CN114433036B - Method for preparing amidoxime functionalized hollow polymer spheres based on solvent mixing-induced bubble template method and application of amidoxime functionalized hollow polymer spheres in uranium extraction - Google Patents
Method for preparing amidoxime functionalized hollow polymer spheres based on solvent mixing-induced bubble template method and application of amidoxime functionalized hollow polymer spheres in uranium extraction Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 32
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000002904 solvent Substances 0.000 title claims abstract description 17
- 238000002156 mixing Methods 0.000 title claims abstract description 16
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 9
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000605 extraction Methods 0.000 title claims abstract description 8
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 48
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 27
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000007983 Tris buffer Substances 0.000 claims description 24
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- 229920001690 polydopamine Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 2
- 238000005422 blasting Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 38
- 239000003463 adsorbent Substances 0.000 abstract description 28
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 11
- 239000003995 emulsifying agent Substances 0.000 abstract description 6
- 239000002101 nanobubble Substances 0.000 abstract description 4
- 238000010828 elution Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 52
- 229960003638 dopamine Drugs 0.000 description 26
- 238000013461 design Methods 0.000 description 14
- 239000013535 sea water Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 9
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 9
- 238000012986 modification Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
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- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- WGYFACNYUJGZQO-UHFFFAOYSA-N aminomethanetriol Chemical compound NC(O)(O)O WGYFACNYUJGZQO-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
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- 239000011877 solvent mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AHMIDUVKSGCHAU-UHFFFAOYSA-N Dopaquinone Natural products OC(=O)C(N)CC1=CC(=O)C(=O)C=C1 AHMIDUVKSGCHAU-UHFFFAOYSA-N 0.000 description 1
- AHMIDUVKSGCHAU-LURJTMIESA-N L-dopaquinone Chemical compound [O-]C(=O)[C@@H]([NH3+])CC1=CC(=O)C(=O)C=C1 AHMIDUVKSGCHAU-LURJTMIESA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229920001222 biopolymer Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003291 dopaminomimetic effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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Abstract
The invention discloses a method for preparing amidoxime functionalized hollow polymer spheres based on a solvent mixing induced bubble template method and application of the amidoxime functionalized hollow polymer spheres in uranium extraction. Deionized water and n-propanol are mixed, stable and uniform nano bubbles are generated by stirring and serve as templates, self-polymerization and self-superior adhesiveness of dopamine hydrochloride under alkaline conditions are utilized, the hollow nano polymer sphere-based adsorbent can be quickly polymerized at a liquid-gas interface, and the defects that the cost of a traditional emulsion template is high, pollution is large, the material structure caused by template elution is damaged and the like are overcome; meanwhile, the problems that the traditional emulsifier pollutes the environment, pickering particles are removed and the like are avoided. Based on the abundant grafting sites provided by the hollow structure, the high-density specific sites are post-modified to prepare the amidoxime functional adsorbent H-PDa-aO, so that the adsorption efficiency, adsorption capacity and selectivity of the material are improved. The H-PDa-aO is applied to the adsorption of U (VI) solution in aqueous solution, the equilibrium is reached within 40min, the maximum adsorption capacity is 350.6mg g ‑1 at room temperature, and the removal rate can reach 96%.
Description
Technical Field
The invention belongs to the technical field of preparation of adsorption separation functional materials, relates to a preparation method of a hollow nano adsorbent suitable for selectively and efficiently enriching uranium (U (VI)) in seawater, and particularly relates to a method for preparing amidoxime functionalized hollow polymer spheres based on a solvent mixing induced bubble template method and application of the amidoxime functionalized hollow polymer spheres in the field of U (VI) extraction in seawater.
Background
With the development of society, various energy consumption has also increased. In the great background of global warming and the increasing exhaustion of fossil energy, renewable energy has become a global pursuit. Nuclear energy is a clean energy source, and has the characteristics of high energy density and low-temperature gas emission, so the development of nuclear energy is a great trend of solving the global energy problem. Uranium is an important nuclear fuel, and our demand for uranium is increasing. To meet this demand, we have focused research on the ocean. About 40 hundred million tons of uranium resources exist in seawater, and a huge resource basis is provided for nuclear energy development.
There are many methods reported for extracting U (VI) from seawater, such as chemical deposition, evaporation concentration, ion exchange, adsorption separation, etc. Among them, the adsorption separation method is one of the most effective methods for extracting U (VI) from seawater because of its advantages of high separation efficiency, easy continuous operation, good stability, low cost, etc. At present, the types of adsorbents used for extracting U (VI) from seawater are various, wherein the amidoxime functional adsorbent is a powerful competitor for extracting U (VI) from seawater due to strong affinity, good selectivity and wide application range for U (VI) and applicability in practical environments. However, the adsorption separation method for extracting U (VI) from seawater aims at achieving the purposes of quick adsorption kinetics, good adsorption selectivity and high adsorption capacity, and often has the problems of low concentration of U (VI), more coexisting interfering ions, low site utilization rate and the like. In order to achieve the purpose of efficiently extracting U (VI), an adsorbent which is friendly to the environment, high in adsorption efficiency and good in adsorption selectivity is urgently developed.
There are many types of adsorbents for ion extraction, and among them, hollow-structure adsorbents are attracting attention because of their advantages of large specific surface area, high loading, small density, rapid mass transfer, and the like. In addition, the amidoxime group can coordinate with U (VI) to achieve the effect of high selective adsorption due to the special space structure. By utilizing the characteristics, the high-density amidoxime functionalized specific site is modified on the hollow structure adsorbent, so that the capacity of rapidly and efficiently extracting U (VI) is provided.
The traditional bubble template method inevitably uses an emulsifier or Pickering particles, the addition of an organic emulsifier can cause serious environmental problems, the addition of Pickering particles can reduce the effective adsorption site number of the adsorbent per unit mass if not removed later, if the Pickering particles are removed later, the damage of a material structure can be caused, and in order to avoid the occurrence of the above conditions, a novel bubble template method is urgently needed to be researched, and is applied to the preparation of a hollow adsorbent for extracting U (VI) from seawater.
Disclosure of Invention
The invention provides a hollow nano-adsorbent (H-PDA-AO) prepared by constructing a hollow nano-adsorbent by a solvent mixing induced bubble template method, taking amidoxime groups as selective ligands and polydopamine as a base material, and solving the problems of environmental pollution, pickering particle 'removal' and the like caused by an emulsifier in the traditional bubble template method.
Based on the principle that the solubility of gas in a solvent is closely related to the polarity of the solvent, after water and water-soluble solvent-n-propanol are mixed in proper proportion, the redundant gas can be discharged in the form of nano bubbles under the condition of stirring, and in addition, a proper amount of trihydroxy aminomethane (Tris) is added, so that the whole solution system reaches the condition of dopamine hydrochloride (DA) self-polymerization, and hollow nano polydopamine spheres (H-PDA) are prepared in one step; then performing a series of post-functionalization on a base material (H-PDA), firstly grafting-CHO by aldehyde-amine condensation reaction by using glutaraldehyde as a cross-linking agent to prepare H-PDA-CHO; then grafting a functional monomer diamino maleic nitrile (DAMN) to prepare H-PDA-CN; finally, hydroxylamine hydrochloride treatment is carried out to prepare the amidoxime functional hollow nano-adsorbent, namely the amidoxime functional hollow polymer spheres (H-PDA-AO). In summary, this work produced two adsorbents, respectively: H-PDA, H-PDA-AO, was used for comparative study.
The technical scheme adopted by the invention is as follows:
(1) A method for preparing amidoxime functionalized hollow polymer spheres based on solvent mixing-induced bubble template method, which comprises the following steps: design synthesis of hollow polydopamine sphere H-PDA
Dissolving a proper amount of trihydroxy aminomethane (Tris) in a certain amount of deionized water, rapidly adding n-propanol which is in a certain proportion with water, reacting for a period of time under the stirring condition of a certain rotating speed, then adding a proper amount of dopamine hydrochloride (DA), and polymerizing for a period of time under the condition of a certain temperature. And collecting the solution, centrifuging, washing the obtained black polymer with absolute ethyl alcohol for several times, drying by blowing, and collecting black powder polymer H-PDA.
(2) Design synthesis of "post-modification" H-PDA-AO
S1: weighing a certain amount of H-PDA powder obtained in the step (1), dispersing in a certain amount of deionized water, adding a proper amount of glutaraldehyde to obtain a mixed solution A, stirring at a certain temperature and under a dark condition, reacting for a period of time, centrifugally collecting, washing with deionized water and absolute ethyl alcohol for a plurality of times, blasting and drying, and collecting a product H-PDA-CHO;
S2: dispersing a certain amount of H-PDA-CHO in a certain amount of absolute ethyl alcohol, adding diamino Ma Laijing (DAMN), performing ultrasonic dispersion to obtain a mixed solution B, stirring under a certain temperature condition, reacting for a period of time, centrifugally collecting, washing the absolute ethyl alcohol for a plurality of times, performing forced air drying, and collecting a product H-PDA-CN;
S3: dispersing a certain amount of H-PDA-CN in a mixed solution of deionized water and absolute ethyl alcohol to obtain a mixed solution C, adding a certain amount of hydroxylamine hydrochloride, performing ultrasonic dispersion, stirring and reacting at a certain temperature, adding sodium hydroxide (NaOH) to regulate the pH of the solution, continuously reacting for a period of time, centrifugally collecting, washing the deionized water and the absolute ethyl alcohol for several times, performing blast drying, and collecting the product amidoxime functionalized hollow polymer spheres, namely H-PDA-AO.
Preferably, in the step (1), the usage ratio of Tris, deionized water, n-propanol and dopamine hydrochloride is 30mg:50mL:6.25mL:40-160mg, the reaction temperature is 20-30 , and the rotating speed is 500-700rpm.
Preferably, in the step (1), the mixing time of the deionized water and the n-propanol is 2.0-10min, and the polymerization time of the dopamine hydrochloride is 10-120min.
Preferably, in the step (2) S1, the dosage ratio of H-PDA, deionized water, glutaraldehyde in the mixed solution a is 100mg:40-60mL:4.0-6.0mL, the reaction temperature is 30-40 under the light-proof condition, the stirring speed is 450-550rpm, and the reaction time is 8.0-12h.
Preferably, in the step (2) S2, the mixed solution B contains H-PDA-CHO, absolute ethanol, and DAMN in an amount ratio of 90-100mg:50-70mL:500-700mg, the reaction temperature is 30-40 , the stirring speed is 450-550rpm, and the reaction time is 8.0-12h.
Preferably, in S3 of step (2),
In the mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:9;
In the mixed solution C, the dosage ratio of H-PDA-CN, deionized water and absolute ethyl alcohol is 90-100mg:4.0-6.0mL:36-54mL.
Hydroxylamine hydrochloride and mixed solution C are used in an amount ratio of 2.0-5.0g:40-60mL, and the ultrasonic dispersion time is 10-20min; the temperature of the stirring reaction is 65-80 , the reaction time is 5-10min, and the stirring speed is 450-550rpm.
Adding NaOH to regulate pH to 7.5-8.5, and reacting at 65-80 deg.c for 6.0-10 hr.
In the steps (1) and (2), the blast drying temperature is 50-70 and the drying time is 8.0-12h.
The hollow polydopamine sphere H-PDA or amidoxime functionalized hollow polymer sphere H-PDA-AO prepared by the invention is used for extracting uranium. Compared with the prior art, the invention has the beneficial effects that:
The invention is based on nano bubbles induced by solvent mixing as a template, DA as a polymerization monomer and DAMN as a functional monomer, and a novel hollow nano adsorbent H-PDA-AO with rapid mass transfer and high density specific sites is prepared and applied to the extraction of U (VI) in seawater. The adsorbent H-PDA-AO can be adsorbed in a solution with the volume of 10mL and the concentration of 10ppm U (VI), the adsorption equilibrium can be reached in 20min, the adsorbent H-PDA-AO can be adsorbed in a solution with the volume of 50mL and the concentration of 10ppm U (VI), the adsorption equilibrium can be reached in 40min, the maximum adsorption capacity of the adsorbent H-PDA-AO can reach 350mg g -1 under the room temperature condition of 25 , and the removal rate of the adsorbent H-PDA-AO to U (VI) can reach 96% at the pH of 7 under the concentration of 10 ppm. The hollow nano adsorbent prepared by the invention has the following advantages:
1) The invention adopts the bubble template method induced by solvent mixing to prepare the hollow nanosphere-based adsorbent, provides a new method for preparing the hollow adsorbent, solves the problems of complex process and easy environmental pollution of the traditional oil-in-water and water-in-oil system, and simultaneously avoids the use of the traditional bubble template method emulsifier and Pickering particles;
2) Dopamine (DA) is a remarkable biopolymer, is secreted by mussels and is easy to oxidize into dopaquinone, and then is crosslinked and polymerized by decomposition reaction, so that the dopaminergic acid (PDA) has strong adhesive force on a substrate, and is generated; in conclusion, the system has the advantages of stable nano bubbles serving as cores and DA rapid polymerization serving as shells, so that the use of an emulsifier is avoided, the whole preparation process is environment-friendly, the operation is simple, and the material structure is adjustable;
3) The material is a hollow nano material, the hollow structure has the advantages of high specific surface area, low density, high abundance of binding sites, high mass transfer rate and the like, the hollow structure greatly reduces the quality of the material, improves the amount of the adsorbent contained in unit mass and the number of effective sites, and has great application potential in the aspect of U (VI) extraction;
4) Based on abundant grafting sites provided by a hollow structure, DAMN is selected as a functional monomer, and the amidoxime functional adsorbent H-PDA-AO is prepared by hydroxylamine hydrochloride treatment, so that the aims of high mass transfer rate, high adsorption capacity and good adsorption selectivity of the adsorbent are realized. In conclusion, the hollow nano adsorbent is constructed by using the solvent mixing induced bubble template method, so that the method is environment-friendly, the specific surface area of the material can be increased, and the problem that the structure of the material is damaged due to subsequent template elution is avoided; the hollow structure is used for grafting high-density specific sites, so that breakthrough of the adsorption efficiency of the adsorbent is realized; has good application potential in the aspect of extracting U (VI) from seawater.
Drawings
FIG. 1 is a graph showing the effect of duration of mixing deionized water and n-propanol solvents on bubble size, a-c being DLS particle size distribution plots for solvent mixtures of 2.0min,5.0min, and 10.0min, respectively.
FIG. 2 is a TEM image of hollow polydopamine sphere H-PDA of examples 1-7 for preparing H-PDA of different structures by adjusting different parameters, a-c are respectively deionized water and n-propanol solvent mixed time periods of 2.0min, 5.0min, 10min; d-f are respectively 40mg, 80mg and 160mg of DA; g-i is polymerization time period of 10min, 60min and 120min respectively.
FIG. 3 is an SEM (a-b) and TEM (c-d) image of the H-PDA and H-PDA-AO, respectively, in example 1.
FIG. 4 is an infrared spectrum of H-PDA, H-PDA-AO in example 1.
FIG. 5 is XPS spectra of H-PDA, H-PDA-CHO, H-PDA-CN, H-PDA-AO in example 1.
FIG. 6 is a Zeta potential-pH-adsorption capacity diagram of H-PDA (a) and H-PDA-AO (b).
FIG. 7 is a time-adsorption capacity diagram of H-PDA-AO.
FIG. 8 is a graph of equilibrium concentration versus adsorption capacity for H-PDA-AO at 288K, 298K, 308K, respectively.
FIG. 9 is a test of H-PDA-AO selectivity to target U (VI) in simulated seawater.
Detailed Description
Example 1:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
30Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 50mL of deionized water, 6.25mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 2.0min, and then 80mg of Dopamine (DA) hydrochloride was added, followed by polymerization at room temperature (25 C.) for 10min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 60and collected as a black powder polymer (H-PDA).
(2) Design synthesis of "post-modification" H-PDA-AO
Weighing 100mg of the H-PDA powder prepared in the step (1), dispersing in 50mL of deionized water, adding 5.0mL of glutaraldehyde, magnetically stirring at 500rpm under the condition of avoiding light at 35 , reacting for 10 hours, centrifuging at 12000rpm for 6.0min, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, drying by blowing at 60 , and collecting a product (H-PDA-CHO); dispersing H-PDA-CHO in 60mL absolute ethyl alcohol, weighing 600mg diamino Ma Laijing (DAMN), dispersing in the solution by ultrasonic, magnetically stirring at 35 for 500rpm, reacting for 10H, centrifuging at 12000rpm for 6.0min, washing with absolute ethyl alcohol for five times, blowing and drying at 60 , and collecting a product (H-PDA-CN); dispersing H-PDA-CN in 5.0mL deionized water and 45mL absolute ethanol mixed solution, weighing 2.0g hydroxylamine hydrochloride, ultrasonically dispersing in the solution, adjusting the pH of the solution to 8.0 by using 1.16g sodium hydroxide (NaOH), magnetically stirring at 70 , reacting for 8.0H, centrifuging at 12000rpm for 6.0min, washing with deionized water for five times, washing with absolute ethanol for three times, blowing and drying at 60 , and collecting the product H-PDA-AO.
FIG. 3 is a SEM (a-b) and TEM (c-d) images of the H-PDA prepared in example 1 (1) and the H-PDA-AO prepared in example 1 (2), in which the H-PDA is uniform in size and smooth in surface, and the H-PDA-AO is less greatly changed in size than the H-PDA, but the surface is slightly rough, indicating successful modification.
FIG. 4 is an infrared spectrum of H-PDA prepared in example 1 (1), H-PDA-AO prepared in example 1 (2), and changes in the surface functional groups of the three materials indicate that the materials were prepared successfully.
FIG. 5 is an XPS spectrum of H-PDA prepared in example 1 (1), H-PDA-CHO prepared in example 1 (2), H-PDA-CN, H-PDA-AO, further demonstrating successful material preparation based on C, N, O split peak spectra.
Example 2:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
30Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 50mL of deionized water, 6.25mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 5.0min, and then 80mg of Dopamine (DA) hydrochloride was added, followed by polymerization at room temperature (25 C.) for 10min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 60and collected as a black powder polymer (H-PDA).
(2) Design synthesis of "post-modification" H-PDA-AO
Weighing 100mg of the H-PDA powder prepared in the step (1), dispersing in 40mL of deionized water, adding 4.0mL of glutaraldehyde, magnetically stirring at 450rpm under the light-shielding condition at 30 , reacting for 8.0H, centrifuging at 12000rpm for 6.0min, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, drying by blowing at 50 , and collecting a product (H-PDA-CHO); dispersing H-PDA-CHO in 50mL absolute ethyl alcohol, weighing 500mg diamino Ma Laijing (DAMN), dispersing in the solution by ultrasonic, magnetically stirring at 30 for 450rpm, reacting for 8.0H, centrifuging at 12000rpm for 6.0min, washing with absolute ethyl alcohol for five times, drying by blast air at 50 , and collecting the product (H-PDA-CN); dispersing H-PDA-CN in 4.0mL deionized water and 36mL absolute ethanol mixed solution, weighing 2.0g hydroxylamine hydrochloride, ultrasonically dispersing in the solution, adjusting the pH of the solution to 8.0 by using 1.16g sodium hydroxide (NaOH), magnetically stirring at 65 for 450rpm, reacting for 6.0H, centrifuging at 12000rpm for 6.0min, washing with deionized water for five times, washing with absolute ethanol for three times, blowing and drying at 50 , and collecting a product (H-PDA-AO).
Example 3:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
30Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 50mL of deionized water, 6.25mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 10min, and then 80mg of Dopamine (DA) hydrochloride was added, followed by polymerization at room temperature (25 C.) for 10min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 60and collected as a black powder polymer (H-PDA).
(2) Design synthesis of "post-modification" H-PDA-AO
Weighing 100mg of the H-PDA powder prepared in the step (1), dispersing in 60mL of deionized water, adding 6.0mL of glutaraldehyde, magnetically stirring at 550rpm under 40 in the dark, reacting for 12H, centrifuging at 12000rpm for 6.0min, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, drying by blowing at 70 , and collecting a product (H-PDA-CHO); dispersing H-PDA-CHO in 70mL absolute ethyl alcohol, weighing 700mg of diamino Ma Laijing (DAMN), dispersing in the solution by ultrasonic, magnetically stirring at 40 for 550rpm, reacting for 12H, centrifuging at 12000rpm for 6.0min, washing with absolute ethyl alcohol for five times, blowing and drying at 70 , and collecting a product (H-PDA-CN); dispersing H-PDA-CN in 6.0mL deionized water and 54mL absolute ethanol mixed solution, weighing 5.0g hydroxylamine hydrochloride, ultrasonically dispersing in the solution, adjusting the pH of the solution to 8.0 by using 2.23g sodium hydroxide (NaOH), magnetically stirring at 80 , reacting for 10H, centrifuging at 12000rpm for 6.0min, washing with deionized water for five times, washing with absolute ethanol for three times, blowing and drying at 70 , and collecting a product (H-PDA-AO).
FIG. 1 is a graph showing the effect of the duration of mixing deionized water and n-propanol solvents on bubble size in examples 1-3, and a-c are DLS particle size distribution plots for solvent mixtures of 2.0min,5.0min, and 10.0min, respectively, showing that bubbles are relatively uniform at 2.0min, about 56.74nm, and over time, the bubbles age, become larger in size, and are less uniform than at 2.0 min.
Example 4:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
30Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 50mL of deionized water, 6.25mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 2.0min, and then 40mg of Dopamine (DA) hydrochloride was added, followed by polymerization at room temperature (25 C.) for 10min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 60and collected as a black powder polymer (H-PDA).
Example 5:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
30Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 50mL of deionized water, 6.25mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 2.0min, and then 160mg of Dopamine (DA) hydrochloride was added, followed by polymerization at room temperature (25 C.) for 10min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 60and collected as a black powder polymer (H-PDA).
Example 6:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
30Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 50mL of deionized water, 6.25mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 2.0min, and then 80mg of Dopamine (DA) hydrochloride was added, followed by polymerization at room temperature (25 C.) for 60min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 60and collected as a black powder polymer (H-PDA).
Example 7:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
30Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 50mL of deionized water, 6.25mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 2.0min, and then 80mg of Dopamine (DA) hydrochloride was added, followed by polymerization at room temperature (25 C.) for 120min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 60and collected as a black powder polymer (H-PDA).
FIG. 2 is a TEM image of hollow polydopamine spheres (H-PDA) of examples 1-7 for preparing H-PDA of different structures by adjusting different parameters,
A-c are respectively the mixing time periods of 2.0min, 5.0min and 10min of deionized water and n-propanol solvents in examples 1-3, and comparison shows that the bubble size gradually increases with the increase of the solvent mixing time period;
d-f are respectively 40mg, 80mg and 160mg of DA in example 1, example 4 and example 5, the dispersibility of the particles is poor along with the increase of the dosage, and the hollow structure of part of the particles is not obvious;
g-i are the polymerization time periods of 10min, 60min and 120min in the examples 1, 6 and 7, respectively, and the thickness of the polymer shell layer gradually increases with the increase of the polymerization time, and the hollow structure of part of the particles gradually becomes unobvious.
Example 8:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
25Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 40mL of deionized water, 6.0mL of n-propanol was rapidly added, stirred for 2.0min at a magnetic stirring speed of 500rpm, and then 80mg of Dopamine (DA) hydrochloride was added to polymerize at 20for 10min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 50and collected as a black powder polymer (H-PDA).
Example 9:
(1) Design synthesis of hollow polydopamine sphere (H-PDA)
35Mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 60mL of deionized water, 6.5mL of n-propanol was rapidly added, stirred for 2.0min at a rotation speed of 700rpm by magnetic stirring, and then 80mg of Dopamine (DA) hydrochloride was added to polymerize at 30for 10min. The solution was collected, centrifuged at 12000rpm for 6.0min to obtain a black polymer, which was washed three times with absolute ethanol, air-dried at 70and collected as a black powder polymer (H-PDA).
Example 10:
2.0mg of the H-PDA prepared in example 1 (1) and the H-PDA-AO prepared in example 1 (2) were weighed separately, 10mL of a U (VI) solution having a concentration of 10ppm, and 50mL of a U (VI) solution having a concentration of 10ppm were added separately, and the mixture was subjected to static adsorption at 25for 1.0H under conditions of pH 3.0, 4.0, 5.0, 6.0, 7.0, 8.0 and 9.0, whereby three sets of parallel experiments were conducted in each case.
FIG. 6 is a Zeta potential-pH-adsorption capacity diagram of H-PDA (a) and H-PDA-AO (b), and it can be seen that the optimal adsorption pH values of H-PDA and H-PDA-AO are 6.0 and 7.0, respectively.
Example 11:
2.0mg of H-PDA-AO prepared in example 1 (2) was weighed out and the adsorption solution was collected at 10mL of a 10ppm concentration of U (VI) solution and 50mL of a 10ppm concentration of U (VI) solution under the optimal pH conditions of H-PDA-AO in example 10, and the adsorption solution was collected at 25for 5.0min, 10min, 15min, 20min, 25min, 30min, 40min, 50min and 60min, respectively, and three parallel experiments were performed in each case.
FIG. 7 is a time-adsorption capacity plot of H-PDA-AO in example 11, showing an adsorption equilibrium time of 20min in a 10mL, 10ppm U (VI) solution and 40min in a 50mL, 10ppm U (VI) solution.
Example 12:
2.0mg of H-PDA-AO prepared in example 1 (2) was weighed, the optimum pH of H-PDA-AO in example 10 was selected, and static adsorption was performed for 1.0H in 50mL of U (VI) solution having a concentration of 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm at temperatures of 288K, 298K, 308K, respectively, and three parallel experiments were performed in each case.
FIG. 8 is a graph of equilibrium concentration versus adsorption capacity for H-PDA-AO in example 12 at 288K, 298K, 308K, respectively, as can be seen: as the temperature increases, the adsorption capacity of H-PDA-AO increases. The maximum adsorption capacity at 288K is 314mg g -1, the maximum adsorption capacity at 298K is 350.6mg g -1, and the maximum adsorption capacity at 308K is 787.3mg g -1.
Example 13:
2.0mg of the H-PDA-AO prepared in example 1 (2) was weighed and added to a simulated seawater solution containing UO2 2+(330ppb),VO3-(260ppb),Fe3+(1.7ppb),Co2+(5.0ppb),Ni+(90ppb),Zn2+(1.05ppb),Pb2+(3.0ppb),K+(0.65*106ppb),Na+(10.26*106ppb),Ca2+(0.92*106ppb),Mg2+(1.22*106ppb), and subjected to static adsorption at room temperature (25 ) for 1.0H, three groups of experiments were performed in parallel, and the supernatant was collected by centrifugation, and the ion concentration was detected by using an inductively coupled plasma emission spectrometer (ICP).
FIG. 9 is a test of the selectivity of H-PDA-AO of example 13 to U (VI) as a target in simulated seawater, which shows that H-PDA-AO has good selectivity to U (VI).
Claims (10)
1. A method for preparing amidoxime functionalized hollow polymer spheres based on solvent mixing-induced bubble template method, which is characterized by comprising the following steps:
(1) Synthesis of hollow polydopamine sphere H-PDA
Dissolving a proper amount of Tris (Tris) in a certain amount of deionized water, rapidly adding n-propanol which is in a certain proportion with water, reacting for a period of time under a stirring condition with a certain rotating speed, then adding a proper amount of dopamine hydrochloride DA, polymerizing for a period of time under a certain temperature condition, collecting a solution, centrifuging to obtain a black polymer, washing with absolute ethyl alcohol for a plurality of times, blowing and drying, and collecting a black powder polymer H-PDA;
The dosage ratio of Tris, deionized water, n-propanol and dopamine hydrochloride is 30 mg:50 mL:6.25 mL:40-160 mg; the mixing time of the deionized water and the n-propanol is 2.0-10 min;
(2) Synthesis of "post-modified" H-PDA-AO
S1: weighing a certain amount of the H-PDA powder obtained in the step (1), dispersing in deionized water, adding glutaraldehyde to obtain a mixed solution A, stirring at a certain temperature under a dark condition, reacting for a period of time, centrifugally collecting, washing with deionized water and absolute ethyl alcohol for several times, blasting and drying, and collecting a product H-PDA-CHO;
S2: dispersing a certain amount of H-PDA-CHO in absolute ethyl alcohol, adding diaminomaleonitrile DAMN, performing ultrasonic dispersion to obtain a mixed solution B, stirring at a certain temperature, reacting for a period of time, centrifugally collecting, washing with absolute ethyl alcohol for a plurality of times, performing forced air drying, and collecting a product H-PDA-CN;
S3: dispersing a certain amount of H-PDA-CN in a mixed solution of deionized water and absolute ethyl alcohol to obtain a mixed solution C, adding a certain amount of hydroxylamine hydrochloride, performing ultrasonic dispersion, stirring and reacting at a certain temperature, adding sodium hydroxide NaOH to regulate the pH of the solution, continuously reacting for a period of time, centrifugally collecting, washing the deionized water and the absolute ethyl alcohol for several times, performing blast drying, and collecting the product amidoxime functionalized hollow polymer spheres, namely H-PDA-AO.
2. The method of claim 1, wherein in step (1), the reaction temperature is 20 to 30 and the rotation speed is 500 to 700 rpm.
3. The method of claim 1, wherein in step (1), the dopamine hydrochloride is polymerized for a period of time ranging from 10 to 120 min.
4. The method of claim 1, wherein in step (2) S1, the mixed solution a comprises H-PDA, deionized water, glutaraldehyde in an amount ratio of 100 mg:40-60 mL:4.0-6.0 mL, under the condition of light shielding, the reaction temperature is 30-40 , the stirring speed is 450-550 rpm, and the reaction time is 8.0-12 h.
5. The method of claim 1, wherein in step (2) S2, the mixed solution B comprises H-PDA-CHO, absolute ethanol, and DAMN in an amount ratio of 90-100 mg:50-70 mL:500-700 mg, reaction temperature of 30-40 , stirring speed of 450-550 rpm and reaction time of 8.0-12 h.
6. The method of claim 1, wherein in step (2) S3, the volume ratio of deionized water to absolute ethanol in the mixed solution of deionized water and absolute ethanol is 1:9;
in the mixed solution C, the dosage ratio of H-PDA-CN, deionized water and absolute ethyl alcohol is 90-100 mg:4.0-6.0 mL:36-54 mL.
7. The method of claim 1, wherein in step (2) S3, the ratio of hydroxylamine hydrochloride to mixed solution C is 2.0 to 5.0 g:40-60 mL, and the ultrasonic dispersion time is 10-20 min; the temperature of the stirring reaction is 65-80 , the reaction time is 5-10min, and the stirring speed is 450-550 rpm.
8. The method according to claim 1, wherein in step (2) S3, sodium hydroxide NaOH is added to adjust the pH of the solution to 7.5-8.5, the reaction is continued at a temperature of 65-80 for a reaction time of 6.0-10 h.
9. The method of claim 1, wherein in the steps (1) and (2), the blast drying temperature is 50-70 and the drying time period is 8.0-12 h.
10. Use of amidoxime-functionalized hollow polymer spheres H-PDA-AO prepared according to any of claims 1 to 9 for uranium extraction.
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