Enhanced Photocatalytic Activity of WS 2 /TiO 2 Nanoﬁbers for Degradation of Phenol under Visible Light Irradiation

: Binary composite WS 2 /TiO 2 nanoﬁbers (WTN) were elaborated by electrospinning technique. The photocatalytic efﬁciency of the binary nanoﬁbers was changed via different ratios between WS 2 and TiO 2 . The structural, morphological and optical properties of the prepared nanoﬁbers were evaluated by Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and UV-Vis diffuse reﬂectance spectroscopy (UV-vis/DRS), respectively. The prepared nanofibers showed a remarkable performance in photocatalytic efficiency of phenol compound degradation under visible light. WTN nanofibers showed superior photocatalytic activity (83%) and high stability of several cycles under visible light. Therefore, WS 2 /TiO 2 nanoﬁbers have great prospects for the treatment of wastewater from toxic organic contamination due to their excellent photocatalytic performance reusability and recyclability. respectively (JCPDS No. 01-084-1285) of WS 2 [13]. The narrow and sharp peaks suggest that the product is highly crystalline. Where, the different weight ratios of TiO 2 to WS 2 (1:0, 0.9:0.1, 0.8:0.2, 0.7:0.3, 0.6:0.4 and 0.5:0.5) to obtain (TW0, TW10, TW20, TW30, TW40 and TW50, respectively).


Introduction
The development of industries throughout the world has led to increase water contamination which implies a serious threat to humans and environment [1,2]. Water pollution is a matter of concern worldwide. Wastewater is caused by synthetic chemicals being released from a variety of anthropogenic industry sources. In particular, the petroleum refinery waste, which is one of the harmful sources for water, along with phenol compound which is one of these mischievous sources [3]. The different technologies for water treatment and purification have been extensively discussed in the literature as the design and the operation of affordable methods remains a challenge. The treatment methods include membrane separation, electrochemical method, chemical precipitation, adsorption, photocatalysis, etc. [4]. It is pertinent to highlight that all treatment methods have their own technical and economic limitations for real-life applications. However, photocatalysis technique is one important method as it prevents to form the secondary pollutants [5].
Titanium dioxide (TiO 2 ) is one of the most significant photocatalysts, which is extensively utilized in various fields, such as electrochemistry and photocatalysis due to its several benefits such as low cost, nontoxicity, good chemical stability and excellent oxidizing power [3]. However, it has some drawbacks such as lack of activity in the abundant visible light energy because TiO 2 generally exhibits good photocatalytic activity in near ultraviolet (UV), due to its large bandgap energy (3.2 eV) [6]. To address these issues, it has been combined with other nanomaterials to enhance its photo-adsorption capacity  [7,8]. The photocatalytic efficiency of TiO 2 -NFs can be improved by metals, non-metals and semiconductors [9,10]. In addition, titanium dioxide is extensively utilized for environmental purification applications [11] and tungsten disulfide (WS 2 ) is one of the important materials for TiO 2 enhancement.
Tungsten disulfide (WS 2 ) is one of the transition-metal dichalcogenide compounds which have inherent excellent photoactivity. The bandgap of WS 2 is approximately 1.9 eV when the thickness is reduced down to monolayers, which access the absorption from visible light and utilize solar energy sufficiently [12].
In this contribution, WS 2 /TiO 2 nanofibers were elaborated by combined 1D and 2D structures by electrospinning. The morphology, structure and optical properties of the nanocomposites were evaluated. The photocatalytic efficiency of WS 2 /TiO 2 nanofibers for the degradation of phenol, as an organic pollutant, was estimated under the visible light illumination.
Tungsten disulfide (WS2) is one of the transition-metal dichalcogenide compounds which have inherent excellent photoactivity. The bandgap of WS2 is approximately 1.9 eV when the thickness is reduced down to monolayers, which access the absorption from visible light and utilize solar energy sufficiently [12].
In this contribution, WS2/TiO2 nanofibers were elaborated by combined 1D and 2D structures by electrospinning. The morphology, structure and optical properties of the nanocomposites were evaluated. The photocatalytic efficiency of WS2/TiO2 nanofibers for the degradation of phenol, as an organic pollutant, was estimated under the visible light illumination.  The WS2/TiO2 nanofibers with different ratio between tungsten disulfide and titanium dioxide were observed with the use of Raman measurements. Moreover, Raman spectra of the prepared nanofibers are presented in Figure 2. In W sample, the bands at The WS 2 /TiO 2 nanofibers with different ratio between tungsten disulfide and titanium dioxide were observed with the use of Raman measurements. Moreover, Raman spectra of the prepared nanofibers are presented in Figure 2. In W sample, the bands at 126.28, 255.03, 320.11, 409.71, 701.09 and 799.35 cm −1 can be ascribed to the vibration bands of WS 2 nanosheets [14,15]. For pure TiO 2 sample, the bands observed at 147.41, 198.17, 389.58, 502.31 and 626.37 cm −1 in the Raman spectrum can be assigned to E 1 g , E 2 g , B 1g (1), B 1g (2) + A 1g and E 3 g modes of anatase, respectively [16]. The combination of WS 2 with TiO 2 (in TW10, TW20, TW30, TW40 and TW50) resulted in a slight change in the anatase bands. In TW40 and TW50, the main band of anatase at 150 cm −1 is significantly changed due to the overlapping between the bands of TiO 2 and WS 2 and it means that there is a high conjugation between TiO 2 and WS 2 .

Characterization of TWx Nanofibers
(in TW10, TW20, TW30, TW40 and TW50) resulted in a slight change in the anatase bands. In TW40 and TW50, the main band of anatase at 150 cm −1 is significantly changed due to the overlapping between the bands of TiO2 and WS2 and it means that there is a high conjugation between TiO2 and WS2.
The conjugation between WS2 and TiO2 can also be detected by the FTIR transmission spectra presented in Figure 2b. The band located around 3450 cm −1 is attributed to the O-H bonds for all nanofibers [17][18][19]. The overlap between the peaks of Ti-O and W-S was presented for all nanocomposite samples of TWx which confirmed the successful conjugation between TiO2 and WS2.
The surface area results showed that SBET of TW0, TW10, TW20, TW30, TW40 and TW50 are 17, 25, 42, 61, 73 and 78 m 2 /g. The surface area of (1D) TiO2 was enhanced by interacting with the (2D) structure of WS2. It is well known that TiO2 with large surface area has excellent photocatalytic activity as a result of providing more active adsorption sites and speed transport channels for large organic molecules which were detected in TiO2 with WS2. The morphology of fabricated nanofibers was observed using scanning electron microscope as presented in Figure 3a-f. The T, TW10, TW20, TW30, TW40 and TW50 nanofibers have 97 ± 8, 120 ± 5, 188 ± 4, 210 ± 8, 240 ± 7 and 290 ± 9 nm average diameter, respectively. The increase in the diameter of the WS2-enriched nanofibers was attributed to the viscosity of electro-spun solution coming from WS2, which contributed to the successful incorporation between WS2 and TiO2 nanofibers. These findings are consistent with The conjugation between WS 2 and TiO 2 can also be detected by the FTIR transmission spectra presented in Figure 2b. The band located around 3450 cm −1 is attributed to the O-H bonds for all nanofibers [17][18][19]. The overlap between the peaks of Ti-O and W-S was presented for all nanocomposite samples of TWx which confirmed the successful conjugation between TiO 2 and WS 2 .
The surface area results showed that S BET of TW0, TW10, TW20, TW30, TW40 and  TW50 are 17, 25, 42, 61, 73 and 78 m 2 /g. The surface area of (1D) TiO 2 was enhanced by interacting with the (2D) structure of WS 2 . It is well known that TiO 2 with large surface area has excellent photocatalytic activity as a result of providing more active adsorption sites and speed transport channels for large organic molecules which were detected in TiO 2 with WS 2 .
The morphology of fabricated nanofibers was observed using scanning electron microscope as presented in Figure 3a-f. The T, TW10, TW20, TW30, TW40 and TW50 nanofibers have 97 ± 8, 120 ± 5, 188 ± 4, 210 ± 8, 240 ± 7 and 290 ± 9 nm average diameter, respectively. The increase in the diameter of the WS 2 -enriched nanofibers was attributed to the viscosity of electro-spun solution coming from WS 2 , which contributed to the successful incorporation between WS 2 and TiO 2 nanofibers. These findings are consistent with those of Raman measurements. EDX mappings for TW40 are presented in Figure 3g-  The optical characteristics of the fabricated nanofibers were determined using UV-Vis diffuse reflectance (UVDR), as presented in Figure 4. The UVDR-spectra of the nanofibers were examined in the range of 200-800 nm using UV-Vis optical spectroscopy. The optical band gaps (Eg) were obtained by the following equation: where α is the absorption coefficient, v is the frequency of light and n is the constant of proportionality (n equals 4 for the indirect transition in the prepared nanofibers) [20][21][22]. The prepared nanofibers had a red shift due to joining of WS2 with TiO2. As per the following sequence: 3.18, 2.87, 2.72, 2.68, 2.57 and 2.45 eV for TW0, TW10, TW20, TW30, The optical characteristics of the fabricated nanofibers were determined using UV-Vis diffuse reflectance (UVDR), as presented in Figure 4. The UVDR-spectra of the nanofibers were examined in the range of 200-800 nm using UV-Vis optical spectroscopy. The optical band gaps (Eg) were obtained by the following equation: where α is the absorption coefficient, v is the frequency of light and n is the constant of proportionality (n equals 4 for the indirect transition in the prepared nanofibers) [20][21][22].

Photocatalytic Degradation of Phenol under Visible Light by TWx Nanofibers
The adsorption test was evaluated in the dark for 1 h before illumination. Then the photocatalytic activity of phenol degradation was detected every hour during 4 h. The photodegradation of phenol reached 13, 47, 57, 74, 83 and 66% for TW0, TW10, TW20, TW30, TW40 and TW50, respectively, as presented in Figure 5a. The TW0 sample (TiO2 nanofibers) provided low activity for photodegradation of phenol ~13% due to large band gap of 3.18 eV. In contrast, the combination of WS2 with TiO2 enhanced the catalytic activity of phenol degradation, reaching 83% for TW40. This can be attributed to the band gap decrease followed by active absorption of visible light, as obtained by UV-Vis diffuse reflectance spectra. In addition, the photocatalytic active sites were increased by the incorporation of 1D WS2 with 2D TiO2 nanofibers. The kinetic of phenol photodegradation by prepared nanofibers is presented in Figure 5b. The phenol degradation follows the first-order kinetics model of Langmuir−Hinshelwood which is presented in Equation (3) [23]. The apparent order rate constant (k) for TW0, TW10, TW20, TW30, TW40 and TW50 is 2.235 × 10 −4 , 0.0017, 0.0024, 0.0043, 0.0057 and 0.0028 min −1 , respectively. Rate constants grow in this order: TW40 > TW30 > TW50 > TW20 > TW10 > TW0. The TW40 sample has the maximum rate constant (0.0057) that is attributed to the high interaction between WS2 and TiO2, as presented in SEM and Raman, besides the synergistic effect between WS2 and TiO2 nanofibers. In order to determine the role of hydroxyl radicals ( • OH), holes (h + ) and superoxide anions ( • O 2− ) in the efficiency of photodegradation of phenol, we used different free radical trapping agents with TW40 nanofibers, as presented in Figure 5c. The scavengers were Tert-butyl alcohol (TBA), disodium ethylenediaminetetraacetic acid (Na2-EDTA) and p-benzoquinone (BQ) to trap free radicals of hydroxyl radicals ( • OH), holes (h + ) and superoxide radicals ( • O 2− ), respectively [24,25]. The photodegradation of phenol varied according to different sacrificial agents. Predominantly, the photocatalytic degradation in presence of the TBA (5 mM) reduced to 36%. Therefore, the photogenerated • OH radical is the important free radical component during the phenol photodegradation process [24,25]. Moreover, TW40 has high photodegradation stability up to five cycles, as presented in Figure 5d. The phenol photodegradation remained at the level of 80% after 5 cycles. The results obtained for the TW40 sample indicate a high photocatalytic The prepared nanofibers had a red shift due to joining of WS 2 with TiO 2 . As per the following sequence: 3.18, 2.87, 2.72, 2.68, 2.57 and 2.45 eV for TW0, TW10, TW20, TW30, TW40 and TW50, respectively. This recorded shift was due to the conjugation between WS 2 and TiO 2 , also this conjugation was detected in the Raman and FTIR [14]. The TW40 sample has reflectance lower than other nanofibers due to the high absorption of light. In contrast, TW50 had a greater amount of WS 2 , which led to the aggregation of WS 2 and reduced light absorbed, as seen in the SEM image.

Photocatalytic Degradation of Phenol under Visible Light by TWx Nanofibers
The adsorption test was evaluated in the dark for 1 h before illumination. Then the photocatalytic activity of phenol degradation was detected every hour during 4 h. The photodegradation of phenol reached 13, 47, 57, 74, 83 and 66% for TW0, TW10, TW20, TW30, TW40 and TW50, respectively, as presented in Figure 5a. The TW0 sample (TiO 2 nanofibers) provided low activity for photodegradation of phenol~13% due to large band gap of 3.18 eV. In contrast, the combination of WS 2 with TiO 2 enhanced the catalytic activity of phenol degradation, reaching 83% for TW40. This can be attributed to the band gap decrease followed by active absorption of visible light, as obtained by UV-Vis diffuse reflectance spectra. In addition, the photocatalytic active sites were increased by the incorporation of 1D WS 2 with 2D TiO 2 nanofibers. The kinetic of phenol photodegradation by prepared nanofibers is presented in Figure 5b. The phenol degradation follows the first-order kinetics model of Langmuir−Hinshelwood which is presented in Equation (3) [23]. The apparent order rate constant (k) for TW0, TW10, TW20, TW30, TW40 and TW50 is 2.235 × 10 −4 , 0.0017, 0.0024, 0.0043, 0.0057 and 0.0028 min −1 , respectively. Rate constants grow in this order: TW40 > TW30 > TW50 > TW20 > TW10 > TW0. The TW40 sample has the maximum rate constant (0.0057) that is attributed to the high interaction between WS 2 and TiO 2 , as presented in SEM and Raman, besides the synergistic effect between WS 2 and TiO 2 nanofibers. In order to determine the role of hydroxyl radicals ( • OH), holes (h + ) and superoxide anions ( • O 2− ) in the efficiency of photodegradation of phenol, we used different free radical trapping agents with TW40 nanofibers, as presented in Figure 5c. The scavengers were Tert-butyl alcohol (TBA), disodium ethylenediaminetetraacetic acid (Na 2 -EDTA) and p-benzoquinone (BQ) to trap free radicals of hydroxyl radicals ( • OH), holes (h + ) and superoxide radicals ( • O 2− ), respectively [24,25]. The photodegradation of phenol varied according to different sacrificial agents. Predominantly, the photocatalytic degradation in presence of the TBA (5 mM) reduced to 36%. Therefore, the photogenerated • OH radical is the important free radical component during the phenol photodegradation process [24,25]. Moreover, TW40 has high photodegradation stability up to five cycles, as presented in Figure 5d. The phenol photodegradation remained at the level of 80% after 5 cycles. The results obtained for the TW40 sample indicate a high photocatalytic degradation of phenol with a narrow bandgap, as well as an excellent stability of photocatalytic activity. We can note also that the crystallinity of TW40 nanofibers ( Figure S1) and the morphology ( Figure S2) were stable after five cycles as confirmed by XRD and SEM, respectively.
Inorganics 2022, 10, x FOR PEER REVIEW 7 degradation of phenol with a narrow bandgap, as well as an excellent stability of p catalytic activity. We can note also that the crystallinity of TW40 nanofibers (Figur and the morphology ( Figure S2) were stable after five cycles as confirmed by XRD SEM, respectively.

Preparation of WS2/TiO2 Nanofibers
Tungsten disulfide (WS2) with TiO2 nanofibers was prepared using the electro ning technique by different ratio between WS2 and TiO2. First, the solution (a) was pared by 0.3 g of PVP dissolved in 3 mL of ethanol and 2 mL of acetic acid while sti for 30 min, then 1.5 mL of TTIP was added with stirring for 30 min. The solution (b prepared with different weight ratios of WS2 in 2 mL of ethanol and sonicated for 2 obtain (TW0, TW10, TW20, TW30, TW40 and TW50 for TiO2: WS2 is 1:0, 0.9:0.1, 0. 0.7:0.3, 0.6:0.4 and 0.5:0.5, respectively). After that, solution (b) was mixed to solutio

Preparation of WS 2 /TiO 2 Nanofibers
Tungsten disulfide (WS 2 ) with TiO 2 nanofibers was prepared using the electrospinning technique by different ratio between WS 2 and TiO 2 . First, the solution (a) was prepared by 0.3 g of PVP dissolved in 3 mL of ethanol and 2 mL of acetic acid while stirring for 30 min, then 1.5 mL of TTIP was added with stirring for 30 min. The solution (b) was prepared with different weight ratios of WS 2 in 2 mL of ethanol and sonicated for 2 h to obtain (TW0, TW10, TW20, TW30, TW40 and TW50 for TiO 2 : WS 2 is 1:0, 0.9:0.1, 0.8:0.2, 0.7:0.3, 0.6:0.4 and 0.5:0.5, respectively). After that, solution (b) was mixed to solution (a) with stirring for 30 min. The solution was added in syringe with a stainless-steel nozzle with a diameter of 0.7 mm under flow rate 1 mL/h and voltage power (1.5 kV/cm) between the nozzle and the rotating collector. The collected nanofibers were calcined at 400 • C for 3 h.

Characterization
The nanofiber vibrational properties were observed using a dispersive Raman microscope with a laser wavelength of 532 nm and a power of 10 mW (Senterra, Bruker, Bremen, Germany). The functional groups of the prepared composite nanofibers were recognized using FTIR spectrometer (Perkin Elmer, Waltham, MA, USA) with the use of standard KBr pellet technique. The surface area of the nanofibers was detected from nitrogen adsorption-desorption isotherms at liquid nitrogen temperature using Micromeritics ASAP 2010 equipment (degassing conditions: 200 • C/12 h). The titanium and tungsten elemental concentrations in the as-prepared nanofibers were determined using atomic absorption spectroscopy (AAS) (Analyst 400, PerkinElmer, Bremen, Germany). The morphology of nanofibers was detected by SEM (Quanta-250 FEG, FEI, Netherlands) methods. The UV-Vis-DR spectra were measured by a Jasco V-570 (Jasco Inc., Easton, MD, USA).

Photocatalytic Activity Measurement
The photocatalytic activity of the WS 2 /TiO 2 nanofibers was detected by tracing the photodegradation of phenol. The photocatalyst efficiency was detected by analyzing the decrease of phenol concentration during exposure to visible light radiation. The reaction temperature was fixed at 25 ± 0.2 • C by circulating water over the photoreactor. The photocatalytic performance was detected by using 10 mg of photocatalyst in 200 mL of phenol solution (50 ppm) under a 500 W linear halogen lamp (visible light radiation). The solution mixture was stirred in the dark for 1 h to obtain the adsorption/desorption equilibrium of phenol [26]. Then, the mixture was exposed to visible light for 4 h. Following, the sample was collected from reactor every 1 h and the catalyst was eliminated by a centrifuge to detect the organic pollutants' concentration in the solution by high-performance liquid chromatography (HPLC) equipped with a photodiode array detector (Agilent 1200 series, Agilent, Colorado Springs, CO, USA).
The degradation efficiency was measured by the following equation: degradation efficiency % = (((C 0 − C))/(C 0 )) * 100 (2) where C 0 and C are the initial and final phenol concentration, respectively [27]. The kinetics of phenol photocatalytic degradation were calculated as follows (where k (min −1 ) is the apparent rate constant):

Conclusions
In brief, we have successfully prepared WS 2 /TiO 2 nanofibers with different ratios between WS 2 (1D) and TiO 2 (2D). Structural and morphological analyses of the prepared nanofibers confirmed the incorporation between WS 2 and TiO 2 . Significantly, the photocatalytic efficiency of TW40 for phenol degradation was as high as 83%. The remarkable photocatalytic performance of TW40 (1D/2D structure) was attributed to the synergism effect between WS 2 and TiO 2 to improve electron transfer. In addition, the linkage between WS 2 and TiO 2 enhanced the photocatalytic stability of the nanofibers. The trapping test for the photogenerated free radicals and holes of TW40 demonstrated that the photogenerated hydroxyl radicals ( • OH) have a significant role in the photodegradation of phenol as an organic pollutant. Therefore, WS 2 /TiO 2 nanofibers act as promising materials for photo-degradation of organic pollutants in water.