Catalysis Today

The influence of the UV radiation on the hydrophilicity of the photocatalytic thin films
--Manuscript Draft--

Manuscript Number:

Article Type: 2022: SPEA11

Keywords: TiO2-GO double-layered composites; UV radiation effect; TiO2-GO hydrophilicity;

TiO2-GO photocatalytic efficiency

Corresponding Author: Anca Duta, Prof. dr. eng.

Transilvania University of Brasov
Brasov, ROMANIA

First Author: Ioana Tismanar

Order of Authors: Ioana Tismanar

Alexandru Cosmin Obreja

Octavian Buiu

Anca Duta, Prof. dr. eng.

Abstract: The hydrophilicity of the thin films is considered among the most important properties
associated to the photocatalytic materials, especially when used as self-cleaning
surfaces. The wettability of these materials was reported to increase when irradiated
with UV radiation leading to an increased photocatalytic process efficiency. This paper
reports on the hydrophilicity changes in the composites with titanium dioxide matrix
and graphene oxide filler deposited as double-layer thin films using spray pyrolysis
deposition coupled with the sol-gel technique. The thin films were deposited and left in
dark for 5 months, then these were tested in terms of hydrophilicity, roughness and
transmittance before and after conditioning using UV radiation at different irradiation
durations up to 2 hours (irradiance G~24 W/m 2 , close to the average UV irradiance
value in the solar radiation over the year in a temperate climate). The characterization
results were correlated with the photocatalytic efficiency recorded when using the thin
films (conditioned and not) and the results show that UV pre-conditioning improved the
performance of the photocatalyst thus such a pre-treatment is recommended to
increase the overall efficiency of the process.

Suggested Reviewers: Jose Manuel Gatica

University of Cadiz
josemanuel.gatica@uca.es

Honey John
Cochin University of Science and Technology
honey@cusat.ac.in

Oh Joong Kwon
Incheon National University
ojkwon@inu.ac.kr

László Janovak
University of Szeged
janovakl@chem.u-szeged.hu

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Cover Letter

Letter to the editor

Dear Editor,

Please find attached the manuscript of the paper:

Title: “The influence of the UV radiation on the hydrophilicity of the photocatalytic thin
films“

Ioana Tismanar, Alexandru Cosmin Obreja, Octavian Buiu, Anca Duta

Contact authors: Anca Duta a.duta@unitbv.ro; Ioana Tismanar ioana.tismanar@unitbv.ro

to be considered for publication in the Catalysis Today Journal – Special Issue of SPEA11
Conference

The work presented in this paper is original, unpublished, and not being considered
elsewhere.

Please consider the following possible reviewers:

1. Jose Manuel Gatica, josemanuel.gatica@uca.es

Departamento C.M., I.M. y Química Inorgánica, Universidad de Cádiz, Puerto Real,
11510, Spain

2. Honey John, honey@cusat.ac.in

Department of Polymer Science and Rubber Technology, Cochin University of
Science and Technology, Kerala, 682022, India

3. Oh Joong Kwon, ojkwon@inu.ac.kr

Department of Energy and Chemical Engineering, Incheon National University, 12-1,
Songdo-dong, Yeonsu-gu, Incheon 406-840, Republic of Korea

4. László Janovak, janovakl@chem.u-szeged.hu

Department of Physical Chemistry and Materials Science, University of Szeged, H-
6720, Szeged, Rerrich B. tér 1, Hungary

Sincerely yours,
Anca Duta, on behalf of all co-authors
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Guest Editors: CATALYSIS TODAY-Special issue SELECTED CONTRIBUTIONS OF THE 11TH

EUROPEAN MEETING ON SOLAR CHEMISTRY AND PHOTOCATALYSIS: ENVIRONMENTAL
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Highlights (for review)

Highlights

 TiO2/TiO2–GO films were deposited by spray pyrolysis deposition and sol spraying.
 The composites hydrophilicity after 5 month of dark storage significantly depends on the
GO content.
 The thin films reached super-hydrophilicity after 30 minutes of UV exposure, regardless
the GO content.
 The optimum UV pre-conditioning duration is 1.5 hours.
 The pre-conditioned films show higher photocatalytic efficiencies.
Graphical Abstract (for review) Click here to access/download;Graphical Abstract (for review);Graphical abstract CatToday
(SPEA11)_A. Duta.pdf
Conditioned double-layered composites thin films TiO2 / TiO2-GO

Water contact angle (WCA) variation

WCA after 5 WCA after UV irradiation [o]
Thin film
months in dark [o] 0.5h 1h 1.5h 2h
TiO2/TiO2-GO 1.4%w 87.3 8.8 8.9 6.8 7.1
TiO2/TiO2-GO 3%w 12.0 9.3 7.9 7.4 7.9

The effect of pre-conditioning in methylene blue photo-degradation

30 30
28 28

dark adsorption-desorption equilibrium

dark adsorption-desorption equilibrium

26 26
24 24
22 22
20 20
18 18
16 16
t

t
14 14
12 12
10 10
8 8
6 6
4 TiO2 / TiO2-GO 1.4 %w _non-irradiated 4 TiO2 / TiO2-GO 3 %w _non-irradiated
2 TiO2 / TiO2-GO 1.4 %w _UV irradiated 2 TiO2 / TiO2-GO 3%w _UV irradiated
0 0
0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
Photocatalytic process duration t [hours] Photocatalytic process duration t [hours]
Manuscript Click here to view linked References

The influence of the UV radiation on the hydrophilicity of the

photocatalytic thin films

Ioana Tismanara, Alexandru Cosmin Obrejab, Octavian Buiub, Anca Dutaa*

a) R&D Center Renewable Energy System and Recycling, Transilvania University of Brasov,
Eroilor 29, 500036 Brasov, Romania

E-mail: ioana.tismanar@unitbv.ro; a.duta@unitbv.ro

b) National Institute for Research and Development in Microtechnologies, IMT-Bucharest,

Erou Iancu Nicolae 126A, 077190 Voluntari, Ilfov, Romania

E-mail: cosmin.obreja@imt.ro; octavian.buiu@gmail.com

* Corresponding author: a.duta@unitbv.ro

Abstract

The hydrophilicity of the thin films is considered among the most important properties
associated to the photocatalytic materials, especially when used as self-cleaning surfaces. The
wettability of these materials was reported to increase when irradiated with UV radiation leading
to an increased photocatalytic process efficiency. This paper reports on the hydrophilicity changes
in the composites with titanium dioxide matrix and graphene oxide filler deposited as double-layer
thin films using spray pyrolysis deposition coupled with the sol-gel technique. The thin films were
deposited and left in dark for 5 months, then these were tested in terms of hydrophilicity, roughness
and transmittance before and after conditioning using UV radiation at different irradiation
durations up to 2 hours (irradiance G~24 W/m2, close to the average UV irradiance value in the
solar radiation over the year in a temperate climate). The characterization results were correlated
with the photocatalytic efficiency recorded when using the thin films (conditioned and not) and
the results show that UV pre-conditioning improved the performance of the photocatalyst thus
such a pre-treatment is recommended to increase the overall efficiency of the process.

Keywords: TiO2-GO double-layered composites; UV radiation effect; TiO2-GO hydrophilicity;

TiO2-GO photocatalytic efficiency

1
 1. Introduction

Photocatalytic self-cleaning surfaces have been intensively studied during the recent years,
the applications being multiple and varied in different industries, nowadays the mostly used being
the use of these surfaces in the automotive industry. The materials recommended as self-cleaning
surfaces are usually similar to the photocatalytic materials used in the advanced wastewater
treatment applications. These materials are semiconductors that under irradiation produce
electrons and holes that react with water, hydroxide ions or oxygen to produce oxidizing species
(mainly hydroxil radicals) responsible for the degradation of pollutants adsorbed on the surface of
the self-cleaning materials, [1].
Photocatalytic materials such as TiO2 or ZnO are intensively investigated in the advanced
wastewater treatment or in self-cleaning applications because of their suitable properties: stability
in the aqueous media over a wide pH range, high process efficiency, non-toxicity, low cost. The
main barrier for the wide spread use of these materials is their activation energy that requires UV
radiation (Eg = 3.0…3.2eV) that significantly increases the process costs, [2]. To overcome this
issue, research focused on novel photocatalytic materials that can be activated by Vis- and/or Solar
radiation thus the process cost strongly decreases. The most often reported are the composites with
an n-type semiconductor coupled with a p-type one forming, due to the suitable energy bands
aligniament, n-p diode heterostructures, [3, 4]. Recent studies indicate the TiO2 – GO composites
as Vis(Solar)-active materials because of this suitable alignment of the energy bands that supports
the development of an n-p junction, [5, 6]. Along with the activation using low or non cost
radiation, other composite properties (crystallinity degree, morphology, roughness, hydrophilicity)
have also to be considered.
One of the mostly investgated property is the ability to wet the self-cleaning surface. For
surfaces with (very) good wetting properties, called (super)hydrophilic surfaces, self-cleaning is
done when the water is spread over the surface and washes out the contaminant(s). On the other
hand, for surfaces with (very) low wetting properties, called (super)hydrophobic surfaces, self-
cleaning occurs by collecting the pollutant(s) molecules/ aggregates and removing them by rolling
the aqueous droplets on the surface of the material, [7]. In both cases the contaminants are not
degraded, they are only removed. When using the photocatalytic materials, cleaning is done
following the reactions of the holes with the water molecules in the atmosphere (e.g. moist air) to

2
produce oxidizing species that degrade organic pollutants (eq. 1) or even atmospheric
contaminants resulted from fuels burning as presented for NOx (eq. 2), [8].

(+ O2)
h+
VB + H2O/HO + organic pollutnts → HO. + organic pollutnts → CO2 + H2O + (intermediate
-

products) (1)
2HO. + NO(g) → NO2 (ads) + H2O(ads) or (2)
HO. + NO2 (ads, g) → NO3 (ads)- + H+(ads) or
O−∙
2
NOx (ads ) → NO3-(ads)

For these materials supehydrophilicity is targeted (water contact angle < 10o). The
(super)hydrophilicity of the photocatalytic materials can be induced by applying UV radiation and
this behavior was firstly analyzed by Wang et al, [9] that used TiO2 films to check the
hydrophilicity variation when exposed to UV.
The mechanisms involved in the photo-induced hydrophilicity are mostly realated to the
generation of oxygen vacancies (as e.g. 2Ti4+  2Ti3+ + VO∙∙ for the TiO2 photocatalyst) correlated
with the adsorption of the water molecules at the level of these defects, forming hydrophilic areas
or producing the photo-oxidation of hydrophobic carbonaceous species (by-products from the
organic precursor system), [10]. This photo-induced hydrophilicity is reversible thus the
photocatalyst reduces its wettability when irradiation is not applied, [11, 12]. Studies developed in
the last decade focused on the photo-induced hydrophilicity of the composites with TiO2 matix
and graphene derivative fillers, [10, 12, 13] and the results outline a hydropilicity increase of the
composite films without any degradation of the photocatalyst under irradiation. However, the
hydrophilicity variation when the films are not irradiated must be checked when considering the
commercialization of these self-cleaning surfaces after the films were kept in dark for a long period
of time.
This paper reports on the wettability of the TiO2/TiO2-GO double-layered thin films after
UV irradiation, with the irradiance value close to that in the natural solar radiation (G ~ 24W/m2).
The self-cleaning properties were investigated for samples kept in dark for a long duration (5
months) and after UV irradiation (up to two hours) and the results were correlated with the
performance of these materials in photocatalytic processes using the methylene blue (MB) diluted

3
soulution (10ppm), according to the standard ISO 10678:2010, [14]. Transmittance spectras were
used to estimate the stability under irradiation of these surfaces and also to indicate the potential
applications of these composites (transparent glazings or facades/interior walls as opaque self-
cleaning surfaces). The results provide insights on the recommended pre-conditioning of the
photocatalytic materials before their use in photocatalytic applications.

2. Materials and Methods

For deposition there were used 1.5 x 1.5 cm2 FTO substrates (glass covered with fluorine
doped tin oxide) cleaned with water and detergent, rinsed with deionized water and further with
ethanol under sonicatation and dried in air.
The deposition procedure followed two steps:
(1) The deposition of a first TiO2 layer by spray pyrolysis (SPD) using a precurosr system
consisting of titanium tetra-isopropoxide (TTIP, Sigma Aldrich, 97%) mixed under consinous
stirring with acetylacetone (AcAc, Scharlau, 99%) and ethanol (EtOH, Chemical Company,
99.3%) in a volume ratio TTIP:AcAc:EtOH = 1:1:15. The substrates were placed on a heating plate
set at 400oC and the precurosr system was sprayed using an ABB/IRB5400 robot and 30 spraying
sequences with 60s break between two consecutive pulses. This first TiO2 layer was annealed at
450oC for 3 hours to increase the cristallinity degree of the thin film.
(2) The second TiO2-GO composite layer was deposited by robotic spraying at 100oC (to prevent
the GO decomposition) using 15 spraying sequences, with 60s breaks between pulses. The
deposited dispersion was obtained using the sol-gel method from the system consisting of TTIP,
EtOH, AcAc and acetic acid (HAC, Scharlau 99.8%) in a volume ratio TTIP:EtOH:AcAc:HAC =
1:0.8:0.04:0.009. To form the sol, an aqueous GO dispersion (25 mg/mL, obtained following the
Hummers method) was added in the precursor system. The as prepared sol was sonicated for 1.5h
and diluted using ethanol in the volume ratio sol:EtOH = 1:5. The diluted sol was deposited over
the first layer. After depositing the second layer, the composite was thermally treated for 1 hour at
150oC to decompose/remove the by-products without degrading the GO filler.
The main role of the first TiO2 layer was to support an ordered growth of the second layer
on the crystalline substrate, considering that the final thermal treatment does not support the
crystalline phases formation in the TiO2-GO composite, as previously discused, [6]. Two different

4
samples were comparatively investigated: TiO2/TiO2-GO 1.4%w and TiO2/TiO2-GO 3%w having
1.4%w GO and respectively 3%w GO in the composite layer.
The composites were investigated to evaluate the self-cleaning properties using samples
kept in dark for a period of 5 months and samples irradiated with UV radiation with the irradiance
value close to the natural conditions (G ~ 24W/m2). The hydrophilicity was evaluated by
measuring the water contact angle (WCA) using a DataPhysics OCA 20 goniometer and a 10 µL
volume of the water droplet. The surface morphology and the roughness were analyzed using
atomic force microscopy (AFM, NT-MDT model BL222RNTE) and the transmittance of the
composite layers was evaluated using UV–VIS-NIR spectrophotometer (Perkin Elmer Lambda
950). The irradiated and the non-irradiated composite films with different GO content were tested
in photocatalytic processes using the standard methylene blue (MB) aqueous solution of 10 ppm
concentration, [14]. 50 mL quartz beakers were used in which 20 mL of MB solution was added
and then the composite films were immersed. At the beginning of the tests, the samples were left
for 1h in dark to reach the adsorption/desorption equilibrium and then these were placed under
irradiation for 8h, in a photoreactor equipped with 2 UV and 5 VIS lamps. The measured irradiance
at the photoreactor level (recorded with a Delta-T, type BF3 pyranometer) was G ~ 55 W/m2, out
of which 3 W/m2 corresponded to the UV radiation. After 1h in dark and at each hour of irradiation
the absorbance of the MB solution was measured using a spectrophotometer (UV-Vis-NIR Perkin
Elmer Lambda 950) to calculate the photocatalytic efficiency, using the absorbance values
recorded at the wavelength corresponding to the absorption maximum for MB (λ = 665 nm) at the
initial moment (A0) and after the photocatalytic process at different process times (At) according
to eq. (3):

ηt = (A0 – At / A0) * 100 (3)

Based on the photocatalytic efficiency values, the effect of pre-conditioning the composite
thin films was discussed.

5
 3. Results and Discussions

The water contact angle (WCA) was measured on the samples kept in the dark for 5 months
and on those irradiated with UV radiation at different irradiation durations (0.5h; 1h; 1.5h; 2h) and
the results are inserted in Table 1.
Table 1 WCA for the films before and after UV irradiation

WCA after 5 WCA after UV irradiation [o]

Composite layers
months in dark [o] 0.5h 1h 1.5h 2h
TiO2/TiO2-GO 1.4%w 87.3 8.8 8.9 6.8 7.1
TiO2/TiO2-GO 3%w 12.0 9.3 7.9 7.4 7.9

The results in Table 1 show that for the films with 1.4%w GO content the initial contact
angle corresponds to a surface with low hydrophilicity that reaches a WCA corresponding to a
superhydrophilic surface after 0.5 hours of irradiation with UV radiation. Similar results were
obtained for the composite with 3%w GO. It is to notice that the films with a lower GO content are
more strongly influenced (in terms of hydrophilicity) by dark storage conditions. Previous work,
[12], outlined this behavior even when the composite films with low GO content were kept in dark
for a shorter period of time when the WCA varied from ~20o right after the deposition to WCA ~
55o after 7 days stored in dark. Correlated with the results in Table 1 it can be concluded that the
major changes in the wettability of these composites are produced during the first days after
deposition, possible due to surface finishing reactions after deposition, involving by-products. The
hydrophilic domains resulted after the UV irradiation facilitate the increase in the wettability of
both composites. The results indicate the optimal UV irradiation duration of 1.5 hours as after this
duration, the WCA does not substantially change.
The wettability variation was correlated with the morphology and with the variation in the
roughness values of the composite thin films.
The roughness (RMS) values are inserted in Table 2 and outline that for the sample with
1.4%ԝ GO the RMS significantly decreases with the increase of the irradiation duration, while for
the sample with 3%w GO there is only a slight change in the RMS values.
A possible densification under UV radiation may occur for the films with a lower GO
content and, possible due to the fact that TiO2 can link to GO in several ways, in the case of the
composite with 3%w GO this densification was not observed. Narayanam et al., [15], outlined the

6
direct correlation between the WCA and the RMS values suggesting an increase in the
hydrophobicity of the composites with TiO2 matrix with the increse in the surface roughness
mainly due to the insertion of air between the droplet of water and the TiO2 surface following thus
the Cassie-Baxter mechanism, [16]. The decrease in the RMS values after UV irradiation due to
densification also supported by the hydrophilic domains formation facilitate the full contact
between the droplet of water and the composite surface.

Table 2 AFM images and RMS values for the films before and after UV irradiation
After 5 After UV irradiation
Thin film months in
dark 0.5h 1h 1.5h 2h

TiO2/TiO2-
GO 1.4%w

RMS [nm]
267.4 227.6 187.1 159.5 160.7

TiO2/TiO2-
GO 1.4%w

RMS [nm]
122.7 133.4 141.7 115.4 131.0

The AFM results correlated with the high RMS values in Table 2 indicate a morphology
with many large aggregates especially for the composite with 1.4% w GO. It can also be noticed

7
the possible cracks formation especially for the sample with lower GO content after the UV
irradiation indicating a potential moisture removal during/after the conditioning process. These
type of morphology with agglomerates at the film surface may lead to higher photocatalytic
efficiencies due to a higher number of active sites available for the pollutant adsorption as first
step in the heterougenous photocatalysis mechanism. Even if the sample with low GO content has
significantly higher RMS value, indicating a possible superior efficiency in the photocatalytic
processes, a higher concentration of the filler can lead to an improved photocatalytic efficiency
due to the higher likelihood to develop bonds between the matrix and the filler thus creating
continuous and more stable interfaces. Along the adequate surface morphology correlated with the
RMS values, the crystallinity degree of the photocatalytic materials should be high in order to
increase the charge’s carrier mobility leading to limited recombination thus improved
photocatalytic efficiency. Previous studies indicated a 37.0% crystalline degree for the first TiO2
layer while the double-layered thin film with 1.4%w GO had a crystallinity degree of 42.5% and
the one with 3%w GO content had 42.9%. The increase in the crystalline degree from the first film
to the double-layered composite confirms the good choice for the ordered growth of the second
layer over the first one without applying high temperature treatement, [17, 18].
The thin film transmittance (T%) was recorded for glass, for the glass/FTO substrate, for
the first layer and for the double-layered composites before and after 2h of UV irradiation, Fig.1.

100
90
(1)
80 (2)
70 (3)

60 (4)
T [%]

(4')
50 (5)
(5')
40
glass substrat (1) TiO2 / TiO2-GO 1.4 % initial (5)
30 w
FTO substrat (2) TiO2 / TiO2-GO 3 %w initial (4)
20
TiO2 (3) TiO2 / TiO2-GO 3%w after UV (4')
10
TiO2 / TiO2-GO 1.4% after UV (5')
w
0
300 400 500 600 700 800
 nm

Fig. 1 Transmittance spectrum for the substrate and for the films before and after UV irradiation

8
 As the results in Fig. 1 show, the composites have lower transmittance values than 80%
thus can be used as self-cleaning surfaces applied on opaque facades or interior walls but are not
recommended to be used on transparent glazed surfaces. The composite thin film with lower GO
content has a lower transmittance as results of the higher RMS value that supports light scattering
in a certain extend. The results recorded before and after UV irradiation indicate a very small
variation suggesting a good stability of the composite thin films under irradaiton. A small
transmittance decrease after the conditioning treatment was observed in both cases that can be
correlated with the possible densification of the composite thin films.
The Vis-activation of these composites and the optimum duration of the adsorption step
(1h in dark to reach adsorption/desorption equilibrium) were previously outlined, [6]. This work
focuses on the photocatalytic results recorded under UV-Vis irradiation to outline the influence of
the pre-conditioning of the composites on the process efficiency. The composite thin films were
pre-conditioned with UV radiation before use at the optimum irradiation duration (1.5h) and the
photocatalytic results (Fig. 2) show higher efficiencies on the films with a higher filler content:
23.57% for the sample with 1.4%w and 28.34% for the film with 3%w GO; this may be the
consequence of the more extended matrix-filler interfaces produced in the film with 3%w GO
content despite the higher RMS value of the composite with lower GO content.

30 30
28 28
dark adsorption-desorption equilibrium

dark adsorption-desorption equilibrium

26 26
24 24
22 22
20 20
18 18
16 16
t

t

14 14
12 12
10 10
8 8
6 6
4 TiO2 / TiO2-GO 1.4 %w _non-irradiated 4 TiO2 / TiO2-GO 3 %w _non-irradiated
2 TiO2 / TiO2-GO 1.4 %w _UV irradiated 2 TiO2 / TiO2-GO 3%w _UV irradiated
0 0
0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
Photocatalytic process duration t [hours] Photocatalytic process duration t [hours]
Fig. 2 Efficiency of MB photodegradation using composites with 1.4%w GO (left) and 3%w GO
(right) non-irradiated and pre-conditioned by UV irradiation for 1.5 hours

9
 The results recorded on the not irradiated samples show efficiencies with about 5% lower
than the results recorded on the UV conditioned films. It can be noticed in both cases that the
efficiencies in the adsorption step (1h in dark before the beginning of the photocatalytic process)
for the conditioned films were higher compared with the non-irradiated films outlining that the
superhydrophilicity of the composite supported higher adsorption efficiencies. It is therefore
recommended to pre-condition the photocatalytic films before use by using UV radiation. In the
case of self-cleaning surfaces exposed to UV radiation (for example, the facade of a house), it is
expected the films to be more effective after a period of irradiation.

4. Conclusions

Double-layered TiO2 / TiO2–GO composite thin films were deposited using two up scalable
techniques: spray pyrolysis (layer 1) and sol-gel spraying (layer 2). After deposition, the first layer
was thermally treated at 450°C, to increase the crystallinity degree. The second composite layer
TiO2-GO with 1.4%w GO and 3%w GO content was deposited by spraying a diluted sol. The
synthesis method was selected considering that GO is stable only up to about 180°C. Therefore,
thermal treatment applied for the final material was at 150°C.
The double-layered structure was selected to increase the crystallinity in the composite
without applying a final high temperature treatment, by depositing the second layer over the
crystalline structure of the first one when the structure of layer 2 will partially adopt the crystalline
structure of layer 1.
The as deposited composite thin films were stored in dark for 5 months. After this period,
the composites were conditioned using UV radiation. The films were characterized to estimate the
hydrophilicity (water contact angle measurements) for both types of layers (kept in dark and UV
irradiated at different irradiation durations). The films were irradiated to increase the
hydrophilicity until the contact angle decreased down to a constant value and the optimum
irradiation duration was found to be at 1.5 h. The roughness values constantly decreased on the
samples irradiated for different durations in the case of the film with 1.4%w GO possibly due to
the material’s densification in the composite layer. This effect was not observed on the samples
with a higher GO content (3%w). The transmittance values demonstrate that these films can only
be used for opaque surfaces (e.g. facades or interior walls) because the T% was less than 80%
which makes them unsuitable for self-cleaning glazed surfaces.

10
 The photocatalytic experiments using the samples conditioned at the optimum UV
irradiation duration (1.5h) and on unconditioned samples outline that an activation step using UV
radiation is recommended for the composite films to increase their efficiency.

Acknowledgements
This work was supported by the grant of the Romanian Ministry of Research and Innovation,
CCCDI-UEFISCDI, project number PN-III-P1-1.2-PCCDI-2017-0619, contract no. 42
PCCDI/2018 within PNCDI that is gratefully acknowledged.

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Declaration of Interest Statement

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

The authors have no financial interests/personal relationships to declare.