Next Article in Journal
Stability Analysis and Structure Optimization of Unequal-Pitch End Mills
Previous Article in Journal
Process Parameter Optimization of a Polymer Derived Ceramic Coatings for Producing Ultra-High Gas Barrier
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Preparation of BiOCl/Bi2WO6 Photocatalyst for Efficient Fixation on Cotton Fabric: Applications in UV Shielding and Self-Cleaning Performances

1
College of Textile and Clothing, Yancheng Institute of Technology, Yancheng 224051, China
2
School of Textile Science and Engineering, Jiangnan University, Wuxi 214122, China
3
School of Textile and Clothing, Nantong University, Nantong 226019, China
*
Author to whom correspondence should be addressed.
Materials 2021, 14(22), 7002; https://doi.org/10.3390/ma14227002
Submission received: 1 November 2021 / Revised: 13 November 2021 / Accepted: 15 November 2021 / Published: 18 November 2021
(This article belongs to the Topic Nanomaterials for Sustainable Energy Applications)

Abstract

:
In this work, a visible-light-driven BiOCl/Bi2WO6 photocatalyst was obtained via a facile hydrothermal method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), ultraviolet/visible light diffuse reflection spectroscopy (UV/Vis), and photocurrent (PC). BiOCl/Bi2WO6 was modified with (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride to obtain the cationized BiOCl/Bi2WO6. Cotton fabric was pretreated with sodium hydroxide (NaOH) and sodium chloroacetate solution to obtain carboxymethylated cotton fabric, which was further reacted with cationized BiOCl/Bi2WO6 to achieve finished cotton fabric. The cotton fabrics were characterized by Fourier-transform infrared spectroscopy (FT-IR), XRD, SEM, and EDS. The photocatalytic activity of the BiOCl/Bi2WO6 photocatalyst and cotton fabrics was assessed by photocatalytic degradation of MB (methylene blue) solution under simulated visible light. The self-cleaning property of cotton fabrics was evaluated by removing MB solution and red-wine stains. Results revealed that the coated cotton fabrics exhibited appreciable photocatalytic and self-cleaning performance. In addition, anti-UV studies showed that the finished cotton fabrics had remarkable UV blocking properties in the UVA and UVB regions. Therefore, the finished cotton fabric with BiOCl/Bi2WO6 can provide a framework for the development of multifunctional textiles.

1. Introduction

Semiconductor-based photocatalysis is regarded as a promising and cost-effective approach to realize environmental decontamination [1,2,3,4,5]. Traditional semiconductor materials with a wide bandgap (e.g., TiO2, ZnO, and BiOCl) are widely utilized in practical application due to their commendable chemical stability, biosafety, photostability, and low cost [6,7,8,9]. BiOCl with a layered structure is a potential candidate for semiconductor photocatalysis owing to its superior photocatalytic activity. However, it displays a relatively low quantum efficiency in the visible wavelength range that hinders its practical implementation [8,9,10,11]. Another bismuth compound, namely, Bi2WO6, with its comparatively narrow bandgap, is capable of adsorbing visible light. Nevertheless, the rapid recombination of photogenerated electron–hole pairs in Bi2WO6 reduces its photocatalytic efficiency [12,13,14]. Interestingly, the lattice of Bi2WO6 and BiOCl can be well matched and form heterojunctions to promote the separation of photogenerated carriers [15,16]. Tahmasebi et al. fabricated a Bi2WO6/BiOCl composite through a facile hydrothermal method with the aid of hydrochloric acid (HCl) as a Cl source, and the obtained Bi2WO6/BiOCl exhibited preferable photocatalytic activity [17]. Visible light-responsive Bi2WO6/BiOCl heterojunctions were successfully prepared via a simple one-step hydrothermal method by Liang and his coworkers, and the results revealed that Bi2WO6/BiOCl had superior degradation efficiency under visible-light illumination than bare BiOCl and Bi2WO6 [18].
Cotton fabric is a very common natural fabric that has been widely used as the substrate of functional textiles due to its exceptional moisture absorption, breathability, comfortability, etc. [19,20,21,22]. Cotton fabrics have been finished with semiconductor materials by many researchers to obtain properties such as self-cleaning, UV-shielding, superhydrophobic, water–oil separating, and antibacterial [23,24,25]. Tudu et al. developed a superhydrophobic cotton fabric using a mixture of perfluorodecyltriethoxysilane (PFDTS) and TiO2 nanoparticles, and the coated cotton fabric presented outstanding self-cleaning, stain resistance, rust stain resistance, antiwater absorption, and antibacterial abilities [26]. BiOCl nanosheet-coated cotton fabric was obtained via a pad–dry–cure method by Jin and his colleagues; the finished cotton fabric showed appreciable UV protection and photocatalytic performance [27]. To the best of our knowledge, a cotton fabric finished with BiOCl/Bi2WO6 photocatalyst has not been reported to study its various functionalities, such as self-cleaning, UV-shielding, and photocatalytic properties.
In this study, we coupled BiOCl with Bi2WO6 through a facile one-step hydrothermal method and characterized it by XRD, SEM, EDS, XPS, UV/Vis DRS, PC, and photocatalytic activity. Thereafter, the cotton fabric was pretreated by NaOH and sodium chloroacetate solution to obtain carboxymethylated cotton fabric, and then finished with cationized BiOCl/Bi2WO6 to obtain multifunctional cotton fabric via double-dip/double-roll technology. The UV protection, photocatalytic, and self-cleaning properties of the cotton fabric coated with BiOCl/Bi2WO6 were investigated.

2. Experimental

2.1. Materials

Bismuth nitrate pentahydrate (Bi(NO3)3·5H2O, AR) and methylene blue (MB, AR) were purchased from Tianjin Damao Chemical Reagent Co., Ltd. (Tianjin, China). Sodium tungstate dehydrate (Na2WO4·2H2O, AR), acetic acid (CH3COOH, AR), and anhydrous ethanol (AR) were obtained from Sinopharm Chemical Reagent Co., Ltd. Sodium chloride (NaCl, AR) and sodium hydroxide (NaOH, AR) were provided by Jiangsu Tongsheng Chemical Reagent Co., Ltd. (Yixing, China). (3-Chloro-2-hydroxypropyl) trimethyl ammonium chloride (60%, AR) and sodium chloroacetate (AR) were purchased from Aladdin Biochemical Technology Co., Ltd. (Shanghai, China). Red wine (food grade) was bought from Greatwall Wine (Beijing, China). Cotton fabric (linear density, 20 tex × 20 tex; fabric density, 300 fiber/10 cm × 300 fiber/10 cm; weight, (120 ± 10) g/m2; plain) was obtained from Nantong Weiteng Textile Co., Ltd. (Nantong, China).

2.2. Preparation of BiOCl/Bi2WO6

In a typical preparation run [28], 5 mmol of Bi(NO3)3·5H2O was added to 40 mL of deionized water under ultrasonic oscillation for 30 min. An appropriate amount of NaCl was added to the aforementioned suspension and stirred for 30 min. Simultaneously, a stoichiometric amount of Na2WO4·2H2O was dissolved in 20 mL of deionized water to obtain a uniformly transparent solution and was added dropwise to the above mixture under constant magnetic stirring (Shanghai Sile Instruments Co. Ltd., Shanghai, China) for 60 min. The mixture was transferred to a 100 mL Teflon-lined stainless-steel autoclave and maintained at 160 °C for 8 h. After the reaction, the precipitate was centrifuged and rinsed with deionized water and anhydrous ethanol three times. Finally, the samples were dried at 60 °C for 10 h to acquire BiOCl/Bi2WO6. The prepared samples with Cl and W at molar ratios of 1:3, 1:2, 1:1, 2:1, and 3:1 were denoted Cl/W-1-3, Cl/W-1-2, Cl/W-1-1, Cl/W-2-1, and Cl/W-3-1, respectively. For comparison, bare Bi2WO6 and BiOCl were prepared without adding NaCl and Na2WO4·2H2O under the same conditions.

2.3. Modification of BiOCl/Bi2WO6

In brief, 5 g of (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride was dissolved in 100 mL of deionized water under sonication for 30 min. The solution was added with 1 g of BiOCl/Bi2WO6 (Cl/W-1-2) and stirred for 30 min. The precipitate was collected by centrifugation (Changsha Xiangyi Centrifuge Instrument Co. Ltd., Changsha, China) and dried in an oven (Shanghai Jing Hong Laboratory instruments Co. Ltd., shanghai, China) at 60 °C for 12 h to obtain modified BiOCl/Bi2WO6 powder [29].

2.4. Pretreatment of Cotton Fabrics

Alkalized cotton fabrics: Cotton fabrics were cut into 6 cm × 6 cm pieces and washed in an ultrasound water bath to remove impurities. The pieces were immersed in NaOH aqueous solution (15 wt.%) at 20 °C for 10 min, rinsed with deionized water, and dried at 60 °C to obtain alkalized cotton fabrics.
Carboxymethylated cotton fabrics: In brief, 10 g of sodium chloroacetate was dissolved in 100 mL of ethanol/water (v/v = 6/4) solution. The prepared alkalized cotton fabrics were immersed in the above solution at 20 °C for 10 min and then dried at 70 °C for 1 h. The cotton substrates were washed by deionized water, treated with 2 g/L acetic acid solution, washed with deionized water, and dried at 60 °C to obtain carboxymethylated cotton fabrics [30].

2.5. Finishing of Cotton Fabrics

First, 0.1 g, 0.2 g, and 0.3 g of modified BiOCl/Bi2WO6 were dispersed in 50 mL of deionized water under ultrasonication (Kunshan Ultrasonic Instrument Co. Ltd., Suzhou, China) for 30 min to form a uniform suspension. From the schematic diagram of the preparation of BiOCl/Bi2WO6-cotton fabrics as shown in Figure 1, 1 g of the carboxymethylated cotton fabrics were soaked in the above suspension for 30 min. The cotton fabrics were finished via the double-dip/double-roll technology and dried at 60 °C to achieve cotton fabrics functionalized with BiOCl/Bi2WO6. The cotton fabrics were labeled Cl/W-0.1 cotton fabric, Cl/W-0.2 cotton fabric, and Cl/W-0.3 cotton fabric on the basis of the amount of modified BiOCl/Bi2WO6.

2.6. Characterization

X-ray diffraction was investigated using an X PERT3 POWDER diffractometer (PANalytical, Amsterdam, The Netherlands) to detect the crystalline structures of the as-prepared samples. Surface morphologies were characterized using a Nova Nano SEM 450 field-emission scanning electron microscope (FEI, Hillsboro, OR, USA). The SEM was equipped with a VANTAGE-DS1 energy-dispersive spectrometer (Oxford Instruments, Oxford, UK) to study the elemental compositions and their contents. X-ray photoelectron spectra were recorded on an ESCALAB 250Xi X-ray photoelectron spectrometer (Thermo Fisher Scientific, Waltham, MA, USA) to investigate the surface chemical states and their composite structures. UV/Vis diffuse reflectance spectra were inspected using TU-1901 UV/Vis diffuse reflectometer (Persee, Beijing, China) with the wavelength of 200–800 nm to record the optical absorption properties. Fourier-transform infrared spectra were recorded using a NEXUF-670 Fourier infrared spectrometer (NICOLET, Madison, GA, USA) to evaluate the chemical compositions. Photoelectric properties were measured on a CHI 660D electrochemical workstation (CHI, Shanghai, China) with a three-electrode system.

2.7. Photocatalytic Activity Measurement

Photocatalytic activities of photocatalyst and cotton fabric were determined via the photodegradation of aqueous MB and RhB (Rhodamine B) under simulated visible-light illumination. Typically, 0.01 g of the as-obtained photocatalyst was dispersed in 100 mL of 10 mg/L aqueous MB to form a suspension. Cotton samples (6 cm × 6 cm) were cut into 1 cm × 1 cm pieces and placed in 50 mL of 10 mg/L RhB solution under magnetic stirring (Shanghai Sile Instruments Co. Ltd., Shanghai, China). After being agitated in the dark for 30 min to reach the adsorption–desorption equilibrium, the suspension was irradiated and constantly stirred under a 300 W xenon lamp (Perfect Light, Beijing, China) with a 400 nm cut-off filter. About 3 mL of the reaction solution was taken at the 10 min time interval and then centrifuged for 5 min to remove photocatalyst particles. The absorbances of aqueous MB and RhB were investigated by UV/Vis spectrophotometry at 664 nm and 554 nm with deionized water as the reference at time intervals of 10 min during photocatalytic reaction. The photodegradation rate was calculated as the ratio of the concentration difference before and after irradiation compared with the concentration before irradiation (Equation (1)).
D = (1 − Ct/C) × 100%,
where D is the photodegradation rate, C is the absorbance of 10 mg/L aqueous MB and RhB, and Ct is the absorbance of aqueous MB and RhB after t min of illumination [31,32].

2.8. Assessment of Cotton Fabrics

UV-blocking performance of cotton fabrics was recorded by YG (B) 912E textile anti-UV performance tester (Darong, Wenzhou, China).
Self-cleaning performance was assessed with aqueous MB and red wine as the stains. In brief, 0.2 mL of 20 mg/L MB and red wine were dropped on the cotton fabrics (6 cm × 6 cm). After drying in air under ambient conditions, the samples were irradiated by simulated visible light [26]. The photos were taken at intervals of 40 min.

3. Results and Discussion

3.1. XRD Analysis of the Photocatalysts

XRD analysis is performed to investigate the crystal structure of the sample, and the powder XRD pattern is shown in Figure 2. The peaks at 11.98°, 24.09°, 25.86°, 32.49°, and 33.45° were assigned to the (001), (002), (101), (110), and (102) planes of tetragonal phase BiOCl (JCPDS No. 06-0249) [33,34]. The sharp and narrow peaks indicate the distinctive monophase of the good crystallinity of BiOCl. The diffraction peaks at 2θ = 28.31°, 32.79°, 47.16°, and 55.83° were attributed to the (113), (200), (220), and (313) planes of orthorhombic russelite phase Bi2WO6 (JCPDS No. 73-1126), and no other impurity peaks were identified [35]. BiOCl/Bi2WO6 in Figure 2b–e exhibited a consistent position in the XRD patterns, indicating that all the samples were BiOCl/Bi2WO6. Moreover, no diffraction peaks of BiOCl were detected in Cl/W-1-3 from Figure 2a, which may be due to the insufficient content of BiOCl/Bi2WO6.

3.2. SEM and EDS Analyses of the Photocatalysts

Figure 3 displays the SEM images and EDS of Cl/W-1-2. As displayed in Figure 3a,b, nanoflower-shaped Cl/W-1-2, 2–3 μm in diameter, was composed of hierarchical nanosheets. EDS is illustrated in Figure 3c to further reveal the chemical components of Cl/W-1-2. The weight percentages of Bi, W, O, and Cl accounted for 72.78%, 6.93%, 10.17%, and 10.13%, respectively, which verified the successful fabrication of BiOCl/Bi2WO6.

3.3. XPS Analysis

Figure 4 presents the XPS spectra of Cl/W-1-2. The XPS survey spectrum in Figure 4a revealed that the Cl/W-1-2 composite contains Bi, O, Cl, and W, while C was the residue of the apparatus. The contents of Bi, O, Cl, and W accounted for about 59.75%, 15.29%, 4.22%, and 20.73%, respectively. The peaks at 159.5 eV and 164.7 eV in Figure 4b corresponded to Bi 4f7/2 and Bi 4f5/2, respectively, which confirmed the presence of Bi3+ ions [36]. The peaks at 530.0 eV and 531.8 eV in Figure 4c could be ascribed to the lattice oxygen of the BiOCl/Bi2WO6 composite and the hydroxyl groups of the absorbed H2O molecules, respectively [37]. The Cl 2p spectrum in Figure 4d was fitted by two peaks with the binding energy at 199.8 eV and 198.2 eV, corresponding to Cl 2p1/2 and Cl 2p3/2 peaks, respectively [38]. The two peaks at 36 eV and 38.1 eV in Figure 4e were in accordance with W 4f7/2 and W 4f5/2, respectively, corresponding to W6+ in BiOCl/Bi2WO6 [39]. The XPS analysis proved that BiOCl was successfully coupled with Bi2WO6, which was consistent with the XRD patterns.

3.4. UV/Vis DRS Analysis of the Photocatalysts

UV/Vis DRS of Bi2WO6, Cl/W-1-2, and BiOCl are given in Figure 5. The absorption bandgap energy of the as-prepared samples was estimated according to Eg = 1240/λg, where Eg is the bandgap and λg is the absorption edge [40]. As shown in Figure 5, the absorption edges of Bi2WO6, Cl/W-1-2, and BiOCl at about 444 nm, 415 nm, and 375 nm were inspected. The bandgaps of Bi2WO6, Cl/W-1-2 and BiOCl were calculated to be 2.79 eV, 2.98 eV, and 3.31 eV, respectively. Compared with BiOCl, Cl/W-1-2 exhibited a relatively narrower bandgap and, therefore, an expanded photoreponse range.

3.5. PC Analysis of the Photocatalysts

The photoelectrochemical properties of the photocatalysts were investigated to determine the photocatalytic activity under simulated visible light. PC intensity is an index of recombination efficiency of photogenerated electron–hole pairs. A higher PC intensity denotes a lower recombination of photogenerated carriers. As shown in Figure 6, the PC intensity of Cl/W-1-2 was higher than that of Bi2WO6 and BiOCl. This might be explained by the increasing interfacial charge carrier transfer efficiency and the decreasing photogenerated carrier recombination, owing to the combination of Bi2WO6 and BiOCl. The result showed that Cl/W-1-2 was beneficial to the photocatalytic degradation of pollutants.

3.6. Photocatalytic Activity of the Photocatalysts

Figure 7 displays the photocatalytic activities and pseudo-first-order kinetic models of the as-prepared samples under simulated visible-light irradiation. As shown in Figure 7a, BiOCl showed poor photocatalytic efficiency, while the other photocatalysts exhibited definite adsorption of MB solution in the dark reaction. The photodegradation rate for BiOCl/Bi2WO6 increased with the increasing content of W. The photocatalyst had no obvious change when the molar ratio of Cl to W reached 1:2. Furthermore, Cl/W-3-1 showed a higher degradation rate than BiOCl but a lower one than Bi2WO6, which may be attributed to the insufficient content of W. The heterostructure of BiOCl/Bi2WO6 restrained the recombination of electron–hole pairs to increase the surface active sites, thereby enhancing the photocatalytic capacity. Cl/W-1-2 had good photodegradation of MB as high as 90% in 60 min. Hence, Cl/W-1-2 ranked the first in the photodegradation of MB under visible-light irradiation.

3.7. XRD Analysis of Cotton Fabrics

Figure 8 presents the XRD patterns of cotton fabric, Cl/W-0.3 cotton fabric, and Cl/W-1-2. As shown in Figure 8a, the diffraction peaks at 2θ of 14.9°, 16.6°, 22.6°, and 34.4° were observed in cotton fabric, corresponding to the (101), (110), (002), and (040) planes of cellulose [41,42]. As shown in Figure 8c, the diffraction peaks at 2θ = 28.3°, 36.7°, 47.1°, and 53.5° were indexed to the (113), (016), (220), and (131) planes of Bi2WO6 (JCPDS No. 73-1126), while the diffraction peaks at 2θ of 11.9°, 25.8°, 32.5°, 58.6°, and 74.9° were related to the (001), (101), (110), (212), and (214) planes of BiOCl (JCPDS NO. 06-0249). In the XRD pattern of Cl/W-0.3 cotton fabric in Figure 8b, the (101), (110), (002), and (040) planes of the cellulose, as well as the (001), (101), (110), (212), and (220) planes of the modified BiOCl/Bi2WO6 photocatalyst, were observed. According to the above analysis, the modified BiOCl/Bi2WO6 was successfully loaded onto cotton fabric.

3.8. FT-IR Analysis

The typical FT-IR spectra of cotton fabric, Cl/W-1-2, and Cl/W-0.3 measured within 400–4000 cm−1 are illustrated in Figure 9. For the cotton fabric in Figure 9a, the absorption peaks at 3440 cm−1 and 2910 cm−1 were respectively derived from the stretching vibrations of –OH groups and –CH/CH2 groups in cotton fabric. The absorption peak at 1636 cm−1 was credited to the absorption peak of water molecules on the cotton surface. The absorption peaks at 1110 cm−1 and 1156 cm−1 were related to the symmetrical and asymmetrical stretching vibrations of C–O–C in cotton fabric. Cl/W-1-2 in Figure 9b also contained –OH groups, whose absorption peak of stretching vibration corresponded to 3440 cm−1. The peak at 1607 cm−1 was generated by the absorption peak of water molecules. The Bi–O absorption peak and W–O asymmetrical stretching vibration peak appeared at 400–636 cm−1. After loading with modified BiOCl/Bi2WO6, Cl/W-0.3 cotton fabric in Figure 9c presented a similar shape and position of absorption peaks as cotton fabric between 1093 and 4000 cm−1. Furthermore, the absorption bands at 400–639 cm−1 were assigned to Cl/W-1-2. The results showed that the BiOCl/Bi2WO6 photocatalyst was successfully loaded on cotton fabric [34].

3.9. SEM and EDS Analyses

The SEM images and EDS of cotton fabrics are presented in Figure 10. As shown in Figure 10a,c, the cotton fabric had a smooth surface before modification. After being treated with cationized BiOCl/Bi2WO6, Cl/W-0.3 cotton fabric showed a rough appearance due to the loading of numerous nanoparticles on its surface. As shown in Figure 10e, the EDS images confirmed the presence of Cl, W, Bi, C, and O on the Cl/W-0.3 cotton fabric. The weight fractions of Cl, W, and Bi were about 0.61%, 47.12% and 6.85%, respectively. Therefore, the SEM images and EDS confirmed the loading of the BiOCl/Bi2WO6 photocatalyst on cotton fabric.

3.10. Ultraviolet Resistance Evaluation

The ultraviolet resistance property of all the fabrics is recorded in Table 1. The cotton fabric had higher UVA and UVB levels than the finished cotton fabrics. The UPF (ultraviolet protection factor) of cotton fabric was only 5.95, which demonstrated poor ultraviolet resistance compared with the finished cotton fabrics. After modification with BiOCl/Bi2WO6 photocatalyst, the UVA and UVB of cotton fabrics obviously decreased, while the UPF significantly increased. In particular, Cl/W-0.3 cotton fabric exhibited the optimal ultraviolet resistance performance, with UPF reaching 40.15.

3.11. Photocatalytic Activity of the Cotton Fabrics

As shown in Figure 11a, with the extension of irradiation time, the photodegradation efficiency of cotton fabric to RhB was basically unchanged, while Cl/W-0.3 cotton fabric had a high photodegradation rate of 97.06%. Therefore, the finished cotton fabric had remarkable photocatalytic performance. As shown in Figure 11b, the pseudo-first-order kinetic constant of the Cl/W-0.3 cotton fabric was about 368.9 × 10−4 min−1, which was about 51.76 times that of cotton fabric (7.12702 × 10−4 min−1). Hence, the finishing of BiOCl/Bi2WO6 onto the cotton fabric increased the photocatalytic rate.

3.12. Self-Cleaning Evaluation

Figure 12 shows the self-cleaning effects of cotton fabric and Cl/W-0.3 cotton fabric to organic pollutants under simulated visible-light irradiation. Cotton fabric faded indistinctively after irradiation for 120 min. For Cl/W-0.3 cotton fabric, after 40 min of exposure to visible light, the red wine and MB solution showed slight decoloration. After 120 min of irradiation, the solutions stained with red wine and MB were both obviously discolored, indicating that the finished cotton fabric with BiOCl/Bi2WO6 had far better self-cleaning performance than cotton fabric [43].

4. Conclusions

A nanoflower-shaped BiOCl/Bi2WO6 photocatalyst was synthesized through a simple and efficient hydrothermal method. When the molar ratio of Cl to W was 1:2, the prepared BiOCl/Bi2WO6 exhibited higher photocatalytic activities than the bare BiOCl, Bi2WO6, and other BiOCl/Bi2WO6 composites under simulated visible-light illumination. Cotton fabric was carboxymethylated with NaOH and sodium chloroacetate solution and further finished with cationized BiOCl/Bi2WO6 to achieve the finished cotton fabric. The experimental results showed that the cotton fabric finished with the BiOCl/Bi2WO6 photocatalyst exhibited commendable UV shielding, photocatalytic, and self-cleaning properties. Hence, the BiOCl/Bi2WO6-finished cotton fabrics have broad application prospects in the textile, environmental purification, and medical industries.

Author Contributions

Conceptualization, J.C. and K.W.; methodology, J.C. and K.W.; software, Jiayi Chen and K.W.; validation, Z.Q. and C.W.; formal analysis, J.C. and K.W.; investigation, J.T.; resources, N.L.; data curation, W.Y. and Y.C.; writing—original draft preparation, J.C. and N.L.; writing—review and editing, J.C. and C.W.; supervision, C.W. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Ye, M.; Chen, Z.; Wang, W.; Ma, J.; Shen, J. Hydrothermal synthesis of TiO2 hollow microspheres for the photocatalytic degradation of 4-chloronitrobenzene. J. Hazard. Mater. 2010, 184, 612–619. [Google Scholar] [CrossRef]
  2. Rueda-Marquez, J.J.; Levchuk, I.; Ibañez, P.F.; Sillanpää, M. A critical review on application of photocatalysis for toxicity reduction of real wastewaters. J. Clean. Prod. 2020, 258, 120694. [Google Scholar] [CrossRef]
  3. Iervolino, G.; Zammit, I.; Vaiano, V.; Rizzo, L. Limitations and Prospects for Wastewater Treatment by UV and Visible-Light-Active Heterogeneous Photocatalysis: A Critical Review. Top. Curr. Chem. 2020, 378, 7. [Google Scholar] [CrossRef]
  4. Liu, W.; He, T.; Wang, Y.; Ning, G.; Xu, Z.; Chen, X.; Hu, X.; Wu, Y.; Zhao, Y. Synergistic adsorption-photocatalytic degradation effect and norfloxacin mechanism of ZnO/ZnS@ BC under UV-light irradiation. Sci. Rep. 2020, 10, 11903. [Google Scholar] [CrossRef]
  5. Ivetić, T.B.; Finčur, N.L.; Abramović, B.F.; Dimitrievska, M.; Štrbac, G.R.; Čajko, K.O.; Miljević, B.B.; Đačanin, L.R.; Lukić-Petrović, S.R. Environmentally friendly photoactive heterojunction zinc tin oxide nanoparticles. Ceram. Int. 2016, 42, 3575–3583. [Google Scholar] [CrossRef]
  6. Jeon, J.; Kweon, D.H.; Jang, B.J.; Ju, M.J.; Baek, J. Enhancing the Photocatalytic Activity of TiO2 Catalysts. Adv. Sustain. Syst. 2020, 4, 2000197. [Google Scholar] [CrossRef]
  7. Gu, X.; Li, C.; Yuan, S.; Ma, M.; Qiang, Y.; Zhu, J. ZnO based heterojunctions and their application in environmental photocatalysis. Nanotechnology 2016, 27, 402001. [Google Scholar] [CrossRef] [PubMed]
  8. Yao, L.; Yang, H.; Chen, Z.; Qiu, M.; Hu, B.; Wang, X. Bismuth oxychloride-based materials for the removal of organic pollutants in wastewater. Chemosphere 2021, 273, 128576. [Google Scholar] [CrossRef]
  9. Fazal, T.; Razzaq, A.; Javed, F.; Hafeez, A.; Rashid, N.; Amjad, U.S.; Rehman, M.S.U.; Faisal, A.; Rehman, F. Integrating adsorption and photocatalysis: A cost effective strategy for textile wastewater treatment using hybrid biochar-TiO2 composite. J. Hazard. Mater. 2020, 390, 121623. [Google Scholar] [CrossRef] [PubMed]
  10. Chang, J.; Zhong, Y.; Hu, C.; Luo, J.; Wang, P. Hollow microspheres of BiOCl assembled with nanosheets: Spray drying synthesis and drastically enhanced photocatalytic activity. J. Environ. Chem. Eng. 2018, 6, 6971–6978. [Google Scholar] [CrossRef]
  11. Chang, X.; Gondal, M.A.; Al-Saadi, A.A.; Ali, M.A.; Shen, H.; Zhou, Q.; Zhang, J.; Du, M.; Liu, Y.; Ji, G. Photodegradation of Rhodamine B over unexcited semiconductor compounds of BiOCl and BiOBr. J. Colloid Interf. Sci. 2012, 377, 291–298. [Google Scholar] [CrossRef] [PubMed]
  12. Gao, X.; Fei, J.; Dai, Y.; Fu, F. Hydrothermal synthesis of series Cu-doped Bi2WO6 and its application in photo-degradative removal of phenol in wastewater with enhanced efficiency. J. Mol. Liq. 2018, 256, 267–276. [Google Scholar] [CrossRef]
  13. An, W.; Wang, S.; Fu, Y.; Guan, Y.; Li, Z.; Xu, T.; Wang, H. Construction of Bi2WO6 with oxygen vacancies and investigation on mechanisms of significantly enhanced photocatalytic activity. Desalin. Water Treat. 2021, 216, 151–161. [Google Scholar] [CrossRef]
  14. Guo, M.; Zhou, Z.; Yan, S.; Zhou, P.; Miao, F.; Liang, S.; Wang, J.; Cui, X. Bi2WO6–BiOCl heterostructure with enhanced photocatalytic activity for efficient degradation of oxytetracycline. Sci. Rep. 2020, 10, 18401. [Google Scholar] [CrossRef] [PubMed]
  15. Yang, K.; Li, X.; Yu, C.; Zeng, D.; Chen, F.; Zhang, K.; Huang, W.; Ji, H. Review on heterophase/homophase junctions for efficient photocatalysis: The case of phase transition construction. Chin. J. Catal. 2019, 40, 796–818. [Google Scholar] [CrossRef]
  16. Ivetic, T.B.; Fincur, N.L.; Merkulov, D.V.S.; Despotovic, V.N.; Cetojevic-Simin, D.D.; Armakovic, S.J.; Uzelac, M.M.; Bognár, S.I.; Zec, N.J.; Lukic-Petrovic, S.R.; et al. Water-Active Titanium/Molybdenum/Mixed-Oxides: Removal Efficiency of Organic Water Pollutants by Adsorption and Photocatalysis and Toxicity Assessment. Catalysts 2021, 11, 1054. [Google Scholar] [CrossRef]
  17. Tahmasebi, N.; Maleki, Z.; Farahnak, P. Enhanced photocatalytic activities of Bi2WO6/BiOCl composite synthesized by one-step hydrothermal method with the assistance of HCl. Mat. Sci. Semicon. Proc. 2019, 89, 32–40. [Google Scholar] [CrossRef]
  18. Liang, Z.; Zhou, C.; Yang, J.; Mo, Q.; Zhang, Y.; Tang, Y. Visible light responsive Bi2WO6/BiOCl heterojunction with enhanced photocatalytic activity for degradation of tetracycline and rohdamine B. Inorg. Chem. Commun. 2018, 93, 136–139. [Google Scholar] [CrossRef]
  19. Pal, S.; Mondal, S.; Maity, J. Synthesis, characterization and photocatalytic properties of ZnO nanoparticles and cotton fabric modified with ZnO nanoparticles via in-situ hydrothermal coating technique: Dual response. Mater. Technol. 2018, 33, 884–891. [Google Scholar] [CrossRef]
  20. Wang, C.; Lv, J.; Ren, Y.; Zhou, Q.; Chen, J.; Zhi, T.; Lu, Z.; Gao, D.; Ma, Z.; Jin, L. Cotton fabric with plasma pretreatment and ZnO/Carboxymethyl chitosan composite finishing for durable UV resistance and antibacterial property. Carbohyd. Polym. 2016, 138, 106–113. [Google Scholar]
  21. Yang, M.; Liu, W.; Jiang, C.; Xie, Y.; Shi, H.; Zhang, F.; Wang, Z. Facile construction of robust superhydrophobic cotton textiles for effective UV protection, self-cleaning and oil-water separation. Colloid. Surf. A 2019, 570, 172–181. [Google Scholar] [CrossRef]
  22. Hu, J.; Gao, Q.; Xu, L.; Wang, M.; Zhang, M.; Zhang, K.; Liu, W.; Wu, G. Functionalization of cotton fabrics with highly durable polysiloxane–TiO2 hybrid layers: Potential applications for photo-induced water–oil separation, UV shielding, and self-cleaning. J. Mater. Chem. A 2018, 6, 6085–6095. [Google Scholar] [CrossRef]
  23. Wang, Y.; Ding, X.; Zhang, P.; Wang, Q.; Zheng, K.; Chen, L.; Ding, J.; Tian, X.; Zhang, X. Convenient and recyclable TiO2/g-C3N4 photocatalytic coating: Layer-by-layer self-assembly construction on cotton fabrics leading to improved catalytic activity under visible light. Ind. Eng. Chem. Res. 2019, 58, 3978–3987. [Google Scholar] [CrossRef]
  24. Cao, C.; Wang, F.; Lu, M. Superhydrophobic CuO coating fabricated on cotton fabric for oil/water separation and photocatalytic degradation. Colloid. Surf. A 2020, 601, 125033. [Google Scholar] [CrossRef]
  25. Wang, K.; Song, X.; Li, Y.; Tian, J.; Zhang, C.; Qi, Z.; Liu, S.; Gao, D.; Liu, G.; Ren, Y.; et al. In Situ Precipitation of Ag6Si2O7 on the Surface of Cotton Fabric Modified by Plasma Treatment for Highly Efficient and Durable Photocatalytic Activity. Integr. Ferroelectr. 2021, 219, 111–118. [Google Scholar] [CrossRef]
  26. Tudu, B.K.; Sinhamahapatra, A.; Kumar, A. Surface modification of cotton fabric using TiO2 nanoparticles for self-cleaning, oil–water separation, antistain, anti-water absorption, and antibacterial properties. ACS Omega 2020, 5, 7850–7860. [Google Scholar] [CrossRef] [Green Version]
  27. Jin, J.; Feng, K.; Liu, X. Enhanced photocatalytic degradation and UV protection properties of BiOCl nanosheets coating for cotton fabric. Funct. Mater. Lett. 2018, 11, 1850052. [Google Scholar] [CrossRef]
  28. Wu, J.; Zhang, W.; Tian, Z.; Zhao, Y.; Shen, Z. Facile fabrication of Bi2WO6/BiOCl hierarchical structure as adsorbents for methylene blue dye removal. Mater. Res. Express 2019, 6, 055034. [Google Scholar] [CrossRef]
  29. Qi, Z.; Wang, K.; Jiang, Y.; Zhu, Y.; Chen, X.; Tang, Q.; Ren, Y.; Zheng, C.; Gao, D.; Wang, C. Preparation and characterization of SnO2−x/GO composite photocatalyst and its visible light photocatalytic activity for self-cleaning cotton fabrics. Cellulose 2019, 26, 8919–8937. [Google Scholar] [CrossRef]
  30. Liu, Y.; Xia, L.; Guo, H.; Wang, A.; Hu, J.; Zhang, W.; Xu, W.; Wang, Y. Kinetics and thermodynamics studies of cationic dye adsorption onto carboxymethyl cotton fabric. J. Nat. Fibers 2020, 1–12. [Google Scholar] [CrossRef]
  31. Wang, C.; Xu, L.; Wang, K.; Chen, H.; Jiang, W.; Qi, Z.; Gao, D.; Liu, S.; Song, X.; Liu, G.; et al. Ag6Si2O7/CNTs with highly efficient and stable visible light photocatalytic activity. Integr. Ferroelectr. 2019, 198, 73–79. [Google Scholar] [CrossRef]
  32. Wang, K.; Zhuo, Y.; Chen, J.; Gao, D.; Ren, Y.; Wang, C.; Qi, Z. Crystalline phase regulation of anatase–rutile TiO2 for the enhancement of photocatalytic activity. RSC Adv. 2020, 10, 43592–43598. [Google Scholar] [CrossRef]
  33. Gao, D.; Wang, L.; Wang, C.; Chen, T. Photocatalytic self-cleaning cotton fabrics coated by Cu2(OH)PO4 under Vis/NIR irradiation. Materials 2019, 12, 238. [Google Scholar] [CrossRef] [Green Version]
  34. Zhao, Y.; Chen, T.; Ma, R.; Du, J.; Xie, C. Synthesis of flower-like CeO2/BiOCl heterostructures with enhanced ultraviolet light photocatalytic activity. Micro. Nano Lett. 2018, 13, 1394–1398. [Google Scholar] [CrossRef]
  35. Zhou, Y.; Lv, P.; Zhang, W.; Meng, X.; He, H.; Zeng, X.; Shen, X. Pristine Bi2WO6 and hybrid Au-Bi2WO6 hollow microspheres with excellent photocatalytic activities. Appl. Surf. Sci. 2018, 457, 925–932. [Google Scholar] [CrossRef]
  36. Hojamberdiev, M.; Kadirova, Z.C.; Zahedi, E.; Onna, D.; Marchi, M.C.; Zhu, G.; Matsushita, N.; Hasegawa, M.; Bilmes, S.A.; Okada, K. Tuning the morphological structure, light absorption, and photocatalytic activity of Bi2WO6 and Bi2WO6-BiOCl through cerium doping. Arab. J. Chem. 2020, 13, 2844–2857. [Google Scholar] [CrossRef]
  37. Dumrongrojthanath, P.; Saksoong, T.; Patiphatpanya, P.; Phuruangrat, A.; Thongtem, S.; Thongtem, T. Microwave-assisted hydrothermal synthesis of BiOCl/Bi2WO6 nanocomposites for the enhancement of photocatalytic efficiency. Res. Chem. Intermed. 2019, 45, 2301–2312. [Google Scholar] [CrossRef]
  38. Ma, Y.; Chen, Z.; Qu, D.; Shi, J. Synthesis of chemically bonded BiOCl@ Bi2WO6 microspheres with exposed (0 2 0) Bi2WO6 facets and their enhanced photocatalytic activities under visible light irradiation. Appl. Surf. Sci. 2016, 361, 63–71. [Google Scholar] [CrossRef]
  39. Zhu, S.; Yang, C.; Li, F.; Li, T.; Zhang, M.; Cao, W. Improved photocatalytic Bi2WO6/BiOCl heterojunctions: One-step synthesis via an ionic-liquid assisted ultrasonic method and first-principles calculations. Mol. Catal. 2017, 435, 33–48. [Google Scholar] [CrossRef] [Green Version]
  40. Qi, Z.; Wang, K.; Chen, J.; Gao, D.; Ren, Y.; Wang, C. Cotton fabric loaded with self-dispersive and reactive biphasic TiO2 for durable self-cleaning activity and ultraviolet protection. New J. Chem. 2021, 45, 11119–11129. [Google Scholar] [CrossRef]
  41. Wang, J.; Wei, Y.; Yang, B.; Wang, B.; Chen, J.; Jing, H. In situ grown heterojunction of Bi2WO6/BiOCl for efficient photoelectrocatalytic CO2 reduction. J. Catal. 2019, 377, 209–217. [Google Scholar] [CrossRef]
  42. Thi, V.H.T.; Lee, B.-K.J. Development of multifunctional self-cleaning and UV blocking cotton fabric with modification of photoactive ZnO coating via microwave method. Photoch. Photobiol. A 2017, 338, 13–22. [Google Scholar]
  43. Zheng, C.; Qi, Z.; Shen, W.; Chen, G. Self-cleaning Bombyx mori silk: Room-temperature preparation of anatase nano-TiO2 by the sol-gel method and its application. Color. Technol. 2014, 130, 280–287. [Google Scholar] [CrossRef]
Figure 1. Schematic diagram of the preparation of BiOCl/Bi2WO6-cotton fabrics.
Figure 1. Schematic diagram of the preparation of BiOCl/Bi2WO6-cotton fabrics.
Materials 14 07002 g001
Figure 2. XRD patterns: Bi2WO6, (a) Cl/W-1-3, (b) Cl/W-1-2, (c) Cl/W-1-1, (d) Cl/W-2-1, (e) Cl/W-3-1, and BiOCl.
Figure 2. XRD patterns: Bi2WO6, (a) Cl/W-1-3, (b) Cl/W-1-2, (c) Cl/W-1-1, (d) Cl/W-2-1, (e) Cl/W-3-1, and BiOCl.
Materials 14 07002 g002
Figure 3. SEM imagesand EDS of Cl/W-1-2: (a) Cl/W-1-2 (×100,000), (b) Cl/W-1-2 (×50,000), and (c) EDS of Cl/W-1-2.
Figure 3. SEM imagesand EDS of Cl/W-1-2: (a) Cl/W-1-2 (×100,000), (b) Cl/W-1-2 (×50,000), and (c) EDS of Cl/W-1-2.
Materials 14 07002 g003
Figure 4. XPS spectra of Cl/W-1-2: (a) survey, (b) Bi 4f, (c) O 1s, (d) Cl 2p, and (e)W 4f.
Figure 4. XPS spectra of Cl/W-1-2: (a) survey, (b) Bi 4f, (c) O 1s, (d) Cl 2p, and (e)W 4f.
Materials 14 07002 g004
Figure 5. UV/Vis DRS of the photocatalysts: (a) BiOCl, (b) Cl/W-1-2, and (c) Bi2WO6.
Figure 5. UV/Vis DRS of the photocatalysts: (a) BiOCl, (b) Cl/W-1-2, and (c) Bi2WO6.
Materials 14 07002 g005
Figure 6. Photocurrent of the photocatalysts: (a) BiOCl, (b) Bi2WO6, and (c) Cl/W-1-2.
Figure 6. Photocurrent of the photocatalysts: (a) BiOCl, (b) Bi2WO6, and (c) Cl/W-1-2.
Materials 14 07002 g006
Figure 7. Photocatalytic degradation for MB by photocatalysts: (a) photodegradation curves and (b) pseudo-first-order kinetic curves.
Figure 7. Photocatalytic degradation for MB by photocatalysts: (a) photodegradation curves and (b) pseudo-first-order kinetic curves.
Materials 14 07002 g007aMaterials 14 07002 g007b
Figure 8. XRD patterns: (a) cotton fabric, (b) Cl/W-0.3 cotton fabric, and (c) Cl/W-1-2.
Figure 8. XRD patterns: (a) cotton fabric, (b) Cl/W-0.3 cotton fabric, and (c) Cl/W-1-2.
Materials 14 07002 g008
Figure 9. FTIR spectra: (a) cotton fabric, (b) Cl/W-1-2, and (c) Cl/W-0.3 cotton fabric.
Figure 9. FTIR spectra: (a) cotton fabric, (b) Cl/W-1-2, and (c) Cl/W-0.3 cotton fabric.
Materials 14 07002 g009
Figure 10. SEM images and EDS of cotton fabrics: (a) cotton fabric (×5000), (b) Cl/W-0.3 cotton fabric (×5000), (c) cotton fabric (×10,000), (d) Cl/W-0.3 cotton fabric (×10,000), and (e) EDS of Cl/W-0.3 cotton fabric.
Figure 10. SEM images and EDS of cotton fabrics: (a) cotton fabric (×5000), (b) Cl/W-0.3 cotton fabric (×5000), (c) cotton fabric (×10,000), (d) Cl/W-0.3 cotton fabric (×10,000), and (e) EDS of Cl/W-0.3 cotton fabric.
Materials 14 07002 g010
Figure 11. Photocatalytic degradation for RhB by cotton fabrics: (a) photodegradation curves and (b) pseudo-first-order kinetic curves.
Figure 11. Photocatalytic degradation for RhB by cotton fabrics: (a) photodegradation curves and (b) pseudo-first-order kinetic curves.
Materials 14 07002 g011
Figure 12. Self-cleaning effects of (a,c) cotton fabric, and (b,d) Cl/W-0.3 cotton fabric.
Figure 12. Self-cleaning effects of (a,c) cotton fabric, and (b,d) Cl/W-0.3 cotton fabric.
Materials 14 07002 g012
Table 1. Ultraviolet resistance evaluation.
Table 1. Ultraviolet resistance evaluation.
SampleUVA (%)UVB (%)UPF
Cotton fabric2015.455.95
Cl/W-0.1 cotton fabric8.362.6331.92
Cl/W-0.2 cotton fabric5.773.1037.96
Cl/W-0.3 cotton fabric3.513.4540.15
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Chen, J.; Wang, K.; Tian, J.; Yu, W.; Chen, Y.; Li, N.; Qi, Z.; Wang, C. Preparation of BiOCl/Bi2WO6 Photocatalyst for Efficient Fixation on Cotton Fabric: Applications in UV Shielding and Self-Cleaning Performances. Materials 2021, 14, 7002. https://doi.org/10.3390/ma14227002

AMA Style

Chen J, Wang K, Tian J, Yu W, Chen Y, Li N, Qi Z, Wang C. Preparation of BiOCl/Bi2WO6 Photocatalyst for Efficient Fixation on Cotton Fabric: Applications in UV Shielding and Self-Cleaning Performances. Materials. 2021; 14(22):7002. https://doi.org/10.3390/ma14227002

Chicago/Turabian Style

Chen, Jiayi, Kuang Wang, Jialong Tian, Wenhui Yu, Yujie Chen, Na Li, Zhenming Qi, and Chunxia Wang. 2021. "Preparation of BiOCl/Bi2WO6 Photocatalyst for Efficient Fixation on Cotton Fabric: Applications in UV Shielding and Self-Cleaning Performances" Materials 14, no. 22: 7002. https://doi.org/10.3390/ma14227002

APA Style

Chen, J., Wang, K., Tian, J., Yu, W., Chen, Y., Li, N., Qi, Z., & Wang, C. (2021). Preparation of BiOCl/Bi2WO6 Photocatalyst for Efficient Fixation on Cotton Fabric: Applications in UV Shielding and Self-Cleaning Performances. Materials, 14(22), 7002. https://doi.org/10.3390/ma14227002

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop