CN112892497B - Preparation method and application of basin-covering type hollow porous polymer microspheres - Google Patents
Preparation method and application of basin-covering type hollow porous polymer microspheres Download PDFInfo
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Abstract
The invention belongs to the technical field of adsorption separation functional materials, and relates to a preparation method of a basin-type hollow porous polymer microsphere and application of the basin-type hollow porous polymer microsphere in uranium extraction; the invention aims to combine the advantages of the micro-nano structure, and utilizes a water-in-air Pickering emulsion template method to enable mesoporous silica nanoparticles to be embedded on a micron-sized porous particle carrier in a Pickering particle form into a basin-coated hollow porous micron-sized adsorbent, so that the advantages of the nano structure can be exerted, and the defects of the nano structure can be avoided; meanwhile, an amidoxime group is selected as a selective ligand of uranyl ions, and Salicylaldoxime (SO) is grafted on the mesoporous silica nanoparticles, SO that the selectivity of the uranyl ions is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of adsorption separation functional materials, and particularly relates to a method for preparing a basin-type hollow porous adsorbent by a gas-in-water Pickering emulsion template method and selective uranium extraction application thereof.
Background
Nuclear energy plays a crucial role as an efficient, clean energy source in ensuring global energy supply and reducing the demand for fossil fuels. The uranium is the most important element in the nuclear industry, and the rapid selective separation of the uranium is of great significance in the development and application of nuclear energy. Mature uranium separation technology is only limited to extraction of terrestrial uranium ores, but the terrestrial uranium ores are limited in reserves and cannot be used continuously for a long time. Therefore, a new uranium ore source is urgently required. The reserve of uranium in seawater is abundant (about 45 million tons) and is thousands of times that in land ore. Therefore, extraction of uranium from seawater is a potential strategy to meet the growing demand for uranium. At present, a variety of methods are commonly used for extracting uranium, such as ion exchange method, liquid-liquid extraction method, chemical precipitation method, evaporation concentration method, adsorption separation method, and the like. Among them, the adsorption separation method has become one of the commonly used methods for extracting uranium from seawater due to its advantages of environmental friendliness, simple operation, wide adaptability, low cost, and no secondary pollution. However, the concentration of uranium in seawater is low (less than 3.3 ppb), the coexistence of a large number of interfering ions and the complexity of a matrix, and the adsorption separation method for extracting uranium from seawater faces a great challenge. In order to effectively enrich and extract uranium resources from seawater, a new method for preparing an adsorbent which is environment-friendly, high in selectivity, easy to separate and high in separation efficiency is urgently needed to be developed.
Nano-sized adsorbents are of great interest in the separation and purification field due to their high specific surface area, abundance of active sites, and excellent mass transfer rates. The amidoxime group modified nano adsorbent can achieve the effect of selective adsorption with uranyl ions through coordination. Based on the principle, the amidoxime group can be modified on the nano material to have the capability of selectively adsorbing uranyl ions. However, nano-adsorbents are more prone to agglomeration than larger adsorbents, and the attachment of particles to each other tends to mask part of the active sites, thereby reducing their adsorption efficiency; and secondly, the nano adsorbent is not easy to recover, and complete solid-liquid separation is difficult to realize. These problems have limited further industrial application of the nano-adsorbent. Micron-sized adsorbents have better dispersibility in solution and larger particles are easier to separate than nano-sized adsorbents. However, micron-sized adsorbents have problems of limited specific surface area, low binding capacity, slow adsorption rate, and the like.
Disclosure of Invention
Aiming at the defects of the existing materials, the invention aims to make up the problems of easy agglomeration and difficult separation by combining the advantages of a micro-nano structure and utilizing the advantages of high specific surface area, rich active sites, excellent mass transfer rate and the like of a nano adsorbent, provides a method for preparing an amine oxime functionalized basin-type hollow porous adsorbent by using a gas-in-water Pickering emulsion template method of replacing a surfactant with micro/nano solid particles, and turns the nano material into a micron-sized material in the form of Pickering particles so as to realize 1+1 integral material>2. The hollow porous adsorbent (MF @ mSiO) with amidoxime groups grafted on mesoporous silica nanoparticles is prepared by taking amidoxime groups as selective ligands, mesoporous silica nanoparticles as Pickering particles and melamine resin as porous particle carriers 2 -SO)。
In order to achieve the purpose, the invention adopts the following technical scheme:
(1) Preparation of mesoporous silica nanoparticles:
dissolving a certain amount of tannic acid in ethanol, heating, adding a certain amount of concentrated NH under magnetic stirring 3 ·H 2 O; then, a certain amount of tetraethyl orthosilicate (TEOS) is dripped, and the formed mixed solution reacts for a period of time under the magnetic stirring; after the reaction is finished, centrifugally collecting the product, and washing the product with deionized water and ethanol respectivelyWashing until the supernatant is colorless, and drying to obtain the mesoporous silica nanoparticles, which are recorded as mSiO 2 (ii) a Dispersing the obtained mesoporous silica nano particles in deionized water to obtain a mesoporous silica aqueous dispersion for later use;
(2) Preparing the basin type hollow porous polymer microspheres:
under a certain temperature condition, adding melamine into a formaldehyde solution to form a mixed solution A, mechanically stirring the mixed solution A, adjusting the pH value of the mixed solution A, and continuously reacting for a period of time after the solution is changed from milky color to clear; adding the mesoporous silica aqueous dispersion under the same stirring condition to form a mixed solution B, cooling to a certain temperature after a period of time, reacting for a period of time, adjusting the pH value of the mixed solution B, continuing to react for a period of time, stopping stirring, and performing standing polymerization under the water bath condition; finally, the product was collected by centrifugation, washed with deionized water and ethanol and collected by centrifugation, and dried to give a powder sample, designated MF @ mSiO 2 ；
(3) MF @ mSiO prepared in the step (2) 2 Dispersing the mixture in ethanol a solution by ultrasonic treatment to obtain a mixed solution C; adding a certain amount of 3-Aminopropyltriethoxysilane (APTES) and glacial acetic acid into the mixed solution C under magnetic stirring; then magnetically stirring and reacting for a period of time at a certain temperature; centrifugally collecting a product after reaction, washing the obtained product with ethanol, centrifugally collecting the product and drying to obtain the basin-type hollow porous polymer microsphere with the surface grafted with amino, and marking as MF @ mSiO 2 -NH 2 ；
Then MF @ mSiO 2 -NH 2 Adding Glutaraldehyde (GA) into the ethanol b to obtain a mixed solution D, and then placing the mixed solution D under magnetic stirring in a water bath condition for light-resistant reaction; after the reaction is finished, washing the product with deionized water and ethanol respectively, centrifuging, drying and collecting to obtain the basin-type hollow porous polymer microsphere with the surface grafted with aldehyde groups, and marking as MF @ mSiO 2 -CHO；
(4) MF @ mSiO prepared in step (3) 2 Suspending CHO and Salicylaldoxime (SO) in deionized water, and ultrasonically treating to obtain mixed solution E, and magnetically stirringStirring, placing in an oil bath, adjusting the pH value with NaOH solution, and carrying out reflux reaction at a certain temperature; after reacting for a period of time, washing, centrifuging and drying to obtain the basin-type hollow porous polymer microsphere with the surface grafted with salicylaldoxime, which is marked as MF @ mSiO 2 -SO。
Preferably, in the step (1), the tannic acid, tetraethyl orthosilicate, ethanol and NH 3 ·H 2 The dosage ratio of O is (0.068-0.272) g: (0.2-0.4) mL: (40-60) mL: (20-30) mL, wherein ethanol and NH 3 ·H 2 The volume ratio of O is 2.
In the step (1), the concentration of the mesoporous silica aqueous dispersion is 1.5wt%.
Preferably, in the step (2), the certain temperature condition is 80-90 ℃.
Preferably, in the step (2), the ratio of the melamine, the formaldehyde solution and the mesoporous silica nanoparticle aqueous dispersion is (1.0-1.5) g: (1.5-2.5) mL: (10-20) mL; the volume fraction of the formaldehyde solution was 37%.
Preferably, in the step (2), the pH of the mixed solution A is adjusted by using Na 2 CO 3 Adjusting the pH value of the solution to 9.0-10; the Na is 2 CO 3 The concentration of the solution was 2.0M.
Preferably, in the step (2), the rotation speed of the mechanical stirring in the mixed solution A is 1200-1600rpm; the solution is changed from milky white to clear and then continuously reacted for a period of 2.0-4.0min.
Preferably, in the step (2), the reaction time after the mesoporous silica nanoparticle aqueous dispersion is added is 1.0-3.0min, and the rotation speed of mechanical stirring in the mixed solution B is 1200-1600rpm; cooling the mixed solution B to a certain temperature of 30-50 ℃; the reaction is continued for 5.0-10min after the temperature is reduced; the pH adjusting range of the mixed solution B is 5.0-6.0; the solution used to adjust the pH was 2.0M HCl; and stopping stirring after the reaction time is 20-60 min.
Preferably, in the step (2), the temperature of the water bath for standing polymerization is 30-50 ℃; the standing polymerization reaction time is 3.0-5.0h; the drying temperature is 60-80 ℃.
Preferably, in step (3), the MF @ mSiO 2 The dosage ratio of the 3-aminopropyltriethoxysilane to the ethanol a to the glacial acetic acid is (0.4-0.6) g: (2.0-3.0) mL: (40-60) mL:10 μ L.
Preferably, in the step (3), the time of the ultrasonic treatment is 5.0-10min; the temperature of the water bath of the mixed solution C is 35-45 ℃, and the reaction time is 10-12h; the drying temperature is 60-80 ℃.
Preferably, in step (3), the MF @ mSiO 2 -NH 2 The dosage ratio of the glutaraldehyde to the ethanol b is (0.4-0.5) g: (4.0-6.0) mL: (30-50) mL; the volume fraction of glutaraldehyde is 50%.
Preferably, in the step (3), the temperature of the water bath of the mixed solution D is 30-40 ℃, and the reaction time is 5.0-8.0h; the drying temperature is 60-80 ℃.
Preferably, in step (4), the MF @ mSiO 2 -CHO, salicylaldoxime (SO) and deionized water in a ratio of (0.2-0.4) g: (0.08-0.12) g: (20-40) mL; the ultrasonic treatment time of the mixed solution E is 5.0-10min.
Preferably, in the step (4), the pH of the mixed solution E is adjusted to be between 8.0 and 9.0 by using NaOH solution; the concentration of the NaOH solution was 0.1M.
Preferably, in the step (4), the reflux reaction temperature under the oil bath condition is 90-100 ℃; the oil bath reaction time is 5.0-7.0h; the drying temperature is 60-80 ℃.
Where ethanol a and ethanol b are both ethanol, the letters a and b are merely for the distinction of expressions.
The basin-covering type hollow porous polymer microsphere prepared by the method is applied to selective extraction of uranyl ions. The invention has the beneficial effects that:
(1) The invention selects amidoxime groups as selective ligands of uranyl ions, takes mesoporous silica nano particles as Pickering particles and melamine resin as porous particle carriers to prepare a coating with amidoxime functional groups grafted on the mesoporous silica nano particlesBasin-shaped hollow porous adsorbent (MF @ mSiO) 2 -SO) that specific adsorption of uranyl radicals is achieved.
(2) According to the invention, mesoporous silica nanoparticles are embedded on the surface of a hollow porous melamine resin particle carrier in a Pickering particle form by an air-in-water Pickering emulsion template method to form the basin-covering type micro polymer microspheres. The method keeps the advantages of the nano-material, simultaneously enables the whole material to have the characteristics of good dispersion performance and easy separation, realizes the combination of the advantages of the micro-nano structure and achieves 1+1>2; the specific combination with uranyl radical ions is realized by grafting high-density amidoxime sites on mesoporous silica, the adsorption capacity of the adsorbent is improved, and the adsorption capacity is improved through MF @ mSiO 2 With MF @ mSiO 2 As can be seen from the results of the experimental study on adsorption equilibrium by SO, the adsorbent grafted with amidoxime groups has higher adsorption amount of uranyl ions than the adsorbent not grafted with amidoxime groups.
Drawings
In FIG. 1 a and b are mSiO prepared as in example 1 2 A TEM image and an SEM image of (A); c-h are MF @ mSiO prepared at different off-stir times in example 1 2 SEM picture of (c, e-MF @ mSiO) 2 -35、d-MF@mSiO 2 -30、f-MF@mSiO 2 -40、g-MF@mSiO 2 -50、h-MF@mSiO 2 -60)。
FIG. 2 is the MF @ mSiO prepared in example 1 2 、MF@mSiO 2 -NH 2 、MF@mSiO 2 -CHO and MF @ mSiO 2 -infrared spectrum of SO.
FIG. 3 a is the MF @ mSiO prepared in example 1 2 -XPS spectrum of SO; b is MF @ mSiO prepared as in example 1 2 -C1 s high resolution spectrum of SO; c is MF @ mSiO prepared as in example 1 2 -N1 s high resolution spectrum of SO; d is MF @ mSiO prepared in example 1 2 High resolution spectrum of O1s of-SO.
FIG. 4 is the MF @ mSiO prepared in example 1 2 -solid nuclear magnetic resonance carbon spectrum of SO.
FIG. 5 is a graph of MF @ mSiO prepared as in example 1 at various pH values 2 -SO-30、MF@mSiO 2 -SO-35 and MF @ mSiO 2 -SO-40 adsorption capacity.
FIG. 6 is the MF @ mSiO prepared in example 1 2 -adsorption kinetics of SO at different initial concentrations and a model fit curve thereof.
FIG. 7 is the MF @ mSiO obtained in example 1 at different temperatures 2 -adsorption equilibrium of uranyl ions by SO and a model fitting curve thereof.
FIG. 8 is the MF @ mSiO prepared in example 1 2 、MF@mSiO 2 -SO-HF and MF @ mSiO 2 -comparison of adsorption equilibrium of SO on uranyl ions.
Detailed Description
The identification performance evaluation in the embodiment of the invention is carried out according to the following method: this was done using static adsorption experiments. 2.0mg of MF @ mSiO 2 -SO-30，MF@mSiO 2 -SO-35 and MF @ mSiO 2 -SO-40 testing the adsorption capacity of uranyl ions in the range of pH =3.0-9.0, measuring the adsorbed uranyl ion concentration by an ultraviolet visible light spectrometer by adopting an azoarsenic III method, and determining the optimal adsorption pH and the optimal adsorbent according to the result; to study MF @ mSiO 2 -adsorption rate of uranyl ions by SO under optimum pH conditions, we used 5.0mg of MF @ mSiO 2 -SO carrying out adsorption kinetics study under the condition that the initial concentration of the uranyl radical is 4ppm, 8ppm and 10ppm, and fitting the data by adopting a quasi first-order model and a quasi second-order model; for studying MF @ mSiO 2 Maximum adsorption capacity of SO, carrying out an adsorption equilibrium test in the range of uranyl ion concentration of 10-70ppm, fitting adsorption data by adopting a Langmuir model and a Freundlich model, and calculating the adsorption capacity according to the result.
The invention is further illustrated by the following examples.
Example 1:
(1) Preparation of mesoporous silica nanoparticles:
preparation of mesoporous silica nanoparticles using tannic acid as porogen: in a beaker, 0.204g of tannic acid is added into 50mL of ethanol and dissolved by ultrasonic; heating to 35 deg.C with a magnetic stirrer, and adding 25mL of the solution under magnetic stirring at 800rpmNH 3 ·H 2 O and 0.3mL TEOS; reacting for 2.0h after the mixed solution becomes turbid; after the reaction is finished, centrifuging and collecting a product, and washing the product respectively by using deionized water and ethanol until supernatant is colorless; drying to obtain the mesoporous silica nano particles with the diameter of 200 nm.
(2) Preparing the basin type hollow porous polymer microspheres:
1.26g of melamine was added to 2.0mL of 37% formaldehyde solution over 2.0M Na 2 CO 3 Adjusting the pH value of the solution to 9.5, and carrying out pre-crosslinking reaction at 85 ℃ under the mechanical stirring of 1500 rpm; when the solution turns clear from milky white, the solution continues to react for 3.0min, and 15mL of 1.5wt% mesoporous silica aqueous dispersion is added under mechanical stirring; reacting for 1.0min, cooling the solution to 40 ℃, continuing to react for 7.0min, dropwise adding 2.0M HCl to adjust the pH to 5.5, continuing to react for 35min, stopping stirring, and polymerizing for 4.0h under the condition of water bath at 40 ℃; finally, the product was collected by centrifugation, washed with deionized water and ethanol, centrifuged, and dried at 60 ℃ to give a powder sample, designated MF @ mSiO 2 -35；
(3) 0.5g of MF @ mSiO prepared in step (2) 2 -35 dispersing in a single-neck flask containing 50mL of ethanol solution by ultrasonic treatment for 10min; then 2.5mL of 3-Aminopropyltriethoxysilane (APTES) and 10. Mu.L of glacial acetic acid were added with magnetic stirring; reacting the formed mixture for 12h under the water bath condition of 40 ℃, centrifuging and collecting the product, washing the obtained product with ethanol, centrifuging again and collecting the product, and drying at 60 ℃ to obtain the raspberry type hollow porous polymer microsphere with the surface grafted with amino, which is recorded as MF @ mSiO 2 -NH 2 -35；
0.45g of MF @ mSiO 2 -NH 2 Adding 35 to 5.0mL of Glutaraldehyde (GA) into 45mL of ethanol, performing ultrasonic treatment for 10min to obtain a mixed solution, and then placing the mixed solution under magnetic stirring in a water bath at 35 ℃ for reaction for 6.0h in a dark place; after the reaction is finished, washing the product with deionized water and ethanol respectively, centrifuging, drying at 60 ℃ and collecting to obtain the basin-covered type hollow porous polymer microsphere with the surface grafted by aldehyde group, and marking as MF @ mSiO 2 -CHO-35；
(4) Take 0.3g of MF @mSiO 2 Performing ultrasonic dispersion treatment on-CHO-35 and 0.1g Salicylaldoxime (SO) in 30mL deionized water for 10min to obtain a mixed solution, and placing the mixed solution in an oil bath at 95 ℃ under magnetic stirring; adjusting the pH value of the solution to 8.5 by using 0.1M NaOH solution, and carrying out reflux reaction at the temperature of 95 ℃ for 6.0h; after the reaction is finished, washing, centrifuging and drying at 60 ℃ to obtain the basin-type hollow porous polymer microsphere with the surface grafted with the amidoxime group, which is marked as MF @ mSiO 2 -SO-35。
Comparative example 1 preparation procedure the same as in (1) to (4) above, except that MF @ mSiO prepared in step (4) 2 Corroding mesoporous silica nano particles by using HF solution, washing by using deionized water, centrifuging, and drying at 60 ℃ to obtain hollow porous polymer microspheres marked as MF @ mSiO 2 -SO-HF。
Comparative example 2 preparation procedure the same as above (1) to (4) except that the reaction continued for 35min in step (2) was replaced by 30min, 40min,50min,60min to obtain other materials, noted MF @ mSiO 2 -30、MF@mSiO 2 -40、MF@mSiO 2 -50，MF@mSiO 2 -60。
Shown in FIG. 1 as mSiO 2 TEM image, SEM image and MF @ mSiO 2 SEM picture of (1); from the TEM image, we can find that the mesoporous silica particle diameter is about 200nm and the mesopores are disordered, and from the SEM image, we can find that MF @ mSiO 2 The microsphere dispersibility is mSiO 2 Preferably, the diameter is about 3.0 μm, the mesoporous silica is uniformly distributed on the surface of the microsphere, and the mosaic state of the mesoporous silica is deepened along with the increase of the stirring stopping time.
By FT-IR, XPS, and CP-MAS 13 C NMR Spectroscopy investigating MF @ mSiO 2 -grafting and chemical modification of SO. MF @ mSiO 2 、MF@mSiO 2 -NH 2 、MF@mSiO 2 -CHO and MF @ mSiO 2 The FT-IR spectrum of-SO is shown in FIG. 2; at MF @ mSiO 2 In the-SO spectrum, about 900cm -1 The characteristic absorption peak of N-O appears, which indicates that the Salicylaldoxime (SO) modification is successful.
As shown in FIG. 3, is MF @ mSiO 2 XPS spectrum of-SO, in which a shows that it shows three strong peaks at 287.08eV, 399.08eV and 532.08eV, corresponding respectively to those observedC1s, N1s and O1s core energy levels; panel b shows the C1s high resolution spectrum from which we can find that the C1s high resolution spectrum can be resolved into four peaks corresponding to C = N, C = C, C-O and C-N; panel c is MF @ mSiO 2 -N1 s high resolution spectrum of SO, separable into 3 characteristic absorption peaks, the three peaks being attributed to N-O, C = N and C-N, respectively; FIG. d is MF @ mSiO 2 The O1s high resolution spectrogram of the-SO can also be split into 3 characteristic absorption peaks respectively attributed to C-O-H, N-O-H and Si-O.
FIG. 4 shows MF @ mSiO 2 CP-MAS of-SO 13 C NMR spectrum, from which two signal peaks of 110.46ppm,163.99ppm, corresponding to carbon absorption peaks of-C = C-and C = NOH, respectively, are evident; all the above results can prove that MF @ mSiO 2 Successful preparation of-SO.
Example 2:
(1) Preparation of mesoporous silica nanoparticles:
preparation of mesoporous silica nanoparticles using tannic acid as porogen: in a beaker, 0.068g of tannic acid is added into 40mL of ethanol and dissolved by ultrasonic; the temperature of the magnetic stirrer is raised to 30 ℃ by heating, and 20mL of NH is added under the magnetic stirring of 700rpm 3 ·H 2 O and 0.2mL TEOS; reacting for 3.0h after the mixed solution becomes turbid; after the reaction is finished, centrifuging and collecting the product, and washing the product by using deionized water and ethanol respectively until supernatant is colorless; drying to obtain the mesoporous silica nano particles with the diameter of 200 nm.
(2) Preparing the basin type hollow porous polymer microspheres:
1.0g of melamine was added to 1.5mL of 37% formaldehyde solution using 2.0M Na 2 CO 3 Adjusting the pH value of the solution to 9.0, and carrying out pre-crosslinking reaction at 80 ℃ under the mechanical stirring of 1200 rpm; when the solution turns clear from milky color, the solution continues to react for 2.0min, and 10mL of 1.5wt% mesoporous silica aqueous dispersion is added under mechanical stirring; after 2.0min, cooling the solution to 35 ℃, continuing to react for 5.0min, dropwise adding 2.0M HCl to adjust the pH value to 5.0, continuing to react for 35min, stopping stirring, and polymerizing for 3.0h under the condition of a water bath at 35 ℃; finally, the product was collected by centrifugation and washed with deionized water and ethanolWashing and drying at 70 ℃ to obtain a powder sample which is marked as MF @ mSiO 2 ；
(3) 0.4g of MF @ mSiO prepared in step (2) 2 Dispersing in a single-neck flask filled with 40mL of ethanol solution after ultrasonic treatment for 5.0 min; then 2.0mL of 3-Aminopropyltriethoxysilane (APTES) and 10. Mu.L of glacial acetic acid were added with magnetic stirring; reacting the formed mixture for 10 hours in a water bath condition at 35 ℃, centrifuging to collect a product, washing the obtained product with ethanol, centrifuging again, drying at 70 ℃, collecting the product and drying to obtain the raspberry type hollow porous polymer microsphere with the surface grafted with amino, wherein the mark is MF @ mSiO 2 -NH 2 ；
0.4g of MF @ mSiO 2 -NH 2 Adding 4.0mL of Glutaraldehyde (GA) into 30mL of ethanol, performing ultrasonic treatment for 5.0min to obtain a mixed solution, and placing the mixed solution under magnetic stirring in a water bath at 30 ℃ for dark reaction for 5.0h; after the reaction is finished, washing the product with deionized water and ethanol, centrifuging, drying at 70 ℃ and collecting the product to obtain the basin-type hollow porous polymer microsphere with the surface grafted aldehyde group, and marking as MF @ mSiO 2 -CHO；
(4) Taking 0.2g of MF @ mSiO 2 -CHO and 0.08g Salicylaldoxime (SO) are ultrasonically treated for 5.0min and dispersed in 20mL deionized water to obtain a mixed solution, the mixed solution is placed in an oil bath at 90 ℃ under magnetic stirring, the pH is adjusted to 8.0 by using 0.1M NaOH solution, and the reflux reaction is carried out for 5.0h at 90 ℃; after the reaction is finished, washing and centrifuging are carried out, and then drying is carried out at 70 ℃ to obtain the basin-type hollow porous polymer microsphere with the surface grafted with salicylaldoxime, which is marked as MF @ mSiO 2 -SO。
Example 3:
(1) Preparation of mesoporous silica nanoparticles:
preparation of mesoporous silica nanoparticles using tannic acid as porogen: in a beaker, 0.272g of tannic acid is added into 60mL of ethanol and dissolved by ultrasonic; the magnetic stirrer is heated to 40 ℃, 30mL of NH is added under the magnetic stirring of 1000rpm 3 ·H 2 O and 0.4mL TEOS; reacting for 2.5h after the mixed solution becomes turbid; after the reaction is finished, centrifugally collecting products, and respectively using deionized water and BWashing with alcohol until the supernatant is colorless; drying to obtain the mesoporous silica nano particles with the diameter of 200 nm.
(2) Preparing the basin type hollow porous polymer microspheres:
1.5g of melamine was added to 2.5mL of 37% formaldehyde solution over 2.0M Na 2 CO 3 Adjusting the pH value of the solution to 10, and carrying out pre-crosslinking reaction at 90 ℃ under mechanical stirring at 1600rpm; continuously reacting for 4.0min after the solution turns from milky white to clear, and adding 20mL of 1.5wt% mesoporous silica aqueous dispersion under mechanical stirring; after 3.0min, cooling the solution to 50 ℃, continuing to react for 10min, dropwise adding 2.0M HCl to adjust the pH value to 6.0, continuing to react for 35min, stopping stirring, and polymerizing for 5.0h under the water bath condition of 50 ℃; finally, the product was collected by centrifugation, washed with deionized water and ethanol, and dried at 80 ℃ to give a powder sample, designated MF @ mSiO 2 ；
(3) 0.6g of MF @ mSiO prepared in step (2) 2 -35 dispersing in a single-neck flask containing 60mL of ethanol solution by ultrasonic treatment for 10min; then 3.0mL of 3-Aminopropyltriethoxysilane (APTES) and 10. Mu.L of glacial acetic acid were added with magnetic stirring; reacting the formed mixture for 12h under the water bath condition of 45 ℃, centrifuging and collecting a product, washing the obtained product with ethanol, centrifuging again, drying and collecting the product at 80 ℃, and drying to obtain the raspberry type hollow porous polymer microsphere with the surface grafted with amino, wherein the mark is MF @ mSiO 2 -NH 2 ；
0.5g of MF @ mSiO 2 -NH 2 Adding 6.0mL of Glutaraldehyde (GA) into 50mL of ethanol, performing ultrasonic treatment for 10min to obtain a mixed solution, and then placing the mixed solution under magnetic stirring in a water bath at 40 ℃ for light-proof reaction for 8.0h; after the reaction is finished, washing the product with deionized water and ethanol, centrifuging, drying at 80 ℃ and collecting to obtain the basin-type hollow porous polymer microsphere with the surface grafted aldehyde group, and marking as MF @ mSiO 2 -CHO；
(4) Taking 0.4g of MF @ mSiO 2 Ultrasonic treating with-CHO-35 and 0.12g Salicylaldoxime (SO) for 10min, dispersing in 40mL deionized water to obtain mixed solution, placing the mixed solution in 100 deg.C oil bath under magnetic stirring, and treating with 0.1MAdjusting the pH value of the NaOH solution to about 9.0, and carrying out reflux reaction for 7.0h; after the reaction is finished, washing, centrifuging and drying at 80 ℃ to obtain the basin-type hollow porous polymer microsphere with the surface grafted with salicylaldoxime, which is marked as MF @ mSiO 2 -SO。
And (3) performance testing:
the pH value of the water environment has great influence on the adsorption process of the adsorbent on the metal ions; therefore, study of MF @ mSiO 2 -30、MF@mSiO 2 -35 and MF @ mSiO 2 -40 effect on adsorption capacity of uranyl ions in the pH range of 3.0 to 9.0, results are shown in FIG. 5. As can be seen from FIG. 5, MF @ mSiO at a pH of not higher than 7.0 2 -SO-30、MF@mSiO 2 -SO-35 and MF @ mSiO 2 The adsorption capacities of SO-40 all show a gradual increasing trend with increasing pH, with the adsorption capacity decreasing with increasing pH above 7.0 and MF @ mSiO 2 the-SO-35 is higher than MF @ mSiO under the condition of higher pH of adsorption capacity 2 -SO-30 and MF @ mSiO 2 -adsorption capacity of SO-40.
MF@mSiO 2 The adsorption kinetics of uranyl ions by-SO are shown in FIG. 6. As can be seen, MF @ mSiO 2 The adsorption capacity of the SO increases rapidly within the first 10min, reaching a maximum adsorption capacity within 30min, and its maximum adsorption capacity increases with increasing initial concentration.
For studying MF @ mSiO 2 Maximum adsorption capacity of SO, we performed adsorption equilibrium experiments in the range of uranyl ion concentration of 10-70ppm, fitted the adsorption data using Langmuir model and Freundlich model, and explored the influence of temperature on adsorption capacity. As shown in fig. 7, the adsorption capacity increases with increasing temperature over the test temperature range.
In order to prove that an amidoxime group is completely grafted on mesoporous silica nanoparticles instead of a melamine resin porous particle carrier and can specifically adsorb uranyl radical, the preparation method compares MF @ mSiO SiO prepared by etching mesoporous silica particles with HF solution after completely grafting salicylaldoxime 2 -SO-HF, MF @ mSiO without chemical modification 2 With MF @ mSiO 2 -SO in the range of 5-70ppm of uranyl ion concentrationComparison of adsorption equilibrium tests was performed. As shown in FIG. 8, at 25 deg.C, MF @ mSiO 2 Adsorption Capacity ratio of-SO MF @ mSiO 2 High, MF @ mSiO 2 the-SO-HF has no adsorption effect on uranyl ions at all.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. The preparation method of the basin-covering type hollow porous polymer microsphere is characterized by comprising the following steps of:
(1) Preparing mesoporous silica nano particles, and dispersing the mesoporous silica nano particles in deionized water to obtain mesoporous silica aqueous dispersion for later use;
(2) At the temperature of 80-90 ℃, melamine is added into formaldehyde solution to form mixed solution A, the mixed solution A is mechanically stirred, the pH value of the mixed solution A is adjusted to 9.0-10, and the mixed solution A continuously reacts for 2.0-4.0min after the solution turns from milky white to clear; adding the mesoporous silica aqueous dispersion under the same stirring condition to form a mixed solution B, cooling to 30-50 ℃ after 1.0-3.0min, reacting for 5.0-10min, adjusting the pH of the mixed solution B to 5.0-6.0, continuing to react for 20-60min, stopping stirring, and carrying out standing polymerization under the water bath condition; finally, the product was collected by centrifugation, washed with deionized water and ethanol and collected by centrifugation, dried to give a powder sample designated MF @ mSiO 2 ；
(3) MF @ mSiO prepared in the step (2) 2 Dispersing the mixture in an ethanol a solution by ultrasonic treatment to obtain a mixed solution C; adding a certain amount of 3-Aminopropyltriethoxysilane (APTES) and glacial acetic acid into the mixed solution C under magnetic stirring; then magnetically stirring and reacting for a period of time at a certain temperature; centrifugally collecting the product after reaction, washing the obtained product with ethanolCentrifugally collecting the product and drying to obtain the basin-type hollow porous polymer microsphere with the surface grafted with amino, and marking as MF @ mSiO 2 -NH 2 ；
Then MF @ mSiO 2 -NH 2 Adding glutaraldehyde GA into ethanol b to obtain a mixed solution D, and then placing the mixed solution D under magnetic stirring in a water bath condition for light-resistant reaction; after the reaction is finished, washing the product with deionized water and ethanol respectively, centrifuging, drying and collecting to obtain the basin-type hollow porous polymer microsphere with the surface grafted with aldehyde groups, and marking as MF @ mSiO 2 -CHO；
(4) MF @ mSiO prepared in step (3) 2 Suspending CHO and salicylaldoxime SO in deionized water, performing ultrasonic treatment to obtain a mixed solution E, placing the mixed solution E under magnetic stirring in an oil bath, adjusting the pH value with NaOH solution, and performing reflux reaction at a certain temperature; after reacting for a period of time, washing, centrifuging and drying to obtain the basin-type hollow porous polymer microsphere with the surface grafted with salicylaldoxime, which is marked as MF @ mSiO 2 -SO。
2. The method according to claim 1, wherein the aqueous dispersion of mesoporous silica is present in a concentration of 1.5wt% in step (1).
3. The method according to claim 1, wherein in the step (2), the melamine, the formaldehyde solution and the mesoporous silica aqueous dispersion are used in a ratio of (1.0-1.5) g: (1.5-2.5) mL: (10-20) mL; the volume fraction of the formaldehyde solution was 37%.
4. The method according to claim 1, wherein the pH of the mixed solution A is adjusted using Na in the step (2) 2 CO 3 Adjusting the pH value of the solution to 9.0-10; the Na is 2 CO 3 The concentration of the solution was 2.0M; the rotation speed of the mechanical stirring is 1200-1600rpm.
5. The method according to claim 1, wherein in the step (2), the solution for adjusting the pH of the mixed solution B is 2.0M HCl; the temperature of the water bath for standing polymerization is 30-50 ℃; the standing polymerization reaction time is 3.0-5.0h; the drying temperature is 60-80 ℃.
6. The production method according to claim 1, wherein, in the step (3), the MF @ mSiO 2 The dosage ratio of the 3-aminopropyltriethoxysilane to the ethanol a to the glacial acetic acid is (0.4-0.6) g: (2.0-3.0) mL: (40-60) mL:10 mu L of the solution; the ultrasonic treatment time is 5.0-10min; the temperature of the water bath of the mixed solution C is 35-45 ℃, and the reaction time is 10-12h; the drying temperature is 60-80 ℃.
7. The production method according to claim 1, wherein, in the step (3), the MF @ mSiO 2 -NH 2 The dosage ratio of the glutaraldehyde to the ethanol b is (0.4-0.5) g: (4.0-6.0) mL: (30-50) mL; the volume fraction of the glutaraldehyde is 50%; the temperature of the water bath of the mixed solution D is 30-40 ℃, and the reaction time is 5.0-8.0h; the drying temperature is 60-80 ℃.
8. The production method according to claim 1, wherein, in the step (4), the MF @ mSiO 2 -CHO, salicylaldoxime and deionized water in a ratio of (0.2-0.4) g: (0.08-0.12) g: (20-40) mL; the ultrasonic treatment time of the mixed solution E is 5.0-10min.
9. The method according to claim 1, wherein in the step (4), the pH of the mixed solution E is adjusted to be between 8.0 and 9.0 by using NaOH solution; the concentration of the NaOH solution is 0.1M; the reflux reaction temperature under the oil bath condition is 90-100 ℃; the oil bath reaction time is 5.0-7.0h; the drying temperature is 60-80 ℃.
10. The basin-type hollow porous polymer microspheres prepared by the method of any one of claims 1 to 9 are used for selective extraction of uranyl ions.
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