2. Experimental

2.1. Modified SnO
2
anodes preparation

The following anodes: Ti/RuO
2
/SnO
2
-Sb
2
O
5
-RuO
2
and
Ti/RuO
2
/SnO
2
-Sb
2
O
5
-Bi2O
3
were prepared by using
titanium plates as a support. The plates were treated by
sand-blasting followed by a chemical treatment with
technical hydrochloric acid 15 % for 20 minutes
under boiling. Then, the plates were washed with


water, distilled water and absolute ethylic alcohol reagent
degree Chimopar Bucuresti) followed by drying in open
air. The precursors solution was brushed onto plates
surface.
The intermediate layer of RuO
2
was obtained by
thermal decomposition of a precursor solution obtained by
dissolving RuCl
3
.
nH2O (Fluka) in isopropanol reagent
degree (Chimopar Bucuresti) at 450 C.
The electrocatalytic layer of SnO
2
-Sb
2
O
5
-RuO
2
and
SnO
2
-Sb
2
O
5
-Bi
2
O
3
was prepared as follows: the precursors
solution was obtained by dissolving the appropriate amount
of SnCl
4
.
5H
2
O (Aldrich), SbCl
3
(Aldrich) and RuCl
3
.
nH2O
(Fluka) or Bi(NO
3
)
3
.
5H
2
O (Chimopar Bucuresti) in the
solution containing hydrochloric acid (37%) and
isopropanol reagent degree (Chimopar Bucuresti). The
molar ratio Sn:Sb:Ru or Sn:Sb:Bi in precursors solution
was 94:3:3.
The anodic material was further treated by heating to
110 C in a drying cabinet. After that, the electrode was
treated at 550 C for 10 minutes to decompose the salts
from precursors solution. This cycle brushing drying
thermal decomposition was repeated 15 times. Finally, a
thermal treatment was applied for 1 hour to stabilize the
oxide film.

2.2. Electrolysis

Electrochemical degradation of pollutants was carried
out in a plexiglass cell at modified SnO
2
anodes. Two
anodes and three stainless steel cathodes were inserted at
1 cm gap. The active surface area was 38 cm
2
. Experiments
were carried out by applying current densities of 50, 75,
100 and 300 A/m
2
at various electrolysis times: 30, 60 and
120 minutes.

Chem. Bull. "POLITEHNICA" Univ. (Timioara) Volume 54(68), 1, 2009

47
Experiments were carried out in working solutions that
contained a mixture of 0.1 g/L RB5 and 0.1 g/L NP9EO
(RB5-NP9EO) in 0.1 M Na
2
SO
4
as supporting electrolyte.
For comparison purposes, experiments were carried out
only in solutions of 0.1 g/L RB5 in 0.1 M Na
2
SO
4
as
supporting electrolyte. The pH of initial solutions
(RB5-NP9EO or only the dye) was 5.8. RB5 and NP9EO
were technical products and they were used as suppliers
provided them. Solutions were prepared with distilled
water and Na
2
SO
4
(Chimopar Bucureti) reagent grade.
Chemical structure of RB5 and NP9EO is shown in
figures 1 and 2.




Figure 1. Chemical structure of RB5

O(CH
2
CH
2
O)
9
H
C
9
H
19


Figure 2. Chemical structure of NP9EO



Figure 3. UV spectra of the individual components and the mixture
(dilution 1:2.5)
1. RB5-NP9EO in 0.1 M Na2SO4; pH=5.8; 2. RB5 in 0.1 M Na2SO4;
cini =0.1 g/L; pH=5.8 3. NP9EO in 0.1 M Na2SO4; cini =0.1 g/L

2.3. UV-VIS spectra

The UV-VIS spectra were recorded by a Jasco V-530
spectrophotometer controlled by computer.
The individual UV spectra of the RB5 and NP9EO
and also the spectrum of the RB5-NP9EO are shown in
figure 3.

Fig.ure 4. UV spectra of nonylphenols ethoxylates in
0.1 M Na2SO4: 1. NP9EO 2. NP16EO 3. NP40EO
NPnEO concentration: 0.1 g/L

The spectrum in the visible range of the RB5-NP9EO
is shown in figure 5.



Figure 5. Spectra in visible range of RB5-NP9EO in 0.1 M Na2SO4;
pH=5.8; dilution 1:2.5


3. Results and discussion


3.1. UV spectra analysis

At pH 5.8 the UV spectra of RB5 exhibits three
absorbance peaks at 229 nm, 256 nm and 310 nm. In
accordance to the literature data [6], the absorbance peak at
229 nm was assigned to benzene ring, while those of
310 nm to naphthalene ring.
The absorbance peaks at 225 nm and 276 nm in the
UV spectrum of the NP9EO were assigned to the benzene
ring, as it can be inferred from Fig. 4. Thus, it can be
observed that the absorbance peaks appeared at the same
wavelength for any nonylphenol ethoxylate. Because the
absorbance decreased as the number of the ethoxy units
increased for any peaks and the weight of the benzene ring
in the molecular weight of the nonylphenol ethoxylate
decreased, the absorbance peaks at 225 nm and 276 nm in
the NP9EO spectrum can be assigned to the benzene ring.
The spectrum of the RB5-NP9EO exhibits absorbance
peaks at 225 nm, 258 nm and 310 nm. It can be observed
that the absorbance peak of 310 nm appeared in the
spectrum only as contribution of RB5.

Chem. Bull. "POLITEHNICA" Univ. (Timioara) Volume 54(68), 1, 2009

48
3.2. Electrochemical degradation experiments

The electrochemical degradation experiments proved
that as the electrolysis time increased for any applied
current density and anodic composition the value of the
absorbance at 225 nm and 310 nm decreased (Table 1).


TABLE 1. Working conditions, values of absorbance at 225 nm
and 310 nm for RB5-NP9EO in 0.1 M Na
2
SO
4
; *Aini_225=1.41;
*Aini_310=1.02


Anodic composition
Current
density /
(A/m
2
)
Time /
(min)
*A225 *A310
30 1.32 0.71
50 60 1.28 0.63
120 1.17 0.60
30 1.38 0.69
Ti/RuO2/SnO2-Sb2O5-RuO2 75 60 1.29 0.63
120 1.10 0.58
30 1.31 0.68
100 60 1.25 0.62
120 0.98 0.52
30 1.35 0.71
50 60 1.27 0.60
120 1.09 0.56
30 1.35 0.69
Ti/RuO2/SnO2-Sb2O5-Bi2O3 75 60 1.20 0.57
120 0.96 0.48
30 1.33 0.67
100 60 1.16 0.55
120 0.84 0.42
* dilution 1:2.5

As it is shown in figure 6 and 7, at 120 minutes of
electrolysis, the absorbance peak flattening is more
enhanced, as the applied current density is higher for both
anodic compositions. However, it can be observed that the
degradation process occurred more efficiently at
Ti/RuO
2
/SnO
2
-Sb
2
O
5
-Bi
2
O
3
anodes.



Figure 6. UV spectra of RB5-NP9EO in 0.1 M Na2SO4 (dilution 1:2.5)
anodic composition: Ti/RuO2/SnO2-Sb2O5-RuO2; electrolysis time: 120
min; current density: i - initial solution1 - 50 A/m
2
; 2 - 75 A/m
2
;
3 - 100 A/m
2


Figures 6 and 7 show also that the shape of spectra of
the electrolysed solutions was the same for both anodic
compositions. In addition, the absorbance peaks attributed
to the aromatic rings decreased as the applied current
densities increased and no additional peak absorbance
appeared in the spectra.
The electrochemical degradation of RB5-NP9EO at
Ti/RuO
2
/SnO
2
-Sb
2
O
5
-RuO
2
in the following conditions:
300 A/m
2
and 120 or 180 minutes led to almost
disappearance of the absorbance peaks (figure 8). Also, no
new peaks appeared in the electrolysed solutions spectra
that could suggest the formation of additional compounds
with aromatic structures.



Figure 7. UV spectra of RB5-NP9EO in 0.1 M Na2SO4 (dilution 1:2.5)
anodic composition: Ti/RuO2/SnO2-Sb2O5-Bi2O3; electrolysis time:
120 min; current density: i initial solution; 1 - 50 A/m
2
; 2 - 75 A/m
2
;
3 - 100 A/m
2





Figure 8. UV spectra of RB5-NP9EO in 0.1 M Na2SO4 (dilution 1:2.5)
anodic composition: Ti/RuO2/SnO2-Sb2O5-RuO2; current density:
300 A/m
2
; electrolysis time: i initial solution; 1- 120 min; 2 180 min


These findings suggest the aromatic ring opening and
there are in accordance with the literature data [7 - 9]. The
authors reported that the electrochemical oxidation of the
organic compounds at anodes that exhibit high
overpotential towards the oxygen evolution, such as
Ti/SnO
2
or Ti/SnO
2
-Sb
2
O
5
, leads to CO
2
.
The 310 nm absorbance peak in the RB5-NP9EO
spectrum is due exclusively to the RB5 presence.
Therefore, it is possible a comparison between the
degradation efficiency of the dye individual (Table 2) as
well in the mixture (Table 1).
The data from Tables 1 and 2 revealed that the
differences between the absorbance peak at 310 nm
(assigned to the naphthalene ring) in the spectra of the
solutions of the RB5-NP9EO and only the dye are
insignificant. Consequently, the presence of NP9EO did
not hamper the oxidation process of RB5 in relation to
naphthalene ring.

Chem. Bull. "POLITEHNICA" Univ. (Timioara) Volume 54(68), 1, 2009

49
TABLE 2. Working conditions and absorbance at 310 nm after
electrolysis for RB5 in 0.1 M Na
2
SO
4
; c
in RB5
=0.1 g/L; electrolysis
time: 120 minutes

Anodic composition
Current
density /
(A/m
2
)
Cell
voltage /
(V)

*A310

50 3.4 0.62
Ti/RuO2/SnO2-Sb2O5-RuO2 75 3.5 0.57
100 3.7 0.50
50 3.5 0.46
Ti/RuO2/SnO2-Sb2O5-Bi2O3 75 3.8 0.42
100 4.1 0.39
* dilution 1:2.5

3.3. Colour removal efficiency

As it is shown in figure 5 the spectrum of the
RB5-NP9EO presented a maximum of the absorbance in
the visible range at 597 nm. The presence in the spectrum
of this absorbance peak is due to RB5, as it is well known
NP9EO is colourless.
The colour removal efficiency was calculated from
the relative decrease of absorbance at 597 nm peaks and the
results are listed in Tables 3 and 4.

TABLE 3. Working conditions, colour removal efficiency for
RB5-NP9EO in 0.1 M Na
2
SO
4
and RB5 (c
in RB5
=0.1 g/L) in
0.1 M Na
2
SO
4
at Ti/RuO
2
/SnO
2
-Sb
2
O
5
-RuO
2


Current
density/
A/m
2

Time/
min
Cell
voltage/
V
Colour
removal
efficiency
(mixture) /
%
*Colour removal
efficiency
(individual) /
%
30 3.3 70.05 -
50 60 3.4 83.24 -
120 3.4 93.68 97.27
30 3.5 69.23 -
75 60 3.5 85.16 -
120 3.5 95.32 97.27
30 3.7 73.07 -
100 60 3.7 89.01 -
120 3.7 98.07 97.57
* - no experiments were carried out


TABLE 4. Working conditions, colour removal efficiency for
RB5-NP9EO in 0.1 M Na
2
SO
4
and RB5 (c
in RB5
=0.1 g/L) in
0.1 M Na
2
SO
4
at Ti/RuO
2
/SnO
2
-Sb
2
O
5
-Bi
2
O
3


Current
density/
A/m
2

Time/
min
Cell
voltage/
V
Colour removal
efficiency
(mixture) /
%
*Colour
removal
efficiency
(individual) /
%
30 3.6 63.73 -
50 60 3.5 84.61 -
120 3.5 94.78 97.57
30 3.8 63.73 -
75 60 3.8 87.36 -
120 3.8 97.52 97.87
30 4.0 71.70 -
100 60 4.1 90.38 -
120 4.1 98.62 98.18
* - no experiments were carried out

It can be easily observed that generally for both
anodic compositions the colour removal efficiency from
RB5-NP9EO solutions increase with the increase of the
current density and the electrolysis time.
The colour removal efficiency was higher for the
anodic composition with Bi
2
O
3
in the electrocatalytic layer,
excepting the 30 minutes of electrolysis time at any applied
current density.
For both anodic compositions at 120 minutes of
electrolysis and applied current densities of 50 and 75 A/m
2

the colour removal efficiency is higher for RB5 individual
degradation than in the mixture.


4. Conclusions


In this study, the electrochemical degradation of a
mixture of RB5 and NP9EO was investigated at modified
SnO
2
anodes.
The Ti/RuO
2
/SnO
2
-Sb
2
O
5
-RuO
2
and Ti/RuO
2
/SnO
2
-
Sb
2
O
5
-Bi
2
O
3
anodes were prepared by thermal
decomposition of the appropriate precursors.
The UV spectra analysis showed the aromatic ring
opening in the working conditions of 50, 75 and 100 A/m
2

applied current densities at 30, 60 and 120 minutes of
electrolysis for both anodic compositions.
The degradation of the naphthalene ring of RB5 from
the mixture of pollutants at modified SnO
2
anodes was not
hampered by the presence of NP9EO.
The best colour removal efficiencies (about 98%)
were obtained for both anodic compositions at 100 A/m
2

and 120 minutes of electrolysis.



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