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Catalytic use of TiO 2 nanowires in the photodegradation of Benzophenone-4

as an active ingredient in sunscreens

Article in Journal of Environmental Management · July 2019

DOI: 10.1016/j.jenvman.2019.07.005

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Journal of Environmental Management

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Research article

Catalytic use of TiO2 nanowires in the photodegradation of Benzophenone-4 T

as an active ingredient in sunscreens
Loraine Soto-Vázqueza, Frankie Rolón-Delgadoa, Keila Riveraa, María C. Cottoa, José Ducongéa,
Carmen Morantb, Sergio Pinillab, Francisco M. Márquez-Linaresa,*
a
Nanomaterials Research Group, School of Natural Sciences and Technology, Universidad Ana G. Méndez-Gurabo Campus, PR, 00778, USA
b
Department of Applied Physics and Instituto Nicolás Cabrera, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: Water contamination has compromised the quality of this resource during the last years with the presence of
TiO2 persistent organic pollutants. Because of the resistance of these compounds to degradation, several advance
Photocatalysis oxidation techniques have been proposed. In this study, we report the employment of an advance oxidation
Benzophenone-4 technique in the degradation of benzophenone-4 (BP-4), using TiO2 as catalyst, which was obtained following a
Sunscreen
fast-hydrothermal method. TiO2 nanowires (TiO2NWs) were fully characterized considering the morphology,
Hydrothermal synthesis
elemental composition, oxidation states, vibrational modes and crystalline structure with SEM and TEM, EDS,
XPS, FTIR and XRD, respectively. The photocatalytic degradation was carried out using a home-made photo-
reactor under slightly acidic conditions achieving an average of 90% removal. It was determined that the
photocatalysis is the most probable route of degradation since the photolysis or catalysis procedures produce
negligible contributions. An apparent kinetic constant of 1.29 × 10−2 min−1 was determined, according to a
pseudo-first order reaction.

1. Introduction
Water is the most fundamental resource for the humankind survival.
It is set as a global priority since its quality affects our education,
economy and health (Cronk et al., 2015). Despite our planet composi-
tion the water scarcity has spread worldwide due to the unsuitable
available forms of it. Constantly the public health is threatened by
water pollution, since hundreds of persistent organic pollutants (POPs)
and pharmaceutical and personal care products (PPCPs) are released at
elevated rates that have led to their detection in waters (Celeiro et al.,
2018; Abdelraheem et al., 2016). The PPCPs are products that are
present in almost every community since it includes, lotions, cosmetics
and sunscreen products (Zhou et al., 2013; Soto-Vázquez et al., 2016).
Because of their multiple uses and variety of forms these compounds
enter the aquatic environment directly or indirectly from recreational
activities or bathing (Richardson and Ternes, 2014).
Recently was demonstrated that sunscreens, mostly benzophenone-
types, are polluting the urban ground waters (Jurado et al., 2014). Most
of the benzophenone-types of UV-filters are insoluble in water; how-
ever, benzophenone-4 (BP-4) is an exception. BP-4 is an organic pol-
lutant that is very resistant to degradation and now is been detected in
rivers, sea, treated effluents of wastewaters, swimming pools and re-
creational ponds (Rodil et al., 2008; Grabicova et al., 2013). Few stu-
dies are available regarding the effect of BP-4 in organisms; however, it
is known that BP-4 led to the alteration of gene expression of adult
males of zebra fish (Zucchi et al., 2011). This organism showed several
limitations when compared to mammals. However, this organism has
been employed as a powerful biomaterial in multiple research areas.
Moreover, it has been reported that drugs showed similar effects on
zebra fish and mammalian systems. (Lin et al., 2016). The negatively
effect of BP-4 in zebrafish, and the fact that this organism is similar to
mammalian organisms urges the research to remove this compound
from our water sources.
Most of the known procedures of remediation are unsuitable for the
removal of BP-4 due to the fact that this compound is water soluble.
Furthermore, due to the resistance of BP-4 to traditional remediation
techniques, more sophisticated techniques such as Advanced Oxidation
Processes (AOPs) are desirable (Teh and Mohamed, 2011;
Krishnakumar and Swaminathan, 2011). AOPs are a group of methods
that have the ability to oxidize organic substances by generating •OH
radicals. In recent years, the AOPs have experienced a tremendous in-
terest due to the fact that they are considered a real alternative to

*
Corresponding author.
E-mail address: fmarquez@suagm.edu (F.M. Márquez-Linares).

https://doi.org/10.1016/j.jenvman.2019.07.005
Received 23 April 2019; Received in revised form 6 June 2019; Accepted 4 July 2019
0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
L. Soto-Vázquez, et al.
traditional remediation techniques.
Photocatalysis, as an AOP, is an alternative remediation method
that provides major advantages, such as offering a good-substitute for
conventional methods of intensive use of energy; or capability to de-
grade the pollutants in contrast to conventional methods that only
transfer from one medium to other (Kabra et al., 2004). The photo-
catalysis has been proved to be efficient in the degradation of anti-
biotics, azo dyes, and drugs of abuse in aqueous media (Elmolla and
Chaudhuri, 2010; Sobana et al., 2013; Kuo et al., 2015). Several
semiconductors have been proposed as efficient catalysts for these
processes such as ZnS, Fe3O4, and TiO2. The latter is widely used be-
cause it is a low cost, stable and naturally benign catalyst (Liu et al.,
2016; Hu et al., 2015). With band gap energy of 3.0 eV for rutile phase,
TiO2 has been employed in the photocatalytic degradation of toxic,
chloroaromatic compounds, and antibiotics (Zhang et al., 2011; Yang
et al., 2010; Lu et al., 2011; Zhu et al., 2013).
In a recent study, the aerobic biodegradation of BP-4 was evaluated
(Beel et al., 2013). The authors concluded that the pollutant remains
almost constant during the first five days of treatment. Our hypothesis
is that BP-4 could be degraded in less time and the efficiency of the
process could be improved by a photocatalytic route. Addressing the
degradation by this approach will permit the reaction to be led by
oxygen radicals that are extremely reactive and non-specific to organic
compounds. This non-specificity of the reaction is helpful in order to
achieve the degradation of the parent compound and the by-products
formed. Unfortunately, very little is known about this procedure and far
less is known about BP-4 as a potential organic pollutant in water
sources. Because of this, studies are necessary to understand the
chemistry, the reaction kinetics, and how the parameters involved in
the process affect the photocatalysis.
The objectives of this research were to obtain shape-controlled TiO2
through a hydrothermal synthetic procedure. Since is of general
knowledge that TiO2 exhibits high photocatalytic performance, the as-
synthesized nanowires were employed in the degradation of BP-4. Also,
as part of our research objectives we evaluated several parameters in
order to establish the most probable conditions for the optimal catalytic
degradation. The synthesized material was characterized by Scanning
Electron Microscopy (SEM), Field Emission Scanning Electron
Microscopy (FE-SEM), Transmission Electron Microscopy (TEM),
Energy Dispersive Spectrometry (EDS), X-Ray Photoelectron
Spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR)
and X-Ray Diffraction (XRD). The synthesized material was then used to
degrade BP-4 under optimal experimental conditions in the minimum
possible reaction time.
2. Experimental methods
2.1. Reagents
All the reagents were used as received, without further purification.
The reagents used for the synthesis of TiO2NWs were provided by Acros
Chemicals, and consisted of acetone, isopropyl alcohol 99.9%, TiCl4
99.9% and HCl 37%. Si wafers (Si < 100 > , 300 μm thickness, p-type,
single-side polished), provided by EL-CAT Inc., were used for the
growth of TiO2NWs. For the photocatalytic experiments, hydrogen
peroxide 50%, and NaOH ≥97% were obtained from Fisher Scientific.
5-Benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid (BP-4) ≥97%
was provided from Sigma Aldrich. In addition, Whatman 0.45 μm syr-
inge filters were used to follow the degradation of BP-4. All the ex-
perimental solutions were prepared using ultra pure water (Milli-Q
water, 18.2 MΩ cm−1 at 25 °C).
2.2. Synthesis of TiO2NWs
The synthetic procedure of TiO2NWs has been discussed in our
previous work (Soto-Vázquez et al., 2016; Pinilla et al., 2018).
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Journal of Environmental Management 247 (2019) 822–828
Typically, Si < 100 > substrates were rinsed with isopropyl alcohol,
water and acetone, and dried at 60 °C before used. TiO2NWs were ob-
tained by a hydrothermal method. For this, a HCl 35%:H2O (1:1, v/v)
solution was prepared and magnetically stirred. Then, the titania pre-
cursor (TiCl4) was added dropwise, and the reaction was kept under
stirring for 15 min. The solution was transferred to a Teflon liner and
placed into stainless steel autoclaves. Si < 100 > substrates were
placed inside the Teflon liner and the autoclaves were closed tightly
and placed in an oven for 2 h at 180 °C. The autoclaves were opened
once they reached room temperature and the obtained product was
thoroughly rinsed with deionized water and dried at 60 °C overnight,
and finally stored until further use.
2.3. TiO2NWs characterization
The as-synthesized TiO2NWs were characterized by Scanning
Electron Microscopy (SEM), using a JEOL JSM6010LV. A Philips XL30
S-FEG field emission electron microscope (FE-SEM), and a JEOL 300
high-resolution transmission electron microscope (HRTEM) were also
used. The presence of the TiO2 was determined by Fourier-Transform
Infrared (FTIR) Spectroscopy, using a Bruker Tensor 27 equipped with
an ATR diamond crystal accessory. Afterwards the TiO2NWs crystalline
structure was characterized by X-ray diffraction (XRD), in Theta/2
Theta configuration in the range of 20–60°, at 2 °min−1, using a Rigaku
Smart Lab III at 40 kV and 44 mA. The elemental composition of the as-
synthesized TiO2NWs was determined using a Genesis 2000 Energy
Dispersive Spectrometer (EDS) operating at 20 kV. X-ray photoelectron
spectra (XPS) were carried out on a PHI Quantum 2000 (Physical
Electronics) with monochromatic Al Kα radiation (1486.6 eV), at a pass
energy of 117.40 eV (for survey analysis), and 58.70 eV (for multiplex
analysis). All binding energies were corrected according to the C1s
hydrocarbon peak at 284.8 eV. The specific surface area was obtained
according to the Brunauer–Emmett–Teller (BET) method, using a
Micromeritics ASAP2020 sorption analyzer.
2.4. Photocatalytic experiments
To evaluate the catalytic activity of TiO2NWs in the degradation
process of BP-4, a homemade photoreactor was built, and described in
our previous research (Soto-Vázquez et al., 2016). This photoreactor is
composed of several light bulbs and mirrors surrounding the place
where the reaction is occurring. According to previous experiments the
reactions were studied at pH 5, and then different amounts of the cat-
alyst (TiO2NWs) were added. After adding the catalyst and setting the
pH, the system was kept in the dark for 30 min in order to let the system
reach the adsorption-desorption equilibrium. Then, a small amount of
H2O2 was added, and the system was exposed to air bubbling. The
lightbulbs were switched on, and the photocatalytic system was main-
tained under constant stirring and irradiation. The reaction was mon-
itored during a period of 180 min, and the kinetic of the photo-
degradation was studied by taking aliquots periodically. After filtering
the aliquots with 0.45 μm membrane filters, the samples were analyzed
with a Shimadzu UV-2401PC spectrophotometer.
3. Results and discussion
3.1. Synthesis and characterization of TiO2NWs
The TiO2NWs obtained consisted of white flakes grown over the
Si < 100 > substrates (see Fig. 1A and B). These nanowires began to
grow from the first 30 min of reaction as single wires, and then connect
to each other (Fig. 2A). After 45 min of exposure and reaction, the
branched structure begins its organization (Fig. 2B). After 2 h of the
synthetic procedure the grown nanowires consisted of very homo-
geneous wires in shape and size. At higher magnifications (see Fig. 2C
and D) is observed the branching level of the TiO2NWs, which can
L. Soto-Vázquez, et al. Journal of Environmental Management 247 (2019) 822–828

Fig. 1. TiO2NWs obtained by a hydrothermal procedure. (A) TiO2NWs grown over the Si < 100 > surface; (B) flakes after being removed from the substrate at 100X
magnification.

explain the unexpectedly high surface area obtained of 512 m2 g−1.
Also, is noticed that each nanowire is composed of narrower wires. As
can be observed in the TEM image (see Fig. 2F) each single nanowire
consisted of 10–20 nm in diameter and several hundreds of nm in
length.
TiO2NWs showed the expected elemental composition of mainly Ti
and O. The EDS spectrum showed the presence principally of Ti-K, and
O-K transitions, corresponding to TiO2 (see Fig. 3A). Also, it was no-
ticed a minimal contribution of Cl-K, attributed to the presence of
chlorine during the reaction of the synthesis (from HCl and TiCl4). In
the EDS analyses no foreign elemental signal was detected, suggesting
the elemental purity of the synthesized TiO2NWs. Similar results were
obtained by XPS analysis. Fig. 3B shows the XPS survey spectrum, with
noticeable photoelectron energies for Ti and O, and weak signals for C
and Cl, below 600 eV. The photoelectron peaks of Ti 2p, with main
binding energies at ca. 458.3 and ca. 463.9 eV, have been identified as
Ti 2p3/2 and Ti 2p1/2, respectively, for Ti(IV) species, characteristic of
TiO2 (Raja et al., 2006; Tan et al., 2014). Furthermore, by deconvolu-
tion of the peaks, additional signals were noticed at 459.0 eV and
464.8 eV (see Fig. 3CDC). The signal at 459.0 eV has been previously
ascribed to Ti species with oxygen vacancies; this result suggests the
additional presence of Ti(III) (Bharti et al., 2016; Tan et al., 2014).

Fig. 2. SEM images of TiO2NWs after different stages of growth: (A) after 30 min of reaction (15,000X); (B) after 45 min of reaction (12,000X); (C) TiO2NWs
completely formed after 2 h (10,000X); (D) TiO2NWs at 35,000X; (E) FE-SEM image of the TiO2NWs at 200,000X and; (F) TEM of the as-synthesized TiO2NWs.

824
L. Soto-Vázquez, et al. Journal of Environmental Management 247 (2019) 822–828

Fig. 3. Elemental characterization of the TiO2NWs. (A) EDS spectra; (B) XPS survey; (C) Ti2p multiplex; and (D) O1s O1s multiplex. Multiplex peaks are presented
with their corresponding deconvolutions.

These are in agreement with the XPS spectrum obtained for O1s. As can
be seen there, a main contribution at ca. 529.8 eV, corresponding to the
lattice oxygen of TiO2 (Moulder et al., 1995; Bharti et al., 2016) was
observed. Moreover, a weak shoulder was observed at ca. 531.0 eV,
which has been attributed to oxygen vacancies (or non-lattice oxygen)
(see Fig. 3C) (Bharti et al., 2016).
The FTIR spectrum of TiO2NWS showed vibrational signals at ca.
3320 and 1616 cm−1, which were attributed to stretching and bending
modes of hydroxyl groups, respectively (see Fig. 4A). This may be as-
sociated to water adsorbed at the TiO2NWs surface. Also, a strong vi-
brational signal at 488 cm−1 was observed, which was attributed to the
Ti-O stretching mode (Martínez-Vargas et al., 2015; Hu et al., 2015).
XRD diffraction pattern of TiO2NWs is shown in Fig. 4B. All dif-
fraction peaks were assigned to rutile phase. The diffraction signals
observed at ca. 27.4°, 36.0°, 39.1°, 41.2°, 44.0°, 54.2° and 56.5° have
been unequivocally associated to (110), (101), (200), (111), (210),
(211) and (220) planes of rutile phase, respectively. As indicated in
previous references (Lin et al., 2011), and according to the reference
card JCPDS No. 211-1272, the characteristic peak of anatase ((101), at
approximately 25.3°) is not observed.

Fig. 4. TiO2NWs characterization by (A) FTIR, and (B) X-Ray diffraction.

825
L. Soto-Vázquez, et al.
Fig. 5. Study of the photocatalytic degradation of BP-4 at different catalyst loadings (A); and reaction progress of the different catalyst loadings through the time (B).
3.2. BP-4 photocatalytic degradation
3.2.1. Catalyst loading
The degradation of BP-4 by a photocatalytic route was studied at pH
5, according to previous studies carried out in our laboratory. Different
amounts of the catalyst were added to a solution containing 60 μM of
BP-4 and the effect of catalyst loading was determined. The catalyst
loading was studied up to 1.2 gL-1 since higher catalyst concentration
are undesirable to employ due to filtration problems and scattering of
light in subsequent phases of the research. The photocatalytic de-
gradation of BP-4 with TiO2NWs showed a higher optimal catalyst
loading, in comparison with previous researches performed in our la-
boratory on p-aminobenzoic acid under similar conditions (Soto-
Vázquez et al., 2016). At catalyst loadings below the optimum amount
the photodegradation was less than 50%, which may indicate the need
for longer reaction times in order to reach higher photodegradation
rates (see Fig. 5A). However, as the catalyst loading increases, higher
degradation was obtained reaching ca. 60% when 1.2 g L−1 was used.
In a similar study was found that 99% of benzophenone could be de-
graded using from 3 to 4 gL−1(Escobar et al., 2010). The degradation
results seem to follow a more efficient procedure; however, higher
catalyst concentrations may not be a practical condition to transfer into
a real environment because of the possible side-effects that may be
caused by the presence of excessive undissolved particles in the matrix
and, therefore, an increase in the treatment costs when upscaling. The
trend observed through the degradation process as the catalyst loading
increases suggests that the interaction between BP-4 molecules and
Fig. 6. Study of the photocatalytic degradation of BP-4 at different initial BP-4 concentrations (A); and reaction progress, at different initial BP-4 concentrations over
time (B).
826
Journal of Environmental Management 247 (2019) 822–828
TiO2NWs is enhanced. A continuous increase without an apparent de-
crement in the degradation suggests that saturation on the catalyst
surface does not occur and that is not expected to occur soon. As stated
before, when the catalyst loading was at its minimum the degradation
rate was negligible, which can be confirmed since the degradation
obtained during the first 60 min is ca. 5% (see Fig. 5B).
Moreover, during the first 60 min of reaction time, the degradation
progress observed was very similar for catalyst loading ranging from
0.6 to 1.2 g L−1. However, after this time the degradation rate from 0.6
to 1.0 g L−1 showed a clear decrease (contrary to the pattern observed
with loadings of 1.2 g L−1). This may suggest that the highest catalyst
loading of, at least, 1.2 g L−1 is necessary to provide additional active
sites to the photoproducts obtained that compete in the degradation
process. This competition and the lack of active sites at lower catalyst
loadings may explain the decrease of the degradation progress over
time. Because of this, the standard catalyst concentration to be used in
the next experiments was 1.2 g L−1.
3.2.2. Effect of BP-4 concentration
A significant factor that affects the efficiency of photodegradation of
a system is the concentration of organic pollutants. This concentration
must be in a suitable range to improve the interaction with the active
sites of the catalyst, avoiding the interaction between the con-
taminating molecules, which could decrease the degradation rate. For
this, the effect of the initial BP-4 concentration on the photocatalytic
degradation was studied in the range of 10–80 μM. The BP-4 was de-
graded in ca. 90% when the initial concentration was below 20 μM (see
L. Soto-Vázquez, et al.
Fig. 6A). The photocatalytic activity was enhanced at lower initial
concentrations, suggesting that the interaction between TiO2NWs and
BP-4 increased under these conditions. The decrease observed in the
photocatalytic degradation rate may be associated to the photoproducts
formed in the process, which may compete also for active sites. Also, at
higher concentrations, the TiO2NWs surface may be saturated with BP-4
molecules. In consequence, some BP-4 molecules cannot interact with
the catalyst surface, producing a decrease of the photodegradation rate.
This result agrees with a similar research carried out with a recalcitrant
dye (Mohamed et al., 2012). In the said research, the authors reported
an increase in the photocatalytic degradation of methylene blue at
lower concentrations of the pollutant. Since the catalyst dose, the time,
and the intensity of irradiation remain constant, the concentrations of
the photogenerated radicals must remain practically constant. This fact
means that a constant concentration of a radical is expected to be
available to react with higher amounts of the organic pollutants, and
therefore the photocatalytic degradation efficiency decreases (Nguyen
and Juang, 2015). Even when the concentration of BP-4 increased, the
catalyst could degrade the contaminant by at least 50%, when the in-
itial concentration of this organic contaminant is up to 60 μM.
The photodegradation process of BP-4, using an initial concentra-
tion of 20 μM, reached degradation levels in the range of 30–40%,
approximately, during the first 30 min of reaction (see Fig. 6B). Fur-
thermore, at 10 or 20 μM of initial concentration the trends observed
through the time were very similar. These results confirm that the
photocatalytic degradation is a promising technique at lower con-
centrations (Mohamed et al., 2012). Interestingly, a very constant de-
gradation was observed when the initial concentration was 60 μM,
which confirms the ability of the catalyst to degrade both, the by-pro-
ducts and the parent compound at higher concentrations.
In previous investigations carried out in our laboratory, it was de-
monstrated that the effectiveness of photocatalysis depends on the in-
teraction between the semiconductor and the organic pollutant and,
therefore, different results could be obtained when the catalyst is
varied. Moreover, photocatalysis, as an AOP, is a promising remedia-
tion technique and further investigations are needed for the better
understanding of the interaction between catalyst-organic pollutant and
what are the most effective combinations to upscale into real environ-
ments. However, these results and the fact that photocatalysis is a non-
specific reaction, which means that can degrade various organic pol-
lutants simultaneously validate our scientific opinion that the technique
can be used in a wider range of pollutants. Also, these results showed
that the photocatalysis as an alternative remediation method can be
employed in the future in a very sustainable manner in the cleanup of
negatively impacted sites by pollution and treat several contaminants
concurrently.
Under optimal experimental conditions, an apparent kinetic con-
stant of 1.29 × 10−2 min−1 was determined, according to a pseudo-
first order reaction, with an R2 > 0.99 (see Fig. 7A). This apparent
constant seems to be higher in comparison with previous results pub-
lished on the degradation of p-chlorophenol, methyl orange, and phe-
nanthrene in soils (Nguyen and Juang, 2015; Wilson et al., 2012; Gu
et al., 2012).
3.2.3. Alternative degradation methods
In order to evaluate alternative routes for the degradation of BP-4,
such as photolysis and catalysis, control experiments were performed
under optimal experimental conditions. These experiments were per-
formed at pH 5 with an initial BP-4 concentration of 20 μM, and
1.2 g L−1 of catalyst loading. As shown in Fig. 7B, the degradation of
BP-4 occurs mainly by a photocatalytic route since the contribution of
the photolysis and catalysis was practically negligible. This might be
explained due to the high photocatalytic activity of the TiO2NWs that
are the result of both, high surface area and the presence of oxygen
vacancies. These oxygen vacancies have a direct influence on its che-
mical and electrical properties since it can behave as important active
827
Journal of Environmental Management 247 (2019) 822–828
sites and therefore enhance the heterogeneous catalysis. Also, the pre-
sence of these oxygen vacancies can effectively expand the absorption
of light in TiO2 (Pan et al., 2013). This means that titania could make a
more suitable use of the light sources.
The role of a catalyst in any reaction is to accelerate the reaction
rate without being consumed in it (Kabra et al., 2004). As shown, when
the reaction is carried out by photolysis a negligible effect is produced,
since the efficiency of the light by itself is very low when the results are
compared with those obtained when light and catalyst are present. In
order to determine the influence of oxygen in the reaction media, ex-
periments were conducted under anoxic conditions. For this, the
oxygen sources were replaced with a constant nitrogen bubbling. It was
observed that in absence of oxygen only about 20% of BP-4 was de-
graded, suggesting that photogenerated oxygen radicals are the most
important species in the reaction pathway. Our results demonstrated
that the degradation is the result of the synergistic effect due to the
presence of catalyst, light and oxygen sources, and none of them by
their own could degrade BP-4 in an effective way. Our experimental
design is an asset for this research area in order to upscale into open
water systems since employed only a minimum amount of H2O2 and a
constant air-bubbling as our oxygen sources. Higher amounts of H2O2
are not desirable since can be counterproductive to the environment
and their living species.
The results clearly show the stability of BP-4 under normal condi-
tions, which explains the high levels of BP-4 in urban wastewater
(Jurado et al., 2014). As stated before, the efficiency of the process
strongly depends on the interaction of catalyst-pollutant. This and the
fact that BP-4 is a recalcitrant organic pollutant might be the first step
to fill the current gap of information that exists today to employ this
technique on-site to remediate our water sources when traditional
techniques are not suitable.
4. Conclusions
In this research an alternative method to remove BP-4 as an organic
pollutant was proposed by following a photocatalytic approach using
TiO2 as catalyst. The photocatalysis was successfully employed in the
degradation of BP-4 using TiO2NWs that were obtained following a
hydrothermal procedure with TiCl4 as the precursor. It was shown that
these nanowires begin to grow at 30 min of the reaction as individual
wires and then continue to organize themselves as a branched structure.
The individual nanowires were observed as elongated structures with a
rutile crystalline phase. These nanowires were responsible for the
photodegradation of BP-4, acting as the catalyst of the reaction, and
resulting in 90% degradation after only 3 h of radiation. It should be
noted that BP-4 is highly stable under normal conditions, and that
photolysis and catalysis, on their own, produce negligible degradation
results. Due to the production and consumption of PPCP in recent years,
the photocatalysis, as part of the advanced oxidation processes, is a
promising technology for environmental remediation purposes in order
to improve the quality of the environment and water sources. It should
be noted that our research was conducted in a controlled environment
and, therefore, more research should be carried out that addresses other
variables, as well as natural environments. However, to our knowledge,
this research is one of the few addressing BP-4 as an organic pollutant,
and the first focusing in the degradation of it by a photocatalytic route.
The problem addressed in this research is of global importance, since
traditional remediation techniques do not seem to be able to maintain
water quality standards for the oncoming years.
Acknowledgments
Financial support from the U.S. Department of Energy, through the
Massie Chair Project at Universidad del Turabo; from the U.S.
Department of Defense, under Grant W911NF-14-1-0046; and from
Ministerio de Economía y Competitividad of Spain, under Grant
L. Soto-Vázquez, et al.
Fig. 7. Study of the photocatalytic degradation of BP-4 under optimal experimental conditions. (A) Kinetic study under optimal conditions with TiO2NWs; (B)
Alternative degradation methods under optimal conditions.
ENE2014-57977-C2-1-R are gratefully acknowledged. The authors
thank to the Materials Characterization Center, Inc. and the Molecular
Science Research Center at University of Puerto Rico (USA) for the use
of the characterization facilities. Authors also thanks the technical as-
sistance of I. Poveda from “Servicio Interdepartamental de
Investigacion, SIdI” at UAM.
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