nanomaterials

Article
Paper Functionalized with Nanostructured TiO2/AgBr:
Photocatalytic Degradation of 2–Propanol under Solar
Light Irradiation and Antibacterial Activity
Mouheb Sboui 1 , Soraa Bouattour 1 , Michelangelo Gruttadauria 2 , Giuseppe Marcì 3, *,
Leonarda Francesca Liotta 4, * and Sami Boufi 5, *
1 Faculty of Sciences, University of Sfax, Lions Club International (LCI), Sfax BP1171-3018, Tunisia;
sboui.mouheb@gmail.com (M.S.); soraa.boufi@yahoo.com (S.B.)
2 Dipartimento di Scienze e Tecnologie Biologiche, Chimiche e Farmaceutiche (STEBICEF), Università degli
Studi di Palermo, Viale delle Scienze, Ed. 17, 90128 Palermo, Italy; michelangelo.gruttadauria@unipa.it
3 Dipartimento di Ingegneria (DI), Università degli Studi di Palermo, Viale delle Scienze Ed. 6,
90128 Palermo, Italy
4 Istituto per lo Studio dei Materiali Nanostrutturati (ISMN-CNR), Via Ugo La Malfa 153, 90146 Palermo, Italy
5 Faculty of Sciences, University of Sfax, Laboratoire Sciences des Matériaux et Environnement,
Sfax BP1171-3018, Tunisia
* Correspondence: giuseppe.marci@unipa.it (G.M.); leonardafrancesca.liotta@cnr.it (L.F.L.);
Sami.Boufi@fss.rnu.tn (S.B.); Tel.: +39-091-238-63737 (G.M.); +39-091-680-9371 (L.F.L.);
Tel./Fax: +216-9758-5217 (S.B.); Fax: +39-091-680-9399 (L.F.L.)




Received: 9 February 2020; Accepted: 29 February 2020; Published: 5 March 2020


Abstract: A facile method to produce paper–TiO2 decorated with AgBr nanoparticles by a mild
hydrothermal process at 140 ◦ C was reported. The synthesis method was based on the immersion
of the paper in a ready-made suspension of TiO2 /AgBr, comprising TiO2 sol solution prepared in
acidic conditions and AgBr solution (10−4 M). A paper–TiO2 sample was prepared and used as
reference. The formation of crystalline phases of titanium oxide (TiO2 ) and silver bromide (AgBr)
was demonstrated by XRD, Raman and EDX analyses. The surface morphology of the TiO2 –AgBr
was investigated by Field Effect Scanning Electronic Microscopy (FE–SEM). The photocatalytic
performances of the prepared material were evaluated in the degradation of 2-propanol in the gas
phase, under simulated sunlight illumination. Its antibacterial properties against Escherichia coli
(E. coli) were also assessed. The efficiency of photodegradation and the anti-bacterial properties of
paper–TiO2 –AgBr were attributed to an improvement in the absorption of visible light, the increased
production of reactive oxygen species (ROS) and the low recombination of photogenerated charge
carriers due to the synergistic effect between TiO2 and AgBr/Ag nanoparticles.

Keywords: Paper–TiO2 –AgBr; 2-propanol photodegradation; antibacterial activity; sunlight

irradiation

1. Introduction
Cellulose paper is a flexible and versatile material present in our daily lives for a wide range
of applications. Besides its traditional use as the main support in printing media (e.g., newspapers,
books and printing paper) and eco-friendly packaging material, cellulose-based paper arouses much
interest for new innovative applications, including electronic, smart functional packaging, and
sensor, energy storage and catalysis after hybridization with metallic or oxide NPs, as reported
in recent interesting reviews [1,2]. The use of cellulose-based papers and fabrics as a platform in
multifunctional material has attracted great attention [3,4] due to the numerous advantages offered

Nanomaterials 2020, 10, 470; doi:10.3390/nano10030470 www.mdpi.com/journal/nanomaterials

Nanomaterials 2020, 10, 470 2 of 13

by this class of material, including a low cost, lightweight, low thermal expansion coefficient, good
thermal stability of up to 200 ◦ C, bendability and foldability and good mechanical properties. More
specifically, the hybridization of paper with TiO2 nanostructured coating has aroused much interest
for commercial application as a deodorizing filter or indoor air purification. The first work dates
back to 1995, where Matsubara et al. described the production of paper–TiO2 using a papermaking
technique, with an effective ability to degrade acetaldehyde in air under weak fluorescent light
illumination [5]. Since then, many papers were reported with a focus on improving the immobilization
approach and enhancing the photocatalytic efficiency of the hybrid paper–TiO2 toward large classes
of pollutants, including dyes, amines and nitro organic compounds, as well as volatile organic
solvents. Two interesting comprehensive reviews enumerating the methods of immobilization, as well
as the applications of nanoparticle-functionalized paper with different metal oxide nanostructures,
including TiO2 , have been reported by Pelton et al. [6] and Chauhan et al. [7]. The water sensitivity of
paper could be addressed by a polymer additive imparting a certain hydrophobic effect, as recently
reported by Garusinghe et al. [8]. They prepared water-resistant photocatalytic paper based on
micro-fibrillated cellulose-polyamide-amine epichlorohydrin with immobilized TiO2 nanoparticles by
a simple two-step mixing process, and the composite mater showed effective photocatalytic activity
versus the degradation of dyes under UV-light irradiation. Examples of commercial development
based on a paper–TiO2 photocatalyst were also reported by Nippon, where newsprint coated with
TiO2 was proposed as an effective air cleaning material under UV illumination [9]. An air-deodorizing
tissue box with TiO2 -coated paper was also proposed for air purification in the interior vehicle [9].
In our previous works, two facile methods for the preparation of paper–TiO2 photocatalysts have
been reported using either an in-situ route starting from Ti(OBu)4 as a precursor or a ready formed TiO2
sol, followed by a hydrothermal process at a low temperature [10]. It was shown that both methods
produced highly efficient photocatalysts able to convert 2-propanol to carbon dioxide and water.
Moreover, the composite paper–TiO2 was revealed as competitive as TiO2 P25 (Evonik) powder, known
to be the most effective commercial photocatalyst. Aiming to boost the photocatalytic activity under
the visible light of the paper–TiO2 composite, Cu2 O in the form of tiny nanoparticles (NPs) has been
associated with the TiO2 layer to produce paper–TiO2 –Cu2 O and paper–Cu2 O–TiO2 photocatalysts by
a reduction process to form Cu2 O nanoparticles [11]. It was shown that the inclusions of Cu2 O in the
form of tiny NPs improves photocatalytic activity and shifts the absorption edge to the visible domain.
However, the paper–Cu2 O–TiO2 failed to degrade organic solvents under the gas phase.
Despite the effectiveness of paper–TiO2 composite material of degrading organic molecules under
UV-light, its widespread application in indoor cleaning air and volatile organic compounds (VOCs)
treatment is handicapped by the shortcoming of TiO2 , namely (i) the lack of a visible light response, due
to its large bandgap (3.2 eV for anatase), and (ii) the rapid recombination rate of the photo-generated
charge carriers (h+ /e− ), reducing the overall quantum yield of TiO2 . A promising approach to alleviate
these limitations consisted of coupling TiO2 , in a controlled level, with Ag/AgBr heterojunction, giving
rise to a new class of photocatalysts referred to as plasmonic photocatalysis. The presence of tiny Ag
NPs generated in-situ by light reduction will extend the response of the TiO2 catalyst to visible light
through the localized surface plasmon resonance (SPR) of noble metal nanostructures [12]. In addition,
metal Ag has been found to improve the charge separation by acting as an electron trap [13]. The first
reports on the use of silver halides in combination with TiO2 as visible-light plasmonic photocatalysts
are quite recent, dating back to 2006 with the pioneering works of Hu et al. [12] (TiO2 /Ag/AgBr) and
Wang et al. [14].
Given the lack of literature data concerning the coupling of AgBr with paper–TiO2 composites,
we considered it worthy to investigate how the coupling of AgBr with TiO2 would affect the efficiency
of photoactive TiO2 −containing paper for the degradation of 2-propanol as a VOC model molecule
under simulated sunlight irradiation and room temperature. Due to the sensitivity of cellulose
paper to thermal degradation, a mild approach for the functionalization of paper with TiO2 –AgBr
nanostructured coating was adopted. The prepared paper–TiO2 –AgBr was characterized by Raman,
Nanomaterials 2020, 10, 470 3 of 13

XRD, UV-Vis absorption and SEM observation. This work is a continuation of our work carried out
on the functionalization of paper with TiO2 for the degradation of VOCs [10]. Presently, the main
objective is to enhance the photocatalytic activity under sunlight, taking advantage of the plasmon
of Ag to transfer the energy to TiO2 , and the property of Ag to reduce the recombination rate of the
electron-hole charge carriers.
In fact, 2-propanol (C3 H7 OH) was chosen as a VOC model molecule in this work due to its
extensive use, particularly in medical centers. It is an organic compound that belongs to the group of
alcohols. 2-propanol is known for several properties, such as being volatile and flammable. It has a
distinctive, non-repulsive smell, which it can be stinging when inhaling it in large doses. 2-propanol is
usually used in hospitals or medical clinics, as it is often used in the installation of sterilizers (antiseptic
or antibacterial). In addition, it is used in cosmetics and pharmaceutical preparations. As a result of
the serious health risks connected with the existence of 2-propanol in the environment, particularly in
the air (gas phase), we believe its use as a model for VOCs is interesting to study.

2. Materials and Methods

2.1. Materials
All chemical products used in this work are provided by Aldrich (Grenoble, France), including:
titanium (IV) butoxide (97%); ethanol (≥99.0%); nitric acid (≥65%); potassium bromide (≥99%); silver
nitrate (≥99.8%); and 2-propanol (≥99.5%). The paper used is a conventional filter paper provided by
Whatman (Grenoble, France), with a grammage and thickness of 87 g/m2 and 180 µm, respectively.

2.2. Synthesis of Paper–TiO2 –AgBr

TiO2 sol was synthesized as follows: 1 (w/v) % of titanium (IV) butoxide was added as a precursor
to a mixture of ethanol and acetic acid (90/10 wt %) under constant stirring overnight at an ambient
temperature. Subsequently, 20 mL of nitric acid solution (1 M) was added dropwise to the mixture
with continuous stirring. After that, the entire mixture was placed in an autoclave and heated at 140 ◦ C
for 3 h in order to form TiO2 sol nanoparticles (hydrothermal procedure). An aqueous solution of AgBr
was freshly prepared by mixing a solution of AgNO3 (10−4 M) with a solution of KBr (10−4 M), and
then 20 mL of such AgBr solution (10−4 M) was added to TiO2 sol under constant stirring for 1 h at
room temperature, and finally the cellulose paper was immersed in the TiO2 –AgBr suspension for 2 h
at an ambient temperature. After removing the paper from the TiO2 –AgBr suspension, we dried it in
the oven at 60 ◦ C for 3 h. This sample is referred to as paper–TiO2 –AgBr.
For paper–TiO2 , the same steps were used to prepare paper–TiO2 –AgBr, but without adding the
AgBr solution.

2.3. Characterization
In this work, the prepared samples were characterized by several techniques:
Raman spectra were recorded on a LabRAM Analytical Raman micro-spectrograph (Jobin-Yvon,
Horiba group, Longjumeau Cedex, France) using a He–Ne laser source as exciting radiation
(λ = 632.8 nm) and an air-cooled CCD (Charge-Coupled Device) detector. The acquisition time
was 100 s.
FE–SEM characterization was performed using a Merlin FEG SEM from Carl Zeiss (ZEISS
SUPRA40, Oberkochen, Germany), coupled with an SDD XMAX Energy Dispersive X-ray spectrometer
(EDX) from Oxford Instruments and powered with the AZtec system (Carrollton, TX, USA). Prior to
SEM analysis, the samples were coated with about 1 nm of platinum.
X-ray diffraction patterns were registered using a BRUKER AXS diffractometer (Madison, WI,
USA) with a Cu-Kα radiation, generated at 30 kV, and an incident current of 100 mA. Samples in the
form of thin film were analyzed from 2θ = 5◦ to 70◦ , using scanning steps of 0.05◦ and a time per step
of 100 s.
Nanomaterials 2020, 10, 470 4 of 13

The optical properties of the prepared sample were evaluated using a Perkin Elmer Lambda 35
spectrophotometer (Perkin Elmer, Waltham, MA, USA) operating system of between 200 and 700 nm.
The UV-vis spectra were recorded in the reflectance mode on the dried samples. The reflectance
R was obtained from each sample in the UV-vis spectral regions, and the remission function F(R),
corresponding to the absorbance of the sample, was calculated using the Kubelka–Munk equation for
optically thick samples.
To investigate the quantity of TiO2 and AgBr deposited on the surface of the paper,
thermogravimetric analysis was performed using a TGA 400 (Perkin Elmer, Waltham, MA, USA). The
paper sample was heated from 30 ◦ C to 600 ◦ C at a rate of 10 ◦ C min−1 under an air flow (30 mL/min).

2.4. Photoactivity Experiments

All photodegradation tests of 2-propanol in the gaseous phase were carried out in a batch type
reactor by prepared photocatalysts. The reactor used in this work was made of Pyrex glass, and has a
cylindrical form (height: 14.0 cm, diameter: 9.0 cm and volume of 890 cm3 ).
Before starting the photodegradation process of 2-propanol, the photoreactor was purified from
any gas by saturating the reactor with oxygen for 30 min. Subsequently, 2-propanol was injected by a
septum positioned in a side wall of the photoreactor. The initial concentration of 2-propanol in the gas
phase was adjusted to 91 µM.
Before illumination, the system is kept in dark conditions for 1 h in order to reach adsorption
equilibration between the catalyst and the contaminant (2-propanol). The reactor was located inside
the SOLARBOX apparatus (CO.FO.ME.GRA., Milan, Italy) and equipped from the top with a Xenon
lamp (1500 W) that simulates solar power. It is also equipped with a water filter placed between the
reactor and the lamp in order to cutoff the infrared radiation and maintain the temperature inside
the reactor at 27 ◦ C. In this work, the ultraviolet irradiation emitted by the Xenon lamp used was
equal to 10 W m−2 in the range of 315–400 nm, and was measured by the UVX Digital radiometer. The
photocatalytic test for each sample prepared in this work lasted about 5 h of illumination. During fixed
time periods, 200 µL of gas was withdrawn from the photoreactor by means of a gas-tight syringe
for analysis.
Concentrations of 2-propanol and intermediate products were monitored by a GC–17A
Shimadzu gas chromatograph equipped with a HP–1 column and a flame ionization detector (FID)
(Shimadzu Europa GmbH, Albert-Hahn-Str. 6-10, Duisburg, Germany), while CO2 was measured
by a 60/80 Carboxen column in an HP6890 gas chromatograph equipped with a TCD (Thermal
Conductivity Detector).

2.5. Bacteria Preparation and Antibacterial Activity Tests

The antibacterial activity was evaluated by the disc diffusion method, without the evaluation of
possible silver released, using E. coli ATCC 25,922 as (Gram-) bacterium [15]. In brief, the bacterial
preinoculum cultures were grown overnight at 37 ◦ C in 20 mL of nutrient broth (made of 1 g/L beef
extract; 5 g/L neutralized peptone; 2 g/L yeast extract; and 5 g/L NaCl) subjected to horizontal shaking
at 250 rpm. Then, 100 µL of the culture suspension with a concentration of 106 CFU/mL was spread on
the agar plates. Circular samples of paper–TiO2 –AgBr and of the neat paper (used for comparison)
were cut (approximately 1.5 cm in diameter) and placed on the surface of the inoculated culture
medium. After incubation under daylight for 24 h at 37 ◦ C, samples were visually examined for the
growth of bacteria in the area surrounding the film.

3. Results and Discussion

3.1. Raman Spectroscopy

Raman was used to confirm the presence of TiO2 on the surface of the modified paper. Thanks to
the strong Raman scattering of TiO2 , it is possible to probe its presence, even at content lower than 1%.
Nanomaterials 2020, 10, 470 5 of 13

Nanomaterials 2020, 10 5 of 13
In Figure 1, the appearance of an intense band at ~147 cm−1 (Eg ) and two minor bands at 637 cm−1
(E g ) and 516
According the−1literature,
to cm (A1g ) proved the at
the band presence
~147 cmof−1(Ecrystalline TiOto
g) is assigned 2 anatase on cellulose
the symmetric paper
stretching [10,16].
vibration
According to while
the literature, −1
of O–Ti–O, the twothe bandat
bands at 637
~147cm
cm (E(E
−1 ) is assigned
g) gand 516 cm to(A
−1 the
1g)symmetric stretching vibration
are due, respectively, to the
of O–Ti–O, stretching
symmetric while the vibration
two bandsand 637 cm−1 (Eg ) and
at antisymmetric bending516 cm −1 (A ) are due, respectively, to the
vibration 1g of O–Ti–O in TiO 2 . Features of
symmetric stretching vibration and antisymmetric bending vibration of
cellulose were also observed, with typical bands at 329, 375, 439, 1094, 1116, 1292, 1414 andO–Ti–O in TiO 2 . Features of
1469 cm −1,
cellulose
which arewere also observed,
consistent with typical
with cellulose bands atNo
I data [10,17]. 329, 375, 439,of1094,
evolution 1116, 1292,of1414
the frequency cm−1 ,
and 1469 bands
the cellulose
which are consistent
was noted followingwith cellulose I data [10,17].
the functionalization Nosuggesting
process, evolution ofthatthethe
frequency
graftingofofthe
TiOcellulose bands
2 took place at
was noted following
the surface the functionalization
of the cellulose fiber, and also process,
that the suggesting
cellulose that
paperthecontinued
grafting ofto
TiO 2 took place
maintain at the
its crystal
surface of the cellulose fiber, and also that the cellulose paper continued to maintain its crystal structure.
structure.

Figure1.1. Raman
Figure Ramanspectra
spectraof
ofneat
neatpaper
paper(a),
(a),paper–TiO
paper–TiO22(b)
(b) and
and paper–TiO
paper–TiO22–AgBr
–AgBr (c).
(c).

For
For paper–TiO
paper–TiO22–AgBr,
–AgBr, thethe intensities
intensities of
of the
the three
three characteristic
characteristic peaks
peaks of
of anatase
anatase TiO
TiO22 changed
changed
compared to those observed for paper–TiO , and such an effect might be induced
compared to those observed for paper–TiO2, and such an effect might be induced by the presence of
2 by the presence
of AgBr [18–20]. The Thegreatest
greatestpeak
peak at
at 146.62
146.62 cm cm−1−1 detected for the paper–TiO shifted at higher
AgBr[18,19,20]. detected for the paper–TiO22 shifted at higher
wavenumbers −1 −1
wavenumbersof of148.98
148.98cm
cm−1 after
after loading
loadingthe
theAgBr.
AgBr.In Inaddition,
addition,thethepeak
peakatat259
259cmcm−1,, which
which is
is typical
typical
of AgBr, was clearly detected, along with both bands of TiO and cellulose, respectively,
of AgBr, was clearly detected, along with both bands of TiO2 and cellulose, respectively, confirming
2 confirming
the
the successful
successful loading
loading ofof AgBr
AgBr andand TiO
TiO22 on
on the
the surface
surface ofof the
the paper.
paper.

3.2.
3.2. SEM
SEM Observation
Observation
In
In order
order toto study
study the
the surface
surface morphology
morphology of of various
various prepared
prepared samples,
samples, the
the FE–SEM
FE–SEM technique
technique
was
was adopted. The FE–SEM images of paper cellulose before and after being treated with TiO
adopted. The FE–SEM images of paper cellulose before and after being treated with TiO22 are
are
shown
shownininFigure Figure2. The untreated
2. The paperpaper
untreated comprises an intertwined
comprises fibrous network,
an intertwined with the regulation
fibrous network, with the
of fibers in aofrandom
regulation fibers inplane orientation,
a random planewhich is the origin
orientation, which of is
thethe
strength
originofofpaper. Regarding
the strength paper
of paper.
treated
Regarding withpaper
TiO2 , treated
fine elements
with TiO of cellulose fibers no longer appeared, masked by a thin coating layer,
2, fine elements of cellulose fibers no longer appeared, masked by
presumably associated to TiO 2 . In
a thin coating layer, presumably associated topaper–TiO 2 –AgBr, thepaper–TiO
TiO2. In surface of 2the paper
–AgBr, theissurface
coated with
of thea paper
layer of
is
TiO 2
coated, masking the morphological details of cellulose fibers, revealing at higher magnification
with a layer of TiO2, masking the morphological details of cellulose fibers, revealing at higher tiny NPs
of about 50 to 100
magnification tinynmNPsinofsize immobilized
about 50 to 100 nmonin the topimmobilized
size of the TiO2 layer.
on theFurther
top of the indication about
TiO2 layer. the
Further
chemical composition of the layer coating the surface of the paper was provided
indication about the chemical composition of the layer coating the surface of the paper was provided from EDX analysis
(Figure
from EDX 3), revealing the presence
analysis (Figure of Ti, or
3), revealing Ti,presence
the Ag and of Br,Ti,
in or
addition
Ti, Ag to
andC Br,
andinO,addition
in paper–TiO
to C and2 andO,
paper–TiO
in paper–TiO 2 –AgBr, respectively.
2 and paper–TiO2–AgBr, respectively.
Nanomaterials 2020, 10, 470 6 of 13
Nanomaterials 2020, 10 6 of 13
Nanomaterials 2020, 10 6 of 13

A B
A B

C D
C D

E F
E F

TiO2layer
TiO2layer

AgBrNPs
AgBrNPs

Figure 2. FE–SEM images

FE–SEM of of
images neat paper (A,B), paper–TiO (C,D)and
paper–TiO2 2(C,D) and paper–TiO 2–AgBr
(E,F).(E,F).
Figure
Figure 2.2.FE–SEM images of neat
neatpaper
paper(A,B),
(A,B), paper–TiO2 (C,D) paper–TiO2 –AgBr
and paper–TiO 2–AgBr (E,F).

Figure 3. EDX spectra of paper–TiO22 (a) and paper–TiO22–AgBr

–AgBr (b).
(b).
Figure 3. EDX spectra of paper–TiO2 (a) and paper–TiO2–AgBr (b).
3.3. XRD Characterization
3.3. XRD Characterization
 Nanomaterials 2020, 10 7 of 13
Nanomaterials 2020, 10, 470 7 of 13

The XRD pattern of paper–TiO2–AgBr is shown in Figure 4, with the superposition of the
diffraction pattern of AgBr and TiO2anatase. The main intensity peaks that are clearly visible are those
3.3. XRD Characterization
corresponding to cellulose I at 14.9°, 16.6°, 22.65°and 34.4° 2θ assigned to (1–10), (110), (200) and (004),
The XRD[21].
respectively pattern
Otherofminor
paper–TiO 2 –AgBr
peaks with weakis intensity
shown in Figure
at 30.9°, 4, with
44.3° and 55.0°the 2θ
superposition
were assigned oftothe
diffraction pattern of AgBr and
the AgBr phase, according to the TiO anatase. The main intensity peaks that are clearly
2 Inorganic Crystal Structure Database (ICSD) reference. The visible are those
corresponding to cellulose ◦ ◦ ◦ ◦
diffraction peaks of TiO2I anatase—the
at 14.9 , 16.6 presence
, 22.65 and of 34.4
which2θwas assigned to (1–10),
confirmed (110), (200)
by Raman (Figureand1)—(004),
respectively [21]. Other
cannot be clearly minor
identified, peaks with
although an evidentshoulder 30.9◦ , 44.3◦ and
weak intensityinatcorrespondence of 55.0 ◦ 2θ were assigned
the most intense peak
to of
thetheAgBr
TiO2 phase,
anatase according to the
ICSD reference Inorganic
at 25.2° 2θ canCrystal
be seenStructure Database
in the diffraction (ICSD)
patterns of reference.
both samples The
of the paper–TiO
diffraction peaks of2–AgBr (as preparedpresence
TiO2 anatase—the and afterof thewhich
photocatalytic test, curves
was confirmed by Raman a, b). (Figure 1)—cannot
be clearlyAfter the photocatalytic
identified, althoughtest, the peaks assigned
an evidentshoulder in to AgBr (marchedof
correspondence with
the asterisk *) disappeared,
most intense peak of the
TiOlikely due
anatase to the
ICSD formation
reference of
at 25.2 ◦ 2θ can
metallic Ag not
be easily
seen in detectable
the due
diffraction to its
patterns nanometric
of both size,
samples and/or
of the
2
because the mean peak at 38.2° 2θ can be overlapped by secondary
paper–TiO2 –AgBr (as prepared and after the photocatalytic test, curves a, b). TiO 2 anatase features.

Figure
Figure X-ray
4. 4. X–Raydiffractograms
diffractograms ofoffresh
freshpaper–TiO
paper–TiO22–AgBr
–AgBr (a), paper–TiO22–AgBr
(a), paper–TiO –AgBrafter
afterphotocatalytic
photocatalytic
testtest
(b),(b),
TiOTiO ◦ ◦
2 anatase ICSD
2 anatase reference
ICSD reference (n (n°
9853) (c),(c),
9853) AgBr ICSD
AgBr reference
ICSD (n (n°
reference 52246) (d),(d),
52246) metallic Ag Ag
metallic ICSD
reference (n◦ 44387)
ICSD reference (n°(e).
44387) (e).

3.4.After theCharacterization
UV-Vis photocatalytic test, the peaks assigned to AgBr (marched with asterisk *) disappeared,
likely due to the formation of metallic Ag not easily detectable due to its nanometric size, and/or
The UV-Vis absorption spectra of neat paper, paper–TiO2, fresh paper–TiO2–AgBr and paper–
because the mean peak at ~38.2◦ 2θ can be overlapped by secondary TiO2 anatase features.
TiO2–AgBr after the photocatalytic test under simulated sunlight illumination are shown in Figure 5.
3.4.The neat paper
UV-Vis presents a weak absorption in the UV domain without any absorption in the visible
Characterization
range, which is consistent with the chemical structure of paper composed mainly of cellulose. The
Theabsorption
weak UV-Vis absorption
in the UV isspectra
presumably of neat
due topaper, paper–TiO
the presence 2 , fresh
of small paper–TiO
residual lignin in2 –AgBr and
cellulose
paper–TiO –AgBr after the photocatalytic test under simulated sunlight illumination
fibers. In2paper–TiO2, absorption in the UV-domain of between 300 to 400 nm was strongly enhanced, are shown
in which
Figureis5.consistent
The neatwithpaper thepresents a weak absorption
optical properties in the
of TiO2 with UV domain
a bandgap without
of around anyIn
3.2 eV. absorption
paper–
in TiO
the 2visible range,out
–AgBr stored which is consistent
of light, with the
the absorption chemical
in the UV domainstructure of paper
is further composed
enhanced mainly of
in comparison
with that
cellulose. Theof weak
paper–TiO 2, without
absorption any
in the UV absorption in thedue
is presumably visible domain.
to the presenceAfter exposure
of small to sunlight
residual lignin in
stimulant
cellulose and In
fibers. photocatalytic
paper–TiO2 ,degradation
absorption in test,
thethe absorptionof
UV-domain inbetween
the UV-domain further
300 to 400 nm wasincreased,
strongly
and a broad
enhanced, absorption
which in the visible
is consistent with the range of between
optical 450–600
properties nm 2can
of TiO withbe seen. This absorption
a bandgap of around could
3.2 eV.
be due to the formation of Ag NPs on the surface of immobilized AgBr
In paper–TiO2 –AgBr stored out of light, the absorption in the UV domain is further enhanced+ in particles by the Ag
photoreduction
comparison under
with that sunlight irradiation.
of paper–TiO Indeed, this absorption band, in the visible range,
2 , without any absorption in the visible domain. After exposure
corresponds to the Ag surface plasmon
to sunlight stimulant and photocatalytic degradation resonance (SPR).
test, the absorption in the UV-domain further
increased, and a broad absorption in the visible range of between 450–600 nm can be seen. This
absorption could be due to the formation of Ag NPs on the surface of immobilized AgBr particles by
the Ag+ photoreduction under sunlight irradiation. Indeed, this absorption band, in the visible range,
corresponds to the Ag surface plasmon resonance (SPR).
Nanomaterials 2020, 10 8 of 13
Nanomaterials 2020, 10, 470 8 of 13
Nanomaterials 2020, 10 8 of 13

Figure 5. UV–vis absorption spectra of neat paper (a), paper–TiO2 (b), fresh paper–TiO2–AgBr (c) and
Figure 5.2UV–vis
Figure 5.
paper–TiO –AgBr absorption
UV–visafter spectra
spectra of
photocatalytic
absorption neat
oftest paper
paper(a),
(d).
neat (a),paper–TiO
paper–TiO22(b),
(b), fresh
fresh paper–TiO
paper–TiO22–AgBr
–AgBr (c)
(c) and
and
paper–TiO
paper–TiO22–AgBr
–AgBr after
after photocatalytic
photocatalytic test
test (d).
(d).
3.5. Thermogravimetric Analysis (TGA)
3.5. Thermogravimetric Analysis (TGA)
3.5. Thermogravimetric Analysis (TGA)
Under air flow, TGA analysis of the different paper samples has been performed to assess the
Under air flow, TGA analysis of the different paper samples has been performed to assess the
thermal Under air flow,
stability afterTGA analysis
surface of the different paper
functionalization, samples
andestimate
also has been
estimate performed
theofamount to assess
of the
TiO2–AgBr
thermal stability after surface functionalization, and also the amount TiO2 –AgBr appended
thermal stability
appended after surface Forfunctionalization, and thealso estimate the amount of °C,
TiOfollowed
2–AgBr
on paperon paper6).
(Figure (Figure 6).studied
For all all studied
samples,samples,
the material material
was stablewasupstable up ◦to
to 250 C,250
followed by a
appended
byrapid
a rapid on paper
weight (Figure
loss from 6). For all studied samples, the material was stable up to 250 °C, followed
weight loss from 280 to280350to◦ C,350 °C, related
related to the deterioration
to the deterioration of the structure
of the cellulose cellulose through
structure
by a rapid
through weight loss
the cleavage from
of the 280 to 350
glycosidic °C, No
bonds. related to the deteriorationofofthe
meaningful the cellulose structure
the cleavage of the glycosidic bonds. No meaningful evolutionevolution initial
of the initial temperature temperature
of thermalof
through
thermal the cleavage
degradation of the glycosidic
could bonds. No meaningful evolution of the initialmeaning
temperature that of
degradation could be seen be seen
after theafter the modification
modification with TiO withand TiO and TiO
TiO 2 –AgBr, 2–AgBr,that
meaning the presence the
thermal degradation could be seen after the modification2with TiO22 and TiO2–AgBr, meaning that the
presence of TiO
of TiO2 and AgBr2 and
did AgBr did not
not improve theimprove the thermal
thermal stability of thestability of the paper
paper substrate. The ashsubstrate.
content for The ash
neat
presence of TiO2 and AgBr did not improve the thermal stability of the paper substrate. The ash
content for neat paper,
paper, paper–TiO and paper–TiO
paper–TiO 2 andwas
–AgBr paper–TiO
equal to –AgBr
24.9, 8.3 was
and equal
9.1 wt%, to 4.9, 8.3
respectively. and
This9.1 wt%,
means
content for neat2 paper, paper–TiO 2
2 and paper–TiO2–AgBr was equal to 4.9, 8.3 and 9.1 wt%,
respectively. This means
that the amounts of TiO2that the2amounts
or TiO and AgBrofpresent
TiO2 orinTiO and AgBr
the2 loaded present
paper were in the 3.4%
about loaded andpaper
4.2% were
for
respectively. This means that the amounts of TiO2 or TiO2 and AgBr present in the loaded paper were
about 3.4% and
paper–TiO and 4.2% for
paper–TiOpaper–TiO
–AgBr, 2 and paper–TiO
respectively. 2 –AgBr, respectively.
about 3.4%2 and 4.2% for paper–TiO
2
2 and paper–TiO2–AgBr, respectively.

Figure
Figure
Figure 6. Thermogravimetricanalysis
6. 6.
Thermogravimetric curvesof
analysiscurves
curves ofneat
of neatpaper
neat paper(a),
paper (a),paper–TiO
(a), paper–TiO222(b)
paper–TiO (b) and
(b)and paper–TiO
andpaper–TiO –AgBr
22–AgBr
paper–TiO (c).
(c).
2–AgBr (c).

3.6.3.6. Photocatalytic
Photocatalytic Activity
Activity
Nanomaterials 2020, 10, 470 9 of 13

3.6. Photocatalytic Activity

In order to check the efficiency of prepared photocatalysts, they were used to remove 2-propanol,
as a model of VOCs, under simulated sunlight illumination and in dry conditions. Figure 7 displays
the photodegradation of 2-propanol and formed the intermediate products as a result of photocatalytic
activity of both2020,
Nanomaterials paper–TiO
10 2 and paper–TiO2 –AgBr. 10 of 13

Figure
Figure 7. Photodegradation
7. Photodegradation of 2-propanol
of 2-propanol and formation
and formation of acetone
of acetone and COand CO2versus
2 versus irradiation
irradiation time intime
in the presence of paper–TiO (a) and paper–TiO
the presence of paper–TiO2 (a) and paper–TiO2 –AgBr (b).
2 2 –AgBr (b).

Before illumination, the system was kept in dark conditions for 1 h in order to reach the
adsorption equilibration between the catalyst and 2-propanol, although the adsorption of 2-propanol
was3.7. Mechanism
always of Transfer and Separation of Photogenerated Charges
negligible.
In order to check the effect of light, oxygen and catalysts in the photodegradation process of
The major photocatalytic reaction steps involved in the photocatalytic degradation of 2-propanol
2-propanol, some blank reactivity tests of 2-propanol in the gas phase were conducted under the same
in the presence of paper–TiO2–AgBr can be described as follows: under sunlight illumination, AgBr
experimental conditions, but without light, oxygen or a catalyst. All these 0tests concluded that there
in contact with the TiO2 layer would form by the photoreductionof Ag cluster species deposited on
is no reactivity, which means that the presence of light, oxygen and a catalyst are necessary factors
the surface of AgBr. Indeed, some evidences of Ag0 formation can be deduced from the appearance
for the photocatalytic process. Moreover, in order to investigate the stability of the cellulose paper
under sunlight irradiation of a broad absorption band in the visible range of between 450–600 nm
that we adopted in our work as a support, two blank tests were conducted for both untreated paper
(see Section 3.4). However, additional work is needed to confirm the presence of Ag0 species by XPS
and paper treated with TiO2 (paper–TiO2 ) in the same experimental conditions as before, but in the
experiments. The Ag/AgBr can be excited by visible light generating photoinduced electrons (e–) and
absence of 2-propanol and for 12 h of illumination. These two tests confirmed the stability of the paper
holes (h+). The e– will quickly transfer to TiO2 via the heterojunction, while h+ moves to AgBr. The
under illumination.
electrons are captured by adsorbed oxygen forming superoxide radicals •O2−, while the holes combine
Figure 7 shows the ability of photocatalysts prepared for the complete degradation of 2-propanol
with H2O, OH−/or Br− ions to form •OH/or Br• radicals. All of •O2−, •OH and Br• were reactive species
and the formation of acetone and carbon dioxide as intermediate products for this photodegradation.
capable of the degradation of organic molecules. Scheme I illustrates the hypothesized mechanism.
We can also note that0when the concentration of 2-propanol decreases and reaches a minimal value, then
In addition, Ag is expected to reduce the recombination of photogenerated charge carriers, as
the degradation of acetone to carbon dioxide is started. However, the degradation of 2-propanol was
reported in literature data concerning TiO2/Ag/AgBr composites [12].
faster when AgBr nanoparticles were associated with a TiO2 layer in the case of paper–TiO2 –AgBr as a
photocatalyst, confirming the effective and important role of the AgBr/Ag NPs in the photodegradation
process. To compare the activity of the different samples, the initial reaction rate of 2-propanol was
calculated in the presence of both catalysts, and the results are reported in Table 1. This table confirms
the important and useful role of AgBr NPs in improving the photodegradation process of 2-propanol
under sunlight. The increase of the initial reaction rate in the presence of paper–TiO2 –AgBr was not so
much impressive, but it is important to underline that only in the presence of paper–TiO2 –AgBr, as a
catalyst, the acetone, formed during the 2-proponol degradation, was completely degraded during
the 5 h of irradiation. On the contrary, in the presence of the other catalyst, without AgBr, only a
partial degradation of acetone was reached after the 5 h of irradiation, indicating one more time
the best performances of the paper–TiO2 –AgBr catalyst. The reasons for the increased efficiency of
paper–TiO2 –AgBr with respect to paper–TiO2 can be attributed to an improvement in the absorption
Nanomaterials 2020, 10 10 of 13

Nanomaterials 2020, 10, 470 10 of 13

of visible light (see Figure 5), which should increase the production of reactive oxygen species (ROS).
Moreover, thanks to the synergistic effect between TiO2 and AgBr/Ag nanoparticles, it could be also
hypothesized that there is a lower recombination rate of photogenerated charge carriers [22]. In
Figure 7, it also reported the evolution, in the gas phase, of the amount of CO2 deriving from the
mineralization of 2-propanol. For both catalysts, the carbon balance was fulfilled, indicating that
no other carbon containing species were formed, but 2-propanol was totally mineralized only in the
presence of paper–TiO2 –AgBr as catalyst, at least after 5 h of irradiation. This fact is very important for
a possible use of these materials for environmental remediation, as it indicates that paper–TiO2 –AgBr
is able not only to degrade the substrate, but also mineralize it to innocuous species.

Table 1. 2-Propanol initial reaction rate calculated for the different photocatalysts was tested.

Figure 7. Photodegradation of 2-propanol and formation

Photocatalysts of Reaction
Initial acetone and CO
Rate 2versus
(mol. s−1 )irradiation time
in the presence of paper–TiO2 (a) and paper–TiO2–AgBr (b).
paper−TiO2 1.7 × 10−8
paper−TiO2 −AgBr 2.1 × 10−8

3.7.
3.7. Mechanism
Mechanismofof Transfer
Transfer and
and Separation
Separation of
of Photogenerated
Photogenerated Charges
Charges
The
The major
major photocatalytic
photocatalytic reaction
reaction steps
steps involved
involved in inthe
thephotocatalytic
photocatalyticdegradation
degradation of of2-propanol
2-propanol
in
in the
the presence
presence of of paper–TiO
paper–TiO22–AgBr–AgBr can
can be
be described
described as as follows:
follows: under under sunlight
sunlight illumination,
illumination, AgBr AgBr
in contact with the TiO layer would form by the photoreductionof Ag
in contact with the TiO2 layer would form by the photoreductionof Ag cluster species deposited on
2 00 cluster species deposited on

the
the surface
surface ofof AgBr.
AgBr. Indeed,
Indeed, some
some evidences
evidences of of Ag
Ag00 formation
formation can can be be deduced
deduced from from the the appearance
appearance
under
under sunlight
sunlight irradiation
irradiation of of aa broad
broad absorption
absorption bandband in in the
the visible
visible range
range of of between
between 450–600
450–600 nm nm
(see Section 3.4). However, additional work is needed to confirm the presence
(see Section 3.4). However, additional work is needed to confirm the presence of Ag species by XPS of Ag 00 species by XPS

experiments.
experiments. The The Ag/AgBr
Ag/AgBr can can be
be excited
excited byby visible
visible light
light generating
generating photoinduced
photoinduced electronselectrons (e (e−–)) and
and
holes (h+).).The
holes (h +
Theee−will
–
willquickly
quicklytransfer
transfertotoTiO
TiO22 via
via the
the heterojunction,
heterojunction, while while h h+ moves
+
movesto to AgBr.
AgBr. The The
electrons
electrons are
are captured
captured by by adsorbed oxygen forming
adsorbed oxygen forming superoxide
superoxideradicals radicals••O O22−−,,while
whilethe theholes
holescombine
combine
with
with HH22O,
O, OHOH /or
−
− /orBrBr ions
−− ionstotoform
form OH/or
•• OH/or Br
Br radicals.
•
• radicals. All
All ofof O•• O22 , , OH
−− • • OHandandBr Br were
• • werereactive
reactivespecies
species
capable of the degradation of organic molecules. Scheme I illustrates the
capable of the degradation of organic molecules. Scheme 1 illustrates the hypothesized mechanism. In hypothesized mechanism.
In addition,
addition, Ag0Ag is expected
is 0expected to reduce
to reduce the recombination
the recombination of photogenerated
of photogenerated charge carriers,
charge carriers, as reported as
reported in literature
in literature data concerning
data concerning TiO2/Ag/AgBr
TiO2 /Ag/AgBr composites composites
[12]. [12].

Scheme 1. Photocatalytic mechanism scheme of paper–TiO2 –AgBr under sunlight irradiation.

Scheme I. Photocatalytic mechanism scheme of paper–TiO2–AgBr under sunlight irradiation.
Nanomaterials 2020, 10 11 of 13
Nanomaterials 2020, 10, 470 11 of 13

3.8. Antibacterial Properties

3.8. Antibacterial Properties
The antibacterial properties of paper–TiO2 –AgBr were qualitatively assessed by disk-diffusion
The antibacterial properties of paper–TiO2–AgBr were qualitatively assessed by disk-diffusion
protocol using E. coli as Gram–bacteria to evaluate the aptitude of modified paper to resist bacteria
protocol using E. Coli as Gram–bacteria to evaluate the aptitude of modified paper to resist bacteria
growth. For comparison reasons, the experiment was repeated by using neat paper. In material lacking
growth. For comparison reasons, the experiment was repeated by using neat paper. In material
an antibacterial effect, bacteria would adhere to the surface of the films and proliferate around the
lacking an antibacterial effect, bacteria would adhere to the surface of the films and proliferate around
sample, while an inhibition hallow around the films would be observed for samples endowed with
the sample, while an inhibition hallow around the films would be observed for samples endowed
a bactericidal effect. In Figure 8, the digital images of the neat paper and paper–TiO2 –AgBr placed
with a bactericidal effect. In Figure 8, the digital images of the neat paper and paper–TiO 2–AgBr
in an inoculated culture medium of E. coli are compared after incubation at 37 ◦ C for 24 h under
placed in an inoculated culture medium of E. Coliare compared after incubation at 37 °C for 24h under
daylight illumination.
daylight illumination.

2mm

Neat paper Paper–TiO2–AgBr

Figure 8. Digital images of the neat paper and paper–TiO2 –AgBr samples placed in E. coli culture
Figure 8. Digital images of the neat paper and paper–TiO2–AgBr samples placed in E. Coli culture
medium after incubation at 37 ◦ C for 24 h under daylight.
medium after incubation at 37 °C for 24h under daylight.
The neat paper did not show any antibacterial activity, which is expected due to the sensitivity
The neat to
of cellulose paper did not
bacterial showBy
attacks. any antibacterial
contrast, activity,
the sample which is –AgBr
paper–TiO expected due toa the
showed clearsensitivity
inhibition
2
ofzone
cellulose
at thetoouter
bacterial
edge,attacks.
indicatingBy contrast, the sample
that bacteria cannot paper–TiO –AgBr showed
proliferate2nearby the sample. a clear
Theinhibition
activity of
zone at the outer
paper–TiO edge, indicating that bacteria cannot proliferate nearby the sample. The activity of
2 –AgBr is presumably due to the presence of Ag/AgBr coupled with TiO2 , which is able to
paper–TiO 2–AgBr is presumably due to the presence of Ag/AgBr coupled with TiO2, which is able to
kill bacteria after exposure to visible light through a combination of a multitude of effects [23]: (i) the
kill bacteria after
interaction of Agexposure
with the to visibleouter
bacteria lightmembrane,
through a combination of a multitude
inducing structural changesof effects
that lead [23]: (i)death;
to cell the
interaction of Ag with the bacteria outer membrane, inducing structural changes that
(ii) the interaction of released silver ions with sulfur and phosphorus in DNA, resulting in the inactivation lead to cell
death;
of the(ii)
DNAthe interaction
replication;ofand
released silver
(iii) the ions with
generation of sulfur and
reactive phosphorus
oxygen speciesin(ROS)
DNA,upon resulting in theto
exposure
inactivation of the DNA replication; and (iii) the generation of reactive oxygen species (ROS) upon
visible light, catalyzing the destruction of bacteria through a photocatalytic effect [24]. The antibacterial
exposure to visible light, catalyzing the destruction of bacteria through a photocatalytic effect [24].
property of paper–TiO2 –AgBr is of great benefit for the durability of paper-based photocatalysts
The antibacterial property of paper–TiO2–AgBr is of great benefit for the durability of paper-based
when their long-term use is considered. Cellulose-based substrates are known to be sensitive to
photocatalysts when their long-term use is considered. Cellulose-based substrates are known to be
bacteria proliferation [25], namely in humid atmospheres, causing the disintegration of paper through
sensitive to bacteria proliferation [25], namely in humid atmospheres, causing the disintegration of
a biodegradation process. Hence, in addition to its beneficial effect on photocatalytic efficiency under
paper through a biodegradation process. Hence, in addition to its beneficial effect on photocatalytic
simulated sunlight, the presence of AgBr will extend the shelf life of a paper–TiO2 –AgBrphotocatalyst
efficiency under simulated sunlight, the presence of AgBr will extend the shelf life of a paper–TiO2–
when exposed to a humid atmosphere.
AgBrphotocatalyst when exposed to a humid atmosphere.
4. Conclusions
4. Conclusions
In summary, a simple method to produce paper–TiO2 decorated with AgBr nanoparticles was
In summary,
reported. Using an a simple method
inexpensive, to produce
non-toxic paper–TiOprocedure,
hydrothermal 2 decoratedthe with
TiOAgBr nanoparticles was
2 –AgBr composite grows
reported. Using an inexpensive, non-toxic hydrothermal procedure,
directly on the surface of the paper at a mild temperature (140 C). From the FE–SEM◦ the TiO 2 –AgBr compositestudy, grows
it was
directly
observed on the
thatsurface of the paper
TiO2 formed a thinatlayer
a mild temperature
coating the paper(140 °C). From
surface, the top
on the FE–SEM
of whichstudy, it was
AgBr was
observed that TiO 2 formed a thin layer coating the paper surface, on the
immobilized in the form of dispersed NPs in the case of paper–TiO2 –AgBr. The Raman technique top of which AgBr was
immobilized
confirmed the in presence
the form ofofadispersed
thin layer NPs of TiOin2 anatase
the caseonofthe
paper–TiO 2–AgBr.
paper surface. The Raman
Paper–TiO technique
2 –AgBr showed
confirmed the presence
good efficiency of a thin layer
in the removal of TiO2anatase
of 2-propanol in the on
gasthe paper
phase surface.
under Paper–TiO
simulated 2–AgBr
sunlight showed
illumination,
good efficiency in the removal of 2-propanol in the gas phase under simulated
suggesting its potential use for environmental remediation in treating polluted air. In addition, sunlight illumination,
suggesting
paper–TiOits potential use for environmental remediation in treating polluted air. In addition,
2 –AgBr is characterized by a very good antibacterial ability. The enhanced photocatalytic
paper–TiO
activity was 2–AgBr is characterized
attributed by a very good
to several concomitant antibacterial
factors, such as theability. The enhanced
good dispersion of AgBr photocatalytic
nanoparticles,
activity was attributed to several concomitant factors, such as the good dispersion of AgBr
Nanomaterials 2020, 10, 470 12 of 13

the in-situ formation of Ag0 NPs on the AgBr surface with enhanced visible-light absorption and the
hypothesized efficient separation of the photo-generated charge (h+ /e− ).
In conclusion, the immobilization of TiO2 –AgBr on a flexible support as cellulose paper offers
wide possibilities for its application in the removal of indoor VOCs and bacteria. Work is in progress
to investigate the photocatalytic activity under halogen lamps and LEDs.

Author Contributions: Conceptualization—M.S. and S.B. (Soraa Bouattour); Validation—G.M., L.F.L. and
S.B. (Sami Boufi); Investigation—M.S. and G.M.; Resources—S.B. (Soraa Bouattour), M.G., G.M., L.F.L. and
S.B. (Sami Boufi); Data Curation—M.S.; Writing—Original Draft Preparation—M.S.; Writing—Review and
Editing—G.M., L.F.L. and S.B. (Sami Boufi); Visualization—M.S.; Supervision—S.B. (Sami Boufi) and M.G.;
Funding Acquisition—L.F.L. All authors have read and agreed to the published version of the manuscript.
Funding: The Italian MIUR Projects PON (2015–2020) “Energie per l’Ambiente”–TARANTOARS01_00637 and
PON ARS01_00293 “Thalassa” are acknowledged for partially funding this research.
Acknowledgments: This work has been carried out in the field of the COST Action CA17136-Indoor Air Pollution
Network. The authors are grateful to F. Giordano (ISMN–CNR) for XRD measurements, and to S. Romeo
(ISMN-CNR) and G. Napoli (ISMN–CNR) for assistance in the financial management of PON Projects.
Conflicts of Interest: The authors declare no conflict of interest.

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