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Manuscript Number: APCATB-D-09-00146
Title: Synergistic effect of TiO2 and iron oxide supported on fluorocarbon films. Part 2: Long term
stability assessment and influence of pH, temperature, NaCl on photoactivated degradation of
pollutants
Article Type: Full Length Article
Keywords: heterogeneous photo-Fenton, TiO2 photocatalysis, synergistic effects, influence of
temperature, pH and NaCl on heterogeneous photocatalytic rates, solar detoxification
Synergistic effect of TiO
2
and iron oxide supported on fluorocarbon films. Part 2:
Long term stability assessment and influence of pH, temperature, NaCl on
photoactivated degradation of pollutants
F. Mazille
a
, A. Lopez
b
, C. Pulgarin
a
*.
a
Institute of Chemical Sciences and Engineering, SB, GGEC, Ecole Polytechnique
Fdrale de Lausanne, 1015, Lausanne
Switzerland
b
Istituto di Ricerca Sulle Acque C.N.R, Via F. De Blasio 5, 70123 Bari, Italy
Keywords: heterogeneous photo-Fenton, TiO
2
photocatalysis, synergistic effects,
influence of temperature, pH and NaCl on heterogeneous photocatalytic rates, solar
detoxification
* Corresponding author: Tel: +41 21 693 47 20; Fax: +41 21 693 6161
E-mail: cesar.pulgarin@epfl.ch
* Manuscript
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2
Abstract
The degradation of hydroquinone (HQ) and nalidixic acid (NA) mediated by TiO
2
and
iron oxide immobilized on functionalized polyvinyl fluoride films (PVF
f
-TiO
2
-Fe oxide)
in presence of H
2
O
2
, at neutral pH under simulated solar light has been examined. The
results show that the contribution of homogeneous photo-Fenton oxidation to the overall
process was low and that the degradation and mineralization rates were not dependant of
initial pH. Heterogeneous photocatalytic activity of PVF
f
-TiO
2
-Fe oxide was enhanced by
(i) increasing temperature; (ii) NaCl addition; (iii) long-term utilization.
The PVF
f
-TiO
2
-Fe oxide surface was characterized by scanning electron microscopy
(SEM) and X-ray photoelectron spectroscopy (XPS) at different state of utilization.
Correlations between the catalyst surface composition and degradation kinetics are
discussed. Long-term stability evaluated by repetitive pollutant degradations was
outstanding. The presence of TiO
2
seems to (i) limit contact between polymer film and
highly reactive radicals in solution and (ii) act as a charge trap. Moreover, during the
photocatalysis using by PVF-TiO
2
-Fe oxide, some leaching of supported iron increased
the amount of the top TiO
2
layer exposed to the light increasing the synergistic effects
between the two oxides leading to enhanced pollutant degradation.
3
1 Introduction
The aimed characteristics for supported TiO
2
-Fe oxide as heterogeneous photocatalysts
are: (i) low leaching out of photoactive species from support surface during operation; (ii)
adequate degradation rates at neutral pH and under solar illumination; (iii) resistance of
support to oxidation by radicals in solution; (iv) catalyst showing long-term stability and
(v) catalyst manufacture should be sustainable from the environmental and economical
point of view.
Some recent studies described TiO
2
-Fe oxide coatings on different supports [1-2]
including polymer films [3]. However the effect of pH, temperature and NaCl addition on
rates has not been reported. In the case of supported heterogeneous photo-Fenton systems
[4-11], degradation rates are strongly pH-dependant with highest performance at pH 3
and lower as we move to neutral pH. In these systems, the degradation rates increase as
the temperature increases [6].
The dissolution of iron ions is a common process during heterogeneous photo-Fenton
oxidation. In the presence of ligands (aliphatic acids, humic acids) and light,
particularly under acidic conditions, iron is released by photo-reductive dissolution
increasing the contribution of homogeneous photo-Fenton reaction [12-14].
The sequential preparation of PVF
f
-TiO
2
-Fe oxide by TiO
2
photocatalytic surface
functionalization-deposition (TiO
2
PSFD) treatment of PVF followed by forced
hydrolysis of a FeCl
3
solution was described in detail in a previous study [3]. Some of the
preparation conditions of PVF
f
-TiO
2
-Fe oxide were optimized and the catalyst surfaces
were characterized by SEM, XPS and UV-visible spectroscopy. From these results, the
optimized PVF
f
-TiO
2
-Fe oxide can be described as a highly efficient photocatalyst due to
4
synergistic effects of TiO
2
and iron oxide deposited on functionalized PVF film (i.e
containing groups as C-OH, COOH, C=O).
In this work, hydroquinone (HQ) has been selected as a model substance whereas
nalidixic acid was used because it is an antibiotic present in pharmaceutical wastewater.
The objectives of this study are: (i) to examine the performance of PVF
f
-TiO
2
-Fe oxide in
the degradation of HQ and NA under different reaction conditions (pH, temperature,
NaCl content), (ii) Correlate the photoactivity enhancement to the surfaces modifications
(iii) To test the long term stability of the catalyst.
2 Experimental
2.1 Chemicals. Hydroquinone, nalidixic acid (Figure 1), NaOH, NaCl, HNO
3
, FeCl
3
,
FeSO
4
.7H
2
O, ferrozine, hydroxylamine hydrochloride, acetate buffer (pH=4.65) were
Fluka p.a. reagents (Buchs, Switzerland) and used as received. Hydrogen peroxide (35%)
was supplied by Merck AG (Darmstadt, Germany) and TiO
2
P25 (anastase to rutile ratio
between 70:30 and 80:20) by Degussa. The Tedlar