A tetragonal BaZr x Ti 1-x O3 ceramic self-cleaning membrane and preparation method thereof

Abstract

The present invention discloses a tetragonal BaZr x Ti 1‑x A method for preparing an O3 ceramic self-cleaning membrane, wherein barium chloride is used as a barium salt, butyl titanate is used as a titanium salt, ethanolamine is used as a reaction chelating agent, and tetragonal zirconium oxide is used as a dopant, and a rotary evaporation method is used to prepare tetragonal BaZr x Ti 1‑x The precursor powder of O3 was used, and polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, propylene glycol, and glycerol were used as film-forming agents. The tetragonal BaZr was prepared by dry pressing and sintering. x Ti 1‑x O3 ceramic self-cleaning membrane; tetragonal BaZr prepared by the present invention x Ti 1‑x The O3 ceramic self-cleaning membrane has a high water flux, a smooth surface and good hydrophilicity, and an excellent self-cleaning and anti-fouling effect. It can efficiently filter pollutants and prevent pollutant scaling, solving the problem of membrane pore blockage during long-term use of the anti-fouling membrane. This method is low-cost, simple and easy to use, has good repeatability, is green and safe, and is suitable for large-scale production.

Description

Technical Field

[0001] The present invention belongs to the membrane separation technology field, and specifically relates to a tetragonal BaZr x Ti 1-x O3 ceramic self-cleaning membrane and preparation method thereof. Background Art

[0002] Amidst the global push for green development, wastewater treatment has become a major focus of attention worldwide. Numerous approaches have been explored to address wastewater treatment, including photocatalysis, distillation, advanced oxidation processes, electrocoagulation, adsorption, and membrane separation. However, in practice, many of these technologies have been constrained by practical limitations and have been limited in their widespread adoption. Advanced membrane separation technology, designed and refined since the 1960s, has emerged as a cost-effective, scalable solution. While membrane separation offers the advantages of cost-effectiveness, it still faces several challenges. The most significant challenge in membrane separation technology is pore clogging—the accumulation of pollutants on the membrane surface and within its pores, ultimately leading to reduced water flux, reduced filtration performance, and increased operating costs. Methods such as backwashing and chemical cleaning have been used to address pore clogging. While these methods can temporarily restore membrane filtration and antifouling properties, they all have drawbacks. Backwashing can cause structural damage to the membrane and increase economic costs, while chemical cleaning can lead to secondary contamination from chemical reagents. With today's complex and diverse pollutant systems and the problem of pore clogging, static membranes are no longer able to achieve their desired cost-effectiveness. At this time, the development of functional membranes with self-cleaning capabilities has become the focus of solving the problem. Summary of the Invention

[0003] Aiming at the membrane fouling problem existing in membrane separation technology, the present invention provides a tetragonal BaZr x Ti 1-x Preparation method of O3 ceramic self-cleaning membrane, a tetragonal BaZr with high water flux, smooth surface and good hydrophilicity, excellent self-cleaning effect and mechanical properties that meet the requirements is prepared. x Ti 1-x O3 ceramic self-cleaning membrane. The present invention solves the problem of anti-fouling membrane pore clogging and improves its filtration performance. The preparation method is simple and easy, suitable for large-scale production, and the prepared tetragonal BaZr x Ti 1- x O3 ceramic self-cleaning membrane is a promising membrane for sewage pollution treatment.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A tetragonal BaZr x Ti 1-xThe preparation method of the O3 ceramic self-cleaning membrane specifically comprises the following steps:

[0006] Step 1, prepare chelating agent solution

[0007] Weigh the chelating agent and dissolve it in deionized water, stirring until it is completely dissolved to obtain a chelating agent solution;

[0008] Step 2: Prepare barium salt solution

[0009] Weigh BaCl2 and dissolve it in deionized water, stirring until it is completely dissolved to obtain a colorless barium salt solution system;

[0010] Step 3, prepare titanium salt solution

[0011] Weigh C 16 H 36 O4Ti was dissolved in anhydrous ethanol and stirred evenly to obtain a colorless titanium salt solution system;

[0012] Step 4: Prepare alkaline solution

[0013] Weigh KOH and dissolve it in deionized water and stir until the KOH particles are completely dissolved to obtain a colorless alkaline solution;

[0014] Step 5: Prepare barium titanate precursor solution

[0015] Slowly adding the chelating agent solution prepared in step 1 and the barium salt solution prepared in step 2 to the titanium salt solution prepared in step 3, stirring evenly to form a mixed solution system, then adding the alkaline solution prepared in step 4 to the mixed solution system, and finally reacting under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution;

[0016] Step 6: Prepare barium zirconate titanate precursor solution

[0017] Add ZrO2 powder into the BaTiO3 precursor solution prepared in step 5 and stir evenly to obtain BaZr x Ti 1-x O3 precursor solution;

[0018] Step 7, preparation of BaZr x Ti 1-x O3 powder

[0019] The BaZr prepared in step 6 x Ti 1-x The O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction, and the obtained white precipitate was centrifuged and dried to obtain BaZr x Ti 1-x O3 precursor powder; BaZr x Ti 1-xThe O3 precursor powder was placed in an air furnace and calcined at high temperature to obtain tetragonal BaZr x Ti 1-x O3 powder;

[0020] Step 8: Prepare film-forming solution

[0021] Weigh a film-forming agent, dissolve it in deionized water, and stir evenly to obtain a film-forming agent solution, wherein the film-forming agent is any one of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, propylene glycol, and glycerol;

[0022] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane

[0023] Weigh the tetragonal BaZr prepared in step 7 x Ti 1-x O3 powder is placed in a mortar, and the film-forming agent solution prepared in step 8 is dropped into it. After being ground evenly, it is added to a pressure mold and a tablet press is used to form a ceramic film blank. The obtained ceramic blank is placed in an air furnace and calcined at high temperature to obtain tetragonal BaZr x Ti 1-x O3 ceramic membrane; the pressing pressure of the ceramic membrane green body formed by the tablet press is 8Mpa-15Mpa, the pressure holding time is 60s-180s, the high-temperature calcination temperature is 1200℃-1400℃, and the high-temperature calcination time is 1h-4h.

[0024] Furthermore, a magnetic stirrer is used in the stirring process in step 1, step 2, step 3, step 4, step 5, step 6, and step 8.

[0025] Furthermore, the chelating agent in step 1 is ethanolamine.

[0026] Furthermore, the ZrO2 powder in step 6 is tetragonal nanoparticles.

[0027] Furthermore, the rotary evaporation reaction process in step 7 consists of two stages. The reaction conditions of the first stage are: water bath temperature 50°C-60°C, rotary evaporator pressure 142mbar-146mbar, and time 30min-60min; the reaction conditions of the second stage are: water bath temperature 60°C-70°C, rotary evaporator pressure 72mbar-76mbar, and time 90min-120min; the centrifugation process includes three water washes and three alcohol washes; the drying conditions are: the white precipitate is dried in an oven at a drying temperature of 60°C-100°C and a drying time of 12h-36h; BaZr x Ti 1-x The high-temperature calcination temperature of the O3 precursor powder is 800°C-1200°C, and the high-temperature calcination time is 1h-4h.

[0028] According to the above-mentioned tetragonal BaZr x Ti 1-x Preparation method of O3 ceramic self-cleaning membrane prepared by tetragonal BaZr x Ti 1-x O3 ceramic self-cleaning membrane.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The raw materials used in the present invention are inexpensive, readily available, green and pollution-free reagents. The designed synthesis method uses a rotary evaporation device that can be scaled up from experimental to industrial levels to prepare the powder, which is conducive to mass production, has good process stability, is suitable for industrial production, and can promote the commercialization of high-performance ceramic materials.

[0031] (2) The present invention prepares ceramic self-cleaning membranes by traditional dry pressing and sintering method, which is simple and easy to operate, highly repeatable, and compatible with the production lines of most ceramic enterprises. x Ti 1-x The O3 ceramic self-cleaning membrane has low cost, better sewage self-cleaning effect than existing commercial products, and is economical and practical. It can promote the commercialization of high-performance ceramic self-cleaning membranes in sewage treatment.

[0032] (3) The tetragonal BaZr prepared by the present invention x Ti 1-x The O3 ceramic self-cleaning membrane has uniform pore size distribution, smooth surface, strong hydrophilicity, and good piezoelectricity, which can achieve efficient self-cleaning. It can still maintain high water flux in pollutant solution, meeting the requirements of an excellent anti-fouling surface.

[0033] (4) The tetragonal BaZr prepared by the present invention x Ti 1-x O3 ceramic self-cleaning membrane has good mechanical properties and no longer requires traditional support to meet the mechanical performance requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The present invention provides a tetragonal BaZr x Ti 1-x Process flow chart of the preparation method of O3 ceramic self-cleaning membrane.

[0035] Figure 2 The tetragonal BaZr prepared in Example 1 of the present invention x Ti 1-x Schematic diagram of XRD pattern of O3 ceramic self-cleaning membrane;

[0036] Figure 3The tetragonal BaZr prepared in Example 2 of the present invention x Ti 1-x SEM diagram of O3 ceramic self-cleaning membrane;

[0037] Figure 4 The tetragonal BaZr prepared in Example 3 of the present invention x Ti 1-x Schematic diagram of the two-dimensional and three-dimensional morphologies of O3 ceramic self-cleaning membranes;

[0038] Figure 5 The tetragonal BaZr prepared in Example 3 of the present invention x Ti 1-x Schematic diagram of the elastic modulus of the O3 ceramic self-cleaning membrane;

[0039] Figure 6 The tetragonal BaZr prepared in Example 3 of the present invention x Ti 1-x Schematic diagram of the hydrophilic angle of the O3 ceramic self-cleaning membrane;

[0040] Figure 7 The tetragonal BaZr prepared in Example 5 of the present invention x Ti 1-x Macroscopic filtration experiment diagram of O3 ceramic self-cleaning membrane;

[0041] Figure 8 The tetragonal BaZr prepared in Example 3 of the present invention x Ti 1-x Schematic diagram of water flux in BSA-contaminated liquid through O3 ceramic self-cleaning membrane. DETAILED DESCRIPTION

[0042] Here, exemplary embodiments will be described in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Instead, they are only examples consistent with some aspects of the present invention described in detail in the appended claims.

[0043] like Figure 1 As shown, the present invention provides a tetragonal BaZr x Ti 1-x The preparation method of the O3 ceramic self-cleaning membrane specifically comprises the following steps:

[0044] Step 1, preparing a chelating agent solution, weighing 0.05 mol-0.25 mol of a chelating agent (ethanolamine) and dissolving it in 50 mL-250 mL of deionized water, stirring with a magnetic stirrer for 10 min-60 min until completely dissolved to obtain a chelating agent solution;

[0045] Step 2: prepare a barium salt solution by weighing 0.05 mol-0.25 mol BaCl2 and dissolving it in 50 mL-250 mL deionized water. Stir using a magnetic stirrer for 10 min-60 min until it is completely dissolved to obtain a colorless barium salt solution system.

[0046] Step 3: Prepare titanium salt solution, weigh 0.04mol-0.25mol C 16 H 36 O4Ti is dissolved in 30mL-150mL of anhydrous ethanol and stirred using a magnetic stirrer for 10min-60min until uniformly stirred to obtain a colorless titanium salt solution system;

[0047] Step 4: prepare an alkaline solution by weighing 0.3 mol-0.7 mol KOH and dissolving it in 50 mL-100 mL deionized water. Stir using a magnetic stirrer for 10 min-60 min until the KOH particles are completely dissolved to obtain a colorless alkaline solution.

[0048] Step 5: preparing a barium titanate precursor solution, slowly adding the chelating agent solution and the barium salt solution to the titanium salt solution, stirring with a magnetic stirrer for 10-60 minutes, stirring evenly to form a mixed solution system, then adding the alkaline solution to the mixed solution system, and finally reacting under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution;

[0049] Step 6: prepare a barium zirconate titanate precursor solution, add 0.001mol-0.03mol of ZrO2 powder (tetragonal nanoparticles) to the BaTiO3 precursor solution, stir it with a magnetic stirrer for 10min-60min, and stir evenly to obtain BaZr x Ti 1-x O3 precursor solution;

[0050] Step 7, preparation of BaZr x Ti 1-x O3 powder: BaZr x Ti 1-x The O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction. The rotary evaporation reaction process consisted of two stages. The reaction conditions of the first stage were: water bath temperature 50℃-60℃, rotary evaporator pressure 142mbar-146mbar, and time 30min-60min; the reaction conditions of the second stage were: water bath temperature 60℃-70℃, rotary evaporator pressure 72mbar-76mbar, and time 90min-120min; after the rotary evaporation reaction, the obtained white precipitate was centrifuged and dried. The centrifugation process included three water washes and three alcohol washes. The drying conditions were: the white precipitate was dried in an oven at a drying temperature of 60℃-100℃ and a drying time of 12h-36h to obtain BaZrx Ti 1-x O3 precursor powder; the precursor powder is placed in an air furnace and calcined at a high temperature of 800℃-1200℃ and a high temperature calcination time of 1h-4h to obtain tetragonal BaZr x Ti 1-x O3 powder;

[0051] Step 8, preparing a film-forming agent solution, weighing a film-forming agent and dissolving it in deionized water, stirring with a magnetic stirrer for 10 minutes to 60 minutes, and stirring until uniform to obtain a film-forming agent solution; the film-forming agent is any one of polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), propylene glycol, and glycerol, and the mass fraction of the film-forming agent is 2wt% to 8wt%;

[0052] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane: weigh 0.5g-3.0g of tetragonal BaZr x Ti 1-x O3 powder is placed in a mortar, and the film-forming agent solution is dropped into it. After being ground evenly, it is added to a pressure mold and a tablet press is used to form a ceramic film blank. The pressing pressure is 8Mpa-15Mpa and the pressure holding time is 60s-180s. The obtained ceramic blank is then placed in an air furnace for high-temperature calcination at a temperature of 1200℃-1400℃ for 1h-4h. After high-temperature calcination, tetragonal BaZr x Ti 1-x O3 ceramics.

[0053] Example 1

[0054] Step 1: prepare a chelating agent solution by weighing 0.05 mol of ethanolamine and dissolving it in 50 mL of deionized water, and stirring it with a magnetic stirrer for 10 minutes to obtain a chelating agent solution;

[0055] Step 2: Prepare a barium salt solution by weighing 0.05 mol of BaCl2 and dissolving it in 50 mL of deionized water. Stir the mixture using a magnetic stirrer for 10 minutes to obtain a colorless barium salt solution.

[0056] Step 3: Prepare titanium salt solution, weigh 0.048 mol C 16 H 36 O4Ti was dissolved in 30 mL of anhydrous ethanol and stirred for 30 min using a magnetic stirrer to obtain a colorless titanium salt solution system;

[0057] Step 4: prepare an alkaline solution by weighing 0.5 mol of KOH and dissolving it in 100 mL of deionized water. Stir the mixture with a magnetic stirrer for 30 min to obtain a colorless alkaline solution.

[0058] Step 5: Prepare a barium titanate precursor solution, slowly add the chelating agent solution and the barium salt solution to the titanium salt solution, use a magnetic stirrer to stir for 30 minutes, and form a mixed solution system after stirring evenly. Then, add the alkaline solution to the mixed solution system, and finally react under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution.

[0059] Step 6: Prepare a barium zirconate titanate precursor solution. Weigh 0.002 mol of tetragonal ZrO2 nanopowder and add it to the BaTiO3 precursor solution. Stir it with a magnetic stirrer for 60 min to obtain BaZr x Ti 1-x O3 precursor solution.

[0060] Step 7, preparation of BaZr x Ti 1-x O3 powder: BaZr x Ti 1-x The O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation. The parameters for the first stage were: water bath temperature 55°C, rotary evaporator pressure 142 mbar, and time 60 min; the parameters for the second stage were: water bath temperature 65°C, rotary evaporator pressure 74 mbar, and time 120 min. The obtained white precipitate was washed three times with ultrapure water and then three times with anhydrous ethanol. Finally, it was dried in an oven at 60°C for 24 hours to obtain BaZr x Ti 1-x O3 precursor powder; the precursor powder is placed in an air furnace and calcined at a high temperature of 1000 ° C and a holding time of 2 h to obtain tetragonal BaZr x Ti 1-x O3 powder;

[0061] Step 8: Prepare a film-forming agent solution by weighing 2 g of PVA and dissolving it in 100 mL of deionized water. Use a magnetic stirrer to stir for 10 minutes to obtain a film-forming agent solution.

[0062] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane: weigh 2g of tetragonal BaZr x Ti 1-x O3 powder was placed in a mortar, 4 mL of film-forming agent solution was dropped into it, and after being ground evenly, it was added to a pressure mold with a diameter of 25 mm. The pressure was 10 MPa and the pressure was maintained for 90 seconds. A tablet press was used to form a ceramic film blank. The obtained ceramic blank was placed in an air furnace and calcined at a high temperature of 1200 ° C for 2 hours. After calcination, tetragonal BaZr x Ti 1-x O3 ceramic membrane.

[0063] Figure 2 The prepared tetragonal BaZr x Ti 1-x XRD pattern of O3 ceramic self-cleaning membrane. Tetragonal BaZr x Ti 1- x The O3 ceramic self-cleaning membrane is highly consistent with the standard card of tetragonal BaTiO3 (JCPDS NO:05-0626), and a clear characteristic peak of tetragonal BaTiO3 appears at 45°, which proves that the tetragonal BaZr x Ti 1-x O3, further magnification of the characteristic peak at 45° shows that the diffraction peak shifts significantly to the left after doping, proving the success of doping.

[0064] Example 2

[0065] Step 1: prepare a chelating agent solution by weighing 0.05 mol of ethanolamine and dissolving it in 50 mL of deionized water, and stirring it with a magnetic stirrer for 20 minutes to obtain a chelating agent solution;

[0066] Step 2: Prepare a barium salt solution by weighing 0.05 mol of BaCl2 and dissolving it in 50 mL of deionized water. Stir the mixture with a magnetic stirrer for 20 min to obtain a colorless barium salt solution.

[0067] Step 3: Prepare titanium salt solution, weigh 0.045 mol C 16 H 36 O4Ti was dissolved in 30 mL of anhydrous ethanol and stirred for 30 min using a magnetic stirrer to obtain a colorless titanium salt solution system;

[0068] Step 4: prepare an alkaline solution by weighing 0.5 mol of KOH and dissolving it in 100 mL of deionized water. Stir the mixture with a magnetic stirrer for 30 min to obtain a colorless alkaline solution.

[0069] Step 5: Prepare a barium titanate precursor solution, slowly add the chelating agent solution and the barium salt solution to the titanium salt solution, use a magnetic stirrer to stir for 30 minutes, and form a mixed solution system after stirring evenly. Then, add the alkaline solution to the mixed solution system, and finally react under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution.

[0070] Step 6: Prepare a barium zirconate titanate precursor solution. Weigh 0.005 mol of tetragonal ZrO2 nanopowder and add it to the BaTiO3 precursor solution. Stir it with a magnetic stirrer for 45 minutes to obtain BaZr x Ti 1-x O3 precursor solution.

[0071] Step 7, preparation of BaZr x Ti 1-x O3 powder: BaZr x Ti 1-x The O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction, with a water bath temperature of 50°C, a rotary evaporator pressure of 146 mbar, and a reaction time of 60 minutes. The parameters for the second stage were: water bath temperature of 60°C, a rotary evaporator pressure of 76 mbar, and a reaction time of 120 minutes. The obtained white precipitate was washed three times with ultrapure water and then three times with anhydrous ethanol. Finally, it was dried in an oven at 80°C for 12 hours to obtain BaZr x Ti 1-x O3 precursor powder; the precursor powder is placed in an air furnace and calcined at a high temperature of 900 ° C and a holding time of 3 h to obtain tetragonal BaZr x Ti 1-x O3 powder;

[0072] Step 8: Prepare a film-forming agent solution by weighing 2 g of PVP and dissolving it in 100 mL of deionized water. Use a magnetic stirrer to stir for 10 minutes to obtain a film-forming agent solution.

[0073] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane: weigh 2g of tetragonal BaZr x Ti 1-x O3 powder was placed in a mortar, 4 mL of film-forming agent solution was dropped into it, and after being ground evenly, it was added to a pressure mold with a diameter of 25 mm. The pressure was 15 MPa and the holding time was 90 s. A tablet press was used to form a ceramic film blank. The obtained ceramic blank was placed in an air furnace and calcined at a high temperature of 1400 ° C and a holding time of 2 h. After calcination, tetragonal BaZr x Ti 1-x O3 ceramic membrane.

[0074] Figure 3 The prepared tetragonal BaZr x Ti 1-x SEM image of O3 ceramic self-cleaning membrane; Figure 3 (a) The magnification is 1k, and it can be seen that the surface is relatively dense. Figure 3 (b) Magnification is 10k.

[0075] Figure 3 (a) Tetragonal BaZr x Ti 1-x The surface of the O3 ceramic self-cleaning membrane is smooth and flat, without obvious large pores. Figure 3(b) shows that the gaps between particles are small, the particles tend to connect with each other, the grain size is small, and the grain boundaries are blurred. Overall, the tetragonal BaZrxTi1-xO3 ceramic self-cleaning film is smooth, dense, and defect-free.

[0076] Example 3

[0077] Step 1: prepare a chelating agent solution by weighing 0.05 mol of ethanolamine and dissolving it in 50 mL of deionized water, stirring it with a magnetic stirrer for 30 minutes to obtain a chelating agent solution;

[0078] Step 2: prepare a barium salt solution by weighing 0.05 mol of BaCl2 and dissolving it in 50 mL of deionized water. Stir the mixture using a magnetic stirrer for 30 minutes to obtain a colorless barium salt solution.

[0079] Step 3: Prepare titanium salt solution, weigh 0.042 mol C 16 H 36 O4Ti was dissolved in 30 mL of anhydrous ethanol and stirred for 30 min using a magnetic stirrer to obtain a colorless titanium salt solution system;

[0080] Step 4: prepare an alkaline solution by weighing 0.6 mol KOH and dissolving it in 100 mL deionized water. Stir the mixture with a magnetic stirrer for 30 min to obtain a colorless alkaline solution.

[0081] Step 5: Prepare a barium titanate precursor solution, slowly add the chelating agent solution and the barium salt solution to the titanium salt solution, use a magnetic stirrer to stir for 30 minutes, and form a mixed solution system after stirring evenly. Then, add the alkaline solution to the mixed solution system, and finally react under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution.

[0082] Step 6: Prepare a barium zirconate titanate precursor solution. Weigh 0.008 mol of tetragonal ZrO2 nanopowder and add it to the BaTiO3 precursor solution. Stir it with a magnetic stirrer for 40 minutes to obtain BaZr x Ti 1-x O3 precursor solution.

[0083] Step 7, preparation of BaZr x Ti 1-x O3 powder: BaZr x Ti 1-xThe O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction, with a water bath temperature of 60°C, a rotary evaporator pressure of 142 mbar, and a reaction time of 45 minutes. The parameters for the second stage were: a water bath temperature of 65°C, a rotary evaporator pressure of 72 mbar, and a reaction time of 100 minutes. The obtained white precipitate was washed three times with ultrapure water and then three times with anhydrous ethanol. Finally, it was dried in an oven at 60°C for 36 hours to obtain BaZr x Ti 1-x O3 precursor powder; the precursor powder is placed in an air furnace and calcined at a high temperature of 800 ° C and a holding time of 4 h to obtain tetragonal BaZr x Ti 1- x O3 powder;

[0084] Step 8: Prepare a film-forming agent solution by weighing 2 g of PEG and dissolving it in 100 mL of deionized water. Use a magnetic stirrer to stir for 10 minutes to obtain a film-forming agent solution.

[0085] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane: weigh 2g of tetragonal BaZr x Ti 1-x O3 powder was placed in a mortar, 4 mL of film-forming agent solution was dropped into it, and after being ground evenly, it was added to a pressure mold with a diameter of 25 mm. The pressure was 12 MPa and the holding time was 100 s. A tablet press was used to form a ceramic film blank. The obtained ceramic blank was placed in an air furnace and calcined at a high temperature of 1200 ° C and a holding time of 2 h. After calcination, tetragonal BaZr x Ti 1-x O3 ceramic membrane.

[0086] Figure 4 The tetragonal BaZr prepared in this example x Ti 1-x Two-dimensional and three-dimensional morphology of O3 ceramic self-cleaning membrane, tetragonal BaZr x Ti 1-x The two-dimensional and three-dimensional morphologies of the surface of the O3 ceramic self-cleaning membrane are observed. From the two-dimensional morphology, the tetragonal BaZr x Ti 1-x The surface of the O3 ceramic self-cleaning membrane is relatively dense, and there are no macroscopic cracks or defects. The color distribution of the three-dimensional morphology can be used to determine whether the sample surface is flat. x Ti 1-x The surface of the O3 ceramic self-cleaning membrane is smooth, with a surface roughness of 1.714 μm.

[0087] Figure 5The tetragonal BaZr prepared in this example x Ti 1-x Schematic diagram of the elastic modulus of O3 ceramic self-cleaning membrane, for tetragonal BaZr x Ti 1-x The elastic modulus of O3 ceramic self-cleaning membrane was studied to explore its mechanical properties. The elastic modulus can reach 189.552MPa, which has excellent mechanical properties.

[0088] Figure 6 The tetragonal BaZr prepared in this example x Ti 1-x Schematic diagram of the hydrophilic angle of O3 ceramic self-cleaning membrane. It can be seen from the figure that the tetragonal BaZr x Ti 1-x The hydrophilic angle of the O3 ceramic self-cleaning membrane is 0°, and the material is completely wetted and has super hydrophilicity.

[0089] Figure 8 The tetragonal BaZr prepared in this example x Ti 1-x Schematic diagram of water flux in BSA contaminated liquid of O3 ceramic self-cleaning membrane, using three-plate ceramic membrane tester to measure the tetragonal BaZr x Ti 1-x The water flux of O3 ceramic self-cleaning membrane in the polluted liquid was tested to provide the tetragonal BaZr x Ti 1-x The water flux of the O3 ceramic self-cleaning membrane did not change significantly within 1 hour and could still maintain a high water flux. However, under constant pressure conditions, the flux dropped to 0 within 30 minutes and no longer had the membrane separation function. x Ti 1-x O3 ceramic self-cleaning membrane has good self-cleaning effect and can realize the treatment of pollutants.

[0090] Example 4

[0091] Step 1: prepare a chelating agent solution by weighing 0.1 mol of ethanolamine and dissolving it in 100 mL of deionized water, and stirring it with a magnetic stirrer for 10 minutes to obtain a chelating agent solution;

[0092] Step 2: Prepare a barium salt solution by weighing 0.1 mol of BaCl2 and dissolving it in 100 mL of deionized water. Stir the mixture with a magnetic stirrer for 10 minutes to obtain a colorless barium salt solution.

[0093] Step 3: Prepare titanium salt solution, weigh 0.09 mol C 16 H 36 O4Ti was dissolved in 60 mL of anhydrous ethanol and stirred for 30 min using a magnetic stirrer to obtain a colorless titanium salt solution system;

[0094] Step 4: prepare an alkaline solution by weighing 0.4 mol of KOH and dissolving it in 100 mL of deionized water. Stir the mixture with a magnetic stirrer for 30 min to obtain a colorless alkaline solution.

[0095] Step 5: Prepare a barium titanate precursor solution, slowly add the chelating agent solution and the barium salt solution to the titanium salt solution, use a magnetic stirrer to stir for 30 minutes, and form a mixed solution system after stirring evenly. Then, add the alkaline solution to the mixed solution system, and finally react under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution.

[0096] Step 6: Prepare a barium zirconate titanate precursor solution. Weigh 0.01 mol of tetragonal ZrO2 nanopowder and add it to the BaTiO3 precursor solution. Stir it with a magnetic stirrer for 40 minutes to obtain BaZr x Ti 1-x O3 precursor solution.

[0097] Step 7, preparation of BaZr x Ti 1-x O3 powder: BaZr x Ti 1-x The O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction, with a water bath temperature of 60°C, a rotary evaporator pressure of 143 mbar, and a reaction time of 50 min. The parameters for the second stage were: water bath temperature of 70°C, a rotary evaporator pressure of 72 mbar, and a reaction time of 90 min. The obtained white precipitate was washed three times with ultrapure water and then three times with anhydrous ethanol. Finally, it was dried in an oven at 60°C for 24 h to obtain BaZr x Ti 1-x O3 precursor powder; the precursor powder is placed in an air furnace and calcined at a high temperature of 1100 ° C and a holding time of 2 h to obtain tetragonal BaZr x Ti 1-x O3 powder;

[0098] Step 8: Prepare a film-forming agent solution by weighing 3 g of PVP and dissolving it in 100 mL of deionized water. Use a magnetic stirrer to stir for 10 minutes to obtain a film-forming agent solution.

[0099] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane: weigh 3g of tetragonal BaZr x Ti 1-xO3 powder was placed in a mortar, 5 mL of film-forming agent solution was dropped into it, and after being ground evenly, it was added to a pressure mold with a diameter of 25 mm. The pressure was 8 MPa and the holding time was 150 s. A tablet press was used to form a ceramic membrane blank. The obtained ceramic blank was placed in an air furnace and calcined at a high temperature of 1200 ° C for 2 h. After calcination, tetragonal BaZr x Ti 1-x O3 ceramic membrane.

[0100] Example 5

[0101] Step 1: prepare a chelating agent solution by weighing 0.15 mol of ethanolamine and dissolving it in 100 mL of deionized water, and stirring it with a magnetic stirrer for 15 minutes to obtain a chelating agent solution;

[0102] Step 2: Prepare a barium salt solution by weighing 0.15 mol of BaCl2 and dissolving it in 100 mL of deionized water. Stir the mixture with a magnetic stirrer for 15 minutes to obtain a colorless barium salt solution.

[0103] Step 3: Prepare titanium salt solution, weigh 0.144 mol C 16 H 36 O4Ti was dissolved in 100 mL of anhydrous ethanol and stirred for 15 min using a magnetic stirrer to obtain a colorless titanium salt solution system;

[0104] Step 4: prepare an alkaline solution by weighing 0.7 mol of KOH and dissolving it in 100 mL of deionized water. Stir the mixture with a magnetic stirrer for 30 min to obtain a colorless alkaline solution.

[0105] Step 5: Prepare a barium titanate precursor solution, slowly add the chelating agent solution and the barium salt solution to the titanium salt solution, use a magnetic stirrer to stir for 45 minutes, and form a mixed solution system after stirring evenly. Then, add the alkaline solution to the mixed solution system, and finally react under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution.

[0106] Step 6: Prepare a barium zirconate titanate precursor solution. Weigh 0.006 mol of tetragonal ZrO2 nanopowder and add it to the BaTiO3 precursor solution. Stir it with a magnetic stirrer for 45 minutes to obtain BaZr x Ti 1-x O3 precursor solution.

[0107] Step 7, preparation of BaZr x Ti 1-x O3 powder: BaZr x Ti 1-xThe O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction, with a water bath temperature of 55°C, a rotary evaporator pressure of 144 mbar, and a reaction time of 60 min. The parameters for the second stage were: water bath temperature of 65°C, a rotary evaporator pressure of 72 mbar, and a reaction time of 100 min. The obtained white precipitate was washed three times with ultrapure water and then three times with anhydrous ethanol. Finally, it was dried in an oven at 100°C for 12 h to obtain BaZr x Ti 1-x O3 precursor powder; the precursor powder is placed in an air furnace and calcined at a high temperature of 1200 ° C and a holding time of 3 h to obtain tetragonal BaZr x Ti 1-x O3 powder;

[0108] Step 8: Prepare a film-forming agent solution by weighing 8 g of propylene glycol and dissolving it in 100 mL of deionized water. Use a magnetic stirrer to stir for 30 minutes to obtain a film-forming agent solution.

[0109] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane: weigh 3g of tetragonal BaZr x Ti 1-x O3 powder was placed in a mortar, 6 mL of film-forming agent solution was dropped into it, and after being ground evenly, it was added to a pressure mold with a diameter of 25 mm. The pressure was 12 MPa and the holding time was 120 s. A tablet press was used to form a ceramic film blank. The obtained ceramic blank was placed in an air furnace and calcined at a high temperature of 1400 ° C and a holding time of 1 h. After calcination, tetragonal BaZr x Ti 1-x O3 ceramic membrane.

[0110] Figure 7 The tetragonal BaZr prepared in this example x Ti 1-x Macroscopic filtration experiment diagram of O3 ceramic self-cleaning membrane. x Ti 1-x The O3 ceramic self-cleaning membrane was used to filter Oil Red O dye. This macroscopic filtration experiment simulates the filter material's ability to filter actual oily pollutants. The Oil Red O dye exhibited a vibrant red color, making the filtration effect visible at a macroscopic level. Figure 7 The filtrate on the left is deep red before filtration, while the filtrate on the right is after filtration through the self-cleaning membrane. The filtrate's transparency is significantly improved after filtration through the self-cleaning membrane, becoming essentially clear overall. This demonstrates the membrane's effective retention of pollutants and excellent filtration performance. The left side of the membrane above shows the membrane before filtration, while the right side shows the membrane after filtration. The reddened surface also demonstrates the effective retention of Oil Red O.

[0111] Example 6

[0112] Step 1: prepare a chelating agent solution by weighing 0.05 mol of ethanolamine and dissolving it in 50 mL of deionized water, stirring it with a magnetic stirrer for 30 minutes to obtain a chelating agent solution;

[0113] Step 2: prepare a barium salt solution by weighing 0.05 mol of BaCl2 and dissolving it in 50 mL of deionized water. Stir the mixture using a magnetic stirrer for 30 minutes to obtain a colorless barium salt solution.

[0114] Step 3: Prepare titanium salt solution, weigh 0.042 mol C 16 H 36 O4Ti was dissolved in 50 mL of anhydrous ethanol and stirred for 30 min using a magnetic stirrer to obtain a colorless titanium salt solution system;

[0115] Step 4: prepare an alkaline solution by weighing 0.45 mol KOH and dissolving it in 100 mL deionized water. Stir the mixture with a magnetic stirrer for 30 min to obtain a colorless alkaline solution.

[0116] Step 5: Prepare a barium titanate precursor solution, slowly add the chelating agent solution and the barium salt solution to the titanium salt solution, use a magnetic stirrer to stir for 30 minutes, and form a mixed solution system after stirring evenly. Then, add the alkaline solution to the mixed solution system, and finally react under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution.

[0117] Step 6: Prepare a barium zirconate titanate precursor solution. Weigh 0.008 mol of tetragonal ZrO2 nanopowder and add it to the BaTiO3 precursor solution. Stir it with a magnetic stirrer for 30 minutes to obtain BaZr x Ti 1-x O3 precursor solution.

[0118] Step 7, preparation of BaZr x Ti 1-x O3 powder: BaZr x Ti 1-x The O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction, with a water bath temperature of 50°C, a rotary evaporator pressure of 145 mbar, and a reaction time of 30 minutes. The parameters for the second stage were: water bath temperature of 70°C, a rotary evaporator pressure of 72 mbar, and a reaction time of 90 minutes. The obtained white precipitate was washed three times with ultrapure water and then three times with anhydrous ethanol. Finally, it was dried in an oven at 80°C for 12 hours to obtain BaZr x Ti 1-xO3 precursor powder; the precursor powder is placed in an air furnace and calcined at a high temperature of 1200 ° C and a holding time of 4 hours to obtain tetragonal BaZr x Ti 1-x O3 powder;

[0119] Step 8: Prepare a film-forming agent solution by weighing 6 g of PEG and dissolving it in 100 mL of deionized water. Use a magnetic stirrer to stir for 10 minutes to obtain a film-forming agent solution.

[0120] Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane: weigh 1g of tetragonal BaZr x Ti 1-x O3 powder was placed in a mortar, 2 mL of film-forming agent solution was dropped into it, and after being ground evenly, it was added to a pressure mold with a diameter of 25 mm. The pressure was 15 MPa and the holding time was 100 s. A tablet press was used to form a ceramic film blank. The obtained ceramic blank was placed in an air furnace and calcined at a high temperature of 1200 ° C and a holding time of 3 h. After calcination, tetragonal BaZr x Ti 1-x O3 ceramic membrane.

[0121] The foregoing description is intended only to provide specific embodiments of the present invention, which will enable those skilled in the art to understand and implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention.

[0122] It should be understood that the present invention is not limited to the above description and that various modifications and changes may be made without departing from the scope thereof. The scope of the present invention is limited only by the appended claims.

Claims

1. A tetragonal BaZr x Ti 1-x The preparation method of O3 ceramic self-cleaning membrane is characterized in that: The specific steps include: Step 1, prepare chelating agent solution Weigh the chelating agent and dissolve it in deionized water, stirring until it is completely dissolved to obtain a chelating agent solution; Step 2: Prepare barium salt solution Weigh BaCl2 and dissolve it in deionized water, stirring until it is completely dissolved to obtain a colorless barium salt solution system; Step 3, prepare titanium salt solution Weigh C 16 H 36 O4Ti was dissolved in anhydrous ethanol and stirred evenly to obtain a colorless titanium salt solution system; Step 4: Prepare alkaline solution Weigh KOH and dissolve it in deionized water and stir until the KOH particles are completely dissolved to obtain a colorless alkaline solution; Step 5: Prepare barium titanate precursor solution Slowly adding the chelating agent solution prepared in step 1 and the barium salt solution prepared in step 2 to the titanium salt solution prepared in step 3, stirring evenly to form a mixed solution system, then adding the alkaline solution prepared in step 4 to the mixed solution system, and finally reacting under alkaline conditions to obtain a turbid liquid system with a colorless upper layer and a white lower layer, thereby obtaining a BaTiO3 precursor solution; Step 6: Prepare barium zirconate titanate precursor solution Add ZrO2 powder into the BaTiO3 precursor solution prepared in step 5 and stir evenly to obtain BaZr x Ti 1-x O3 precursor solution; Step 7, preparation of BaZr x Ti 1-x O3 powder The BaZr prepared in step 6 x Ti 1-x The O3 precursor solution was poured into an eggplant-shaped flask for rotary evaporation reaction, and the obtained white precipitate was centrifuged and dried to obtain BaZr x Ti 1-x O3 precursor powder; BaZr x Ti 1-x The O3 precursor powder was placed in an air furnace and calcined at high temperature to obtain tetragonal BaZr x Ti 1-x O3 powder; Step 8: Prepare film-forming solution Weigh a film-forming agent, dissolve it in deionized water, and stir evenly to obtain a film-forming agent solution, wherein the film-forming agent is any one of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, propylene glycol, and glycerol; Step 9, preparation of BaZr x Ti 1-x O3 ceramic self-cleaning membrane Weigh the tetragonal BaZr prepared in step 7 x Ti 1-x O3 powder is placed in a mortar, and the film-forming agent solution prepared in step 8 is dropped into it. After being ground evenly, it is added to a pressure mold and a tablet press is used to form a ceramic film blank. The obtained ceramic blank is placed in an air furnace and calcined at high temperature to obtain tetragonal BaZr x Ti 1-x O3 ceramic membrane; the pressing pressure of the ceramic membrane green body formed by the tablet press is 8Mpa-15Mpa, the holding time is 60s-180s, the high-temperature calcination temperature is 1200℃-1400℃, and the high-temperature calcination time is 1h-4h.

2. A tetragonal BaZr according to claim 1 x Ti 1-x The preparation method of O3 ceramic self-cleaning membrane is characterized in that: A magnetic stirrer is used in the stirring process in step 1, step 2, step 3, step 4, step 5, step 6, and step 8.

3. A tetragonal BaZr according to claim 1 x Ti 1-x The preparation method of O3 ceramic self-cleaning membrane is characterized in that: The chelating agent in step 1 is ethanolamine.

4. A tetragonal BaZr according to claim 1 x Ti 1-x The preparation method of O3 ceramic self-cleaning membrane is characterized in that: The ZrO2 powder in step 6 is tetragonal nanoparticles.

5. A tetragonal BaZr according to claim 1 x Ti 1-x The preparation method of O3 ceramic self-cleaning membrane is characterized in that: The rotary evaporation reaction process in step 7 consists of two stages. The reaction conditions of the first stage are: water bath temperature 50°C-60°C, rotary evaporator pressure 142 mbar-146 mbar, and time 30 min-60 min; the reaction conditions of the second stage are: water bath temperature 60°C-70°C, rotary evaporator pressure 72 mbar-76 mbar, and time 90 min-120 min; the centrifugation process includes three water washes and three alcohol washes; the drying conditions are: the white precipitate is dried in an oven at a drying temperature of 60°C-100°C and a drying time of 12 h-36 h; BaZr x Ti 1-x The high-temperature calcination temperature of the O3 precursor powder is 800°C-1200°C, and the high-temperature calcination time is 1 h-4 h.

6. A tetragonal BaZr according to any one of claims 1 to 5 x Ti 1-x Preparation method of O3 ceramic self-cleaning membrane prepared by tetragonal BaZr x Ti 1-x O3 ceramic self-cleaning membrane.

Images