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ELECTROCHEMICAL DEGRADATION AND DETERMINATION OF

PENTACHLOROPHENOL FROM WATER USING TIO2-MODIFIED


ZEOLITE-CARBON COMPOSITE ELECTRODES

gnes Jakab1, Aniela Pop1, Corina Orha2, Florica Manea1 , Rodica Pode1

1
Department of Applied Chemistry and Engineering of Inorganic Compounds and Environmen,
Faculty of Industrial Chemistry and Enviromental Engineering, Politehnica University Timioara
V. Parvan no. 6, 300223, Timioara, Romania
2
National Institute for Research and Development in Electrochemistry and Condensed Matter,
Timioara, Condensed Matter Department, 1 P. Andronescu Street, 300254, Timioara, Romania

Abstract
In this study, TiO2-zeolite modified carbon nanotubes-epoxy (TiO2-Z-CNT-Epoxy) and TiO2-
zeolite modified carbon nanofibers-epoxy (TiO2-Z-CNF-Epoxy) composite electrodes were applied
for degradation and determination of pentachlorophenol (PCP) in aqueous solution. The structural
and morphological aspects of these electrodes were examined by scanning electron microscopy.
The electrochemical behaviour of the electrodes was investigated under UV irradiation
presence/absence, using cyclic voltammetry (CV) in 0.1 M sodium sulphate solution supporting
electrolyte. The electrooxidation and photoelectrooxidation process under potentiostatic conditions
were carried out using chronoamperometry (CA). A synergy effect at 1.5 V applied potential was
observed for photoelectrochemical process in comparison with each electrochemical and
photocatalytic one. The optimum operation conditions in relation with electrode type, and applied
potential were established.

Key words: pentachlorophenol; photoelectrocatalytic activity; TiO2-zeolite-modified


nanostructured carbon composite electrodes; wastewater

1. Introduction
Pentachlorophenol (PCP), a highly chlorinated phenol (Kim et al., 2007) belongs to the
priority toxic pollutant group listed by the both European Comission Legislation (Hincapi et al.,
2005) and United States of America Environmental Protection Agency (Xu et al., 2010). PCP is

Author to whom all correspondence should be addressed e-mail: florica.manea@chim.upt.ro; phone:(+40)256403070,


fax: (+40)256403069; web: www.upt.ro
widely used as a biocide (Hong and Zeng, 2002) in many agriculture (Kazunga et al., 1999) and
industrial applications, especially as a wood preservative (Wu, 2010). Its high toxicity (Quan et al.,
2007), carcinogenicity (Carvalho et al., 2011; Gunlazuardi and Lindu, 2005) and persistence (Agbo
et al., 2011) reclaims to find new methods for accurate determination and degradation of PCP from
wastewater. Chromatography and spectrophotometry (Wu, 2009) have been reported for the
determination of PCP in contaminated samples. Compared with these methods, the electrochemical
detection is very convenience, reliable and low cost. The new carbon materials, carbon nanotubes
(CNTs) and carbon nanofibers (CNFs) have similar physicochemical properties in many aspects
(Qin et al., 2010), such as chemical stability (Xie et al., 2012) and good electrical conductivity
(Allaoui et al., 2008; Chen et al., 2010). Moreover, carbon composite materials have attracted
considerable interest in several fields, electrochemical detection and photoelectrocatalytic
degradation of phenol compounds (Liu et al., 2008; Zhang et al., 2011). The environmental friendly
zeolites shows a significant interest in electrochemical applications (Carvalho et al., 2006) due to
their excellent properties, such as unique microporous structure, thermal stability and good
conductivity (Carvalho et al., 2008; Li et al., 1995). In addition, combining the selected
characteristics of zeolites and the photoactive TiO2 (Qiu et al., 2011) can be increased the
photoelectrocatalytic performance of the nanostructured carbon composite electrodes in different
applications. The aim of this study was to investigate the performances of TiO2-zeolite-modified
carbon nanotubes-epoxy (TiO2Z-CNT-Epoxy) and TiO2-zeolite-modified carbon nanofibers-epoxy
(TiO2Z-CNF-Epoxy) composite electrodes to degrade and determine PCP from wastewater
envisaging their practical applications in wastewater treatment and process control.

2. Materials and methods


Pentachlorophenol (PCP), sodium hydroxide (NaOH), sodium sulphate (Na2SO4) and
titanium dioxide (TiO2) were of analytical grade from Merck. Romanian zeolitic mineral from
Mirsid, used as support for TiO2 loading, was supplied by CEMACON Company, Romania. The
epoxy resin used for composites preparation was AralditeLY5052/ Aradur5052 purchased from
Huntsman Advanced Materials, Switzerland. The experimental set-up consisted a three-electrode
quartz cell, an ultraviolet light source and an Autolab potentiostat/galvanostat PGSTAT 302
(EcoChemie, The Netherlands) controlled with GPS 4.9 software. The potentiostat was connected
with a Pt counter electrode, a reference electrode (saturated calomel electrode) and the carbon based
composite working electrode. To obtain TiO2-modified zeolite hybrid material, sol-gel method was
used. The TiO2Z-CNT-Epoxy and TiO2-Z-CNF-Epoxy composite electrodes were obtained by an
effective two-roll mill procedure (TRM). The ratios of the electrode compositions were chosen to
reach 20% wt. CNT/CNF, 20% wt. TiO2-modified zeolite and 60% wt. epoxy resin. The UV lamp
(maximum wavelength of 365 nm, I0 = 2.1 mWcm-2) was positioned 5 mm below the
electrochemical cell.
Cyclic voltammetry (CV) technique was used to characterize the electrochemical and
photoelectrochemical behaviors of the composite electrodes in the presence of PCP and 0.1 M
Na2SO4 supporting electrolyte. The chronoamperometry (CA) technique was used to achieve the
electrochemical and photoelectrochemical oxidation, for 1.5 V applied potential under
potentiostatic conditions. The PCP concentration before and after degradation process was
determined by an UV method at the wavelength of 218 nm using a Varian Cary 100 UV-VIS
Spectrophotometer.
The PCP degradation process efficiency, , was determined based on Eq. (1):
C PCP C PCP t / C PCP 100%
0 0
(1)

where C PCP0 - initial concentration of PCP, mgL-1;

C PCPt - concentration of PCP at time t, mgL-1;

In addition to the PCP removal process efficiency, the electrochemical efficiency for PCP
oxidation, E amper , was obtained based on the Eq. (2) (Ratiu et al., 2010):


E amper C PCP0 C PCPt / C S V g / C cm 2 (2)

where C PCP0 - initial concentration of PCP, mgL-1;

C PCPt - concentration of PCP at time t, mgL-1;

C - charge consumption corresponding to a certain time, C;


V- the sample volume, 50 ml;
S - the area of the electrode, cm2.

3. Results and discussion

3.1. Morphological characterization

Figure 1 a and b shows the comparative SEM images of both TiO2-zeolite-modified nanostructured
carbon composite electrodes. A relative uniform distribution of nanostructured carbon within epoxy
is noticed, especial for carbon nanofibers based composite, which is responsible for providing more
reactive sites for the reactants than the agglomerated particles. TiO2-modified zeolite conferred a
porous structure of the composite electrode. The electrical conductivity value of about 0.65 Scm-1
determined for TiO2-Z-CNF-Epoxy is about three times higher than TiO2-Z-CNT-Epoxy electrical
conductivity (0.21 Scm-1), which should be explained also, by the more uniform distribution of
CNF versus CNT.

(a) (b)
Figure 1. SEM images of (a) TiO2-Z-CNT-Epoxy and (b) TiO2-Z-CNF-Epoxy composite electrodes

3.2. Cyclic voltammetry measurements

Figure 2 a and b shows the comparative CVs recorded with the TiO2Z-CNT-Epoxy and
TiO2Z-CNF-Epoxy in 0.1 M Na2SO4 supporting electrolyte non-irradiated and UV irradiated. The
background current recorded at TiO2Z-CNT-Epoxy composite electrode is higher than the one
recorded at TiO2Z-CNF-Epoxy composite electrode due to the better electrocatalytic activity of
CNT in comparison with CNF. For both electrodes, under UV irradiation higher background
current is noticed, the difference between the dark and light current being the photocurrent. For
TiO2Z-CNT-Epoxy composite electrode, the photocurrent represent about 30% and for TiO2Z-
CNT-Epoxy about 27% .

Figure 2. Cyclic voltammograms recorded with the (a) TiO2-Z-CNT-Epoxy and (b) TiO2-Z-CNF-
Epoxy electrodes in 0.1 M Na2SO4 supporting electrolyte: (1) background; (2) background under
UV irradiation
Cyclic voltammograms recorded at both electrodes in 0.1 M Na2SO4 supporting electrolyte,
at various PCP concentrations are shown in Figure 3. The electrocatalytic activity towards PCP
oxidation is evidenced by the anodic oxidation peak corresponding to direct oxidation of PCP on
the electrode surface recorded at about 0.97 V vs. SCE. A linear dependence between anodic
current and PCP concentration was achieved for both electrodes, which gives information about a
possible diffusion-controlled process, very desired for electroanalysis. Under UV irradiation, the
oxidation process is slightly influenced by appearance of a new oxidation peak prior to that
recorded in dark (Figure 4). This new small oxidation peak recorded at about +0.68 V vs. SCE for
both composite electrodes did not depend linearly on the PCP concentration, but inform that under
UV irradiation the oxidation process of PCP occurred earlier.

Figure 3. CVs recorded with the (a) TiO2-Z-CNT-Epoxy and (b) TiO2-Z-CNF-Epoxy composite
electrodes in 0.1 M Na2SO4 supporting electrolyte (1) without UV irradiation and in the presence
of different PCP concentrations: 10; 20; 30; 40 50M (curves 2-6). Inset: Calibration plot of the
anodic currents recorded at E = +0.97 V/SCE vs. PCP concentration

Figure 4. CVs recorded with the (a) TiO2-Z-CNT-Epoxy and (b) TiO2-Z-CNF-Epoxy composite
electrodes in 0.1 M Na2SO4 supporting electrolyte (1) under UV irradiation and in the presence of
different PCP concentrations: 10; 20; 30; 40 50 M (curves 2-6). Inset: Calibration plot of the
anodic currents recorded at E = +0.97 V/SCE vs. PCP concentration
The results are summarized in Table 1 and confirm that UV irradiation enhanced the
electrocatalytic performance of both electrodes for direct anodic oxidation of PCP on their surfaces.
Therefore, the electrocatalytic activity was improved only with about 10% for both composite
electrodes in comparison with photocurrent degree above-presented, which should be explained by
a possible adsorption of PCP on the electrode surface. These results are very promising for the
application of both composite electrode for voltammetric determination of PCP within the PCP
concentration ranged from 10 to 50 M PCP, the electrocatalytic activity being in this case the
sensitivity for PCP detecting. UV irradiation did not enhance significantly the sensitivity for PCP
detection, this means that the composite electrodes are suitable for voltammetric detection of PCP
from aqueous solution. However, TiO2-Z-CNT-Epoxy composite electrode exhibited better
photelectrocatalytic activity and it was selected for further studies regarding photoelectrocatalytic
degradation of PCP. Morever, PCP electrooxidation is improved by UV irradiation evidenced by
process starting at lower potential value.

Table 1. Electroanalytical performance of the TiO2-Z-CNT-Epoxy and TiO2-Z-CNF-Epoxy


composite electrodes for the detection of PCP in 0.1 M Na2SO4 supporting electrolyte, without and
under UV irradiation.

Potential Electrocatalytic Correlation


UV
Electrode types value, activity, coefficient,
irradiation
V vs. SCE A/M R2
no +0.97 1.470 0.996
TiO2-Z-CNT-Epoxy
yes +0.97 1.590 0.979
no +0.97 0.263 0.986
TiO2-Z-CNF-Epoxy
yes +0.97 0.284 0.993

3.3. Effect of the scan rate

In order to study some mechanistic aspects of the overall oxidation process of PCP on the
electrode surface, the evolution of CVs recorded on both TiO2-Z-CNT-Epoxy and TiO2-Z-CNF-
Epoxy electrode at various scan rates, in the presence of 50 M PCP was investigated, without and
under UV irradiation. CVs recorded at TiO2-Z-CNT-Epoxy composite electrode at various scan
rates ranged between 0.01 to 0.2 Vs-1 are shown in Figure 5. The current of the oxidation peak
corresponding to PCP oxidation recorded at +0.97 V vs. SCE increased linearly with the square root
of scan rate for all studied conditions, suggesting that the reaction is diffusion-controlled. The
anodic peak potential shifted towards positive potential when increasing the potential scan rate
indicating an irreversible character of the electrooxidation process of PCP on both composite
electrode, taking into account the lack of the cathodic peak corresponding to the anodic one (inset
of Figure 5a). Under UV irradiation, the peak corresponding to early oxidation stage recorded at
+0.68 V vs. SCE increased also linearly with the square root of the scan rate, which informed about
diffusion-controlled process, but the its non-linear dependence with the PCP concentration makes it
to be inappropriate for PCP detection (Figure 6). However, it can be noticed that this peak is more
evidenced at higher scan rate, which denotes that a fast photoelectrocatalytical oxidation process
occurred under UV irradiation, which is very promising for further electrophotocatalytic
degradation experiments.

Figure 5. (a) CVs recorded at TiO2-Z-CNT-Epoxy composite electrode in 0.1 M Na2SO4


supporting electrolyte and 50 M PCP with different scan rates: 0.01, 0.02, 0.03, 0.04, 0.05, 0.07,
0.09, 0.1, 0.2 Vs-1(curves 1-9), potential range: -0.5 and +1.25 V/SCE, without UV irradiation.
Inset: The peak potential Ep vs log (v). (b) The anodic peak current vs. square root of scan rate

Figure 6. (a) CVs recorded at TiO2-Z-CNT-Epoxy composite electrode in 0.1 M Na2SO4


supporting electrolyte and 50 M PCP with different scan rates: 0.01, 0.02, 0.03, 0.04, 0.05, 0.07,
0.09, 0.1, 0.2 Vs-1 (curves 1-9), potential range: -0.5 and +1.25 V/SCE, under UV irradiation.
Inset: The peak potential Ep vs log (v). (b) The anodic peak current vs. square root of scan rate
3.4. Photoelectrodegradation of pentachlorophenol

Chronoamperometry is considered as easiest electrochemical technique that can be used to simulate


the practical application of electrolysis under potentiostatic conditions. It is known that the
photoelectrons and holes generated in the photocatalysis process are separated under an applied
electric field. The higher the applied electric field, the better the separation and higher degradation
rate should be achieved. In addition, hydroxyl radicals generation is favoured by higher applied
potential. However, it is well-known that with increasing potential the charge consumption
increased and the current efficiency decreased, the economic aspect that limits the application of a
high potential.
Various potential values were applied for the photoelectrochemical of PCP at TiO2-Z-CNT-
Epoxy composite electrode.
The results of application of three potential values, 1, 1.5 and 2 V vs. SCE are gathered in
Table 2, and can be noticed that for the potential value higher than 1.5 V vs. SCE, no efficiency
increasing was reached. Also, a decrease of the electrochemical efficiency was noticed with
potential value increasing. Based on these results, the potential value of 1.5 V vs. SCE was selected
in the application of photoelectrocatalytic degradation of PCP.

Table 2. Photoelectrochemical efficiencies of 50 mgL-1 PCP after 2 h photoelectrooxidation time,


at the different potential values using TiO2-Z-CNT-Epoxy composite electrode

Potential value, V Degradation efficiency, % Electrochemical efficiency, g/Ccm2


1 62.24 9.96
1.5 71.10 0.77
2 71.57 0.11

In Table 3 are presented the results of the application of photolysis and comparative
photoelectrocatalysis on both composite electrodes under the potential value of 1.5 V vs. SCE after
two reaction hours, expressed as degradation efficiency and the electrochemical efficiency for PCP
degradation. The application of the electrooxidation led to PCP degradation efficiency of about 5 %
versus photolysis that assure a degradation efficiency of about 55%, while the photoelectrocatalytic
system allowed reaching 71% for TiO2-Z-CNT-Epoxy composite electrode.
Table 3. Degradation and electrochemical efficiencies of 50 mgL-1 PCP after 2 h reaction time
Degradation Electrochemical efficiency,
Electrode types UV irradiation
efficiency, % g/Ccm2
- Photolysis 55.29 -
no 4.26 0.05
TiO2-Z-CNT-Epoxy
yes 71.10 0.77
no 5.47 7.64
TiO2-Z-CNF-Epoxy
yes 64.94 46.54

Figure 7. The linear variation of the plot ln(C0/Ct) versus time in the Langmuir-Hinshelwood kinetic
model by various methods: photolysis; photoelectrooxidation on TiO2-Z-CNT-Epoxy; -
photoelectrooxidation on TiO2-Z-CNF-Epoxy

PCP degradation exhibited pseudo-first-order kinetics described by the simplified


Langmuir-Hinshelwood equation ln C0 / Ct kKt kappt ( kapp is apparent rate constant, min-1), the

linearization results being shown in Figure 7, for all applied processes. The apparent rate constants
and regression coefficients of PCP photoelectrocatalysis by both composites electrodes in
comparison with direct photolysis are shown in Table 4. The correlation coefficients higher than 0.9
for all applied systems informed that the equation is suitable for kinetics description. Rate constants
were calculated to be 10.5210-3 min-1, 8.9410-3 min-1 for photoelectroxidation with TiO2-Z-CNT-
Epoxy and TiO2-Z-CNF-Epoxy, and 6.9610-3 min-1 for photolysis, respectively. The rate constants
for electrochemical system with both composite electrodes were about ten times smaller than the
photoelectrocatalysis, thus to assess the synergy effect only photoelectrocatalysis and the
photocatalysis processes were taken into consideration. The highest synergy effect coefficiency was
about 1.5 (1.5=10.52/6.96) at TiO2-Z-CNT-Epoxy composite electrode at 1.5 V vs. SCE.
Table 4. Kintetic parameters for 50 mgL-1 PCP degradation, at the 1.5 V potential value, after 2 h
photolysis and photoelectrooxidation time

Methods kapp103, min-1 R2


Photolysis 6.96 0.988
Photoelectrooxidation on TiO2-Z-CNT-Epoxy 10.52 0.998
Photoelectrooxidation on TiO2-Z-CNF-Epoxy 8.94 0.992

4. Conclusions

TiO2-Z-CNT-Epoxy and TiO2-Z-CNF-Epoxy composite electrodes were successfully


obtained by two-roll mill procedure. A good distribution of nanostructured carbon and TiO2-zeolite
within epoxy matrix was evidenced. Both TiO2-zeolite-modified nanostructured carbon composite
electrodes exhibited suitable characteristics for application in voltammetric determination of PCP
from aqueous solution without UV irradiation demand. The comparative photoelectrocatalytic
application using both composite electrodes in PCP degradation led to good degradation efficiency,
especial for TiO2-Z-CNT-Epoxy composite electrode. The degradation rate in photoelectrocatalytic
application in comparison with photolysis and electrochemical process demonstrated the synergy
effect between the photolysis and electrochemical processes. In this work, it was demonstrated that
both carbon-based composite electrodes displayed the dual functionality as detectors for PCP
presence and electrode material for degradation application of PCP. However, TiO2-Z-CNT-Epoxy
exhibited superiority in terms of electrocatalytic and photoelectrocatalytic performance and it is
very promising for dual application in photoelectrocatalytic degradation of PCP and its
concentration monitoring by voltammetric method.

Acknowledgments
This work was partially supported by the Romanian-Swiss Research Programme IZERZ0 -
142210/1 (24 RO-CH/01.01.2013) funded by SNSF and UEFISCDI, partially by the PNII-60/2012
(WATUSER) and partially by the PNII-Ideas-165/2011.

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