WO 3-x Preparation method thereof, 3D printing self-supporting membrane and membrane reactor

Abstract

The present invention relates to a WO 3‑x The present invention successfully prepared a 3D printed self-supporting membrane with rich W by precisely controlling the solvent thermal reaction conditions and the innovative OA / OLA mixed ligand system. 5+ Active sites and ordered oxygen vacancy defects in WO 3‑x Nanomaterials. This invention innovatively utilizes direct writing (DIW) 3D printing technology to successfully construct a three-dimensional self-supporting membrane. This not only provides an efficient, stable, and economical solution for the treatment of antibiotic contamination in aquatic environments, but also opens up new avenues for the design and manufacture of novel functional materials. Its comprehensive performance indicators and application potential significantly surpass existing technologies, enabling industrial application. Furthermore, this technology can be applied in sewage treatment, medical wastewater treatment, and other fields, benefiting environmental protection and public health.

Description

Technical Field

[0001] The present invention relates to the field of environmental protection technology, and in particular to a WO 3-x and a preparation method thereof, a 3D printed self-supporting membrane, and a membrane reactor. Background Art

[0002] In recent years, fluoroquinolone antibiotics (such as ciprofloxacin (CIP)) have been widely used in medicine and animal husbandry due to their broad-spectrum antimicrobial properties. However, their environmental residues are becoming increasingly serious. Therefore, the development of efficient and economical CIP removal technologies has become an urgent need for environmental remediation. Among the numerous treatment technologies, adsorption has attracted considerable attention due to its ease of operation and significant cost-effectiveness. However, existing adsorbent materials still have significant limitations. Traditional adsorbents (such as activated carbon (AC)) suffer from low regeneration efficiency (desorption rate is only 16.9%). Nanocomposites (such as Fe3O4 / GO) offer the advantage of magnetic recovery but are expensive to synthesize. Furthermore, existing adsorption mechanisms primarily rely on physical interactions (such as van der Waals forces and π-π interactions) and are susceptible to interference from environmental pH and ionic strength. While chemical adsorption (such as covalent bonding) offers high stability, its high activation energy limits its practical application. Therefore, the development of new adsorbent materials that combine high adsorption capacity, excellent selectivity, and environmental adaptability is a key research challenge.

[0003] In recent years, tungsten oxide (WO 3-x ) Nanomaterials have shown significant advantages in the field of pollutant treatment due to their unique physical and chemical properties: (1) Abundant surface hydroxyl groups and tunable electronic structures provide active sites for pollutant adsorption; (2) The multivalent state characteristics of tungsten (W4 + / W6 + ) can enhance the specific binding with organic pollutants through coordination; (3) Compared with traditional nanomaterials, WO 3- x has better cost-effectiveness and environmental compatibility. However, powder WO 3-x There are two major challenges in practical applications: (1) the difficulty in efficiently recovering suspended catalysts; and (2) the potential risk of environmental leakage of nanoparticles. Summary of the Invention

[0004] Therefore, the technical problem addressed by this invention is to overcome the shortcomings of existing technologies. The three-dimensional, self-supporting membrane materials constructed using 3D printing technology effectively overcome the limitations of traditional materials and provide a new strategy for achieving efficient and customizable water treatment membrane materials. Furthermore, combined with relevant structural characterization, the key role of the coordination groups on the material's surface was systematically revealed, providing theoretical guidance for the design of high-performance adsorption materials.

[0005] In order to achieve the above purpose,

[0006] The present invention first provides a WO3-x Nanomaterials, WO 3-x Nanomaterials are linear nanomaterials.

[0007] Preferably, the linear nanomaterial has a length of 7 nm to 15 nm and a width of 1 nm to 3 nm.

[0008] The present invention provides a defective WO 3-x The preparation method comprises the following steps:

[0009] S1: Separately measure oleic acid and oleylamine and mix them to obtain solution A; the volume ratio of oleic acid to oleylamine is 20:5 to 20:1;

[0010] S2: Weigh tungsten chloride and add it to solution A, then add anhydrous ethanol and stir under ultrasonication to obtain solution B; the proportion of anhydrous ethanol should be controlled within 10% to 50% of the total volume;

[0011] S3: adding anhydrous ethanol to solution B to obtain solution C; the proportion of anhydrous ethanol is controlled to be 10% to 50% of the total volume;

[0012] S4: reacting solution C at 150° C. to 240° C. to obtain a specific type of product according to the reaction time, and cooling to obtain a reaction solution;

[0013] S5: After washing and drying, the sample was obtained and named WO 3-x Nanomaterials.

[0014] Preferably, the reaction time in S4 is 6 h, that is, WO 3-x - 6h.

[0015] Preferably, S1: 20 mL of oleic acid and 2 mL of oleylamine are respectively measured and placed in a 100 mL beaker, and mixed evenly to obtain solution A;

[0016] S2: Weigh 0.397 g of tungsten chloride and add it to solution A. Then add 5 mL of anhydrous ethanol and stir ultrasonically for 15-30 minutes to obtain solution B.

[0017] S3: Add 5 mL of anhydrous ethanol to solution B to obtain solution C;

[0018] S4: Transfer solution C to a 50 mL polytetrafluoroethylene-lined bottle, then transfer it to a 50 mL reactor, place it in a forced air drying oven, react at 180°C for 1 h, 6 h, or 12 h, and then naturally cool to room temperature to obtain a reaction solution;

[0019] S5: The reaction solution was centrifuged and washed 3-5 times with anhydrous ethanol, the supernatant was discarded, and the sample was dried overnight at 60°C in a vacuum drying oven to obtain a sample named WO 3-x .

[0020] The present invention also provides a 3D printed nano-scale defective WO 3-x A self-supporting film comprising a WO-based 3-x The membrane structure formed by 3D printing, the WO 3-x Prepared by the above method.

[0021] Preferably, the printing material also includes an auxiliary binder, such as attapulgite powder or cellulose powder. 3-x The mass ratio of the WO to the auxiliary material binder is 1:1 to 1:10, and the WO 3-x Mixed with attapulgite powder for 3D printing.

[0022] The present invention also provides a 3D printed nano-scale defective WO 3-x A method for preparing a self-supporting film comprises the following steps:

[0023] S1: WO 3-x Dissolve in water under stirring and mix to obtain solution A;

[0024] S2: Add auxiliary binder to solution A and stir until a uniform slurry is formed;

[0025] S3: Construction and molding through 3D printing strategy;

[0026] S4: After printing, the entire structure is solidified;

[0027] S5: The solidified overall structure is placed in a muffle furnace at 300 to 500 °C to obtain a 3D printed three-dimensional self-supporting film.

[0028] Preferably, the following steps are included:

[0029] S1: Weigh 5.0 g of WO 3-x , dissolved in 50 mL of deionized water under stirring, and ultrasonicated for 1.5-2.0 h to obtain solution A;

[0030] S2: Weigh 45 g of attapulgite powder and gradually add it to solution A under mechanical stirring, and gradually stir until a uniform slurry state is formed;

[0031] S3: Using a monolithic adsorbent to build and shape using a direct writing printing strategy;

[0032] S4: After printing, the entire structure was cured at 25°C for 24 h;

[0033] S5: The solidified overall structure was heated to 400°C in a muffle furnace at a heating rate of 5°C / min and maintained for 240 min to obtain a 3D-printed three-dimensional self-supporting film.

[0034] 3D printed nano-scale defective WO of the present invention 3-x Application of free-standing membranes for selective removal of fluoroquinolone antibiotics.

[0035] The present invention also provides a membrane reactor, comprising:

[0036] The reaction container is divided into an upper space and a lower space, and the three-dimensional self-supporting membrane constructed by 3D printing is located between the upper space and the lower space;

[0037] a back pressure valve, communicating with the upper space;

[0038] a liquid inlet, disposed on one side of the upper space, for inputting liquid to be processed for removing fluoroquinolone antibiotics;

[0039] A liquid outlet is arranged on one side of the lower space, and the liquid outlet is used to discharge the purified liquid.

[0040] Preferably, the top of the upper space is a quartz glass window, one side of the lower space is provided with an observation window, and one side of the lower space is provided with an air outlet; the air outlet is used to be connected to an external vacuum pump.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] In terms of material design and preparation, the present invention successfully prepared a novel OA / OLA mixed ligand system with rich W 5+ Active sites and ordered oxygen vacancy defects in WO 3-x Nanomaterials. XPS analysis confirmed that the optimized WO 3-x W in the material 5+ The high proportion of sites enables it to exhibit excellent adsorption performance for fluoroquinolone antibiotics such as ciprofloxacin, with a removal rate of over 95%. Through systematic TEM, XRD, and FTIR characterization and analysis, it was found that the oxygen vacancy defects formed in the material and the specific surface functional groups are the key structural features that achieve efficient adsorption.

[0043] In terms of material structure design and manufacturing process, this invention innovatively utilizes direct-write (DIW) 3D printing technology to successfully construct a three-dimensional self-supporting membrane. This groundbreaking design fully preserves the active sites of the nanomaterial while effectively addressing the industry's difficulty in recycling nanopowder materials in practical applications. This unique structural design enables the material to simultaneously meet the dual requirements of efficient adsorption and ease of engineering application.

[0044] The successful development of this technology not only provides an efficient, stable, and economical solution for the treatment of antibiotic contamination in aquatic environments, but also opens up new avenues for the design and manufacture of novel functional materials. Its comprehensive performance indicators and application potential significantly surpass existing technologies, making it suitable for industrial application. Furthermore, this technology can be applied in sewage treatment, medical wastewater treatment, and other fields, benefiting environmental protection and public health. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0046] Figure 1 Schematic diagram of the synthesis steps of samples of Examples 1 to 3 of the present invention;

[0047] Figure 2 TEM images of samples of Examples 1 to 3 of the present invention;

[0048] Figure 3 XRD patterns of samples from Examples 1 to 3 of the present invention;

[0049] Figure 4 FTIR spectra of samples of Examples 1 to 3 of the present invention;

[0050] Figure 5 The XPS spectra of samples of Examples 1 to 3 of the present invention are as follows;

[0051] Figure 6 Graphs showing the adsorption performance of samples from Examples 1 to 3 of the present invention;

[0052] Figure 7 This is a schematic diagram of the membrane reactor of the sample of Example 4 of the present invention;

[0053] Figure 8 for Figure 7 Schematic diagram of the internal structure after the middle section;

[0054] Figure 9This is a diagram showing the structure of the sample of Example 4 of the present invention and the CIP removal performance of its membrane reactor. DETAILED DESCRIPTION

[0055] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0056] Reagents and instruments

[0057] Reagent: Cyclohexane (C6H 12 ) and anhydrous ethanol (C2H6O) were purchased from Sinopharm Chemical Reagent Co., Ltd. (China). Tungsten chloride (WCl6), oleic acid (OA), oleylamine (OLA), and ciprofloxacin (CIP) were purchased from Aladdin (Shanghai, China). Attapulgite was purchased from Xuyi Xingchen Molecular Sieve Co., Ltd. All chemical reagents used in the experiments were of analytical grade and were not further purified. Deionized water was used in all experimental procedures.

[0058] Instruments: Transmission electron microscope (TEM, Talos F200X G2), X-ray diffractometer (XRD, BrukerVertex 80V), Fourier transform infrared spectroscopy (FTIR, ThermoFisher Scientific), X-ray photoelectron spectroscopy (XPS, Thermo Scientific Escalab OXi), scanning electron microscope (SEM, JEOL JSM-7800F).

[0059] Example 1

[0060] Defective WO for selective removal of fluoroquinolone antibiotics 3-x The preparation method of (1h) comprises the following steps:

[0061] S1. Measure 20 mL of oleic acid (OA) and 2 mL of oleylamine (OLA) into a 100 mL beaker and mix evenly to obtain solution A.

[0062] S2. Weigh 0.397 g of tungsten chloride (WCl6) and add it to solution A. Then add 5 mL of anhydrous ethanol and stir ultrasonically for 15-30 minutes to obtain solution B.

[0063] S3. Add 5 mL of anhydrous ethanol to solution B to obtain solution C;

[0064] S4. Transfer solution C to a 50 mL polytetrafluoroethylene-lined bottle, then transfer to a 50 mL reactor, place in a forced air drying oven, react at 180° C. for 1 h, and then naturally cool to room temperature to obtain a reaction solution;

[0065] S5. The reaction solution was centrifuged and washed 3-5 times with anhydrous ethanol, the supernatant was discarded, and the sample was dried overnight at 60°C in a vacuum drying oven to obtain a sample named WO. 3-x (1 h).

[0066] Example 2

[0067] The defective WO selectively removes fluoroquinolone antibiotics in this embodiment. 3-x The preparation method of (6 h) is basically the same as that of Example 1, except that the reaction heat time in S4 is 6 h.

[0068] Example 3

[0069] The defective WO selectively removes fluoroquinolone antibiotics in this embodiment. 3-x The preparation method of (12 h) is basically the same as that of Example 1, except that the reaction heat time in S4 is 12 h.

[0070] Example 4

[0071] The method for constructing a three-dimensional self-supporting membrane by 3D printing includes the following steps:

[0072] S1. Weigh 5.0 g of WO 3-x (6 h), dissolved in 50 mL of deionized water under stirring and sonicated for 1.5-2.0 h to obtain solution A;

[0073] S2. Weigh 45 g of attapulgite powder and gradually add it to solution A under mechanical stirring, and gradually stir until a uniform slurry is formed;

[0074] S3, using a monolithic adsorbent to build and shape using a direct writing (DIW) printing strategy;

[0075] S4. After printing, the entire structure was cured at 25°C for 24 h;

[0076] S5. The solidified overall structure was heated to 400°C in a muffle furnace at a heating rate of 5°C / min and maintained for 240 min to obtain a 3D-printed three-dimensional self-supporting film.

[0077] Attapulgite powder is an auxiliary binder. In other embodiments, the auxiliary binder may also be cellulose powder or other suitable materials.

[0078] 1. WO prepared in Examples 1 to 3 3-x (1 h), WO 3-x (6 h) and WO 3-x (12 h) Material synthesis and analysis:

[0079] Figure 1 Outlined i.) WO 3-x (1 h); ii.) WO 3-x (6 h) and ⅲ.) WO 3-x (12 h) Material synthesis route. This synthesis process uses a solvent thermal method and successfully prepares WO with oxygen vacancies through multi-step coordinated regulation. 3-x First, the mixed system of OA and OLA not only acts as a non-polar solvent and surfactant, but also the synergistic coordination between the carboxyl and amine groups can effectively regulate the nucleation of nanocrystals. At the same time, the reducing property of OLA promotes W 6+ Partially reduced to low-valent tungsten. The subsequently added WCl6 precursor undergoes coordination exchange with the ligand to form a tungsten-carboxylate complex, laying the structural foundation for the subsequent crystal phase formation. The experiment innovatively adopted a step-by-step ethanol addition strategy: the first addition initiated the reduction reaction and promoted the dissolution of the precursor, and the reaction uniformity was ensured by vigorous stirring; when the system exhibited a characteristic dark blue color (indicating the localized surface plasmon resonance effect caused by oxygen vacancies), ethanol was added a second time to further regulate the polarity of the reaction system and the passivation of the nanocrystal surface. The final solvothermal process achieved controllable crystal growth in a closed and high-pressure environment. The high temperature conditions not only promoted the desorption of lattice oxygen to form oxygen vacancies, but also adjusted the reaction kinetics to orderly distribute the defect structure, thereby obtaining WO with a stable non-stoichiometric ratio. 3-x Nanomaterials.

[0080] 2. WO prepared in Examples 1 to 3 3-x (1 h), WO 3-x (6 h) and WO 3-x (12 h) Material characterization:

[0081] 2.1. Material Characterization: Transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) were used to characterize the materials. TEM was used to analyze the morphology and microstructure of the samples; XRD was used to analyze the chemical structure of the samples; FTIR was used to analyze the surface groups of the samples, and XPS spectroscopy was used to further analyze and confirm the component elements and elemental states.

[0082] 2.2 Results and Discussion

[0083] (1) Transmission electron microscope (TEM)

[0084] Depend on Figure 2Transmission electron microscopy (TEM) images show that WO 3−x The growth process is from points to lines, and there is a situation where the line disappears after reaching a certain length. 3−x (6 h) ( Figure 2 b) is significantly longer than WO 3−x (1 h) ( Figure 2 a) and WO 3−x (12 h) ( Figure 2 c), which may affect the adsorption performance of the material. In terms of diameter, as time goes by, the diameter of the nanowire becomes shorter, indicating that there may be a quantum confinement effect, and as time goes by, WO 3−x The particle diameter variation range gradually becomes smaller, indicating a more uniform distribution of nanowires. These particle size differences have an important impact on the specific surface area and pore structure of the material, which in turn affects its adsorption performance. 3−x The larger length and better dispersion of WO (6 h) may provide more adsorption sites, which is beneficial to improve the adsorption efficiency and stability. 3−x (6 h) is a more preferred solution, specifically the range of the preferred solution is WO 3−x (6 h ± 1h).

[0085] From the electron microscope TEM, the WO obtained by the present invention 3-x The nanomaterial is a linear nanomaterial, and preferably, the linear nanomaterial has a length of 7 nm to 15 nm and a width of 1 nm to 3 nm.

[0086] (2) XRD was used to analyze the phase structure of the sample, using Cu target Kα radiation and a scanning speed of 7° min −1 , scanning angle 10° - 60°, scanning step 0.07°.

[0087] Figure 3 The XRD patterns of samples 1 to 3 of the present invention are shown in Table 1. All samples have W 18 O 49 The two typical characteristic peaks of W are well maintained. 18 O 49 The basic crystal structure of the original W 18 O 49 The diffraction peaks at 23.5° and 48.2° correspond to the (010) and (020) crystal planes, respectively. The (010) crystal plane reflects the layered arrangement characteristics of the crystal along the b-axis, and the (020) crystal plane is the secondary diffraction peak of the (010) crystal plane, which further confirms the layered characteristics of the crystal structure. 3−xThe diffraction peak intensity at (6 h) is the highest, indicating that at this reaction time, the material achieves optimal crystallinity, a complete and well-ordered crystal structure, and a potential for improved adsorption performance. Furthermore, the diffraction angles of the synthesized materials decrease relative to the original diffraction angles, indicating that an increase in oxygen vacancies in the material leads to lattice expansion and increased interplanar spacing.

[0088] (3) Fourier transform infrared spectroscopy (FTIR)

[0089] Figure 4 The FTIR spectra of the samples of Examples 1 to 3 of the present invention are shown in Figure 1. The obtained materials have a FTIR spectrum of 1000-400 cm −1 The peaks in the spectral region are typical of WO 3−x vibrations, including O−W−O at 726 cm −1 The bending vibration and W−O−W at 819 cm −1 stretching vibrations, and O=W at 925 cm −1 These results confirm that WO 3−x The formation of nanostructures. −1 The absorption peaks at 1605 and 1465 cm-1 belong to the bending vibration of −OH, which can prove the existence of W−OH. −1 The absorption can also be attributed to the stretching vibration of C=O and the bending vibration of C−O. −1 The broad peak at is due to the stretching vibration of O−H and N−H bonds, which may be related to the residual oleic acid and oleylamine on the catalyst surface. These results indicate that the prepared WO 3−x The oxygen-containing functional groups attached to the surface of the nanostructures are beneficial to the dispersion of the nanostructures in water or ethanol media.

[0090] (4) X-ray photoelectron spectroscopy (XPS)

[0091] Depend on Figure 5 The XPS spectra of samples 1 to 3 of Examples 1 to 3 of the present invention are shown in FIG. Figure 5 a, 5b, Figure 5 In a, the peaks at binding energies (BE) of 530.53, 530.00, and 529.77 eV are attributed to WO 3−x (1 h), WO 3−x (6 h) and WO 3−x The peaks at 531.12, 530.68 and 529.51 eV of lattice oxygen of (12 h) are attributed to chemically adsorbed oxygen species. 3−x (6 h) has the highest proportion of adsorbed oxygen, which provides a possibility for improving the adsorption performance of the catalyst. Figure 5 In b), the four peaks correspond to W6+ and W 5+ The W (4f 5 / 2) and W (4f 7 / 2) core levels of cations, WO 3−x (6h) as an example, the binding energy peaks observed at 37.35 and 35.42 eV are consistent with the W 6+ The peaks at 36.27 and 34.16 eV are attributed to W 5+ With the extension of reaction time, the peak positions of W (4f 5 / 2) and W (4f 7 / 2) photoelectron lines move to lower binding energy. 3−x (6 h) W 5+ The highest proportion, this catalyst has more sites for adsorption. However, it can be calculated that WO 3−x W 6+ Peak and W 5+ The energy separation between the peaks is not significantly different, which indicates that WO 3−x There is no phase shift due to the different reaction times. This characterization also shows that WO 3−x (6 h) and ±1h are the preferred options.

[0092] 3. WO prepared in Examples 1 to 4 3-x (1 h), WO 3-x (6 h) and WO 3-x (12 h) The adsorption performance of the material and the 3D-printed three-dimensional self-supporting film was tested. The specific experimental process was as follows: a certain amount of ciprofloxacin standard was weighed and dissolved in deionized water to prepare a 10 mg / L ciprofloxacin aqueous solution as the working solution; 30 mg of WO prepared in Examples 1 to 3 was weighed and dissolved in deionized water to prepare a 10 mg / L ciprofloxacin aqueous solution as the working solution; 3-x (1 h), WO 3-x (6 h) and WO 3-x (12 h) The material was placed in a 100 mL three-necked flask, 50 mL of a 10 mg / L ciprofloxacin aqueous solution was added thereto, and the solutions were placed in a constant temperature water bath at 298 K, 308 K, and 318 K, respectively. After reaching equilibrium, the solution was centrifuged and the residual concentration of CIP (ciprofloxacin) was analyzed by UV spectrophotometry. Batch kinetic studies were similar to the adsorption experiments, and water samples were collected at predetermined time intervals. At each time point, 3 mL of solution was sampled, centrifuged to remove the adsorbent particles, and the absorbance of the supernatant was measured using a Shimadzu UV-2600 spectrophotometer at a wavelength of 272 nm. The adsorption efficiency of CIP ( E ) using the following formula:

[0093] ;

[0094] in, C 0 andC are the concentrations of CIP solution before and after adsorption, A 0 and A are the absorbance values ​​of CIP before and after adsorption, respectively.

[0095] The 3D printed three-dimensional self-supporting membrane in Example 4 was tested in the same manner as described above, except that a suction filtration device was used to contact the membrane with the ciprofloxacin aqueous solution.

[0096] The present invention investigated the adsorption performance of Examples 1 to 3 at three temperatures (25°C, 35°C and 45°C). Figure 6 ac shown, WO 3-x (1 h), WO 3-x (6 h) and WO 3-x The adsorption removal efficiency of CIP reached over 95% within 12 h. Furthermore, it was found that the adsorption capacity increased rapidly between 0 and 30 min due to the high number of collisions between adsorption sites and the CIP solution. However, as adsorption time increased and the number of adsorption sites decreased, the adsorption capacity slowly increased. After 60 min of adsorption, the adsorption capacity remained essentially unchanged, indicating that the surface CIP completely occupied the adsorption sites.

[0097] Figure 7 and Figure 8 Schematic diagram of the membrane reactor of the sample of Example 4 of the present invention.

[0098] The membrane reactor includes a reaction vessel 10, which is divided into an upper space 11 and a lower space 12. The three-dimensional self-supporting membrane 13 constructed by 3D printing in the above embodiment is located between the upper space 11 and the lower space 12.

[0099] The back pressure valve 14 is in communication with the upper space 11;

[0100] A liquid inlet 15 is provided on one side of the upper space 11, and the liquid inlet 15 is used to input liquid to be treated to remove fluoroquinolone antibiotics;

[0101] A liquid outlet 16 is provided on one side of the lower space 12 , and the liquid outlet 16 is used to discharge the purified liquid.

[0102] Preferably, the top of the upper space 11 is a quartz glass window 17, one side of the lower space 12 is provided with an observation window 18, and one side of the lower space 12 is provided with an air outlet 19. The air outlet 19 is used to connect an external vacuum pump to control the pressure difference between the upper and lower layers and control the fluid flow rate.

[0103] The prepared 3D membrane material is integrated into the membrane reactor, and the internal pressure of the container is controlled by the back pressure valve 14 to adjust the reactor fluid flow parameters (such as flow rate, residence time, etc.), optimize the contact efficiency between the pollutants and the membrane surface, and ensure efficient mass transfer and adsorption performance; the reactor has the following advantages: ① Fluid dynamics design of the reaction liquid: by regulating the liquid flow rate and membrane porosity, the mass transfer efficiency of the reactants on the membrane surface is improved; ② Modular design of the reactor: convenient for replacement and reuse of membrane materials, and can be expanded for large-scale water treatment applications.

[0104] Figure 9 The structure of the sample of Example 4 of the present invention and its membrane reactor removal CIP performance diagram. Figure 9 As shown in ac, it was found that adding WO 3-x After (6 h), the pore space of the 3D membrane is occupied, and WO 3-x (6 h) The membrane thickness was 8 µm. Experimental results showed that the material achieved a ciprofloxacin (CIP) removal rate exceeding 95% after just two adsorption cycles. The adsorption efficiency remained stable throughout multiple cycles, with no significant desorption. This property demonstrates the significant application potential and industrial value of this three-dimensional free-standing membrane for the removal of water pollutants.

[0105] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A WO 3-x The method for preparing a nanomaterial is characterized in that: WO with oxygen vacancies was prepared by a solvothermal method through multi-step coordinated regulation. 3-x Nanomaterials, including the following steps: S1: Separately measure oleic acid and oleylamine and mix them to obtain solution A; the volume ratio of oleic acid to oleylamine is 20:5 to 20:1; S2: Weigh tungsten chloride and add it to solution A. Then add anhydrous ethanol and stir it ultrasonically for 15-30 minutes. The tungsten chloride precursor will dissolve and a dark blue solution B will be obtained. The proportion of anhydrous ethanol is controlled at 10%~50% of the total volume; S3: adding anhydrous ethanol to solution B to obtain solution C; S4: reacting solution C at 150°C to 240°C for 6 h ± 1 h to obtain a product, and cooling to obtain a reaction solution; S5: The reaction solution was washed with anhydrous ethanol and then dried to obtain a sample of WO 3-x Nanomaterials.

2. WO according to claim 1 3-x The method for preparing a nanomaterial is characterized in that: S1: Measure 20 mL of oleic acid and 2 mL of oleylamine into a 100 mL beaker and mix evenly to obtain solution A. S2: Weigh 0.397 g of tungsten chloride and add it to solution A. Then add 5 mL of anhydrous ethanol and stir ultrasonically for 15-30 minutes to obtain solution B. S3: Add 5 mL of anhydrous ethanol to solution B to obtain solution C; S4: Transfer solution C to a 50 mL polytetrafluoroethylene-lined bottle, then transfer to a 50 mL reactor, place in a forced air drying oven, react at 180°C for 6 h, and then naturally cool to room temperature to obtain a reaction solution; S5: The reaction solution was centrifuged and washed 3-5 times with anhydrous ethanol, the supernatant was discarded, and the sample was dried overnight at 60°C in a vacuum drying oven to obtain a sample named WO 3-x .

3. A WO 3-x Nanomaterials, characterized in that The WO according to claim 1 or 2 3-x The preparation method of nanomaterials is prepared, WO 3-x Nanomaterials are linear nanomaterials.

4. WO according to claim 3 3-x Nanomaterials, characterized in that The linear nanomaterial has a length of 7 nm to 15 nm and a width of 1 nm to 3 nm.

5. A 3D printed nano-defective WO 3-x A self-supporting film, characterized in that Including WO-based 3-x The membrane structure formed by 3D printing, the WO 3-x WO according to any one of claims 3 to 4 3-x Nanomaterials.

6. The 3D printed nano-defective WO according to claim 5 3-x A self-supporting film, characterized in that The printing material also includes auxiliary material binder, the WO 3-x The mass ratio of the adhesive to the auxiliary material is 1:1 to 1:

10.

7. The 3D printed nano-defective WO according to claim 5 or 6. 3-x Free-standing membranes for selective removal of fluoroquinolone antibiotics.

8. A 3D printed nano-defective WO 3-x A method for preparing a self-supporting film suitable for 3D printing nano-defective WO according to claim 5 or 6 3-x A self-supporting film, characterized in that The following steps are involved: S1:WO 3-x Dissolve in water under stirring and mix to obtain solution A; S2: Add auxiliary binder to solution A and stir until a uniform slurry is formed; S3: Construction and molding through 3D printing strategy; S4: After printing, the entire structure is solidified; S5: The solidified overall structure is placed in a muffle furnace at 300 to 500 °C to obtain a 3D printed three-dimensional self-supporting film.

9. A membrane reactor, characterized in that include: The reaction container is divided into an upper space and a lower space, and the space between the upper space and the lower space is the 3D printed nano-scale defective WO according to claim 5 or 6. 3-x Self-supporting membrane; a back pressure valve, communicating with the upper space; a liquid inlet, provided on one side of the upper space, for inputting liquid to be processed for removing fluoroquinolone antibiotics; A liquid outlet is arranged on one side of the lower space, and the liquid outlet is used to discharge the purified liquid.

10. A membrane reactor according to claim 9, characterized in that: The top of the upper space is a quartz glass window, one side of the lower space is provided with an observation window, and one side of the lower space is provided with an air outlet; the air outlet is used for connecting to an external vacuum pump.

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