CHEMICAL ENGINEERING TRANSACTIONS
VOL. 47, 2016
A publication of
The Italian Association
of Chemical Engineering
Online at www.aidic.it/cet
Guest Editors: Angelo Chianese, Luca Di Palma, Elisabetta Petrucci, Marco Stoller
Copyright © 2016, AIDIC Servizi S.r.l.,
I SBN 978-88-95608-38-9; I SSN 2283-9216
Synthesis of Nanostructured Materials for
Photoelectrochemical Oxidation of Organic Compounds
Laura Mais*
a
, Pablo Ampudia
a
, Simonetta Palmas
a
, Annalisa Vacca
a
, Michele
Mascia
a
, Francesca Ferrara
b
a
Dipartimento di Ingegneria Meccanica, Chimica e dei Materiali, Università degli Studi di Cagliari, via Marengo 2, 09123
Cagliari, Italy
b
Sotacarbo S.p.A., c/o Grande Miniera di Serbariu, 09013 Carbonia, Italy
l.mais@dimcm.unica.it
The present work relates to the use of titanium dioxide nanotubular array (NT) as photoanode for the
photoelectrochemical oxidation of phenol used as model of organic compounds. Moreover, surface
modification of NT structures has been carried out by deposition of tungsten oxide in order to enhance the
response of the system toward wave lengths in the near visible range.
Nanotubular structures were prepared by electrochemical oxidation of Ti foils in a water / organic solution with
0.14 M of NH
4
F at room temperature. Tungsten oxide was electrochemically deposited on NTs structures in a
hierarchical structure.
The electro- and photoelectro-oxidation of phenol was studied in a typical three-electrode cell equipped with a
quartz window. Irradiation of the photoanode was performed by a Xenon lamp (nominal power 300 W).
Different electrochemical techniques, such as potential ramps and potential steps were adopted to investigate
the performance of the system.
SEM analysis was also performed to investigate on the morphology of the photoanode. Spectrophotometric
analyses have been used to analyse the variation of the organic compound concentration.
1. Introduction
Nowadays, the contamination of natural and drinking water supplies and of the aquatic environment has
become a serious environmental problem worldwide. Phenolic compounds are major pollutants of the aquatic
environment due to their widespread use in agricultural, petrochemical, textile, paint, plastic, and pesticidal
chemical industries. They are well known to be biorecalcitrant and to have acute toxicity with carcinogenic and
mutagenic characters (Lathasree et al., 2004).
Titanium dioxide (TiO
2
) has been widely studied as a photocatalyst (PC) for environmental applications, such
as purification of waters and wastewaters. Actually, its favourable characteristics, such as remarkable charge
transport properties and superior oxidation ability, long-term chemical stability, non-toxicity, inertness and low
price, make it competitive with respect to other semiconductors (Qin et al., 2012). The TiO
2
features determine
to a great extent the efficiency and the performance of the degradation process. Under illumination, the
photogenerated holes (free in the valence band or trapped at surface states) are responsible for oxidizing the
organic substrates. However, the low utilization efficiency of visible light and the high recombination rate of
photoinduced electron–hole pairs, hold back its application in water treatment. Photoelectrocatalysis (PEC)
promotes the separation of electron–hole pairs by driving the electron transfer to an external circuit: thanks to
the applied potential bias a significant enhance of the PC efficiency, by suppressing the recombination of
photogenerated electrons and holes, can be achieved (Zhang et al., 2012). In PEC processes, the
degradation rate of organic pollutants depends, to some extent, on the activity of the photoanode; therefore,
improving its activity has become a primary research focus.
One of the most studied approaches to increase the activity of TiO2
is compositional doping with anions or
transition metals (Shankar et al., 2009). Another approach is coupling TiO
2
with another metal oxide with
narrower bandgap, such as WO
3
(Eg=2.6 eV); this coupling approach is expected to provide a better charge
DOI: 10.3303/CET1647027
Please cite this article as: Mais L., Ampudia P., Palmas S., Vacca A., Mascia M., Ferrara F., 2016, Synthesis of nanostructured materials for
photoelectrochemical oxidation of organic compounds, Chemical Engineering Transactions, 47, 157-162 DOI: 10.3303/CET1647027
157