Enhanced Photocatalytic Degradation of Organic Dyes via Defect-Rich TiO2 Prepared by Dielectric Barrier Discharge Plasma

The dye wastewater produced in the printing and dyeing industry causes serious harm to the natural environment. TiO2 usually shows photocatalytic degradation of dye under the irradiation ultravilet light rather than visible light. In this work, a large number of oxygen vacancies and Ti3+ defects were generated on the surface of the TiO2 nanoparticles via Ar plasma. Compared with pristine TiO2 nanoparticles, the as-obtained Ar plasma-treated TiO2 (Ar-TiO2) nanoparticles make the energy band gap reduce from 3.21 eV to 3.17 eV and exhibit enhanced photocatalytic degradation of organic dyes. The Ar-TiO2 obtained exhibited excellent degradation properties of methyl orange (MO); the degradation rate under sunlight irradiation was 99.6% in 30 min, and the photocatalytic performance was about twice that of the original TiO2 nanoparticles (49%). The degradation rate under visible light (λ > 400 nm) irradiation was 89% in 150 min, and the photocatalytic performance of the Ar-TiO2 was approaching ~4 times higher than that of the original TiO2 nanoparticles (23%). Ar-TiO2 also showed good degradation performance in degrading rhodamine B (Rho B) and methylene blue (MB). We believe that this plasma strategy provides a new method for improving the photocatalytic activity of other metal oxides.

To improve the photocatalytic performance of TiO 2 , some transition metal oxides were introduced into TiO 2 , such as FeO x [28], CuO x [29,30], NiO [31], CeO 2 [32] and ZnO [33]. Metal doping could make electrons easier to excite and reduce the recombination of electron-hole pairs of TiO 2 [34][35][36]. Furthermore, enhanced photo-response could be obtained by TiO 2 with doping non-metals, such as N [37], C [38], F [39] and S [40]. In addition, the defects generated on the surface of TiO 2 are able to effectively hinder the recombination of photogenerated electron-hole pairs. Surface defects of TiO 2 , for instance, Ti 3+ defects and oxygen vacancies, promote the formation of the original intermediate band, which plays an important role in photoelectron capture [41].
Low temperature plasma can cause defects and oxygen vacancies on the catalyst surface to improve the catalytic efficiency [42][43][44]. The effect of treating the catalyst with low temperature plasma under different atmospheres is different. Nanowires and nanoparticles of TiO 2 treated under a hot hydrogen atmosphere have better photocatalytic degradation of dye properties because of the presence of oxygen vacancies and Ti 3+ forming an intermediate layer [45,46]. The application of oxygen and nitrogen plasma reduced the TiO 2 powder and produced an intermediate state, resulting in an increase in its optical activity in the visible region [47]. The trapping of charge carriers, decreases the electron-hole recombination rate. However catalyst mechanisms, irradiation conditions and defects have not been fully explained.
Herein, we successfully prepared TiO 2 nanoparticles by titanium alkoxide hydrolysis method, and etched them in Ar atmosphere with low temperature dielectric barrier discharge (DBD) plasma [48,49]. The results showed that the plasma-etched TiO 2 nanoparticles had more oxygen vacancies and Ti 3+ defects than of the original TiO 2 , and thus have excellent photocatalytic degradation properties under sunlight. We believe that DBD plasma provides a new strategy for etching the surface of catalysts.

Sample Preparation
The TiO 2 photocatalyst was prepared using an alkoxide hydrolysis process with titanium n-butoxide (Ti (OC 4 H 9 ) 4 , AR, Macklin, Shanghai, China) used as the precursor for TiO 2 . 3 g of titanium n-butoxide was added to 100 g of ethanol (C 2 H 5 OH, AR, Fuyu Fine Chemical Co., Ltd., Tianjin, China) to obtain a mixed solution A; 5 g of deionized water was dissolved in 100 mL of absolute ethanol and stirred for 30 min to make it evenly mixed to obtain a homogeneous solution B; then the solution A was slowly dropped into solution B, and a white precipitate after about 5 min. The solution obtained was stirred vigorously for 1 h, aged for 12 h, and then the white precipitate was filtered, washed 4 times with the alcohol-water mixture, dried in a drying oven at 80 • C for 24 h, and then ground to obtain TiO 2 nanoparticles. The dried powders were then calcined in air for 5 h with the temperature ranging from 30 to 450 • C. The pristine TiO 2 obtained was separately subjected to plasma treatment in a dielectric barrier discharge (DBD) plasma reactor at a voltage of 50 V, a current of 1.5 A, and an Ar atmosphere for 20 min to obtain TiO 2 (Ar-TiO 2 ).

Catalyst Characterization
The catalyst crystal structure was identified by X-ray diffractometer (XRD) with Cu-Kα (40 kV, 40 mA, k = 1.5406 Å and 2θ range from 10-90 • ) radiation (Karlsruhe, Baden-Württemberg, German). The Raman spectrum was measured by Raman spectroscopy using a Renishaw inVia (Renishaw, London, UK) with a laser power of 5 mW and a laser excitation of 532 nm (wavenumber range 100-3200 cm −1 ). Using KBr as diluents, the Fourier transforms infrared spectra (FTIR) of the samples were collected with a Thermo spectrum system (Thermo Fisher Scientific, Massachusetts, MA, USA). The samples were subjected to X-ray photoelectron spectroscopy (XPS, Thermo Scientific Escalab 250Xi, Thermo Fisher Scientific, Massachusetts, MA, USA) by using Al Kα radiation (1486.6 eV). All binding energies were calibrated using the C1s peak (BE = 284.8 eV) as a standard. Morphology and microstructure were determined by transmission electron microscopy (TEM, Tecnai G2 F30 S-TWIN 200 KV, Hillsboro, OR, USA), high resolution TEM (HRTEM) and selective area electron diffraction (SAED). Measurement of electron paramagnetic resonance (EPR) spectra was performed at 300 K using a Bruker A200 EPR spectrometer (Bruker, Karlsruhe, Germany). The samples were subjected to UV-Vis testing using Shimadzu UV3600 (Shimadzu, Tokyo, Japan). Brunauer-Emmett-Teller (BET) surface area, pore volumes and pore diameter of the samples were determined by using a Micromeritics ASAP 2020C surface area and porosity analyzer (Micromeritics ASAP 2020 BET apparatus, Atlanta, Georgia, GA, USA). The samples were degassed for 4 h at 200 degrees and then analyzed using N 2 adsorption-desorption in liquid nitrogen.

Photocatalytic Activity Measurements
Photocatalytic performance was investigated by using a 300 W Xeon lamp equipped with a 400 nm cut-off filter to degrade methyl orange (MO), rhodamine B (Rho B) and MB under sunlight and visible light. Water cooled the reactor, to keep the temperature at 25 • C. To put it simply, 50 mg photocatalyst was mixed with 100 mL 10 mg·L −1 organic dye solution, and the mixed solution was placed 20 cm away from the photosource. Meanwhile, the mixture was stirred stably. The sample solution was then collected every 30 min of irradiation. The solution collected was centrifuged at 10,000 rpm for 2 min, the mixed solution was separated, and the supernatant was extracted for ultraviolet testing. The dye solutions collected (MO, Rho B and MB) were subjected to absorbance detection using UV-Vis (TU-1900). The degradation efficiencies of MO, Rho B and MB were analyzed by changes in absorption peaks at 462, 554 and 660 nm. The degradation rates of MO, Rho B and MB are calculated by the formula ln (C 0 /C) = kt, where k is the reaction rate constant, C 0 and C are the initial concentration of the dye and the concentration after the reaction time t.

Apparent Quantum Efficiency Measurement
The photocatalytic H 2 -production experiments were performed in a 300 mL sealed jacket beaker at ambient temperature and atmospheric pressure. In a typical photocatalytic experiment, 100 mg of Ar-TiO 2 composite photocatalyst was suspended in 100 mL of aqueous solution containing methanol (20.0 V%) as sacrificial agents for trapping holes. Proper amount of H 2 PtCl 6 aqueous solution was added in the above solution. Therefore, 3.0 wt% Pt, as a co-catalyst, was in-suit reduced during the photocatalytic hydrogen evolution reaction. Then, evacuation was performed with a vacuum pump to ensure that the reactor was under vacuum. A continuous magnetic stirrer was applied at the bottom of the reactor in order to keep the photocatalyst particles in suspension status during the whole experiment. After 0.5 h of irradiation, the chromatographic inlet was opened, and hydrogen was analyzed by gas chromatograph (GC7806, Beijing Shiwei Spectrum Analysis Instrument Co., Ltd., Beijing, China, TCD, with nitrogen as a carrier gas and 5 A molecular sieve column). All glassware was carefully rinsed with deionized water prior to use. The apparent quantum efficiency (AQE) was measured under the same photocatalytic reaction conditions. A Xe lamp source (300 W, 385 nm) was placed 10 cm directly above the reactor to serve as a light source to initiate a photocatalytic reaction. The optical power density of the Xe lamp source is measured by a strong optical power meter (CEL-NP2000) Nanomaterials 2019, 9, 720 4 of 14 and the focused area on the beaker is 30 cm 2 . We measured and calculated the number of photons according to Equation (1): We measured and calculated apparent quantum efficiencies (AQE) according to Equation (2): [50] where h is the Planck constant (J·s), c is Speed of light (m/s) and λ is the wavelength of linght (nm).  211) and (204) lattice planes. The XRD pattern of the modified TiO 2 has a higher strength than the original TiO 2 , which indicated that the Ar plasma caused an improvement in the crystallinity of the modified TiO 2 . The broadened diffraction peaks indicated that the size of the nanocrystals is small [51]. There was no significant difference between the two samples.   Figure 1b shows the Raman spectrum of the original TiO 2 and Ar-TiO 2 in Ar atmosphere. The original sample peaks were: 146 cm −1 (E g ), 196 cm −1 (E g ), 399 cm −1 (B 1g ), 514 cm −1 (A 1g or B 1g ) and 640 cm −1 (A 1g ) respectively typical Anatase phase [52][53][54]. The treated sample showed a scattering peak only at 146 cm −1 (E g ). The peak intensity and width of TiO 2 treated with plasma in Ar atmosphere were lower and wider than those of the original TiO 2 . This indicated that there were some defects on the surface of TiO 2 after plasma treatment [55]. The Raman scattering selection rule was broken, indicating the surface characteristics of the disordered phase [56]. Raman analysis showed that the molecular vibration of the surface crystallinity of TiO 2 was seriously affected by the plasma treatment.

Physicochemical Properties of Catalysts
The FTIR spectra of the original and Ar-TiO 2 are shown in Figure 1c. An absorption peak appearing near 523 cm −1 was due to the Ti-O-Ti bond of nano-titanium dioxide, and the absorption peaks at 3500-3000 cm −1 and 1630 cm −1 were caused by the tensile vibration of the hydroxyl group. The hydroxyl group was adsorbed on the surface of the material [57]. The C-O band (1437 cm −1 ) was detected due to the formation of CO 2 on the surface of TiO 2 [58,59].
X-ray photoelectron spectroscopy (XPS) demonstrates the defects and the chemical composition of Ar-TiO 2 . The XPS spectra of the elements O 1s and Ti 2p are shown in Figure 2b,c. In Figure 2b, O 1s was divided into three peaks, 530.0, 531.6 and 533.1 eV, respectively, which corresponds with lattice oxygen (O latt ), defect oxygen (O def ) and surface oxygen (O surf ) [60,61]. Electron paramagnetic resonance (EPR) was used to further demonstrated oxygen vacancies and Ti 3+ defects of the samples. The magnetization results recorded at 300 K clearly showed surface oxygen vacancies and unpaired spins electrons of Ti 3+ 3d1 in the samples. Figure 2d shows the EPR results of the original TiO2 and Ar-TiO2. The index values of the g peaks at 1.95 and 2.004 corresponded to Ti 3+ and oxygen vacancies in the TiO2 lattice, respectively [60,64,65]. The content of Ti 3+ and oxygen vacancies in plasma treatment were significantly higher than that of the original TiO2, which was consistent with the analysis results of the XPS spectrum. In order to test the optical performance of the photocatalyst, UV-Vis among 200 nm and 800 nm was surveyed. As shown in Figure 3a, all of the TiO2 photocatalysts showed the significant absorption of light in the ultraviolet region (< 400 nm) and the light absorption of the Ar-TiO2 photocatalyst moved toward the visible region. The band gap of each sample was estimated by the simulation calculation, TiO2 was 3.21 eV and the Ar-TiO2 was 3.17 eV (inset of Figure 3a). This value is the effect of the extrapolation to zero (αhν) 1/2 curve on photon energy, where α is the absorption factor and hν is the light quantum energy. [53,56] Based on the XPS valence band (VB) spectrum (Figure3b), the valence band position of Ar-TiO2 was 2.93 eV, which was lower than the original TiO2 (3.02 eV). These results indicated that the oxygen vacancies (or Ti 3+ species) were produced during the Ar gas plasma treatment and caused the band gap of the Ar-TiO2 photocatalyst to be narrowed. The electronic bandgap structure and photocatalytic degradation mechanism of TiO2 samples were shown in Figure 4.  Figure 2b shows that, compared with the original TiO 2 , the O def content in the Ar-TiO 2 is significantly increased, indicating that the plasma effectively removed oxygen, and thus some oxygen vacancies are produced in the crystal lattice of TiO 2 . In calculation, the defect-oxygen content of the plasma-treated TiO 2 was four times that of the original TiO 2 (Table 1) [60].  Figure 2c presents the Ti 2p photoelectron spectra of TiO 2 , the Ti 2p peaks at 464.76, 463.7, 459.03, and 458.48 eV were observed corresponding to Ti 4+ 2p 1/2 , Ti 3+ 2p 1/2 , Ti 4+ 2p 3/2 , and Ti 3+ 2p 3/2 , respectively [55,62]. However, it can be seen that after the plasma treatment in the Ar atmosphere, the peaks of Ti 4+ at 459.03 eV and 464.76 eV were shifted by 0.36 eV and 0.24 eV, and the content of Ti 3+ peak was increased, implying that Ti 3+ was generated as a result of the Ti 4+ reduction. A large amount of Ti 3+ and oxygen vacancy in Ar-TiO 2 could make the coordination number of Ti-O-Ti and the surface lattice structure change, thus generating the defects [63]. According to the results of XPS analysis, the plasma-treated titanium dioxide had abundant defects and oxygen vacancies, which played a key role in the degradation of the photocatalyst.
Electron paramagnetic resonance (EPR) was used to further demonstrated oxygen vacancies and Ti 3+ defects of the samples. The magnetization results recorded at 300 K clearly showed surface oxygen vacancies and unpaired spins electrons of Ti 3+ 3d1 in the samples. Figure 2d shows the EPR results of the original TiO 2 and Ar-TiO 2 . The index values of the g peaks at 1.95 and 2.004 corresponded to Ti 3+ and oxygen vacancies in the TiO 2 lattice, respectively [60,64,65]. The content of Ti 3+ and oxygen vacancies in plasma treatment were significantly higher than that of the original TiO 2 , which was consistent with the analysis results of the XPS spectrum.
In order to test the optical performance of the photocatalyst, UV-Vis among 200 nm and 800 nm was surveyed. As shown in Figure 3a, all of the TiO 2 photocatalysts showed the significant absorption of light in the ultraviolet region (<400 nm) and the light absorption of the Ar-TiO 2 photocatalyst moved toward the visible region. The band gap of each sample was estimated by the simulation calculation, TiO 2 was 3.21 eV and the Ar-TiO 2 was 3.17 eV (inset of Figure 3a). This value is the effect of the extrapolation to zero (αhν) 1/2 curve on photon energy, where α is the absorption factor and hν is the light quantum energy [53,56]. Based on the XPS valence band (VB) spectrum (Figure 3b), the valence band position of Ar-TiO 2 was 2.93 eV, which was lower than the original TiO 2 (3.02 eV). These results indicated that the oxygen vacancies (or Ti 3+ species) were produced during the Ar gas plasma treatment and caused the band gap of the Ar-TiO 2 photocatalyst to be narrowed. The electronic band-gap structure and photocatalytic degradation mechanism of TiO 2 samples were shown in Figure 4.

Morphological Characterization
In order to eliminate the impact of catalyst adsorption on photocatalytic performance, BET tests were carried out on the two materials. The N2 adsorption-desorption isotherms and Barrett-Joyner-Halenda (BJH) pore size distribution curves of TiO2 and Ar-TiO2 catalysts are shown in Figure 1d. Both catalyst isotherms are typical type IV isotherms, H1 type hysteresis loops, indicating that the International Union of Pure and Applied Chemistry (IUPAC) classification are a mesoporous material. [66] The BET surface areas of TiO2 and Ar-TiO2 were about 124.7 m 2 /g and 121.3 m 2 /g, respectively ( Table 2), indicating that the specific surface areas of the two catalysts were not much different.

Morphological Characterization
In order to eliminate the impact of catalyst adsorption on photocatalytic performance, BET tests were carried out on the two materials. The N 2 adsorption-desorption isotherms and Barrett-Joyner-Halenda (BJH) pore size distribution curves of TiO 2 and Ar-TiO 2 catalysts are shown in Figure 1d. Both catalyst isotherms are typical type IV isotherms, H1 type hysteresis loops, indicating that the International Union of Pure and Applied Chemistry (IUPAC) classification are a mesoporous material [66]. The BET surface areas of TiO 2 and Ar-TiO 2 were about 124.7 m 2 /g and 121.3 m 2 /g, respectively (Table 2), indicating that the specific surface areas of the two catalysts were not much different. Table 2. BET specific surface are, pore volume and pore size of TiO 2 and Ar-TiO 2 catalysts, respectively.

Sample
Surface Area (m 2 /g) Pore Volume (cm 3 /g) Pore Size (nm) The pore size distribution (Figure 1d) was determined by the BJH method from the desorption branch of the isotherm, indicating that these TiO 2 nanoparticles have a very pronounced mesoporous structure. The average pore diameters of TiO 2 and Ar-TiO 2 were 5.6 and 5.6 nm, respectively ( Table 2). The mesoporous size distribution of the TiO 2 nanoparticles and the mesoporous size distribution of the plasma-treated TiO 2 nanoparticles were not greatly different, indicating that the pore size uniformity of the two materials were near same. The effect of physical adsorption on photocatalytic performance can be ruled out.
TEM and HRTEM images of TiO 2 and Ar-TiO 2 are shown in Figure 5. Figure 5a,d shown that there were no significant changes in the morphology of the TiO 2 after the treatment, and both of them exhibit irregular large spherical nanoparticles. These irregular spherical nanoparticles consist of a plurality of small particles. As shown in Figure 5c, the TiO 2 catalyst showed clear lattice fringes. The lattice spacing values were 0.352, 0.2378 and 0.189 nm, corresponding to the (101), (004) and (200) crystal faces of TiO 2 , respectively. However, in Figure 5f, after plasma treatment (Ar-TiO 2 ), the surface of TiO 2 changed significantly, localized regions were destroyed and uneven, lattice defects were generated, and many deformations occurred. The lattice can increase the amorphous crystal structure and oxygen vacancies [56]. Therefore, defects on the surface of the catalyst after plasma treatment expose more active sites, improving photocatalytic activity.
The lattice spacing values were 0.352, 0.2378 and 0.189 nm, corresponding to the (101), (004) and (200) crystal faces of TiO2, respectively. However, in Figure 5f, after plasma treatment (Ar-TiO2), the surface of TiO2 changed significantly, localized regions were destroyed and uneven, lattice defects were generated, and many deformations occurred. The lattice can increase the amorphous crystal structure and oxygen vacancies. [56] Therefore, defects on the surface of the catalyst after plasma treatment expose more active sites, improving photocatalytic activity.

Photocatalytic Performance
The photocatalytic degradation experiments of MO, Rho B and MB dye solutions in TiO2 and Ar-TiO2 photocatalysts under sunlight and visible light (λ ≥ 400 nm) were estimated. In a typical photocatalytic reaction, TiO2 absorbs energy greater than its forbidden band width and excites electron-hole pairs in the conduction and valence bands. Then these segregated charges transfer to the catalyst surface to take part in the following photocatalytic degradation reaction. Above all, the strong active O species (O2 -· and ·OH) produced in the photocatalytic process have superior redox properties and are used to degrade organic pollutants in water, resulting in an effective photocatalytic degradation reaction. Figure 6a shows that the Ar-TiO2 (99.6% efficiency) photocatalyst achieved better MO degradation performance than TiO2 (49% efficiency) after 30 minutes of sunlight exposure.

Photocatalytic Performance
The photocatalytic degradation experiments of MO, Rho B and MB dye solutions in TiO 2 and Ar-TiO 2 photocatalysts under sunlight and visible light (λ ≥ 400 nm) were estimated. In a typical photocatalytic reaction, TiO 2 absorbs energy greater than its forbidden band width and excites electron-hole pairs in the conduction and valence bands. Then these segregated charges transfer to the catalyst surface to take part in the following photocatalytic degradation reaction. Above all, the strong active O species (O 2 −· and ·OH) produced in the photocatalytic process have superior redox properties and are used to degrade organic pollutants in water, resulting in an effective photocatalytic degradation reaction. Figure 6a shows that the Ar-TiO 2 (99.6% efficiency) photocatalyst achieved better MO degradation performance than TiO 2 (49% efficiency) after 30 min of sunlight exposure. Degradation rate k (kt = ln(C 0 /C)), the degradation rate of the TiO 2 sample was 0.66 h −1 , and the degradation rate of Ar-TiO 2 sample was 5.38 h −1 . Similarly, Ar-TiO 2 photocatalyst showed excellent performance in the degradation of MO solution after visible light (λ ≥ 400 nm) for 150 min (Figure 6b). The degradation rate of TiO 2 was 0.26 h −1 , and the degradation rate of Ar-TiO 2 was 2.14 h −1 . As shown in Figure 6c-f, similar results were obtained for additional degradation experiment of Rho B and MB under sunlight and visible light (λ ≥ 400 nm) illumination. The degradation rate after dye degradation is shown in Table 3.     Figure 6c,e show that the Ar-TiO 2 sample has excellent removal performance in the degradation test of Rho B and MB solution under 120 min of sunlight, while the degradation efficiency of the TiO 2 sample was relatively lower. Under sunlight, the degradation efficiency of Ar-TiO 2 to MO was higher than that of Rho B and MB. Therefore, the photodegradation properties of the Ar-TiO 2 sample depend on the dye used, MO (anionic dye), Rho B and MB (cationic dye). This was because the degradation efficiency of the catalyst is impacted by the pH value of the organic dye solution. The pH changed the surface electric charge of TiO 2 , which affected the adsorption of the organic dye on the surface of TiO 2 , and influenced the rate on reaction and changed the degradation performance of the photocatalyst [67]. The same test on photocatalyst under visible light (λ ≥ 400 nm) was performed. It can be seen from the Figure 6b,d,f that Ar-TiO 2 catalyst exhibited excellent degradation performance in degrading MO, Rho B and MB under 150 min visible light irradiation. The excellent photocatalytic performance of the Ar-TiO 2 sample was attributed to the reduction of the TiO 2 band gap by plasma treatment, resulting in an expansion of the optical absorption range from the ultraviolet to the visible region, and an increase in the amount of active oxygen and Ti 3+ defects.
The apparent quantum efficiencies (AQE) of the TiO 2 and Ar-TiO 2 catalysts was calculated by photocatalytic hydrogen production experiments under full-spectrum conditions. As shown in Table 4, the optical power density was 800 mW·cm −2 by the strong optical power meter measured. The number of incident photons were 4.615 × 10 19 calculated by the Formula (1) calculated. As can be seen from Table 4, the sample of TiO 2 exhibited a H 2 evolution rates (HER) of 320 µmol·g −1 ·h −1 with a quantum efficiency of 41.7 % under UV light irradiation (λ = 385 nm) after 2.5 h. Compared with TiO 2 , the sample of Ar-TiO 2 exhibited the highest H 2 evolution rates (530 µmol·g −1 ·h −1 ) with a quantum efficiency of 69.0 %. It can be concluded Ar-TiO 2 has higher light utilization efficiency.

Conclusions
In conclusion, low temperature DBD plasma was successfully employed to treat the surface of TiO 2 nanoparticles in Ar atmosphere. The Ar-TiO 2 obtained was used for photocatalytic degradation of organic dyes. The results indicated that a large number of oxygen vacancies and Ti 3+ defects were subsequently generated to promote the decomposition of the reactant molecules, thereby improving the reaction efficiency. Plasma treatment shortened the width of the TiO 2 band gap and expanded the light absorption range. The photocatalytic performance indicated that the plasma-treated TiO 2 was much better than the original TiO 2 nanoparticles in photocatalytic degradation of organic dyes under sunlight. Therefore, plasma can be an effective means to optimize photocatalytic degradation of TiO 2 nanoparticles.
Author Contributions: F.Y. conceived, designed and administered the experiments. Y.L. contributed to the synthesis and characterization of materials. W.W., F.W., S.Z. and Y.Y. helped in collected and analyzed data. S.Y. helped to revise the grammar. L.D., B.D. and C.M gave conceptual advice. All authors analyzed, discussed the data and wrote the manuscript.
Funding: This work was financially supported the National Natural Science Foundation of China (No. 21663022).

Conflicts of Interest:
The authors declare no conflict of interest.