CN114570339B - Method for preparing salicylaldoxime/polydopamine hollow nano adsorbent by one-step method and uranium removal application thereof - Google Patents
Method for preparing salicylaldoxime/polydopamine hollow nano adsorbent by one-step method and uranium removal application thereof Download PDFInfo
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- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 title claims abstract description 36
- 239000003463 adsorbent Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 30
- 229910052770 Uranium Inorganic materials 0.000 title abstract description 4
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 17
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 30
- 239000007983 Tris buffer Substances 0.000 claims description 27
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 9
- WGYFACNYUJGZQO-UHFFFAOYSA-N aminomethanetriol Chemical compound NC(O)(O)O WGYFACNYUJGZQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005422 blasting Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 30
- 238000002360 preparation method Methods 0.000 abstract description 11
- 150000002923 oximes Chemical class 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000010828 elution Methods 0.000 abstract description 4
- 239000000839 emulsion Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical group O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 125000003544 oxime group Chemical group 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 58
- 229960003638 dopamine Drugs 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000013461 design Methods 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002101 nanobubble Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- -1 uranyl ions Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KPCUHKOWTBLDJY-UHFFFAOYSA-N NC(C(C1O)=N)=CC=C1O Chemical compound NC(C(C1O)=N)=CC=C1O KPCUHKOWTBLDJY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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Abstract
The invention belongs to the technical field of environment-friendly functional materials, and discloses a method for preparing salicylaldoxime/polydopamine hollow nano-adsorbent by a one-step method and application of uranium removal U (VI). According to the invention, dopamine hydrochloride DA is used as a polymerization monomer, salicylaldoxime is used as a functional monomer, and an oxime functional hollow nano adsorbent H-PDA-SO is prepared by a one-step method, SO that the defects that the traditional emulsion template method is limited in size control, the subsequent template elution can cause structural damage, the organic reagent can pollute the environment and the like are overcome; in addition, the co-deposition of PDA and salicylaldoxime not only solves the problems of high time cost, high complexity and low oxidation efficiency in the prior preparation of oxime functionalized nano-structure adsorbent, but also combines the ionic property of PDA multifunctional surface modification with the excellent pairing capability of oxime group to uranyl ion. The H-PDA-SO preparation only needs 130min, and the H-PDA-SO preparation can reach equilibrium within 40-50min when applied to U (VI) solution adsorption in aqueous solution, and the maximum adsorption capacity at room temperature is 96.5 mg.g ‑1 。
Description
Technical Field
The invention belongs to the technical field of preparation of environment-friendly functional materials, and particularly relates to a method for preparing an oxime functional hollow nano adsorbent by using nano bubbles as templates through a one-step method and application of the oxime functional hollow nano adsorbent in the field of rapid removal of nuclide U (VI) in water environment.
Background
With the development of science and technology, nuclear pollution has become a hot topic in the current generation, the existence of nuclides in water body seriously threatens human health, and the U (VI) -containing water body has the characteristics of wide source, more total amount, high complexity, high hazard and the like. Uranium is a main element in nuclear energy production, and is one of the most dangerous radioactive elements, and rapid treatment of leaked U (VI) in water environment plays a key role in emergency treatment and environmental pollution improvement. Whether for environmental protection or maintenance of human health, we are pressing to develop a highly efficient adsorbent for the rapid treatment of U (VI) generated by nuclear leaks.
At present, the methods for U (VI) emergency treatment include an ion exchange method, an electrochemical method, a chemical precipitation method, a photocatalysis method, an adsorption separation method and the like, wherein the adsorption separation method is one of the effective methods for U (VI) -containing water treatment due to the advantages of high separation efficiency, good selectivity, simple operation, low cost and the like. However, there are three inherent limitations to the use of physicochemical adsorption for the extraction of U (VI) in water resources. First, the rate of uranyl ion diffusion to the adsorbent surface is slow due to the low U (VI) concentration in the aqueous environment. Second, the adsorbed cations are positively charged and therefore will reject the incoming uranyl ions due to coulomb repulsion, rendering most of the surface active sites inaccessible. Finally, other cations, such as sodium and calcium, have concentrations many orders of magnitude higher than U (VI), which results in strong competition for adsorption of active sites that will become blocked while reducing U (VI) collection capacity when unwanted species adsorb to the adsorbent surface.
The adsorbents for enriching U (VI) are various in types, wherein the hollow nano adsorbent has the advantages of large specific surface area, high load, low density, high abundance of binding sites, rapid mass transfer and the like, and is widely applied to the field of adsorption separation. The traditional emulsion template method has the defects of limited size control, structural damage caused by subsequent template elution, environmental pollution caused by the use of organic reagents and the like. In addition, oxime functionalized hollow nanosorbents are one of the most promising U (VI) adsorption candidate materials.
However, the current preparation methods mainly focus on grafting and oxidation, so that the method for obtaining the nano-adsorbent is inefficient. In order to avoid the defects, a novel preparation method is urgently developed, and the hollow nano adsorbent is rapidly constructed and applied to treatment of U (VI) -containing water bodies.
Disclosure of Invention
The invention provides a method for constructing a hollow nano adsorbent by adopting a bubble template method, taking dopamine hydrochloride (DA) as a polymerization monomer and salicylaldoxime as a functional monomer, and the method is used for preparing the salicylaldoxime/polydopamine hollow nano adsorbent (H-PDA-SO) by a one-step method and treating a water body containing U (VI) in order to solve the problems that the traditional emulsion template method has limited size control, structural damage caused by subsequent template elution, environmental pollution caused by the use of an organic reagent and the like, and the U (VI) adsorbent has complex preparation process, insufficient adsorption rate and poor adsorption selectivity.
According to the invention, by utilizing rapid polymerization of dopamine hydrochloride (DA) and deposition of salicylaldoxime, after DA polymerization for 7.0min, salicylaldoxime is added to copolymerize with DA to form a salicylaldoxime/polydopamine shell layer, and a high-density oxime functional hollow nano adsorbent, namely the salicylaldoxime/polydopamine hollow nano adsorbent (H-PDA-SO), is rapidly prepared. Meanwhile, hollow polydopamine spheres (H-PDA) are also prepared as a comparison material. In summary, this work separately prepares two adsorbents: H-PDA, H-PDA-SO for comparative study.
The method for preparing the salicylaldoxime/polydopamine hollow nano adsorbent by the one-step method comprises the following steps:
dissolving a proper amount of trihydroxy aminomethane (Tris) in a certain amount of deionized water, quickly adding n-propanol, stirring for a period of time under a certain rotating speed condition to obtain a mixed solution O, adding a proper amount of dopamine hydrochloride (DA), polymerizing for a period of time under a certain temperature condition, adding a certain amount of salicylaldoxime, and polymerizing for a period of time. Collecting solution, centrifuging to obtain black polymer, washing with absolute ethanol for several times, air-blasting and drying, and collecting black powder polymer, namely salicylaldoxime/polydopamine hollow nano adsorbent H-PDA-SO.
Wherein, the dosage ratio of Tris to deionized water is 25-35mg:40-60mL, and mixing to obtain pH 8.5-8.8, reaction temperature 20-30deg.C, and rotation speed 500-700rpm.
Wherein the dosage ratio of deionized water to n-propanol is 40-60mL:6.0-6.5mL, and rotating speed is 500-700rpm.
Wherein the temperature required by stirring and mixing the deionized water and the n-propanol is 20-30 ℃, and the stirring time is 2.0-10.0min.
Wherein, the dosage ratio of the dopamine hydrochloride to the mixed solution O is 50-100mg:46-66.5mL, dopamine hydrochloride polymerization temperature of 20-30 ℃, rotating speed of 500-700rpm and reaction time of 0-7.0min.
Wherein the dosage of the dopamine hydrochloride and the salicylaldoxime is 50-100mg:200-400mg, the polymerization time is 1.0-3.0h after adding salicylaldoxime, and the reaction temperature is 20-30 ℃.
By contrast, the invention also synthesizes hollow polydopamine spheres (H-PDA), which comprises the following specific steps:
dissolving a proper amount of trihydroxy aminomethane (Tris) in a certain amount of deionized water, quickly adding n-propanol, 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. The solution was collected, centrifuged to obtain a black polymer, which was washed with absolute ethanol several times, air-dried, and collected as a black powder polymer (H-PDA).
Wherein, the dosage ratio of Tris, deionized water, n-propanol and dopamine hydrochloride is 30mg:50mL:6.25mL: 50-100mg.
Wherein the stirring speed is 450-700rpm, and the reaction temperature is 20-30 ℃.
Wherein the polymerization time of the dopamine hydrochloride is 10-30min, and the polymerization temperature is 20-30 ℃.
Wherein the drying temperature is 50-70 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation process of the adsorbent H-PDA-SO is simple, the nano bubble is used as a template, DA is used as a main polymerization monomer, salicylaldoxime is used as a functional monomer, and the novel salicylaldoxime/polydopamine hollow nano adsorbent (H-PDA-SO) with rapid mass transfer and high-density active sites is rapidly prepared by a one-step method and is used for treating water bodies containing U (VI).
(2) The adsorbent H-PDA-SO is adsorbed in 10mL of U (VI) solution with the concentration of 10ppm for 40min to reach adsorption equilibrium, is adsorbed in 50mL of U (VI) solution with the concentration of 10ppm for 50min to reach adsorption equilibrium, and the maximum adsorption capacity of the adsorbent H-PDA-SO can reach 103mg g at the room temperature of 25 DEG C -1 。
(3) The invention adopts the bubble template method to prepare the hollow nano adsorbent, solves the problems that the traditional emulsion system has limited size control, structural damage can be caused by subsequent template elution, environmental pollution can be caused by the use of organic reagents, and the like;
(4) The choice of substrate, DA, can attach to the surface of almost all substrates by self-polymerization, and the polymerization rate is very fast, 10min being sufficient to coat the substrate with a poly-dopamine (PDA) functional layer. PDA has a large number of functional groups such as: amino, imino, catechol, etc., while also having strong non-covalent interactions such as: electrostatic interactions, hydrogen bonding, complexation or chelation, etc.; these groups and interactions provide superior adhesion and secondary reactivity to PDA. Also because of its versatility, we apply it as a substrate to the removal of U (VI) in a body of water;
(5) The co-deposition of PDA and salicylaldoxime not only solves the problems of high time cost, high complexity and low oxidation efficiency in the prior preparation of oxime functionalized nano-structure adsorbent, but also perfectly combines the ionic property of PDA multifunctional surface modification with the excellent pairing capability of oxime group to uranyl ion.
Drawings
FIG. 1 is an SEM (a-b) and TEM (c-d) images of H-PDA-SO and H-PDA prepared in example 1, respectively;
FIG. 2 is an infrared spectrum of H-PDA-SO, H-PDA prepared in example 1;
FIG. 3 is XPS spectra of H-PDA-SO, H-PDA prepared in example 1;
FIG. 4 is a Zeta potential-pH-adsorption capacity diagram of H-PDA (a) and H-PDA-SO (b);
FIG. 5 is a graph of H-PDA-SO time-adsorption capacity;
FIG. 6 is a graph of equilibrium concentration versus adsorption capacity for H-PDA-SO at 288K, 298K, 308K temperature, respectively;
FIG. 7 is a graph showing the selectivity of H-PDA-SO to U (VI) target in a complex body of water containing U (VI).
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Example 1:
(1) Design synthesis of "one-step synthesis" H-PDA-SO
30mg of trihydroxy aminomethane (Tris) is dissolved in 50mL of deionized water, 6.25mL of n-propanol is rapidly added, stirring is carried out for 2.0min under the condition of magnetic stirring at 600rpm, then 80mg of dopamine hydrochloride (DA) is added, reaction is carried out for 7.0min under the condition of 25 ℃, 300mg of salicylaldoxime is added, and polymerization is carried out for 2.0h. 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 60℃and collected as a black powder polymer (H-PDA-SO).
(2) 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 for 2.0min at a magnetic stirring speed of 600rpm, and then 80mg of Dopamine (DA) hydrochloride was added, followed by polymerization at 25℃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 60℃and collected as a black powder polymer (H-PDA).
FIG. 1 is a SEM (a-b) and TEM (c-d) image of H-PDA-SO prepared in step (1) of example 1, H-PDA prepared in step (2) of example 1, in which it can be seen that H-PDA is uniform in size and smooth in surface, and H-PDA-SO is larger in size than H-PDA.
FIG. 2 is an infrared spectrum of H-PDA-SO prepared in step (1) of example 1, H-PDA prepared in step (2) of example 1, and the change in surface functional groups indicates that the material preparation was successful.
FIG. 3 is an XPS spectrum of H-PDA-SO prepared in step (1) of example 1, H-PDA prepared in step (2) of example 1, which can further demonstrate the success of material preparation based on a C, N, O peak-splitting spectrum.
Example 2:
(1) Design synthesis of "one-step synthesis" H-PDA-SO
25mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 40mL of deionized water, 6.0mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 2.0min, then 80mg of Dopamine (DA) hydrochloride was added, reacted at 25℃for 7.0min, 300mg of salicylaldoxime was added, and polymerization was carried out for 2.0h. 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 50℃and collected as a black powder polymer (H-PDA-SO).
(2) 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 for 2.0min at a magnetic stirring speed of 600rpm, and then 50mg of Dopamine (DA) hydrochloride was added, followed by polymerization at 25℃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 50℃and collected as a black powder polymer (H-PDA).
Example 3:
(1) Design synthesis of "one-step synthesis" H-PDA-SO
35mg of Tris (hydroxy-aminomethane) (Tris) was dissolved in 60mL of deionized water, 6.5mL of n-propanol was rapidly added, stirred at a magnetic stirring speed of 600rpm for 2.0min, then 80mg of Dopamine (DA) hydrochloride was added, reacted at 25℃for 7.0min, 300mg of salicylaldoxime was added, and polymerization was carried out for 2.0h. 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 60℃and collected as a black powder polymer (H-PDA-SO).
(2) 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 for 2.0min at a magnetic stirring speed of 600rpm, and 100mg of Dopamine (DA) hydrochloride was then added to polymerize at 25℃for 30min. 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 70℃and collected as a black powder polymer (H-PDA).
Example 4:
(1) Design synthesis of "one-step synthesis" H-PDA-SO
30mg of trihydroxy aminomethane (Tris) is dissolved in 50mL of deionized water, 6.25mL of n-propanol is rapidly added, the mixture is stirred for 5.0min under the condition of magnetic stirring at 500rpm, then 80mg of dopamine hydrochloride (DA) is added, the mixture is reacted for 7.0min under the condition of 20 ℃, 300mg of salicylaldoxime is added, and polymerization is carried out for 2.0h. 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 60℃and collected as a black powder polymer (H-PDA-SO).
(2) 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 for 2.0min at a rotation speed of 450rpm by magnetic stirring, and then 80mg of Dopamine (DA) hydrochloride was added to polymerize at 20℃for 20min. 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 50℃and collected as a black powder polymer (H-PDA).
Example 5:
(1) Design synthesis of "one-step synthesis" H-PDA-SO
30mg of trihydroxy aminomethane (Tris) is dissolved in 50mL of deionized water, 6.25mL of n-propanol is rapidly added, stirring is carried out for 10min under the condition of magnetic stirring at 700rpm, then 80mg of dopamine hydrochloride (DA) is added, reaction is carried out for 7.0min under the condition of 30 ℃, 300mg of salicylaldoxime is added, and polymerization is carried out for 2.0h. 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 70℃and collected as a black powder polymer (H-PDA-SO).
(2) 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 for 2.0min at a rotation speed of 700rpm by magnetic stirring, and then 80mg of Dopamine (DA) hydrochloride was added to polymerize at 30℃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 60℃and collected as a black powder polymer (H-PDA).
Example 6:
(1) Design synthesis of "one-step synthesis" H-PDA-SO
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, then 50mg of Dopamine (DA) hydrochloride was added, reacted at 25℃for 0min, 200mg of salicylaldoxime was added, and polymerization was carried out for 1.0h. 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 60℃and collected as a black powder polymer (H-PDA-SO).
Example 7:
(1) Design synthesis of "one-step synthesis" H-PDA-SO
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, then 100mg of Dopamine (DA) hydrochloride was added, reacted at 25℃for 7.0min, 400mg of salicylaldoxime was added, and polymerization was carried out for 3.0h. 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 70℃and collected as a black powder polymer (H-PDA-SO).
Example 8:
2.0mg of the H-PDA-SO prepared in example 1 (1) and the H-PDA prepared in example 1 (2) were weighed separately, 10mL of a U (VI) solution having a concentration of 10ppm was added separately, and the mixture was statically adsorbed at 25℃for 1.0H under conditions of pH 3.0, 4.0, 5.0, 6.0, 7.0, 8.0 and 9.0, and three parallel experiments were performed in each case.
FIG. 4 is a Zeta potential-pH-adsorption capacity plot of H-PDA and H-PDA-SO of example 8, wherein it can be seen that the H-PDA-SO (b) and H-PDA (a) each have an optimal adsorption pH of 6.0; the main adsorption mechanism is electrostatic action under the acidic condition, and electrostatic repulsion is generated between the surface charge of the adsorbent and uranyl radical under the alkaline condition, so that the adsorption mechanism is mainly coordination action.
Example 9:
2.0mg of H-PDA-SO prepared in example 1 (1) was weighed, and the adsorbed solutions were collected at 10mL of U (VI) solution at 10ppm concentration and 50mL of U (VI) solution at 10ppm concentration, at 25℃for 5.0min, 10min, 15min, 20min, 25min, 30min, 40min, 50min and 60min, respectively, under the optimal pH conditions of the material in example 8, and three parallel experiments were performed in each case.
FIG. 5 is a graph of H-PDA-SO time versus adsorption capacity for example 9, showing that the H-PDA-SO adsorption equilibrium time in a 10mL, 10ppm U (VI) solution is 40min and the H-PDA-SO adsorption equilibrium time in a 50mL, 10ppm U (VI) solution is 50min.
Example 10:
2.0mg of H-PDA-SO prepared in example 1 (1) was weighed and statically adsorbed for 1.0H in 50mL volumes of U (VI) solutions of concentrations 10ppm, 20ppm, 30 ppm, 40ppm, 50ppm, 60ppm at the optimum pH for the material in example 8, at temperatures 288K, 298K, 308K, respectively, three parallel sets of experiments were performed in each case.
FIG. 6 is a graph of equilibrium concentration versus adsorption capacity for H-PDA-SO at 288K, 298K, 308K, respectively, in example 10, as can be seen: as the temperature increases, the adsorption capacity of H-PDA-SO increases. Its maximum adsorption capacity at 288K is 81.25mg g -1 The maximum adsorption capacity at 298K is 96.5mg g -1 Maximum adsorption capacity at 308K is 132.25mg g -1 。
Example 11:
2.0mg of H-PDA-SO prepared in example 1 (1) was weighed and added with UO 2 2+ (330ppb)，VO 3- (260 ppb)，Fe 3+ (1.7ppb)，Co 2+ (5.0ppb)，Ni + (90ppb)，Zn 2+ (1.05ppb)，Pb 2+ (3.0ppb)，K + (0.65*10 6 ppb)，Na + (10.26*10 6 ppb)，Ca 2+ (0.92*10 6 ppb)，Mg 2+ (1.22*10 6 ppb), static adsorption is performed at room temperature for 1.0h, three groups of experiments are performed in parallel, supernatant is collected by centrifugation, and ion concentration is detected by using an inductively coupled plasma emission spectrometer (ICP).
FIG. 7 shows the selectivity of H-PDA-SO to U (VI) as a target in a complex water containing U (VI) in example 11, which shows that the H-PDA-SO has good adsorption selectivity to U (VI).
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (6)
1. The method for preparing the salicylaldoxime/polydopamine hollow nano adsorbent by the one-step method is characterized by comprising the following steps of:
dissolving Tris (trihydroxy aminomethane) in a certain amount of deionized water, rapidly adding n-propanol, stirring for 2.0-10.0min at a rotating speed of 500-700rpm to obtain a mixed solution, then adding dopamine hydrochloride, polymerizing for a period of time at a certain temperature, then adding a certain amount of salicylaldoxime, polymerizing for a period of time, collecting the solution, centrifuging to obtain a black polymer, washing with absolute ethyl alcohol for several times, blasting and drying, and collecting the black powder polymer, namely the salicylaldoxime/polydopamine hollow nano adsorbent H-PDA-SO;
the dosage ratio of Tris, deionized water and n-propanol is 25-35mg:40-60 mL: 6.0-6.5. 6.5 mL.
2. The method for preparing salicylaldoxime/polydopamine hollow nano-adsorbent according to claim 1, wherein the temperature required for stirring is 20-30 ℃.
3. The method for preparing salicylaldoxime/polydopamine hollow nano-adsorbent according to claim 1, wherein the dosage ratio of the dopamine hydrochloride to the mixed solution is 50-100mg: 46-66.5-mL, dopamine hydrochloride polymerization temperature is 20-30 ℃, and reaction time is 0-7.0min.
4. The method for preparing the salicylaldoxime/polydopamine hollow nano-adsorbent according to the one-step method of claim 1, wherein the usage amount of the dopamine hydrochloride and the salicylaldoxime is 50-100mg:200-400 and mg, the polymerization time is 1.0-3.0h after adding salicylaldoxime, and the reaction temperature is 20-30 ℃.
5. A salicylaldoxime/polydopamine hollow nano-adsorbent prepared by the method of any one of claims 1-4.
6. Use of the salicylaldoxime/polydopamine hollow nanosorbent according to claim 5 for treating U (VI) containing water.
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Application publication date: 20220603 Assignee: Lihong Microspheres Technology (Zhejiang) Co.,Ltd. Assignor: Shanghai Nahong Microspheres Technology Co.,Ltd. Contract record no.: X2024980005780 Denomination of invention: A one-step method for preparing hollow nano adsorbents of salicylaldehyde oxime/polydopamine and their application in uranium removal Granted publication date: 20231205 License type: Common License Record date: 20240514 |