One-step preparation method of morphology-controllable graded ordered porous ZrO2 adsorption material

Abstract

The invention belongs to the technical field of adsorption material preparation, and particularly relates to a one-step preparation method of a morphology-controllable graded ordered porous ZrO2 adsorption material. According to the preparation method, two kinds of PS microsphere primary pulp emulsion with uniform particle size from micron-scale to nano-scale particle size distribution can be prepared, subsequent treatment is not needed, and a binary PS colloidal crystal template with controllable morphology is directly self-assembled; in the process, the particle sizes of the two kinds of PS microspheres are regulated and controlled by controlling the adding amount, the dripping rate, the adding time and the reaction time of KPS; regulating and controlling the proportion of the PS microspheres with two different particle sizes by regulating the mass ratio of the secondarily added styrene monomer to the PS microspheres in the primary pulp emulsion; and mixing a ZrO2 precursor with the binary PS colloidal crystal, dipping, carrying out suction filtration, and calcining to obtain the morphology-controllable graded ordered porous ZrO2 adsorption material with different aperture matching from micron to nano. The material can more accurately filter pollutants such as suspended particles with different sizes in water, and has longer service life and more stable filtering performance.

Description

Technical Field

[0001] The invention belongs to the technical field of adsorption material preparation, and in particular relates to a one-step preparation method of a hierarchical ordered porous ZrO2 adsorption material with controllable morphology. Background Art

[0002] With the continuous improvement of people's living standards and the increasing attention to health, the quality of drinking water has become the focus of social attention. As an effective device to improve the quality of drinking water, the performance of water purifiers is directly related to people's drinking water safety and health. As the core component of the water purifier, the selection of materials for the filter element is crucial. As a commonly used water treatment filter element, the membrane filter element plays an important role in many aspects such as household water purification and industrial liquid separation and purification. However, there are still many problems that are difficult to completely solve in the existing membrane filter element. For example, the filtration accuracy needs to be further improved in some harsh application scenarios. When facing some pollutants with small particle sizes and complex properties, there are still "dead corners" in filtration, and comprehensive and accurate interception cannot be achieved. Moreover, the membrane filter element will inevitably be contaminated after long-term use, which not only leads to a significant decrease in filtration flux and affects the normal water supply efficiency, but also greatly reduces the service life of the filter element. Frequent replacement of the filter element increases the use cost and maintenance workload.

[0003] In recent years, ZrO2 has attracted wide attention due to its excellent physical and chemical properties. As an advanced inorganic material, ZrO2 has the characteristics of high hardness, high strength, corrosion resistance, excellent chemical stability, etc. It is not easily corroded by chemicals in water, and can ensure the stability and reliability of the filter element during long-term use. In addition, ZrO2 also has good biocompatibility and will not cause any harm to human health. The use of porous ZrO2 in the water purifier filter element can ensure that the filtered water is safe and healthy, meeting people's demand for high-quality drinking water. Although porous ZrO2 has many advantages, its preparation process is relatively complicated and costly. Traditional preparation methods usually include sol-gel method, gel casting method, vapor deposition method, etc. Although these methods can prepare ZrO2 materials with better performance, the process is relatively cumbersome and the production cost is high. In addition, how to control the pore structure and size of ZrO2 during the preparation process to achieve the best filtration effect is also a technical problem. Summary of the invention

[0004] The purpose of the present invention is to provide a one-step preparation method of a morphology-controllable hierarchical ordered porous ZrO2 adsorption material, so as to obtain a morphology-controllable hierarchical ordered porous ZrO2 adsorption material with different pore sizes from micron to nanometer scale, which can be used in water purifier filter elements to achieve more accurate filtration of pollutants such as suspended particles of different sizes in water.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: In a first aspect, the present invention provides a one-step preparation method of a hierarchical ordered porous ZrO2 adsorption material with controllable morphology, which specifically comprises the following steps: S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate to form a first mixed solution, placing it in a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; S2: dissolving 1%-3% of KPS by mass in water to form a KPS solution, and adding all of the KPS solution dropwise into the first mixed solution for 15-60 min; reacting in a constant temperature water bath for 7-10 h to form a stock emulsion; S3: taking out a portion of the stock emulsion, measuring the mass ratio of the PS microspheres in the portion of the stock emulsion, and obtaining the mass ratio of the PS microspheres in the stock emulsion, thereby obtaining the mass of the PS microspheres in the stock emulsion; adding styrene monomer to the stock emulsion to form a second mixed solution, placing it in a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; wherein the mass ratio of the styrene monomer to the PS microspheres in the stock emulsion in S3 is (5-2):1; S4: dissolving 1%-3% of the mass percentage of KPS in the styrene monomer described in S3 in water again to form a KPS solution, and dropping all of the KPS solution into the second mixed solution for 30-90 minutes; after reacting in a constant temperature water bath, pouring the solution into a crystallization dish, and obtaining binary PS colloidal crystals with controllable morphology after ultrasonic dispersion and drying; S5: mixing and stirring methanol and zirconium acetate to obtain a ZrO2 precursor; S6: The ZrO2 precursor and binary PS colloidal crystals are mixed, impregnated, filtered and calcined to obtain a hierarchical ordered porous ZrO2 adsorption material with controllable morphology.

[0006] Preferably, the styrene monomer is extracted with NaOH and water respectively before use.

[0007] Preferably, the mass of potassium bicarbonate in S1 is 1.92% of the styrene monomer in S1; the mass of sodium p-styrene sulfonate in S1 is 0.13% of the styrene monomer in S1.

[0008] Preferably, the temperature of the constant temperature water bath is 70-80°C.

[0009] Preferably, the constant temperature water bath reaction time in S4 is 16 to 20 hours.

[0010] Preferably, the mass ratio of methanol to zirconium acetate in S5 is 1:1.

[0011] Preferably, the mass ratio of the ZrO2 precursor to the binary PS colloidal crystals is (15-10):1.

[0012] Preferably, the diameter of the crystallization dish is 6 cm.

[0013] In a second aspect, the present invention provides a hierarchical ordered porous ZrO2 adsorption material with controllable morphology, which is prepared by the preparation method described in the claims above.

[0014] In a third aspect, the present invention provides a morphology-controllable hierarchical ordered porous ZrO2 adsorption material for use in the technical field of water purifier filter elements.

[0015] Compared with the prior art, the present invention has the following beneficial effects: The one-step polymerization method of the present invention controls the particle size of two PS microspheres by controlling the addition amount of KPS, the dripping rate, the addition time and the reaction time; the ratio of two PS microspheres with different particle sizes is controlled by adjusting the mass ratio of the secondary added styrene monomer and the PS microspheres in the stock emulsion, so as to obtain two PS microsphere stock emulsions with uniform particle sizes and different particle gradations from micrometer to nanometer. The emulsion does not need subsequent treatment, and directly self-assembles to obtain binary PS colloidal crystals with controllable morphology. Using this as a template, the obtained hierarchical ordered porous structure has more flexible pore size matching, can more accurately filter impurities, tiny particles, bacteria, viruses and other pollutants of different sizes, and has better filtration performance; the method of the present invention has a simple preparation process, good repeatability and low production cost.

[0016] Secondly, ZrO2 has good chemical stability, which ensures the safety of filtered water. Compared with traditional filter elements that need to be replaced frequently, ZrO2 filter elements have higher hardness and wear resistance, longer service life and lower cost of use. At the same time, ZrO2 is a strong oxidant with certain antibacterial properties, which can effectively inhibit the growth of bacteria on the filter element and reduce the risk of secondary pollution. The present invention not only has a breakthrough in improving the performance of water purifier filter elements, but also has positive significance in reducing use costs and improving resource utilization efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0018] Figure 1 These are the SEM and EDS images of the morphology-controllable hierarchical ordered porous ZrO2 adsorption material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0019] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0020] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0021] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0022] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0023] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0024] The first object of the present invention is to provide a one-step preparation method of a hierarchical ordered porous ZrO2 adsorption material with controllable morphology, which specifically comprises the following steps: S1: Styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate are mixed to form a first mixed solution, and the solution is placed in a constant temperature water bath to maintain the water bath temperature at 70-80° C., and N2 is introduced for deoxygenation under continuous stirring; wherein the mass of the potassium bicarbonate is 1.92% of the styrene monomer described in S1; and the mass of the sodium p-styrene sulfonate described in S1 is 0.13% of the styrene monomer described in S1.

[0025] S2: Dissolve 1%-3% of potassium persulfate (KPS) by mass in hot water at 70-80°C (the temperature of the hot water is consistent with the water bath temperature in S1) to form a KPS solution, and drip all of the KPS solution into the first mixed solution for 15-60 minutes; keep the water bath temperature at 70-80°C, and stop the reaction in a constant temperature water bath after 7-10 hours to form a stock emulsion, and the stock emulsion contains unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS, etc.; S3: taking out a portion of the stock emulsion, measuring the mass ratio of polystyrene (PS) microspheres in the portion of the stock emulsion, and obtaining the mass ratio of PS microspheres in the stock emulsion, thereby obtaining the mass of PS microspheres in the stock emulsion; adding styrene monomer to the stock emulsion to form a second mixed solution, maintaining the water bath temperature at 70-80°C, performing a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; wherein the mass ratio of styrene monomer to PS microspheres in the stock emulsion in S3 is (5-2):1; S4: Dissolve 1%-3% of KPS by mass in hot water at 70-80°C (the temperature of the hot water is consistent with the water bath temperature in S3) to form a KPS solution, and add all of the KPS solution dropwise into the second mixed solution for 30-90 minutes; react in a constant temperature water bath for 16-20 hours, pour into a Φ6 cm crystallization dish, and obtain binary PS colloidal crystals with controllable morphology after ultrasonic dispersion and drying; S5: mixing methanol and zirconium acetate in a mass ratio of 1:1 and stirring to obtain a ZrO2 precursor; S6: The ZrO2 precursor and binary PS colloidal crystals are mixed in a mass ratio of (15 ~10):1, and after impregnation and filtration, they are calcined at 600~750℃, with the heating rate controlled at 1-1.5℃ / min to obtain a hierarchical ordered porous ZrO2 adsorption material with controllable morphology.

[0026] Wherein, the styrene monomer is extracted by NaOH and water respectively before use.

[0027] The present invention uses KPS as an initiator, potassium bicarbonate as a pH regulator, and sodium p-styrene sulfonate as an emulsifier, and adopts a one-step polymerization method to prepare two kinds of PS microsphere stock emulsions with uniform particle sizes from micron to nanometer particle grading. The stock emulsions do not need subsequent treatment and directly self-assemble into binary PS colloidal crystals with controllable morphology. The particle sizes of the two PS microspheres are regulated by controlling the amount of KPS added, the drop rate, the timing of addition, and the reaction time. The ratio of the two PS microspheres with different particle sizes is regulated by adjusting the mass ratio of the secondary added styrene monomer to the PS microspheres in the stock emulsion. After mixing, impregnating, filtering, and calcining a ZrO2 precursor with the binary PS colloidal crystals, a hierarchical ordered porous ZrO2 adsorption material with controllable morphology of micron and submicron, submicron and nanometer pore sizes is obtained. The preparation process of the present invention is simple, repeatable, and has low production cost.

[0028] The second object of the present invention is to provide a hierarchical ordered porous ZrO2 adsorption material with controllable morphology, which has a larger specific surface area and better adsorption performance, and can effectively remove various impurities in water, such as suspended particles, organic matter and heavy metal ions.

[0029] The third purpose of the present invention is to provide a morphology-controllable hierarchical ordered porous ZrO2 adsorption material for use in the field of water purifier filter element technology. The morphology-controllable hierarchical ordered porous ZrO2 adsorption material is mainly used for water purifier filter elements, which can more accurately filter suspended particles, colloids, viruses, bacteria and other pollutants of different sizes in water, and at the same time has a longer service life and more stable filtration performance.

[0030] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0031] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0032] Example 1 S1: Styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate are mixed to form a first mixed solution, which is placed in a constant temperature water bath, the water bath temperature is maintained at 70° C., and N2 is passed through under continuous stirring for deoxygenation; wherein the mass of potassium bicarbonate is 1.92% of the styrene monomer in S1; and the mass of sodium p-styrene sulfonate in S1 is 0.13% of the styrene monomer in S1.

[0033] S2: dissolving KPS accounting for 1% of the mass percentage of the styrene monomer in S1 in hot water at 70°C to form a KPS solution, and dripping all of the KPS solution into the first mixed solution for 15 minutes; maintaining the water bath temperature at 70°C, and stopping the reaction in a constant temperature water bath after 7 hours to form a stock emulsion, and the stock emulsion contains unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS, etc.; S3: taking out part of the stock emulsion, measuring the mass ratio of the PS microspheres in part of the stock emulsion, and obtaining the mass ratio of the PS microspheres in the stock emulsion, thereby obtaining the mass of the PS microspheres in the stock emulsion; adding styrene monomer to the stock emulsion to form a second mixed solution, maintaining the water bath temperature at 70°C, performing a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; wherein, the mass ratio of styrene monomer to PS microspheres in the stock emulsion in S3 is 2:1; S4: Dissolve 1% KPS by mass of the styrene monomer in S3 in hot water at 70°C to form a KPS solution, and drip all of the KPS solution into the second mixed solution for 30 minutes; react in a constant temperature water bath for 16 hours, pour into a Φ6 cm crystallization dish, and obtain binary PS colloidal crystals with controllable morphology after ultrasonic dispersion and drying; S5: mixing methanol and zirconium acetate in a mass ratio of 1:1 and stirring to obtain a ZrO2 precursor; S6: The ZrO2 precursor and binary PS colloidal crystals were mixed in a mass ratio of 10:1, and after impregnation and filtration, they were calcined at 600°C with a heating rate of 1°C / min to obtain a hierarchically ordered porous ZrO2 adsorption material with controllable morphology.

[0034] Wherein, styrene monomer was extracted by NaOH and water respectively before use.

[0035] Example 2 S1: Styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate are mixed to form a first mixed solution, which is placed in a constant temperature water bath, the water bath temperature is maintained at 73° C., and N2 is introduced for deoxygenation under continuous stirring; wherein the mass of potassium bicarbonate is 1.92% of the styrene monomer in S1; and the mass of sodium p-styrene sulfonate in S1 is 0.13% of the styrene monomer in S1.

[0036] S2: dissolving KPS accounting for 1.5% of the mass percentage of styrene monomer in S1 in hot water at 73°C to form a KPS solution, and dripping all the KPS solution into the first mixed solution for 30 minutes; keeping the water bath temperature at 73°C, and stopping the reaction in a constant temperature water bath after 8 hours to form a stock emulsion, and the stock emulsion contains unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS; S3: taking out part of the stock emulsion, measuring the mass ratio of the PS microspheres in part of the stock emulsion, and obtaining the mass ratio of the PS microspheres in the stock emulsion, thereby obtaining the mass of the PS microspheres in the stock emulsion; adding styrene monomer to the stock emulsion to form a second mixed solution, maintaining the water bath temperature at 73°C, performing a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; wherein, the mass ratio of styrene monomer to PS microspheres in the stock emulsion in S3 is 3:1; S4: Dissolve KPS accounting for 1.5% of the mass percentage of styrene monomer in S3 in hot water at 73°C to form a KPS solution, and add all the KPS solution dropwise into the second mixed solution for 45 minutes; after reacting in a constant temperature water bath for 18 hours, pour into a Φ6 cm crystallization dish, and obtain binary PS colloidal crystals with controllable morphology after ultrasonic dispersion and drying; S5: mixing methanol and zirconium acetate in a mass ratio of 1:1 and stirring to obtain a ZrO2 precursor; S6: The ZrO2 precursor and binary PS colloidal crystals were mixed in a mass ratio of 12:1. After impregnation and filtration, they were calcined at 650°C with a heating rate of 1.2°C / min to obtain a hierarchically ordered porous ZrO2 adsorption material with controllable morphology.

[0037] Wherein, styrene monomer was extracted by NaOH and water respectively before use.

[0038] Example 3 S1: Styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate are mixed to form a first mixed solution, which is placed in a constant temperature water bath, the water bath temperature is maintained at 75° C., and N2 is introduced for deoxygenation under continuous stirring; wherein the mass of potassium bicarbonate is 1.92% of the styrene monomer in S1; and the mass of sodium p-styrene sulfonate in S1 is 0.13% of the styrene monomer in S1.

[0039] S2: dissolving KPS accounting for 2% of the mass percentage of the styrene monomer in S1 in hot water at 75°C to form a KPS solution, and dripping all of the KPS solution into the first mixed solution for 45 minutes; maintaining the water bath temperature at 75°C, and stopping the reaction in a constant temperature water bath after 9 hours to form a stock emulsion, and the stock emulsion contains unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS, etc.; S3: taking out part of the stock emulsion, measuring the mass ratio of the PS microspheres in part of the stock emulsion, and obtaining the mass ratio of the PS microspheres in the stock emulsion, thereby obtaining the mass of the PS microspheres in the stock emulsion; adding styrene monomer to the stock emulsion to form a second mixed solution, maintaining the water bath temperature at 75°C, performing a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; wherein, the mass ratio of styrene monomer to PS microspheres in the stock emulsion in S3 is 4:1; S4: Dissolve KPS accounting for 2% of the mass percentage of styrene monomer in S3 in hot water at 75°C to form a KPS solution, and add all the KPS solution dropwise into the second mixed solution for 60 minutes; after reacting in a constant temperature water bath for 19 hours, pour into a Φ6 cm crystallization dish, and obtain binary PS colloidal crystals with controllable morphology after ultrasonic dispersion and drying; S5: mixing methanol and zirconium acetate in a mass ratio of 1:1 and stirring to obtain a ZrO2 precursor; S6: The ZrO2 precursor and binary PS colloidal crystals were mixed in a mass ratio of 13:1, and after impregnation and filtration, they were calcined at 700°C with a heating rate controlled at 1.4°C / min to obtain a hierarchically ordered porous ZrO2 adsorption material with controllable morphology.

[0040] Wherein, styrene monomer was extracted by NaOH and water respectively before use.

[0041] Example 4 S1: Styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate are mixed to form a first mixed solution, which is placed in a constant temperature water bath, the water bath temperature is maintained at 80° C., and N2 is introduced for deoxygenation under continuous stirring; wherein the mass of potassium bicarbonate is 1.92% of the styrene monomer in S1; and the mass of sodium p-styrene sulfonate in S1 is 0.13% of the styrene monomer in S1.

[0042] S2: dissolving KPS accounting for 3% of the mass percentage of the styrene monomer in S1 in hot water at 80°C to form a KPS solution, and dripping all of the KPS solution into the first mixed solution for 60 minutes; keeping the water bath temperature at 80°C, and stopping the reaction in a constant temperature water bath after 10 hours to form a stock emulsion, and the stock emulsion contains unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS; S3: taking out part of the stock emulsion, measuring the mass ratio of the PS microspheres in part of the stock emulsion, and obtaining the mass ratio of the PS microspheres in the stock emulsion, thereby obtaining the mass of the PS microspheres in the stock emulsion; adding styrene monomer to the stock emulsion to form a second mixed solution, maintaining the water bath temperature at 80°C, performing a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; wherein, the mass ratio of styrene monomer to PS microspheres in the stock emulsion in S3 is 5:1; S4: Dissolve KPS accounting for 3% of the mass percentage of styrene monomer in S3 in hot water at 80°C to form a KPS solution, and add all the KPS solution dropwise into the second mixed solution for 90 minutes; after reacting in a constant temperature water bath for 20 hours, pour into a Φ6 cm crystallization dish, and obtain binary PS colloidal crystals with controllable morphology after ultrasonic dispersion and drying; S5: mixing methanol and zirconium acetate in a mass ratio of 1:1 and stirring to obtain a ZrO2 precursor; S6: The ZrO2 precursor and binary PS colloidal crystals were mixed in a mass ratio of 15:1, and after impregnation and filtration, they were calcined at 750°C with a heating rate controlled at 1.5°C / min to obtain a hierarchically ordered porous ZrO2 adsorption material with controllable morphology.

[0043] Wherein, styrene monomer was extracted by NaOH and water respectively before use.

[0044] like Figure 1 As shown, (a) is the SEM image of the morphology-controllable hierarchical ordered porous ZrO2 adsorption material prepared in Example 1 of the present invention; (b) is the EDS image corresponding to the EDS point in (a). It can be seen that this point only contains C, N, O and Zr elements.

[0045] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A one-step preparation method of a hierarchical ordered porous ZrO2 adsorption material with controllable morphology, characterized in that: The specific steps include: S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate to form a first mixed solution, placing it in a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; S2: dissolving 1%-3% of KPS by mass in water to form a KPS solution, and adding all of the KPS solution dropwise into the first mixed solution for 15-60 min; reacting in a constant temperature water bath for 7-10 h to form a stock emulsion; S3: taking out a portion of the stock emulsion, measuring the mass ratio of the PS microspheres in the portion of the stock emulsion, and obtaining the mass ratio of the PS microspheres in the stock emulsion, thereby obtaining the mass of the PS microspheres in the stock emulsion; adding styrene monomer to the stock emulsion to form a second mixed solution, placing it in a constant temperature water bath, and passing N2 for deoxygenation under continuous stirring; wherein the mass ratio of the styrene monomer to the PS microspheres in the stock emulsion in S3 is (5-2):1; S4: dissolving 1%-3% of the mass percentage of KPS in the styrene monomer described in S3 in water again to form a KPS solution, and dropping all of the KPS solution into the second mixed solution for 30-90 minutes; after reacting in a constant temperature water bath, pouring the solution into a crystallization dish, and obtaining binary PS colloidal crystals with controllable morphology after ultrasonic dispersion and drying; S5: mixing and stirring methanol and zirconium acetate to obtain a ZrO2 precursor; S6: The ZrO2 precursor and binary PS colloidal crystals are mixed, impregnated, filtered and calcined to obtain a hierarchical ordered porous ZrO2 adsorption material with controllable morphology.

2. The one-step preparation method of a morphology-controllable hierarchical ordered porous ZrO2 adsorption material according to claim 1, characterized in that: The styrene monomer was extracted with NaOH and water respectively before use.

3. The one-step preparation method of a morphology-controlled hierarchical ordered porous ZrO2 adsorption material according to claim 1, characterized in that: The mass of potassium bicarbonate described in S1 is 1.92% of the styrene monomer described in S1; the mass of sodium p-styrene sulfonate described in S1 is 0.13% of the styrene monomer described in S1.

4. The one-step preparation method of a morphology-controlled hierarchical ordered porous ZrO2 adsorption material according to claim 1, characterized in that: The temperature of the constant temperature water bath is 70-80°C.

5. The one-step preparation method of a morphology-controllable hierarchical ordered porous ZrO2 adsorption material according to claim 1, characterized in that: The reaction time in the constant temperature water bath in S4 is 16 to 20 hours.

6. The one-step preparation method of a morphology-controllable hierarchical ordered porous ZrO2 adsorption material according to claim 1, characterized in that: The mass ratio of methanol to zirconium acetate in S5 is 1:

1.

7. The one-step preparation method of a morphology-controlled hierarchical ordered porous ZrO2 adsorption material according to claim 1, characterized in that: The mass ratio of the ZrO2 precursor to the binary PS colloidal crystal is (15-10):

1.

8. The one-step preparation method of a morphology-controlled hierarchical ordered porous ZrO2 adsorption material according to claim 1, characterized in that: The diameter of the crystallization dish is 6 cm.

9. A morphology-controlled hierarchical ordered porous ZrO2 adsorption material, characterized in that: The method is prepared by the preparation method according to any one of claims 1 to 8.

10. Application of the morphology-controllable hierarchical ordered porous ZrO2 adsorption material according to claim 9 in the field of water purifier filter technology.

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