polymers

Article
Antibacterial Nanocellulose-TiO2/Polyester Fabric for the
Recyclable Photocatalytic Degradation of Dyes
Jiacheng Tan 1,† , Hangjun Deng 1,† , Fangfang Lu 2 , Wei Chen 3 , Xiuping Su 1, * and Hairong Wang 2, *

1 Key Laboratory of Functional Fibers and Intelligent Textiles, Yuanpei College, Shaoxing University,
Shaoxing 312000, China; [email protected] (J.T.); [email protected] (H.D.)
2 Zhoushan Institute of Calibration and Testing for Quality and Technology Supervision,
Zhoushan 316000, China; [email protected]
3 College of Textile Science and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China;
[email protected]
* Correspondence: [email protected] (X.S.); [email protected] (H.W.)
† These authors contributed equally to this work.

Abstract: In this paper, we report an antibacterial, recyclable nanocellulose–titanium dioxide/polyester

nonwoven fabric (NC-TiO2 /PET) composite for the highly efficient photocatalytic degradation of
dyes. The NC-TiO2 was loaded onto the surface of flexible PET nonwoven fabric through a simple
swelling and dipping method. The NC-TiO2 in the particle size range of ~10 nm were uniformly
attached to the surface of the PET fibers. The NC-TiO2 /PET composite has the ability to achieve
the stable photocatalytic degradation of dyes and presents antibacterial properties. The degradation
rates to methylene blue (MB) and acid red (AR) of the NC-TiO2 /PET composite reached 90.02% and
91.14%, respectively, and the inhibition rate of Escherichia coli was >95%. After several rounds of
cyclic testing, the photocatalytic performance, antibacterial performance, and mechanical stability of
the NC-TiO2 /PET composite remained robust.

Keywords: TiO2 ; polyester; nanocellulose; photocatalytic degradation; antibacterial property

Citation: Tan, J.; Deng, H.; Lu, F.; 1. Introduction

Chen, W.; Su, X.; Wang, H.
Antibacterial Nanocellulose-TiO2 /
Despite the clean, non-toxic tap water consumed by most urban dwellers in modern
Polyester Fabric for the Recyclable
societies, water pollution still poses a threat to less developed regions [1,2]. Also, the
Photocatalytic Degradation of Dyes.
coronavirus pneumonia that has been raging over the past few years reminds us, once again,
Polymers 2023, 15, 4376. https:// of the threat that microorganisms and viruses pose to human life and health [3,4]. Dye-
doi.org/10.3390/polym15224376 containing wastewater can destroy the ecological balance and also cause cancer if consumed
by organisms (including humans) for long periods of time, even at low concentrations [5–7].
Academic Editor: Antonio Pizzi
Therefore, researchers have invested significant efforts in studying wastewater treatment
Received: 6 September 2023 materials [8].
Revised: 31 October 2023 Titanium dioxide (TiO2 ), a nontoxic, cheap, stable, and excellent photocatalyst, shows
Accepted: 1 November 2023 its excellent treatment ability for various types of water pollutants [9,10]. However, the
Published: 10 November 2023 large-scale application of nanoparticles still poses problems, such as their easy aggregation
and difficulties in their separation from water treatment systems. Recently, the doping
of TiO2 with nonmetals and metals or its coupling with other semiconductors have been
studied to improve its photocatalytic performance. Li et al. [11], using the co-graft poly-
Copyright: © 2023 by the authors.
merization of 2-hydroxyethyl acrylate (HEA) with TiO2 nanoparticles on cotton fabrics
Licensee MDPI, Basel, Switzerland.
via γ-ray irradiation, prepared a photocatalytic composite highly efficient against organic
This article is an open access article
pollutants. Alhalili et al. [12] removed dithioterethiol (DTT) from water using membranes
distributed under the terms and
conditions of the Creative Commons
of cellulose acetate (AC) and AC-doped ZnO/TiO2 nanoparticles.
Attribution (CC BY) license (https://
Other scientists are embedding nanomaterials into fibers to advance their stability.
creativecommons.org/licenses/by/ Wang et al. [13] used a layer-by-layer (LBL) self-assembly strategy to load TiO2 /g-C3 N4 on
4.0/).

Polymers 2023, 15, 4376. https://doi.org/10.3390/polym15224376 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 4376 2 of 11

cotton fabrics in order to obtain an efficient, stable, and reusable visible light catalytic func-
tional material. However, to further improve the stability of organic–inorganic composites,
we found that it is crucial to select efficient organic and inorganic linkers. Nanocellulose
(NC) is an ideal environmentally friendly material that is sustainable and inexpensive [14].
NC can be extracted from plants, bacteria, and marine shellfish, meaning that it is degrad-
able, flexible, hydrophilic, and rich in surface functional groups [15]. NC can act as an
interfacial “bridge” between polymers and inorganic nanomaterials, making it ideal for the
interfacial chemistry of composite materials [16–18]. Xue et al. [19] report a limited growth
strategy mediated by the self-assembly of cellulose nanocrystal (CNC) to prepare anatase
TiO2 nano-catalyst with dominantly exposed (001) reactive facets and hierarchical pore
structure for high photocatalytic activity.
Herein, this work aims to provide a simple, low-cost, and recyclable material for
the treatment of water bodies. Its recycling and reusability can be facilitated through the
use of a polyester nonwoven substrate. The TiO2 was stably loaded onto the polyester
nonwoven fabric using a simple swelling and dipping method, and the NC was introduced
as a “bridge” to facilitate the dispersion of the nanomaterials and make them firmly bonded
to each other. Finally, stable NC-TiO2 /PET composites were synthesized to treat organic
pollutants and eliminate bacteria in environmental water bodies.

2. Experimental Section
2.1. Materials
Polyester nonwovens (PET) with a gram weight of 135 g m−2 were purchased from
Texas Hongrui Geomaterials Co., Ltd. (Shandong, China). Cellulose, titanium diox-
ide nanoparticles, methylene blue (MB), acid red (AR), sodium hydroxide (NaOH), and
cetyltrimethylammonium bromide (CTAB) were purchased from Aladdin Chemistry Co.,
Ltd. (Shanghai, China).

2.2. Alkali Reduction Pretreatment of Fabric and Preparation of NC

A certain amount of clean polyester nonwoven fabric was washed and immersed in
an alkali reduction treatment solution (5 g L−1 sodium hydroxide and 1 g L−1 CTAB) with
a bath ratio of 1:20. Then, it was stirred at 95 ◦ C for 30 min, washed, and dried. The PET
fabrics used in this paper were subjected to the alkali reduction treatment. The NC was
obtained by dissolving cellulose powder in an alkaline urea solution (7 wt% of NaOH and
12 wt% of urea). After the reaction, the NC solutions were filtered and freeze-dried at
−70 ◦ C for 72 h to obtain the dry NC.

2.3. Preparation of NC-TiO2 /PET

A total of 0.2 wt% of NC and 0.2 wt%–1.0 wt% of nano-titanium dioxide (TiO2 ) were
ultrasonically dispersed for 30 min to obtain the NC-TiO2 suspension. Then, the pretreated
PET fabric was dipped into the NC-TiO2 suspension for 20 min and put under 0.3 MPa roll
pressure for one dip and one tie. Then, it was baked in a shaping dryer at 90 ◦ C for 5 min,
and the procedure for impregnating the rolls and drying them was repeated twice. Finally,
the samples were cleaned and then transferred into an 80 ◦ C vacuum-oven and baked for
40 min to obtain the NC-TiO2 /PET samples. We also prepared a group of samples without
the NC, named TiO2 -PET.

2.4. Characterization
The micromorphology and elemental composition of the materials were character-
ized using a field emission scanning electron microscope (FE-SEM, Sigma 300, ZEISS,
Oberkochen, Germany) with energy-dispersive X-ray spectroscopy (EDS). The TiO2 con-
tent on the fabric was quantified using a atomic absorption spectrometer (AAS, Solaar
M6, Thermo, Waltham, MA, USA) with an air-acetylene flame. Separate hollow cathode
lamps radiating at wavelengths of (Ti) 248.3 nm were used to determine the amount of
TiO2 . The material phases of dried NC-TiO2 /PET fabric and PET fabric surface structures
Polymers 2023, 15, 4376 3 of 11

were analyzed using XRD. The crystal phases in the samples were analyzed using X-ray
diffractometry (XRD, D8, Bruker, Frankfurt, Germany). Fourier-transform infrared (FTIR)
spectrometry (FTIR, Nicolet IS50, Thermo, Waltham, MA, USA), equipped with an ATR
accessory, was used to examine the functional groups of the samples. All the spectra
were recorded in the wavenumber range from 4000 to 450 cm−1 , with a 4 cm−1 resolution.
An X-ray photoelectron spectroscopy (XPS, K-Alpha Thermo, Waltham, MA, USA) was
performed using an electronic spectrometer. The mechanical strength of the samples was
tested through a universal testing machine (Instron 5943, Norfolk, MA, USA).

2.5. Photocatalytic Performance

The PET and NC-TiO2 /PET materials were cut into sizes of 2 × 2 cm. First, the mock-
contaminants MB (20 mg L−1 ) and AR (20 mg L−1 ) were prepared, and then 150 mL of
these solutions was poured into clean Petri dishes. The NC-TiO2 /PET and PET nonwoven
fabrics were added to the Petri dishes and left in a dark room for 2 h to reach adsorption
equilibrium. After reaching the adsorption equilibrium, the dishes were transferred to
a 16 W UV lamp (λ ≈ 280 nm) for light irradiation, and the vertical irradiation distance
between the dishes and the UV lamp was adjusted to a uniform 20 cm. Color changes of the
fabric’s surface and of the contaminant solution in the dishes were observed 30 min, 60 min,
120 min, and 180 min after light irradiation had begun. Changes in the dye solutions’
concentration were measured under a UV spectrophotometer and recorded using digital
photography. The absorbance of the MB and AR dye solutions were tested at 664 nm and
532 nm. All the photocatalytic degradation experiments were performed three times, and
the average value was taken. The degradation rate of the dyes was analyzed using the
UV absorption spectrum. The degradation rates (%) of the MB and AR solutions were
calculated as follows:
C0 − C
Degradation rate(%) = 100% (1)
C0
where C is the dye (MB and AR)’s concentration (mg L−1 ) at time t (min), and C0 is the
initial dye concentration (mg L−1 ). All the experiments of photocatalytic degradation of
the dyes were carried out three times, and the average value was taken.

2.6. Antibacterial Performance

The Gram-negative bacterium Escherichia coli (E. coli, ATCC 25922) was selected to
test the antibacterial performance of the NC-TiO2 /PET. The procedure was carried out on
a clean bench, and all the materials used in the antimicrobial activity test were sterilized
in an autoclave. The samples were evaluated for their antibacterial performance using
the qualitative agar diffusion method and the quantitative mean colony-forming unit
method [20]. The antimicrobial rates of the samples were calculated as follows:

N0 − N1
Antimicrobial Rates(%) = 100% (2)
N
0

where N1 is the average number of E. coli in the liquid medium in which the NC-TiO2 /PET
was immersed, and N0 is the average number of E. coli in a pure medium with normal
bacterial growth.

3. Results and Discussion

3.1. Microscopic Surface Structures
The microscopic surface structures of the PET and NC-TiO2 /PET were observed
using FE-SEM. From Figure 1a–c, it can be seen that the surface structure of the pretreated
polyester fiber was rough and that the fiber’s diameter was about 10–20 µm. Figure 1d–f
shows the magnified images of the NC-TiO2 /PET. The high-resolution FESEM image
in Figure 1f shows that the surface of the NC-TiO2 /PET had an even distribution of
Polymers 2023, 15, x FOR PEER REVIEW 4 of 11

Polymers 2023, 15, 4376 4 of 11

shows the magnified images of the NC-TiO2/PET. The high-resolution FESEM image in
Figure 1f shows that the surface of the NC-TiO2/PET had an even distribution of nanopar-
ticles (NPs) on(NPs)
nanoparticles the individual fibers and
on the individual thatand
fibers thethat
average diameter
the average of theseofNPs
diameter was
these NPs10
nm. 10
was Compared to the pure
nm. Compared PET
to the fabric,
pure PETthe atomic
fabric, thepercentage of Ti on the
atomic percentage NC-TiO
of Ti on the2/PET
NC-
surface
TiO reported
2 /PET surfacewas aboutwas
reported 0.77%,
aboutaccording to the EDStoresults
0.77%, according the EDS inresults
Figurein
1g,h. Further-
Figure 1g,h.
more, the EDS mapping in Figure 1i indicates that the TiO2 was densely
Furthermore, the EDS mapping in Figure 1i indicates that the TiO 2 and homogene-
was densely and
ously distributed on the surface of the PET fabric.
homogeneously distributed on the surface of the PET fabric.

Figure1.1.Microstructure
Figure Microstructureandandelemental
elemental compositions
compositions of PET
of PET andand NC-TiO
NC-TiO 2/PET.
2 /PET. (a–c)
(a–c) FE-SEM
FE-SEM im-
images
ages
of of (d–f)
PET; PET; FE-SEM
(d–f) FE-SEM
imagesimages of NC-TiO
of NC-TiO 2 2
/PET; /PET;
(g,h) (g,h)
EDS ofEDS
PETof PET
and and
NC-TiO NC-TiO
2 /PET,2 /PET, respec-
respectively;
tively;
and and (i)
(i) EDS EDS mapping
mapping of NC-TiO
of NC-TiO 2 /PET.
2/PET.

3.2. Chemical
3.2. Chemical Characterizations
Characterizations
The chemical characterization
The chemical characterizationof ofthe
thePET,
PET,NC, NC, PET-TiO
PET-TiO 2, and NC-TiO
2 , and NC-TiO2/PET werewere
2 /PET per-
formed using
performed using FTIR spectroscopy.
FTIR spectroscopy. In In
Figure
Figure2, it
2, can bebe
it can seen that
seen thatthethe
characteristic
characteristicpeak
peakof
−1 . The peaks at 1090 and 1240 cm−1 were
thethe
of -C=O
-C=O in in
thethePET
PET waswasobserved
observed atat
1700
1700cmcm−1. The peaks at 1090 and 1240 cm−1 were the
−1
vibrations
the of the
vibrations -C-O
of the groups
-C-O groupsin the PET.
in the TheThe
PET. characteristic
characteristicpeakspeaksat 1015 cmcm
at 1015 −1 andand720
− 1
cm−1cm
720 corresponded
corresponded to theto-C-H of theofPET.
the -C-H Compared
the PET. Comparedto thetoPET, the characteristic
the PET, peak
the characteristic
peak at 2899 −1
at 2899 cm−1 cmin thein the NC-TiO
NC-TiO /PET was the typical band for the cellulose nanomaterial
2/PET2 was the typical band for the cellulose nanomaterial mol-
molecules, and the strong characteristic peaks below 700−1cm −1
ecules, and the strong characteristic peaks below 700 cm were were
due toduetheto the bending
bending of the
of the -Ti-O bonds in the
-Ti-O bonds in the NC-TiO2/PET [21]. NC-TiO 2 In addition, the characteristic peaks of the peaks
/PET [21]. In addition, the characteristic of
cellulose
the cellulose nanofibers were clearly visiblebands’
in the3600–3000
broad bands’ − 1
nanofibers were clearly visible in the broad cm−13600–3000
region andcm were region
caused
and were caused by telescopic
by telescopic vibrations within vibrations
and betweenwithin
the and
O-H between
bonds. Thethe O-H
large bonds. The in
absorption large
the
absorption in the 1200–860 cm −1 spectral region was caused by the vibrations of the glucose
1200–860 cm spectral region was caused by the vibrations of the glucose rings of C-H, C-
−1
rings of C-H, C-O, and C-O-C of the NC-TiO2 /PET. The FTIR of the NC-TiO2 /PET showed
O, and C-O-C of the NC-TiO2/PET. The FTIR of the NC-TiO2/PET showed intense absorp-
intense absorption peaks associated with O-H stretching−1at 3430 cm−1 and O-H bending at
tion peaks associated with O-H stretching at 3430 cm and O-H bending at 1630 cm−1,
1630 cm−1 , which were similar to those observed in the NC, which were shifted to lower
which were similar to those observed in the NC, which were shifted to lower
wavenumbers. The observed shift was related to the involvement of the -OH groups in the
formation of strong, intermolecular hydrogen-bonding interactions between the hydroxyl
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Polymers 2023, 15, x FOR PEER REVIEW 5 of 11

Polymers 2023, 15, 4376 5 of 11

wavenumbers. The observed shift was related to the involvement of the -OH groups in
wavenumbers. The observed shift was related to the involvement of the -OH groups in
the formation of strong, intermolecular hydrogen-bonding interactions between the hy-
the formation of strong, intermolecular hydrogen-bonding interactions between the hy-
droxyl groups in the cellulose chains and the Ti-OH groups in the TiO2 nanoparticles.
droxyl
groups groups in the cellulose
in the cellulose chains chains
and the and the Ti-OH groups in the TiO2 nanoparticles.
Interestingly, since -OH promotes theTi-OH groups
formation ofin the
-OH TiO2 nanoparticles.
radicals Interestingly,
in the photocatalytic pro-
Interestingly,
since -OH since
promotes -OH
the promotes
formation the
of -OHformation
radicalsof
in-OH
the radicals in theprocess,
photocatalytic photocatalytic pro-
the increase
cess, the increase of surface groups’ -OH may positively affect the photodegradation ac-
cess,
of the increase
surface groups’ of
-OHsurface groups’ -OH
may positively may
affect thepositively affect theactivity
photodegradation photodegradation
of the NC-TiOac-2
tivity of the NC-TiO 2 nanocomposites [22].
tivity of the NC-TiO
nanocomposites [22].2 nanocomposites [22].

Figure 2. FTIR spectra of PET, NC-TiO2/PET, and NC.

Figure 2. FTIR
FTIR spectra of PET, NC-TiO2/PET,
/PET,and
andNC.
NC.

Figure3a
Figure 3a showsthethe XPSsurvey
survey spectraofofthe the PETand and NC-TiO/PET,2/PET, which show
Figure 3a shows
shows the XPS
XPS survey spectra
spectra of the PET PET and NC-TiO which show
NC-TiO22/PET, which show
that the
that the
the PETPET contained
PET contained only
contained only C and O, while the NC-TiO 2 /PET also contained Ti. Figure 3b
that only C
C and
and O,O, while
while the
the NC-TiO
NC-TiO22/PET /PET alsoalso contained
contained Ti.
Ti. Figure
Figure 3b
3b
shows
shows the the Ti
the Ti 2p
Ti2p spectra,
2pspectra, where
spectra,where the
wherethe peaks
thepeaks
peaksof 2p 1/2 and 2p 3/2 appeared at 464.3 eV and 458.5
shows ofof2p2p and
1/2 1/2
and2p3/22p 3/2 appeared
appeared at 464.3
at 464.3 eV and eV458.5
and
eV, respectively,
458.5 eV, indicating
respectively, the presence
indicating the of Ti4+of
presence 4+ (TiO
Ti ) [23].
4+ 2(TiO ) [23].
eV, respectively, indicating the presence of Ti (TiO2) [23]. 2

Figure3.3.XPS
Figure XPSspectra
spectraofofPET
PETand
andNC-TiO
NC-TiO 2/PET.(a)
2 /PET. (a)XPS
XPSsurvey
surveyspectra
spectraofofPET
PETand
andNC-TiO
NC-TiO 2/PET.
2 /PET.
Figure 3. XPS spectra of PET and NC-TiO2/PET. (a) XPS survey spectra of PET and NC-TiO2/PET.
(b)High-resolution
(b) High-resolutionXPS
XPS2p 2pspectra
spectraofofNC-TiO
NC-TiO 2/PET.
2 /PET.
(b) High-resolution XPS 2p spectra of NC-TiO2/PET.
3.3.
3.3.Crystal
CrystalPhase
PhaseStructure
StructureAnalysis
Analysis
3.3. Crystal Phase Structure Analysis
The XRD pattern of the
The XRD pattern of the PET PETshowed
showed a characteristic
a characteristic diffraction
diffraction peakpeak of polyester
of polyester fiber
fiber The
at XRD
2θ = pattern
17.68 of another
◦ and the PET peak
showedneara characteristic
22.86 ◦ (Figurediffraction
4). The peakpattern
XRD of polyester
of the fiber
at 2θ = 17.68° and another peak near 22.86° (Figure 4). The XRD pattern of the NC-
NC-
at
TiO2θ = 17.68° and aanother peak near 22.86° peak
(Figure 4). The XRD ◦pattern of thetoNC-
TiO22/PET showed
/PET showed characteristic
a characteristic diffraction
diffraction peak of of TiO
TiO at 27.45 , in addition the
2 at2 27.45°, in addition to the char-
TiO 2/PET showed
characteristic a characteristic
diffraction peak of diffraction
the PET. Thepeak of TiO2 at 27.45°,
characteristic in addition
diffraction peak to
of the
the char-
(110)
acteristic diffraction peak of the PET. The characteristic diffraction peak of the (110) and
acteristic
and diffraction peakofofthe
theTiO
PET. The characteristic diffraction
27.45◦ and peak of the which
42◦ , respectively, (110) and
(111)(111) crystal
crystal planes
planes of the TiO 2 appeared
2 appeared atat27.45° and 42°, respectively, which are
are
(111) crystal
consistent planes
with ofinthe
results theTiO 2 appeared
previous at 27.45°
literature and implies
[24]. This 42°, respectively, which
that the surface of are
the
polyester fiber was successfully loaded with anatase-phase TiO2 nanoparticles.
Polymers 2023, 15, x FOR PEER REVIEW 6 of 11

Polymers 2023, 15, 4376 consistent with results in the previous literature [24]. This implies that the surface of6 the
of 11
polyester fiber was successfully loaded with anatase-phase TiO2 nanoparticles.

Figure
Figure4.4.XRD
XRDpatterns
patternsofofPET
PETand
andNC-TiO
NC-TiO2/PET.
2 /PET.

3.4.Performance
3.4. PerformanceofofPhotocatalytic
PhotocatalyticDegradation
Degradation
TiO22nanomaterials
TiO nanomaterialsare arewidely
widelyused
usedbecause
becauseofoftheir
theirexcellent
excellentphotocatalytic
photocatalyticactivity,
activity,
and the use of UV light for removing organic dyes has become an area of great
and the use of UV light for removing organic dyes has become an area of great interest in interest
in the
the water
water treatment
treatment field
field [25].
[25]. Most
Most previousphotocatalytic
previous photocatalyticmaterials
materialsfor
fortreating
treatingdye
dye
wastewater have been powder materials, which are difficult to recycle and reuse in practical
wastewater have been powder materials, which are difficult to recycle and reuse in practical
applications. Therefore, in this study, PET fabric was used as a flexible substrate, onto which
applications. Therefore, in this study, PET fabric was used as a flexible substrate, onto which
TiO2 nanomaterials were loaded to facilitate recycling and avoid secondary pollution.
TiO2 nanomaterials were loaded to facilitate recycling and avoid secondary pollution.
The effects of the composition ratio on the catalytic degradation properties of the
The effects of the composition ratio on the catalytic degradation properties of the NC-
NC-TiO2 /PET materials are shown in Table 1. The ratios of NC to TiO2 in the preparation
TiO2/PET materials are shown in Table 1. The ratios of NC to TiO2 in the preparation of the
of the composite materials were determined after a preliminary experiment optimization.
composite materials were determined after a preliminary experiment optimization. The
The degradation rate of the MB was increased from 65.07% to 90.02%, when the mass
degradation rate of the MB was increased from 65.07% to 90.02%, when the mass ratio of the
ratio of the NC/TiO2 was increased from 0.2 wt%/0.4 wt% to 0.2 wt%/0.8 wt%. However,
NC/TiO2 was increased from 0.2 wt%/0.4 wt% to 0.2 wt%/0.8 wt%. However, when the ratio
when the ratio reached 0.2 wt%/1.0 wt% of NC/TiO2 , the catalytic efficiency began to
reached 0.2 wt%/1.0 wt% of NC/TiO2, the catalytic efficiency began to decrease, as the nano-
decrease, as the nanoparticles on the surface of the sample tended to aggregate. The sample
particles
which was on the surface
formed of the
using 0.2sample
wt%/0.8 tended
wt% to
of aggregate. The sample
NC/TiO2 exhibited anwhich was catalytic
excellent formed
using 0.2 wt%/0.8
degradation ability.wt% of NC/TiO 2 exhibited an excellent catalytic degradation ability.

Table 1. The degradation rate (MB) of samples synthesized with various mass ratios of NC/TiO2 for 3 h.
Table 1. The degradation rate (MB) of samples synthesized with various mass ratios of NC/TiO2 for
3 h. Sample NC/TiO2 Degradation Rate (%)
PET
Sample
0
NC/TiO2
6.47
Degradation Rate (%)
TiO2/PET 0 wt%/0.8 wt% 89.79
PET 0 6.47
NC-TiO 2/PET-0.4
TiO2 /PET
0.20 wt%/0.4 wt%
wt%/0.8 wt%
65.07
89.79
NC-TiO 2/PET-0.6
NC-TiO2 /PET-0.4 0.2
0.2 wt%/0.4wt%
wt%/0.6 wt% 79.37
65.07
NC-TiO
NC-TiO 2/PET
2 /PET-0.6 0.2
0.2wt%/0.8
wt%/0.6wt%
wt% 90.02
79.37
NC-TiO
NC-TiO22/PET-1.0
/PET 0.2
0.2wt%/1.0
wt%/0.8wt%
wt% 79.71
90.02
NC-TiO2 /PET-1.0 0.2 wt%/1.0 wt% 79.71

To investigate the photocatalytic performance of the NC-TiO2/PET materials, cationic

methylene blue (MB)the
To investigate and anionic acid performance
photocatalytic red (AR) dyesofwere used as2 /PET
the NC-TiO modelmaterials,
contaminants to
cationic
determine
methylenethe photocatalytic
blue decomposition
(MB) and anionic activity
acid red (AR) of were
dyes the materials
used as against the dyes un-
model contaminants
der UV light. To
to determine thetrack changes indecomposition
photocatalytic their concentration, theofabsorbance
activity of the
the materials MB and
against AR
the dyes
dye solutions were tested at 664 nm and 532 nm, respectively, from the UV-vis absorption
under UV light. To track changes in their concentration, the absorbance of the MB and AR
peak (Figure 5a,b). Samples of 2 × 2 cm of fabric were immersed in two Petri dishes with
dye solutions were tested at 664 nm and2 532 nm, respectively, from the UV-vis absorption
certain concentrations
peak (Figure of dyes, of
5a,b). Samples and2 the cm2 of fabric
× 2medium was placed
were in a dark room
immersed for 2Petri
in two h to dishes
reach
with certain concentrations of dyes, and the medium was placed in a dark room for 2 h to
reach the absorption–desorption equilibrium. Subsequently, the photocatalytic reaction
was performed by exposing the solution to a UV lamp. Six reaction times were set to
Polymers 2023, 15, x FOR PEER REVIEW 7 of 11

Polymers 2023, 15, 4376 7 of 11

the absorption–desorption equilibrium. Subsequently, the photocatalytic reaction was

performed
degrade thebyMB exposing
and ARthe dyesolution
solutionstousing
a UV the
lamp. Six reaction
NC-TiO times were set to degrade
2 /PET composite; these were 0, 30,
the MB and AR dye solutions using the NC-TiO 2/PET composite; these were 0, 30, 60, 90,
60, 90, 120, and 180 min, respectively. The concentration of the dye solution sampled from
120, and 180
the Petri min,atrespectively.
dishes The concentration
certain irradiation of the dye
times was measured to solution
monitor sampled from the
the photocatalytic
Petri dishes at certain irradiation times was measured to monitor the
reaction, and the results are shown in Figure 5. The chromaticity of the solution began photocatalytic reac-
tion, andatthe
to fade 0.5results are shown inand
h of illumination, Figure
the5.concentration
The chromaticity of MB
of the the solution
and AR began to fade
dye solutions
at 0.5 h of illumination,
decreased by 40.22% and and49.19%
the concentration
(Figure 5d,e),of the MB and AR
respectively. Thedyecolor
solutions
of thedecreased
solutions
by 40.22% and
continued 49.19%
to fade after(Figure
60 min5d,e), respectively.
of illumination, and The color
the of the solutions
chromaticity of bothcontinued
MB and AR to
fade after 60 min of illumination, and the chromaticity of both MB and
decreased significantly at 180 min of illumination. The degradation rates of the MB and AR decreased signif-
icantly at 180 min
AR solutions of illumination.
reached 90.02% and The91.14%,
degradation rates of the
respectively. WeMB andobserved
also AR solutions reached
a significant
90.02%
changeand 91.14%,
in the NC-TiO respectively. We also
2 /PET fabric, observed
as shown a significant
in Figure 5c. Thechange
color in
of the
the NC-TiO /PET
surface 2of the
fabric, as shown in nonwoven
dye-contaminated Figure 5c. The color
fabric wasofslightly
the surface
fadedofafter
the 30
dye-contaminated nonwoven
min of illumination, greatly
fabric
fadedwasat 60slightly
min, andfaded aftercompletely
almost 30 min of illumination,
faded after 2greatly faded at 60 min,
h of illumination. As a and almost
control, we
completely
also used purefaded after
PET 2 h of illumination.
materials As a control,
for the photocatalytic we also used
degradation of pure PET materials
pollutants. for
The results
the photocatalytic
showed that the dyedegradation
degradationof pollutants.
rate was The6.47% results
aftershowed that the dye degradation
3 h of illumination. It could be
rate was that
judged 6.47% theafter 3 h of2 illumination.
NC-TiO /PET fabric has It could be judged
an efficient that the NC-TiO
photocatalytic 2/PET fabric
degradation has
ability
an efficient
against photocatalytic
organic pollutants. degradation ability against organic pollutants.

Figure
Figure5.5.Degradation
Degradationrate
ratecurves
curvesof
ofthe
theNC-TiO
NC-TiO22/PET
/PETfor
forthe
theMBMBand
andARARdyes
dyesatatdifferent
differenttimes
times(a);
(a);
photos
photos of
of the dye solution
the dye solutionand
andthe
theNC-TiO
NC-TiO 2/PETmaterials
2 /PET materialsatatdifferent
differentphotocatalytic
photocatalytic light
light irradia-
irradiation
tion times,
times, (b,c);
(b,c); andand the UV-vis
the UV-vis spectra
spectra and and chemical
chemical formulas
formulas ofdyes
of the the dyes MBand
MB (d) (d) and AR (e).
AR (e).

During
DuringUV UVirradiation
irradiationofofthe
theNC-TiO
NC-TiO 2/PET,
2 /PET,a series of physicochemical
a series of physicochemical reactions oc-
reactions
curred
occurredin in
thethe
solution
solutionand
andononthethesurface
surfaceofofthe theNC-TiO
NC-TiO22/PET,
/PET,including
includingthe thefollowing:
following:
the
theTiO
TiO22 absorbed
absorbed energy
energy (hv)
(hv) toto electrons
electrons (e(e−−)) and
and generated holes (h
generated holes (h++),), and these ee−
and these − and
and
+
hh+ reacted
reactedfurther
furtherwith
withoxygen
oxygenand andwater
watertotoproduce
producereactive
reactiveoxygen
oxygenspecies
species(ROS)
(ROS)suchsuch
Polymers 2023, 15, x FOR PEER REVIEW 8 of 11

as superoxide radicals (·O2−) and hydroxyl radicals (·OH). The photocatalytic degradation
Polymers 2023, 15, 4376 8 of 11
mechanism can be deduced as follows [23]:

NC-TiO2/PET + hv → NC-TiO2/PET+ + e− (3)

−)
as superoxide radicals (·O2 and hydroxyl radicals (·OH). The photocatalytic degradation
e− + O2→·O2−
mechanism can be deduced as follows [23]: (4)

NC-TiO
NC-TiO 2 /PET 2+ hv →
/PET +→NC-TiO
NC-TiO22/PET +
++e−
/PET + h (5)
(3)

eh−+ +
+HO22O→·OH
→ ·O2 − + h+ (6)
(4)

ROS ++ MB
NC-TiO2 /PET → CO2 +/PET
→ NC-TiO H2O + h+ (7)
(5)
2
Firstly, the ·OH radical attacks the -N = bond and the -S = bond of the MB to interrupt
the MB molecule. In the second hstep, +
+ Hthe
2 Oformed
→ ·OH ROS + h+ degrades the dye molecules. The (6)
MB split product is oxidized to diphenol, phenol, etc., because diphenol and phenol have
an electron donor -OH present ROS on the benzene
+ MB → COring, which is beneficial to ·OH electrical
2 + H2 O (7)
attacks, especially in the presence of -OH on the para and ortho positions. The diphenol
Firstly,
can be quickly ·OH radical
the oxidized attacks the -N =and
to benzoquinone, bondtheand the -S
phenol can= bond of the MB
be oxidized to interrupt
to catechol, res-
the
orcinol, hydroquinone, etc. Thirdly, the intermediate product of the aromatic ring isThe
MB molecule. In the second step, the formed ROS degrades the dye molecules. fur-
MB
thersplit product
oxidized by is
·OHoxidized to diphenol,carboxylic
into a short-chain phenol, etc., acidbecause
such as diphenol and fumaric
oxalic acid, phenol have
acid,
an electron donor -OH present on the benzene ring, which is beneficial
formic acid, etc., and these short-chain carboxylic acids can be rapidly degraded into non- to · OH electrical
attacks,
toxic and especially
harmlessinwater
the presence
and carbon of -OH on the
dioxide para
[13]. Theandfinalortho positions.
product The diphenol
of the photocatalytic
can be quickly oxidized to benzoquinone,
decomposition of acid red using TiO2 is H2O and CO2 [26]. and the phenol can be oxidized to catechol,
resorcinol, hydroquinone, etc. Thirdly, the intermediate product of the aromatic ring is
further oxidized
3.5. Recycling by ·OH into
Performance anda Stability
short-chain carboxylic acid such as oxalic acid, fumaric acid,
formic acid, etc., and these short-chain carboxylic acids can be rapidly degraded into non-
Flexible
toxic and fabrics
harmless are easily
water reusable,
and carbon and the
dioxide [13].photocatalytic
The final product degradation performance
of the photocatalytic
of the NC-TiO 2/PET samples in this study was tested over five reuse cycles. We performed
decomposition of acid red using TiO2 is H2 O and CO2 [26].
the cycles by simply rinsing the samples with distilled water. Figure 6a shows that the
photocatalytic
3.5. degradation
Recycling Performance andrate of the NC-TiO2/PET was maintained at 81.08% for the MB
Stability
and Flexible
at 77.25% for the AR after five
fabrics are easily reusable, cycles.
andForthethe cycling experiments
photocatalytic of the
degradation TiO2-PET, the
performance of
first degradation rate of the MB was 89.20% at 2 h, 56.17% for the
the NC-TiO2 /PET samples in this study was tested over five reuse cycles. We performed 2nd cycle, and decreased
to 35.09%
the cycles byforsimply
the 3rdrinsing
cycle. theThesamples
TiO2-PET without
with the water.
distilled NC had a poor
Figure 6a cycling
shows thatstability
the
relative to thedegradation
photocatalytic NC-TiO2/PET. rateThese
of theresults
NC-TiO verify
2 /PET that
was the NC acted
maintained as
at a bridge
81.08% for between
the MB
the nanoparticles
and at 77.25% for theandAR theafter
fibers tocycles.
five stabilize
Forthe
theconnection between the
cycling experiments of two [27].
the TiO 2 -PET, the
To further investigate the stability of the material during use, we
first degradation rate of the MB was 89.20% at 2 h, 56.17% for the 2nd cycle, and decreased examined changes
in its mechanical strength before and after cycling, and its tensile
to 35.09% for the 3rd cycle. The TiO2 -PET without the NC had a poor cycling stability fracture was tested using
a universal mechanical tester. The results indicated that the strength
relative to the NC-TiO2 /PET. These results verify that the NC acted as a bridge between and durability of the
material
the were good
nanoparticles andafter
the recycling.
fibers to stabilize the connection between the two [27].

Figure 6. (a) Photocatalytic cyclic degradation of MB and AR using NC-TiO2 /PET; (b) circulating
antibacterial rate of NC-TiO2 /PET against bacteria.
Polymers 2023, 15, 4376 9 of 11

To further investigate the stability of the material during use, we examined changes in
its mechanical strength before and after cycling, and its tensile fracture was tested using a
universal mechanical tester. The results indicated that the strength and durability of the
material were good after recycling.

3.6. Antibacterial Properties and Stability

Generally, nanoscale TiO2 has strong antibacterial properties, so the samples were
tested for their antibacterial properties using Gram-negative bacteria E. coli as a represen-
tative. The antibacterial properties of the materials were determined using plate colony
counts. Table 2 shows that the CFU (colony forming units) counts of the E. coli colonies on
the media decreased to 142 after the NC-TiO2 /PET was immersed in the bacterial test tubes
for 30 min. The CFU of the blank, control PET fabric remained at 602. The antibacterial
rates of the NC-TiO2 /PET against E. coli reached 95.12%, indicating that the composite
had a strong antibacterial activity. Normally, antibacterial hydrogen peroxide (H2 O2 ) is
produced on the surface of titanium dioxide and binds to bacterial cell membranes, af-
fecting their permeability and respiratory function, and, eventually, leading to bacterial
death [28]. In addition, experiments were conducted to verify the antibacterial ability
of the NC-TiO2 /PET and the stability of the material for five cycles (Figure 6b). After
five cycles, the NC-TiO2 /PET showed an excellent stability against E. coli by maintaining
an antimicrobial rate of 85.24% and CFU counts of 201. This study showed that the NC-
TiO2 /PET composite has a stable and long-lasting antimicrobial performance for use in
aqueous environments.

Table 2. Results of AAS, mechanical properties, and antibacterial ratios of the samples.

Antibacterial
TiO2 per NC-TiO2 /PET Breaking Strength
Sample Properties against
(mg g−1 ) (N)
E. coli (CFU mL−1 )
PET -- 470.21 ± 3.59 602
NC-TiO2 /PET 10.11 ± 0.78 468.54 ± 3.44 142
NC-TiO2 /PET
9.29 ± 0.86 448.17 ± 3.57 201
after Fifth cycle

4. Conclusions
In this study, excellent antibacterial PET composite materials with recyclable pho-
tocatalytic degradation properties were achieved by incorporating nano-TiO2 through a
simple swelling and dipping method and fixing them with NC. The porous and loose
structure of the fabrics provides a high adsorption ability against pollutants and impels
the active species to quickly capture pollutants in order to degrade them. As a result, the
NC-TiO2 /PET composite presents an efficient photocatalytic performance for both cationic
dye MB and cationic dye AR liquid pollutants’ decomposition. Under UV irradiation, the
composite showed both decomposition and removal effects on methylene blue (90.02%)
and acid red (91.14%), and the composite’s inhibition rate against E. coli was 95.12%. Finally,
the photocatalytic degradation, antibacterial experiments, and AAS test results showed
that the composite material exhibits good stability during recycling.

Author Contributions: Methodology, J.T. and H.D.; Validation, J.T.; Formal analysis, J.T. and H.D.;
Investigation, F.L.; Resources, X.S.; Writing—original draft, J.T., H.D. and X.S.; Writing—review &
editing, X.S.; Supervision, H.W.; Project administration, H.W.; Funding acquisition, X.S. and H.W.;
W.C. Formal analysis, Methodology, Writing—review & editing. All authors have read and agreed to
the published version of the manuscript.
Funding: This research was funded by the following: the Zhejiang Provincial Natural Science Foun-
dation of China under grant No. LGF21E030002; the Technology Planning Project of Zhoushan, under
grant No. 2022C31068; the Technology Planning Project of Jiaxing, under grant No. 2020AY10027; the
national innovation and entrepreneurship training program for College Students, under grants No.
Polymers 2023, 15, 4376 10 of 11

202210349041 and 202310349009; and the Zhejiang Provincial Science and Technology Innovation
Program (New Young Talent Program) of 2022.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: There are legitimate reasons to request data from the corresponding author.
Acknowledgments: This research was supported by the following: the Zhejiang Provincial Natural
Science Foundation of China under grant No. LGF21E030002; the Technology Planning Project of
Zhoushan, under grant No. 2022C31068; the Technology Planning Project of Jiaxing, under grant
No. 2020AY10027; the national innovation and entrepreneurship training program for College
Students, under grants No. 202210349041 and 202310349009; and the Zhejiang Provincial Science and
Technology Innovation Program (New Young Talent Program) 2022.
Conflicts of Interest: The authors declare no conflict of interest.

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