Ytterbium-based fluoride multi-chamber nanomaterial and its preparation method and application

Abstract

The present invention belongs to the technical field of dye wastewater adsorption, and specifically relates to an ytterbium-based fluoride multi-chamber nanomaterial, its preparation method, and application. The preparation method of the ytterbium-based fluoride multi-chamber nanomaterial comprises the following steps: (1) mixing ytterbium acetate and water to obtain an ytterbium acetate aqueous solution; (2) mixing praseodymium acetate and water to obtain a praseodymium acetate aqueous solution; (3) adding the praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution, stirring evenly, then dropwise adding a sodium fluoride solution, and hydrothermally reacting at room temperature; (4) centrifuging the mixed solution obtained in step (3), taking the precipitate, washing it, and finally freeze-drying it to obtain the ytterbium-based fluoride multi-chamber nanomaterial. The ytterbium-based fluoride multi-chamber nanomaterial of the present invention has a small diameter, a large pore size, and many defects. It can provide multiple adsorption sites, effectively increase the contact area between the pollutant and the adsorbent, and can achieve rapid and efficient adsorption and removal of pollutants in dye wastewater.

Description

Technical Field

[0001] The invention belongs to the technical field of dye wastewater adsorption, and particularly relates to an ytterbium-based fluoride multi-chamber nanomaterial, a preparation method and an application thereof. Background Art

[0002] Refractory dye wastewater poses a significant threat to human, animal, and plant health and safety, as well as to ecosystems. Among all methods for treating refractory wastewater, adsorption has attracted widespread attention due to its low investment, minimal footprint, simple operation, and ability to remove refractory pollutants from wastewater. However, traditional adsorption technologies suffer from numerous drawbacks in practical applications, such as the high amount of adsorbent material (adsorbent), high cost, slow adsorption rate, and limited adsorption capacity. To address these challenges, the development of adsorbents with fast adsorption rates and high adsorption capacities has become a key area of ​​research in this field.

[0003] Chinese invention patent publication number CN113896220B discloses a mixed matrix membrane modulated by porous cerium fluoride nanosheets, its preparation method, and applications, belonging to the field of gas separation membrane technology. Specifically, the invention discloses a porous cerium fluoride nanosheet composed of fluorine-cerium monoatomic layers with alternating acetate groups stacked between the layers. The fluorine-cerium monoatomic layers consist of fluorine and cerium atoms arranged in a six-membered honeycomb pattern. Furthermore, the invention provides a mixed matrix membrane modulated by porous cerium fluoride nanosheets, comprising the aforementioned porous cerium fluoride nanosheets and a polymer matrix. The invention also provides methods for preparing the porous cerium fluoride nanosheets and a mixed matrix membrane modulated by the porous cerium fluoride nanosheets, both of which are simple to operate. The invention utilizes a polymer matrix membrane filled with porous cerium fluoride nanosheets for gas dehumidification / humidification, preferentially permeating water vapor and exhibiting high water vapor separation performance. However, the patent describes a two-dimensional nanosheet material, which has a completely different morphological structure from ytterbium-based fluoride multi-chamber nanomaterials, and does not disclose its application in the adsorption of dye wastewater. Summary of the Invention

[0004] In view of the shortcomings of the existing methods, the present invention provides an ytterbium-based fluoride multi-chamber nanomaterial and its preparation method and application, which can achieve rapid and efficient adsorption and removal of pollutants in dye wastewater.

[0005] To achieve the above purpose, the present invention adopts the following technical means:

[0006] A method for preparing an ytterbium-based fluoride multi-chamber nanomaterial comprises the following steps:

[0007] (1) mixing ytterbium acetate and water to obtain an ytterbium acetate aqueous solution;

[0008] (2) mixing praseodymium acetate and water to obtain a praseodymium acetate aqueous solution;

[0009] (3) adding praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution, stirring evenly, then adding sodium fluoride solution dropwise, and conducting hydrothermal reaction at room temperature;

[0010] (4) Centrifuging the mixed solution obtained from the reaction in step (3), taking the precipitate, washing it, and finally freeze-drying it to obtain the ytterbium-based fluoride multi-chamber nanomaterial.

[0011] Preferably, the mass ratio of ytterbium acetate to water in step (1) is 1:5~30.

[0012] Preferably, the mass ratio of praseodymium acetate to water in step (2) is 1:5-30.

[0013] Preferably, the volume ratio of the ytterbium acetate aqueous solution to the praseodymium acetate aqueous solution in step (3) is 1:1-10.

[0014] Preferably, the concentration of the sodium fluoride solution in step (3) is 0.5-5 g / L, and the volume ratio of the sodium fluoride solution to the total volume of the ytterbium acetate aqueous solution and the praseodymium acetate aqueous solution is 0.1-2:1.

[0015] Preferably, the room temperature hydrothermal reaction time in step (3) is 12 to 24 hours.

[0016] Preferably, the freeze-drying temperature in step (4) is -60 to -70°C, and the time is 12 to 14 hours.

[0017] An ytterbium-based fluoride multi-chamber nanomaterial prepared by the preparation method.

[0018] Preferably, the diameter of the nanomaterial is 30-100 nm, and the pore size is 3-20 nm.

[0019] The invention discloses an application of the ytterbium-based fluoride multi-chamber nanomaterial prepared by the preparation method in adsorbing dye wastewater pollutants.

[0020] The positive beneficial effects of the present invention are:

[0021] 1. The present invention uses ytterbium acetate and praseodymium acetate as raw materials, water as solvent, and sodium fluoride as a fluorine source. A room-temperature hydrothermal synthesis reaction is performed. After the reaction is completed, the ytterbium-based praseodymium fluoride multi-chamber nanomaterial is obtained after centrifugation, washing, and freeze-drying. The preparation method is simple, does not require any additional templates or surfactants, is environmentally friendly, can be mass-produced, and is suitable for the adsorption and removal of pollutants in dye wastewater.

[0022] 2. The ytterbium-based fluoride multi-chamber nanomaterial obtained in the present invention has a diameter of 30-100 nm and a pore size of 3-20 nm. Its small diameter and large pore size, as well as the presence of many defects, can provide multiple adsorption sites, effectively increasing the contact area between pollutants and adsorbents, and can achieve rapid and efficient adsorption and removal of pollutants in dye wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a scanning transmission electron microscope-high-angle dark field image of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in Example 1.

[0024] Figure 2 This is a high-magnification transmission electron microscope photograph of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in Example 1.

[0025] Figure 3 This is a graph showing the adsorption performance of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in Example 1 for pollutants in Congo red dye.

[0026] Figure 4 This is a high-magnification transmission electron microscope photograph of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in Example 2.

[0027] Figure 5 This is a graph showing the adsorption performance of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in Example 2 for pollutants in Congo red dye.

[0028] Figure 6 This is a high-magnification transmission electron microscope photograph of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in Example 3.

[0029] Figure 7 This is a graph showing the adsorption performance of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in Example 3 for pollutants in Congo red dye. DETAILED DESCRIPTION

[0030] The present invention is further described below with reference to some specific embodiments.

[0031] Example 1

[0032] A method for preparing an ytterbium-based fluoride multi-chamber nanomaterial comprises the following steps:

[0033] (1) mixing ytterbium acetate and water in a mass ratio of 1:10 to obtain an ytterbium acetate aqueous solution;

[0034] (2) mixing praseodymium acetate and water in a mass ratio of 1:10 to obtain a praseodymium acetate aqueous solution;

[0035] (3) Add praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution described in step (1) at a volume ratio of 1:1, stir for 30 minutes, then dropwise add sodium fluoride solution with a concentration of 1 g / L, the volume ratio of sodium fluoride solution to the total volume of ytterbium acetate aqueous solution and praseodymium acetate aqueous solution being 0.1:1, and stir for another 12 hours;

[0036] (4) The mixed solution obtained from the reaction in step (3) was centrifuged, the precipitate was collected, washed with ethanol, and finally freeze-dried at -60°C for 12 h to obtain the ytterbium-based praseodymium fluoride multi-chamber nanomaterial.

[0037] Figure 1 and Figure 2 These are high-angle dark field and high-magnification transmission electron micrographs of the obtained product, respectively. It can be seen that there are a large number of cavities in the ytterbium-based praseodymium fluoride multi-chamber nanomaterial. The diameter of the material is 50 nm and the pore size is 5-15 nm.

[0038] The ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in this example was used to study the adsorption of Congo red dye wastewater. The specific experimental conditions were as follows: the volume of the dye wastewater was 10 ml, the concentration was 200 mg / L, the pH was 7.00, and the mass of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial required was 0.01 g.

[0039] The adsorption study results are as follows Figure 3 As shown in the figure, the sample can remove 80.05% of Congo red dye within 10 min, and the adsorption capacity is as high as 1600 mg / g.

[0040] Example 2

[0041] A method for preparing an ytterbium-based fluoride multi-chamber nanomaterial comprises the following steps:

[0042] (1) mixing ytterbium acetate and water in a mass ratio of 1:30 to obtain an ytterbium acetate aqueous solution;

[0043] (2) mixing praseodymium acetate and water in a mass ratio of 1:5 to obtain a praseodymium acetate aqueous solution;

[0044] (3) Add praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution described in step (1) at a volume ratio of 1:3, stir for 30 minutes, and then dropwise add sodium fluoride solution with a concentration of 0.5 g / L, with the volume ratio of sodium fluoride solution to the total volume of ytterbium acetate aqueous solution and praseodymium acetate aqueous solution being 2:1, and stir for another 12 hours;

[0045] (4) The mixed solution obtained from the reaction in step (3) was centrifuged, the precipitate was collected, washed with ethanol, and finally freeze-dried at -70°C for 12 h to obtain the ytterbium-based praseodymium fluoride multi-chamber nanomaterial.

[0046] Figure 4This is a high-magnification transmission electron micrograph of the obtained product. It can be seen that there are a large number of cavities in the ytterbium-based praseodymium fluoride multi-chamber nanomaterial. The diameter of the material is 50 nm and the pore size is 4-10 nm.

[0047] The adsorption of Congo red by the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in this example was studied under the following experimental conditions: the volume of dye wastewater was 20 ml, the concentration was 100 mg / L, the pH was 7.00, and the mass of the required ytterbium-based praseodymium fluoride multi-chamber nanomaterial was 0.01 g.

[0048] The adsorption study results are as follows Figure 5 As shown in the figure, the sample can remove 87.5% of Congo red dye within 2 minutes, and the adsorption amount is as high as 1750 mg / g.

[0049] Example 3

[0050] A method for preparing an ytterbium-based fluoride multi-chamber nanomaterial comprises the following steps:

[0051] (1) mixing ytterbium acetate and water in a mass ratio of 1:5 to obtain an ytterbium acetate aqueous solution;

[0052] (2) mixing praseodymium acetate and water in a mass ratio of 1:30 to obtain a praseodymium acetate aqueous solution;

[0053] (3) Add praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution described in step (1) at a volume ratio of 1:10, stir for 15 minutes, and then dropwise add sodium fluoride solution with a concentration of 3 g / L, with the volume ratio of the sodium fluoride solution to the total volume of the ytterbium acetate aqueous solution and the praseodymium acetate aqueous solution being 1:1, and stir for another 12 hours;

[0054] (4) The mixed solution obtained from the reaction in step (3) was centrifuged, the precipitate was collected, washed with ethanol, and finally freeze-dried at -60°C for 14 h to obtain the ytterbium-based praseodymium fluoride multi-chamber nanomaterial.

[0055] Figure 6 This is a high-magnification transmission electron micrograph of the obtained product. It can be seen that there are a large number of cavities in the ytterbium-based praseodymium fluoride multi-chamber nanomaterial. The diameter of the material is 80 nm and the pore size is 8-13 nm.

[0056] The adsorption of Congo red by the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in this example was studied under the following experimental conditions: the volume of the dye wastewater was 10 ml, the concentration was 400 mg / L, the pH was 7.00, and the mass of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial required was 0.01 g.

[0057] The adsorption study results are as follows Figure 7As shown in the figure, the sample can remove 89.1% of Congo red dye within 80 min, and the adsorption capacity is as high as 3564 mg / g.

[0058] Example 4

[0059] A method for preparing an ytterbium-based fluoride multi-chamber nanomaterial comprises the following steps:

[0060] (1) mixing ytterbium acetate and water in a mass ratio of 1:5 to obtain an ytterbium acetate aqueous solution;

[0061] (2) mixing praseodymium acetate and water in a mass ratio of 1:10 to obtain a praseodymium acetate aqueous solution;

[0062] (3) Add praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution described in step (1) at a volume ratio of 1:3, stir for 15 minutes, and then dropwise add sodium fluoride solution with a concentration of 5 g / L, with the volume ratio of sodium fluoride solution to the total volume of ytterbium acetate aqueous solution and praseodymium acetate aqueous solution being 0.5:1, and stir for another 24 hours;

[0063] (4) The mixed solution obtained from the reaction in step (3) was centrifuged, the precipitate was collected, washed with ethanol, and finally freeze-dried at -60°C for 12 h to obtain the ytterbium-based praseodymium fluoride multi-chamber nanomaterial.

[0064] The adsorption of Congo red by the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in this example was studied under the following experimental conditions: the volume of the dye wastewater was 20 ml, the concentration was 200 mg / L, the pH was 7.00, and the mass of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial required was 0.02 g.

[0065] Adsorption study results showed that the sample could remove 95.5% of Congo red dye within 15 min, with an adsorption capacity of up to 1910 mg / g.

[0066] Example 5

[0067] A method for preparing an ytterbium-based fluoride multi-chamber nanomaterial comprises the following steps:

[0068] (1) mixing ytterbium acetate and water in a mass ratio of 1:20 to obtain an ytterbium acetate aqueous solution;

[0069] (2) mixing praseodymium acetate and water in a mass ratio of 1:20 to obtain a praseodymium acetate aqueous solution;

[0070] (3) Add praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution described in step (1) at a volume ratio of 1:5, stir for 15 minutes, and then dropwise add sodium fluoride solution with a concentration of 2.5 g / L, with the volume ratio of the sodium fluoride solution to the total volume of the ytterbium acetate aqueous solution and the praseodymium acetate aqueous solution being 1:1, and stir for another 12 hours;

[0071] (4) The mixed solution obtained from the reaction in step (3) was centrifuged, the precipitate was collected, washed with ethanol, and finally freeze-dried at -70°C for 14 h to obtain the ytterbium-based praseodymium fluoride multi-chamber nanomaterial.

[0072] The adsorption of Congo red by the ytterbium-based praseodymium fluoride multi-chamber nanomaterial prepared in this example was studied under the following experimental conditions: the volume of the dye wastewater was 40 ml, the concentration was 100 mg / L, the pH was 7.00, and the mass of the ytterbium-based praseodymium fluoride multi-chamber nanomaterial required was 0.01 g.

[0073] Adsorption study results showed that the sample could remove 86% of Congo red dye within 40 minutes, with an adsorption capacity of up to 3440 mg / g.

[0074] Example 6

[0075] An ytterbium-based fluoride multi-chamber nanomaterial prepared by the preparation method described in any one of Examples 1-5 above.

[0076] Furthermore, the diameter of the nanomaterial is 30-100 nm, and the pore size is 3-20 nm.

[0077] Example 7

[0078] An application of an ytterbium-based fluoride multi-chamber nanomaterial prepared by the preparation method described in any one of Examples 1-5 above in adsorbing dye wastewater pollutants.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention and are not limiting. Other modifications or equivalent substitutions made to the technical solution of the present invention by ordinary technicians in this field should be included in the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing an ytterbium-based fluoride multi-chamber nanomaterial, characterized in that: The steps include: (1) mixing ytterbium acetate and water to obtain an ytterbium acetate aqueous solution; (2) mixing praseodymium acetate and water to obtain a praseodymium acetate aqueous solution; (3) adding praseodymium acetate aqueous solution to the ytterbium acetate aqueous solution, stirring evenly, then adding sodium fluoride solution dropwise, and performing hydrothermal reaction at room temperature; (4) centrifuging the mixed solution obtained from the reaction in step (3), taking the precipitate, washing it, and finally freeze-drying it to obtain the ytterbium-based fluoride multi-chamber nanomaterial; The mass ratio of ytterbium acetate to water in step (1) is 1:5-30; The mass ratio of praseodymium acetate to water in step (2) is 1:5-30; The volume ratio of the ytterbium acetate aqueous solution to the praseodymium acetate aqueous solution in step (3) is 1:1 to 10; The concentration of the sodium fluoride solution in step (3) is 0.5-5 g / L, and the total volume ratio of the sodium fluoride solution to the ytterbium acetate aqueous solution and the praseodymium acetate aqueous solution is 0.1-2:1; The room temperature hydrothermal reaction time in step (3) is 12 to 24 hours; The multi-chamber nanomaterial has a diameter of 30 to 100 nm and a pore size of 3 to 20 nm.

2. The method for preparing the ytterbium-based fluoride multi-chamber nanomaterial according to claim 1, wherein: The freeze-drying temperature in step (4) is -60 to -70°C, and the time is 12 to 14 hours.

3. An ytterbium-based fluoride multi-chamber nanomaterial prepared by the preparation method according to claim 1 or 2.

4. Use of an ytterbium-based fluoride multi-chamber nanomaterial prepared by the preparation method according to claim 1 or 2 in adsorbing dye wastewater pollutants.

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