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View Article OnlineView Journal | View Issue

Hydrothermal sy

aSchool of Textile and Clothing, Nantong Un

E-mail: 1731mqh@ntu.edu.cnbKey Laboratory of Eco-textiles, Ministry o

Jiangsu, 224122, China. E-mail: minmin042

† Electronic supplementary informationand antibacterial property of compositeeffects of preparation pH value andefficiency; the FTIR spectra of comBiVO4/Ag/cotton-K; comparison of fabric s

‡ These authors contributed equally toco-rst authors.

Cite this: RSC Adv., 2020, 10, 39295

Received 4th September 2020Accepted 19th October 2020

DOI: 10.1039/d0ra07588d

rsc.li/rsc-advances

This journal is © The Royal Society o

nthesis of cotton-based BiVO4/Agcomposite for photocatalytic degradation of C.I.Reactive Black 5†

Jiangang Qu, ‡a Jiaqi Qian,‡a Mengtao Wu,a Qinghui Mao*a and Min Li *b

Photocatalytic materials with high efficiency and convenient recyclability have attracted great interest for

the treatment of printing and dyeing wastewater. In this paper, a narrow band gap BiVO4 photocatalyst

was loaded onto Ag modified cotton fabric by a hydrothermal method. The prepared composite

materials were characterized by scanning electron microscopy with energy dispersive X-ray

spectroscopy (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and ultraviolet

visible light absorption spectroscopy (UV-vis). The composite materials as prepared show superb

photocatalytic activity and reusable performance for the degradation of C.I. Reactive Black 5 (RB5). The

degradation rate can reach 99% within 90 min under 1 kW xenon lamp irradiation, and over 90% of the

photocatalytic performance is preserved even after five recycles. Furthermore, the photocatalytic

mechanism was proposed by spectral analysis and free radical trapping experiments.

1. Introduction

Nowadays, photocatalytic technology is favored for its highefficiency, low energy consumption and wide applicationrange.1,2 Fujishima found that oxygen and hydrogen can beobtained by electrolyzing water with a TiO2 electrode, markingthe beginning of the photocatalytic era.3,4 Nevertheless, theband gap of TiO2 (>3.2 eV) is too large, and can drive a catalyticreaction only under ultraviolet light irradiation, and is inca-pable of fully utilizing the visible light which accounts for 43%of sunlight.5

Compared with TiO2, bismuth vanadate (BiVO4) hasa narrow band gap of about 2.4–2.6 eV, and can absorb visiblelight from 400 nm to 700 nm, showing a better response tovisible light. It is also non-toxic and low cost.6 Therefore,a variety congurations of BiVO4 such as microparticles,7

microspheres,8 microtubes9 were prepared. However, pureBiVO4 photocatalyst has a very high recombination probabilityof photogenerated electron hole, which leads to its lowquantum efficiency. In order to improve the pollutant

iversity, Nantong, Jiangsu 226019, China.

f Education, Jiangnan University, Wuxi,

1@163.com

(ESI) available: Electrical conductivitymaterials; structural formula of RB5;temperature on photodegradation

posite materials; SEM images oftrength. See DOI: 10.1039/d0ra07588d

this work and should be considered

f Chemistry 2020

degradation ability, BiVO4 can be modied. For example, Ag/BiVO4,10 Cu/BiVO4,11 AgI/BiVO4,12 BiFeO3/BiVO4,13 RGO/BiVO4,14

Bi12TiO20/BiVO4,15 Ag@AgVO3/BiVO416 and PDA/g-C3N4/

BiVO417 ternary systems and binary systems have been re-

ported. Nevertheless, the modied BiVO4 has some disadvan-tages, such as small specic surface area, poor adsorptioncapacity and easy precipitation.

In order to solve the above problems, modied ber-basedBiVO4 photocatalytic materials can be prepared, which cannot only improve the degradation efficiency, but also be reused.Cotton fabric, which has large specic surface area and superiorexibility, can be processed and molded easily. In addition, thepure cotton fabric has no adsorption or degradation effectunder visible light irradiation.18 Photocatalyst particles can bedeposited on cotton fabric to offer photocatalysis effect, butthey are easy to fall off, which will cause secondary pollution. Tostrengthen the interaction between cotton fabrics and photo-catalyst particles, some researchers modied the cotton surfaceto increase active groups. For example, J. H. Ran et al. loadedCuO modied BiVO4 onto PDA-templated cotton, resulting inhigh degradation rate (97.7% aer 200 min).19 H. S. Zhang et al.modied BiVO4 by Fe and connected with cotton fabric toprepare composite photocatalytic material with the 98.4%removal rate of Cr(VI) aer 90 min.20 Compared with Cu and Fe,Ag has better electrical conductivity. Ag nanoparticles also havethe local surface plasmon resonance (SPR) phenomenon, whichcan enhance the absorption of visible light.21,22

In this study, cotton fabrics were modied with silanecoupling agent KH-560 and were then loaded with Ag nano-particles, resulting in certain conductivity and antibacterialproperty (Fig. S1, ESI†). Aerwards, BiVO4 was uniformly loaded

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on the modied cotton fabric by stirring hydrothermal method.The photocatalytic activities of the as prepared compositematerials were studied by photodegradation of C.I. ReactiveBlack 5 (RB5, its structural formula is shown in Fig. S2†), whichis one of the most widely-used azo dyes in printing and dyeingindustry.23

2. Experimental2.1 Materials

Cotton fabric (30 tex � 30 tex, 212/10 cm for warp and 212/10 cm for we) was purchased from Nantong Haihui Co., Ltdand treated with acetone, ethanol and deionized water. Sodiummetavanadate (NaVO3), bismuth nitrate pentahydrate(Bi(NO3)3$5H2O), ethylenediamine tetraacetic acid disodiumsalt (EDTA-2Na), silver nitrate (AgNO3), 3-glycidoxypropyl-trimethoxysilane (KH-560) and trisodium citrate (Na3C6H5O7-$2H2O) were purchased from Shanghai Chemical Reagent Co.,Ltd, and used as received.

2.2 Preparation

0.5 g cotton fabric was dipped in 20 mL KH-560 solution (10 gL�1) with pH of 10, and reacted at 70 �C for 30 min to obtainsilane coupling agent modied cotton fabric (cotton-K). Thecotton-K was immersed in the 0.1mol L�1 AgNO3 solution, heatedto 100 �C, and then the Na3C6H5O7 solution was dropped. Aer

Fig. 1 Schematic diagram of the preparation process of BiVO4/Ag/cotto

39296 | RSC Adv., 2020, 10, 39295–39303

20 min of reaction, the fabric was taken out and dried to obtainthe silver modied cotton fabric (Ag/cotton-K) (Fig. 1).

The Ag/cotton-K was added into the solution with pH of 7containing Bi(NO3)3 (2.911 g), EDTA-2Na (2.500 g) and HNO3 (10mL), and kept for 30 min, then dropped the NaVO3 (0.732 g)solution under stirring condition. The pH value was adjusted to5, then whole solution was put into a micro reactor and reactedat 160 �C for 1 h under stirring to synthesis the BiVO4/Ag/cotton-K. Finally, the product was washed with deionized water anddried. The synthesis condition of BiVO4/Ag/cotton-K has beenoptimized as shown in Fig. S3.†

2.3 Characterization

The surface morphology and element composition of thecomposite materials were studied by SEM (ZEISS Gemini SEM300, Zeiss, German) with energy dispersive X-ray spectrum. XRDpatterns were obtained on a powder X-ray diffractometer(D8ADVANCE, Bruker, German). The 2q scanning angle rangedfrom 10� to 80�. XPS was acquired by X-ray photoelectronspectroscopy (K-Alpha+, Thermo Scientic, America) with an AlK-Alpha source at 30.0 eV. UV-vis was obtained by Ultravioletvisible spectrophotometer (UV-2600, Shimadzu, Japan).

2.4 Analysis of photocatalytic performance

The spectrum of the dye at 400–800 nm was determined by UV-visspectrophotometry every 15 minutes. 50 mL RB5 dye solution(20 mg L�1) was degraded by BiVO4/Ag/cotton-K under the

n-K.

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irradiation of 1 kW xenon lamp for 90 min. The absorbance atmaximum wavelength 598 nm was recorded every 15 minutes tomeasure its concentration. The RB5 photocatalytic degradationefficiency was obtained according to the following equation:

D ¼ C0 � C1

C0

� 100% ¼ A0 � A1

A0

� 100%

where C0 and C1 correspond to the initial and current concen-trations of RB5 dye solution, and A0 and A1 are the initial andcurrent absorbance of RB5 dye solution at 598 nm, respectively.

Aer photodegradation test, the BiVO4/Ag/cotton-K waswashed in deionized water and dried for recycle. Repeated dyedegradation experiments were performed under the samecondition as described above.

3. Results and discussion3.1 Structure and morphology

The morphologies of cotton-K, Ag/cotton-K and BiVO4/Ag/cotton-K were studied by SEM and EDS. As shown in Fig. 2a,an obvious layer of material can be seen on the surface of cottonber, which demonstrates that the cotton has been modied bysilane coupling agent KH-560 (their FTIR spectra are shown inFig. S4†). Ag nanoparticles and KH-560 are distributeduniformly on the fabric surface (Fig. 2b), and color of the fabricchanges from white to dark green. Thanks to KH-560's cross-linking, Ag nanoparticles can be well xed on the surface ofcotton fabric. Fig. 2c and d show the morphology of BiVO4/Ag/cotton-K in different magnications (more images are shownin Fig. S5†). Monoclinic BiVO4 and Ag nanoparticles are evenlydistributed on the ber surface and the fabric color turns yellow(inset in Fig. 2c).24 In Fig. 2d, there are still a lot of Ag nano-particles in the surface of bers aer hydrothermal synthesis.Due to the swelling of cotton ber in the process of hydro-thermal synthesis, some Ag nanoparticles have been diffusedinto the interface of cotton ber, which will make Ag nano-particles more stable. Besides, in the interface of cotton ber,the Ag nanoparticles are in contact with BiVO4 particles. Theelements of the BiVO4/Ag/cotton-K sample were also measuredby EDS spectrum and element mapping. Six elements,including Bi, V, C, O, Si and Ag, are present and scattereddistinctively on BiVO4/Ag/cotton-K (Fig. 2e and f).25 There areobvious Bi and V signals at the position of BiVO4 on the ber.Mapping images of O and Si show that both of O and Si areuniformly distributed on cotton. Due to the presence of BiVO4

particles on the surface of Ag/cotton-K, there is the shadow inthe mapping images of C and Ag.

3.2 XRD analysis

The phase compositions of prepared composite materials werestudied by XRD, which are shown in Fig. 3a. There are fourobvious diffraction peaks of cotton-K appeared at 2q ¼ 14.9�,16.7�, 23.1� and 34.6�, which are attributed to the crystallo-graphic plane (1–10), (110), (200) and (004) of cotton fabric(JCPDS le no. 3-0226),26 respectively. However, the character-istic peaks of Ag/cotton-K and BiVO4/Ag/cotton-K at 14.9�, 16.7�

This journal is © The Royal Society of Chemistry 2020

and 34.6� are disappeared, and the other peak strength at 23.1�

decreases obviously, indicating good combination between BiVO4

and Ag with cotton. Expect for the diffraction peaks of cottonfabrics, the XRD pattern of Ag/cotton-K has extra peaks at 2q ¼38.6�, 44.9�, 64.8� and 77.9�, which are assigned to the (111),(200), (220) and (311) crystallographic plane of Ag (JCPDS le no.65-2871),27 respectively. In the pattern of BiVO4/Ag/cotton-K, thepresence of the Ag and cotton peaks are also found. The peaks ofBiVO4/Ag/cotton-K are 19.4�, 29.5�, 31.1�, 35.1�, 31.8�, 40.5�, 43.0�,46.8�, 47.4�, 47.8�, 50.8�, 53.8�, 59.0� and 60.1�, which are labeledby (110), (121), (040), (200), (002), (211), (150), (132), (240), (042),(202), (161), (321), (123) planes of the crystal faces of monoclinicscheelite type BiVO4 (JCPDS le no. 14-0688).19

3.3 Surface elemental composition analysis

Fig. 3b–h show the elemental compositions of cotton-K, Ag/cotton-K and BiVO4/Ag/cotton-K. Fig. 3b displays that thecotton-K consists of three elements, C, O and Si. In addition tothese elements, the Ag/cotton-K also contains Ag element, indi-cating the successful loading of Ag on cotton-K. The XPS charac-terization reveals that BiVO4/Ag/cotton-K is composed of C, O, S,Ag, Bi and V, and the conclusions are consistent with EDS, indi-cating that BiVO4 is successfully grown on Ag/cotton-K.

As seen in Fig. 3c, the splitting peaks at binding energies of158.6 eV and 163.9 eV, which belong to the Bi 4f7/2 and Bi 4f5/2,are the split signal of Bi 4f of Bi3+.28,29 In Fig. 3d, bindingenergies peaks at 516.1 eV and 523.7 eV are for V 4f3/2 and V 4f1/2, respectively, corresponding to the V5+ peaks of monoclinicBiVO4.29 The high-resolution spectrum of Ag 3d in Fig. 3eperforms the peaks at the 367.1 eV and 373.1 eV binding energyposition for Ag 3d5/2 and Ag 3d3/2, respectively, indicating theexistence of Ag 3d element in the composite catalyst.30 FromFig. 3f, the peak at 102.2 eV for Si 2p suggests the existence ofSi.31 In Fig. 3h, the peak in C 1s spectrum is divided into284.1 eV, 285.9 eV, 287.4 eV. The peak at 284.1 eV is assigned toC–C, and the peaks at 285.9 eV and 287.4 eV are expected to C–Oand C]O, respectively.22 Fig. 3h shows the O 1s spectrum,where deconvolution of the O 1s signals are assigned to Bi–O(529.6 eV), V–O (529.1.9 eV) and C]O (532.2 eV).20,22

3.4 Optical absorption properties

The optical absorption properties of cotton-K, Ag/cotton-K, BiVO4/cotton-K and BiVO4/Ag/cotton-K were studied via UV-vis. Theabsorption of cotton-K is not obvious in the range of 250–800 nm(Fig. 4a). Aer loading with Ag or BiVO4, the absorption of cotton-K is improved. The absorption of Ag/cotton-K compositematerialsin the UV-vis region is higher than that of cotton-K. In addition,BiVO4/cotton-K and BiVO4/Ag/cotton-K both have strong opticalabsorption from 250 nm to 600 nm. The absorption intensity ofBiVO4/Ag/cotton-K is much higher than that of BiVO4/cotton-K inthe range of 250–800 nm. Compared with BiVO4/cotton-K, theabsorption of BiVO4/Ag/cotton-K exhibits a red shi, indicatingstrong visible light response of BiVO4/Ag/cotton-K. It is attributedto the intensive localized SPR effect of Ag.22 Furthermore, theoptical band gap (Eg) of composite materials can be obtained bythe following equation:32,33

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Fig. 2 SEM images of (a) cotton-K, (b) Ag/cotton-K and (c and d) BiVO4/Ag/cotton-K with different magnifications. Insets are digital pictures of(a) cotton-K, (b) Ag/cotton-K and (c) BiVO4/Ag/cotton-K. (e) EDS spectrum of BiVO4/Ag/cotton-K in the area (d). (f) Mapping images of O, V, Ag,Si, C and Bi in the area (d).

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(Ahv)n ¼ C(hv � Eg)

where A, v, C and Eg are the absorption coefficient, the incidentlight frequency, a constant and band gap, respectively. ForBiVO4, n is 2.20 Therefore, according to the plots of (Ahv)2 versusphoton energy (hv) in Fig. 4b, the band gap energy of BiVO4/cotton-K is 2.36 eV and that of BiVO4/Ag/cotton-K is 2.29 eV. Thesmaller band gap implies the better photon-induced carrier

39298 | RSC Adv., 2020, 10, 39295–39303

separation efficiency, as well as superior photocatalytic perfor-mance.25 The photocatalytic activity of as-prepared compositematerials were evaluated by photodegradation of RB5 solutionin the following part.

3.5 Photocatalytic activity and reusable performance

The degradation rate of RB5 by composite materials are shownin Fig. 5a. Under the same conditions, the absorption intensity

This journal is © The Royal Society of Chemistry 2020

Fig. 3 (a) XRD patterns of cotton-K, Ag/cotton-K, BiVO4/Ag/cotton-K. (b) XPS survey spectra. High resolution XPS spectrum of (c) Bi 4f; (d) V 2p;(e) Ag 3d; (f) Si 2p; (g) C 1s; (h) O 1s.

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at 598 nm wasmeasured every 15minutes. The degradation rateof RB5 by BiVO4/cotton-K, Ag/cotton-K and BiVO4/Ag/cotton-Kcan reach 11%, 2% and 99% within 90 min degradation,

This journal is © The Royal Society of Chemistry 2020

respectively. Obviously, Ag/cotton-K has almost no photo-catalytic effect, and the catalytic efficiency of Ag/cotton-K isgreatly improved aer loaded with photocatalyst BiVO4.

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Fig. 4 (a) UV-vis diffuse reflectance spectra of all the samples and (b) band gap energy of BiVO4/cotton-K and BiVO4/Ag/cotton-K.

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Moreover, the degradation rate of RB5 by BiVO4/Ag/cotton-K ismuch higher than that of BiVO4/cotton-K. It is due to therecombination of photo-induced charge carrier on pure BiVO4

and poor conductivity of BiVO4/cotton-K.11,34 In contrast, Agnanoparticles with good conductivity can help the electrontransfer from BiVO4 to the incorporated Ag nanoparticles to

Fig. 5 (a) Photodegradation performance of RB5 under xenon light irradvis absorption spectra of BiVO4/Ag/cotton-K for the degradation of RB5diation. (c) The recyclability of BiVO4/Ag/cotton-K. (d) Trapping experim

39300 | RSC Adv., 2020, 10, 39295–39303

inhibit the recombination of holes and electrons, thus,contributing to greatly improved photocatalytic activity. The UV-vis absorption spectra of RB5 solution processed with BiVO4/Ag/cotton-K were also recorded every 15 min (Fig. 5b). The UV-visabsorption peak of RB5 is at 598 nm, which gets lower and

iation using BiVO4/cotton-K, Ag/cotton-K, BiVO4/Ag/cotton-K. (b) UV-every 15 min. Insets are photos of RB5 solution before and after irra-ents of BiVO4/Ag/cotton-K with different active species scavengers.

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Fig. 6 Photocatalytic mechanism of BiVO4/Ag/cotton-K for RB5degradation under xenon light irradiation.

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lower. Aer 90 min irradiation, the absorption peak disappearsand the solution color completely fades.

The reusability performance of semiconductor photocatalystis also an important indicator of the catalyst. The stability ofBiVO4/Ag/cotton-K was evaluated by recycling in the photo-degradation of RB5 solution. Aer each cycle, the BiVO4/Ag/cotton-K was washed and dried, and the next cycle was pro-cessed under the same condition. As shown in Fig. 5c, thedegradation rate of RB5 by BiVO4/Ag/cotton-K compositematerial is still over 90% aer ve cycles, and the strengthdecline of BiVO4/Ag/cotton-K is less than that of BiVO4/Ag/cotton (their warp and we yarn strength before and aerrecycling ve times are shown in Table S1†), demonstratinghigh photocatalytic activity and stability of BiVO4/Ag/cotton-K.

3.6 Potential photocatalytic mechanism

The photocatalytic mechanism of BiVO4/Ag/cotton-K wasfurther studied by free radical trapping experiment. Oxalic acid(AO), benzoic acid (HA), benzoquinone (BQ), triethylenedi-amine (DABCO) were used to capture h+, cOH, cO2

� and 1O2,respectively.20 As seen in Fig. 5d, DABCO has little effect on thedegradation of RB5, which implies that 1O2 has limited effect onphotocatalytic reaction. In contrast, the degradation efficiencyof RB5 is greatly reduced aer adding scavengers AO, HA andBQ, among them, BQ has the most obvious effect. These resultsshow that h+, cOH and cO2

� play a certain role in the degrada-tion process, and the effect of O2

� is the most signicant.The potential photocatalytic mechanism is proposed based

on the above experimental results, as demonstrated in Fig. 6.Under light irradiation, BiVO4 is excited, as well as electron (e�)and hole (h+) are formed on the surface of photocatalyst.35 In theinterface of cotton ber, the Ag nanoparticles are in contactwith BiVO4 particles for efficient electron transfers. Thus therecombination rate of e� and h+ decreased with the rapidtransport of e� by Ag nanoparticles. Then h+ reacts with H2Oand OH� to produce cOH, and e� reacts with O2 to generatecO2

�. Finally, h+, cOH and cO2� decompose the RB5 into H2O

and CO2. The entire sequences are summarized as follows:

This journal is © The Royal Society of Chemistry 2020

BiVO4 + hv / BiVO4 (h+ + e�)

BiVO4 (e�) + Ag / BiVO4 + Ag (e�)

BiVO4 (h+) + OH� / BiVO4 + cOH

Ag (e�) + O2 / cO2� + Ag

BiVO4 + cOH + cO2� + RB5 / CO2 + H2O

4. Conclusions

In conclusion, Ag modied cotton fabric supported BiVO4

semiconductor photocatalyst has been successfully prepared inthis work, BiVO4/Ag/cotton-K shows high photocatalytic activity,and the degradation rate of RB5 reaches 99% in 90 min underxenon light irradiation. The uniform loading of Ag and BiVO4

on the fabric surface has been conrmed by SEM, EDS, XRD andXPS analysis. The composite materials still have excellentreusability, and the degradation rate can reach over 90% aerve cycles. It is found that h+, cOH and cO2

� participated in thephotocatalytic reaction according to free radical trappingexperiments.

Author contribution

Jiangang Qu, Jiaqi Qian: study design, literature research,writing-original dra, data acquisition, writing-editing, dataanalysis, experimental studies. Mengtao Wu: writing-review &discussion. Qinghui Mao: writing-review, data curation, projectadministration, validation. Min Li: resources, supervision,validation.

Conflicts of interest

The authors declare no competing nancial interest.

Acknowledgements

This work was nancially supported by the Open ProjectProgram of Key Laboratory of Eco-textiles, Ministry of Educa-tion, Jiangnan University (No. KLE1708). This work was alsopartially supported by the National Science Foundation ofChina (No. 81801856), Natural Science Foundation of JiangsuProvince (No. BK20180949) and Nantong Foundation ScienceResearch Project (No. JC2019007). The authors acknowledge theuse of the Analytical Instrumentation Facility at NantongUniversity Analysis & Testing Center. The authors alsoacknowledge Dr Nanfei He from North Carolina State Universityfor the language and writing assistance.

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