Preparation method of inorganic piezoelectric catalytic membrane and application of inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology in water treatment

Abstract

The invention discloses a preparation method of an inorganic piezoelectric catalytic membrane and application of the inorganic piezoelectric catalytic membrane in water treatment by coupling an advanced oxidation technology, and belongs to the technical field of environmental functional materials and water treatment. Technical breakthrough is achieved through a synergistic mechanism of an inorganic piezoelectric material and an advanced oxidation technology, the inorganic piezoelectric catalytic membrane is prepared by taking the piezoelectric material as a core piezoelectric component through ball-milling mixing, dry-pressing forming and high-temperature calcination processes, a multi-stage pore channel structure (the pore diameter is 50-100 nm) is formed, and a piezoelectric electric field larger than or equal to 0.5 V is generated under dynamic mechanical energy; the electric field is used for directionally activating the oxidant to generate high-selectivity singlet oxygen (1O2) by adjusting an electron structure on the surface of the catalyst, and the selectivity of the singlet oxygen reaches 95% or above; the mass transfer efficiency is remarkably improved through the synergistic effect of the membrane confinement effect and the piezoelectric micro-current, efficient removal of refractory pollutants such as sulfamethoxazole and bisphenol A is achieved (the degradation rate within 30 minutes is larger than or equal to 99%), and the self-cleaning function is achieved (the flux recovery rate is larger than or equal to 98%).

Description

Technical Field

[0001] The present invention belongs to the technical field of environmental functional materials and water treatment, and specifically relates to a method for preparing an inorganic piezoelectric catalytic membrane and application of the method coupled with advanced oxidation technology in water treatment. Background Art

[0002] In recent years, advanced oxidation processes (AOPs) have rapidly developed and attracted considerable attention as a highly effective new method for removing organic pollutants. This technology primarily uses chemical means to generate highly oxidizing free radicals and other reactive oxygen species (ROS) in the system to degrade organic pollutants, subsequently mineralizing them into small organic molecules, ultimately reducing them to CO2, H2O, and corresponding inorganic ions, ultimately achieving the goal of removing organic pollutants. Common AOPs include Fenton and Fenton-like processes, catalytic ozone oxidation, sulfate radical-based advanced oxidation processes, and photocatalytic oxidation.

[0003] Singlet oxygen ( 1 Although the oxidation potential of O2 (about 2.2V) is slightly lower than that of hydroxyl radicals (·OH, 2.8V), its longer lifespan (microseconds) and longer migration distance enable it to efficiently degrade pollutants in complex environments. For example, in wastewater treatment, 1 O2 can selectively oxidize difficult-to-degrade organic matter (such as antibiotics, dyes, etc.) to avoid the formation of harmful by-products. 1 The oxidation products of O2 are usually non-toxic small molecules (such as CO2, H2O), and the preparation process does not require the addition of toxic chemical reagents (such as the traditional Fenton method requires Fe 2+ and H2O2) to avoid secondary pollution. In the process of advanced oxidation catalysis, traditional catalysts (such as precious metals or transition metal oxides) usually react through free radical pathways (such as OH, SO4 2- ) and non-radical pathways (e.g. 1 O2, *O3 - ) work together, resulting in the coexistence of multiple reactive oxygen species (ROS), making it difficult to generate them in a targeted manner. 1 O2.

[0004] As the composition of industrial wastewater becomes increasingly complex (including antibiotics, heavy metal complexes, etc.), traditional advanced oxidation technology faces multiple bottlenecks in the treatment of refractory organic matter. Existing catalytic materials (such as MnO x / Al2O3, precious metal catalysts) are usually designed for a single oxidant (such as ozone or H2O2). When switching to persulfate (PMS / PDS) or electro-activation system, the activation efficiency drops by more than 60% due to the mismatch between the surface charge and the active site. For example, ozone catalytic materials are difficult to efficiently generate SO4 in persulfate systems due to the blocked electron transfer path. 2- Free radicals.

[0005] Over the past few decades, membrane technology has been widely used in the treatment of drinking water and the reuse of secondary effluent from sewage treatment plants. Compared with organic membranes, inorganic membranes offer superior thermal, chemical, and mechanical stability, and significantly longer service lives. However, membrane fouling has limited their large-scale application in wastewater treatment. The adsorption and deposition of pollutants (such as organic matter, oils, and microorganisms) on the membrane surface and within its pores can lead to flux attenuation and increased operating costs. Traditional anti-fouling strategies (such as superhydrophilic coatings) can only delay the fouling process but cannot achieve self-cleaning. Frequent downtime for cleaning or the use of chemical cleaning agents is required, resulting in low efficiency and the risk of secondary contamination. Heterogeneous catalytic advanced oxidation coupled with inorganic catalytic membrane filtration processes are gaining increasing attention in the advanced water treatment field due to their effective removal of organic pollutants and self-cleaning properties. The advantage of catalytic membrane-based oxidation filtration is the membrane's good self-cleaning ability. However, traditional advanced oxidation coupled with inorganic catalytic membrane filtration processes are not ideal for removing emerging pollutants, which greatly limits the development of this process.

[0006] Piezoelectric materials (such as BaTiO3 and PVDF / MoS2) can generate piezoelectric voltage through mechanical stress, which can be used to degrade pollutants or prevent membrane fouling. However, existing research has mostly focused on a single mechanism: the direct piezoelectric effect (mechanical energy → electrical energy). For example, this mechanism uses water pressure to induce the piezoelectric effect for anti-fouling, or enhances mass transfer through the inverse piezoelectric effect (electrical energy → mechanical vibration).

[0007] However, these technologies have the following problems:

[0008] (1) The synergistic mechanism between inorganic piezoelectric catalytic membranes and advanced oxidation technology catalysis has not been explored: Existing inorganic piezoelectric membranes are mainly used for anti-pollution or direct degradation of pollutants, and their synergistic effect with advanced oxidation technology has not been explored;

[0009] (2) In recent years, piezoelectric catalysis technology can enhance oxidant activation and pollutant mass transfer by inducing a built-in electric field through mechanical stress. However, existing research focuses on single oxidation systems (such as piezoelectric-ozone synergy) and fails to achieve dynamic adaptation of multiple oxidants (O3, H2O2, PMS) and targeted regulation of ROS;

[0010] (3) Lack of selective regulation of ROS: The free radical oxidation pathways such as OH generated by traditional piezoelectric catalysis are difficult to achieve selective degradation and are easily disturbed by water quality.1 The difficulty of O2 lies in the complexity of the reaction pathway and the inherent limitations of catalytic materials;

[0011] (4) Poor matching between membrane structure design and piezoelectric performance: Most piezoelectric membranes (such as PVDF-based) have low mechanical strength and insufficient porosity, making it difficult to maintain a stable piezoelectric response under dynamic water pressure.

[0012] Therefore, the development of an inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology that can both degrade emerging pollutants and enhance membrane pollution control performance for high-efficiency water treatment applications is of great significance for the development of ceramic membrane catalytic advanced oxidation processes with the advantages of flexible reactor design, strong membrane self-cleaning ability, excellent pollutant removal effect, mild reaction conditions, fast oxidation rate, environmental friendliness, and no secondary pollution. Summary of the Invention

[0013] In order to solve the above technical problems, the present invention proposes a method for preparing an inorganic piezoelectric catalytic membrane and its application in water treatment by coupling with advanced oxidation technology.

[0014] A method for preparing an inorganic piezoelectric catalytic film is specifically completed by the following steps:

[0015] 1. Evenly mixing the nano-piezoelectric material, the nano-catalytic material, Al2O3 and the low-temperature binder in a certain proportion to obtain a raw material mixture;

[0016] The nano-piezoelectric material described in step 1 is one or a mixture of tourmaline, LiNbO3, LiTaO3, ZnO, BaTiO3, potassium sodium niobate, SrTiO3 and sodium bismuth titanate;

[0017] 2. Ball milling the raw material mixture for a period of time, dry pressing at 40kPa to 60kPa, and finally calcining at 700°C to 900°C for a period of time to obtain a catalytic film;

[0018] 3. Polarization:

[0019] The top and bottom of the catalytic membrane are connected to copper electrodes respectively, and then the catalytic membrane is immersed in liquid paraffin, and a DC voltage of 1kV / mm~5kV / mm is coupled to the copper electrode. Under this condition, polarization is carried out for 2h~5h. After the polarized catalytic membrane is taken out and the copper electrode is removed, it is immersed in anhydrous ethanol at a temperature of 50℃~70℃ for 1h~2h. Finally, the liquid paraffin and anhydrous ethanol are removed by water washing, and then dried to obtain an inorganic piezoelectric catalytic membrane.

[0020] Dynamic pulse water pressure is used to trigger the in-situ piezoelectric effect of inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of pollutants in water, or ultrasound is used to trigger the in-situ piezoelectric effect of inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of pollutants in water; the filtration method is cross-flow filtration or dead-end filtration.

[0021] The present invention proposes a method for preparing an inorganic piezoelectric catalytic membrane and its application in water treatment coupled with advanced oxidation technology. Its innovations are as follows:

[0022] (1) For the first time, the piezoelectric effect of inorganic membranes is deeply coupled with advanced oxidation technology. The piezoelectric properties of nano-piezoelectric materials are used to generate a built-in electric field (piezoelectric voltage ≥ 0.5V) under ultrasound and dynamic water pressure to promote the decomposition of oxidants into highly selective singlet oxygen ( 1 O2), breaking through the traditional ROS selectivity bottleneck;

[0023] (2) The piezoelectric field can adjust the electronic structure of the catalyst surface and improve the adsorption energy of the oxidant;

[0024] (3) The collaborative design of membrane confinement effect and piezoelectric performance, multi-level pore structure (pore diameter 50-200nm) combined with Al2O3 reinforced skeleton, achieves efficient mass transfer and mechanical stability (flexural strength ≥30MPa);

[0025] (4) Nano-piezoelectric materials are evenly dispersed in the ceramic matrix to form a continuous piezoelectric network. The pulsed electric field under ultrasound or dynamic water pressure synergistically inhibits membrane fouling with ROS, and the flux recovery rate is ≥98%;

[0026] (5) Green, efficient and economical. Tourmaline is a natural mineral with a cost 70% lower than that of precious metals. No external chemical cleaning agents are required, which reduces water treatment costs. It is suitable for large-scale treatment of industrial wastewater (such as printing and dyeing, pharmaceuticals) and natural water bodies (lake water). BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The piezoelectric butterfly curve and phase hysteresis loop of the inorganic piezoelectric catalytic film prepared in Example 1;

[0028] Figure 2 This is a surface morphology of the inorganic piezoelectric catalytic film prepared in Example 1;

[0029] Figure 3 This is a phase diagram of the inorganic piezoelectric catalytic film prepared in Example 1;

[0030] Figure 4 This is an amplitude diagram of the inorganic piezoelectric catalytic film prepared in Example 1;

[0031] Figure 5 The electrostatic potential diagram of the inorganic piezoelectric catalytic film prepared in Example 1;

[0032] Figure 6 This is the pulse piezoelectric response curve of the inorganic piezoelectric catalytic film prepared in Example 1;

[0033] Figure 7This is a diagram of the quenching experiment of the inorganic piezoelectric catalytic film coupled with the advanced oxidation technology prepared in Example 1;

[0034] Figure 8 Performance diagram of the degradation of 2,4-D, BPA, and RhB using the inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology prepared in Example 1;

[0035] Figure 9 This is a 14-day long-term operating performance diagram of the degradation of SMX by the inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology prepared in Example 1;

[0036] Figure 10 This is a diagram of the back-end dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology cross-flow filtration device;

[0037] Figure 11 This is a diagram of a front-end dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology cross-flow filtration device;

[0038] Figure 12 This is a diagram of a dead-end filtration device using a front-end dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology;

[0039] Figure 13 This is a diagram of a dead-end filtration device using a dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology;

[0040] Figure 14 This is a diagram of a cross-flow filtration device for ultrasonic inorganic piezoelectric catalytic membrane coupled advanced oxidation technology;

[0041] Figure 15 This is a diagram of a dead-end filtration device using ultrasonic inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology. DETAILED DESCRIPTION

[0042] Specific embodiment 1: This embodiment provides a method for preparing an inorganic piezoelectric catalytic film, which is specifically completed by the following steps:

[0043] 1. Evenly mixing the nano-piezoelectric material, the nano-catalytic material, Al2O3 and the low-temperature binder in a certain proportion to obtain a raw material mixture;

[0044] The nano-piezoelectric material described in step 1 is one or a mixture of tourmaline, LiNbO3, LiTaO3, ZnO, BaTiO3, potassium sodium niobate, SrTiO3 and sodium bismuth titanate;

[0045] 2. Ball milling the raw material mixture for a period of time, dry pressing at 40kPa to 60kPa, and finally calcining at 700°C to 900°C for a period of time to obtain a catalytic film;

[0046] 3. Polarization:

[0047] The top and bottom of the catalytic membrane are connected to copper electrodes respectively, and then the catalytic membrane is immersed in liquid paraffin, and a DC voltage of 1kV / mm~5kV / mm is coupled to the copper electrode. Under this condition, polarization is carried out for 2h~5h. After the polarized catalytic membrane is taken out and the copper electrode is removed, it is immersed in anhydrous ethanol at a temperature of 50℃~70℃ for 1h~2h. Finally, the liquid paraffin and anhydrous ethanol are removed by water washing, and then dried to obtain an inorganic piezoelectric catalytic membrane.

[0048] Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the nanocatalytic material in step 1 is a mixture of one or two of a single metal oxide and a composite metal oxide; the single metal oxide is MnO2, TiO2, Fe2O3, FeOOH or Co3O4; the composite metal oxide is ZnAl2O4 or LaMnO3; the diameter of the tourmaline in step 1 is less than or equal to 500nm; the low-temperature binder in step 1 is a mixture of kaolin, potassium feldspar, hydroxypropyl methylcellulose, talc, borax and yellow dextrin, wherein kaolin, potassium feldspar, The mass ratio of hydroxypropyl methylcellulose, talc, borax, and yellow dextrin is 2:1:20:3:4:20; the mass fraction of the nano-piezoelectric material in the raw material mixture described in step 1 is 10% to 50%, the mass fraction of the nano-catalytic material is 10% to 20%, the mass fraction of Al2O3 is 50% to 70%, and the mass fraction of the low-temperature binder is 5% to 10%; the ball milling speed described in step 2 is 400 rpm to 800 rpm, and the ball milling time is 4 hours to 6 hours; the dry pressing time described in step 2 is 5 minutes to 10 minutes; and the calcination time described in step 2 is 4 hours to 6 hours. The other steps are the same as those in the first embodiment.

[0049] Specific embodiment three: This embodiment differs from either specific embodiment one or two in that it utilizes dynamic pulse water pressure to trigger the in-situ piezoelectric effect of an inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of water pollutants, or utilizes ultrasound to trigger the in-situ piezoelectric effect of an inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of water pollutants. The filtration method is cross-flow filtration or dead-end filtration. Other steps are the same as specific embodiments one or two.

[0050] Specific embodiment four: The difference between this embodiment and specific embodiments one to three is that: the filtration method of using the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of water pollutants is cross-flow filtration, and the water treatment device includes a shell 1-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 1-2, an inorganic piezoelectric catalytic membrane 1-3, a pulse water suction pump 1-4 and an oxidant dosing device 1-5; the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 1-2 is respectively connected to the water inlet pipe, the water outlet pipe and the concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane 1-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 1-2, the oxidant dosing device 1-5 is provided on the inorganic piezoelectric catalytic membrane 1-3, and the pulse water suction pump 1-4 is arranged on the concentrated liquid outlet pipe; the oxidant dosing device 1-5 can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate. The other steps are the same as those in the first to third embodiments.

[0051] Specific embodiment five: The difference between this embodiment and specific embodiments one to four is that: the filtration method of using the front-end dynamic pulse water pressure to trigger the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of water pollutants is cross-flow filtration, and the water treatment device includes a shell 2-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 2-2, an inorganic piezoelectric catalytic membrane 2-3, a pulse pressure water pump 2-4 and an oxidant dosing device 2-5; the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 2-2 is respectively connected to the water inlet pipe, the water outlet pipe and the concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane 2-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 2-2, the oxidant dosing device 2-5 is provided on the inorganic piezoelectric catalytic membrane 2-3, and the pulse pressure water pump 2-4 is arranged on the water inlet pipe; the oxidant dosing device 2-5 can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate. The other steps are the same as those in Specific Embodiments 1 to 4.

[0052] Specific embodiment 6: This embodiment differs from specific embodiments 1 to 5 in that: the filtration method for the degradation of pollutants in water by advanced oxidation catalysis is dead-end filtration, using the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane to trigger dynamic pulse water pressure at the front end. The water treatment device includes a housing 3-1, an inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 3-2, an inorganic piezoelectric catalytic membrane 3-3, a pulse pressure water pump 3-4, and an oxidant dosing device 3-5; the inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 3-2 is connected to the water inlet pipe and the water outlet pipe respectively; the inorganic piezoelectric catalytic membrane 3-3 is disposed at the bottom of the inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 3-2; an oxidant dosing device 3-5 is disposed on the inorganic piezoelectric catalytic membrane 3-3; and the pulse pressure water pump 3-4 is disposed on the water inlet pipe; the oxidant dosing device 3-5 can dosing one or a mixture of ozone, H2O2, peracetic acid, periodate, and persulfate. The other steps are the same as specific embodiments 1 to 5.

[0053] Specific embodiment 7: This embodiment differs from specific embodiments 1 to 6 in that the filtration method for the degradation of pollutants in water by advanced oxidation catalysis is dead-end filtration, using the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane to trigger dynamic pulse water pressure at the rear end. The water treatment device includes a housing 4-1, an inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 4-2, an inorganic piezoelectric catalytic membrane 4-3, a pulse water suction pump 4-4, and an oxidant dosing device 4-5. The inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 4-2 is connected to the water inlet pipe and the water outlet pipe respectively. The inorganic piezoelectric catalytic membrane 4-3 is disposed at the bottom of the inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 4-2. The inorganic piezoelectric catalytic membrane 4-3 is provided with an oxidant dosing device 4-5. The pulse water suction pump 4-4 is disposed on the water outlet pipe. The oxidant dosing device 4-5 can add one or a mixture of ozone, H2O2, peracetic acid, periodate, and persulfate. The other steps are the same as specific embodiments 1 to 6.

[0054] Specific embodiment eight: The difference between this embodiment and specific embodiments one to seven is that: ultrasound is used to trigger the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of pollutants in water; the filtration method is cross-flow filtration, and the water treatment device includes a shell 5-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2, an inorganic piezoelectric catalytic membrane 5-3, an oxidant dosing device 5-4 and an ultrasonic device; the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2 is respectively connected to the water inlet pipe, the water outlet pipe and the concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane 5-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2, and an oxidant dosing device 5-4 is provided on the inorganic piezoelectric catalytic membrane 5-3, and the ultrasonic device is arranged outside the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2; the oxidant dosing device 5-4 can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate. The other steps are the same as those in Specific Embodiments 1 to 7.

[0055] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that: it utilizes ultrasound to trigger the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of water pollutants; the filtration method is dead-end filtration, and the water treatment device includes a device housing 6-1, an inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 6-2, an inorganic piezoelectric catalytic membrane 6-3, an oxidant dosing device 6-4, and an ultrasonic device; the inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 6-2 is connected to the water inlet and outlet pipes respectively; the inorganic piezoelectric catalytic membrane 6-3 is disposed below the inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 6-2, an oxidant dosing device 6-4 is disposed on the inorganic piezoelectric catalytic membrane 6-3, and the ultrasonic device is disposed outside the inorganic piezoelectric catalytic membrane-coupled advanced oxidation technology reaction chamber 6-2; the oxidant dosing device 6-4 can dosing one or a mixture of ozone, H2O2, peracetic acid, periodate, and persulfate. Other steps are the same as specific embodiments 1 to 8.

[0056] Specific embodiment 10: The difference between this embodiment and specific embodiments 1 to 9 is that the power of the ultrasound is 0.3W / cm 2 ~0.53W / cm 2 The operating pressure of the inorganic piezoelectric catalytic membrane is ≤2 bar. The pollutants are sulfamethoxazole, 2,4-D, bisphenol A, or rhodamine B. The removal rates for sulfamethoxazole are 98% to 99.9%, for 2,4-D are 95% to 99.8%, for bisphenol A are 92.5% to 99.3%, and for rhodamine B are 95.5% to 99.8%. The other steps are the same as those in Specific Embodiments 1 to 9.

[0057] In the embodiment, the oxidant dosing device (1-5, 2-5, 3-5, 4-5, 5-4, 6-4) adds ozone as the oxidant, and the dosage of ozone is 1 mg / L to 100 mg / L;

[0058] The oxidant dosing device (1-5, 2-5, 3-5, 4-5, 5-4, 6-4) adds H2O2 as the oxidant, and the amount of H2O2 added is 5% to 10%;

[0059] The oxidant added by the oxidant dosing device (1-5, 2-5, 3-5, 4-5, 5-4, 6-4) is peracetic acid, and the dosage of peracetic acid is 0.5 mg / L to 200 mg / L;

[0060] The oxidant added by the oxidant dosing device (1-5, 2-5, 3-5, 4-5, 5-4, 6-4) is periodate, and the dosage of periodate is 0.1mM to 20mM;

[0061] The oxidant added by the oxidant adding device (1-5, 2-5, 3-5, 4-5, 5-4, 6-4) is persulfate, and the dosage of the persulfate is 0.1mM to 20mM.

[0062] The following examples are used to verify the beneficial effects of the present invention:

[0063] Example 1: A method for preparing an inorganic piezoelectric catalytic film is specifically completed by the following steps:

[0064] 1. Evenly mixing the nano-piezoelectric material, the nano-catalytic material, Al2O3 and the low-temperature binder in a certain proportion to obtain a raw material mixture;

[0065] The nano-piezoelectric material described in step 1 is tourmaline, with a diameter less than or equal to 500 nm;

[0066] The nanocatalytic material described in step 1 is MnO2;

[0067] The low-temperature binder described in step 1 is a mixture of kaolin, potassium feldspar, hydroxypropyl methylcellulose, talc, borax and yellow dextrin, wherein the mass ratio of kaolin, potassium feldspar, hydroxypropyl methylcellulose, talc, borax and yellow dextrin is 2:1:20:3:4:20;

[0068] The raw material mixture in step 1 has a mass fraction of 30% of nano-piezoelectric material, a mass fraction of 10% of nano-catalytic material, a mass fraction of 50% of Al2O3, and a mass fraction of 10% of low-temperature binder;

[0069] Second, the raw material mixture was ball-milled at 500 rpm for 5 h, then dry-pressed at 50 kPa for 8 min, and finally calcined at 800 ° C for 5 h to obtain a catalytic film;

[0070] 3. Polarization:

[0071] The top and bottom of the catalytic membrane were connected to copper electrodes respectively, and then the catalytic membrane was immersed in liquid paraffin, and a 3kV / mm DC voltage was coupled to the copper electrode. Under this condition, the polarized catalytic membrane was taken out and the copper electrode was removed. Then, the membrane was immersed in anhydrous ethanol at a temperature of 60°C for 1 hour. Finally, it was washed with ultrapure water three times to remove the liquid paraffin and anhydrous ethanol, and dried to obtain an inorganic piezoelectric catalytic membrane (denoted as Tml@CM).

[0072] The piezoelectric properties of the inorganic piezoelectric catalytic film were characterized by piezoresponse force microscopy (PFM). Figure 1 )show;

[0073] Figure 1 The piezoelectric butterfly curve and phase hysteresis loop of the inorganic piezoelectric catalytic film prepared in Example 1;

[0074] Figure 1 Amplitude is amplitude, Phase is phase;

[0075] from Figure 1 It can be seen that the maximum height difference of the inorganic piezoelectric catalytic membrane prepared in Example 1 is 167.1 nm, which is lower than the height difference of ordinary ceramic membranes (greater than 300 nm), indicating that the addition of tourmaline makes the membrane surface smoother.

[0076] Figure 2 This is a surface morphology of the inorganic piezoelectric catalytic film prepared in Example 1;

[0077] from Figure 2 It can be seen that the surface of the inorganic piezoelectric catalytic film is relatively smooth.

[0078] Phase and amplitude diagram of the inorganic piezoelectric catalytic film prepared in Example 1 ( Figure 3 、 4 ) shows heterogeneous piezoelectric polarization, with contrast changes reflecting the polarization strength and direction of specific domains.

[0079] The bright areas in the phase image of the inorganic piezoelectric catalytic film prepared in Example 1 correspond to the spontaneous ferroelectric polarization areas, while the dark areas indicate the opposite direction.

[0080] Electrostatic potential diagram of the inorganic piezoelectric catalytic film prepared in Example 1 ( Figure 5 ) quantified the local piezoelectric coefficient (d33), calculated as the ratio of amplitude to voltage, confirming the effective electromechanical coupling of the inorganic piezoelectric catalytic film.

[0081] The inorganic piezoelectric catalytic film prepared in Example 1 exhibits a butterfly-shaped amplitude loop and phase lag loop ( Figure 1 The butterfly ring indicates strain reversal under alternating stress, while the phase lag ring shows 180° domain switching under reverse electric field.

[0082] The removal of pollutants by the inorganic piezoelectric catalytic membrane prepared in Example 1 is mainly due to ROS-mediated degradation during the piezoelectric catalytic advanced oxidation process.

[0083] The free radical quenching experiment was carried out on the inorganic piezoelectric catalytic film coupled with advanced oxidation technology prepared in Example 1. Figure 7 As shown in Figure 2, the addition of tert-butyl alcohol (TBA) slightly inhibited the removal of sulfamethoxazole (SMX) (decreased by 8%), indicating that the effect of tert-butyl alcohol was limited. In contrast, the addition of FFA resulted in a significant inhibition (98.8% → 6%), confirming that 1 O2 is the main ROS.

[0084] exist Figure 10-15 Quenching experiments and electron paramagnetic resonance (EPR) spectroscopy were performed on all devices to determine the generation of ROS under ozone conditions. Excess tert-butyl alcohol (TBA) and furfuryl alcohol (FFA) ([quencher] / [O3] molar ratio>10) were used as ·OH and 1 O2 scavenger. The SMX concentration was 5 mg / L, the oxidant was 1 mg / L ozone, and the inorganic piezoelectric catalytic membrane (Tml@CM) prepared in Example 1; in the reaction system, excess TBA only caused a slight decrease in system efficiency (by 6%), which shows that the effect of ·OH on the overall performance is minimal. In addition, the system efficiency dropped significantly after adding FFA (by more than 90%), which proves that 1 O2 dominated the generation of ROS. It was confirmed that the inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology produced ·OH and 1 O2, where 1 O2 plays a leading role.

[0085] The inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology prepared in Example 1 was further used for electron paramagnetic resonance (EPR) analysis to detect reactive oxygen species (ROS) generated in the inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology system. DMPO was used as a scavenger for ·OH, while TEMP was used to capture 1 O2, thus producing a characteristic EPR spectrum. The typical DMPO-·OH signal intensity ratio was observed to be 1:2:2:1, and TEMP- 1The triple O2 signal intensities were equal (1:1:1). These results, combined with the free radical quenching experiments, confirmed that ·OH and 1 The generation of O2, 1 O2 has a selective advantage.

[0086] Example 2: The in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane prepared in Example 1 is triggered by the dynamic pulse water pressure at the rear end to enhance the advanced oxidation catalytic degradation of water pollutants. The filtration method is cross-flow filtration. The water treatment device includes a shell 1-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 1-2, an inorganic piezoelectric catalytic membrane 1-3, a pulse water suction pump 1-4 and an oxidant dosing device 1-5; the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 1-2 is respectively connected to the water inlet pipe, the water outlet pipe and the concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane 1-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 1-2, the oxidant dosing device 1-5 is provided on the inorganic piezoelectric catalytic membrane 1-3, and the pulse water suction pump 1-4 is arranged on the concentrated liquid outlet pipe; the oxidant dosing device 1-5 adds ozone, and the ozone dosage is 1 mg / L.

[0087] Example 3: The in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane prepared in Example 1 is triggered by the front-end dynamic pulse water pressure to enhance the advanced oxidation catalytic degradation of pollutants in water. The filtration method is cross-flow filtration, and the water treatment device includes a shell 2-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 2-2, an inorganic piezoelectric catalytic membrane 2-3, a pulse pressure water pump 2-4 and an oxidant dosing device 2-5; the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 2-2 is respectively connected to the water inlet pipe, the water outlet pipe and the concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane 2-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 2-2, and an oxidant dosing device 2-5 is provided on the inorganic piezoelectric catalytic membrane 2-3, and the pulse pressure water pump 2-4 is arranged on the water inlet pipe; the oxidant dosing device 2-5 adds ozone, and the ozone dosage is 1 mg / L.

[0088] Example 4: The in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane prepared in Example 1 is triggered by the front-end dynamic pulse water pressure to enhance the advanced oxidation catalytic degradation of water pollutants. The filtration method is dead-end filtration. The water treatment device includes a shell 3-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 3-2, an inorganic piezoelectric catalytic membrane 3-3, a pulse pressure water pump 3-4 and an oxidant dosing device 3-5; the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 3-2 is respectively connected to the water inlet pipe and the water outlet pipe; the inorganic piezoelectric catalytic membrane 3-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 3-2, and an oxidant dosing device 3-5 is provided on the inorganic piezoelectric catalytic membrane 3-3, and the pulse pressure water pump 3-4 is arranged on the water inlet pipe; the oxidant dosing device 3-5 adds ozone, and the ozone dosage is 1 mg / L.

[0089] Example 5: The in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane prepared in Example 1 is triggered by the dynamic pulse water pressure at the rear end to enhance the advanced oxidation catalytic degradation of pollutants in water. The filtration method is dead-end filtration. The water treatment device includes a shell 4-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 4-2, an inorganic piezoelectric catalytic membrane 4-3, a pulse water suction pump 4-4 and an oxidant dosing device 4-5; the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 4-2 is respectively connected to the water inlet pipe and the water outlet pipe; the inorganic piezoelectric catalytic membrane 4-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber 4-2, and an oxidant dosing device 4-5 is provided on the inorganic piezoelectric catalytic membrane 4-3, and the pulse water suction pump 4-4 is arranged on the outlet pipe; the oxidant dosing device 4-5 adds ozone, and the ozone dosage is 1 mg / L.

[0090] Example 6: Using ultrasound to trigger the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane prepared in Example 1 to enhance the advanced oxidation catalytic degradation of pollutants in water; the filtration method is cross-flow filtration, and the water treatment device includes a shell 5-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2, an inorganic piezoelectric catalytic membrane 5-3, an oxidant dosing device 5-4 and an ultrasonic device; the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2 is respectively connected to the water inlet pipe, the water outlet pipe and the concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane 5-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2, and an oxidant dosing device 5-4 is provided on the inorganic piezoelectric catalytic membrane 5-3, and the ultrasonic device is arranged outside the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 5-2; the oxidant dosing device 5-4 adds ozone, and the ozone dosage is 1 mg / L.

[0091] Example 7: Using ultrasound to trigger the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane prepared in Example 1 to enhance the advanced oxidation catalytic degradation of pollutants in water; the filtration method is dead-end filtration, and the water treatment device includes a device housing 6-1, an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 6-2, an inorganic piezoelectric catalytic membrane 6-3, an oxidant dosing device 6-4 and an ultrasonic device; the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 6-2 is connected to the water inlet pipe and the water outlet pipe respectively; the inorganic piezoelectric catalytic membrane 6-3 is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 6-2, and an oxidant dosing device 6-4 is provided on the inorganic piezoelectric catalytic membrane 6-3, and the ultrasonic device is arranged outside the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber 6-2; the oxidant dosing device 6-4 adds ozone, and the ozone dosage is 1 mg / L.

[0092] The water treatment device of Example 5 was used to degrade three pollutants, 2,4-D (herbicide), bisphenol A (BPA, phenolic compound) and rhodamine B (Rh B, dye). The original concentration of the three pollutants was 5 mg / L. Ozone was added by the oxidant dosing device 4-5 at a dosage of 1 mg / L. The degradation time was 60 min, and the degradation effect was shown in FIG. Figure 8 As shown;

[0093] Figure 8 Performance diagram of the degradation of 2,4-D, BPA, and RhB using the inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology prepared in Example 1;

[0094] from Figure 8 It can be seen that the removal rates of 2,4-D (herbicide), bisphenol A (BPA, phenolic compound) and rhodamine B (Rh B, dye) reached 95% to 99.8%, 92.5% to 99.3% and 95.5% to 99.8% respectively. These results verify that the inorganic piezoelectric catalytic membrane coupled advanced oxidation technology is driven by continuous piezoelectricity. 1 The versatility of O2 in selectively degrading pollutants with different structures.

[0095] The reusability and stability of the in-situ piezoelectric advanced oxidation catalytic system of inorganic piezoelectric catalytic membrane in the back-end dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology cross-flow filtration, front-end dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology cross-flow filtration, front-end dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology dead-end filtration, back-end dynamic pulse water pressure inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology dead-end filtration, ultrasonic inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology cross-flow filtration, and ultrasonic inorganic piezoelectric catalytic membrane coupled with advanced oxidation technology dead-end filtration were evaluated.

[0096] Five cyclic degradation tests were carried out using the water treatment device of Example 5. The degradation substance was SMX, and the concentration of SMX was 5 mg / L. Ozone was added by the oxidant dosing device 4-5, and the ozone dosage was 1 mg / L. The cyclic degradation was repeated 5 times, and the degradation time for each time was 1 hour. The results showed that the pollutant removal efficiency decreased slightly after cyclic degradation (from 98.9% to 99.9% to 97.8% to 98.3% after 5 cycles).

[0097] The water treatment device of Example 5 was used to conduct a 14-day continuous operation test; the degradation substance was SMX, and the concentration of SMX was 5 mg / L; ozone was added to the oxidant dosing device 4-5, the ozone dosage was 1 mg / L, and the hydraulic retention time was 1 hour; the results showed that: long-term operation ( Figure 9 ) still has an efficiency of ≥97%, confirming the durability of the inorganic piezoelectric catalytic membrane coupled advanced oxidation technology.

[0098] The above specific embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the scope of protection of the present invention. For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes that fall within the meaning and scope of the equivalent elements of the claims are included in the present invention.

Claims

1. A method for preparing an inorganic piezoelectric catalytic film, characterized in that The preparation method is specifically completed according to the following steps:

1. Evenly mixing the nano-piezoelectric material, the nano-catalytic material, Al2O3 and the low-temperature binder in a certain proportion to obtain a raw material mixture; The nano-piezoelectric material described in step 1 is one or a mixture of tourmaline, LiNbO3, LiTaO3, ZnO, BaTiO3, potassium sodium niobate, SrTiO3 and sodium bismuth titanate; 2. Ball milling the raw material mixture for a period of time, dry pressing at 40kPa to 60kPa, and finally calcining at 700°C to 900°C for a period of time to obtain a catalytic film; 3. Polarization: The top and bottom of the catalytic membrane are connected to copper electrodes respectively, and then the catalytic membrane is immersed in liquid paraffin, and a DC voltage of 1kV / mm~5kV / mm is coupled to the copper electrode. Under this condition, polarization is carried out for 2h~5h. After the polarized catalytic membrane is taken out and the copper electrode is removed, it is immersed in anhydrous ethanol at a temperature of 50℃~70℃ for 1h~2h. Finally, the liquid paraffin and anhydrous ethanol are removed by water washing, and then dried to obtain an inorganic piezoelectric catalytic membrane.

2. The method for preparing an inorganic piezoelectric catalytic film according to claim 1, characterized in that The nanocatalytic material described in step 1 is a mixture of one or two of a single metal oxide and a composite metal oxide; the single metal oxide is MnO2, TiO2, Fe2O3, FeOOH or Co3O4; the composite metal oxide is ZnAl2O4 or LaMnO3; the diameter of the tourmaline described in step 1 is less than or equal to 500nm; the low-temperature binder described in step 1 is a mixture of kaolin, potassium feldspar, hydroxypropyl methylcellulose, talc, borax and yellow dextrin, wherein kaolin, potassium feldspar, hydroxypropyl methylcellulose, talc, The mass ratio of borax to yellow dextrin is 2:1:20:3:4:20; the mass fraction of the nano-piezoelectric material in the raw material mixture described in step one is 10% to 50%, the mass fraction of the nano-catalytic material is 10% to 20%, the mass fraction of Al2O3 is 50% to 70%, and the mass fraction of the low-temperature binder is 5% to 10%; the ball milling speed described in step two is 400rpm to 800rpm, and the ball milling time is 4h to 6h; the dry pressing time described in step two is 5min to 10min; and the calcination time described in step two is 4h to 6h.

3. Application of the inorganic piezoelectric catalytic film prepared by the preparation method according to claim 1, characterized in that Dynamic pulse water pressure is used to trigger the in-situ piezoelectric effect of inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of pollutants in water, or ultrasound is used to trigger the in-situ piezoelectric effect of inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of pollutants in water; the filtration method is cross-flow filtration or dead-end filtration.

4. The use of the inorganic piezoelectric catalytic film according to claim 3, characterized in that The invention discloses a cross-flow filtration method for enhancing the filtration of pollutants in water by advanced oxidation catalysis degradation by in-situ piezoelectric effect of an inorganic piezoelectric catalytic membrane triggered by dynamic pulse water pressure at the rear end. The water treatment device comprises a housing (1-1), an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (1-2), an inorganic piezoelectric catalytic membrane (1-3), a pulse water suction pump (1-4) and an oxidant dosing device (1-5); the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (1-2) is respectively connected to a water inlet pipe, a water outlet pipe and a concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane (1-3) is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (1-2); an oxidant dosing device (1-5) is arranged on the inorganic piezoelectric catalytic membrane (1-3); and the pulse water suction pump (1-4) is arranged on the concentrated liquid outlet pipe; the oxidant dosing device (1-5) can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate.

5. The use of the inorganic piezoelectric catalytic film according to claim 3, characterized in that The invention discloses a cross-flow filtration method for enhancing the filtration of pollutants in water by advanced oxidation catalysis degradation by triggering the in-situ piezoelectric effect of an inorganic piezoelectric catalytic membrane by front-end dynamic pulse water pressure. The water treatment device comprises a housing (2-1), an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (2-2), an inorganic piezoelectric catalytic membrane (2-3), a pulse pressure water pump (2-4) and an oxidant dosing device (2-5); the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (2-2) is respectively connected to a water inlet pipe, a water outlet pipe and a concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane (2-3) is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (2-2), an oxidant dosing device (2-5) is arranged on the inorganic piezoelectric catalytic membrane (2-3), and the pulse pressure water pump (2-4) is arranged on the water inlet pipe; the oxidant dosing device (2-5) can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate.

6. The use of the inorganic piezoelectric catalytic film according to claim 3, characterized in that The invention discloses a dead-end filtration method for enhancing the advanced oxidation catalytic degradation of water pollutants by utilizing the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane triggered by the front-end dynamic pulse water pressure. The water treatment device comprises a housing (3-1), an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (3-2), an inorganic piezoelectric catalytic membrane (3-3), a pulse pressure water pump (3-4) and an oxidant dosing device (3-5); the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber (3-2) is respectively connected to the water inlet pipe and the water outlet pipe; the inorganic piezoelectric catalytic membrane (3-3) is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with the advanced oxidation technology reaction chamber (3-2), the oxidant dosing device (3-5) is provided on the inorganic piezoelectric catalytic membrane (3-3), and the pulse pressure water pump (3-4) is arranged on the water inlet pipe; the oxidant dosing device (3-5) can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate.

7. The use of the inorganic piezoelectric catalytic film according to claim 3, characterized in that The invention discloses a dead-end filtration method for enhancing the advanced oxidation catalytic degradation of water pollutants by utilizing the in-situ piezoelectric effect of the inorganic piezoelectric catalytic membrane triggered by the dynamic pulse water pressure at the rear end. The water treatment device comprises a housing (4-1), an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (4-2), an inorganic piezoelectric catalytic membrane (4-3), a pulse water suction pump (4-4) and an oxidant dosing device (4-5); the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (4-2) is respectively connected to a water inlet pipe and a water outlet pipe; the inorganic piezoelectric catalytic membrane (4-3) is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (4-2), an oxidant dosing device (4-5) is provided on the inorganic piezoelectric catalytic membrane (4-3), and the pulse water suction pump (4-4) is arranged on the water outlet pipe; the oxidant dosing device (4-5) can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate.

8. The use of the inorganic piezoelectric catalytic film according to claim 3, characterized in that Ultrasonic triggering of the in-situ piezoelectric effect of an inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of pollutants in water; the filtration method is cross-flow filtration, and the water treatment device comprises a housing (5-1), an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (5-2), an inorganic piezoelectric catalytic membrane (5-3), an oxidant dosing device (5-4) and an ultrasonic device; the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (5-2) is respectively connected to a water inlet pipe, a water outlet pipe and a concentrated liquid outlet pipe; the inorganic piezoelectric catalytic membrane (5-3) is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (5-2), an oxidant dosing device (5-4) is provided on the inorganic piezoelectric catalytic membrane (5-3), and the ultrasonic device is arranged outside the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (5-2); the oxidant dosing device (5-4) can dosing one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate.

9. The use of the inorganic piezoelectric catalytic film according to claim 3, characterized in that Ultrasonic triggering of the in-situ piezoelectric effect of an inorganic piezoelectric catalytic membrane to enhance the advanced oxidation catalytic degradation of pollutants in water; the filtration method is dead-end filtration, and the water treatment device includes a device housing (6-1), an inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (6-2), an inorganic piezoelectric catalytic membrane (6-3), an oxidant dosing device (6-4) and an ultrasonic device; the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (6-2) is respectively connected to a water inlet pipe and a water outlet pipe; the inorganic piezoelectric catalytic membrane (6-3) is arranged at the lower part of the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (6-2), an oxidant dosing device (6-4) is provided on the inorganic piezoelectric catalytic membrane (6-3), and the ultrasonic device is arranged outside the inorganic piezoelectric catalytic membrane coupled with an advanced oxidation technology reaction chamber (6-2); the oxidant dosing device (6-4) can add one or a mixture of several of ozone, H2O2, peracetic acid, periodate and persulfate.

10. The use of the inorganic piezoelectric catalytic film according to claim 3, characterized in that The power of the ultrasound is 0.3W / cm 2 ~0.53W / cm 2 ; The operating pressure of the inorganic piezoelectric catalytic membrane is ≤2 bar; the pollutants are sulfamethoxazole, 2,4-D, bisphenol A or rhodamine B; the removal rate of sulfamethoxazole is 98% to 99.9%, the removal rate of 2,4-D is 95% to 99.8%, the removal rate of bisphenol A is 92.5% to 99.3%, and the removal rate of rhodamine B is 95.5% to 99.8%.

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