Efficient construction and enriched selective adsorption-photocatalytic

activity of PVA/PANI/TiO2 recyclable hydrogel by electron beam

radiation
Xiao-Fang Song,1,2 Jiang-Tao Qin,2 Ting-Ting Li,2 Guo Liu,2 Xiang-Xiang Xia,2 Yue-Sheng Li ,2
Yi Liu1,3
1
College of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan, People’s Republic of China
2
Non-power Nuclear Technology Collaborative Innovation Center, Hubei University of Science & Technology, Xianning, Hubei, People’s
Republic of China
3
Key Laboratory of Analytical Chemistry for Biology and Medicine (MOE), College of Chemistry and Molecular Sciences, Wuhan
University, Wuhan, People’s Republic of China
Correspondence to: Y.-S. Li (E-mail: [email protected]) and Y. Liu (E-mail: [email protected])

ABSTRACT: Enriched selective adsorption-photocatalytic activity of Poly (vinyl alcohol)/Polyaniline/TiO2 (PVA/PANI/TiO2, noted as
PAT) recyclable hydrogel photocatalyst with 3D structures were prepared by self-assembling and electron beam radiation crosslingking
method. TiO2 nanoparticles were successfully introduced into the 3D matrix of the PVA/PANI hydrogel and manifested by FTIR, TG,
XRD, XPS, and SEM-EDS. The microstructure of PAT was characterized further by SEM, TEM, and BET. The highly selective
adsorption-photocatalytic activity of PAT was tested by the degradation of cationic or anionic dye and reduction of heavy metal ion in a
closed and flow system under UV light irradiation. The results showed that PAT had a highest selective adsorption-photocatalytic per-
formance at the appropriate content of PVA (10 wt %), TiO2 (15 wt %) and suitable radiation dose (50 kGy), which could be attributed
to the synergistic effect of excellent selective adsorption and effective photocatalytic degradation. The mechanism of selective
adsorption-photocatalytic on PAT was revealed synchronously in this study. Particularly, the novel PAT photocatalyst with 3D network
structure also affords ease of separation and recycling, which is beneficial to water purification in a flow system. © 2019 Wiley Periodicals,
Inc. J. Appl. Polym. Sci. 2019, 136, 48516.

Received 5 March 2019; accepted 15 May 2019

DOI: 10.1002/app.48516

INTRODUCTION are of nanometer size, which may cause secondary pollution to

With the development of society and modern industry, the the environment.16–18 To provide a complete treatment solution,
annual emissions of pollutants have been increased, so the eco- while secondary pollution is avoided, it is essential to integrate or
logical environment and human health have been seriously couple photocatalysis with recyclable catalyst substrates, such as
infringed.1–3 Therefore, a lot of studies have been focused on porous PVA/TiO2, Polyacrylamide/TiO2 and PANI/TiO2
purifying waste water.4–7 Nowadays, the main methods of purify- hydrogels.19–23 Photoactive composite hydrogel, with 3D biomi-
ing waste water including physical treatment (activated carbon, metic structures that combines photocatalytic degradation with
membrane technology),8,9 biodegradation (bacteria),10,11 and selective adsorption enrichment, could achieve this, and has been
photocatalytic treatment.12–15 However, the regeneration proce- an active research topic in recent years.
dure of a physical adsorbent is quite complex, and the adsorption Soft materials have great promise in catalytic conversion and
effect is limited by the adsorption capacity. The cycling process selective absorption, and provide more active sites for fulfilling
of biodegradation is too long. Photocatalytic technology can min- their functionalities owing to high specific surface areas.24–32 One
eralize organic pollutants completely, but the recycling of photo- of the most familiar soft materials is to plant chloroplasts, which
catalysts is quite difficult as most of the photocatalytic materials can capture energy from absorbed light, and create to a series of

Additional Supporting Information may be found in the online version of this article.
© 2019 Wiley Periodicals, Inc.

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biochemical reactions by driving the Calvin cycle.33 Inspired by Synthesis of PVA/PANI Hydrogel
this, biomimetic photocatalytic soft materials are widely investi- PVA/PANI hydrogel was fabricated by a similar procedure to
gated as a means to generate fuels34–36 and for water purifica- that reported in the literature44: 1.32 g APS was dissolved in
tion.37 Among all the soft materials, hydrogel is one of the major 3 mL DI water (solution A). Solution B was prepared by mixing
representatives, which can effectively enrich organic dyes and of 9 mL PVA solution (5 or 10% wt/wt) and 4.5 mmol AN (the
heavy metal ions in aqueous solution, owing to its super hydro- monomer). The 4.5 mmol ABA was dissolved in 5.0 mL of HCl
philicity. In addition, the matrix prevents the agglomeration of (6 M) to form solution C. Then, all the solution was cooled to
nanoparticles, and increases the exposed surface area. Most 0  C in an ice-water bath. Finally, the solution C was slow added
importantly, the transparent hydrogel carrier does not affect the to the solution B to form an aqueous solution, and then the aque-
transmission of light. Generally, semiconductor particles have to ous solution and solution A were mixed quickly and reacted for
12 h at 0  C. After the end of the reaction, the mixed solutions
be separated from the suspensions of the photocatalyst by centri-
turned dark green and formed gel and then crosslinked by the
fugation, but this step can be eliminated by the immobilization of
method of freeze-drying.45 In order to increase the degree of
catalyst, which could be realized with hydrogel. Therefore, hydro-
crosslinking and concomitant stability, the hydrogel was radiated
gel is very suitable for recyclable photocatalytic carriers.
at doses of 50 kGy, and at a dose rate of 5 kGy/pass by a 1 MeV
TiO2 is the most widely used photocatalyst, but it is very difficult electron accelerator (Wasik Associates) at room temperature.
to remove nanoparticles from solutions.38,39 To solve this prob- Finally, the samples were soaked in deionized water for 48 h and
lem, hydrogel was selected as the recyclable photocatalytic sub- washed in excess water to remove the unreacted components,
strate. As a biopolymer gel, PVA is widely used in water and then the hydrogel was freeze-dried (SCIENTZ-10 N) for
treatment because of its excellent properties, such as biocompati- 24 h. The as-received samples were denoted as PVA/PANI-M%,
bility, nontoxicity, good mechanical properties, and hydrophilic- where M corresponded to the concentration of PVA.
ity.40,41 However, the conductivity of pure PVA hydrogel is poor,
which is not conducive to the migration of carriers, so we have Synthesis of PVA/PANI/TiO2 Hydrogel
introduced conductive PANI on the PVA chain to enhance the The synthesis of PVA/PANI/TiO2 hydrogel was similar to that of
conductivity of hydrogel.42,43 Under the metal–polymer super- PVA/PANI hydrogel. The only difference was that a certain
molecular hydrogel system, TiO2 nanoparticles were uniformly amount of TiO2 (P25) was added to solution B. The as-received
distributed throughout the 3D network matrix of the PVA/PANI samples were denoted as PATX, where X corresponded to differ-
hydrogel. The hydrogel exhibits highly selective adsorption prop- ent mass ratio of TiO2 to PVA/PANI. In our experiments, the
erties and in situ photocatalytic degradation of pollutants. In this hydrogels were randomly cut into irregular microparticles of dif-
process, pollutants are first enriched and concentrated into the ferent sizes (smaller than 75 μm).
3D network of the composite hydrogel, and then the pollutants
were in situ oxidized or reduced via photocatalysis under UV Characterization
light irradiation. Thermal stability and the content of TiO2 in composite hydrogels
were determined by a NETZSCH thermogravimetric analyzer
Herein, we report the highly selective adsorption-photocatalytic prop-
(TG209F3, German). The dried samples were cut into powder in
erties and efficient pollutants removal ability of PVA/PANI/TiO2
a crucible and heated from 30 to 800  C at a heating rate of
(PAT) hydrogel with 3D biomimetic structures. Both the composite
10  C min−1 in nitrogen. The melting temperature of the dried
hydrogel led to a higher rate of adsorption of anionic pollutants
samples were carried out with a differential scanning calorimeter
(methyl orange [MO] and Cr2O72−). In addition, TiO2 locating
(DSC200F3, NETZSCH, German) under nitrogen atmosphere,
nanoparticles into the 3D matrix of the PVA/PANI hydrogel could
which was kept in a heating rate of 5  C min−1 from 30 to
efficiently avoid the loss of catalyst, and pollutants (MO and methyl
240  C. The crystal structures of the hydrogels were characterized
blue [MB]) which are in situ oxidized via photocatalysis under UV
by X-ray powder diffraction (LabX XRD-6100, Shimazdu, Japan).
light irradiation. Overall, the advantages of PAT recyclable hydrogel
The static contact angle of oil on the hydrogel film was measured
with the 3D biomimetic network structure are ease of separation and
at ambient temperature using a modified contact angle goniome-
recycling, which is beneficial to the water purification in flow system.
ter (JY-PHb, China), and the angle was determined by an ellipse
fitting method. Conductivity of the PATX composite hydrogels
EXPERIMENTAL SECTION was tested with the ST2258C multifunction digital four probe tes-
Materials ter (Suzhou Jingge Electronic Co., Ltd.). The mechanical intensity
Poly (vinyl alcohol) (Relative degree of polymerization of was measured at a speed of 10 mm min−1 on a universal testing
1750
50) was purchased from Sinopharm Chemical Reagent machine (CMT4104, Sans, China). The PATX hydrogels were cut
Co., Ltd. (China). TiO2 (P25) nanoparticle (Average particle size into dumbbell shapes by a scalpel and directly measured without
of 30–50 nm) was from Germany Degussa. Aniline (AN) and further drying. The morphology and microstructure were charac-
ammonium persulfate (APS) was purchased from Sinopharm terized by field emission scanning electron microscope (FE-SEM,
Chemical Reagent Co., Ltd. (China). 3-aminobenzeneboronic acid ZEISS Merlin Compact VP, Germany) and scanning electron
(ABA) and hydrochloride were from Aladdin Chemical Co., Ltd. microscopy (SEM; VEGA-3 SBH, Tescan, Czech Republic).
(China) and other reagents were purchased from Wuhan Shenshi Before examination, the hydrogels were freeze-dried. Then, the
Chemical Co., Ltd. (China). All the chemicals are analytical grade dried hydrogels were cut to expose their inner structures, and the
and used as purchased without further purification. cross-sections were observed. Surface element analysis was

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Figure 1. Schemes of the photoactive PVA/PANI/TiO2 composite hydrogel with 3D structures. [Color figure can be viewed at wileyonlinelibrary.com]

conducted using energy dispersive X-ray spectroscopy (EDS, Selective Adsorption Experiment of PAT. Selective adsorption
Oxford Instruments Link ISIS). HRTEM images were obtained behaviors were evaluated through the separation of multifarious
by field emission transmission electron microscopy (JEOL, JEM- dye mixtures or mixtures of chromium solution at room temper-
2010F, Japan). Fourier transform infrared spectra (FTIR) were ature (25
2  C). Then, 10 mg of PAT15 hydrogel was dispersed
recorded on a NICOLET 5700 spectrometer (Thermo Fisher in the 100 mL mixture under magnetic stirring for 30 min in the
Nicolet, America) in the range of 4000–400 cm−1. UV/vis absorp- dark to obtain a comparative removal of dye or chromium from
tion spectra were obtained at room temperature by a UV–Vis the mixture. The initial concentration of each active species is
spectrophotometer (Shimadzu, UV-2600). Brunauer–Emmett– 25 mg L−1. The change of characteristic adsorption peaks of the
Teller (BET) specific surface area of the aerogels was determined dye which was confirmed by UV–Vis spectrophotometer. The
at 77 K by using a Quantachrome NOVA TOUCH LX1. Prior to Cr(VI) and Cr(III) concentration was measured using GDYS-201
the measurements, the samples were heated under vacuum at multiparameter water quality analyzer (Little Swan, China).
423 K for 5 h. X-ray photoelectron spectroscopic (XPS) measure-
ments were performed using Perkin-Elmer PHI 5000C (PE-PHI,
US) X-ray photoelectron spectroscopy.
Evaluation of Photocatalytic Performance in a Closed System.
The photocatalytic performance in closed systems was tested via
Measurement of Adsorption-Photocatalytic Activity of PAT the degradation of MO and MB + MO mixed solutions in an
Adsorption Capacity of PATX. The adsorption activities of PATX agitated reactor (DB-Y) at room temperature (25
2  C). Ten
were tested by using methylene orange (MO) and methylene blue milligrams of photocatalyst was immersed into 100 mL MO
(MB) at room temperature (25
2  C). The adsorption was mea- (100 mg L−1) and mixture solution (100 mg L−1 MO
sured by dispersing 10 mg of PATX hydrogel into 100 mL of MO + 10 mg L−1 MB) for 4 h in the dark to ensure the adsorption–
or MB solution at different concentrations under magnetic stirring desorption equilibrium. Then the mixed solution, including the
for 4 h in the dark to ensure the adsorption–desorption equilibrium. PAT hydrogel, was illuminated under a 100 W mercury lamp
The MO or MB concentration which was monitored by UV–Vis (model: GGZ-100, main wavelength: 365 nm) at 5 cm away from
spectrophotometer (UV1901, China) at a wavelength of 465 or the solution. After each typical photocatalytic experiment,
665 nm, respectively. The adsorption was analyzed by eq. (1) recycling experiments were executed by conventional filtration,
washing with ethanol and water. The recycled products were used
ðC 0 − C e Þ × V as catalysts to remove MO from water. The MO and MB concen-
Q= ð1Þ
W tration was monitored by UV–vis spectrophotometer at a wave-
length of 465 and 665 nm, respectively. The chemical oxygen
>Where C0 and Ce denote the initial and final concentrations, V and demand (COD Cr) was measured by GDYS-201 multiparameter
W represent the volume of solution and weight of adsorbent. water quality analyzer.

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(a) (b)

(c) (d)

Figure 2. (a) FTIR spectra of different composite hydrogels; (b) XRD patterns of TiO2 and different composite hydrogels; (c) Thermogravimetric analysis
profiles of PVA/PANI/TiO2 composite hydrogels under different mass ratio of TiO2; (d) UV–vis diffuse reflectance spectra of different composite hydrogels.
[Color figure can be viewed at wileyonlinelibrary.com]

Testing for Photocatalytic Activity in a Flow System. The PVA/PANI/TiO2 physical crosslinked composite hydrogel by
photocatalytic performance in flow systems was tested via the self-assembly, and then enhance its stability by the electron beam
degradation of 5 mg L−1 MO solution in a biomimetic photo- radiation method. It’s stability has been increased greatly by elec-
catalytic reactor (BPR) at room temperature (25
2  C). A tron beam radiation, which can be proved by Supporting Infor-
100 W mercury lamp at 5 cm away from the solution was used mation Figure S1 and S2. Obviously, the gel fraction of radiated
to provide light. Then, 500 mg PATX cryogel film crosslinked hydrogel was very high (84.5%) in comparison with
(45.0 × 8.0 × 2.0 mm) and baffler was sandwiched between a self-assembling hydrogel (78.7%). In addition, all the hydrogels
PTFE vessel and quartz glass.46 A peristaltic pump provided exhibit porous structure, but the pore size of hydrogel with radia-
motive power, and the flow rate was 0.32 mL s−1. At stated times, tion is smaller, perhaps due to the surface of the self-assembling
3 mL liquid was sampled. The liquid could be analyzed without hydrogel being dissolved during extraction. Supporting
centrifugation. Information Figure S2 shows the DSC curves of PVA/PANI/TiO2
composite hydrogels with (a) unradiated and (b) radiated at
doses of 50 kGy. The initial hydrogel has an endothermic peak
RESULTS AND DISCUSSIONS associated with melting around 211.4  C. However, the melting
Synthesis and Characterization of PAT Hydrogel temperature of radiated hydrogel slightly increases to 218.4  C,
Preparation of PVA/PANI/TiO2 composite hydrogel by self- which suggests the crosslinked degree and thermal stability of the
assembling and electron beam radiation method is illustrated in PAT hydrogel were improved.47 In a word, the stablity of hydro-
Figure 1. It is crucial to first prepare successfully the gel is better after electron beam radiation, and indicating that the

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Table I. Texture properties and adsorption capacity of PATX composite hydrogels under different mass ratio of TiO2

Surface Pore volume Adsorption capacity Adsorption capacity Adsorption capacity

Sample area (m2 g−1) (10−2 cm−3 g−1) of MO (mg g−1) of Cr(VI) (mg g−1) of MB(mg g−1)
PAT0 55.11 9.25 722 87 0.86
PAT2 54.67 8.70 703 78 0.85
PAT5 52.23 8.40 627 66 0.81
PAT10 52.09 8.27 545 60 0.80
PAT15 60.59 10.33 675 72 0.90
PAT20 57.18 10.30 578 66 0.87

Equation (1) Q = ðC0 −W

Ce Þ × V
.

hybrid crosslinked hydrogel can be worked as a carrier to fix peaks (101), (004), (200), (105), (211), and (204) of anatase TiO2,
nanoparticles and is suitable for wastewater treatment. and the peak of 27.4 could be indexed to the characteristic peak
(110) of rutile TiO2. Diffraction peaks at 25 are (110) indicative
Structural Analysis of PANI, which is attributed to the polymer chains of PANI.19 As
the peak intensity of TiO2 was much higher than that of PANI,
FTIR spectra of TiO2, PVA/PANI, and PVA/PANI/ TiO2 com-
the diffraction peaks of PANI could not be observed in PAT
posite hydrogels are shown in Figure 2(a). In the spectra of
composite hydrogels, but it was confirmed by the testing of con-
PVA/PANI, the double peaks at1490 and 1589 cm−1 can be
ductivity according to literature.50 The conductivity of PAT was
attributed to the C C stretching vibrations of the benzenoid
measured to be 7.8 × 10−3 S cm−1, which is higher than pure
rings,48 respectively. The sharp band at 1309 cm−1 is ascribed to
PVA. The above results show that TiO2 nanoparticles were intro-
the stretching vibration of C N in intrinsic PANI. After adding
duced firmly into the composite hydrogel once again, and were
TiO2, the successful introduction of TiO2 was confirmed by the
ensured to give high photocatalytic activity of PVA/PANI/TiO2
presence of intensive and broad absorption bands at 607 cm−1,
composite hydrogel.
which were assigned to the stretching of Ti O Ti vibrations.
Furthermore, the peaks at 3428, 2930, and 1150 cm−1 were The content of TiO2 and the thermal stability of the composite
attributed to the vibrations OH, CH2 and C O bonds of hydrogel were determined by thermo gravimetric analysis in air
PVA, and these peaks can be found in all samples. Thus, FTIR atmosphere.16 Figure 2(c) shows the thermogram of composite
confirms the PVA/PANI and PVA/PANI/TiO2 composite hydro- hydrogels containing different mass ratio of TiO2 (0, 2, 5, 10,
gels have been obtained. 15, and 20%), the weight loss around 6% was slow and represen-
The typical powder XRD pattern of the TiO2, PVA and compos- ted only water evaporation from room temperature to 200  C.
ite hydrogels containing different mass ratios of TiO2 (0, 2, 5, 10, However, the weight loss was accelerated at 200–600  C, which
15, and 20%) is shown in Figure 2(b). PVA showed narrow bands indicated that the temperature accelerated the decomposition of
at 2θ of 19.5 and 40.8 ; which could be indexed to the character- the skeletal chain structure after 200  C. Compared with PAT0,
istic peaks (101) and (111).49 Moreover, a weak peak appeared there was a delay phenomenon for the third stage of the PATX,
near 22.7 , which could be indexed to the characteristic peaks burning until 600  C. Considering the above results, the thermal
(200). With increasing TiO2 content, the hybrid hydrogels give stability of PATX was slightly stronger than that of PAT0 com-
more peaks from TiO2, with peaks around 2θ of 25.4, 37.8, 48.1, posite hydrogel, because TiO2 was introduced. Since the TiO2
54.0, 55.0, and 62.7 , which could be indexed to the characteristic was relatively stable, the loaded TiO2 is exposed after the gel has

Figure 3. SEM images of PVA/PANI composite hydrogels at different PVA concentration. (a) 5%; (b) 10%.

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Figure 4. SEM images of PVA/PANI/TiO2 composite hydrogels under different mass ratio of TiO2. (a) PAT0, (b) PAT2, (c) PAT5, (d) PAT10, (e) PAT15,
(f) PAT20; (g, h) FESEM photographs of TiO2 and PAT15 composite hydrogel; (i–l) The element mapping images of C O N and Ti of PAT15 composite
hydrogel in (h). [Color figure can be viewed at wileyonlinelibrary.com]

been completely decomposed, and the content of TiO2 for PAT2, was compounded. It is demonstrated that the designed photo-
PAT5, PAT10, PAT15, and PAT20 was estimated to be about catalysts should have a better light response. Meanwhile, light
2.3, 5.2, 12.0, 16.2%, and 23.5 wt %, respectively. This is consis- harvesting was improved through efficient light scattering due to
tent with the trend of the theoretical addition, but the actual con- the special 3D biomimetic structure of PATX. Besides, the
tent of TiO2 nanoparticles from TG results were higher than extended light absorption range meant a broader spectral range
theoretical addition, obviously due to the uncrosslinked of hydro- of light can be utilized and enhance significantly the photo-
gel which was dissolved after soaking and washing. catalytic performance of the photocatalyst.
Supporting Information Figure S3 shows the UV–Vis transmit- The texture property of the composite hydrogels was determined
tance spectra of pure PVA hydrogel film. It is clearly seen that by BET gas sorptometry measurements. The results were illus-
the film has high transparency in the whole UV and visible light trated in Supporting Information Figure S4–S5 and Table.I. The
region. This suggests that the PVA matrix does not affect the isotherms of all samples were identified as type IV isotherms with
transmission of light, which provide the possibility to increase a type H3 narrow hysteresis loop, indicating a porous microstruc-
the photocatalytic performance of PATX. Figure 2(d) illustrated ture with open pores, which is consistent with morphologies
UV–Vis absorption spectrums of the composite hydrogels con- analysis of the composite hydrogels (Figure 4). It is seen that the
taining different mass ratio of TiO2. As a dark green material, the texture properties of the PAT15 is higher than that of the as-
PAT0 composite hydrogels exhibited strong absorption in the prepared other PAT sample, the BET specific surface area and
whole UV and visible light region owing to π-π* and πb-πq cumulative pore volume being 60.59 m2 g−1 and 10.33 cm3 g−1,
absorption associated with the benzene structure of PANI.51 It is respectively. The large mesoporous size distribution and high
generally accepted that TiO2 is a UV light absorption BET surface area were advantageous for adsorbing more organic
photocatalyst, but with PVA/PANI/TiO2 composite hydrogel, the dyes or heavy metals on their surface, which will contribute to
photoresponding range was extended when TiO2 and PVA/PINA the enhancement of photocatalytic activity of catalysts.

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Figure 5. TEM image of (a, b) PAT15 composite hydrogel and HRTEM image of (c, d) PAT15 composite hydrogel.

Morphology 70 wt % by thermogravimetry (Supporting Information Figure S7).

Scanning electron microscopy (SEM) was used to examine the Figure 4(g) shows the FESEM image of the pure TiO2 nanoparti-
structural changes of the as-prepared PVA/PANI hydrogel at cle with a diameter of about 30–80 nm. After introduction of
different PVA concentrations. As Figure 3 shows, the pore size increased amounts of TiO2, the pores of nanocomposite hydrogel
of PVA/PANI-10% is much more narrow and uniform than the are more disorderly compared with PAT0. However, TiO2 was
PVA/PANI-5%. Additionally, the specific surface area (SBET) and not found in the composite hydrogel, which is most likely due to
the cumulative pore volume (Vp) of the as-prepared PVA/PANI the overlaps within the skeleton of PVA/PANI hydrogel. How-
sample have been measured (shown in Supporting Information - ever, the EDS mapping of PAT15 composite hydrogel [Figure 4(i-
Figure S4–S5 and Table. S1). It is seen that the texture property l)] demonstrates that C O N and Ti elements were evenly dis-
of the PVA/PANI-10% is higher than that of the PVA/PANI-5% tributed. Therefore, the above results confirm that the TiO2 was
and SBET slightly increases from 47.80 to 55.10 m2 g−1, as well as successfully loaded onto the 3D network nanostructured matrix of
Vp slightly enhanced from 8.10 × 10−2 to 9.25 × 10−2 cm3 g−1. the PVA/PANI hydrogel. The TEM image [Figure 5(a,b)] con-
Such slightly changes might be due to the more hydrogel skele- firms that the TiO2 nanoparticles were evenly deposited onto the
ton having been formed in the high concentration of PVA con- coral-like dendritic PVA/PANI hydrogel, and that the TiO2
ditions, and stacked into more holes, which results in the nanoparticles had coated and bonded together with the 3D net-
increasing of surface area and pore volume. Thus, PVA/PANI- work structure of the hydrogel. In order to validate this point of
10% was selected as the basic research object in the following view, HRTEM images of the selected location were acquired. As
investigations. shown in Figure 5(c), the interplanar spacing of TiO2 is 0.358 nm,
The morphologies of the PATX composite hydrogels are com- corresponding to the anatase (101) plane. The interplanar spacing
pared in Figure 4. Obviously, all the composite hydrogels exhibit of TiO2 is 0.25 nm, corresponding to the rutile (101) plane
porous structure, and the pores in the hydrogels are connected [shown in Figure 5(d)]. It is quite clear that PANI was coated
with each other to form open channels, which effectively facilitate onto the surface of TiO2 nanoparticles. The interplanar spacing of
the migration of water in the channels and increases the perme- the selected bright spot was 0.245 nm, corresponding to the PANI
ability of the hydrogel. Porosity is conducive to the transfer of (222) plane. The HRTEM analysis further confirms the TiO2
fluids, and this has been confirmed through the wetting behavior nanoparticles and PANI chain was in contact with each other,
(Supporting Information Figure S6). Additionally, the water con- which provides the possibility of enhancement of the photo-
tent of the PVA/PANI composite hydrogels was determined to be catalytic performance in aqueous systems of PAT15.

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(a) B1s (b) N 1s

Counts (s)
Counts (s)

410 408 406 404 402 400 398 396 394 392
198 196 194 192 190 188 186 184 182 180
Binding Energy (eV) Binding Energy (eV)

(c) Ti 2p (d) O 1s
Ti 2p3/2
Counts (s)

Counts (s)

Ti 2p1/2

472 470 468 466 464 462 460 458 456 454 452 542 540 538 536 534 532 530 528 526 524 522
Binding Energy (eV) Binding Energy (eV)
Figure 6. XPS survey spectra of PAT15 composite hydrogel: (a) B1s; (b) N1s; (c) Ti2p; (d) O 1s.

XPS Detection evaluated through tensile testing and simple compression testing.
XPS was used to further investigate the surface composition of As is shown in Figure 7, the structure of swollen PAT15 hydrogel
the PAT15 composite hydrogels. The B1s spectra of the PAT15 is did not collapse under 500 g counter weight compression [Fig-
shown in Figure 6(a). There is a weak peak at 192.3 eV attributed ure 7(b)], and recovered immediately its original shape when
to the B O/B C bond of PANI hybrid chain, indicated that the removing strong external forces [Figure 7(c–e)]. Moreover, the
reaction between the boronic acid groups on PANI hybrid chain tensile strength and elongation on breaking of PAT15 is
and hydroxyl groups on PVA.41,50 It also declared the chemical 0.94 MPa and 378%, respectively, indication its favorable
doping ABA was used as the dopant to improve the conductivity mechanical properties for recycling. Besides, gel samples could be
of PANI effectively. The dominant peaks at 399.4 eV correspond
shaped into different forms using a stamping mold [Figure 6(a)],
to N H bond of PANI in PAT hydrogel.43,51 As is shown in
to be suitable for use in different reactors.
Figure 6(c), the peaks at the binding energy of 464.4 eV and
458.3 eV are attributed to Ti 2p1/2 and Ti 2p3/2 binding energies. Swelling behaviors of PAT15 hydrogel at different pH and differ-
The peaks at 532.3 eV correspond to the O2− anion. The results ent NaCl concentration were studied further (Seen in Supporting
from XPS indicated that the TiO2 nanoparticles were successfully Information Figure S8). The swelling ratio of PAT15 hydrogel is
introduced into the hybrid PVA/PANI hydrogels. higher while the range of pH is neutral and weak acid and weak
alkali condition, so the appropriate pH of degradation solution
Mechanical Property and Swelling Behavior should be selected for different reaction systems in the
In general, the catalyst carrier requires a certain mechanical adsorption-photocatalytic experiments. In addition, the ionic
strength. So the mechanical property of swollen PAT15 was strength in the external solution has an important influence on

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Figure 7. (a) Digital pictures of PAT15 composite hydrogels with different geometric shapes; (b) PAT15 composite hydrogel supporting a 500 g counter
weight without structural collapse; (c–e) Digital pictures of PAT15 composite hydrogel upon repeated compression; (f)Tensile curves of the PAT15 compos-
ite hydrogel. [Color figure can be viewed at wileyonlinelibrary.com]

the swelling ratio of PAT15 hydrogel. It can be seen that from the Cr(VI) could be efficiently absorbed (Supporting Information -
Supporting Information Figure S8B, the osmotic pressure inside Figure S9). This rapid enrichment is very beneficial to improve
and outside the PAT15 hydrogel network decreases with the the subsequent photocatalytic degradation, especially in dynamic
increasing of ionic strength, which causes the swelling ratio of the degradation.
PAT15 hydrogel to decrease. Therefore, the solution required for
In addition, PATX hydrogels exhibit superior selectivity for
later experiments will be formulated by deionized water.
adsorption, and were evaluated through the separation of multi-
farious dye mixtures. Figure 9(a), it is evident that the character-
Selective Adsorption Behaviors of PATX istics adsorption peak of MO had disappeared within 30 min,
The adsorption activities of PATX were tested by using MO and while the changing of adsorption peak in MB was not remark-
MB. The adsorption of MO and MB at different initial concentra- able, and the color of the solutions turned from green to blue.
tions was studied at room temperature. [Figure 8(a,b)]. The
This result can also be confirmed by the difference in the maxi-
adsorption of MO and MB to the PAT0 hydrogel was 722 mg g−1
mum adsorption of MO and MB dye. For this, a simple filter was
and 0.86 mg g−1, respectively. The UV–vis spectra change of
constructed to achieve the purpose of water purification
100 mg L−1 MO dye in the presence of 10 mg PAT0 showed that
(Supporting Information Figure S10), PAT15 aerogel was filled in
the color of MO weakened and the adsorption rate reached 72%
the self-made filter, and we found that anionic MO could still be
in 2 h [Figure 8(e)]. Nevertheless, negligible absorbance change
for MB at 665 nm was observed [Figure 8(f)]. In the same condi- rapidly enriched by PAT in high flow rates compared with cat-
tions, the adsorption of PATX containing different mass ratios of ionic MB [Figure 9(d)]. Figure 9(b) represents rapid removal of
TiO2 were also measured, and the adsorption of MO weakened MO (within 30 min) from a mixture of cationic dyes
gradually with the increase of TiO2 in low loading, but still (Rhodamine B, RhB). To further support the assumption of the
exhibited better adsorption [Figure 8(c)]. However, the adsorp- above-mentioned selective adsorption, the adsorption behavior of
tion capability has been improved in high loading (>10%) due to a heavy metal solution in a mixed valence state was investigated
high specific surface area and porosity enhancing the contact area [Figure 9(c)]. It is found that the ratio of Cr(VI)/Cr(III) adsorp-
with the organic dyes, but the adsorption of PAT0 is still the tion capacity is about 82.5. Therefore, the above results clearly
highest. By contrast, the adsorption of MB is very low, and indicate that the presence of active cationic groups in the
increased slightly with high specific surface area [Figure 8(d)]. To functionalized polymer facilitates the selective adsorption of MO
further understand the adsorption capability of PATX, chromium and Cr(VI). This selective adsorption is contributing to the
(Cr2O72−) was also investigated, and it was found that enhancement of photocatalytic activity, because the initial and

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(a) (b)

(c) (d)

(e) (f)

Figure 8. Adsorption performance of PAT0 at different MO (a) and MB (b) concentrations; Histogram showing the maximum adsorption capacity of MO
(c) and MB (d) at the different samples; UV–Vis spectral changes of MO (e) and MB (f) dye in the presence of PAT0. [Color figure can be viewed at
wileyonlinelibrary.com]

intermediate product can be enriched, and the final product can degradation with MO in a closed system was investigated.
be desorbed in the photocatalytic process. 52,53 Figure 10(a) shows the removal rate of MO with PAT at differ-
ent mass ratios of TiO2 (0, 2, 5, 10, 15, and 20%) and at
Photocatalytic Activities of PAT Hydrogel different times. It could be concluded that MO showed slight
Photocatalytic Performance in Closed Systems. The effect of self-degradation under UV light irradiation and the adsorption-
TiO2 content on the property of adsorption-photocatalytic photocatalytic activity of PAT15 exhibits the highest activity in

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ARTICLE WILEYONLINELIBRARY.COM/APP

(a) (b)

(c) (d)

Figure 9. (a) Selective removal of anionic MO from mixtures of MO and MB; (b) Selective removal of anionic MO from mixtures of MO and RhB;
(c) Adsorption capacities for Cr(VI) and Cr(III) on PAT15 in a mixed solution containing 25 mg L−1 Cr(VI) and 25 mg L−1 Cr(III). The pH of the
Cr(VI or III) solution was adjusted to 3; (d) The MB and MO removal abilities of PAT15 aerogel hydrogel via the homemade filter in dynamic system for
120 min, the initial solution concentration is 10 mg L−1 and the solution flow rate is 0.32 mL s−1. [Color figure can be viewed at wileyonlinelibrary.com]

comparison to these mass ratio the range of 0–20%, owing to areas of the active TiO2 NPs have been increased with high
the synergistic effect of adsorption-enrichment and photo- mass ratio of TiO2.54 Figure 10(d) gives the cycling experiment
catalytic degradation. The UV–Vis spectra change of MO dye in of the adsorption-photocatalytic and adsorption activity of
the presence of PAT15 showed that the color of MO weakened, MO in the presence of PAT15. It is clear that the adsorption
which initially displayed deep orange yellow color, and became performance is gradually declining after each cycle run, indicat-
colorless (Supporting Information Figure S11). Because of the ing that the adsorption sites were occupied by MO which could
energy of activation cannot be obtained without carrying out not be further removed, and the desorption experiment also
the reaction at different temperatures, the adsorption rate and attests to this (Supporting Information Figure S12). Although
degradation rate were discussed in this case. The total removal the adsorption-photocatalytic degradation rate was slightly
rate of PAT0, PAT2 PAT5, PAT10, PAT15, PAT20 toward decreased from 92 to 88.6% after the five cycle of the degrada-
anionic MO dye were 72, 84, 86, 85, 92, and 89%, respectively. tion of MO by PAT15, but the removal ability still remained
Figure 10(c) also shows that the COD Cr removal rate of MO and was high, indicating that the MO adsorbed by the hydrogel
over PAT15 is higher (88.3%). Although the adsorption capacity matrix could be further reduced through in situ degradation by
of PATX hydrogel decreased slightly, the photocatalytic activity TiO2 under UV light irradiation, showing a high recycle, renew-
was improved with increasing mass ratio of TiO2 [Figure 10(b)]. able and separation free ability. Beyond the results, the synergy
Because of this case, TiO2 NPs were trapped in the hydrogel of adsorption and photocatalysis significantly improved the
matrix, and so, only TiO2 NPs that were on the surface of the reusability, and maintained the performance of PAT under con-
hydrogel could participate in dye degradation, and the surface tinuous working conditions.

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1.0
PAT0 (a) Light on (b)
PAT2 1.0

PAT5
0.8 0.9
PAT10
Light off PAT15 0.8
PAT20
0.6 0.7
Light on

Ct/C0
Ct/C0

0.6

0.4
0.5 PAT0
PAT2
0.4 PAT5
0.2 PAT10
0.3
PAT15
PAT20
0.2
0.0
0 20 40 60 80 100 120
-4 -3 -2 -1 0 1 2
Time (h) Time (min)

100 Adsorption-photocatalysis (c) 100 Adsorption-photocatalysis (d)

Adsorption Adsorption

80 80
MO Removal (%)

60 60
%

40 40

20 20

0 0
1 2 3 4 5
Ct/C0 CODt/COD0 Recycle Times
Figure 10. Adsorption-photocatalytic (a) and photocatalytic (b) performance of different composite hydrogels; (c) Adsorption-photocatalysis and adsorption
rate of MO in in the presence of PAT15 composite hydrogel; (d) Recycling runs of PAT15 in removing MO without desorption. [Color figure can be viewed
at wileyonlinelibrary.com]

In order to further understand the mechanism of adsorption in respectively. The PAT hydrogel film photocatalyst and baffler was
order to enhance photocatalytic activity, multifarious dye mix- sandwiched between in PTFE vessel and quartz glass. The baffler
tures were also investigated. To ensure the adsorption equilib- conducive to intimate contact, promote turbulence. The vertical of
rium, PAT15 was combined with in multifarious dye mixtures reactor was maintained stably during the reaction to keep the
(100 mg L−1 MO + 10 mg L−1 MB) for 4 h, and then illuminated. whole film completely immersed, and liquid flows in from the
As is expected (Figure 11), the mixture solution became colorless lower corner and then flows out from the top corner. 100 W mer-
in the presence of PAT15 at 2 h. The MO shows a much faster cury lamps were used to light in each side of the reactor at 5.0 cm
photodegradation rate compared to MB, and the final degrada- away from the reactor. Peristaltic pump provided the power. As
tion rate was 81.1 and 72.3%, respectively. In addition, the MB can be seen, liquid flows in from the lower corner and then flows
degradation rate is seriously lagging behind compared to MO, out from the upper corner. At the intervals of given time, 3 mL ali-
quots were sampled from the top corner of the reactor. The ali-
which indicates that selective adsorption enrichment is beneficial
quots did not need to be centrifuged and were directly analyzed.
to improve the photocatalytic activity.
Figure 12(d) shows the photocatalytic degradation of MO in
dynamic system over PAT15 hydrogel with 0.32 mL s−1 flow
Photocatalytic Performance in Flow Systems. The photocatalytic rates. The flow system runs for 30 min before illumination, in
activities of PAT15 in a flow BPR system under a 100 W mercury order to reach the adsorption–desorption equilibrium, and the
lamp at 5 cm away from the solution are shown in Figure 12(a–c). adsorption proportion of MO was about 8.0%. However, the MO
The biomimetic photocatalytic reactor (BPR) (10.0 × 7.0 × 1.0 cm) begins to degrade when illuminated, the equilibrium degradation
was made from PTFE and quartz glass (avoid the light shielding). proportion of MO was about 4.5%, and the overall removal rate
The inlet and outlet were located at down and up ends, was 12.5%. The MO concentration gradually increased when the

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(a) 1.0
MO (b)
0min MB
2.0 15min
30min 0.8
45min
1.5 60min
Absorbance

90min
120min 0.6

Ct/C0
1.0

0.4

0.5

0.2
0.0
300 400 500 600 700 800 0 20 40 60 80 100 120
Wavelength (nm) Time (min)
Figure 11. (a) UV–Vis spectra changes of MB and MO mixed aqueous solution in the presence of PAT15; (b) Comparison of photocatalytic activities of
MB and MO; The inset photographs highlight the photodegradation effects along with the increasing contact time. [Color figure can be viewed at
wileyonlinelibrary.com]

Figure 12. Photocatalytic degradation of MO in flow system over PAT15 composite hydrogel with 0.32 mL s−1 flow rate. [Color figure can be viewed at
wileyonlinelibrary.com]

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ARTICLE WILEYONLINELIBRARY.COM/APP

30.938 (a) (b)

30.936
0.2
Mass (g)

Absorbance
30.934

0.0
30.932

30.930
-0.2

30.928

0 10 20 30 40 50 200 300 400 500 600 700

IrradiationTime (h) Wavelength (nm)
Figure 13. (a) Stability of PAT hydrogel in air under 100 W UV light irradiation. (b) UV absorption spectrum of the 50 mL water with only 0.25 g PAT
hydrogel under 100 W UV light for 50 h. [Color figure can be viewed at wileyonlinelibrary.com]

lights are turned off again. Obviously, the hydrogels exhibit a carrier to fix photocatalyst (e.g., TiO2) and applied for wastewater
porous structure, interconnected with each other to form open treatment. Furthermore, no obvious degradation products of
channels (Figure 4), which effectively facilitate the migration of PAT hydrogel were observed as Figure 13(b). This probably dem-
water in the channels. So pollutants can be enriched and concen- onstrated that PAT hydrogel possesses good stability and
trated into the 3D network of the composite hydrogel, then the reutilization under light irradiation.55,56
pollutants are in situ oxidized via photocatalysis under UV light
irradiation on the transmissive light side. This demonstrated that Mechanism of Selective Adsorption-Photocatalytic Activity
photocatalytic degradation of MO can be done by PAT recyclable To reveal the mechanism of selective adsorption-photocatalytic
hydrogel and inhibit the loss of catalyst for application in the sus- degradation of MO with the addition of holes and radical scaven-
tainability field. ger under UV light irradiation was investigated. As shown in
Figure 14, the addition of t-BuOH as hydroxyl radicals (•OH)
Figure 13(a) shows the stability of PAT hydrogel in air under UV
scavenger, formic acid as holes (h+) scavenger and N2 as super-
light irradiation (100 W mercury lamps, Shanghai). Then, 0.50 g
oxide anions (•O2−) scavenger were used to investigate selective
PAT hydrogel was put onto a 90 mm culture dish with UV light
adsorption-photocatalytic degradation performances. Obviously,
irradiation. At the intervals of given time, the mass of the whole
the photo-generated holes were the main active oxidative species.
system (culture dish and PAT hydrogel) were weighed. Obvi-
The activity of PAT15 under UV light irradiation reduced slightly
ously, the mass of the whole system remained almost unchanged
with the addition of hydroxyl radical scavenger and superoxide
after 50 h, which indicates that PAT hydrogel can be worked as a
anions, which suggested these radicals were the partial active oxi-
dative species.
1.0 From the above characterizations, we could deduce the possible
schematic as is shown in Figure 15. Initially, anionic dyes were
adsorbed and enriched onto the surface of the TiO2 nanoparticles
0.8 in the 3D network nanostructure of PVA/PANI hydrogel, owing
to the electrostatic interaction, and additionally the high specific
surface area and porosity enhanced the contact area with the
organic dyes.16,18 Then the anionic dye was in situ degraded
Ct/C0

0.6
under UV light irradiation, to realize the synergistic effect of
adsorption and photocatalysis. The photogenerated electrons and
holes are generated on the conduction band (CB) and valence
0.4 band (VB) of TiO2 when irradiated by UV light. As the VB posi-
Formic acid
Nitrogen purging tion of TiO2 is lower than the highest occupied molecular orbital
t-BuOH (HOMO) of PANI,57,58 the photogenerated holes on the VB of
No scavengar
0.2 TiO2 could be easily transferred to the HOMO orbit of PANI
0 20 40 60 80 and then transferred out through the 3D network nanostructure
Time (h) of PANI hydrogel, which improves the separation efficiency of
Figure 14. Photocatalytic degradation of MO with the addition of hole and electrons and holes and enhances the photocatalytic activity. In
radical scavenger under UV light irradiation. [Color figure can be viewed at addition, the excellent adsorption-photocatalytic activity and 3D
wileyonlinelibrary.com] biomimetic network structure of PVA/PANI/TiO2 hydrogel is

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Figure 15. Mechanism of adsorption-photocatalytic degradation on PAT15 composite hydrogel. [Color figure can be viewed at wileyonlinelibrary.com]

convenient for separation and recycling, which is also beneficial Project of Hubei University of Science & Technology
to water purification in the flow systems. (No. 2019-20KZ01).

CONCLUSIONS
In summary, PVA/PANI/TiO2 hydrogel (PAT) with 3D biomi-
REFERENCES
metic structure has been successfully prepared by a self-
assembling and electron beam radiation method. TiO2 1. Harper, C.; Snowden, M. Environment and Society: Human
nanoparticles were successfully introduced into the 3D biomimetic Perspectives on Environmental Issues; Taylor & Francis:
network matrix of the PVA/PANI hydrogel and manifested by Abingdon, 2017.
FTIR, TG, XRD, XPS, FESEM-EDS, and HRTEM. It was also 2. Zhang, M.; Jiang, W. J.; Liu, D.; Wang, J.; Liu, Y. F.;
found that PAT photocatalysts show excellent selective Zhu, Y. Y.; Zhu, Y. F. Appl. Catal. B Environ. 2016,
adsorption-photocatalytic performance, owing to the synergistic 183, 263.
effect of adsorption-enrichment and in situ photocatalytic degra- 3. Choi, J.; Lee, H.; Choi, Y.; Kim, S.; Lee, S.; Lee, S.; Lee, J.
dation. At the same time, PAT has the advantage of separation- Appl. Catal. B Environ. 2014, 147, 8.
free characteristics in bulk materials and avoids secondary pollu- 4. Jiang, W. J.; Luo, W. J.; Zong, R. L.; Yao, W. Q.; Li, Z. P.;
tion, indicating that PAT is easy to recycle. Electrochemical Zhu, Y. F. Small. 2016, 12, 4370.
behavior and effect on 3D biomimetic structure of PAT
5. Zhou, J. H.; Hao, B. Z.; Wang, L. B.; Ma, J. Z.; Cheng, W. J.
photocatalyst remains to be explored in the future. Also, given the Sep. Purif. Technol. 2017, 176, 193.
photostability of the 3D biomimetic network structure, it may
6. Chen, P. P.; Liu, X. Y.; Jin, R. D.; Nie, W. Y.; Zhou, Y. F.
have good potential for application in the field of water pollution
Carbohydr. Polym. 2017, 167, 36.
treatment.
7. Sangareswari, M.; Sundaram, M. M. Appl Water Sci. 2017,
7, 1781.
ACKNOWLEDGMENTS
8. Kacan, E. J. Environ. Manag. 2016, 166, 116.
This work was supported by the National Natural Science Foun-
9. Lively, R. P.; Sholl, D. S. Nat. Mater. 2017, 16, 276.
dation of China (No.11405050, 21302150), the Project of the
Science and Technology Department of Hubei Province 10. Menzies, J. Z.; McDonough, K.; McAvoy, D.; Federle, T. W.
(No. 2018AFB150), the Key Projects of the Education Depart- Biodegradation. 2017, 28, 1.
ment of Hubei Province (No. D20182803), the Science Develop- 11. Gao, D. W.; Wen, Z. D. Sci. Total Environ. 2016, 541, 986.
ment Foundation of Hubei University of Science & Technology 12. Sarkar, A. K.; Saha, A.; Tarafder, A.; Panda, A. B.; Pal, S.
(No. 2018-19KZ05), the Nuclear Technology Key Subject ACS Sustain. Chem. Eng. 2016, 4, 1679.

48516 (15 of 16) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.48516

ARTICLE WILEYONLINELIBRARY.COM/APP

13. Lucic, M.; Milosavljevic, N.; Radetic, M.; Šaponjic, Z.; 36. Xu, Y. F.; Zhang, C.; Lu, P.; Zhang, X. H.; Zhang, L. X.;
Radoicic, M.; Krušic, M. K. Sep. Purif. Technol. 2014, 122, 206. Shi, J. L. Nano Energy. 2017, 38, 494.
14. Wu, D. B.; Yi, M. R.; Duan, H. Y.; Xu, J. Y.; Wang, Q. G. 37. Koo, H. J.; Velev, O. D. J. Mater. Chem. A. 2013, 1, 11106.
Carbon. 2016, 108, 394. 38. Gao, P.; Liu, Z. Y.; Tai, M. H.; Sun, D. D.; Ng, W. Appl.
15. Ma, Y. H.; Wang, J. J.; Xu, S. M.; Zheng, D. D.; Du, J.; Catal. B Environ. 2013, 138, 17.
Feng, S.; Wang, J. D. RSC Adv. 2017, 7, 15077. 39. Chen, L.; Yang, S. D.; Hao, B.; Ruan, J. M.; Ma, P. C. Appl.
16. Li, Y. S.; Qin, J. T.; Han, Y.; Du, J. F.; Dong, Z. B.; Catal. B Environ. 2015, 166, 287.
Sun, S. F.; Liu, Y. Appl. Catal. B Environ. 2017, 218, 101. 40. Koosha, M.; Mirzadeh, H.; Shokrgozar, M. A.; Farokhi, M.
17. Mai, N. X. D.; Bae, J.; Kim, I. T.; Park, S. H.; Lee, G. W.; RSC Adv. 2015, 5, 10479.
Kim, J. H.; Hur, J. Environ. Sci. Nano. 2017, 4, 955. 41. Li, Y. S.; Cai, H. H.; Han, Y.; Huang, H. T.; Qin, J. T.;
18. Thomas, M.; Naikoo, G. A.; Sheikh, M. U. D.; Bano, M.; Song, Z. Y.; Sun, S. F.; Liu, Y. J. Appl. Polym. Sci. 2016,
Khan, F. J. Photochem. Photobiol. A Chem. 2016, 327, 33. 133, 44150.
19. Jiang, W. J.; Liu, Y. F.; Wang, J.; Zhang, M.; Luo, W. J.; 42. Huang, H. B.; Yao, J. L.; Li, L.; Zhu, F.; Liu, Z. T.;
Zhu, Y. F. Adv. Mater. Interfaces. 2016, 3, 1500502. Zeng, X. P.; Huang, Z. L. J. Mater. Sci. 2016, 51, 8728.
20. Jiang, W. J.; Zhu, Y. F.; Zhu, G. X.; Zhang, Z. J.; 43. Gonzalez-Rodriguez, J. G.; Lucio-Garcia, M. A.;
Chen, X. J.; Yao, W. Q. J. Mater. Chem. A. 2017, 5, 5661. Nicho, M. E.; Cruz-Silva, R.; Casales, M.; Valenzuela, E.
21. Chen, F. Y.; An, W. J.; Li, Y.; Liang, Y. H.; Cui, W. Q. Appl. J. Power Sources. 2007, 168, 184.
Surf. Sci. 2018, 427, 123. 44. Li, W.; Gao, F.; Wang, X.; Zhang, N.; Ma, M. Angew. Chem.
22. Zhang, Y.; Cui, W. Q.; An, W. J.; Liu, L.; Liang, Y. H.; Int. Ed. 2016, 128, 9196.
Zhu, Y. F. Appl. Catal. B Environ. 2018, 221, 36. 45. Mukai, S. R.; Nishihara, H.; Shichi, S.; Tamon, H. Chem.
23. Cui, W. Q.; He, J.; Wang, H.; Hu, J. S.; Liu, L.; Liang, Y. H. Mater. 2004, 16, 4988.
Appl. Catal. B Environ. 2018, 232, 232. 46. Chen, Y. F.; Liu, H. Z.; Geng, B. Y.; Ru, J.; Cheng, C.;
24. Zhu, H. J.; Li, Z. K.; Yang, J. H. Chem. Eng. J. 2018, 334, 1679. Zhao, Y.; Wang, L. K. RSC Adv. 2017, 7, 17279.
25. Zhao, K. Y.; Feng, L. Z.; Lin, H. Q.; Fu, Y. F.; Lin, B. B.; 47. Guo, D. Radiat. Phys. Chem. 2017, 130, 202.
Cui, W. K.; Li, S. D.; Wei, J. F. Catal. Today. 2014, 236, 127. 48. Ranka, P.; Sethi, V.; Contractor, A. Q. Thin Solid Films.
26. Yang, J. H.; Li, Z. K.; Zhu, H. J. Appl. Catal. B Environ. 2016, 615, 44.
2017, 217, 603. 49. Jiang, X. C.; Jiang, T.; Zhang, X. F.; Zhang, X.; Dai, H.
27. Fourmond, V.; Stapf, S.; Li, H.; Buesen, D.; Birrell, J.; Polym. Eng. Sci. 2013, 53, 1181.
Rüdiger, O.; Léger, C. J. Am. Chem. Soc. 2015, 137, 5494. 50. Yao, B. W.; Wang, H. Y.; Zhou, Q. Q.; Wu, M. M.;
28. Sun, J.; Schmidt, B. V.; Wang, X.; Shalom, M. ACS Appl. Zhang, M.; Li, C.; Shi, G. Q. Adv. Mater. 2017, 29,
Mater. Interfaces. 2017, 9, 2029. 1700974.
29. Mao, Q.; Shi, S. J.; Wang, H. L. ACS Sustain. Chem. Eng. 51. Huang, H.; Li, W.; Wang, H.; Wang, Q.; Yang, Y. ACS
2015, 3, 1915. Appl. Mater. Interfaces. 2014, 6, 1595.
30. Chevry, M.; Vanbésien, T.; Menuel, S.; Monflier, E.; et al. 52. Li, Y. L.; Bian, Y. Y.; Qin, H. X.; Zhang, Y. X.; Bian, Z. F.
Cat. Sci. Technol. 2017, 7, 114. Appl. Catal. B Environ. 2016, 206, 293.
31. Ai, L. H.; Gao, X. Y.; Jiang, J. J. Power Sources. 2014, 53. Li, Q.; Xue, D. X.; Zhang, Y. F.; Zhang, Z. H.; Gao, Z. W.;
257, 213. Bai, J. F. J. Mater. Chem. A. 2017, 5, 14182.
32. Qiao, Z.; Zhang, H. G.; Karakalos, S.; Hwang, S.; Xue, J.; 54. Kazemi, F.; Mohamadnia, Z.; Kaboudin, B.; Karimi, Z.
Chen, M. J.; Su, D.; Wu, G. Appl. Catal. B Environ. 2017, J. Appl. Polym. Sci. 2016, 133, 43386.
219, 629. 55. Mai, N. X. D.; Park, D.; Yoon, J.; Hur, J. J. Nanosci.
33. Umena, Y.; Kawakami, K.; Shen, J. R.; Kamiya, N. Nature. Nanotechnol. 2018, 18, 1361.
2011, 473, 55. 56. Habiba, U.; Joo, T. C.; Siddiqu, T. A.; Salle, A.; An, B. C.;
34. Weingarten, A. S.; Kazantsev, R. V.; Palmer, L. C.; Afifi, A. M. Int. J. Biol. Macromol. 2017, 104, 1133.
McClendon, M.; Koltonow, A. R.; Samuel, A. P.; 57. Yang, C. X.; Dong, W. P.; Cui, G. W.; Zhao, Y. Q.;
Stupp, S. I. Nat. Chem. 2014, 6, 964. Shi, X. F.; Xia, X. Y.; Tang, B.; Wang, W. L. Electrochim.
35. Weingarten, A. S.; Kazantsev, R. V.; Palmer, L. C.; Acta. 2017, 247, 486.
Fairfield, D. J.; Koltonow, A. R.; Stupp, S. I. J. Am. Chem. 58. Zhang, H.; Zong, R.; Zhao, J.; Zhu, Y. Environ. Sci. Technol.
Soc. 2015, 137, 15241. 2008, 42, 3803.

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