Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

Contents lists available at ScienceDirect

Journal of Photochemistry and Photobiology C:

Photochemistry Reviews
journal homepage: www.elsevier.com/locate/jphotochemrev

Applied photoelectrocatalysis on the degradation of organic

pollutants in wastewaters
Sergi Garcia-Segura ∗ , Enric Brillas ∗
Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i
Franquès 1-11, 08028 Barcelona, Spain

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

Article history: A large variety of electrochemical advanced oxidation processes (EAOPs) have been recently developed
Received 20 October 2016 to remove organic pollutants from wastewaters to avoid their serious health-risk factors from their envi-
Received in revised form 16 January 2017 ronmental accumulation and to reuse the treated water for human activities. The effectiveness of EAOPs
Accepted 30 January 2017
is based on the in situ production of strong reactive oxygen species (ROS) like hydroxyl radical (• OH).
Available online 9 February 2017
Photoelectrocatalysis (PEC) has emerged as a promising powerful EAOP by combining photocatalytic and
electrolytic processes. It consists in the promotion of electrons from the valence band to the conduction
Keywords:
band of a semiconductor photocatalyst upon light irradiation, with production of positive holes. The fast
Hydroxyl radical
Organics degradation
recombination of the electron/hole pairs formed is avoided in PEC by applying an external bias potential
Photocatalysis to the photocatalyst that extracts the photogenerated electrons up to the cathode of the electrolytic cell.
Photoelectrocatalysis Organics can be oxidized directly by the holes, • OH formed from water oxidation with holes and other
TiO2 photoanode ROS produced between the electrons and dissolved O2 . This paper presents a general and critical review
Wastewater treatment on the application of PEC to the remediation of wastewaters with organic pollutants. Special attention
is made over the different kinds of photocatalysts utilized and preparation methods of the most ubiqui-
tous TiO2 materials. Typical PEC systems and main operation variables that affect the effectiveness of the
degradation process are also examined. An exhaustive analysis of the advances obtained on the treat-
ment of dyes, chemicals and pharmaceuticals from synthetic solutions, as well as of real wastewaters, is
performed. Finally, research prospects are proposed for the future development of PEC with perspectives
to industrial application.
© 2017 Elsevier B.V. All rights reserved.

Abbreviations: A, absorbance of the most intense UV/Vis peak; A0 , initial absorbance of the most intense UV/Vis peak; ACF, activated carbon fiber; Ag/AgCl, reference
electrode of Ag/AgCl (KCl saturated); ALD, atomic layer deposition; AOP, advanced oxidation process; APS, atmospheric plasma spray; BDD, boron-doped diamond; BOD5 ,
biochemical oxygen demand at 5 days; c, organic concentration (mM or mg L−1 ); c0 , initial organic concentration (mM or mg L−1 ); CB, conductive band; CVD, chemical vapor
deposition; COD, chemical oxygen demand (mg O2 L−1 ); COD0 , initial chemical oxygen demand (mg O2 L−1 ); DO, direct ozonation; DP, direct photolysis; DRS, diffuse
reflectance spectroscopy; DSA , dimensionally stable anode; EAOP, electrochemical advanced oxidation process; e− CB , electron in the conduction band; EDS, energy dispersive
®

spectrometry; EF, electro-Fenton; EIS, electrochemical impedance spectroscopy; EO, electrochemical oxidation; Eanod , anodic potential (V); Ebg , band gap energy (eV); Ecat ,
cathodic potential (V); Ecell , potential difference of the cell (V); Efb , flat band energy (V); FESEM, field-emission SEM; FTO, fluor-doped tin dioxide; h+ VB , hole in the valence
band; HPLC, high-performance liquid chromatography; I, current (A or mA); ITO, indium-tin oxide; janod , anodic current density (mA cm−2 ); ␭, wavelength of UV/Vis spectrum;
␭max , maximum wavelength of UV/Vis spectrum; LC–MS, liquid chromatography–mass spectrometry; NB, nanobelt; NT, nanotube; NTA, nanotube array; PANI, polyaniline; PC,
photocatalysis; PEC, photoelectrocatalysis; PEF, photoelectro-Fenton; PTFE, polytetrafluoroethylene; PZC, point of zero charge; ROS, reactive oxygen species; SCE, saturated
calomel electrode; SCL, space charge layer; SEM, scanning electron microscopy; SPEC, solar photoelectrocatalysis; t, electrolysis time; TEM, transmission electron microscopy;
TOC, total organic carbon (mg C L−1 ); TOC0 , initial total organic carbon (mg C L−1 ); VB, valence band; UV, ultraviolet; UVA, ultraviolet A; UVB, ultraviolet B; UVC, ultraviolet
C; Vis, visible; XRD, X-ray diffraction; XPS, X-ray photoelectron spectroscopy.
∗ Corresponding authors.
E-mail addresses: sergigarcia@ub.edu (S. Garcia-Segura), brillas@ub.edu (E. Brillas).

http://dx.doi.org/10.1016/j.jphotochemrev.2017.01.005
1389-5567/© 2017 Elsevier B.V. All rights reserved.
2 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Fundamentals of photoelectrocatalysis (PEC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Experimental conditions for PEC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.1. TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.2. WO3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.3. ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.4. Other semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.5. Modified TiO2 materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2. Preparation of TiO2 photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2.1. Thin-film electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2.2. Nanostructured materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.3. Characterization of synthesized photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3. PEC systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.4. Operation parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4. Destruction of organic pollutants by PEC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1. Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.1.1. TiO2 photoanodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.1.2. Doped TiO2 and composites with TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1.3. Other photocatalytic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.2. Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.2.1. TiO2 and composites with TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.2.2. Other photoanodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.3. Pharmaceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.4. Real wastewaters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5. Conclusions and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Acknowlegments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

Dr. Sergi Garcia-Segura is a researcher dedicated to

the development of Electrochemical Advanced Oxidation
Processes to remove organic pollutants from environ- Dyes, chemicals and pharmaceuticals are some of the most com-
ment such photoelectrocatalysis. He has conducted his mon recalcitrant organic pollutants. For instance, many industries
research at the Universitat de Barcelona (Spain), Univer-
sity of Queensland (Australia), Universidade Federal do
including textile, cosmetic, paper, leather, light-harvesting, arrays,
Rio Grande do Norte (Brazil), Chia Nan University of Phar- agricultural research, photoelectrochemical cells, pharmaceutical
macy and Science (Taiwan), Bonn Universität (Germany) and food produce large volumes of wastewater polluted with high
and Arizona State University (USA). He received the
concentration of dyes and other components. As a result, about
International Society of Electrochemistry Prize for Envi-
ronmental Electrochemistry 2014, the Green Talents 280,000 tons of textile dyes are currently discharged in effluents
award 2015 and the Antonio Aldaz prize 2016. He has every year and introduced in the aquatic environment [5]. This
published 40 peer-reviewed papers (h-index = 19). has induced many governments to apply legislation that prescribes
and limits the emission of pollutants. To face this environmen-
Dr. Enric Brillas is Full Professor of Physical Chem- tal problem, three different approaches have been considered: (i)
istry at the Universitat de Barcelona since 1987. He was the development of Green Chemical and Technological Processes,
president of the Electrochemistry Group of the Real
Sociedad Española de Química (2004–2008). His research
(ii) the use of the 3R (reduce, reuse and recycle) sustainability
is pre-eminently devoted on organic electrochemistry, consciousness and (iii) the application of wastewater remedia-
photocatalysis, photoelectrocatalysis, electrocatalysis and tion technologies. The latter approach has received great attention
electrochemical treatments of organic pollutants. He
received the Chemviron Carbon 1995 and the CIDETEC
because it is easily usable and can solve the contamination prob-
2014 Awards. Associate Editor of Chemosphere and mem- lems.
ber of the Editorial Board of Journal of Hazardous Materials Current methods for wastewater treatment have been based on
and Applied Catalysis B: Environmental. He has published
oxidation processes including physicochemical, biological, chem-
330 peer-reviewed papers (h-index = 61) and 22 books
and book chapters, and presented 280 communications ical and electrochemical treatments [5]. Note that no universal
to scientific congresses. strategy on wastewater remediation is feasible because of the
extremely diverse composition of industrial waste that usually con-
tains a complex mixture of organic and inorganic compounds and
1. Introduction mainly depends on the nature and concentration of pollutants.
Physicochemical techniques require high cost of equipment and
One of the main current worldwide concerns is the growth of usually present low effectiveness, particularly over dyes and phar-
water pollution by organic compounds arising from many indus- maceuticals. Biological treatments are environmentally friendly,
trial, agricultural and urban human activities. The vast majority of produce less sludge than physicochemical systems and are rela-
these compounds are persistent organic pollutants, owing to their tively inexpensive. Nevertheless, their application is rather limited
resistance to conventional chemical, biological and photolytic pro- since treatment needs a large land area, has sensitivity toward tox-
cesses. As a result, they have been detected in rivers, lakes, oceans icity of certain chemicals and operation time is very long. Over
and even drinking water all over the world. This constitutes a seri- the past three decades, many advanced oxidation processes (AOPs)
ous environmental health problem mainly due to their toxicity and have been developed as more effective technologies to remove per-
potential hazardous health effects (carcinogenicity, mutagenicity sistent organic pollutants from wastewaters [6]. AOPs are based on
and bactericidality) on living organisms, including human beings the in situ production of highly reactive hydroxyl radicals (• OH)
[1–4]. that non-selectively react with most organics and are able to
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 3

degrade even highly recalcitrant compounds [5–7]. This radical a 140

is the second strongest oxidant known after fluorine, displaying
a high standard reduction potential of E◦ (• OH/H2 O) = 2.80 V (SHE)

Number of publications
120
and rate constants for reaction with several contaminants in the
order of 106 to 1010 M−1 s−1 [6,8]. • OH has so short lifetime, a 100
few nanoseconds in water [9], that can be rapidly self-eliminated 80
from the treatment system. The most ubiquiotous AOPs are chem-
ical, photochemical and photocatalytic systems such as H2 O2 with 60
UVC radiation (H2 O2 /UVC), ozone and ozone based processes (O3 , 40
O3 /UVC, O3 /H2 O2 and O3 /H2 O2 /UVC), titanium dioxide based pro-
cesses (TiO2 /UV and TiO2 /H2 O2 /UV) and Fenton’s reaction based
20
methods (Fenton (Fe2+ /H2 O2 ) and photo-Fenton (Fe2+ /H2 O2 /UV)) 0
[10]. Photocatalysis (PC) uses a semiconductor, usually TiO2 known 2001- 2005- 2008- 2011- 2014-
as the photocatalyst, under light illumination (UV or solar) to 2004 2007 2010 2013 2016
generate electron/hole pairs with ability to degrade most organic b 200
pollutants by producing the strong oxidant • OH at its surface.

Number of publications
This technique has prominent advantages including non-toxicity,
160
low cost, no secondary pollution and thorough mineralization.
However, PC is restricted by its low photonic efficiency. The fast
120
recombination of photogenerated electron/hole pairs at the photo-
catalyst surface represents the major drawback for PC applications.
80
Over the last two decades, electrochemical advanced oxidation
processes (EAOPs) have gained increasing attention as a promising
class of AOPs [5,6,11,12]. They have emerged as novel treatment 40
technologies for the elimination of a broad-range of organic con-
taminants from wastewaters. Several advantages of EAOPs include 0
TiO Modified WO ZnO Other
high energy efficiency, amenability to automation, simple equip- 2
TiO
3
photoanodes
ment, safety because they operate under mild conditions (ambient 2

temperature and pressure) and versatility. From the beginning of c 200

the XXI Century, the combination of electrochemistry and PC in the
Number of publications

so-called photoelectrocatalysis (PEC) method has deserved increas- 160

ing attention. It is based on a semiconductor photoanode that is
irradiated by light with energy equal or greater than its band gap
and simultaneously biased by a gradient of potential. PEC offers the
opportunity to separate the charges of the photogenerated elec-
tron/hole pairs, strongly enhancing the mineralization of organic
pollutants in wastewaters. Note that urban and industrial wastew-
aters usually present conductivity enough to effectively perform
the PEC treatment of their organic pollutants because these water
matrices already contain electrolytes like salts of sulfate, chloride
and carbonate. Since PEC is still in development, most research
has been made using synthetic wastewater prepared with ultra-
pure water and addition of electrolytes. If electrolytes are added
for real PEC application, they should be removed from the final
treated solution before disposal. PEC has also been successfully
applied to inorganic ion reduction, microorganism inactivation,
CO2 reduction, and production of electricity and hydrogen from
water splitting [13–15]. When sunlight is used as energy source, it
is known as solar PEC (SPEC).
Fig. 1a shows the increasing number of papers over PEC classi-
fied for wastewater remediation since 2001, showing the growing
interest over its development. Fig. 1b highlights that TiO2 is the
preferred material as photoanode in PEC, although modified TiO2
and to smaller extent WO3 , ZnO and other materials have been uti-
lized as photoanodes as well. Special attention has been made on
the applications with TiO2 and its modified materials because they
offer important advantages as a result of their non-toxic, optical,
low-cost and biocompatibility properties. Thus, PEC has been used
to remove a large variety of organic pollutants, most of them dyes
and to less extent chemicals, drugs and real wastewaters, as can
be seen in Fig. 1c. The large development of PEC over the last 15
years has open novel ways for the application of this EAOP to water
remediation.
The aim of this paper is to present a general and critical review
on the use of the PEC technology for the remediation of organic
pollutants in wastewaters. The fundamentals of the technique are
120
80
40
0
Dyes Chemicals Drugs Real
wastewaters
Fig. 1. Number of photoelectrocatalysis (PEC) publications over treatment of
organic pollutants in wastewaters as a function of: (a) published year, (b) photoan-
ode used and (c) degraded pollutant.
firstly exposed, followed by an overview about its experimen-
tal conditions including the photocatalysts used, the preparation
methods for the most common TiO2 materials, the kinds of PEC
systems utilized and the main operation parameters that affect the
degradation performance. The application of PEC to the treatment
of dyes, chemicals, pharmaceuticals and real wastewaters, remark-
ing the use of different photoanodes, is discussed. Examples are
given for the different kinds of organics to evidence the advances
achieved in this technique.
Several reviews on the environmental application of PEC have
been published based on the advances of this technology up
to 2011–2012 [16–18]. The present paper shows a much more
detailed review from the research mainly devoted on the latter five
years, where PEC has achieved more mature developments in the
following points: (i) the preparation of new photoanodes not only
based on TiO2 , but also on WO3 , ZnO and other photocatalytic mate-
rials involving ␤-PbO2 , BiVO4 , BiPO4 and ␣-Fe2 O3 , among others,
(ii) the design of new PEC systems for using direct illumination with
sunlight and filter-press flow cells at lab-scale, (iii) the coupling
of PEC with O3 and other EAOPs to enhance its oxidation power,
4 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
and (iv) the use of PEC to treat pharmaceuticals and real wastew-
aters, pre-eminently reported from 2012. Moreover, this review
describes comprehensively the main characteristics or organics
degradation by PEC such as their kinetic decay, mineralization rate
and degree, identification of aromatic and cyclic intermediates, as
well as final carboxylic acid generated, and reaction sequences pro-
posed. The significant effect of operation parameters over organic
degradation is extensively documented and exemplified in selected
figures for better understanding.
2. Fundamentals of photoelectrocatalysis (PEC)
The PEC technique combines both electrolytic and photocat-
alytic processes and has received considerable attention because of
its ability to retard the recombination of electron-hole (e− CB /h+ VB )
pairs, increasing the lifetime of the holes. The basic process of PEC
consists in the ejection of an electron (e− CB ) from the valence band
(VB) of a semiconductor, which is fully filled, to the conductive band
(CB), which is completely empty, generating a positively charged
vacancy or hole (h+ VB ). The band gap is related to the light irradia-
tion utilized. The semiconductor has to be exposed to an irradiation
with greater energy than that of its band gap (Ebg ), giving rise to the
photoexcitation of the e− CB from VB to CB. The light then allows the
generation of e− CB /h+ VB pairs via Reaction (1) [5,18–24]:
Semiconductor + hv → e− CB + h+ VB
h+
Photogenerated VB is a strong oxidizing species, whereas the
promoted e− CB is a potential reductor. Organic pollutants are then
oxidized by the photogenerated h+ VB up to their complete min-
eralization. It is also proposed the reaction of h+ VB with adsorbed
water to form the strong oxidant • OH from Reaction (2) that min-
eralizes the organic pollutants, although there is no clear evidence
for the formation of free hydroxyl radical from h+ VB . The e− CB can
react with adsorbed O2 to form the superoxide radical O2 •− from
Reaction (3).
h+ VB + H2 O → • OH + H+
− •−
e CB + O2 → O2
Other weaker reactive oxygen species (ROS) such as H2 O2 and
hydroperoxyl radical HO2 • can be produced via Reactions (4) and
(5):
O2 •− + H+ → HO2 •
•
2HO2 → H2 O2 + O2
Nevertheless, the promoted e−
CB is an unstable species of an
excited state and tends to return to the ground state either with
adsorbed • OH by Reaction (6) or pre-eminently by recombination
with the unreacted h+ VB from Reaction (7)) [18–24].
e− CB + • OH → OH−
e− CB + h+ VB → Catalyst + heat
The last reaction represents the main drawback for the efficient
use of absorbed photons in the classical PC. To improve the abate-
ment of organic pollutants from wastewaters by this technique,
the separation of charges formed from Reaction (1) has been per-
formed using nanoparticulated photocatalysts with high specific
area in suspension in the effluent, but, unfortunately, the recovery
of these materials after treatment is complicated [25–27]. Research
efforts to solve this problem have then been devoted to the synthe-
sis of nanoparticulated photocatalysts immobilized onto different
substrates [28–31]. The fixation of photocatalysts on supports pro-
duces an inevitable and significant reduction of their active specific
area with the consequent drop in pollutant removal. However,
the efficiency of the immobilized photocatalyst can be strongly
improved if it is deposited onto a conductive substrate to act as
a photoanode in a photoelectrolytic system leading to the PEC pro-
cess [18,20–24].
The PEC process on water splitting was firstly described by
Fujishima and Honda on 1972 and analyzed from the electrochem-
ical point of view by Brockis et al. [33,34] on the early 1980s, but
it was not up to the beginning of XXI Century when it was applied
to wastewater treatment, as stated above. It uses an electrolytic
system containing a thin-film active photoanode subjected to light
illumination with application of a constant bias potential to the
anode (Eanod ), a constant cell potential (Ecell ) or a constant anodic
current density (janod ). This promotes the extraction of photoin-
duced e− CB by the external electrical circuit, thereby yielding an
efficient separation of the e− CB /h+ VB pairs since Reactions (3)–(7)
are inhibited [18,20–24]. The prevention of charge recombination
upgrades the photocatalytic efficiency of the anode with genera-
tion of higher quantities of holes by reaction (1) and acceleration of
organics oxidation compared to classical PC. The lifetime of holes
is increased and they have more opportunities either to directly
oxidize the organic pollutants adsorbed on the photoanode surface
or indirectly destroy them with more amounts of • OH formed from
Reaction (2). In PEC, the photocatalyst can be easily recovered after
usage and recycled for consecutive treatments.
The material more extensively used as semiconductor photocat-
alyst in PEC is the anatase crystalline form of TiO2 , since it can act as
(1)
an active photoanode with low cost, low toxicity, high stability and
wide band gap of 3.2 eV. Fig. 2 illustrates the mechanism of the pro-
cesses taking place in an n-type semiconductor such as TiO2 [18].
The e− CB /h+ VB pairs are produced by irradiating photons of UV light
with h␯ > Ebg of TiO2 . The photogenerated electrons flow through
the external circuit due to a potential gradient from the photoan-
ode to the cathode. The holes can thus attack directly to organics R
and/or generate high amounts of • OH via photo-oxidation of water
in much larger extent than ROS formed from e− CB via O2 photore-
duction because most electrons are lost from the photoanode to the
cathode [18].
(2) As shown in Fig. 2, a typical cathode involves the reduction of
water to H2 . However, it is feasible to enhance the oxidation power
(3)
of PEC by using carbonaceous cathodes that allow the in situ elec-
trogeneration of H2 O2 from two-electron reduction of injected O2
by Reaction (8) [5,11]. The presence of H2 O2 in the electrolytic
medium upgrades the production of oxidant • OH from its reduction
(4) with the promoted e− CB by Reaction (9) [34–38]. Although Reaction
(9) is accepted for authors working in PC and PEC, a recent research
(5) has reported controversial results over its validity [39].
O2 + 2H+ + 2 e− → H2 O2 (8)
e− CB + H2 O2 → • OH + OH− (9)
Apart from the above photolytic processes, a semiconductor M
(6)
submitted to an anodic potential can remove the organics by elec-
(7) trochemical oxidation (EO). This is feasible because it oxidizes the
water to adsorbed hydroxyl radical M(• OH) as follows [40–42]:
M + H2 O → M(• OH) + H+ + e− (10)
Unfortunately, the low conductivity of semiconductors used in
PEC only allows the pass of small janod values, usually < 10 mA cm−2 ,
leading to low M(• OH) production with very poor ability for the
mineralization of organic pollutants. In the PEC treatment of a
wastewater, it is very difficult to know the contribution of EO to the
overall process, since the photogeneration of electron/hole pairs
from Reaction (1) competes with M(• OH) generation from Reaction
(10) at the photocatalyst surface, although the large predominance
of the former process explains the much greater oxidation ability of
PEC than EO [31]. The use of high janod values in PEC causes normally
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
Fig. 2. Mechanism for PEC process using TiO2 photocatalyst. Adapted with permission from ref. [18].
a loss of its performance as a result of a change of the photocatalyst
properties, as will be discussed below.
3. Experimental conditions for PEC
Most papers devoted to the PEC treatment of organic pollutants
in wastewaters present an experimental study in consecutive steps.
Firstly, the pollutant and photocatalyst are selected. Since the pho-
toactive material is not commercially available, its synthesis and
characterization are subsequently described. Finally, the PEC sys-
tem used to explore the process performance is detailed and the
degradation results are reported as function of the operation vari-
ables chosen. This section gives an overview all these experimental
conditions, which are essential to understand the potential appli-
cation of PEC.
3.1. Photocatalysts
The PEC efficiency on organic pollutant remediation is directly
related to the semiconductors selected as photoanodes by their
intrinsic photocatalytical properties. In general, they are metal
oxides with an appropriate Ebg value between the fulfilled VB
and the empty CB to photogenerate electron/hole pairs upon light
irradiation. The different materials used in PEC for wastewater
treatment are detailed below.
3.1.1. TiO2
TiO2 is the most utilized metal oxide photocatalyst for envi-
ronmental remediation applications, as shown in Fig. 1b. It is
an n-type semiconductor with three main crystalline structures,
namely rutile, anatase and brookite. The former is the most ther-
modynamically stable phase, whereas the metastable anatase and
brookite phases can be transformed into the most stable rutile
one under annealing in the range 600−800◦ C [43,44]. The Ebg for
TiO2 is slightly superior to 3.0 eV, with little differences between
its crystalline phases, with values of 3.02 eV for rutile, 3.23 eV for
anatase and 3.14 eV for brookite [45,46]. However, anatase with
the higher Ebg value is the most active phase in PC upon UV irra-
diation [45,47]. This has been justified by the prolonged lifetime of
the photogenerated charge carriers (e− CB and h+ VB ) and the spatial
charge separation promoted by anatase crystalline structure [45].
This behavior is very different under PEC conditions where the per-
formance between the different phases is quite similar since the
5
photogenerated electrons are dragged out by an external electrical
circuit (see Fig. 2) [18].
3.1.2. WO3
WO3 is other n-type semiconductor metal oxide as TiO2 . The
crystalline structure of WO3 is temperature dependent, although
the most common is the monoclinic phase between 17 and 330 ◦ C
[48]. The Ebg values of tungsten oxides are around 2.5–2.7 eV, which
are appreciably lower than those of TiO2 , and for this reason, WO3
presents better performance under visible light irradiation due to
the easier formation of photogenerated electron/hole pairs [49,50].
The main drawback of this material is that it is not as innocuous as
TiO2 , since it is a hazardous, toxic and irritant metal oxide [51]. The
first usage of WO3 photoanode for wastewater remediation was
reported by Hepel and Luo in 2001 [52,53], who well-proven the
potential applicability of this material to the abatement of azo dyes.
This possibility has been recently explored over different pollutants
by a moderate number of articles, as can be seen in Fig. 1b.
3.1.3. ZnO
ZnO is extensively found in the nature and is considerably
cheaper than the above photocatalysts. It is also considered as an
environment-friendly material because of its innocuous character
over the health of living beings [54]. ZnO presents two crys-
talline structures, the hexagonal wurtzite and the cubic zinc blende.
Wurtzite is the most thermodynamically stable structure at ambi-
ent conditions [55]. Its Ebg value is 3.4 eV, with high electrochemical
stability and possible use under natural sunlight irradiation [56,57].
ZnO thin films are transparent and this improves the light pen-
etration into the material and hence, the photogeneration of
electron/hole pairs from Reaction (1). Although the number of pub-
lications related to ZnO as photoanode in PEC is rather limited (see
Fig. 1b), Li et al. [58] have reported that it can present better perfor-
mance even than TiO2 , thus appearing as an alternative functional
material for PEC application to wastewater treatment.
3.1.4. Other semiconductors
Other many pure metal oxide semiconductors have been
checked as photoanode materials in PEC aiming to search inex-
pensive, efficient and highly stable photocatalysts to the electrical
current with ability to absorb greater energy from solar spectrum
to photoinduce electron/hole pairs. Nevertheless, the performance
of such materials cannot be easily compared with that found with
6 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

classical TiO2 because different PEC systems and operation vari-

ables are used for environmental remediation.
The hematite ␣-Fe2 O3 has been considered one of these alter-
native candidates because of its low cost, chemical stability and
high light absorbance. Its low Ebg = 2.2 eV allows its direct applica-
tion to visible light [59,60]. Other promising photocatalyst is MnO
with a very low Ebg = 1.3 eV, being an interesting functional material
with low cost, large surface, electrochemical stability and innocu-
ous character [61,62]. The combination of MnO with polyaniline
demonstrated an enhancement of its PEC properties owing to the
interaction with the polyaniline bandgap of 2.8 eV that reduces the
recombination reaction of electrons and holes [62]. On the other
hand, SnO2 is a chemically and thermally stable semiconductor
with so wide Ebg of 3.5–3.8 eV that is difficultly used as photo-
catalyst [63]. Pure non-conductive SnO2 can be easily doped with
Sb improving considerably its electrical conductivity, although the
resulting Sb-SnO2 material employed as photocatalyst presents low
electrochemical stability with short lifetime upon current appli-
cation [64]. Other semiconductor such as ␤-PbO2 has also been
utilized as photocatalyst due to its very small Ebg = 1.4 eV [65], but
this material is only useful in alkaline medium since under acidic
conditions, it leaches toxic lead ions to the medium. In contrast, sta-
ble bismuth materials like BiVO4 with Ebg = 2.5 eV [66] and Bi2 WO6
with Ebg = 2.8 eV [67] under visible light irradiation and BiPO4 with
Ebg = 3.8 eV [68] under UV illumination have shown an excellent
effectiveness and good performance for the PEC treatment of some
organic pollutants.

3.1.5. Modified TiO2 materials

The PEC performance of a photocatalyst mainly depends on
the following factors: (i) the light absorption properties, (ii) the
reduction and oxidation rates on the surface by the photogener-
ated electrons and holes, and (iii) the recombination rate of such
charges. To enhance the PEC activity of the most ubiquiotous TiO2
photocatalyst, various strategies have been developed including: (i)
the construction of TiO2 nanotubes (NTs), nanotube arrays (NTAs),
nanobelts (NBs) or nanorods structures [69,70], (ii) the doping with
metals like Cr [71], Cu [72] and Fe [73] or non-metals like B [74]
and N [75] (second generation of photocalysts), (iii) the synthesis
of composites with metals like Pd [76], Ag [77] and Au [78], other
metal oxides like SiO2 [79], WO3 [80], Fe3 O4 [81], SnO2 [82] and
Cu2 O [83], metal sulfides like CdS [84] and Sb2 S3 [85], and car-
bonaceous materials like carbon cloth and graphene [86], and (iv) Fig. 3. SEM micrographs for thin films of: (a) TiO2 thin film deposited onto stainless
steel by atmospheric plasma spray. (Reproduced with permission from Ref. [31])
new titanium compounds like TiNbO5 [87] and the cubic double-
and (b) TiO2 nanotube arrays (NTAs) prepared by anodization of a Ti foil in 10 wt%
perovskite CaCu3 Ti4 O12 [88] (third generation of photocalysts). water + 0.5 wt% NH4 F in glycerol at 30 V for 50 h (Reproduced with permission from
TiO2 thin films prepared on substrates like Ti, stainless steel, Ref. [89]).
indium-tin oxide (ITO) and fluor-doped tin dioxide (FTO), among
others, by several procedures have been extensively used in PEC.
These films have granulate, compact and low porosity structure,
as exemplified in the scanning electron microscopy (SEM) micro- the same preparation technique, Liao et al. [69] found an Ebg = 2.7 eV
graph of Fig. 3 [32,89], and this restricts the light absorption to UV for crystalline anatase Ti/TiO2 NTAs, a value much lower than 3.2 eV
radiation with high recombination rate of the photogenerated elec- of a granulate anatase thin film, and that allowed an enhanced PEC
tron/hole pairs, as stated above. Since 2007, highly crystalline and activity using visible light provided by a 60 W incandescent lamp.
ordered TiO2 nanostructures with large surface area and porosity The doping of TiO2 with metals or non-metals introduces new
in the form of nanotubes, nanobelts or nanorods have been synthe- VB and/or CB related to the impurity energy levels that enhance the
sized to improve the PEC activity of thin-film photoanodes. A higher degradation of organic pollutants by PEC compared with undoped
efficiency for organics removal is described using thin nanostruc- photocatalyst. Kerkez et al. [72] synthesized TiO2 nanorod arrays
tures as a result of a synergistic effect of absorbing visible light, films deposited onto FTO doped with CuO up to 0.26% molar of Cu2+
larger semiconductor/electrolyte interface due to higher surface (Cu2+ -TiO2 ). The Ebg value of these materials decreased gradually
area, minority carriers generated within a distance from the surface with raising dopant proportion, from 3.1 eV for the bare TiO2 /FTO
equal to the sum of the width of the depletion layer and the diffu- to 2.6 eV for the higher doped material, which allowed operating
sion length escape recombination, and smaller recombination of under visible light improving PEC treatment of organics. This was
electron/hole pairs [89]. Fig. 3b shows a SEM micrograph of a typi- explained by the transference of the photogenerated e− CB in TiO2
cal nanotubular TiO2 photoanode synthesized by Ti anodization and to the less energetic CB of CuO, producing Cu+ from Reaction (11).
composed of one-dimensional crystalline NTAs with uniform diam- Cu2+ sites then act as traps of photogenerated e− CB increasing the
eters of about 100 nm and wall thicknesses near 10 nm [89]. Using electron/hole lifetime, and the resulting Cu+ can be oxidized to Cu2+
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 7

Fig. 4. Proposed PEC mechanism for: (a) doped B-TiO2 NTs (Reproduced with permission from ref. [74]) and (b) Sb2 S3 /TiO2 composite (Reproduced with permission from
Ref. [85]).

either at the photoanode or with O2 via Reaction (12) to form O2 •−
that can originate the sequence of ROS by Reactions (4)–(5).
Cu2+ + e− CB → Cu+
+ Other strategy for improving the TiO2 photoactivity is the prepa-
Cu + O2 → Cu 2+
+ O2 •−
A different behavior was found when doping TiO2 with a non-
metal compound. An interesting case is the doping of TiO2 NTs
with B in the form of NaBF4 . For this photocatalyst, Bessegato et al.
[74] determined two Ebg values, one of 3.3 eV related to TiO2 and
another of 2.2 eV due to the formation of intermediary energy lev-
els between the VB and CB of TiO2 created by substituted B atoms.
The proposed PEC mechanism with absorption of UV (for TiO2 ) and
visible light (from B dopant level) is illustrated in Fig. 4a. This fig-
ure also shows the bending of all energetic bands upon application
of a bias potential due to the change of the Fermi potential of the
semiconductor [74,85]. This bending leads to the formation of a
space charge layer (SCL) or depletion layer, characterized by the
depletion of photogenerated electrons and corresponding to the
distance between the photocatalyst surface and the beginning of
the flat bands. No SCL exists at the flat band potential (Efb ), where
all bands are flats, and its value grews with increasing the applied
(11) Eanod respect to Efb .
(12)
ration of composites with noble metals and other semiconductors.
An enhancement of the PEC process has been found by decorat-
ing TiO2 NTs with Pd, Ag and Au nanoparticles [76–78]. This has
been ascribed to the lower work function of the noble metal than
the electron affinity of TiO2 NTs that originates a Schottky bar-
rier potential in the interfaces making energetically favorable the
electron transfer from the CB of the semiconductor to the metal
and significantly reducing the recombination of electron/hole pairs
[76]. However, the authors do not consider the feasible simultane-
ous EO of organics by physisorbed hydroxyl radicals formed at the
metal surface from water oxidation by Reaction (10). The integral
treatment by PEC and EO has been reported for a SnO2 /TiO2 com-
posite by assembling sieve-like macroporous Sb-doped SnO2 film
on vertically aligned TiO2 NTs [82]. In contrast, the strong hetero-
8 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
Fig. 5. Schematic diagram illustrating the transfer of the photogenerated holes and
electrons in a TiO2 /graphene/Cu2 O interface.
Source: Reproduced with permission from ref. [86].
junction between TiO2 and other n-type mixed oxides causes larger
photoactivity of their bicomposites. Fig. 4b shows a diagram of the
PEC mechanism for Ti/TiO2 NTAs decorated with Sb2 S3 nanoparti-
cles in orthorhombic phase (stibinite), with Ebg values of 3.2 and
1.7 eV, respectively [85]. The photogenerated electrons in Sb2 S3 by
UV and visible light are injected into the CB of TiO2 because of the
more cathodic potential of the former (-0.77 V) respect to the lat-
ter (−0.50 V). Furthermore, the photogenerated holes in the VB of
TiO2 are transferred to that of Sb2 S3 , creating a high concentra-
tion of holes in the sensitizer/electrolyte interfaces. This decreases
the recombination of the electron/hole pair and increases the PEC
efficiency process, along with the advantage that Sb2 S3 acts as a
sensitizer practically in the entire visible spectrum. The PEC behav-
ior of an interesting TiO2 /graphene/Cu2 O tricomposite has been
recently explored by Yang et al. [86]. As can be seen in Fig. 5, both
TiO2 NTAs and Cu2 O (a p-type semiconductor with Ebg = 2.2 eV) can
be excited by UV/Vis light to produce electron/holes pairs. The elec-
trons of the CB of TiO2 then across the inserted graphene layer and
recombine with the holes of the VB of Cu2 O. In this way, oxidants
• OH can be formed from the holes of VB of TiO from Reaction (2)
2 over ITO and Ti substrates. The main disadvantages of magnetron
without possibility of recombination with the electrons of the CB
of Cu2 O, which can originate the chain of ROS from the starting
Reaction (3) with O2 .
The use of new titanium-metal oxides like CaCu3 Ti4 O12 with
very low Ebg = 1.5 eV [88] and high stability represents a promising
way to be explored in the next future for improving the PEC process
of organic pollutants in wastewaters.
3.2. Preparation of TiO2 photocatalysts
One of the most crucial points of PEC for the remediation of
polluted waters is the preparation of stable and re-utilizable pho-
tocatalysts onto conducting materials as support. Great research
efforts have been carried out to develop novel methodologies
to synthesize a large variety of photoanodes. This subsection is
devoted to detail the most important methodologies for the prepa-
ration of TiO2 thin-film and nanostructured photocatalysts, since
they are the most used materials, as stated above. Unfortunately,
the possible effect of the supporting material on the photocatalytic
response is barely addressed in the literature and will not be con-
sidered here.
3.2.1. Thin-film electrodes
The sol-gel method is the most common technique to synthesize
TiO2 thin-film photocatalysts [90–92]. It consists in the preparation
of a titanium dioxide colloidal suspension by mixing titanium(IV)
isopropoxide (Ti(i-OPr)4 ) with glacial acetic acid under constant
stirring and keeping a molar ratio H+ /Ti = 4, followed by dilution in
2-propanol with 1:1 Ti/alcohol ratio. A stable colloidal suspension
solution is then obtained by adding water and HNO3 under stirring
and keeping molar ratios of H2 O/Ti = 25 and H+ /Ti = 0.5. The thin
film over a typical Ti foil is prepared following a sequence involv-
ing the dipping of the foil into the colloidal suspension, drying and
annealing at 100–300 ◦ C for ca. 3 h. Although the resulting Ti/TiO2
photocatalysts are the easiest applicable ones at lab scale, the coat-
ings obtained by this method present low stability because they
are easily cracked by the gas evolution at the photoanode surface
during PEC treatment. Low janod values are needed to be applied
to upgrade their operational life. The alternative use of the sol-
gel coating laser calcination method allows an improvement of the
adherence of TiO2 coatings onto Ti [93].
Other interesting method is the spray painting and thermal
decomposition [94,95], which consists in spraying a solution of
titanyl acetylacetonate (C10 H14 O5 Ti) onto a conductive substrate.
The solution concentration, solution flow rate, nozzle-to-substrate
distance, and substrate temperature are crucial parameters that
affect the coating properties. Clear and colorless thin films are then
consistently formed through thermal decomposition of the pre-
cursor under oxygen. The painted coating could also be further
annealed at 400- 600 ◦ C to favor the thermal decomposition and
to oxidize the precursors giving a best oxide layer coating. This
methodology is faster than the sol-gel method, allowing coating
larger substrate surfaces in appreciably lower times. However, the
obtained Ti/TiO2 thin-film photoanodes still present low mechan-
ical stability like in the case of sol-gel methodology.
TiO2 thin films can also be prepared by magnetron sputtering,
a physical vapor deposition technology based on a plasma coating
process [96,97]. The sputtering material or precursor is ejected due
to bombardment of ions to the target surface in a vacuum cham-
ber. The ionized plasma beam is accurately directed and focused
in front of the target of the substrate by magnetic fields, giving
excellent layer uniformity and smooth coatings. One strong point
of this technology is that any conducting substrate can be sputtered
without decomposition or coating mechanical failure, because no
substrate heading is required. He et al. [97] prepared TiO2 coating
sputtering are: (i) the slow deposition speed which makes the pro-
cess more expensive, (ii) only small surfaces can be coated, and (iii)
the low adhesion of the coatings that could diminish the opera-
tion life of photoanodes, although it is considerably superior to the
conventional sol-gel coatings.
Chemical vapor deposition (CVD) is an extensively used coating
technology for a wide range of applications [98]. A precursor gas
is flowed into a chamber containing one or more heated objects
to be coated, occurring the chemical reactions to form the coat-
ing on/near the hot surface to be coated. The chemical by-products
required are exhausted out of the chamber along with the unre-
acted precursor gases usually at sub-torr total pressures and at
temperatures typically ranging from 200 to 1600 ◦ C [98]. CVD yields
better adherence of the TiO2 coating onto the conductive sub-
strate than sol-gel, and it allows controlling the film thickness from
nanometers up to micrometers as well as the crystallinity degree of
the coating, although it is much more expensive. The main limita-
tions of CVD are related to the higher cost of the precursors and the
kinds of substrates with smaller surface areas that can be coated.
The different thermal expansion coefficients between the substrate
and the coating can stress the deposited films causing mechani-
cal failure or coating breaking. The first application of CVD coated
photoanodes in PEC remediation of wastewaters was reported by
Hitchman and Tian [99], who prepared TiO2 thin films by low pres-
sure between 257 and 400 ◦ C using titanium tetra-tertbutoxide as
chemical precursor. The coatings obtained presented great photo-
catalytic activity and stability, allowing their reuse.
Atomic layer deposition (ALD) is other chemical thin-film tech-
nology in which the substrate surface is exposed to gaseous
precursors [100,101]. In ALD, the precursors are injected sequen-
tially in non-overlapping pulses after clearing the reactor of
previous ones. The coating reaction ends when all the reactive
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 9

sites on the surface are consumed and thus, the maximum mate-

(211)
(101)
rial depositable in a single exposure cycle is determined by the 1000 Anatase
nature of the surface-precursor interaction. This technology allows Rutile
Ti O

(111)
growing the coatings uniformly in small surfaces with high preci- 800 7 13

Intensity (a.u.)

(110)
sion by increasing the number of ALD cycles. Only the synthesis of

(002)
TiO2 thin films by ALD and its application to wastewater treatment 600

(301)
(211)
has been reported by Heikkila et al. [100], who used Ti(OMe)4 and

(1-21)

(1 4 13)
water as precursors injected into the reactor at 10 mbar, 325 ◦ C and

(101)
400

(220)

(112)
with pulses of 0.5 s. The coating obtained were highly stable and

(-125)
(2 0 12)

(200)
(020)
(-130)

presented good adherence to the substrate.
Finally, thermal spray coating technologies allow the synthe-
sis of high quality and reliable TiO2 coatings with great control of
physical properties like thickness, porosity, roughness and hard-
ness [102]. Atmospheric plasma spray (APS) is the most common
and versatile thermal spray process, where the coating is produced
using a nano or micropowder precursor that is partially or totally
melted during the deposition process by the plasma temperature
between 6000 and 15,000 ◦ C. Typically, Ar is used to generate the
plasma superheated in a DC arc and the powder feedstock intro-
duced in it is accelerated at high temperature toward the substrate
by the plasma jet. Thus, coating of large surfaces at low operation
times is feasible by APS. Garcia-Segura et al. [31] reported for the
first time the use of TiO2 coatings onto stainless steel obtained by
APS (see Fig. 3a) to treat polluted wastewaters by SPEC. The high
stability and reusability of the coating during consecutive treat-
ments was well-proven, showing good efficiencies for Acid Orange
7 decolorization.
3.2.2. Nanostructured materials
Since 2007 TiO2 NTs have been synthesized for PEC purposes.
The main advantage of these tridimensional and highly ordered
nanostructures compared to thin-films electrodes is due to their
higher effective area that allows higher light absorption.
The TiO2 NTs are usually prepared from the anodization of
Ti plates or foils. Before the anodization process, the titanium
sheets were: (i) ultrasonically degreased with water/acetone,
methanol/acetone or ethanol/acetone mixtures for above 30 min
followed by (ii) mechanical polished with abrasive papers [103]
or chemical polished with HF/HNO3 /H2 O mixtures [104,105]. The
substrates were subsequently rinsed with water or subjected to
another ultrasonic degrease. Once the anodic surface was pre-
treated, it was anodized in a two-electrode cell with an inert
cathode of Ni or Pt under vigorous magnetic stirring, employing
glycerol/water mixtures with H3 PO4 , HF or NH4 F as electrolyte
[89,104–107]. Different anodization conditions have been reported
in the literature involving Ecell values from 10 to 60 V for elec-
trolysis times from 30 min to 17 h in order to obtain TiO2 NTs or
one-dimensionally TiO2 NTAs of various diameters and lengths. The
electrochemically synthesized deposits were finally subjected to
annealing between 400 and 600 ◦ C for 1–2 h to induce TiO2 crys-
tallization and improve the PEC performance [105,108,109]. Fig. 3b
exemplifies the TiO2 NTAs obtained by this procedure by anodizing
at +30 V for 50 h [89].
A similar electrochemical procedure is utilized for the synthesis
of TiO2 NBs [70]. In contrast, FTO/TiO2 nanorod arrays are prepared
by a hydrothermal method involving the deposition of the photo-
catalyst onto the cleaned FTO-coated glass from a TiCl4 and HCl
solution heated in a muffle at 180 ◦ C for 2 h [72].
Several authors [110] proposed an alternative sonoelectro-
chemical method for the preparation of TiO2 NTs. The procedure
is a modification of the electrochemical procedure described above
based on the use of ultrasonic waves instead of a magnetic stirrer.
The irradiation with ultrasonic waves during anodization enhances
the mobility of ions inside the solution for leading to more efficient
production of the nanotubes.
(1-41)
(101)
200
0
10 20 30 40 50 60 70 80
22 θ/ (degree
degree )
Fig. 6. XRD spectrum with the corresponding crystallographic planes for each phase
of the TiO2 thin-film photoanode prepared by atmospheric plasma spray and com-
posed of 29% rutile, 9% anatase and 62% Ti7 O13 non-stoichiometric phase.
Source: Reproduced with permission from ref. [31].
It has also been reported the formation of coral-like struc-
tures by changing the electrolyte of the cell during Ti anodization.
Liu et al. [111] described the oxidation of Ti plates in an organic
electrolyte with 1-butyl-3-methylimidazolium tetrafluoroborate
([BMIM][BF4 ]) at +60 V for 20 min leading to a hierarchical TiO2
structure containing nanoholes resembling a coral.
3.2.3. Characterization of synthesized photocatalysts
The physical properties of all the synthesized photocatalysts
are characterized by means of many techniques. The morphology
of deposits can be analyzed by SEM, field-emission SEM (FESEM)
and transmission electron microscopy (TEM). From the images
obtained by these methods, the distribution and size of TiO2 NTs
can be determined, as described above for the SEM micrograph of
Fig. 3b. For thin-film photocatalysts, the porosity, roughness, adhe-
sion and hardness of deposits can be measured [31]. The chemical
composition of coatings can be assessed by energy dispersive spec-
trometry (EDS) and X-ray photoelectron spectroscopy (XPS) and
their crystalline structure ascertained by X-ray diffraction (XRD).
As an example, Fig. 6 presents the XRD pattern of a TiO2 thin film
coating a stainless steel sheet and prepared by APS [31]. From
the crystallographic planes detected, a composition of 29% rutile,
9% anatase and 62% Ti7 O13 (non-stoichiometric phase) was deter-
mined. Furthermore, the crystallites size can be estimated by the
well known Scherrer’s equation:
K
= (13)
␤ cos ␪
where ␶ refers to the mean size of ordered crystalline domains,
K is the Scherrer constant, a dimensionless shape factor usually
with values close to unity, ␭ is the X-ray wavelength, ␤ is the line
broadening at the half value of the maximum intensity in radians
and ␪ is the Bragg angle in degrees.
The optical properties of coatings are usually evaluated by
diffuse reflectance spectroscopy (DRS) using, for instance, an
UV/Vis/NIR spectrometer. Fig. 7a exemplifies the DRS spectra
obtained for bare TiO2 NTs and TiO2 -NTs doped with different
proportions of B [74]. All doped materials presented a second
absorption shoulder in the visible region, at ␭ > 400 nm, due to
the introduction of B atoms into the TiO2 lattice. The inset of
Fig. 7a shows the Tauc’s graph constructed from the DRS data of
the undoped and a B-doped material, which was utilized to esti-
mate the two Ebg values of 3.2 and 2.2 eV, obtained as the intercept
with the X axis corresponding to the energy h␯ irradiated, accord-
ing to ref. [74]. These data allowed the proposal of the previously
discussed PEC mechanism of B-TiO2 NTs shown in Fig. 4a.
10 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
Fig. 7. (a) DRS spectra of: (1) bare TiO2 NTs and doped B-TiO2 NTs with (2) 70, (3)
560, (4) 140 and (5) 280 ppm of NaBF4 . The inset shows the Tauc’s plot and Ebg value
for (1) B280ppm–TiO2 NTs and (2) undoped TiO2 NTs. (b) Photocurrent density vs.
potential curves for (1) dark current, (2) TiO2 NTs before annealing, (3) bare TiO2
NTs and B-doped TiO2 NTs with (4) 70, (5) 140, (6) 560 and (7) 280 ppm of NaBF4 .
Electrolyte 0.1 M Na2 SO4 , scan potential rate 10 mV s−1 and UV/Vis irradiation from
a 125 W mercury lamp. Adapted with permission from ref. [74].
The electronic properties of photocatalysts can be assessed by
measuring the spontaneous photocurrent as function of the applied
Eanod in an electrolytic cell. An example is depicted in Fig. 7b for the
B-doped materials reported in Fig. 7a [74]. The experiments were
conducted using a 0.1 M Na2 SO4 solution of pH 6 and by scanning
the potential at a rate of 10 mV s−1 . Scarce photocurrent can be
observed in the dark (curve 1) and before annealing (curve 2) under
UV/Vis illumination, whereas the photoactivity upgraded strongly
for the bare TiO2 NTs (curve 3). The B-doped samples were more
photoactive than the bare one and showed an increasing photocur-
rent at higher amount of dopant agent from 70 to 280 ppm (curves
4, 5 and 7) due to the enhancing photoactivity of the B, whereas
at 560 ppm (curve 6) the photocurrent decayed since the dopant
also trapped the electrons photogenerated in the material. In all
cases, the photocurrent rose with increasing Eanod because a grad-
ual value higher than Efb was applied and this caused a bending
of the CB and VB bands leading to greater SCL (see Fig. 4a) and
consequently, photocurrent.
An interesting electrochemical method to determine the Efb
value of the photocatalyst and its electron carrier density (ND ) is
the electrochemical impedance spectroscopy (EIS). The interfacial
properties between the solution and the photocatalyst are typi-
cally studied from frequencies of 105 to 0.1 Hz using amplitudes of
5–10 mV at open circuit. Fig. 8a shows the Nyquist plots (imag-
inary impedance vs real impedance) obtained for TiO2 NTs and
Pd/TiO2 NTs composite in the dark and under 300 W Xe light [76].
The semicircles observed are characteristics of a charge transfer
process and its diameter is equal to the charge transfer resistance.
Fig. 8. (a) Nyquist plots for TiO2 NTs and Pd/TiO2 NTs photoanodes in the dark and
under 300 W Xe illumination. (b) Mott−Schottky plot at a fixed frequency of 5 kHz
on TiO2 NTs and Pd/TiO2 NTs under illumination.
Source: Reproduced with permission from ref. [76].
The much smaller arch of the Pd/TiO2 NTs than that of the TiO2
NTs in the dark and also under illumination indicates a reduction
of the recombination of electron/holes pairs by Pd upgrading the
electron mobility. From the corresponding equivalent circuit, the
charge capacitance (C) of the photocatalyst can be determined and
subsequently, related to Efb and ND by means of the following equa-
tion:
1 2 kT
= [(E − Efb ) − ] (14)
C2 ND e ε0 ε anod e
where e is the elemental charge, ␧0 is the permittivity of the
vacuum; ␧ is the relative permittivity of the semiconductor, k is
the Boltzmann constant and T is the absolute temperature. The
corresponding Mott-Schottky plots for the TiO2 NTs and Pd/TiO2
NTs under illumination are presented in Fig. 8b, where C values
were acquired beginning at negative Eanod . Thus, an Efb = −0.294 V
was found for the former material, a value more negative than
−0.137 V determined for the latter one that facilitates the electron
transfer at any positive Eanod . This was also reflected in the lower
ND = 2.05×1021 cm−3 for TiO2 NTs compared with 8.55 × 1021 cm−3
for Pd/TiO2 NTs that is obtained, indicating a faster carrier (electron)
transfer for the latter, which presupposes a best PEC performance.
The structural characteristics of the photoanodes can affect the
photoelectrocatalytic efficiency. Parameters such coating thickness
or roughness should not be miss considered. However, the study
of the influence of these structural parameters has been barely
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
attended in the literature to the difficulties to modify and con-
trol these parameters during the anode synthesis. For instance,
the effect of the film thickness on the PEC performance could be
ascribed to two main effects: (i) the light penetration into the
film to photogenerate electron/hole pairs by Reaction (1) and (ii)
the coating conductivity. Obviously both effects are related to the
photocatalyst material. According to Hitchman and Tian [99], the
maximum penetration depth of incident irradiation into TiO2 coat-
ings is defined by 1/␣, where ␣ is the absorption coefficient of TiO2
at the incident light wavelength. It should be noted that the holes
generated in the depletion layer width should diffuse to the pho-
toanode surface in order to react with water to release • OH by
Reaction (2) or directly mineralize organics. These holes generated
in the minority carrier length, which is the distance that the holes
move into a field-free region before recombination from Reaction
(7), may diffuse to the depletion layer boundary and transported to
the photoanode surface. On the other hand, the material resistivity
rises when thickness increases, diminishing the efficient removal of
photopromoted electrons by the external electric circuit [35,112].
Thereby, the increase of coating thickness enhances the photogen-
eration up to a limit, where a further increase diminishes the PEC
performance.
Since photocatalytical processes are directly related to surface
processes, the surface roughness of thin films plays a key role
on the PEC efficiency [112]. Photoanode materials with higher
superficial roughness quadratic average will then result in higher
performance. Consequently, the photocatalyst roughness should be
determined in order to be able to compare in equality conditions
the different catalytic materials response.
3.3. PEC systems
Lab-scale photoelectrochemical devices have been utilized up
to present to check the PEC treatment of organic wastewater. The
systems are basically composed of an electrolytic cell with the pho-
tocatalyst, a potentiostat or power source to provide the electrical
energy and a light source to illuminate the photoanode. Never-
theless, a large variety of PEC systems have been described, with
different cells and kinds and positions (outside or inside the cell)
of the light source, which can be UVC (␭ < 300 nm), UVA (␭ from
320 to about 400 nm) or UV/Vis lamps, as well sunlight that can
be simulated with a Xe lamp. In most works, any criterion is given
about the selection of the PEC system applied and as much, the use
of a visible radiation is argued to justify larger absorption in this
region from photoanodes different from classical TiO2 . This variety
of conditions makes impossible a realistic comparison of the PEC
performance reported by different authors over a given organic pol-
lutant, thereby being needed a vast development of optimized PEC
systems for their possible scale-up to be applicable to industrial
level.
The electrolytic cells can be differentiated by their form and
the number of compartments and electrodes. The most ubiquitous
cell is a tank reactor, although flow cells are also utilized. One can
then operate with: (i) a one-compartment or undivided cell and
(ii) a two-compartment or divided one, with a separator between
the anolyte (anodic solution) and catholyte (cathodic solution). The
former arrangement is usually preferred for avoiding the potential
penalty of the separator of the latter one. In both cases, it is feasible
the use of two or three electrodes. The systems with two electrodes
contain the photoanode and cathode (inert for the degradation pro-
cess or not), providing a constant Ecell or janod by a power source. In
contrast, the three-electrode cells are equipped with an additional
reference electrode that makes possible the supply of a constant
Eanod to the photoanode by a potentiostat.
Examples of undivided three-electrode PEC systems are
depicted in Fig. 9. The arrangement of Fig. 9a was composed of
11
a quartz glass tank reactor, an UVC light source and a potentiostat
[113]. Note that this kind of high energetic light can also photolyze
directly the organic pollutants. The tank reactor contained a Ti/TiO2
photoanode and an inert Cu cathode, both placed in parallel, and the
reference electrode to control the potential of the photoanode was
a saturated calomel electrode (SCE). The lamp was positioned verti-
cally in a double-walled U-tube outside the reactor, surrounded by
circulating water to decrease the heating effect of the lamp. The UVC
irradiation supplied by the lamp was perpendicular to the photo-
catalyst surface and crossed the quartz glass wall without intensity
loss. A porous titanium plate was used to provide dissolved oxygen
for enhancing the degradation process by O2 − production via Reac-
tion (3) and pre-eminently, the mass transport of organics toward
the photocatalyst by the stirring of the solution. On the other hand,
Fig. 9b shows a similar three-electrode configuration, but with an
inside thermostated Xe light source [114]. The photocatalyst was a
Ti/B-TiO2 NTs, the cathode was an inert Ni sheet and the reference
electrode was a SCE.
A recent paper of Martin de Vidales et al. [115] reported a flow
PEC system with a three-electrode cell to degrade methyl orange
azo dye from wastewater. Fig. 10a depicts an expanded view of the
undivided electrochemical cell utilized, in which the photoanode
was a Ti plate coated with TiO2 NTs and the inert cathode was a
Ti mesh coated with RuOx attached over a glass end for the pas-
sage of the UV light [115]. The reference electrode was an Ag/AgCl
(3 M KCl), connected to the electrolyte exit of the cell, near the
photoanode. The arrangement used is illustrated in Fig. 10b. The
experiments were made with 1 L of solution, which was introduced
in the reservoir, thermostated at 15 ◦ C with water bath and recir-
culated through the circuit with a centrifugal pump (batch mode).
After passing through the cell, its flow rate was regulated between
20 and 100 L h−1 with a flowmeter before come back to the reser-
voir.
Fig. 11a and b presents two examples of undivided two-
electrode PEC systems for wastewater remediation [31,36]. Daghrir
et al. [37] studied the oxidation of chlortetracycline hydrochlo-
ride in aqueous solution using the arrangement of Fig. 11a with
a Ti/TiO2 thin film as the photoanode. The tank reactor was made
of acrylic material and a quartz window was disposed on one face of
it to illuminate the photocatalyst with UVC light of ␭max = 254 nm.
Apart from the Ti/TiO2 , one cathode of the same surface area
was placed in parallel. Different cathode materials such as stain-
less steel, vitreous carbon, graphite and amorphous carbon were
utilized. The solution was stirred with a magnetic bar. Fig. 11b
illustrates a sketch of the set-up used for Garcia-Segura et al.
[31] to degrade Acid Orange 7 azo dye solutions submitted to
solar irradiation by SPEC. A 5 cm2 TiO2 photoanode and a 3 cm2
carbon-polytetrafluoroethylene (PTFE) air-diffusion cathode were
used as electrodes. The TiO2 thin-film material was synthesized
over stainless steel by APS technology and the cathode produced
continuously H2 O2 from the two-electron reduction of oxygen from
injected air by Reaction (8), upon vigorous magnetic stirring. This
cathode acted in the degradation process since the generated H2 O2
can directly attack organic pollutants or its oxidation products
and/or produce more potent ROS like • OH by Reaction (9).
A limited number of papers have described the use of divided
cells for PEC treatment. Fig. 12a exemplifies the three-electrode
arrangement utilized by Selcuk et al. [116] to study the removal
of humic acid. The anolyte of the tank reactor of 100 mL capac-
ity was equipped with a TiO2 photoanode and a SCE, whereas
the catholyte with the same solution volume contained a Pt foil
cathode. Both compartments were separated by a Nafion 117 mem-
brane and the photocatalyst was illuminated with an outside Xe
lamp through a quartz glass window. An interesting study of Ding
et al. [117] compared the performance of divided and undivided
two-electrode semi-circular quartz glass cylinder cells to degrade
12 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

Fig. 9. Typical set-up of undivided three-electrode cells for wastewater treatment by PEC. (a) TiO2 thin-film photocatalyst for the degradation of a 20 mg L−1 Acid Blue 7 azo
dye solution with external light (Reproduced with permission from Ref. [113]). (b) Doped B-TiO2 NTs photocatalyst for the degradation of a 20 mg L−1 methyl orange azo dye
solution with inner light (Reproduced with permission from Ref. [114]).

200 mL of rhodamine B dye, as shown Fig. 12b. The photoanode
was formed by Bi2 WO6 nanoplates deposited on FTO and the cath-
ode was composed of Fe@Fe2 O3 core-shell nanoparticles supported
on activated carbon fiber (ACF). The anolyte and catholyte of the
divided cell were connected with a saturated KCl salt bridge and
the photocatalyst was illuminated with a visible light by means of
an outside 300 W tungsten halogen lamp with ␭ > 420 nm. Fresh air
was injected near the cathode to generate H2 O2 by Reaction (8) for
coupling PEC process with electro-Fenton (EF) one. This occurred
thanks to the iron ions released by the cathode during current cir-
culation, which originated • OH in the bulk from Fenton’s Reaction
(15) [5,11,118]:
H2 O2 + Fe2+ → Fe3+ + • OH + OH−
3.4. Operation parameters
The degradation of organics from wastewaters during PEC
process is monitored from the variation of experimental parame-
ters such as the absorbance at the maximum wavelength (␭max )
of the solution, usually for dyes, determined by UV/Vis spec-
trometry, the concentration of the parent molecule measured by
high-performance liquid chromatography (HPLC) and total organic
carbon (TOC) or chemical oxygen demand (COD) of the solution.
The two former parameters assess the destruction of the starting
pollutant/s, the third one informs about its mineralization (conver-
sion into CO2 ) and the latter one evaluates its transformation into
small by-products like short-linear carboxylic acids and oxidizable
inorganic species. The change of these parameters can be expressed
(15) in terms of:

A
Decolorization = (16)
The coupling of PEC with EF mineralized more largely the dye A0
solution in the catholyte of the divided cell than in the undivided
one as a result of a greater accumulation of H2 O2 in the former A0 − A
Percentage of color removal = × 100 (17)
system because it was partly anodically oxidized in the latter one. A0
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 13

Fig. 10. (a) Expanded view of the undivided electrochemical cell with TiO2 NTs photocatalyst and (b) scheme of the set-up of the flow PEC system used for the removal of
1 L of a 0.25 mM methyl orange azo dye solution at pH 3, 15 ◦ C and flow rate of 100 L h−1 .
Reproduced with permission from ref. [115].

c0 − c where A0 . c0 , TOC0 and COD0 denote the absorbance, concentra-

Percentage of organic removal = × 100 (18)
c0 tion, total organic carbon and chemical oxygen demand at initial
time t, and A, c, TOC and COD are the corresponding values at elec-
TOC0 − TOC trolysis time t. It is necessary to remark the typical confusion in
Percentage of TOC removal = × 100 (19)
TOC0 many papers over the indiscriminate use of Eq. (18) instead of Eq.
(17) for dyes solutions. It is well-known that dyes oxidation origi-
COD0 − COD
Percentage of COD removal = × 100 (20) nates colored by-products that can absorb at the same ␭max as the
COD0
14 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

Fig. 11. Schematic diagram of coupled systems of PEC with generated H2 O2 at the cathode using TiO2 thin-film photocatalysts. Treatment of: (a) 1 L of chlortetracycline
hydrochloride solutions (Reproduced with permission from Ref. [36]). (b) 100 mL of a 15 mg L−1 Acid Orange 7 azo dye solution under direct solar irradiation (Reproduced
with permission from Ref. [31]).

parent molecule and hence, the percentage of color removal of the
solution determined from absorbance decay from Eq. (17) increases
over time much more slowly than the decay of dye content found
by HPLC from Eq. (18) [119]. Decolorization results reported in the
literature then need to be carefully analyzed for avoiding such bad
interpretation.
Several operation variables can modify the above experimen-
tal parameters and affect the effectiveness of the PEC treatment of
organic pollutants in wastewaters. The most important variables
are the external bias potential and light intensity [13–15,18,20–24].
As stated above, the application of an increasing Eanod respect to
Efb accelerates the pass of photogenerated electrons to the exter-
nal circuit causing a bending of the CB and VB of the photocatalyst
with the consequent formation of a SCL. Nevertheless, it is found
that the degradation process of organics is enhanced up to a maxi-
mum Eanod when the majority of photoexcited electrons are drawn
inside the semiconductor and extracted at the back contact, con-
ditions under which the reaction kinetics is only limited by the
photon flux. At superior Eanod values, the width of SCL can exceed
the thickness of the photocatalyst and the charge is redistributed
in the SCL with the consequent reduction of PEC activity and grow-
ing of the energy consumption [86]. The light intensity has then to
influence largely the degradation by PEC since it regulates the quan-
tity of photogenerated electrons that can be extracted at maximum
Eanod . Nevertheless, most authors do not consider this variable and
use a high UV or visible intensity to ensure the highest effectiveness
of PEC.
Other important variables are the solution pH, its conductivity
related to the electrolyte concentration and the organic concen-
tration that determines the oxidation ability of ROS and dissolved
O2 [18,21,22]. The effect of pH in PC is explained from the point
of zero charge (PZC) corresponding to the pH where the surface
charge of the photocatalyst is zero, a value approximately 6 for
TiO2 , and the adsorption of organics below and above it [18]. In
contrast, the PZC is not valid in PEC because the surface charge
becomes strongly positive upon a given Eanod and the degradation
process is limited by the generated oxidizing ROS due to the low
recombination of electron/hole pairs. The best pH then has to be
experimentally determined in each case since it depends on the
molecule nature and its interaction with the charged photocata-
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 15

Fig. 12. (a) Set-up of a divided PEC system with a TiO2 photocatalyst for treating 100 mL in the photoanode (anolyte) compartment of a 25 mg L−1 humic acid solution
(Reproduced with permission from Ref. [116]). (b) Schematic diagrams of divided (left) and undivided (right) PEC semi-cylindrical cells with a Bi2 WO6 /FTO photoanode and
a Fe@Fe2 O3 /ACF cathode for H2 O2 generation to degrade 10.44 ␮M rhodamine B dye solutions. In both systems, PEC was coupled with electro-Fenton (EF) (Reproduced with
permission from Ref. [117]).

lyst. On the other hand, Na2 SO4 is usually added to the treated
solution for upgrading its conductivity in order to obtain a higher
janod at a given Eanod , improving the PEC effectiveness by a larger
ROS production. A sufficient amount of dissolved O2 also promotes
oxidizing conditions in PEC, because it helps to avoid the recombi-
nation of photogenerated electron/hole pairs by acting as electron
acceptor from Reaction (3) to form more quantity of ROS as illus-
trated in Figs. 2 and 5. The effect of the temperature and the stirring
rate or flow rate, which determines the reaction rate and the mass
transfer of reactants/products toward/from the electrodes, respec-
tively, has been reported by a limited number of authors in PEC,
despite their basic role in the EAOPs treatments of wastewaters
[11,118].
It should be noteworthy that the elucidation of the oxidation
reaction of organics, the changes in toxicity and biodegradability
and energy costs have been scarcely determined for the PEC treat-
ment of organic pollutants [82,86,107,120,121]. More research over
these points should be made in order to corroborate the viability of
PEC for future scale-up at industrial level.
4. Destruction of organic pollutants by PEC
The application of PEC to wastewater remediation has been
preferentially centered on the treatment of dyes, chemicals and
pharmaceuticals spiked in synthetic aqueous solutions, usually
containing Na2 SO4 as electrolyte. Unfortunately, less attention has
been pay on the remediation of real wastewaters due to the com-
plexity of their nature and composition. This section is devoted
to show and discuss the main results and advances found for the
treatments of all these kinds of organic pollutants, which will be
16 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
separately analyzed for a better remark of their degradation char-
acteristics.
4.1. Dyes
As highlighted in Fig. 1c, synthetic dyes solutions represent the
major number of wastewaters treated by PEC. Their fast decoloriza-
tion upon the action of generated ROS can be easily monitored
by UV/Vis spectrometry, even for very low dye concentrations,
and this allows checking the performance of this technology.
Apart from the large variety of dyes tested, synthesized photoan-
odes such as TiO2 thin films [31,90,93,95,113,122–136], TiO2 NTs
[69,106,108,115,137–143], doped TiO2 [72,74,114,129,144–146],
composites with TiO2 [38,76,79,80,84,85,147–158] and other pho-
tocatalytic materials [52,53,59,60,65,66,117,159–166] have been
utilized in these studies. The main reason for preparing such high
number of photocatalysts is the search of materials with larger abil-
ity to photogenerate electron/hole pairs than TiO2 thin films upon
sunlight irradiation.
4.1.1. TiO2 photoanodes
Table 1 collects the percentages of color and TOC removals
obtained for different dye solutions treated by PEC under selected
conditions using undivided cells with either TiO2 thin-film or NTs
photocatalyst (see Figs. 9–11). A look of these data allows con-
cluding that artificial UVC (␭max = 254 nm), UV (from 180 to ca.
600 nm) and sometimes Xe lamps with high intensity were pref-
erentially used to irradiate the photocatalyst. Exposure to UVA
(␭max = 360 nm) lamps [90] and direct sunlight [31,95] has been
utilized, as well. Dye concentrations were typically low (normally
< 25 mg L−1 ) due to the small oxidation ability of PEC, because low
Eanod values, associated with small photocurrents, were utilized
to preserve the fragile photoactivity of the TiO2 photoanode. For
this reason, operation in batch mode with long electrolysis times
of 2–3 h were commonly applied to achieve more than 70% of color
removal (see Table 1).
Comparative tests for given dyes using both, TiO2 thin-film
and TiO2 NTs photocatalyst under the same experimental PEC
conditions have been scarcely reported. The superior mechani-
cal integrative structure and photoactivity of the nanoestructured
material is assumed by most authors without verification. The
Zanoni’s group [138,140] described that after 240 min of PEF treat-
ment at Eanod = +1.0 V (Ag/AgCl) under UV irradiation, 0.05 mM
Disperse Red 1, Disperse Orange 1 and Disperse Red 13 in chloride
solutions undergone 87–97% mineralization using a TiO2 NTs pho-
toanode prepared by anodization, values much higher than 54–60%
obtained for a TiO2 thin-film one prepared by sol-gel. These authors
also found a strong reduction of the toxicity of the treated dye
solutions, thereby showing that PEC is a very interesting method
for wastewater remediation. This is due to the conversion of the
toxic aromatic dye and its aromatic intermediates into biodegrad-
able products like short-linear carboxylic acids. The formation of
tartaric, succinic, acetic and oxamic acids and their removal over
electrolysis time has been reported for the SPEC process of Acid
Orange 7 [31].
Several papers have described the best performance of PEC over
individual processes for dye decolorization. Fig. 13 exemplifies the
decolorization abatement for 50 mg L−1 methyl orange in 0.01 M
Na2 SO4 by different methods [106]. Individual processes like direct
photolysis (DP) under 15 W UVC, EO at Eanod = +0.75 V (Ag/AgCl) and
PC under 15 W UVC led to a poor decolorization lower than 20%.
In contrast, the PEC treatment yielded 97% color removal, demon-
strating that it was much more potent and synergistic to EO and
PC because the larger separation of the photoexcited electron/hole
pairs under the applied Eanod generated much greater amount of
• OH from photogenerated holes via Reaction (2) that oxidized more
1.2
1.0
Decolorization
0.8
0.6
0.4
0.2
0.0
0 30 60 90 120 150 180 210
Time (min)
Fig. 13. Change of decolorization with electrolysis time for 36 mL of 50 mg L−1 of
methyl orange azo dye in 0.01 M Na2 SO4 using an undivided cell with Ti/TiO2 NTAs
photocatalyst at Eanod = +0.75 V (Ag/AgCl) upon 15 W UVC light. ( ) Direct photolysis
(DP) without photoanode, ( ) photocatalysis (PC) without applied current, ( )
electrochemical oxidation (EO) without UVC illumination and ( ) PEC. Adapted
with permission from Ref. [106].
rapidly the dye. The same synergistic behavior for PEC has been
shown for Acid Orange 7 [31], Remazol Brilliant Orange 3R [90],
rhodamine B [93] and orange G [136].
The operation variables most studied in dye degradation are
the solution pH, the applied Eanod , the dye concentration, the elec-
trolyte concentration and the kind of electrolyte used. Fig. 14
illustrates the effect of the above operation variables over the
degradation of 350 mL of methyl orange solutions in sulfate
medium by PEC with a TiO2 thin film upon 350 W UV illumination
[129]. Fig. 14a evidences that the best pH for the process was 2.0,
with percentages of color removal slightly higher than that of pH 3.5
and much more superior to those of pH 5.2. This behavior is diffi-
cult to explain and differs from the optimum pH values reported
by other authors using Ti/TiO2 thin films. Fu et al. [113] also
described an optimum acidic pH = 3.4 with 90% color removal for
20 mg L−1 of Acid Blue 7 in sulfate medium using the cell of Fig. 9a at
Eanod = +0.68 V (SCE) upon 11 W UVC for 1 h (see Table 1), whereas
Garcia-Segura et al. [31] found a pH = 7.0 as optimal for 100% decol-
orization of 100 mL of 15 mg L−1 of Acid Orange 7 solutions in
0.05 M Na2 SO4 using the cell of Fig. 11b at janod = 1.0 mA cm−2 and
35 ◦ C after 120 min of electrolysis under direct sunlight. Conversely,
Li et al. [93] reported an increasing decolorization from pH 2.0–10.0
when 50 mL of a 0.015 mM rhodamine B solution in 0.10 M Na2 SO4
was treated at Eanod = +0.50 V (SCE) exposed to 30 W UVA, attain-
ing the best color removal of 95% after 70 min of electrolysis at
the higher pH = 10.0. This discrepant behavior for pH can be mainly
related to: (i) the different systems, photocatalysts and operation
conditions utilized that change the amounts of • OH produced from
photogenerated holes and the interaction of organics with the pho-
tocatalyst and (ii) the different colored products formed from each
dye that interfere the absorbance measurements for decoloriza-
tion [31]. When 0.50 M NaCl was used as electrolyte, Zanoni et al.
[90] reported a maximum TOC removal of 28% for 30 mL of 0.05 mM
Remazol Brilliant Orange 3R at pH 6.0 as the anolyte of a divided cell
operating at Eanod = +1.0 V (SCE) upon 450 W Xe–Hg arc illumina-
tion for 30 min. The superior degradation at this pH explored within
the range 2–11 could be explained by the synergistic action of the
strong oxidant • OH formed from Reaction (2) and active chlorine
species like HClO and Cl• produced from Cl− oxidation by Reactions
(21)–(23), respectively [129].
2Cl− → Cl2 + 2 e− (21)
− +
Cl2 + H2 O → HClO + Cl + H (22)
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 17

Table 1
Per cent of color and TOC removals for selected PEC treatments of dyes using undivided cells with TiO2 photoanodes.

Dye co (mg L−1 ) Experimental conditions % color removal % TOC Ref.

decay

Acid Blue 7 20 Solution of pH 3.4, Eanod = +0.68 V (SCE), 90 −c [113]

11 W UVC for 1 ha
Methyl orange 10 165 mL of solution, Eanodl = +0.6 V, 100 −c [122]
20 125 W UV for 2 ha 78
Triazo leather dye 10 70 mL of solution with 0.1 M KCl, 35 ◦ C, 98 −c [127]
Eanod = +0.8 V (Ag/AgCl), 125 W UV for (pH 6.14)
8 ha 72
(pH 3.35)
Methyl orange 20 350 mL of solution with 0.1 M Na2 SO4 , 97 −c [129]
pH 2.0, Eanod = +0.75 V (Ag/AgCl), 350 W
UV for 150 mina
Reactive Orange 16 100 70 mL of solution with 0.1 M KCl, 100 −c [134]
Reactive Black 5 100 pH 3.35, 30 ◦ C, Ecell = 5 V, 125 W UV 92 −c
Reactive Red RB 133 100 for 5 ha 70 −c
Rhodamine B 5 20 mL of solution with 0.1 M 53 −c [135]
phosphate, pH 7, Eanod = +0.8 V
(Ag/AgCl), 500 W Xe for 2 ha
Rhodamine B 0.01d 45 mL of solution with 0.1 M Na2 SO4 , 72 −c [69]
Eanod = +0.6 V (SCE), 60 W visible light
for 3 hb
Methyl orange 50 36 mL of solution with 0.01 M Na2 SO4 , 98 −c [106]
Eanod = +0.75 V, 15 W UVC for 3 hb
Methyl orange 0.25d 1 L of solution with 0.1 M Na2 SO4 , pH 3, 51 −c [115]
15 ◦ C, Eanod = +1.50 V (Ag/AgCl), flow
rate 100 L h−1 , 20.5 A of UV for
150 minb
Drimaren Red 243 X −6BN 25 2 L of solution with 4.2 mM KCl, 93 −c [142]
Eanod = +1.50 V (Ag/AgCl), 30 W UVC for
1 hb
a
TiO2 thin film.
b
TiO2 NTs.
c
Not determined.
d
Initial concentration in mM.

HClO + hv → Cl• + • OH
Fig. 14b highlights that increasing Eanod from +0.2 to +1.0 V
(Ag/AgCl) accelerated the degradation process of methyl orange
because more current was gradually generated enhancing the sep-
aration of electrons and holes. However, the degradation rate
decreased for Eanod = +2.0 V (Ag/AgCl) suggesting a redistribution
of charges in SCL with greater electron/hole recombination despite
the circulation of a higher current through the electrodes. Low
optimum Eanod values have also been shown for the degradation
of several dyes using TiO2 thin-films or TiO2 NTs photoanodes
in different systems, varying between +0.6 and +1.2 V (SCE)
[90,93,106,113,122,127,129], although up to +1.50 V (Ag/AgCl) has
been reported [115].
The expected decay of the percentage of color removal with
increasing methyl orange concentration from 10 to 30 mg L−1 is
depicted in Fig. 14c. This is a typical behavior of EAOPs and can be
accounted for by the destruction of lower percentage of organics
with increasing their concentration since a similar amount of • OH
oxidants is produced from photogenerated holes via Reaction (2)
[5].
Fig. 14d shows that increasing Na2 SO4 concentration up to
0.10 M as bakcground electrolyte caused greater degradation rate
of the dye as a result of the rise of the solution conductivity. giving
rise to a higher current that produced more holes and consequently,
more quantity of • OH to oxidize methyl orange. Finally, Fig. 14e
evidences that the decolorization rate for different 0.10 M elec-
trolytes slightly increased in the order: NaNO3 < KCl < Na2 SO4 . This
sequence could be tentatively ascribed to the growing conductiv-
ity of the solutions at pH 2.0, with little influence of the additional
production of: (i) • OH from NO3 − photolysis by Reaction (24), (ii)
lesser oxidant active chlorine species from Cl− oxidation by Reac-
(23) tions (21)–(23), and (iii) H2 O2 from SO4 2− oxidation via Reactions
(25)–(26), which could generate extra • OH by Reaction (9).
NO3 − + H2 O + h␯ → NO2 • + • OH + OH− (24)
2− 2− −
2SO4 + h␯ → S2 O8 + 2e (25)
2− −
S2 O8 + 2H2 O → 2HSO4 + H2 O2 (26)
The action of these additional oxidants differed for other dyes.
For instance, Zanoni et al. [90] described a large rise in TOC removal
in the order: Na2 SO4 < NaNO3 < KCl when 0.05 mM Remazol Bril-
liant Orange 3R solutions in 0.50 M of such electrolytes at pH 6.0
as the anolyte of a divided cell were treated at Eanod = +1.0 V (SCE).
In this case, the dye molecule was more effectively attacked by
generated active chlorine species than by • OH.
The positive effect of temperature from 20 to 35 ◦ C and of
light intensity from 44 to 132 mW m−2 on the decolorization of
25 mg L−1 Acid Black 1 dye using an undivided cell are shown in
Fig. 15a and b, respectively [108]. Macedo et al. [127] described a
similar behavior respect to temperature for the color abatement of
a 10 mg L−1 triazo leather dye solution in 0.10 M KCl of pH 3.35 and
6.14 using a TiO2 thin film at Eanod of +0.8 and +1.2 V (SCE) under
125 W UV operating between 21 and 35 ◦ C. This trend is expected
by the concomitant enhancement of the mass transport of reac-
tants toward/from the photoanode and the increase in rate of all
chemical and electrochemical reactions involved in the decoloriza-
tion process. For much higher intensities between 5 and 20 W m−2
of UVC illumination, Fu et al. [113] found that 16 W m−2 was opti-
mal for the decolorization of a 20 mg L−1 Acid Blue 7 solution using
the cell of Fig. 9a at Eanod = +0.68 V (SCE), indicating a saturation of
photoexcited electrons in the VB of a TiO2 photocatalyst at high
enough light intensity.
Martin de Vidales et al. [115] used the flow cell of Fig. 10 to
degrade 1 L of 0.25 mM methyl orange in 1 M Na2 SO4 at pH 3, 15 ◦ C
18 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

a b
100 100

80 80

60 60

40 40 0.2 V
pH 2.0 0.6 V
pH 3.5 1.0 V
20 pH 5.2 20 1.5 V

0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
c d
100 100
% Color removal

80 80

60 60

40 -1 40
10 mg L
L-1 0M
-1
20 mg L
L-1 0.05 M
-1
20 30 mg L
L-1 20 0.10 M

0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
e
100

80

60

40
NaNO
NaNO33
KCl
KCl
20 Na SO
Na2SO4
2 4

0
0 30 60 90 120 150 180
Time (min)

Fig. 14. Percentage of color removal vs. electrolysis time for the degradation of 350 mL of methyl orange solutions in sulfate medium by PEC using an undivided cell with
Ti/TiO2 thin-film photocatalyst upon 350 W UV illumination. (a) Effect of pH, 20 mg L−1 methyl orange, 0.10 M Na2 SO4 , Eanod = +1.0 V (Ag/AgCl), (b) influence of the applied Eanod ,
20 mg L−1 methyl orange, 0.10 M Na2 SO4 , pH 2.0, (c) effect of methyl orange content, 0.10 M Na2 SO4 , pH 2.0, Eanod = +1.0 V (Ag/AgCl). In (d) influence of sulfate concentration
and (e) effect of different 0.10 M electrolytes for 20 mg L−1 methyl orange, pH 2.0 and Eanod = +1.0 V (Ag/AgCl). Adapted with permission from ref. [129].

and Eanod = +1.50 V (Ag/AgCl) by varying the flow rate. After 150 min
of electrolysis, the color removal grew from 20% at 20 L h−1 to 51% at
100 L h−1 . At the higher flow rate the process achieved the best effi-
ciency because it was controlled by the mass-transport of reactants
and the oxidation products were rapidly removed to the solution
leaving the surface photoactive sites available for further organic
oxidation. This condition can also be easily attained in tank reactors
with vigorous stirring (mechanic, magnetic or by bubbling O2 ) of
the solution, as shown in the systems of Figs. 9–12.
The coupling of PEC with cathodically generated H2 O2 has
also been explored aiming to enhance its degradation power
[31,123,126,136]. Xie and Li [126] proposed the use of an undivided
tank reactor similar to that of Fig. 9a equipped with a Ti/TiO2 mesh
photocatalyst upon outside 8 W UVA and a reticulated vitreous car-
bon cathode fed with 120 mL min−1 of air. The anode mesh allowed
the illumination of 30 mL of a 30 mg L−1 Orange G dye solution in
0.01 M Na2 SO4 with 0.15 mM Fe2+ of pH 3.0 and room temperature.
Under the application of a cathodic potential (Ecat ) of −0.71 V (SCE),
H2 O2 was continuously produced at the cathode by Reaction (8) and
oxidizing • OH radicals were pre-eminently formed from photogen-
erated holes by Reaction (2) and in the bulk from Fenton’s Reaction
(15). Furthermore, the UVA illumination of the solution allowed the
application of the photoelectro-Fenton (PEF) process involving: (i)
the additional generation of • OH with Fe2+ regeneration by photol-
ysis of Fe(OH)2+ species (the most stable Fe(III) species at pH 3.0)
from Reaction (27) and (ii) the photolysis of Fe(III) complexes with
final carboxylic acids by the general Reaction (28) [5,11]:
Fe(OH)2+ + h → Fe2+ + • OH (27)
Fe(OOCR) 2+
+ h → Fe 2+
+ CO2 + R• (28)
The coupled PEC/PEF process led to total decolorization in
300 min with 74% mineralization. This method was much more
powerful than the PEC treatment alone, without Fe2+ addition,
which yielded only 50% color removal at the same time.
Another proposed coupled system involves the combination of
PEC and EF in a divided tank reactor similar to that of Fig. 12b [123].
The anolyte contained 100 mL of 30 mg L−1 of Acid Scarlet 3R dye
in 0.02 M Na2 SO4 and a Ti/TiO2 thin-film electrode illuminated by a
125 W UV light. The catholyte was separated of the anolyte by a salt
bridge and contained 50 mL of the same solution adjusted to pH 3.0
with 0.036 mM Fe2+ and a graphite electrode fed with an air flow of
2.5 L min−1 . Operating at Ecat = −0.66 V (SCE) for 70 min, 60% color
removal was achieved in the anolyte through PEC process, whereas
a much higher decolorization of 92% was found in the catholyte by
EF. This work evidences that a coupled PEC/EF process with a “dual
cell” can upgrade the dye degradation compared with single PEC.
Recently, Bessegato et al. [143] showed the combination of PEC
and ozonation for improving the destruction of Acid Yellow 1 dye
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 19

1.2 a
a 100
1.0 20 ºC
25 ºC 80

% Color removal
30 ºC
Decolorization

0.8
35 ºC 60
0.6
40

0.4
20

0.2 0
0 30 60 90 120 150
0.0 Time (min)
0 10 20 30 40 50 60 70
Time (min) b
100
1.2
b 80

% TOC removal
-2
44 mW
44 mW m--2
m
1.0 -2
88 mW m
88 60
-2
132 mW m
132
Decolorization

0.8
40
0.6
20

0.4 0
0 30 60 90 120 150
0.2 Time (min)

0.0
0 10 20 30 40 50 60
Time (min)
Fig. 15. Decolorization vs. electrolysis time for the PEC treatment of 100 mL of a
25 mg L−1 Acid Black 1 dye solution using an undivided cell with Ti/TiO2 NTs photo-
catalyst irradiated by UVC light (Eanod was not specified). (a) Effect of temperature
at light intensity of 44 mW m−2 and (b) influence of light intensity at 25 ◦ C. Adapted
with permission from Ref. [105].
solutions up to 100 mg L−1 in 0.01 M Na2 SO4 at pH 3.0. A TiO2 NTs
photoanode in an annular bubble reactor operating at Ecell = 2.0 V
with 36 W UVB irradiation in the presence of 1.25 × 10−4 mol min−1
of O3 was employed. Total decolorization and mineralization were
attained in 20 and 60 min for the coupled PEC/O3 , respectively,
which presented much higher oxidation ability than individual pro-
cesses.
4.1.2. Doped TiO2 and composites with TiO2
A high number of modified TiO2 photocatalysts has been synthe-
sized with the aim of upgrade the performance of the PEC process
of dyes using visible light as radiation source. Most of published
articles have only detailed the comparative decolorization and
mineralization of these pollutants in sulfate medium between the
modified TiO2 and the pristine material. Fig. 16a and b exemplify
the change of the percentage of color and TOC removals with elec-
trolysis time, respectively, for different treatments of 100 mg L−1 of
solutions of a nitronaphthol dye like Acid Yellow 1 in 0.1 M Na2 SO4
at pH 2 and 25 ◦ C [74]. The cell was a tank reactor with an arrange-
ment similar to that of Fig. 9b equipped with either a TiO2 NTs
or a doped B-TiO2 photoanode under 125 W UV/Vis irradiation by
applying an Eanod = +1.2 V (Ag/AgCl) in EO and PEC [74]. EO in the
dark practically did not yield any removal of the dye, indicating
that it was not oxidized at the anode. A large decolorization with
poor TOC reduction can be observed under DP, suggesting that the
dye and some of its by-products were directly and slowly pho-
tolyzed by the incident light. The decay of both parameters was
strongly enhanced by PC pre-eminently by the larger oxidation
effectiveness of • OH radicals formed from Reaction (2). As expected,
Fig. 16. Percentage of (a) color removal at ␭ = 393 nm and (b) TOC removal for the
70 degradation of 500 mL of a 100 mg L−1 Acid Yellow 1 with 0.1 M Na2 SO4 solution at
pH 2.0 and 25 ◦ C in an undivided cell. Method: ( ) EO with Ti/B-TiO2 NTs, ( ) DP,
( ) PC with Ti/TiO2 NTs, ( ) PC with Ti/B-TiO2 NTs, ( ) PEC with Ti/TiO2 NTs and
( ) PEC with Ti/B-TiO2 NTs. Irradiation with 125 W UV/Vis light and Eanod = +1.2 V
(Ag/AgCl) in EO and PEC. Adapted with permission from ref. [74].
the much smaller recombination of the electron/hole pairs under
Eanod = +1.2 V (Ag/AgCl) in PEC yielded quicker destruction of organ-
ics. Under these conditions, as well as in PC, the doped B-TiO2 NTs
photocatalyst gave better degradation than TiO2 NTs one. This is
due to the reduction of the Ebg value of the former material from
3.2 to 2.2 eV due to the B-doping level (see Fig. 4a). The better results
of 100% color removal and 93% TOC decay were obtained with an
amount of 280 ppm of B as doping agent.
A similar enhancement of PEC with dopant B has been reported
by Su et al. [114], who used the arrangement of Fig. 9b to remark the
beneficial of B-TiO2 NTs photocatalysts under Xe illumination over
methyl orange decolorization. While improved PEC processes for
dyes were also found for dopant Cu2+ [72] and codopants W and
N [145], any effect was observed using either Fe3+ [144] or V, Ce
and F [129] as doping agents of TiO2 thin films. On the other hand,
positive PEC performance of different dyes has been described by
using composites of TiO2 with metals [76,147] and other materials
[79,80,84,85,148–157].
The percentage of color and TOC removals for several dyes
degraded by PEC using different doped TiO2 and composites with
TiO2 photoanodes under selected conditions are summarized in
Table 2. The smaller Ebg values of these photocatalysts compared to
that of TiO2 allowed their best irradiation with visible light alterna-
tively to UVC and UVA. The data of Table 2 show the use of potent
Xe lamps in many cases for photo-excitation, which simulate in
the laboratory the role of sunlight. Higher Eanod values than those
used for TiO2 in Table 1 can be observed in Table 2 because of
the larger stability of the modified materials. Good color removals,
usually >80%, were obtained, although electrolysis times as long
as 2–3 h were needed operating in batch mode. Similarly, TOC
removals >70% were found under these conditions when dye con-
tents <50 mg L−1 were degraded. Greater contents required much
longer electrolysis times. For instance, a 105 mg L−1 rhodamine 6G
20 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

Table 2
Percentage of color and TOC removals for selected degradations of dyes by PEC using undivided cells with doped TiO2 and composites with TiO2 photoanodes.

Dye co (mg L−1 ) Experimental conditions % color removal % TOC decay Ref.

Acid Yellow 1 50 500 mL of solution with 0.01 M Na2 SO4 , pH 2, 100 93 [74]
25 ◦ C, B-TiO2 NTs photocatalyst, Eanod = +1.2 V
(Ag/AgCl), 125 W UV for 2 h
Methyl orange 20 500 mL of solution with 0.1 M Na2 SO4 , 25 ◦ C, 92 −a [114]
B-TiO2 NTs photocatalyst, Eanod = +2.0 V (SCE),
300 W Xe for 2 h
Methyl orange 10 50 mL of solution with 0.2 M Na2 S, CdS/TiO2 89 −a [84]
NTAs photocatalyst, Eanod = +0.5 V (SCE), 300 W
Xe for 3 h
Methyl orange 10 200 mL of solution with 0.1 M NaCl, pH 2.7, 97 −a [79]
SiO2 /TiO2 photocatalyst, Eanod = +0.8 V (SCE),
9 W UVC for 30 min
Methylene blue 5 3 mL of solution with 0.5 M Na2 SO4 , pH 6, 25 ◦ C, 63 −a [72]
Cu-TiO2 NTAs photocatalyst, Eanod = +1.0 V
(Ag/AgCl), 105 W visible light for 4 h
Methylene blue 4 10 mL of solution with 0.1 M KCl, 89 −a [154]
graphene/TiO2 /carbon cloth, Eanod = +0.9 V
(SCE), 150 W Xe for 160 min
Methylene blue 4 Each solution with 0.05 M Na2 SO4 , Pd/TiO2 NTs 100 −a [76]
photocatalyst, Eanod = +0.5 V (Ag/AgCl), 300 W
Rhodamine B 2.5 Xe for 3 h 84 −a
Rhodamine B 10 Solution with 0.01 M Na2 SO4 , −a 82 [148]
TiO2 /carbon/Al2 O3 membrane, Eanod = +1.2 V
(SCE), 500 W Xe for 2 h
Rhodamine 6G 105 250 mL of solution with 0.1 M Na2 SO4 , 25 ◦ C, 100 69 [152]
W-Ti NTAs photocatalyst, Eanod = +0.3 V (SCE),
80 W UV for 8 h
a
Not determined.

solution needed up to 8 h to achieve 69% TOC reduction [152] (see
Table 2). All these results evidence again the low oxidation ability
of PEC, useful for low organics loads.
Few studies have described the influence of pH [74,79] and
applied Eanod [74,79,114] over the degradation of dyes by PEC.
The analysis of their decolorization process revealed that they
always obeyed a pseudo-first-order kinetics owing to the attack
of a constant • OH content produced from photogenerated holes via
Reaction (2) [72,76,84,114,156]. Fraga et al. [80] treated 30 mL of a
0.033 mM Basic Red 51 solution in 0.1 M Na2 SO4 of pH 2.0 using an
undivided cell with a WO3 /TiO2 bicomposite photoanode and a Pt
cathode. After 120 min of electrolysis at janod = 1.25 mA cm−2 upon
irradiation of the photocatalyst with UV (280–400 nm) and visible
(420–630 nm) light, total decolorization was always attained with
94% and 83% TOC abatement, respectively. Using comparable PC,
only 25% and 30% color removal and 11% and 7% TOC decay were
found. These results corroborate again the superiority of PEC over
PC and the feasible sustainable solar-assisted remediation of water
bodies contaminated with dyes.
The effectiveness of the coupled PEC/PEF process was assessed
by Almeida et al. [38] for 500 mL of 85 mg L−1 orange G solutions
in 0.05 M Na2 SO4 at optimum pH 3.0 and 25 ◦ C using an undi-
vided cell like of Fig. 9a by applying 16.67 mA cm−2 . This method
was conducted with a Pt/TiO2 NTs photoanode irradiated with
a 80 W UV/Vis lamp and a carbon-PTFE air-diffusion cathode for
continuous H2 O2 electrogeneration. It was compared with single
PEC using an alternative Pt cathode and with EF using an alter-
native Pt anode. A 0.5 mM Fe2+ concentration was added to the
solution for PEC/PEF and EF treatments. The dye disappeared com-
pletely in 16, 12 and 6 min for PEC, EF and PEC/PEF, respectively,
always obeying a pseudo-first-order kinetics. After 190 min, TOC
was reduced by 80%, 87% and 97% for the above degradations.
The coupled PEC/PEF process then showed higher oxidation ability
than PEC alone. LC–MS/MS and HPLC analysis of treated solutions
revealed the formation of 12 aromatic intermediates and 4 short-
linear carboxylic acids. From these products, the reaction sequence
for orange G mineralization of Fig. 17 was proposed [35], where the
main oxidizing agents are • OH produced from Reaction (2) and (15).
The degradation of the dye (1) is initiated with its desulfonation
and hydroxylation to give the compound 2. This intermediate can
then undergo: (i) successive hydroxylation to compounds 3 and 4
or (ii) C N cleavage to form the naphthalene products 5 and 6 with
desulfonation. Compound 5 evolves to the benzoic acid derivative
7, whereas the oxidation of 6 yields the benzene compounds 8 and
9, along with the naphthalene compound 10, which can also be pro-
duced from 4. Degradation of 7 leads to the sulfobenzene product 11
that is oxidized to the p-benzoquinone derivative 12, also formed
from compounds 8-10. The ring opening of benzenic intermediates
gives the aliphatic carboxylic acids 13 and 14, which are then trans-
formed into the ultimate oxalic (15) and formic (16) acids. These
acids form Fe(III)-oxalate and Fe(III)-formate complexes that are
photolyzed to CO2 with Fe2+ regeneration via Reaction (28).
The coupling of membrane filtration with PEC has been designed
by Wang et al. [148]. The membrane was constructed deposit-
ing graphitic carbon layer and TiO2 nanoparticles on an Al2 O3
membrane support. When this TiO2 /carbon/Al2 O3 membrane was
irradiated with a 500 W Xe lamp and an Eanod = +1.2 V (SCE) was
provided for 2 h, 82% TOC reduction was obtained for a 10 mg L−1
rhodamine B solution with 0.01 M Na2 SO4 flowing through the
membrane (see Table 2). This removal was 1.3 or 3 times higher
than that found for filtration with light irradiation (using PC pro-
cess) or filtration alone. The coupled PEC/membrane became more
efficient thanks to the greater mineralization of the dye with the
larger amounts of • OH formed from Reaction (2) upon the action of
the applied Eanod .
4.1.3. Other photocatalytic materials
Semiconductor materials like WO3 and composites
[52,53,160,161,166], Bi2 WO6 [117], ZnO [162], BDD-ZnWO4
[159], ␤-PbO2 [65], BiVO4 [66], BiPO4 [164,165] and ␣-Fe2 O3
[59,60,163], with an appropriate Ebg to photo-excite electron/hole
pairs similarly to Reaction (1) for TiO2 , have been checked for
the remediation of dye solutions by PEC. Table 3 collects the
degradation parameters obtained for several dye treatments with
the above photocatalysts using undivided cells under selected
conditions. As can be seen, UVC, UV, visible light and Xe lamps
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 21

Fig. 17. Proposed reaction sequence for orange G mineralization by the coupled PEC/PEF process using an undivided cell with Pt/TiO2 NTs photoanode upon 80 W UV/Vis
irradiation and a carbon-PTFE air-diffusion cathode. Adapted with permission from ref. [38].

were successfully applied to decolorize low dye concentrations
(<25 mg L−1 ) for long times, usually between 2 and 3 h, due to the
low generation of • OH from photogenerated holes. Note that the
experimental conditions used for the photocatalysts of Table 3 are,
in general, quite similar to those applied with undoped TiO2 (see
Table 1) and doped TiO2 and composites with TiO2 (see Table 2).
Most of the above papers corroborated the superior oxida-
tion power of PEC compared to individual processes like DP, EO
and PC [60,65,159,161,163,164]. For example, Chatchai et al. [161]
22 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

Table 3
Per cent of color and TOC removals for selected PEC treatments of dyes in undivided cells with other photocatalytic materials.

Dye co (mg L−1 ) Experimental conditions % color % TOC Ref.

removal decay

Direct Red 80 5 200 mL of solution with 5 g L−1 Na2 SO4 , 25 ◦ C, 88 12 [65]

25 ␤-PbO2 photocatalyst, I = 5 mA, 7 W UVC for 6 h 72 17
X-3B 20 60 mL of solution with 0.1 M Na2 SO4 , 97 −a [159]
ZnWO4 /BDD photocatalyst, Eanod = +2.0 V (SCE),
20 W UV for 3 h
Basic Red 51 0.01b 30 mL of solution with 0.1 M Na2 SO4 , pH 2, 100 63 [160]
W/WO3 photocatalyst, janod = 1.25 mA cm−2 ,
150 W Xe for 2 h
Rhodamine B 0.1 b 200 mL of solution, WO3 photocatalyst, 98 81 [166]
Eanod = +1.5 V (SCE), direct sunlight for 160 min
Methylene blue 5 Solution with 0.1 M Na2 SO4 , pH 6.5, 83 −a [161]
WO3 /BiVO4 photocatalyst, Eanod = +0.2 V
(Ag/AgCl), 500 W Xe (> 420 nm) for 2 h
Methylene blue 0.01b 5 mL of solution with 0.1 M Na2 SO4 , BiVO4 51 −a [66]
photocatalyst, Eanod = +1.4 V (Ag/AgCl), 50 W
visible light for 40 min
Methylene blue 5 25 mL of solution with 0.01 M Na2 SO4 , pH 7, 78 −a [163]
␣-Fe2 O3 photocatalyst, Eanod = +0.6 V (SCE),
350 W Xe for 105 min
Methyl orange 5 50 mL of solution with 0.1 M Na2 SO4 , ␣-Fe2 O3 79 −a [59]
photocatalyst, Eanod = +1.0 V (SCE), 300 W
visible light for 2 h
Methyl blue 10 Solution with 0.1 M Na2 SO4 , pH 7, BiPO4 80 −a [164]
photocatalyst, Eanod = +3.0 V (SCE), 11 W UVC
for 5 h
a
Not determined.
b
Initial concentration in mM.

reported the progressive decay of the more intense visible band of 6

methyl orange at ␭max = 662 nm up to 83% after 2 h of PEC treatment a
Initial specific rate (10 M cm s )
-2 -1

of a 5 mg L−1 dye solution in 0.1 M Na2 SO4 at pH 6.5 using an undi- 5

vided cell equipped with a WO3 /BiVO4 composite photocatalyst
at Eanod = +0.2 V (Ag/AgCl) under a 500 W Xe (>420 nm) irradiation. 4
-9

This process was much more powerful than PC alone, which only
yielded about 26% color removal, whereas the decolorization by DP 3
and EO at Eanod = +0.2 V (Ag/AgCl) was rather insignificant. These
results confirm an excellent separation of the electron/hole pairs 2
upon a bias potential for a WO3 /BiVO4 composite.
Nevertheless, little information has been given over the influ- 1
ence of operation variables like pH [52,53,161], applied Eanod
[52,53,65,159,164], light [52,160,161], dye concentration [52,65] 0
and background electrolytes [52,66]. In their pioneering works 0.0 0.2 0.4 0.6 0.8 1.0 1.2
with a WO3 , Luo and Hepel [52,53] studied the degradation of [NaCl] (M)
the naphthol blue black diazo dye in different electrolytes with a
conventional undivided three-electrode cell like of Fig. 9a under 4
b
Initial specific rate (10 M cm s )

irradiation with an outside 500 W UV/Vis light. For a dye concen-

-2 -1

tration of 8.8 × 10−5 M with 0.5 M electrolytes and Eanod = +1.08 V

(SCE), the decolorization of the PEC process was enhanced in the 3
sequence: Na2 SO4 < NaNO3 < NaClO4 < NaCl. The best performance
-9

in 0.5 M NaCl can be attributed to the very fast attack of active chlo-
rine species formed from Reactions (21)–(23) compared to that of 2
• OH produced from photogenerated holes by Reaction (2), which

are the only oxidants expected in the stable 0.5 M NaClO4 . The faster
decolorization in 0.5 M NaNO3 than in the latter one can then be 1
related to the generation of more amounts of • OH via the photolytic
reaction (24), whereas the lower oxidation ability of S2 O8 2− pro-
duced from Reaction (25) could justify the slowest loss in color 0
achieved in 0.5 M Na2 SO4 . The oxidation action of active chlorine 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
species was confirmed by the linear dependence between the initial [dye] (10 M)
-4

specific rate for decolorization and NaCl concentration depicted in

Fig. 18a [52], assessed under optimum conditions of 8.8 × 10−5 M
dye concentration and Eanod = +1.08 V (SCE). It was also found that
the initial specific rate in 0.5 M NaCl was quite similar in the pH
range 1.0-4.5, whereas it dropped progressively up to pH 12.0 by
the loss of oxidation power of active chlorine species due to the
formation of the weaker oxidant ClO− . Moreover, the illumination
Fig. 18. (a) Initial specific rate vs. NaCl concentration for the decolorization of
8.8 × 10−5 M naphthol blue black diazo dye solutions by PEC using an undivided tank
reactor with WO3 photocatalyst upon 500 W UV/Vis light at Eanod = +1.08 V (SCE). (b)
Initial specific rate vs. naphthol blue black content for the PEC decolorization of dye
solutions in 0.50 M NaCl by illuminating the WO3 photocatalyst with 500 W of ( )
UV/Vis and ( ) visible light at Eanod = +1.08 V (SCE). Adapted with permission from
ref. [52].
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 23

40 1.2 1.2
a a
1.0 1.0
30
EO
% TOC removal

0.8 0.8

Decolorization

TOC / TOC
PEC

20 0.6 0.6

0.4 0.4

0
10
0.2 0.2

0 0.0 0.0
-1
5 mg L 5 mA
-1
25 mg L 5 mA 25 mg L
-1
50 mA 0 20 40 60 80 100 120 140
Time (min)
1.2 1.2 1.2
b
b
1.0 1.0
1.0
Decolorization

0.8 0.8

Decolorization

TOC / TOC
0.8
0.6 0.6
0.6
0.4 0.4

0
0.4 0.2 0.2

0.2 0.0 0.0

0 1 2 3 4 5 6 0 20 40 60 80 100 120 140
Time (h) Time (min)

Fig. 19. (a) Percentage of TOC removal for EO and PEC treatments of 200 mL of 5 and Fig. 20. Time-course of decolorization decay (in red) and normalized TOC removal
25 mg L−1 Direct Blue 80 dye solutions in 5 g L−1 Na2 SO4 at 25 ◦ C using an undivided (in blue) in the (a) undivided and (b) divided semi-cylindrical tank reactors of Fig. 12b
cell equipped with ␤-PbO2 photocatalyst upon 7 W UVC illumination for 6 h at 5 mA for the treatments of 200 mL of a 1.044 × 10−5 M rhodamine B solution in 0.05 M
and 4 h at 50 mA (adapted with permission from Ref. [65]). (b) Decolorization vs. Na2 SO4 of pH 6.2 upon illumination of the Bi2 WO6 /FTO photoanode with 300 W
electrolysis time of a 10 mg L−1 methyl blue dye solution with 0.1 M Na2 SO4 at pH 7 visible light and at janod = 0.1 mA cm−2 . (a) Systems: ( ) Bi2 WO6 /FTO|Pt, ( )
by ( ) EO at Eanod = +3.0 V (SCE), ( ) PC and PEC at Eanod of ( ) +1.0 V, ( ) +2.0 V, Pt|Fe@Fe2 O3 /ACF and ( ) Bi2 WO6 /FTO|Fe@Fe2 O3 /ACF. (b) Catholyte degrada-
( ) +3.0 V and ( ) +4.0 V (SCE) in an undivided cell with a BiPO4 photocatalyst tion in ( ) Pt||Fe@Fe2 O3 /ACF and ( ) Bi2 WO6 /FTO||Fe@Fe2 O3 /ACF. Adapted
under 11 W UVC irradiation (adapted with permission from Ref. [164]). with permission from ref. [117].

with UV/Vis light gave much better decolorization rate than visible
light, as can be seen in Fig. 18b, indicating that the photo-excitation
of electrons in WO3 was mainly due to UV light, despite its low Ebg
of 2.5–2.7 eV (see subsection 3.1.2).
The combined effect of dye concentration and applied current
on TOC decay for the EO and PEC processes of 200 mL of Direct Blue
80 dye solutions in 5 g L−1 Na2 SO4 at 25 ◦ C using an undivided cell
with a ␤-PbO2 photocatalyst upon 7 W UVC light was analyzed by
Florencio et al. [65]. Fig. 19a evidences a strong improvement of
PEC over EO at the greater dye content of 25 mg L−1 and higher
current of 25 mA, which can be ascribed to a large enhancement
of the separation electron/hole pairs upon the action of external
potential. On the other hand, the high optimum Eanod value that can
be applied to a BiPO4 photocatalyst was evidenced by Zeng et al.
[164] when exploring the decolorization of a 10 mg L−1 methyl blue
solution with 0.1 M Na2 SO4 at pH 7 using 11 W UVC illumination.
Fig. 19b shows that the rise of Eanod from 0 to +3 V (SCE) enhanced
the removal of the dye up to a maximum 80% color removal at 5 h
(see Table 3). Further increase to +4 V (SCE) caused the redistribu-
tion of charges in SCL with greater electron/hole recombination and
only 67% color removal was obtained at the same time. For all these
trials, a pseudo-first-order kinetics was always found.
Ding et al. [117] examined the effectiveness of the coupled
PEC/EF treatment of rhodamine B in 0.05 M Na2 SO4 at neutral pH
6.2 in the undivided and divided semi-cylindrical tank reactors
of Fig. 12b using a Bi2 WO6 /FTO photocatalyst exposed to 300 W
visible illumination. The cathode was a Fe@Fe2 O3 /ACF electrode
with ability to release iron ions and electrogenerate H2 O2 to pro-
duce • OH from Fenton’s Reaction (15), as stated above. A very
low janod of 0.1 mA cm−2 was used, thus avoiding the formation of
• OH from water oxidation by Reaction (10). In the undivided cell,
Fig. 20a illustrates that the decolorization and TOC decay for the
coupled PEC/EF process (Bi2 WO6 /FTO|Fe@Fe2 O3 /ACF system) were
greater than the sum of those of PEC (Bi2 WO6 /FTO|Pt system) and
EF (Pt|Fe@Fe2 O3 /ACF system) [117]. The synergistic process of the
coupled treatment can then be accounted for by the larger gener-
ation of • OH from both Reactions (2) and (15). The production of
• OH was enhanced when the dye degradation was performed in
the catholyte of the divided cell, with better performance using a
Bi2 WO6 /FTO photocatalyst than a Pt anode, as shown in Fig. 20b.
These results are rather doubtful, because if a janod = 0.1 mA cm−2
was applied in both cases, the same degradation parameters should
be expected for the EF process taking place in the catholyte. In fact,
the degradation of the catholyte in the divided cell can only be
associated with EF but not with a coupled PEC/EF since the photo-
generated • OH cannot attack the organic load of the solution.
4.2. Chemicals
A high number of wastewaters containing chemicals have been
treated by PEC aiming to show the interest of this technology for
their remediation (see Fig. 1c). Most of these compounds are widely
used toxic and biorefractory industrial products such as anilines,
phenols, bisphenol A and carboxylic acids. Photocatalysts including
24 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
TiO2 thin films and NTs [30,44,89,99,109,116,167–173], doped TiO2
[174–176], composites with TiO2 [70,75,82,86,177–187] and other
materials [60,64,67,188–190] under different Eanod values and illu-
mination sources have been utilized in these studies, as will be
described below.
4.2.1. TiO2 and composites with TiO2
Table 4 collects the degradation characteristics of several chem-
icals destroyed by PEC under the action of TiO2 and composites
with TiO2 photoanodes under selected conditions. High chemi-
cal removals (>92%) along with excellent TOC reductions can be
observed in most cases using any kind of photoanode illuminated
with UV, visible and/or simulated solar light. Long times from 1
to 5 h were again required in view of the relatively low amount of
oxidizing agents originated during the PEC treatment of low con-
tents of chemicals. In some cases, the decay of solution COD was
determined. This parameter reflects the amounts of organic and
inorganic species that can be oxidized by dichromate ion, whereas
TOC accounts for by the amount of organic carbon present in the
solution. The COD/TOC ratio varies with the compound checked
and, for example, attains a value of 2.38 for phenol and only 0.18
for oxalic acid. Thus, the COD value for wastewaters with aromatic
compounds decreases more rapidly than TOC because of the for-
mation of final short-linear aliphatic carboxylic acids like formic
and oxalic [5]. A COD removal up to 95% has been reported for
the destruction of a 10 mM formic acid solution by PEC using Ag-
TiO2 [177] photocatalysts under 500 W visible light at Eanod = +0.8 V
(SCE) for 60 min. On the other hand, it was found that 50 mL with
a 817 mg L−1 solution of this acid underwent a lower COD reduc-
tion of 63.8% after 60 min of PEC treatment in a packed-bed reactor
containing a granular Ti/TiO2 thin film exposed to 500 W visible
illumination at Ecell = 30.0 V [168]. These findings suggest the fea-
sibility of a large mineralization of organic pollutants because the
PEC process is potent enough to remove final carboxylic acids to
large extent.
Similarly to dyes, most works demonstrate the best per-
formance of PEC to destroy chemicals from wastewaters than
individual processes. The superiority of TiO2 NTs [89], doped TiO2
[174,175] and composites with TiO2 [177,178,185] over thin films
of this material has also been well-proven. Fig. 21a shows the com-
parative TOC removal for a 5.0 × 10−6 M 4,4 -oxydianiline solution
with 0.1 M Na2 SO4 at pH 2.0 by several methods and photocatalysts
[89]. DP and PC with Ti/TiO2 thin film and NTAs under 150 W UVA
light only led to 40–50% mineralization in 180 min. At that time,
TOC was more largely reduced by 78% using PEC with a Ti/TiO2
thin-film photocatalyst at Eanod = +1.5 V (Ag/AgCl), whereas total
mineralization was attained in a shorter time of 120 min when the
photocatalyst was a Ti/TiO2 NTAs material. This work shows clearly
the enhancement of the separation of the photogenerated elec-
tron/holes by highly ordered NTAs with much greater photoactive
area than conventional thin films.
Contradictory relative oxidation abilities have been described
referring to the electrolytes used in synthetic solutions. While an
increasing PEC performance in the order NaCl < NaNO3 < Na2 SO4
has been found for 4,4 -oxydianiline [89], humic acid [116] and p-
nitrophenol [167], the sequence NaNO3 < Na2 SO4 < NaCl has been
obtained for microcystin-LR [183]. Moreover, Jorge et al. [167]
reported a superior performance of HClO4 instead of the above
three electrolytes, whereas Daskalaki et al. [172] obtained a bet-
ter removal of bisphenol A using NaCl instead HClO4 . This different
behavior can be associated with the different reactivity of parent
molecules and its oxidation products with generated ROS and/or
active chlorine species, as pointed out above. Several studies in
sulfate medium have confirmed the oxidation preponderance of
• OH formed from reaction (2) over O • − produced from reac-
2
tion (3) during the PEC treatment of tetrabromobisphenol A [70]
a
100
80
% TOC removal
60
40
20
0
0 30 60 90 120 150 180 210
Time (min)
100
b
[Active chlorine] (mg L )
80
-1
60
40
20
0
2.0 4.0 6.0 8.0 10.0
pH
Fig. 21. (a) Percentage of TOC removal with time for 250 mL of a 5.0×10−6 M 4,4 -
oxydianiline solution in 0.1 M Na2 SO4 of pH 2.0 in an undivided cell under 150 W
UVA light. ( ) DP, ( ) PC with Ti/TiO2 thin film, ( ) PC with Ti/TiO2 NTAs, ( )
PEC with Ti/TiO2 thin film at Eanod = +1.5 V (Ag/AgCl) and ( ) PEC with Ti/TiO2
NTAs at Eanod = +1.5 V (Ag/AgCl) (Reproduced with permission from Ref. [89]). (b)
pH-dependence of active chlorine concentration produced in 250 mL of a 0.1 M
NaCl in an undivided cell with a Ti/TiO2 thin-film photocatalyst upon 125 W UV
(315–400 nm) irradiation for 30 min (Reproduced with permission from Ref. [170]).
and 2,4-dichlorophenol [185] from addition of radical scavengers
like tert-butanol (• OH scavenger), oxalate (hole scavenger) and p-
•
benzoquinone (O2 − scavenger).
The effect of pH on the PEC performance was also dependent on
the molecule nature. In most cases, the best removal of chemicals
was obtained in an acidic pH range 1–4 [89,116,169,172,175,183],
although for aniline [44] and dodecyl-benzenesulfonate [174] the
optimum pH values were close to 10 and 6.2, respectively. For 0.05-
0.10 M NaCl, Fraga et al. [170] confirmed the larger production of
active chlorine species at pH 4.0 using an undivided reactor with a
Ti/TiO2 thin-film photocatalyst upon 125 W UV light, as can be seen
in Fig. 21b. They obtained 95% TOC reduction of a 50 ␮g L−1 micro-
cystin solution at this pH using janod = 30 mA cm−2 for 180 min.
Chai et al. [82] presented an interesting study on the degrada-
tion of a 200 mg L−1 p-nitrophenol solution in 0.1 M Na2 SO4 in an
undivided cell similar to that of Fig. 9a to check the performance of
a SnO2 /TiO2 NTs composite under 300 W UV illumination by sev-
eral treatments. A high content of this pollutant was utilized to
better determine the changes in biodegradability and relative tox-
icity index of the treated solution, and the evolution of detected
intermediates. The biodegradability was determined as the ratio
of biochemical oxygen demand at 5 days (BOD5 ) and COD, need-
ing a threshold value of 0.4 for biological post-treatment. The
relative toxicity index with respect to the starting sample was cal-
culated from the change in luminescence of the marine bacterium
Vibrio fisheri. Fig. 22a reveals a very small p-nitrophenol concentra-
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 25

Table 4
Percentage of chemical and TOC removals for selected PEC processes of several organics in undivided cells with TiO2 and composites with TiO2 photocatalyts.

Chemical co (mg L−1 ) Experimental conditions % chemical removal % TOC decay Ref.

4,4 -oxydianiline 0.1a 250 mL of solution with 0.1 M Na2 SO4 , pH 6.0, 92 31 [89]
TiO2 NTs photocatalyst, Eanod = +1.5 V
(Ag/AgCl), 150 W UVA for 180 min
Phenol 9.4 40 mL of solution with 0.1 M Na2 SO4 , pH 6, 95 18 [186]
bifunctional TiO2 NTs and Ni-Sb-SnO2
photocatalyst, Eanod = +2.0 V (SCE), 150 W Xe for
100 min
p-Nitrophenol 200 100 mL of solution with 0.1 M Na2 SO4 , 25 ◦ C, 98 91 [81]
SnO2 /TiO2 NTs photocatalyst, Eanod = +1.5 V
(SCE), 300 W UV for 4 h
p-Nitrophenol 5 60 mL of solution, pH 2, PANI/Cr-TiO2 NTs 99 76c [175]
photocatalyst, Eanod = +0.8 V (SCE), 15 W UVC
for 2 h
Bisphenol A 0.2a 60 mL of solution with 0.1 M NaCl, pH 5, 98 −b [172]
ITO/TiO2 photocatalyst, janod = 0.32 mA cm−2 ,
150 W Xe for 75 min
Bisphenol A 15 160 mL of solution, pH 4.5, 97 −b [86]
TiO2 /graphene/Cu2 O, Eanod = +0.5 V (SCE),
500 W Xe for 150 min
Tetrabromobisphenol A 5 35 mL of solution with 0.5 M Na2 SO4 , Au/TiO2 97 37 [70]
NBs photocatalyst, janod = 20 mA cm−2 , 35 W
visible light for 100 min
Humic acid 25 100 mL of solution with 0.0125 M NaCl, pH 3, 100 83 [169]
Ti/TiO2 photocatalyst, Eanod = +1.0 V (SCE),
450 W Xe for 150 min
Microcystin-LR 1 40 mL of solution with 0.01 M NaNO3 , 92 78 [183]
TiO2 /AgCl/Ag photocatalyst, Eanod = +0.6 V
(SCE), 60 W visible light for 5 h
a
Initial concentration in mM.
b
Not determined.
c
COD decay.

225
a 100 b
200
[p-Nitrophenol] (mg L )
-1

175
80
% TOC removal

150
125 60
100
75 40

50
20
25
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
1.2 5
c d
1.0
4
Relative toxicity index

0.8
BOD /COD

3
0.6
5

2
0.4
1
0.2

0.0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Time (h)

Fig. 22. Change of (a) p-nitrophenol concentration, (b) percentage of TOC removal, (c) biodegradability and (d) relative toxicity index with time for the treatment of 100 mL
of 200 mg L−1 pollutant solution with 0.1 M Na2 SO4 in an undivided cell for 4 h. Method: ( ) PC with Ti/SnO2 , ( ) PC with SnO2 /TiO2 NTs, ( ) EO with TiO2 NTs, ( ) EO
with SnO2 /TiO2 NTs and ( ) PEC with SnO2 /TiO2 NTs. Eanod = +1.5 V (SCE) and illumination with 300 W UV light.
Source: Reproduced with permission from ref. [81].

tion abatement by PC processes with both Ti/SnO2 and SnO2 /TiO2 NTs at the same bias anodic potential in 4 h. The p-nitrophenol con-
NTs photocatalysts [81], which was strongly enhanced by EO at centration decay always obeyed a pseudo-first-order decay. The
Eanod = +1.5 V (SCE), more pronounced for the composite material, same trend can be observed in Fig. 22b for TOC removal, where the
due to the larger generation of • OH via Reaction (10). The addi- most powerful PEC process attained a larger mineralization of 91%.
tional photogeneration of ROS by Reactions (2)–(5) allowed the Under EO and PEC conditions, the biodegradability of the solution
total disappearance of the parent molecule by PEC with SnO2 /TiO2 upgraded to values >0.4, whereas the relative toxicity index was
26 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
reduced to practically zero using these methods with the SnO2 /TiO2
NTs composite. However, low contents of by-products like hydro-
quinone, p-benzoquinone and maleic, fumaric and oxalic acids still
remained in the final solution treated by PEC. These results corrob-
orate the potential applicability of this procedure at industrial level,
being feasible its coupling with a cheaper biological post-treatment
to produce reusable water.
For the PEC process in an undivided cell, optimum Eanod values of
+0.8 V (SCE) for p-nitrophenol with PANI/Cr-TiO2 NTs [175], +1.0 V
(SCE) for p-nitrophenol with TiO2 thin film [167] and dodecyl-
benzenesulfonate with doped W-TiO2 [174], +1.5 V (Ag/AgCl) for
4,4 -oxydianiline with Ti/TiO2 NTAs [89] and +2.0 V (SCE) for phe-
nol with bifunctional TiO2 NTs and Ni-Sb-SnO2 photocatalyst [186],
along with optimum janod = 0.32 mA cm−2 for bisphenol A with
ITO/TiO2 [172], have been found. Moreover, the expected decrease
of the pseudo-first-order rate constant for organic decay and per-
centage of TOC removal with increasing chemical concentration
due to the presence of more organic matter has been confirmed by
several authors [29,44,89,167,174,175]. Similar results have been
described for divided cells [116,169,178]. Selcuk et al. [116,169]
utilized the divided cell of Fig. 12a to degrade 100 mL of 25 mg L−1
humic acid in sulfate or chloride media, contained in the anolyte,
using a Ti/TiO2 photocatalyst exposed to 450 W Xe irradiation. They
found for 0.0125 M NaCl, optimum operation conditions of pH 3 and
Eanod = +1.0 V (SCE) for total pollutant removal with 83% TOC decay
after 150 min of electrolysis (see Table 4), a value quite similar to
that obtained in 0.01 M Na2 SO4 at the same conditions.
The best performance of the PEC process with increasing light
intensity has also been confirmed by Yang et al. [86] from the
decay of the absorbance of the UV band at ␭max = 276 nm of bisphe-
nol A. Fig. 23a and b evidence the large stability of 15 mg L−1 of
this chemical at pH 4.5 upon DP when it was illuminated with
a Xe lamp at 85 and 100 mW cm−2 , respectively. The use of PC
with a TiO2 /Cu2 O mesh caused a notable abatement in bisphenol
A concentration, which was significantly improved by applying a
TiO2 /graphene/Cu2 O mesh due to the effective electron/hole sep-
aration, as shown in Fig. 5. The bisphenol A removal was strongly
upgraded by PEC at Eanod = +0.5 V (SCE), as expected by a greater
extraction of electrons from the CB of Cu2 O enhancing the for-
mation of holes at the VB of TiO2 with higher formation of • OH
radicals from Reaction (2). The removal of this chemical was largely
improved by the production of more quantities of these radicals
upon addition of 50 mM H2 O2 via Reaction (9). Fig. 23b reveals a
97% reduction of bisphenol A after 150 min of PEC (see Table 4),
which decreased to 90 min upon 50 mM H2 O2 addition. Compar-
ison of Fig. 23a and b clearly shows a more rapid destruction of
bisphenol at higher light intensity for both PC and PEC processes
because of the greater photogneration of electron/hole pairs.
It has also been reported the positive action of H2 O2 on PEC
when it was electrogenerated on site at an ACF/PTFE [106] or
boron-doped diamond (BDD) cathode [172] via Reaction (8). With
the latter cathode, for example, the bisphenol A concentration in
60 mL of a 0.2 mM solution in 0.1 M NaCl at pH 5 was reduced
by 98% using an ITO/TiO2 photocatalyst under 150 W Xe light at
janod = 0.32 mA cm−2 for 75 min (see Table 4), whereas the alterna-
tive use of a Zr cathode (no H2 O2 production) only led to 42% of
concentration removal.
4.2.2. Other photoanodes
The effective application of ␣-Fe2 O3 [60], Sb-SnO2 [64], Bi2 WO6
[67,188], WO3 [189] and ZnO [190] semiconductors to the destruc-
tion of phenolic compounds by PEC has also been reported. The
good degradation results obtained for such treatments in undi-
vided cells after long irradiation time with UVA, UVC or Xe lamps
are summarized in Table 5. All these studies described again the
enhancement of PEC performance over individual processes, but
a
1.0
0.8
0.6
0
A/A
0.4
0.2
0.0
0 30 60 90 120 150 180 210 240 270
Time (min)
b
1.0
0.8
0.6
0
A/A
0.4
0.2
0.0
0 30 60 90 120 150 180
Time (min)
Fig. 23. Variation of the relative absorbance decay at ␭ max = 276 nm with elec-
trolysis time for 160 mL of 15 mg L−1 bisphenol A at pH 4.5 under (a) 85 and (b)
100 mW cm−2 Xe illumination. Method: ( ) DP, ( ) PC with TiO2 /Cu2 O mesh,
( ) PC with TiO2 /graphene/Cu2 O mesh, ( ) PEC with TiO2 /graphite/Cu2 O mesh at
Eanod = +0.5 V (SCE) and ( ) PEC with TiO2 /graphite/Cu2 O mesh and 50 mM H2 O2
addition at Eanod = +0.5 V (SCE). Adapted with permission from ref. [86].
little information was given over the optimization of operation vari-
ables. On the other hand, Nissen et al. [189] checked the removal of
60 mL of 40 mg L−1 of 2,4-dichlorophenol in water (without elec-
trolyte) of pH 5.5 in the anolyte of a divided H-cell by supplying
35 W visible irradiation to the immersed WO3 photocatalyst. Since
a very low photocurrent of 7.5 ␮A was applied owing to the low
conductivity of the medium, only 53% of the content of this pollu-
tant was removed after 48 h of treatment.
Phenolic compounds can be directly oxidized at the Bi2 WO6
photocatalyst surface, e.g., at +0.8 V (SCE) for 4-chlorophenol [188],
and hence, a higher Eanod upgrades their direct destruction. The first
step in EO of phenol or chlorinated phenols involves the formation
of a phenoxy radical, which can undergo either radical–radical or
radical–substrate coupling to give polymeric products that remain
adsorbed on the electrode surface and inhibit the process, espe-
cially in alkaline medium where their deprotonated forms are
involved. In contrast, the photogenerated ROS species in PEC can
activate the electrode surface and promote pollutant oxidation.
Fig. 24a shows that the quicker removal of 4-chlorophenol con-
centration at pH 6.5 with Bi2 WO6 exposed to 500 W Xe lamp was
achieved at Eanod = +2.0 V (SCE) [188], where the separation of the
electron/hole pairs was maximal. At higher Eanod values up to +4.0 V
(SCE) the SCL became gradually larger and the photogenerated
electrons were redistributed, facilitating its recombination with
holes and making the process more inefficient. Fig. 24b illustrates
the gradual drop in 2,4-dichlorophenol content abatement for the
above PEC treatment at optimum Eanod = +2.0 V (SCE) when pH var-
ied from an alkaline medium of pH 8.5 to an acidic one of 4.3
[188]. This behavior can be related to a progressive larger adsorp-
tion of the molecule that favors its reaction with oxidizing agents
formed at the photoanode surface, although the smaller forma-
tion of inhibitory polymeric films with decreasing pH could also
contribute to the better efficiency of the process in acidic medium.
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 27

Table 5
Per cent of chemical and TOC removals for selected PEC treatments of phenols using undivided cells with other photocatalytic materials.

Chemical co (mg L−1 ) Experimental conditions % chemical removal % TOC decay Ref.

Phenol 20 100 mL (without electrolyte), SnO2 -Sb2 O4 100 85 [64]

photocatalyst, Ecell = 2.0 V, 250 W UVA for 2 h
Phenol 10 15 mL of solution with 0.5 M Na2 SO4 , Bi2 WO6 78 65 [67]
photocatalyst, Eanod = +0.6 V (SCE), 500 W Xe for
3h
p-Nitrophenol 0.1a 50 mL of solution with 0.1 M Na2 SO4 , pH 3.0, 91 74b [190]
ZnO photocatalyst, Eanod = +1.4 V (SCE), 15 W
UVC for 3 h
p-Nitrophenol 0.05a 50 mL of solution with 0.1 M Na2 SO4 , ␣-Fe2 O3 47 −c [59]
photocatalyst, Eanod = +1.0 V (SCE), 300 W
visible light for 4 h
4-Chlorophenol 10 100 mL of solution with 0.5 M Na2 SO4 , pH 4.3, 68 65 [188]
Bi2 WO6 photocatalyst, Eanod = +2.0 V (SCE),
500 W Xe for 12 h
a
Initial concentration in mM.
b
COD decay.
c
Not determined.

60 4.3. Pharmaceuticals
a
50 Despite the social alarm over the presence of pharmaceu-
% 4-chlorophenol removal

ticals in the aquatic environment, their feasible degradation

40 by PEC has only been assessed for few compounds in the
last years [37,81,88,107,191–200]. The trials were pre-eminently
30 made with TiO2 photoanodes, although composites with TiO2
[81,191,198,199] and new Ti compounds [88] have been utilized as
20 well. Table 6 summarizes the percentages of drug and TOC decays
achieved by this technique for some compounds under selected
10 conditions using undivided cells with TiO2 thin-film and NTs photo-
catalyst. As seen previously, UVA, UVC and Xe lamps were applied to
0 treat the solutions. Low drug concentrations (usually ≤ 20 mg L−1 )
0 1 2 3 4 5
were used to check the oxidation ability of the technique and good
E (V vs. SCE)
anod per cent of drug removals (regularly >80%) were obtained for times
12 longer than 1 h.
b Most authors confirmed the expected larger oxidation ability
10 of PEC to remove drugs over individual processes. The effect of
[4-Chlorophenol] (mg L )
-1

some operation variables such as pH [37,192,196–198], applied

8 Eanod or I [192,196–198] and drug [37,196–198] and electrolyte
[197] concentrations over the process performance was assessed.
6 The kinetics for drug decay [37,88,191,192,196,197], the detection
of oxidation products [37,107,191,198], the drop in toxicity during
4 treatment [37,107,196], economical assessment [37,191] and even
the use of scavengers [197,199] has been reported as well.
2 An interesting work of Daghrir et al. [37] showed that the
optimum PEC treatment of 1 L of 0.025–0.230 mg L−1 chlortetra-
0 cycline solutions in 0.050 M Na2 SO4 took place at pH close to 6,
0 3 6 9 12 15
at I = 0.39 A under 6.9 mW cm−2 UVC irradiation using the arrange-
Time (h) ment of Fig. 11a with a vitreous carbon cathode as compared to
stainless steel, graphite and amorphous carbon ones. Under these
Fig. 24. (a) Percentage of 4-chlorophenol removal vs. anodic bias potential for the
degradation by PEC of 100 mL of 10 mg L−1 organic solution with 0.5 M Na2 SO4 at pH conditions, 98% drug decay and 67% TOC removal after 120 min of
6.5 using an undivided cell like of Fig. 9a with a Bi2 WO6 photoanode under 500 W Xe treatment of a 0.025 mg L−1 solution were obtained (see Table 6),
light for 8 h. (b) 4-Chlorophenol content decay with electrolysis time for the above with similar values in the concentration range tested and an esti-
solution at pH: ( ) 8.5, ( ) 6.5 and ( ) 4.3 and Eanod = +2.0 V (SCE). mated cost of 4.52 US$ m−3 for chemicals plus energy consumption
Source: Reproduced with permission from ref. [188]. [37,193]. The superiority of the vitreous carbon cathode was related
to its ability to produce H2 O2 from Reaction (8), which can be
photolyzed to OH by UVC from Reaction (29), thus enhancing the
Fao et al. [190] found a 91% pollutant reduction with 74% organics removal from • OH generated by Reaction (2).
COD removal after 3 h of PEC treatment of 50 mL of a 0.1 mM p-
nitrophenol solution in 0.1 M Na2 SO4 with a ZnO photocatalyst H2 O2 + hv → 2 • OH (29)
upon 15 W UVC illumination at optimum Eanod = +1.4 V (SCE) and The authors reported a strong reduction of the toxicity of the
pH 3.0 (see Table 5). When the p-nitrophenol concentration grew 0.025 mg L−1 solution after optimum treatment during 120 min
up to 0.5 mM, a gradual loss in its abatement up to 33% was obtained from microtox and microalga tests. Moreover, the primary oxi-
as a result of the larger organic matter treated with similar quan- dation products were detected by LC–MS proposing the reaction
tities of oxidants photogenerated. A pseudo-first-order kinetics for sequence of Fig. 25 [37]. The degradation of chlortetracycline
all concentration decays was always determined. (1) under the main action of OH is initiated by the formation
28 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

Table 6
Per cent of drug and TOC removals for selected PEC treatments of pharmaceuticals using undivided cells with TiO2 photoanodes.

Drug co (mg L−1 ) Experimental conditions % drug removal % TOC decay Ref.

Chlortetracycline 0.025 1 L of solution with 0.05 M Na2 SO4 , 25 ◦ C, pH 98 67 [37]

near 6, I = 0.39 A, 6.9 mW cm−2 UVC for
120 mina
Chlortetracycline 25 1 L of solution with 0.05 M Na2 SO4 , pH 4.8, 74 −c [193]
25 ◦ C, I = 0.39 A, 6.9 mW cm−2 UVC for 120 mina
Tetracycline 10 500 mL of mixed solution with 0.1 M Na2 SO4 , 81 −c [192]
Oxytetracycline 10 pH 7.4, Eanod = +1.0 V (SCE), 15 W UVA for 83 −c
Chlortetracycline 10 180 minb 85 −c
Triclosan 20 50 mL of solution with 0.02 M Na2 SO4 , pH 5.8, 79 60 (1 h) [107]
Eanod = 0 V (SCE), 125 W UVC for 30 minb
Acyclovir 20 0.1 mL of solution with 0.2 M NaNO3 in a 97 −c [194]
thin-layer reactor, pH 5.8, Eanod = +1.0 V
(Ag/AgCl), 10 mWcm−2 UVA for 370 sb
Ofloxacin 40 70 mL of solution with 0.1 M Na2 SO4 , pH 3.0, 100 70 [196]
Eanod = +0.8 V (SCE), 15 W UVC for 35 minb
Sulfamethoxazole 1.3 50 mL of solution with 10 mM NaCl, pH 2.7, 100 − c
[197]
Eanod = +0.5 V (Ag/AgCl), 4 W UVA for 150 mina
Diclofenac 5 80 mL of solution with 0.1 M Na2 SO4 , 100 −c [200]
Eanod = +0.4 V (SCE), 35 W Xe for 10 hb
a
TiO2 thin film.
b
TiO2 NTs.
c
Not determined.

of six derivatives: isochlortetracycline (2) by dechlorination, epi-
demeclocycline (3) and 4-epi-N-demethylchlortetracycline (4) by
demethylation, 4-epi-N-dedismethylchlortetracycline (5) by the
loss of two methyl groups, isochlortetracycline (6) with forma-
tion of a 5-ring heterocycle and its hydroxylated product 7. Further
hydroxylation, demethylation or dedismethylation of 7 yields the
compounds 8, 9 and 10, respectively.
Optimum degradation for this antibiotic and its mixture with
other tetracyclines in the pH range 6–9 has also been reported
by Liu et al. [192], whereas acidic media of pH 1–3 were found
optimal for the oxidation of ofloxacin [196,198] and sulfamethox-
azole [197]. The best performance of chlortetracycline at neutral
pH was explained from the higher electrostatic attraction between
its zwitterionic form and the positively charged surface of Ti/TiO2
[37].
The decay of chlortetracycline [37,192] and sulfamethoxazole
[197] was analyzed from a kinetic equation involving a Langmuir-
Hinshelwood model that presupposes a rapid adsorption of the
molecule at the photocatalyst surface and the limiting step is the
subsequent transformation of the adsorbed species. This model
was found valid for relatively high drug concentrations, but it was
reduced to a pseudo-first-order equation at low contents. The lat-
ter equation has been directly applied to explain the abatement of
ciprofloxacin [88], paracetamol [191] and ofloxacin [196].
The reduction of toxicity of the treated solution by PEC is due to
the destruction of the parent molecule and its oxidation products.
This was clearly shown by Liu et al. [107] for the oxidation of 50 mL
of 20 mg L−1 of the bactericide triclosan in 0.02 M Na2 SO4 at natu-
ral pH 5.0 using an undivided cell with a Ti/TiO2 NTs photocatalyst
at Eanod = 0 V (SCE) under 125 W UVC light for 60 min. They deter-
mined the solution toxicity from the luminescent Photobacterium
phosphoreum T3 spp. bacterium, expressed as equivalent HgCl2 con-
tent. The toxicity was largely reduced during the first 10 min of PEC
due to the loss of the toxic triclosan. Further, it was increased up
to 30 min where it reached a quasi-steady value owing to the for-
mation of the more toxic intermediate 2,7-dichlorodibenzodioxin,
which was degraded more slowly than the parent molecule to be
completely mineralized.
The addition of scavengers to the solution has demonstrated
the generation of oxidizing species in PEC. Fig. 26a exemplifies
the abatement of the normalized sulfamethoxazole concentration
when 50 mL of 2.4 mg L−1 of this antibiotic in 10 mM NaCl of pH 2.7
was degraded in an undivided cell with a Ti/TiO2 thin-film photo-
catalyst by applying Eanod = +0.5 V (Ag/AgCl) exposed to 4 W UVA
light [197]. After 80 min of PEC treatment, the sulfamethoxazole
content dropped to 72%, which was reduced to 60% or 12% by adding
2.4 mg L−1 humic acid or 10% methanol, respectively. The two lat-
ter compounds are well-known scavengers of generated ROS and
active chlorine species and then, it react more rapidly with these
oxidants diminishing the destruction rate of the antibiotic. The
decrease of the corresponding pseudo-first-order rate constant is
depicted in Fig. 26b. This figure also reveals a photocurrent density
near 0.14 mA cm−2 for the systems with sulfamethoxazole alone
or humic acid added, but it underwent an unexpected spectular
growing to 0.46 mA cm−2 by adding 10% methanol. The excep-
tional enhancement of the photocurrent density in the presence of
methanol was justified by current doubling that refers to the release
of additional electrons from reactive solute-hole intermediates. It
was hypothesized the oxidation of a methanol molecule by a hole
to produce a methoxy radical (CH3 O• ) by Reaction (30), followed
by the oxidation of this radical to formaldehyde with release of
one electron by Reaction (31). Nevertheless, more information is
needed to confirm this assumption.
CH3 OH + h+ VB → CH3 O• + H+ (30)
+ −
CH3 O• → CH2 O + H + e CB (31)
4.4. Real wastewaters
The remediation of a very limited number of real wastewaters by
PEC has been investigated at lab-scale using several photocatalysts
upon exposure to UV and visible lights. Good color removal and/or
COD abatements at relatively short times have been found for river
water contaminated with humic acid using Ti/TiO2 thin film [201],
sugarcane factory wastewater using ZnO and doped N-ZnO [202],
pharmaceutical wastewater using Ni/TiO2 thin fim [203], landfill
leachate using codoped Cu/N-TiO2 [205] and textile wastewaters
using Ti/TiO2 thin film decorated or not with Pt [204] and Ti/TiO2
NTs [206]. Relevant results of some of these works are listed in
Table 7. These data encourage for a further intense research to show
the benefits of PEC for treating many real wastewaters in order to
develop a powerful technology at industrial level.
Operation variables were optimized in some cases. For example,
Fang et al. [203] degraded 500 mL of a pharmaceutical wastewa-
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35 29

H3C CH3 H3C CH3

OH N Cl OH N
CH3
OH OH

O O
OH OH
OH O OH O NH2 OH O OH O NH2
2 3

H3C CH3 H3C

Cl OH NH2 Cl OH N Cl OH NH
CH3 CH3 CH3
OH OH OH

O O O
OH OH OH
OH O OH O NH2 OH O OH O NH2 OH O OH O NH2
5 1 4

H3C CH3
Cl H3C N
OH H3C CH3
Cl H3C N
O OH
O
O
OH O
OH O OH O NH2
HO OH
6
OH O O O NH2
7
H3C CH3
Cl H3C N Cl H3C NH2
O OH
O O O
O
HO OH NH2 HO OH
OH H3C
OH O O O Cl H3C NH OH O O O NH2
8 OH 9
O
O
HO OH
OH O O O NH2
10
Fig. 25. Proposed reaction sequence for chlortetracycline degradation by PEC process using the arrangement of Fig. 11a with TiO2 thin-film photocatalyst upon 6.9 mW cm−2
UVC irradiation at 0.39 A. Adapted with permission from ref. [37].

Table 7
Per cent of color and COD removals for selected PEC treatments of real wastewaters using undivided reactors with different photoanodes.

Wastewater COD0 (mg L−1 ) Experimental conditions % color removal % COD decay Ref.

Pharmaceutical 3150 500 mL, 0.5 M NaCl, pH 3.0, Ni/TiO2 78 93 [203]

photocatalyst, Ecell = 10 V, 250 W UVA for 2 h
Landfill leachate 4378 500 mL, pH 2, 30 ◦ C, Cu/N-TiO2 photocatalyst, −a 69 [205]
Ecell = 20 V, 50 W visible light for 210 min
Textile effluent 153 8.5 L, pH 3, 2.9 g L−1 O3 , cylindrical Ti/TiO2 NTs 98 33 [206]
photocatalyst, Ecell = 2.0 V, 100 W UVB for
60 min
a
Not determined.

ter with COD0 = 3150 mg L−1 of pH 5.8 in an undivided cell similar
to that of Fig. 9a equipped with a photocatalyst composed of a
Ni foam coated with TiO2 thin film and a cathode formed by
MnO2 and multi-walled carbon nanotube composite. Air injection
ensured additional • OH generation from MnO2 reduction at the
cathode during the EO and PEC processes and 250 W UVA was
irradiated on the photocatalyst in PC and PEC. The best PEC condi-
tions were obtained by applying an Ecell = 10 V and operating with
0.50 M NaCl and pH 3.0, showing the positive influence of the active
chlorine species produced. Under these conditions, a loss of COD
of 93%, much greater than 79% of color, was found for PEC (see
Table 7), values much higher than 66% and 53% for EO and 43% and
30 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35

1.2
a
1.0

0.8
0
c/c

0.6

0.4

0.2

0.0
0 10 20 30 40 50 60 70 80 90
Time (min)
0.025 0.50
b

Photocurrent density (mA cm )

0.45
0.020
0.40

0.35
(min )

0.015
-1

0.30
dapp

0.010 0.25
k

0.20
0.005
0.15
-2

0.000 0.10
1 2 3
Treatment

Fig. 26. (a) Relative sulfamethoxazole concentration decay with time for the PEC
treatment of 50 mL of several antibiotic solutions in 10 mM NaCl of pH 2.7 using
an undivided cell with Ti/TiO2 thin-film photocatalyst at Eanod = +0.5 V (Ag/AgCl)
under 4 W UVA light. (b) Apparent rate constant and photocurrent density for the
same trials. Treatment: ( ,1) 2.4 mg L−1 sulfamethoxazole, ( ,2) 2.4 mg L−1 sul-
famethoxazole + 10 mg L−1 humic acid and ( ,3) 2.4 mg L−1 sulfamethoxazole + 10%
methanol. Adapted with permission from ref. [197].
Fig. 27. (a) Scheme of the annular bubble reactor developed for the degradation
of a real textile wastewater by direct ozonation (DO), DP, PC and PEC processes.
1: reactor glass wall; 2: gas inlet; 3: sintered glass diffusers for injecting O2 /O3 ;
4: rubber tip; 5: glass tube to accommodate the UVB 100 W lamp; F: cylindrical
TiO2 NTs; G: DSA used as cathode. (b) Electrical energy per order after 60 min of
the different treatments at pH 3 and 8 by injecting O3 at 2.9 g h−1 . Adapted with
permission from ref. [206].

59% for PC, demonstrating again the superiority of PEC over indi-
vidual processes. For a landfill leachate with COD0 = 4378 mg L−1 ,
ate ions, despite the production of • OH and other ROS from O3
TOC0 = 2583 mg L−1 and a very low BOD5 /COD = 0.01 of pH 7.8, Zhou
decomposition in alkaline medium:
et al. [205] studied the degradation by PEC of 500 mL wastewaters
in a cell like of Fig. 9a with a codoped Cu/N-TiO2 photoanode and O3 + OH− → • OH + (O2 •− ↔ HO2 • ) (32)
a graphite cathode, but without air injection. An outside 50 W vis-
For DO and coupled DP/O3 , PC/O3 and PEC/O3 trials, a compara-
ible light was utilized to illuminate the catalyst and pH 2, 30 ◦ C
tive energetic study was made from the electrical energy per order
and Ecell = 20 V were found as optimum operation variables, lead-
of magnitude consumed during 60 min, defined as follows:
ing to the best COD reduction of 69% in 210 min (see Table 7).
These authors also proposed a doubtful dynamic kinetic model to Electrical energy per order (kWh m−3 order−1 )
explain the COD decay rate as a function of COD, Ecell and pH, from
1000P t
which an activation energy of 63.5 kJ mol−1 for the process was = (33)
Vs log (color0 /color f )
estimated.
A more recent paper of Cardoso et al. [206] compared the degra- where P stands for the rated power (in kW) of the oxidation
dation of a real textile wastewater with color0 = 1080 mg Pt/Co L−1 system, t is the treatment time (in h), Vs denotes the treated vol-
and COD0 = 153 mg L−1 by direct ozonation (DO), DP, PC and PEC. ume (in L) and color0 and colorf mean the initial and final color
Additionally, the latter three processes were combined with ozone. measurements in Pt/Co units. As expected, Fig. 27b makes in evi-
Fig. 27a presents the 4 annular reactors used by bubbling O2 or O3 . dence an enhancement of this energetic parameter in the order:
The solution volume was 12 L for DO and 8.5 L for the other three DO < DP/O3 < PC/O3 < PEC/O3 , with greater values at pH 8 than at
photoassisted treatments due to the volume occupied by the inside pH 3. These differences may be cancelled by using free sunlight
100 W UVB lamp with ␭max = 315 nm. The PEC process was per- and solar photovoltaic panels, for example, to power the electrical
®
formed with a Ti/TiO2 NTs photoanode and a DSA cathode with devices, which need to be taken into account in the next future to
an optimum Ecell = 2.0 V. Poor color removal of 32%, 42% and 55%, design competitive PEC systems for wastewater remediation.
with scarce COD removal, was obtained by DP, PC and PEC by bub-
bling O2 at acidic pH 3 for 60 min, whereas 98% color decay with 5. Conclusions and prospects
33% COD abatement was found for DO at 2.9 g h−1 O3 flow rate.
When ozonation was coupled to the photoassisted processes, sim- Over the last 15 years, the potential applicability of PEC as
ilar results were always obtained. A slightly slower performance an emerging EAOP to the remediation of wastewaters containing
was obtained at pH 8 due to the presence of scavengers bicarbon- toxic and/or biorefractory organic pollutants has been well-proven.
 S. Garcia-Segura, E. Brillas / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 31 (2017) 1–35
It appears as one of the most highly promising water treatment
technologies to deal with recalcitrant organic contaminants pol-
lution in water streams. The development of this technology has
been feasible thanks to the preparation of many novel semiconduc-
tors such as nanostructured, doped and composite TiO2 materials
with ability enough to absorb more light intensity and/or expand
their photoactivity to the visible region compared with UV lamps
used to illuminate classical TiO2 thin-film, WO3 and ZnO photoan-
odes, initially checked for an effective separation of photogenerated
electron/hole pairs. PEC systems have been designed at lab-scale,
usually being composed of tank reactors or flow cells with two- or
three-electrodes, upon illumination of the photoanode with inter-
nal or external UVA, UVC, visible and/or Xe lamps. Good removal of
color or initial substrate with smaller COD or TOC abatement were
generally obtained for synthetic wastewaters containing dyes, typ-
ical industrial chemicals and pharmaceuticals. Nevertheless, low
organic loads with long treatment times were tested because of
the low generation of oxidizing ROS due to the small photocur-
rent produced. The superiority of PEC over individual processes was
well-demonstrated in many cases. The effect of operation variables
like pH, applied Eanod or janod , kind and concentration of electrolyte,
pollutant concentration and temperature on the degradation per-
formance of synthetic effluents was also analyzed to ascertain the
optimum PEC conditions. The decay of low pollutant concentrations
usually obeyed a pseudo-first-order kinetics, but high contents fol-
lowed an adsorption Langmuir-Hinshelwood model in some cases.
Scarce studies have been devoted to the detection of oxidation
products formed, the changes of toxicity and biodegradability, and
the estimation of the energy costs of the PEC process. An enhance-
ment of the oxidation ability of PEC was found for coupled PEC/O3 ,
PEC/EF and PEF/SPEF systems. Promising good loses of color and
COD have been described for few real wastewaters by PEC and
PEC/O3 processes.
On the basis of the present available data, more fundamental
research is still needed to develop a mature PEC technology with
perspectives to treating real wastewaters at industrial scale in the
next future. It seems necessary to continue searching novel photo-
catalysts with enhanced photoactivity under sunlight irradiation to
improve the actual photoefficiencies and PEC performance on pol-
lutants abatement. These materials should be coupled to suitable
reactors in pilot plants to show the viability of PEC degradation over
real wastewaters for its further scale-up to industrial level. The effi-
cient design of novel photoelectrochemical reactors will become a
future challenge to the scientist and engineers, since these reactors
should embody the photocatalytical requirements in electrochem-
ical reactors. In these systems, the use of free sunlight to illuminate
the photoanodes, along with renewable energies such as photo-
voltaic or wind devices to power the electrical instruments, should
be designed to have a competitive process with minimum cost
requirements for wastewater remediation. This point is highly fea-
sible due to the lower energy requirement of PEC systems as far
as we know. Since no overall removal of the organic pollutants is
expected, viability trials with pilot plants should include at least: (i)
the optimization of color reduction and COD and/or TOC removal of
the treated effluent and (ii) the assessment of the decay in toxicity
and the enhancement of biodregradability during the degradation
process. Coupling or combination with other powerful oxidation
techniques could also be investigated in order to develop treat-
ments with higher oxidation power of the organic load. It can then
be envisaged that if the biodegradability of a given industrial efflu-
ent can be enhanced up to values >0.4 with an adequate single
or coupled PEC process, the resulting wastewater could be post-
treated by a biological process, suitable for high volumes of water,
before disposal to the public sewage or reuse in human activities
such as agriculture or industrial manufacture of goods.
31
Acknowlegments
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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