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Effective photocatalytic degradation and physical

Cite this: RSC Adv., 2020, 10, 23936
adsorption of methylene blue using cellulose/GO/
TiO2 hydrogels†
Open Access Article. Published on 23 June 2020. Downloaded on 1/8/2025 12:41:51 PM.

Yian Chen,a Zhouyang Xiang, a

Desheng Wang,b Jian Kang*b and Haisong Qi *a

Environmentally friendly cellulose/GO/TiO2 hydrogel photocatalyst has been successfully fabricated via
a green, simple, and one-step method and evaluated as the photocatalyst and adsorbent for the removal
of methylene blue (MB). The XRD and FTIR analysis suggested the strong interaction among cellulose,
GO and TiO2, resulting from the formation of hydrogen bonds. Due to the unique porous structure of
cellulose hydrogel and introduction of GO, the cellulose/GO/TiO2 hydrogel showed superior
(degradation ratio
93%) and reproducible (no significant change during the ten consecutive cycles)
performance in the removal of MB under UV light. Consequently, the prepared cellulose/GO/TiO2
Received 21st May 2020
Accepted 17th June 2020
hydrogel can be applied as an eco-friendly, high-performance, reproducible, and stable photocatalyst
and adsorbent for the removal of MB. This green hydrogel is a promising candidate for dye wastewater
DOI: 10.1039/d0ra04509h
treatment. Moreover, this work is expected to extend the scope of bio-templated synthesis of other
rsc.li/rsc-advances nanomaterials for various applications.

highly effective, low cost, and being available in tonnage

1. Introduction quantities.
Dye wastewater is mainly from textile, leather, paper, rubber, In recent years, bio-templating techniques with
plastics, cosmetics, pharmaceutical, and food industries. polysaccharides-based material (cellulose, chitosan, lignin, etc.)
Because dye wastewater always comes in large quantities, with are actively explored in the elds of metal oxides synthesis due
a complex composition and colour depth, and is of high toxicity, to their environmentally friendly process, facile, required low
it causes severe environmental pollution and human health energy and cost-effective concerns. Cellulose is a natural poly-
hazards if it is not treated properly before discharging into the saccharide which has the widest distribution and most abun-
natural water. dance on earth. Above all, they can be regenerated. The beads,
Current treatment methods for dye wastewater include lms, and resins made from natural cellulose were used for
physical, chemical, and biological methods, and so on. Various heavy metals13–15 and hazardous azo dyes adsorptions.16,17 High
removal methods have been studied by adsorption,1–3 chemical adsorption enthalpies generated by dyes allow as many
catalytic degradation,4–6 liquid membrane separation,7 elec- aromatic cores to come close to the cellulose surfaces as
trolysis,8 biological treatments,9 oxidation,10 and other possible.18 Furthermore, cellulose is applicable for supporting
processes.11 However, these processes vary in their effective- TiO2 nanoparticles owing to its good compatibility with TiO2
ness, costs, and environmental impacts.12 Among these nanoparticles. Several types of low-dimensional cellulose
processes, the physical adsorption process and chemical cata- materials have been reported, including cellulose nanobers
lytic degradation are much more competitive than other and lms by electrospinning and phase separation method,
methods for their ready availability, lower cost, and a wider respectively.19–23
range of applications. It is of vital importance to search for However, as compared to other polysaccharides-based
adsorbents which meet the requirements and standards of the materials, cellulose-based materials are the most popular bio-
water treatment industry and also are environmentally friendly, templates used because of their insolubility, which renders
them more appropriate for bio-replication than for nanoparticle
growth control. For instance, Lu and co-worker had successfully
fabricated a millimetre-long TiO2 ber with nanostructures
using bamboo cellulose bre as a template. Moreover, cellulose-
a
State Key Laboratory of Pulp and Paper Engineering, South China University of
Technology, Guangzhou 510640, China. E-mail: [email protected]
b
based material not only can be employed as a bio-template but
State Key Laboratory of NBC Protection for Civilian, Beijing, 100191, China. E-mail:
also to form organic–inorganic hybrid materials with resultant
[email protected]
† Electronic supplementary information (ESI) available. See DOI:
nanomaterials. In the case of zinc oxide (ZnO), bacterial cellu-
10.1039/d0ra04509h lose (BC) membrane was successfully prepared as a host matrix

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to promote hybridization with Zn2+ ions. The resulting nano- area.11,30 Therefore, based on the cellulose adsorption proper-
composites exhibited good mechanical properties and high ties and the intrinsic properties of graphene oxide, we
photocatalytic activity in the degradation of methyl orange. combined them and introduced TiO2 to make the removal of
Recently, there is increasing attention in the development of dyes more efficient.
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visible light-driven TiO2 photocatalyst.24–29 This is because the In our previous works, we have reported the successful
traditional TiO2 possesses a relatively large band gap, which preparation of porous cellulose materials (as lms or hydro-
means that it can only be activated under UV region. This gels) by dissolving cellulose and dispersing GO in sodium
property limits the practical efficiency for solar applications. hydroxide/urea/water solution.31,32 It provides a platform for us
Currently, there is increasing attention in the doping of TiO2 to prepare the “dip-catalyst” hydrogels for the removal of
with non-metal atoms since it can avoid deteriorating thermal methylene blue (MB) dyes. A “dip-catalyst” is accentuated by
stability of the TiO2 lattice structure. Titania is one of the most its great recyclability and convenient deployment, especially
Open Access Article. Published on 23 June 2020. Downloaded on 1/8/2025 12:41:51 PM.

important and widely studied inorganic materials, with a broad due to the fact that its immersion/removal into the reaction
range of applications such as pigmenting, gas sensors, corro- media can turn the reaction on/off almost instantaneously. In
sion protection, optical coatings, solar cells, and photocatalysis. this work, we aimed to fabricate the green polymer composite
TiO2 can be prepared as lms, rods, or nanoparticles as aerogel via the addition of TiO2 in the cellulose/GO hydrogels.
required for the desired applications. For the preparation of In the present paper, it is believed that the resultant cellulose/
catalytically active TiO2 nanoparticles at a larger scale, many GO hydrogels can be used as an effective bio-template nano-
methods have been developed, but the only ones of industrial reactor for the dispersion of TiO2 nanostructures through its
importance are ame pyrolysis and chemical vapour synthesis. three-dimensional porous structures and suitable nanopore
Cellulose-based TiO2 nanocomposite materials, combining the size distribution. Although, the cellulose matrix contains GO
advantages of green support with the photocatalytic properties and TiO2 nanoparticles, it maintains the hydrogel structure
of the TiO2, are currently intensely studied for applications in during the catalyst reaction, which will not result in secondary
photocatalysis, water purication, or self-cleaning materials. pollution.
Graphene oxide (GO), an oxidation product of graphene, is
a single sheet from graphite and has the ideal two-dimensional
(2D) structure with a monolayer of carbon atoms packed into
2. Experimental
a honeycomb crystal plane. Considerable attention has been 2.1 Materials
drawn to both graphene and the oxide form over the past several The cellulose samples (cotton linters, DP 500) supplied by
years because of their unique physical and chemical properties Hubei Chemical Fiber Group Ltd. (Xiangfan, China) were used.
and potential applications in various research and industrial GO dispersion (4 mg ml1), titanium oxide nanopowder (21 nm,
elds. Recent studies showed that the graphene oxide is ideal 99.5% trace metals basis) were purchased from Sigma-Aldrich.
for adsorption of dyes and good for acting as a catalyst carrier Sodium hydroxide (NaOH), urea, and other reagents were
substance due to its good mechanical strength and large surface used as received.

Fig. 1 Fabrication of cellulose/GO/TiO2 composite hydrogel.

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2.2 Preparation of cellulose/GO/TiO2 hydrogels prepared aerogel was cryo-fractured in liquid nitrogen for
5 min, and then coated with a thin layer of gold. The samples
Fig. 1 shows the preparation of cellulose/GO/TiO2 hydrogel.
were prepared by ash freezing aer immersion in water, and
Firstly, the specic amount of TiO2 nanoparticles was added in
then sputtered with an approximately 5 nm platinum layer. X-
80 ml GO dispersions. A solution of NaOH/urea/H2O (7 : 12 : 81
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ray diffraction (XRD) was performed using a D/MAX-1200

by weight) was prepared as the solvent. The designated amounts
(Rigaku Co., Japan) with a wavelength of 0.154 nm and a Lynx
of NaOH and urea were added into distilled water and then the
Eye detector at a scanning rate of 2q ¼ 1 min1. Fourier-
solvent was pre-cooled to 12  C. The designated amount of
cellulose was added and dissolved into the solvent under transform infrared spectroscopy (FTIR) in the range of 4000–
vigorous stirring for 5 min to obtain a cellulose solution. 500 cm1 was performed on a Spectrum 400 FT-IR/ATR spec-
trometer (PerkinElmer, USA). X-ray photoelectron spectroscopy
Secondly, the GO/TiO2 solution was added into the cellulose
(XPS) was performed using an ESCALAB 250 XPS meter with Al
solution under stirring. Aer degasication, the resulting
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Ka monochromatization. Electrochemical impedance spec-

solution was cast on a glass plate to give a thickness of 500 mm
troscopy (EIS) were carried out on an electrochemical worksta-
for a gel sheet, and immersed into a coagulation bath with
tion (CHI 660E Chenhua Instrument Company, Shanghai,
5 wt% H2SO4 for 5 min at room temperature to coagulate and
China) based on a conventional three-electrode system with
regenerate. The resultant lms were washed with running water
and deionized water to remove urea and NaOH. Finally, the a frequency range from 0.01 Hz to 100 kHz at the circuit
cellulose/GO/TiO2 hydrogels consisting of 100 g water, 4 g potential.
cellulose, 8 wt% GO and 25 wt% TiO2 related to the cellulose
amount, were obtained. 2.4 Photocatalytic activity evaluation
The photocatalytic activity of cellulose/GO/TiO2 hydrogel was
conducted by the degradation of MB as the model of pollutants
2.3 Characterization of morphology and microstructure in aqueous solution at ambient temperature. Typically, 5 g
For the characterization of the composites, the cellulose/GO/ hydrogel in the shape of a thick lm of about 120  80  0.5
TiO2 hydrogel was rapidly frozen in liquid nitrogen for 5 min mm3 were dipped into the 10 mg L1 of MB (200 ml), and stored
and then lyophilized in a freeze drier (Alpha 1-2 LDplus, Christ in the dark place for 60 min to reach adsorption–desorption
GmbH, Germany) for 24 h to obtain the of cellulose/GO/TiO2 equilibrium. The solution containing photocatalysts was
aerogel. The scanning electron microscope (SEM) was per- exposed to the UV irradiation by a 125 W mercury lamp (Vilber
formed using an Ultra 55 (Carl Zeiss SMT AG, Germany). The Laurmat, l ¼ 312 nm) for 1 h and was collected at regular time

Fig. 2 (a) SEM images of cellulose/GO/TiO2 aerogel (cross-section) (b) SEM images of cellulose/GO/TiO2 aerogel (surface); (c) XRD spectrum of
cellulose/GO/TiO2, cellulose/TiO2, and cellulose/GO; (d) FTIR spectrum of cellulose/GO/TiO2, cellulose/TiO2, and cellulose/GO.

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intervals during irradiation to evaluate the photocatalytic The crystal structures of cellulose/GO/TiO2, cellulose/TiO2,
activity. In order to analysis the effect of absorption of hydrogel and cellulose/GO composites were further characterized using
on the removal of MB, the solution containing photocatalysts XRD (Fig. 2c). The peaks at 2q value of 25.3, 37.8, 48.0, 54.0,
was also under dark condition for 24 h and was also collected at 55.1, 62.7, 68.8, 70.3, and 75.1 were indexed to (101), (004),
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regular time intervals. The concentration of MB was measured (200), (105), (211), (204), (116), (220), and (215) crystal planes of
by recording its absorbance at 664 nm wavelength with a UV-Vis anatase TiO2 in cellulose/GO/TiO2 and cellulose/TiO2
spectrophotometer (Analytik Jena, Germany) from which the composite, respectively. XPS spectrum of cellulose/GO/TiO2,
degradation efficiency was calculated. The UV-Vis spectra of the and cellulose/GO were also carried out to study the element
samples were recorded in air atmosphere at room temperature composition and chemical states of elements. As shown in
from 200 to 800 nm. The degradation percentages of MB in Fig. S1a,† the typical photoelectron peaks of C, O and Ti
aqueous solution was calculated as follows: Degradation (%) ¼ elements conrmed the presence of these three elements. The
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(C0  Ct)/C0  100, where C0 is the initial concentration at time t Ti 2p spectrum of cellulose/GO/TiO2 and bare TiO2 shows two
¼ 0, and Ct is the concentration at time interval. For the 10 symmetrical peaks with binding energies at 459.4 and 465.1 eV,
consecutive cycles, the hydrogel sample was taken from the which are attributed to Ti 2p3/2 and Ti 2p1/2, respectively (shown
solution and washed thoroughly with deionized water, and then in Fig. S1b†).
it was added into fresh MB solution. Fig. 2d shows the FTIR spectrum of cellulose/GO/TiO2,
cellulose/TiO2, and cellulose/GO. As compared to the cellulose/
GO composite, it was observed that O–H stretching absorption
peaks in cellulose/GO/TiO2 composite was slightly shied from
3. Results and discussion high (3336 cm1) to low absorption peak (3274 cm1), and its
3.1 Characterization and analysis of hydrogels intensity signicantly increased. This could be attributed by the
The results of structural and morphological analysis of cellu- interaction between the O–H groups of cellulose and Ti–O bond
lose/GO/TiO2 composites are shown in Fig. 2. During the freeze- of TiO2. Previous study suggested that this might be due to
drying method, water served as a forming agent (more than a strong interaction between the hydroxyl groups of cellulose
90%), was rst frozen and then sublimated during the freeze- and the TiO2 particles through hydrogen bonding interac-
drying process, leading to the generation of highly 3D porous tions.33 Zhang et al.34 also suggested that it might be due to the
network structure. Therefore, as shown in Fig. 2a, the cellulose/ partial C–OH occupied by a Ti–O bond. Therefore, it promoted
GO/TiO2 aerogel own open and highly porous structures with the strong interfacial interaction between cellulose chain and
diameters of 300–500 nm. The cellulose hydrogel as the catalyst TiO2 nanoparticles. The strong interfacial interaction increases
support provides ideal conditions for the uniform dispersion of the durability of the nanoparticles within the nanocomposite
TiO2 nanoparticles and GO sheets, while preserving the struc- membrane and decreases the detachment tendency of the
ture of the cellulose matrix. The TiO2 nanoparticles are densely nanollers in the polymer matrices.35
and uniformly coated on the GO sheets and cellulose chains
(Fig. 2a and b). The average size of the TiO2 nanoparticles is
3.2 Photocatalytic analysis of composite hydrogels
about 20–22 nm. It is also worth mentioning that the TiO2
nanoparticles were directly coated onto the GO surface and In order to study the photocatalytic degradation performance of
cellulose without having any molecular linkers, which is due to cellulose/GO/TiO2 hydrogel, MB was used as a probe pollutant
the strong hydrogen bonds. to clarify the removal efficiency of cellulose/GO/TiO2 hydrogel.
Fig. 3 displays that absorptive intensity of MB at 664 nm grad-
ually decreased with the increasing reaction time, when the
cellulose/GO/TiO2 hydrogel was taken into the MB solution
under UV light at room temperature. This result indicates that
MB underwent degradation behaviour under the catalysis of
cellulose/GO/TiO2 hydrogel. If the degradation ratio is dened
as the ratio between the decreased absorptive intensity and that
of the initial methylene blue solution, the degradation ratio was
about 93% when the mixed solution was irradiated for 120 min.
This implies that the prepared cellulose/GO/TiO2 hydrogel has
good photocatalytic activity for MB and are likely to be an effi-
cient photocatalyst.
The removal efficiency of different hydrogels under UV light
is presented in Fig. 4a. It can be seen that cellulose and
cellulose/GO hydrogels have almost no photoactivity on the
removal of MB under UV light. The insignicant removal effi-
ciency of MB was due to the adsorption of MB molecules on the
Fig. 3 UV-Vis analysis of the photocatalytic degradation of MB by surface of cellulose and GO sheets. These results indicated that
cellulose/GO/TiO2 hydrogel with the increasing reaction time. the photocatalytic degradation of MB did not occur without

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Fig. 4 (a) Photocatalytic degradation rate of MB over the different samples under UV light; (b) absorption rate of MB over the different samples
under dark condition.

TiO2 in the cellulose matrix. While
93 and
80% of the initial under dark condition were also carried out in Fig. 5. The pho-
MB dyes were decomposed by cellulose/GO/TiO2 and cellulose/ todegradation and adsorption of MB was monitored for ten
TiO2 hydrogel aer 120 min under UV light. The excellent consecutive cycles, each for 120 min (under UV light) and 24 h
performance in removal efficiency of MB can be attributed to (under dark condition), respectively. Aer each cycle, the
the synergistic effects between GO sheets and TiO2 and the cellulose/GO/TiO2 hydrogel was taken off from MB solution and
adsorption of MB molecules on the surface of cellulose and GO washed thoroughly with water, then taken into the fresh MB
sheets. To clarify the absorption effect on the removal efficiency solution. In Fig. 5a, there was no signicant decrease in the
of MB dyes, the adsorption activity of different hydrogels was removal efficiency of MB under UV light during the ten
carried out under dark condition for 24 h. As shown in Fig. 4b, consecutive cycles, indicating the excellent reproducible and
the cellulose/GO/TiO2 hydrogel was transformed to nattier blue durability of the cellulose/GO/TiO2 hydrogel for the photo-
aer soaking in the MB solution for 24 h, and many MB degradation of MB. Notedly, in the case of UV light, the pho-
molecules remain in the cellulose/GO/TiO2 hydrogel. Further- todegradation of MB which is due to the synergetic effect
more, the existence of GO sheets could enhance the absorption between TiO2 and GO played a major role in the removal of MB.
capacity and therefore, will promote high removal efficiency of The introduction of GO sheets probably brought in an inter-
MB under the dark condition for 24 h. Furthermore, the cellu- mediate energy level above the valence band of TiO2, thereby
lose/GO/TiO2 hydrogel also exhibited higher photoactivity on narrowing the band-gap to induce UV light absorption. There-
the removal of MB, compared to bare TiO2 and GO/TiO2 system fore, the high and stable performance of the cellulose/GO/TiO2
(shown in Fig. S2†). hydrogel for the photodegradation of MB should be attributed
The reproducible of our cellulose/GO/TiO2 hydrogel for the to the co-effect of between TiO2 and GO. Moreover, with the
photodegradation of MB under UV light and adsorption of MB unique porous structure of cellulose hydrogel and two-

Fig. 5 (a) The long-term stability of photocatalytic degradation of cellulose/GO/TiO2 hydrogel was tested by repeated use for MB under UV light;
(b) the long-term stability of absorption performance of cellulose/GO/TiO2 hydrogel was tested by repeated use for MB under dark condition.

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Fig. 6 Diffuse reflectance absorption spectra of cellulose/TiO2 and

Fig. 7 Electrochemical impedance spectroscopy (EIS) Nyquist plots of
cellulose/GO/TiO2 hydrogel. cellulose/TiO2 and cellulose/GO/TiO2 hydrogel.

dimensional planar structure of GO, the enhanced absorptivity removal of MB under UV light. Therefore, the schematic
of cellulose/GO/TiO2 hydrogel also promoted the high and representation of photocatalytic degradation and absorption
stable performance of this hydrogel. mechanism of cellulose/GO/TiO2 hydrogel for MB under UV
Conversely, there was an obvious decrease in the removal light was proposed (Fig. 8). The enhanced photocatalytic and
efficiency of MB under dark condition in Fig. 5b. In the case of adsorption performance for the cellulose/GO/TiO2 hydrogel can
dark condition, the removal of MB is ascribed to the absorption be ascribed to their unique structure with the following
of MB on the surface of cellulose and GO due to the porous favourable properties: (i) the porous structure of cellulose
structure of hydrogel. As shown in Fig. 5b, there is an obvious hydrogel with a relatively high surface area can provide more
change in the cellulose/GO/TiO2 hydrogel aer the rst active sites and increase surface adsorption of reactant species
absorption run. Although the hydrogel was washed thoroughly on the surface of composite photocatalysts; (ii) the conjugated
with water before the next run, many MB molecules remain in MB molecules could bind to large aromatic domains on GO
the cellulose/GO/TiO2 hydrogel, leading to the weakening of the sheets via p–p stacking, which could favour increased reac-
next absorption effect of this hydrogel. tivity36 and effectively improve the light absorption in the visible
In addition, light absorption plays an important role in the region; (iii) the high photocatalytic and reproducible perfor-
photodegradation of MB. Fig. 6 shows the electronic absorption mance of our hydrogel could also be a result of the strong
spectra of cellulose/TiO2 and cellulose/GO/TiO2 hydrogel. There coupling between TiO2 and GO which facilitates interfacial
is a clear red shi in the absorption edge of cellulose/GO/TiO2 charge transfer (with GO as an electron acceptor) and inhibits
hydrogel, compared to cellulose/TiO2 hydrogel. This result can electron–hole recombination.37
be attributed to the interaction between GO and TiO2. The In order to have a rough estimation of the removal efficiency
introduction of GO sheets probably brought in an intermediate of cellulose/GO/TiO2 hydrogel as the catalyst to degrade MB, the
energy level above the valence band of TiO2, thereby narrowing degradation performance and stability were compared with
the band-gap to induce UV light absorption. This narrowing is those reported in the literature. Table 1 contains different
also benecial for a more efficient utilization of light in the catalysts able to degrade MB dye at similar operational condi-
removal of MB. tions. Under this condition, most of the recent reports have
Charge transfer efficiency is another important factor during lower removal percentage of MB than the here reported ones.
the photocatalysis process. As shown in Fig. 7, the typical Compared to them, the cellulose/GO/TiO2 hydrogel exhibited
electrochemical impedance spectra of cellulose/TiO2 and good degradation performance and excellent recyclability.
cellulose/GO/TiO2 hydrogel were presented as Nyquist plots, Moreover, another advantage of the hydrogel as the catalyst is
and it is observed that, arc radius on the plot of cellulose/GO/ that the cellulose matrix contains GO and TiO2 nanoparticles
TiO2 hydrogel is smaller than that of cellulose/TiO2 hydrogel, and maintains the hydrogel structure during the catalyst reac-
which indicated the higher efficiency of charge separation. GO tion, which will not result in secondary pollution. The “dip-
here acted as an electron acceptor and inhibited electron–hole catalyst” can be easily removed from the polluted water aer the
recombination, and the strong coupling between TiO2 and GO degradation reaction. In other words, it is easy to start and stop
facilitated interfacial charge transfer. the degradation reaction by taking in and out the whole
Overall, cellulose/GO/TiO2 hydrogel was prepared by hydrogel. It is obvious that the cellulose/GO/TiO2 hydrogel, with
a simple, green and one-step process. Owing to its unique its sustainable feature, convenient fabrication, great catalytic
porous structure and introduction of GO, cellulose/GO/TiO2
hydrogel showed superior and reproducible performance in the

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Fig. 8 The schematic representation of photocatalytic degradation and absorption mechanism of cellulose/GO/TiO2 hydrogel for MB under UV
light.

Table 1 Photocatalytic degradation activity of MB over different systems under UV light

Reaction time
Sample Removal efficiency (min) Reproducible Ref.

Cellulose/TiO2 lms 75% 60 5 38

Polymer nanobers/TiO2 70% 180 4 22
Niobium oxyhydroxide dispersed poly(3-hydroxybutyrate) lms 92% 120 7 39
Cellulose/GO/TiO2 hydrogel 93% 120 10 This work

efficiency, good recyclability, and easy removability is expected Conflicts of interest

to be very useful in MB dyes removal.
There are no conicts to declare.

4. Conclusions
In summary, environmentally friendly cellulose/GO/TiO2
Acknowledgements
hydrogel photocatalyst has been successfully fabricated via The authors are grateful for the nancial support for this work
a green, simple, and one-step method and evaluated as the by the National Natural Science Foundation of China
photocatalyst and adsorbent for the removal of MB. The XRD (21774036), Guangdong Province Science Foundation
and FTIR analysis suggested the strong interaction among (2017B090903003, 2017GC010429).
cellulose, GO and TiO2, resulting from the formation of
hydrogen bonds. Due to the unique porous structure of cellu-
lose hydrogel and introduction of GO, the cellulose/GO/TiO2 Notes and references
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