Degradation of dibutyl phthalate by ozonation in the ultrasonic cavitation–rotational flow interaction coupled-field: performance and mechanism

Dibutyl phthalate (DBP) is present in hydraulic fracturing flowback and produced water. Degradation of DBP in aqueous by means of ozonation in ultrasonic cavitation–rotational flow interaction coupled-field (UC-RF coupled-field) was studied. The effect of ozone dosage, ozone intake flow, operating temperature, initial pH, DBP initial concentration, liquid flow rate, and ultrasonic power on the DBP removal was investigated. Results indicated that the DBP degradation rate was strongly influenced by the liquid flow rate and the ultrasonic power over the range investigated. HCO3− and Cl− revealed an inhibitory effect on the DBP removal. SO42− seemed to have no effect on DBP removal. The ozone utilization efficiencies in the UC-RF coupled-field were 2.77 and 1.13 times higher than those in the conventional microporous aeration (CMA) and rotating-flow microbubble aeration (RFMA), respectively. The DBP degradation rate was diminished in the presence of tert-butyl alcohol. Cavitation bubbles are considered as innumerable microreactors. Degradation of DBP by direct ozonation, hydroxyl radical (·OH) oxidation, high pressure, and high-temperature pyrolysis was demonstrated. Finally, a possible degradation pathway of DBP is obtained on the basis of the main reaction intermediates.


Introduction
Phthalate esters (PAEs) are an important kind of industrial chemicals that have received extensive research attention due to their broader range of applications. They are used as plasticizers for the improvement of the flexibility and workability of polymeric materials (Staples et al. 1997) and as additives in personal care products, coatings, synthetic fibers, toys, varnishes (Schettler 2006), insect repellents, and medical products (Sun et al. 2012). In recent years, shale gas development is thriving in China. Large volumes of flowback water are produced during shale gas production. Many studies have shown PAEs are present in hydraulic fracturing flowback and produced water (Hayes 2009;Lester et al. 2015;Höfer and Bigorra 2007;Wang et al. 2020a, b). Wang et al. (2020a, b) considered di-(2-ethylhexyl) phthalate (DEHP) as a representative organic contaminant in the in the fracturing wastewater. Orem et al. (2014) found that phthalate present in the produced and formation water was collected from the Marcellus Shale (Pennsylvania) and the New Albany Shale (Indiana and Kentucky). Leach, migrate, Responsible Editor: Ricardo A. Torres-Palma or evaporate processes allow PAEs to escape into the environment (Moreira et al. 2015). Therefore, PAEs are often detected in soil, air, and water all over the world (Chen and Sung 2005). They are considered as harmful compounds to human health because of their connection with birth defects, infertility, organ damage, and cancer (Medellin-Castillo et al. 2013). While DBP is the major phthalate in the environmental samples (Peijnenburg and Struijs 2006), it usually preferred to be used as a target pollutant. The nature of DBP is not easy to be changed in the environment. Its hydrolysis half-life is estimated at around 20 years, and slow biodegradation occurs from up to several days to months (Staples et al. 1997). DBP degradation has been a hot area of research in recent years due to its highly toxicity and carcinogenic properties. The conventional technologies reported for DBP removal are shown in Table 1. Integration of the advanced oxidation processes (AOPs) to the conventional process in degrading refractory organic contaminants in waters and wastewater has already become an emphasis of the research.
For the AOPs, the production of ·OH is the most critical step, which is accomplished by chemical, photochemical, and ultrasonic cavitation. Among various AOPs, ultrasonic cavitation has attracted great interest because of its unique comparative advantages, such as absence of catalyst, good safety, and low requirements for solution transparency (Song et al. 2005). The ultrasonic cavitation process is composed of formation, growth, and sudden collapse of gas bubbles in a minimal time (Staples et al. 1997). Cavitation is a processing of local high temperature (up to 10,000 K) and high pressure (10-500 MPa) (Musmarra et al. 2016). The pyrolysis of water molecules under such conditions is believed to yield ·OH radicals (Capocelli et al. 2014). On the other hand, ultrasonic cavitation shows good results when combined with other techniques (Zhang et al. 2021;Hewage et al. 2021). Ozonation treatment could effectively remove organic pollutants from wastewater (Ji et al. 2018;Chen and Wang 2021;Garcia-Costa et al. 2021;Inchaurrondo et al. 2021). Ozone is a powerful oxidizing molecule, and ozonation could occur directly via molecular O 3 , or indirectly by ·OH formed in situ in water.
Several different types of ozone contactors or through other methods have been proposed and developed. The typical gas-liquid contactors include the agitator reactor (Luo et al. 2016), the Taylor-Couette vortex bioreactor (Ramezani et al. 2017), the air-lift reactor (Geng et al. 2020), the falling film microreactor (Lokhat et al. 2016), the rotating packed bed (RPB) reactor (Gao et al. 2017), the rotor-stator spinning disc reactor (Haseidl et al. 2016), the micro-channel reactor (Tan et al. 2012;Haseidl et al. 2016), and the high shear reactor (HSR) (Shi et al. 2014). They have their own advantages and disadvantages when employed in the ozonation process. At present, many studies about the ozonation process using an RPB  (Navacharoen and Vangnai 2011) reactor have been reported (Wei et al. 2020). However, few researches have been reported on the ozonation process in a rotating-flow microbubble reactor without rotating packed bed and rotor-stator spinning disc (Li and Tsuge 2005). It is a simple and energy-saving method that could successfully generate numerous microbubbles.
In the past decades, ozonation/ultrasonic cavitation processes were investigated by several groups (Hewage et al. 2020;Liu et al. 2021;Rossi et al. 2021;Sun et al. 2022;Wang et al. 2022) and a great success has been obtained in the removal of pollutants, such as hydrolyzed polyacryamide (HPAM) (Zhang et al. 2022a, b), P-terphenyl (Hewage et al. 2021), and sulfolane (Wang et al. 2021a, b). Significantly, this combination method does not require the addition of chemicals. Ultrasonic cavitation assistance enhanced the degradation of pollutants, and this strengthening effect is due to the formation of ·OH, which is produced by ozonolysis under ultrasonic in bulk solution (Rossi et al. 2021;Xue et al. 2022). Ultrasonic cavitation could accelerate the ozone mass transfer from gas phase to liquid phase (Wang et al. 2019). Up to now, limited studies have focused on ultrasonic cavitation assisted ozonation in a rotating-flow microbubble reactor for pollutant degradation.
In this work, ozonation with ultrasonic cavitation-rotational flow interaction coupled-field was studied using DBP as model pollutant. The effects of ozone dosage, ozone intake flow, operating temperature, initial pH, DBP initial concentration, liquid flow rate, ultrasonic power, and co-existing water matrix components on the DBP removal was investigated systematically. The ozone utilization efficiency was also calculated. In addition, the influence of the presence of TBA on the ozonation of DBP in the UC-RF coupled-field was investigated. Eventually, a possible degradation pathway of DBP was obtained on the basis of the main reaction intermediates.

Materials and reagents
DBP (molecular weight: 278.34, molecular formula: C 16 H 22 O 4 ; CAS: 84-74-2) of analytical reagent grade was purchased from Chengdu Kelong Chemical Co., Ltd. TBA was supplied by Chengdu Kelong Chemical Co., Ltd. Oxygen gas of 99.999% purity (Chengdu Taiyu Industrial Gas Co., Ltd) was consumed as the gas phase. Ozone was generated onside by electric discharge using 99.999% oxygen. All solutions were prepared using ultrapure water. Reagents and chemicals were of analytical grade and not further purified.

Experimental reactor
The experimental setup is presented in Fig. 1. Detailed information on the experimental set up is displayed in our previous literature (Zhang et al. 2022a, b).

Data analysis
The DBP removal (η, in %) was calculated as follows: where C 0 is the initial DBP concentration (mg/L) and C t is the DBP concentration at the specific time (mg/L).
The ozone utilization efficiency was calculated by using the following equation:

Sample characterization
The concentration of ozone in the gas phase was measured with iodine stoichiometry titration method (Rakness et al. 1996;Zhang et al. 2022a, b). Ozone concentration in aqueous solution was determined by indigo method (Bader and Hoigné 1981). The UV-Vis absorption spectra were recorded by using a UV-Vis spectrophotometer (UV-1750; Shimadzu, Japan) in the range of 200 ~ 300 nm. A nitron spin-trapping reagent of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) was used to detect ·OH. The DMPO-OH adduct signal detection was made by using the electron paramagnetic resonance (EPR) experiment (Zhao et al. 2008a). A mass spectrometer equipped with electrospray ionization source (ESI-MS) was used for intermediate degradation products of DBP detection. Other intermediates formed during the ozonation, i.e., organic acids, were detected using a DX-300 ion chromatography (IC).
The concentration of DBP was analyzed by a highperformance liquid chromatograph (HPLC, LC-20A; Shimadzu, Japan) equipped with a chromatographic column (Sepax GP-C18, USA; 250 mm × 4.6 mm, 5 μm particle size) and a UV detector. Methanol/water (80:20, v/v) was employed as the mobile phase with a flow rate of 0.8 mL/min.

Effect of ozone dosage
The influence of ozone dosage from 2.59 to 43.92 mg/L on DBP removal was investigated, as shown in Fig. 2a. The removal rate of DBP was enhanced as the ozone dosage increased. When the ozone dosage increased from 32.38 to 43.92 mg/L, the degradation rate enhanced to > 99% at the end of the reaction. This is because increasing the ozone dosage could accelerate the ozone mass transfer and cause an increase in the formation of ·OH. However, further increase in the ozone dosage to 32.38 mg/L did not significantly increase the degradation efficiency. This phenomenon could be explained by that the excess gas has a negative impact on the cavitation effect, making the cavitation intensity decreased. Therefore, 32.38 mg/L was selected as the optimal ozone dosage for further study.

Effect of ozone intake flow
DBP removal was also investigated at different ozone intake flows (100-400 L/h). As illustrated in Fig. 2b, when the intake flow was increased from 100 to 400 L/h, the degradation rate of DBP reached nearly 97.22%. The reasons for these results are as follows: (1) Increasing the intake flow rate corresponds to a larger net surface area for ozone mass transfer and hence the DBP removal due to the mass transfer controlled characteristics in the ozonation with the UC-RF coupled-field.
(2) With the unduly high ozone flow rate, the contact time of the gas and the liquid shortens. In addition, the ultrasonic system is vulnerable to the operating parameters due to its fragility. Cavitation bubbles break up easily by unduly high gas flow rate and against dissolved ozone (Wang et al. 2019). Thus, the amount of ·OH decreases.

Effect of operating temperature
Temperature is an important parameter in determining efficient reaction. The influence of operating temperature on DBP removal was investigated at four temperatures in the range of 293.15-323.15 K, and the results are depicted in Fig. 2c. As evident in Fig. 2c, the DBP conversion decreased  Temperature affects the gas solubility, viscosity, surface tension, and vapor pressure of the bulk phase (Chiha et al. 2011). Augmentation of the bulk temperature has increased the number of cavitation bubbles leading to the enhancement of ·OH production (Psillakis et al. 2004). However, the solubility of ozone decreased with increasing temperature (Wang and Bai 2017). In addition, an increase in the temperature resulted in an enhancement in the vapor pressure in water . Therefore, when the cavitation bubbles were filled with aqueous vapor, there was an increase in the resistance to the movement inside the bubble was observed during cavitation bubble collapse, leading to the low efficiency of cavitation.

Effect of initial pH
The solution pH plays an important role in chemical reaction (Rodríguez-Chueca et al. 2019); therefore, the ozonation in the ultrasonic cavitation-rotational flow interaction coupledfield was evaluated at different initial pH values from 3.0 to 11.0. As shown in Fig. 2d, increasing the pH favored DBP degradation, and the removal efficiency gradually increased from 52.21 to 98.99%. This finding may be due to the generation of ·OH at higher pH (Eqs. (5)- (7)), which is more reactive toward DBP than ozone molecule (Zhao et al. 2008b;Rodríguez-Chueca et al. 2019). Ozone decomposition gradually enhanced with an increase in pH (Shen et al. 2017). In addition, more ·OH were expected to form in acidic condition during sonolysis of aqueous solution (Jiang et al. 2002). However, at high pH, more free radical scavengers were found, such as CO 3 2− and HCO 3 − , which reacted quickly with ·OH (4.0 × 10 8 L/(mol·s) and 2.0 × 10 7 L/(mol·s)) (Staehelin and Hoigne 1985). Thus, the amount of ·OH decreased.

Effect of DBP initial concentration
Research suggested that the initial organic pollutant concentration plays an important role in the removal efficiency (Braeutigam et al. 2012). As presented in Fig. 2e, an obvious decline in the degradation was observed due to the increment of DBP concentration. Specifically, with the DBP initial concentration increasing from 2.5 to 10 mg/L, the DBP decay rate decreased significantly from over 99.88 to 61.31%. The reason for the debility for the removal performance might be caused by the lack of reactive radicals in higher initial DBP concentration solution. At high initial concentration, ·OH will not be sufficient for DBP oxidation, resulting in a decrease in conversion rate. In addition, higher initial DBP concentration resulted in the generation of more intermediate products, which competed with DBP for reaction with ·OH. Similar results were reported in the literature (Braeutigam et al. 2012).

Effect of liquid flow rate
The effect of liquid flow rate ranging from 10 to 16 L/min on DBP removal was investigated. As seen from Fig. 2f, the percent reduction in DBP increased evidently with the increase in liquid flow rate from 10 to 14 L/min and achieved a steady state in 16 min. The greater the liquid flow rate was, the higher the tangential velocity of fluids and the greater the centrifugal force and shear force were. Thus, the droplets are broken up into smaller ones. Also, the quantity of small bubbles increased. Consequently, the ozone-liquid contact area increased. Meanwhile, at high liquid flow rates, the turbulence in the UC-RF coupled-field increases, leading to the increase in net surface area, and the decrease in mass transfer resistance due to the thinning film thickness, both of which are conducive to ozone mass transfer. However, with further increase in the liquid flow rate from 14 to 16 L/min, the percent reduction in DBP had no significant increase. As the liquid flow rate exceeded the optimum rate, ultrasonic cavitation, which is a condition of partial cavity collapse or inactive cavity collapse, occurred, reducing the cavitation intensity and leading to a decrease in the formation of ·OH (Saxena et al. 2018). Hence, the optimal liquid flow rate was considered to be 14 L/min. Figure 2g represents the effect of different ultrasonic powers on the removal of DBP. The removal efficiencies were 58.28%, 95.56%, 97.75%, and 99.45% at ultrasonic powers of 0, 1000, 1500, and 2000 W, respectively. Compared with the DBP removal with rotating-flow microbubble aeration, the addition of ultrasonic cavitation effectively boosted the DBP degradation rate from 58.28 to 99.45% after 16 min of treatment. Based on the results from "Effect of ozone dosage" section to "Effect of liquid flow rate" section, the findings indicate that ultrasound cavitation could remarkably improve the DBP removal. The ultrasonic power, frequency, and amplitude of the system could influence the ultrasonic cavitation (Neppolian et al. 2002). Ozone bubbles generated in the rotational flow force field provides just the cavitation nucleus for the generation of ultrasonic cavitation. The mechanical effects such as micro-jet, impingement, and acoustic impingement produced with ultrasonic cavitation could cause the turbulence effect of the liquid. Such effect could reduce the liquid film thickness, reduce the resistance of ozone dissolving in water, improve the ozone dissolution rate, improve the ozone mass transfer, and increase its utilization rate. More than anything, ozone bubbles coalesce toward the axis of the reactor in the rotational flow field and grow as they rise. Nevertheless, ultrasound wave could push the bubbles coalesce away, leading to the ozone bubbles rising in a spiral manner, thus the residence time lengthened and the contact area between ozone and liquid increased due to the preventable bubble coalescence in the UC-RF coupled-field. An increase of ultrasonic power may enhance the turbulence and improve the cavitation bubble yield (Siddique et al. 2014). However, further increase in ultrasonic power could also lead to insufficient collapse of the cavitation bubbles and generation of an acoustic screen (Sajjadi et al. 2015). Therefore, more ozone molecules could be degassed and the ·OH production decreased. Appropriate ultrasonic power should be taken into account for energy utilization and cavitation yield.

Influences of co-existing water matrix components
Organic/inorganic components (such as Cl − , HCO 3 − , and SO 4 2− ) in water could react with reactive ·OH and thus compete with DBP for ·OH leading to the negative effect on DBP degradation by using ozonation in the UC-RF coupled-field. Therefore, the experiments were carried out with co-existing Cl − , HCO 3 − , and SO 4 2− to investigate the effect of these ions on the removal of DBP. The coalescence of bubbles was inhibited by the presence of ions (Kawahara et al. 2009). The residence time of the bubbles in liquids increased by decreasing the bubble diameter (Kawahara et al. 2009). In addition, the presence of salt led to the enhancement of ionic strength of the aqueous phase and then making organic pollutants move toward the bubble-bulk interface (Kawahara et al. 2009). More ·OH could also be found in the bubble-bulk interface (Seymour and Gupta 1997). Thus, the degradation of DBP increased.
Based on the results, Cl − had an adverse effect on DBP degradation. It is reported that the following reactions occur in presence of chloride ions (Eqs. (8)-(17)) (Muthukumar and Selvakumar 2004).
where S represents organic moiety.
Based on the above set of equations, it could be concluded that the presence of Cl − leads to the consumption of ozone and depletion of ·OH. A similar result was reported in the literature (Muthukumar and Selvakumar 2004).
An obvious inhibition on the degradation of DBP was observed in the presence of HCO 3 − , an efficient ·OH scavenger that could compete with target containment for ·OH to form carbonate radicals (weak radicals, Eq. (18)) (Ji et al. 2015). The oxidation of these carbonate radicals is unimportant and could be ignored in the removal of most organic pollutants (Crittenden et al. 1999). Thus, HCO 3 − depressed the removal efficiency of DBP in the ozonation with UC-RF coupled-field. A similar result was reported for the reduction in removing DBP in the presence of HCO 3 − (Wang et al. 2018).
Compared to HCO 3 − and Cl − , the presence of SO 4 2− had a slight effect on the DBP removal. SO 4 2− reacted with the ·OH produced by the decomposition of ozone (Eq. 19). In this system, the advantage of adding SO 4 2− to the solution containing DBP offsets its disadvantage. Therefore, the introduction of SO 4 2− did not affect the DBP removal (Fig. 3). Table 2 represents ozone utilization efficiencies in the conventional microporous aeration (CMA), rotating-flow microbubble aeration (RFMA), and ultrasonic cavitation-rotational flow interaction couple-field (UC-RF couple-field), respectively.

Ozone utilization efficiency
As can be seen from Table 2, the ozone utilization efficiencies in the CMA, RFMA, and UC-RF coupled-field systems were 33.43%, 81.75%, and 92.57%, respectively. Considering the high removal efficiency of DBP in the UC-RF coupled-field system, we can conclude that ultrasonic cavitation and rotating-flow microbubbles could enhance ozone mass transfer. Ultrasonic field and rotational flow force field in water produce microbubbles and increase the ozone-liquid contact area. Turbulence produced by ultrasonic cavitation and rotational flow decreased the thickness of the liquid film, leading to an increase in ozone mass transfer. In addition, the ozone microbubbles generated in the rotational flow force field provided just the cavitation nucleus for the generation of ultrasonic cavitation. Thus, the rate of ozone decomposition accelerated and more ·OH were formed. Lower ozone off-gas concentration is desirable for wastewater treatment costs.

Hydroxyl radicals
To identify the main oxidation pathway in ozonation, excess hydroxyl radical scavenger, tert-butyl alcohol (TBA), was added to the solution. As illustrated in Fig. 4a, an obvious reduction in DBP removal efficiency was found in the presence of TBA, confirming the dominance of radical mechanism in DBP degradation. DBP reacted slowly with molecular ozone (0.092 ± 0.042 M −1 s −1 ) and quickly with ·OH ((4.64 ± 0.41) × 10 9 M −1 s −1 ) (Wen et al. 2011). The electron spin resonance (EPR) spectroscopy (Fig. 4b) presented that by using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the trapping agent, quadruple peak signals of DMPO-OH (1:2:2:1, α N = α H = 14.9 mT, g-value = 2.0055) in the ozonation with UC-RF coupled-field could be observed, coinciding with those of the DMPO-OH adduct as demonstrated previously. This finding indicated the production of ·OH in this system (Li et al. 2021).

Fig. 3
Effect of co-existing water matrix components on the DBP removal

Mechanism analysis
To clarify the changes of molecular and structural characteristics of DBP as a result of UC-RF coupled-field enhanced ozonation, the UV-Vis spectra changes of the DBP solution as the function of reaction time were plotted in the range of 200-300 nm in Fig. 5. As could be observed from these spectra, the UV-Vis spectrum comprises two maxima, a weak one at 277 nm (ɛ 277 = 11,801 mol −1 cm −1 ) and a more intense one at 227 nm (ɛ 227 = 77,001 mol −1 cm −1 ) (Bajt et al. 2001). By comparing the changes in the peak value before and after DBP oxidation, it was obvious that the disappearance of the peak value with the time was due to the fragmentation of the DBP links by ozonation attack in the UC-RF coupled-field. Therefore, the system is beneficial to DBP degradation. Further research is needed for the detection of more detailed reaction intermediates and the determination of degradation pathways.
In the UC-RF coupled-field system, the intermediate products formed in the degradation of DBP were investigated. DBP was degraded via electrophilic substitution reaction, hydroxylation, and ring-opening. The degradation of DBP could be attributed to three oxidation mechanisms: (1) direct oxidation by molecular ozone in the bulk solution; (2) hydroxyl radical oxidation produced from ozone decomposition, cavitation bubbles, and microbubble collapse; (3) high-pressure and hightemperature pyrolysis formed by ultrasonic cavitation. According to the above results obtained (Sects. 3.1.4 and 3.4), direct oxidation accounted for 12.68%, ·OH oxidation accounted for 58.35%, and pyrolysis accounted for 23.53% of the overall DBP removal. Therefore, the ·OH oxidation and pyrolysis were considered as the main General reaction pathway proposed for DBP degradation in UC-RF coupled-field system mechanisms for DBP removal. The aliphatic chain and the aromatic ring in the DBP molecule were attacked by ·OH (Yan et al. 2007). ·OH could easily attack the aromatic ring of electron cloud density which is easily affected by the electron-donating group of functional group, causing the fracture of aromatic ring (Yu and Yao 2003). Due to the strong thermal stability of large conjugated bond in the benzene ring, the pyrolysis mainly occurs on the fatty side chain connected by the benzene ring (Wang et al. 2008). The aromatic ring was attacked by ·OH, leading to the formation of two hydroxylated intermediate isomers (compounds B1 and B2). Then, compounds B1 and B2 lost butoxy groups to form compounds B6 and B7 by ·OH oxidation. Compounds B6 and B7 were de-acidized to form benzoic acid (compound B13). The carbon-oxygen double bond and carboxyl group on the carboxylic acid of benzoic acid were broken and oxidized by hydroxyl radical to become benzaldehyde (compound B12). Compound B4 was formed by the cracking of the alkyl-oxygen bond of DBP. Butyl hydrogen phthalate (compound B4) was deacidized to form butyl benzoate (compound B13). Meanwhile, benzoquinone (compound B11) could be obtained by further decarboxylation of benzoic acid and further oxidized and via ring-opening reaction to produce a series of fatty acids such as succinic acid, formic acid, and acetic acid. In addition, the ·OH radicals attacked two carbon atoms in α-position with respect to carboxyl group. The positions could be cleaved, producing compound B5. From the information obtained, a possible degradation pathway of DBP may be proposed, as shown in Fig. 6.

Conclusion
Ozonation with UC-RF coupled-field considerably enhanced the degradation of DBP in solution. Increasing ozone dosage, ozone intake flow, initial pH, liquid flow rate, and ultrasonic power enhanced the DBP removal. However, the DBP removal decreased as the operating temperature and DBP initial concentration increased. HCO 3 − and Cl − showed an inhibition influence on the DBP degradation. SO 4 2− seemed to have no effect on DBP removal. The ozone utilization efficiencies in the UC-RF coupled-field, RFMA system, and CMA systems were 92.57%, 81.75%, and 33.43%, respectively. According to the result that TBA inhibited the DBP removal, it could confirm that ·OH existed in this system. In this work, direct oxidation accounted for 12.68%, ·OH oxidation accounted for 58.35%, and pyrolysis accounted for 23.53% of the overall DBP removal. Author contribution HZ: conceptualization, experimental design, data curation, data analyses, writing original draft, editing, supervision. BW, PT, YL, and CG: experimental design, laboratory measurements, editing.
Funding This work was supported by the financial supports of Science and Technology Cooperation Project of the CNPC-SWPU Innovation Alliance (2020CX020300) and Sichuan Science and Technology Program (2021YFG0116).