A one-step preparation method of hierarchical ordered porous ZrO2 adsorption material with controllable morphology

Abstract

The application belongs to the technical field of adsorbing material preparation, and particularly relates to a one-step preparation method of hierarchical ordered porous ZrO2 adsorbing material with controllable morphology; the application can prepare two kinds of PS microsphere original emulsion with uniform particle size in the particle grading of micron to nanometer, and directly self-assembles into a binary PS colloidal crystal template with controllable morphology without subsequent treatment; in the process, the particle size of the two kinds of PS microspheres is controlled by controlling the adding amount, dropping speed, adding time and reaction time of KPS; the proportion of the two kinds of PS microspheres with different particle sizes is controlled by adjusting the mass ratio of the secondly added styrene monomer and the PS microspheres in the original emulsion; the ZrO2 precursor is mixed with the binary PS colloidal crystal, impregnated, suction filtered and calcined to obtain the hierarchical ordered porous ZrO2 adsorbing material with controllable morphology in the matching of micron to nanometer different pore diameters; the material can realize more accurate filtration of pollutants such as suspended particles with different sizes in water, and has a longer service life and more stable filtration performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adsorbent material preparation, and particularly relates to a one-step preparation method of hierarchical ordered porous ZrO2 adsorbent material with controllable morphology. BACKGROUND

[0002] With the continuous improvement of people's living standards and the increasing emphasis on health, the quality of drinking water has become the focus of social attention. As an effective device for improving the quality of drinking water, the performance of the water purifier is directly related to the safety and health of people's drinking water. The filter core, as the core component of the water purifier, is crucial in material selection. The filter membrane filter core, as a commonly used water treatment filter element, plays an important role in household water purification, industrial liquid separation and purification, and many other aspects. However, the existing filter membrane filter core still has many problems that are difficult to completely solve, such as the need for further improvement of the filtering precision in some harsh application scenarios, the existence of filtering "dead angles" when facing some small particle size and complex nature pollutants, and the inability to achieve comprehensive and accurate interception. Moreover, the filter membrane filter core will inevitably be contaminated after long-term use, which not only leads to a significant decrease in filtration flux, affecting normal water supply efficiency, but also greatly reduces the service life of the filter core, increasing the cost and maintenance workload of frequent filter core replacement.

[0003] In recent years, ZrO2 has attracted widespread attention due to its excellent physical and chemical properties. As an advanced inorganic material, ZrO2 has high hardness, high strength, corrosion resistance, excellent chemical stability, and is not easily eroded by chemicals in water, which can ensure the stability and reliability of the filter core during long-term use. In addition, ZrO2 also has good biocompatibility and does not pose any harm to human health. The use of porous ZrO2 in water purifier filter cores can ensure the safety and health of filtered water, meeting people's demand for high-quality drinking water. Although porous ZrO2 has many advantages, its preparation process is relatively complex and costly. Traditional preparation methods usually include sol-gel method, gel casting method, and vapor deposition method, etc. Although these methods can prepare ZrO2 materials with better performance, the process is more complicated and the production cost is higher. In addition, how to control the pore structure and size of ZrO2 during the preparation process to achieve the best filtering effect is also a technical problem. SUMMARY

[0004] The purpose of the present application is to provide a one-step preparation method of hierarchical ordered porous ZrO2 adsorbent material with controllable morphology, to obtain hierarchical ordered porous ZrO2 adsorbent material with controllable morphology of different pore sizes from micron to nanometer, and to use it in water purifier filter cores to achieve more precise filtration of different sizes of suspended particles and other pollutants in water.

[0005] To achieve the above object, the present application adopts the following technical solutions to achieve the above object:

[0006] In a first aspect, the present application provides a one-step preparation method of hierarchical ordered porous ZrO2 adsorbent material with controllable morphology, which specifically comprises the following steps:

[0007] S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrenesulfonate to form a first mixed solution, performing constant temperature water bath, and deoxidizing under continuous stirring by N2;

[0008] S2: dissolving KPS accounting for 1%-3% of the mass percentage of the styrene monomer in S1 in water to form a KPS solution, adding the KPS solution into the first mixed solution, the dropping time being 15-60 min; performing constant temperature water bath reaction for 7-10 h to form a primary emulsion;

[0009] S3: taking out part of the primary emulsion, measuring the mass ratio of PS microspheres in part of the primary emulsion, obtaining the mass ratio of PS microspheres in the primary emulsion, and thus obtaining the mass of PS microspheres in the primary emulsion; adding styrene monomer into the primary emulsion to form a second mixed solution, performing constant temperature water bath, and deoxidizing under continuous stirring by N2; wherein the mass ratio of the styrene monomer to the PS microspheres in the primary emulsion in S3 is (5-2):1;

[0010] S4: again dissolving KPS accounting for 1%-3% of the mass percentage of the styrene monomer in S3 in water to form a KPS solution, adding the KPS solution into the second mixed solution, the dropping time being 30-90 min; pouring into a crystallization dish after constant temperature water bath reaction, ultrasonic dispersion and drying to obtain binary PS colloidal crystals with controllable morphology;

[0011] S5: mixing and stirring methanol and zirconium acetate to obtain a ZrO2 precursor;

[0012] S6: mixing, impregnating, suction filtering and calcining the ZrO2 precursor and the binary PS colloidal crystals to obtain hierarchical ordered porous ZrO2 adsorbent material with controllable morphology.

[0013] Preferably, the styrene monomer is extracted by NaOH and water respectively before use.

[0014] Preferably, the mass of the potassium bicarbonate in S1 is 1.92% of the mass of the styrene monomer in S1; and the mass of the sodium p-styrenesulfonate in S1 is 0.13% of the mass of the styrene monomer in S1.

[0015] Preferably, the temperature of the constant temperature water bath is 70-80℃.

[0016] Preferably, the time of the constant temperature water bath reaction in S4 is 16-20 h.

[0017] Preferably, the mass ratio of methanol and zirconium acetate in S5 is 1:1.

[0018] Preferably, the mass ratio of the ZrO2 precursor and the binary PS colloidal crystal is (15 ~ 10):1.

[0019] Preferably, the diameter of the crystallization dish is 6 cm.

[0020] In the second aspect, the application provides a hierarchical ordered porous ZrO2 adsorption material with controllable morphology, which is prepared by the preparation method described in the above claims.

[0021] In the third aspect, the application provides an application of the hierarchical ordered porous ZrO2 adsorption material with controllable morphology in the technical field of filter core of water purifiers.

[0022] Compared with the prior art, the application has the following beneficial effects:

[0023] The one-step polymerization method controls the particle size of the two kinds of PS microspheres by controlling the addition amount, dropping speed, addition time and reaction time of KPS; and controls the proportion of the two kinds of PS microspheres with different particle sizes by adjusting the mass ratio of the secondly added styrene monomer and the PS microspheres in the original emulsion, so as to obtain the two kinds of PS microsphere original emulsion with different particle gradations from micron to nanometer. The emulsion does not need subsequent treatment and directly self-assembles to obtain the binary PS colloidal crystal with controllable morphology. The hierarchical ordered porous structure obtained by using the template has more flexible pore size matching, can more accurately filter different sizes of impurities, small particles, bacteria, viruses and other pollutants, and has better filtering performance. The preparation method has simple preparation process, good repeatability and low production cost.

[0024] Secondly, ZrO2 has good chemical stability, which ensures the safety of the filtered water. Compared with the traditional filter core which needs to be frequently replaced, the ZrO2 filter core has higher hardness and wear resistance, longer service life and lower use cost. At the same time, ZrO2 is a strong oxidizing agent and has certain antibacterial performance, which can effectively inhibit the breeding of bacteria on the filter core and reduce the risk of secondary pollution. The application not only has breakthroughs in the performance improvement of the filter core of the water purifier, but also has positive significance in reducing the use cost and improving the resource utilization efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical scheme of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0026] Figure 1 SEM and EDS images of the morphology-controllable hierarchical ordered porous ZrO2 adsorption material prepared in Embodiment 1 of the present application. DETAILED DESCRIPTION

[0027] To enable those skilled in the art to better understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have their usual meanings to those skilled in the art of the present application, and in the event of conflict, the definitions in the specification shall prevail.

[0028] Theories or mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, i.e., the present application can be practiced without regard to any particular theory or mechanism.

[0029] Herein, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, amounts, contents and concentrations, are for the sake of brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0030] Herein, unless otherwise specified, "comprise", "include", "contain", "have" or similar words encompass the meaning of "consist of" and "consist essentially of", for example, "A comprises a" encompasses the meaning of "A comprises a and other" and "A comprises only a".

[0031] Herein, for the sake of brevity, all possible combinations of the various technical features in the various embodiments or examples are not described. Therefore, as long as the combinations of the technical features do not contradict each other, the various technical features in the various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered as the scope of the present specification.

[0032] A first object of the present application is to provide a one-step preparation method of morphology-controllable hierarchical ordered porous ZrO2 adsorption material, which specifically comprises the following steps:

[0033] S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrenesulfonate to form a first mixed solution, performing constant temperature water bath, keeping the water bath temperature at 70-80℃, and deoxidizing with N2 under continuous stirring; wherein the mass of the potassium bicarbonate is 1.92% of the mass of the styrene monomer in S1; the mass of the sodium p-styrenesulfonate in S1 is 0.13% of the mass of the styrene monomer in S1.

[0034] S2: Dissolve potassium persulfate (KPS) accounting for 1%-3% of the mass percentage of the styrene monomer in S1 in hot water (hot water temperature consistent with the water bath temperature in S1) at 70-80℃ to form a KPS solution, and drop the KPS solution into the first mixed solution, with a drop time of 15-60 min; keep the water bath temperature at 70-80℃, stop after constant temperature water bath reaction for 7-10 h, form the original emulsion, and make the original emulsion contain unreacted styrene monomer, potassium bicarbonate, sodium p-styrenesulfonate and KPS, etc.

[0035] S3: Take out part of the original emulsion, measure the mass ratio of polystyrene (PS) microspheres in part of the original emulsion, obtain the mass ratio of PS microspheres in the original emulsion, and thus obtain the mass of PS microspheres in the original emulsion; add styrene monomer to the original emulsion to form a second mixed solution, keep the water bath temperature at 70-80℃, and carry out constant temperature water bath under continuous stirring and N2 deoxidation; wherein the mass ratio of the styrene monomer to the PS microspheres in the original emulsion in S3 is (5-2):1.

[0036] S4: Again dissolve KPS accounting for 1%-3% of the mass percentage of the styrene monomer in S3 in hot water (hot water temperature consistent with the water bath temperature in S3) at 70-80℃ to form a KPS solution, and drop the KPS solution into the second mixed solution, with a drop time of 30-90 min; pour into a Φ6 cm crystallizing dish after constant temperature water bath reaction for 16-20 h, and obtain morphology controllable binary PS colloidal crystals after ultrasonic dispersion and drying;

[0037] S5: Mix methanol and zirconium acetate at a mass ratio of 1:1 and stir to obtain a ZrO2 precursor.

[0038] S6: Mix the ZrO2 precursor and the binary PS colloidal crystals at a mass ratio of (15-10):1, after impregnation and suction filtration, calcine at 600-750℃, control the heating rate at 1-1.5℃ / min, and obtain morphology controllable hierarchical ordered porous ZrO2 adsorbent material.

[0039] The styrene monomers are respectively extracted by NaOH and water before use.

[0040] The present application uses KPS as an initiator, potassium bicarbonate as a pH regulator, and sodium p-styrenesulfonate as an emulsifier to prepare a PS microsphere primary emulsion with two particle sizes of micron to nanometer size grading by one-step polymerization method. The primary emulsion does not need subsequent treatment and is directly self-assembled into binary PS colloidal crystals with controllable morphology. The particle size of the two kinds of PS microspheres is controlled by adjusting the addition amount, dropping speed, addition time and reaction time of KPS. The proportion of the two kinds of PS microspheres with different particle sizes is controlled by adjusting the mass ratio of the second added styrene monomer to the PS microspheres in the primary emulsion. The ZrO2 precursor is mixed with the binary PS colloidal crystals, impregnated, filtered and calcined to obtain a hierarchical ordered porous ZrO2 adsorption material with controllable morphology and a pore size of micron to sub-micron and sub-micron to nanometer. The present application has the advantages of simple preparation process, good repeatability and low production cost.

[0041] The second object of the present application is to provide a hierarchical ordered porous ZrO2 adsorption material with controllable morphology, larger specific surface area and better adsorption performance, which can effectively remove various impurities in water, such as suspended particles, organic matter and heavy metal ions.

[0042] The third object of the present application is to provide an application of the hierarchical ordered porous ZrO2 adsorption material with controllable morphology in the technical field of filter core for water purifiers. The hierarchical ordered porous ZrO2 adsorption material with controllable morphology is mainly used for filter core for water purifiers, which can realize more accurate filtration of pollutants such as suspended particles, colloids, viruses and bacteria with different sizes in water, and has longer service life and more stable filtration performance.

[0043] The present application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. In addition, it should be understood that those skilled in the art can make various modifications or changes to the present application after reading the content taught by the present application, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

[0044] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples are not specified, which are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following examples, unless otherwise specified, conventional commercially available products are used, which are conventional specifications in the art. In the specification of the present application and the following examples, unless otherwise specified, “%” means weight percent, “parts” means weight parts, and the ratio means weight ratio.

[0045] Example 1

[0046] S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate to form a first mixed solution, constant temperature water bath, keeping the water bath temperature at 70℃, deoxidizing with N2 under continuous stirring; wherein the mass of potassium bicarbonate 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.

[0047] S2: dissolving KPS accounting for 1% of the mass percentage of the styrene monomer in S1 in hot water at 70℃ to form a KPS solution, adding the KPS solution into the first mixed solution, the dropping time is 15min; keeping the water bath temperature at 70℃, stopping after constant temperature water bath reaction for 7h, forming the original emulsion, and making the original emulsion contain unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS etc.;

[0048] S3: taking out part of the original emulsion, measuring the mass ratio of PS microspheres in part of the original emulsion, obtaining the mass ratio of PS microspheres in the original emulsion, thereby obtaining the mass of PS microspheres in the original emulsion; adding styrene monomer into the original emulsion to form a second mixed solution, keeping the water bath temperature at 70℃, constant temperature water bath, deoxidizing with N2 under continuous stirring; wherein the mass ratio of styrene monomer in S3 to PS microspheres in the original emulsion is 2:1;

[0049] S4: dissolving KPS accounting for 1%- of the mass percentage of the styrene monomer in S3 in hot water at 70℃ to form a KPS solution, adding the KPS solution into the second mixed solution, the dropping time is 30min; pouring into a Φ6 cm crystallizing dish after constant temperature water bath reaction for 16h, obtaining morphology controllable binary PS colloidal crystal after ultrasonic dispersion and drying;

[0050] S5: mixing methanol and zirconium acetate according to the mass ratio of 1:1 and stirring to obtain ZrO2 precursor;

[0051] S6: mixing the ZrO2 precursor and the binary PS colloidal crystal according to the mass ratio of 10:1, after impregnation and suction filtration, calcining at 600℃, controlling the heating rate at 1℃ / min, obtaining morphology controllable hierarchical ordered porous ZrO2 adsorption material.

[0052] Wherein, the styrene monomer is extracted by NaOH and water before use.

[0053] Example 2

[0054] S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate to form a first mixed solution, carrying out constant temperature water bath, keeping the water bath temperature at 73℃, and deoxidizing by N2 under continuous stirring; wherein the mass of potassium bicarbonate 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.

[0055] S2: dissolving KPS accounting for 1.5% of the mass percentage of the styrene monomer in S1 in hot water at 73℃ to form a KPS solution, adding the KPS solution into the first mixed solution drop by drop, the dropping time being 30 min; keeping the water bath temperature at 73℃, stopping after constant temperature water bath reaction for 8 h, forming a raw emulsion, and making the raw emulsion contain unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS etc.

[0056] S3: taking out part of the raw emulsion, measuring the mass ratio of PS microspheres in part of the raw emulsion, obtaining the mass ratio of PS microspheres in the raw emulsion, thereby obtaining the mass of PS microspheres in the raw emulsion; adding styrene monomer into the raw emulsion to form a second mixed solution, keeping the water bath temperature at 73℃, carrying out constant temperature water bath, and deoxidizing by N2 under continuous stirring; wherein the mass ratio of styrene monomer in S3 to PS microspheres in the raw emulsion is 3:1.

[0057] S4: dissolving KPS accounting for 1.5% of the mass percentage of the styrene monomer in S3 in hot water at 73℃ to form a KPS solution, adding the KPS solution into the second mixed solution drop by drop, the dropping time being 45 min; pouring into a Φ6 cm crystallizing dish after constant temperature water bath reaction for 18 h, and obtaining morphology controllable binary PS colloidal crystals after ultrasonic dispersion and drying;

[0058] S5: mixing methanol and zirconium acetate according to a mass ratio of 1:1 and stirring to obtain ZrO2 precursor;

[0059] S6: mixing the ZrO2 precursor and the binary PS colloidal crystals according to a mass ratio of 12:1, carrying out impregnation and suction filtration, and calcining at 650℃, the control of the heating rate being 1.2℃ / min, to obtain morphology controllable hierarchical ordered porous ZrO2 adsorption material.

[0060] Wherein, the styrene monomer is extracted by NaOH and water respectively before use.

[0061] Example 3

[0062] S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate to form a first mixed solution, constant temperature water bath, keeping the water bath temperature at 75℃, deoxidizing with N2 under continuous stirring; wherein the mass of potassium bicarbonate 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.

[0063] S2: dissolving KPS accounting for 2% of the mass percentage of the styrene monomer in S1 in hot water at 75℃ to form a KPS solution, adding the KPS solution into the first mixed solution, the dropping time is 45min; keeping the water bath temperature at 75℃, stopping after constant temperature water bath reaction for 9h, forming the original emulsion, and making the original emulsion contain unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS etc.;

[0064] S3: taking out part of the original emulsion, measuring the mass ratio of PS microspheres in part of the original emulsion, obtaining the mass ratio of PS microspheres in the original emulsion, thereby obtaining the mass of PS microspheres in the original emulsion; adding styrene monomer into the original emulsion to form a second mixed solution, keeping the water bath temperature at 75℃, constant temperature water bath, deoxidizing with N2 under continuous stirring; wherein the mass ratio of styrene monomer in S3 to PS microspheres in the original emulsion is 4:1;

[0065] S4: dissolving KPS accounting for 2% of the mass percentage of the styrene monomer in S3 in hot water at 75℃ to form a KPS solution, adding the KPS solution into the second mixed solution, the dropping time is 60min; pouring into a Φ6 cm crystallizing dish after constant temperature water bath reaction for 19h, ultrasonic dispersion and drying to obtain the morphology controllable binary PS colloidal crystal;

[0066] S5: mixing methanol and zirconium acetate according to the mass ratio of 1:1 and stirring to obtain ZrO2 precursor;

[0067] S6: mixing the ZrO2 precursor and the binary PS colloidal crystal according to the mass ratio of 13:1, after impregnation and suction filtration, calcining at 700℃, controlling the heating rate at 1.4℃ / min, to obtain the morphology controllable hierarchical ordered porous ZrO2 adsorption material.

[0068] Wherein, the styrene monomer is extracted by NaOH and water before use.

[0069] Example 4

[0070] S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrene sulfonate to form a first mixed solution, carrying out constant temperature water bath, keeping the water bath temperature at 80℃, and deoxidizing by N2 under continuous stirring; wherein the mass of potassium bicarbonate 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.

[0071] S2: dissolving KPS accounting for 3% of the mass percentage of the styrene monomer in S1 in hot water at 80℃ to form a KPS solution, adding the KPS solution into the first mixed solution, the dropping time being 60 min; keeping the water bath temperature at 80℃, stopping after constant temperature water bath reaction for 10 h, forming a raw emulsion, and making the raw emulsion contain unreacted styrene monomer, potassium bicarbonate, sodium p-styrene sulfonate and KPS;

[0072] S3: taking out part of the raw emulsion, measuring the mass ratio of PS microspheres in part of the raw emulsion, obtaining the mass ratio of PS microspheres in the raw emulsion, and thus obtaining the mass of PS microspheres in the raw emulsion; adding styrene monomer into the raw emulsion to form a second mixed solution, keeping the water bath temperature at 80℃, carrying out constant temperature water bath, and deoxidizing by N2 under continuous stirring; wherein the mass ratio of styrene monomer in S3 to PS microspheres in the raw emulsion is 5:1.

[0073] S4: dissolving KPS accounting for 3% of the mass percentage of the styrene monomer in S3 in hot water at 80℃ to form a KPS solution, adding the KPS solution into the second mixed solution, the dropping time being 90 min; pouring into a Φ6 cm crystallizing dish after constant temperature water bath reaction for 20 h, and obtaining morphology-controllable binary PS colloidal crystals after ultrasonic dispersion and drying;

[0074] S5: mixing methanol and zirconium acetate according to a mass ratio of 1:1 and stirring to obtain a ZrO2 precursor.

[0075] S6: mixing the ZrO2 precursor and the binary PS colloidal crystals according to a mass ratio of 15:1, carrying out impregnation and suction filtration, and calcining at 750℃, with the temperature rising rate being controlled at 1.5℃ / min, to obtain morphology-controllable hierarchical ordered porous ZrO2 adsorption material.

[0076] Wherein, the styrene monomer is extracted by NaOH and water respectively before use.

[0077] As shown in FIGS. Figure 1 (a) is an SEM image of the morphology-controllable hierarchical ordered porous ZrO2 adsorption material prepared in Example 1 of the present application; (b) is an EDS image corresponding to the EDS point in (a), and it can be seen that the point only contains C, N, O and Zr elements.

[0078] The above merely describes the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A one-step method for preparing hierarchically ordered porous ZrO2 adsorbent material with controllable morphology, characterized in that, Specifically comprising the following steps: S1: mixing styrene monomer, potassium bicarbonate and sodium p-styrenesulfonate to form a first mixed solution, performing constant temperature water bath, and deoxidizing under continuous stirring by N2; S2: dissolving KPS accounting for 1%-3% of the mass percentage of the styrene monomer in S1 in water to form a KPS solution, adding the KPS solution into the first mixed solution drop by drop, the drop adding time being 15-60 min; performing constant temperature water bath reaction for 7-10 h to form a primary emulsion; S3: taking out part of the primary emulsion, measuring the mass ratio of PS microspheres in the part of the primary emulsion, obtaining the mass ratio of PS microspheres in the primary emulsion, and thus obtaining the mass of PS microspheres in the primary emulsion; adding styrene monomer into the primary emulsion to form a second mixed solution, performing constant temperature water bath, and deoxidizing under continuous stirring by N2; wherein the mass ratio of the styrene monomer to the PS microspheres in the primary emulsion in S3 is (5-2):1; S4: again dissolving KPS accounting for 1%-3% of the mass percentage of the styrene monomer in S3 in water to form a KPS solution, adding the KPS solution into the second mixed solution drop by drop, the drop adding time being 30-90 min; pouring into a crystallization dish after constant temperature water bath reaction, and obtaining morphology-controllable binary PS colloidal crystals after ultrasonic dispersion and drying; S5: mixing and stirring methanol and zirconium acetate to obtain a ZrO2 precursor; S6: mixing, impregnating, suction filtering and calcining the ZrO2 precursor and the binary PS colloidal crystals to obtain morphology-controllable hierarchical ordered porous ZrO2 adsorption material.

2. The one-step method for preparing hierarchically ordered porous Zr02 adsorbent material with controllable morphology according to claim 1, characterized in that, The styrene monomer is respectively extracted by NaOH and water before use.

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

4. The one-step process for preparing hierarchically ordered porous Zr02 adsorbent material with controlled morphology according to claim 1, characterized in that, The temperature of the constant temperature water bath is 70-80℃.

5. The one-step process for the preparation of hierarchically ordered porous Zr02 adsorbent material with controlled morphology as claimed in claim 1, wherein the process is characterized by, The time of the constant temperature water bath reaction in S4 is 16-20 h.

6. The one-step process for preparing hierarchically ordered porous Zr02 adsorbent material with controlled morphology as claimed in claim 1, wherein, The mass ratio of the methanol to the zirconium acetate in S5 is 1:

1.

7. The one-step process for preparing hierarchically ordered porous Zr02 adsorbent material with controlled morphology as claimed in claim 1, wherein the process is characterized by, The mass ratio of the ZrO2 precursor to the binary PS colloidal crystals is (15-10):

1.

8. The one-step process for preparing hierarchically ordered porous Zr02 adsorbent material with controlled morphology as claimed in claim 1, wherein, The diameter of the crystallization dish is 6 cm.

9. A hierarchically ordered porous Zr02 adsorbent material with controllable morphology, characterized in that, The preparation method is prepared by any one of claims 1-8.

10. Application of the morphology-controllable hierarchical ordered porous ZrO2 adsorption material in claim 9 in the technical field of filter core for water purifier.

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