CN113797901A - Hydrophilic amidoxime functionalized porous photonic crystal material and preparation method and application thereof - Google Patents
Hydrophilic amidoxime functionalized porous photonic crystal material and preparation method and application thereof Download PDFInfo
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- CN113797901A CN113797901A CN202111164717.6A CN202111164717A CN113797901A CN 113797901 A CN113797901 A CN 113797901A CN 202111164717 A CN202111164717 A CN 202111164717A CN 113797901 A CN113797901 A CN 113797901A
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 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 46
- 239000004038 photonic crystal Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 40
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- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- COQLPRJCUIATTQ-UHFFFAOYSA-N Uranyl acetate Chemical compound O.O.O=[U]=O.CC(O)=O.CC(O)=O COQLPRJCUIATTQ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
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- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 1
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
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- IONSZLINWCGRRI-UHFFFAOYSA-N n'-hydroxymethanimidamide Chemical group NC=NO IONSZLINWCGRRI-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
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Images
Classifications
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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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- 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
Abstract
The invention discloses a hydrophilic amidoxime functionalized porous photonic crystal material, and a preparation method and application thereof. The material is porous polymer hydrogel which is in a photonic crystal structure, and the polymer in the porous polymer hydrogel is provided with amidoxime groups, amido groups and carboxyl groups. The material provided by the scheme of the invention can be used for efficiently removing and detecting uranyl ions (UO) at the same time2 2+) All the groups and the structures cooperate to ensure that the maximum actual adsorption capacity of the material can reach more than 2.52 mmol/g; sensitive and selective detection of uranyl ions can be easily realized by recording diffraction wavelength shift of the photonic crystal hydrogel or observing color change of the photonic crystal hydrogel, the detection limit can be as low as below 10nM, the interference of co-ions is hardly generated, and the uranium removal rate can reach more than 99.91%; meanwhile, the material also has good regeneration performance and wide application prospect in the aspect of water pollution control.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a hydrophilic amidoxime functionalized porous photonic crystal material, and a preparation method and application thereof.
Background
Uranium is a key raw material in the nuclear industry, and has important significance for the industry, national defense and scientific and technological development of China. However, uranium mining, nuclear waste discharge and nuclear accidents, inevitably occur with the release of uranium into the ecological environment. Uranium is radioactive and chemically toxic and can be enriched in organisms by the food chain, resulting in DNA damage or severe disease. Therefore, the detection and the removal of uranium in the water body have important significance.
In the related art, researchers have developed various functional materials for uranium removal or detection, such as porous inorganic materials, amorphous porous organic polymers, metal organic frameworks, and the like, but these materials have limited uranium removal capability or only enable uranium detection or removal. In recent years, some researchers developed a completely amidoximated nanofiber adsorbent, which can improve extraction of uranium in seawater to a certain extent, and meanwhile, the material needs to be prepared through a grafting reaction, the preparation conditions are severe, and grafting efficiency needs to be limited, so that the industrial application prospect of the material is poor. Therefore, the development of a novel functional material which has a good uranium removal effect and is easy to prepare is of great significance.
Statements in this background are not admitted to be prior art to the present disclosure.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a hydrophilic amidoxime functionalized material which has a good uranium removal effect and is easy to prepare.
The invention also provides a preparation method of the material.
The invention also provides application of the material.
According to one aspect of the invention, a hydrophilic amidoxime functionalized material is provided, wherein the material is a porous polymer hydrogel which has a photonic crystal structure, and polymers in the porous polymer hydrogel have amidoxime groups, amide groups and carboxyl groups.
According to a preferred embodiment of the present invention, at least the following advantages are provided: the material provided by the scheme of the invention can be used for efficiently removing and detecting uranyl ions (UO) at the same time2 2+) The amidoxime ligand on the material provides a specific UO2 2+Binding sites are subjected to hydrophilic modification treatment, so that the adsorption capacity of the binding sites on target ions is remarkably enhanced; the porous photonic crystal structure has a porous structure and a larger specific surface area, the ion permeability is also greatly improved, and the maximum actual adsorption capacity of the material can reach more than 2.52mmol/g (the theoretical adsorption capacity can reach 2.61mmol/g) through the synergy of all groups and structures; sensitive and selective detection of uranyl ions can be easily realized by recording diffraction wavelength shift of the photonic crystal hydrogel or observing color change of the photonic crystal hydrogel, the detection limit can be as low as below 10nM, the interference of co-ions is hardly generated, and the uranium removal rate can reach more than 99.91%; meanwhile, the material also has good regeneration performance and wide application prospect in the aspect of water pollution control.
In some embodiments of the invention, the polymer comprises the following structural units:
wherein n1, n2 and n3 are each independently a natural number.
In some embodiments of the invention, the raw materials for preparing the material comprise the following components: the silicon dioxide nano-particle etching solution comprises monodisperse silicon dioxide microspheres, an etching agent, a gel pre-polymerization solution, hydroxylamine hydrochloride and N, N, N ', N' -tetramethyl ethylenediamine (TEMED), wherein the gel pre-polymerization solution contains acrylamide, acrylonitrile, a cross-linking agent and a photoinitiator; preferably, the cross-linking agent comprises at least one of N, N' -methylenebisacrylamide (BisAA) and polyethylene glycol diacrylate (PEGDA); more preferably, the photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-acetone (HMPP).
In some embodiments of the invention, the monodisperse silica microspheres have a particle size of 100-500 nm; preferably 150-300 nm; more preferably 150 to 200 nm; most preferably about 177.8 nm.
In some embodiments of the invention, the etchant contains hydrogen fluoride.
In some preferred embodiments of the present invention, the mass-to-volume ratio of the monodisperse silica microspheres to the gel pre-polymerization solution is: 30-60%; preferably 50-60%; more preferably 55%. The color or diffraction wavelength of the photonic crystal can be changed to a certain extent due to the silica and gel pre-polymerization liquid with different proportions, and the photonic crystal with different colors or diffraction wavelengths in the components of the invention can be changed in color in the uranyl ion-containing solution, so that the detection purpose of the photonic crystal is not influenced.
In some preferred embodiments of the invention, the cross-linking agent comprises BisAA, and the mass ratio of AA to BisAA in the gel pre-polymerization solution is 5-15: 1.
in some preferred embodiments of the present invention, the crosslinking agent comprises PEGDA, the photoinitiator comprises HMPP, and the volume ratio of AN, PEGDA and HMPP in the gel pre-polymerization solution is 15-25: 10-20: 1.
in some preferred embodiments of the present invention, the total concentration by volume of the gel pre-polymerization solution is50 to 60%.
According to another aspect of the present invention, a preparation method of the hydrophilic amidoxime functionalized material is provided, which comprises the following steps:
s1, mixing the monodisperse silicon dioxide microspheres with the gel prepolymerization solution, and carrying out polymerization reaction under illumination;
s2, adding an etching agent for etching;
s3, adding hydroxylamine hydrochloride to oximate;
s4, adding TEMED for hydrolysis to obtain;
wherein the gel pre-polymerization liquid contains acrylamide, acrylonitrile, a cross-linking agent and a photoinitiator.
According to a preferred embodiment of the present invention, at least the following advantages are provided: the method has simple and convenient steps and mild conditions, does not need strict reaction conditions or complex equipment, and can realize high conversion rate of amidoxime groups on the hydrogel by introducing nitrile groups through photopolymerization.
According to a preferred embodiment of the present invention, the gel pre-polymerization solution comprises acrylamide (AA), Acrylonitrile (AN), N' -methylenebisacrylamide (BisAA), polyethylene glycol diacrylate (PEGDA), and 2-hydroxy-2-methyl-1-phenylpropanone (HMPP).
In some embodiments of the present invention, the step S1 further includes a step of preparing monodisperse silica microspheres, which specifically includes: by using
The monodisperse silicon dioxide nanometer microsphere is synthesized by the method.
In some preferred embodiments of the present invention, the preparation step of the nano-di-silicon dioxide uses ethyl silicate (TEOS) as a raw material.
In some embodiments of the present invention, the step S1 further includes a step of preparing a gel pre-polymerization solution, which specifically includes mixing the raw materials with water, exchanging with an ion exchange resin, and centrifuging to remove the resin.
In some embodiments of the invention, the polymerization is polymerization under ultraviolet light; preferably, the wavelength of the ultraviolet light is 360-370 nm; more preferably about 365 nm.
In some embodiments of the present invention, the step S3 specifically includes the following steps: the product treated in step S2 was reacted with neutralized hydroxylamine hydrochloride in an aqueous methanol solution.
According to a further aspect of the invention, the application of the hydrophilic amidoxime functionalized material in uranium detection, extraction and/or removal is provided.
According to a preferred embodiment of the present invention, at least the following advantages are provided: the material provided by the invention has good selective adsorption performance on uranium, is suitable for efficient treatment of uranium in radioactive wastewater, and has good application prospects in the fields of uranium extraction from seawater, radioactive wastewater treatment, environmental remediation and the like.
A kit for uranium detection, extraction and/or removal comprises the hydrophilic amidoxime functionalized material.
According to a preferred embodiment of the present invention, at least the following advantages are provided: the kit is prepared from the materials, so that the usage and carrying are more convenient, the visual monitoring of uranium can be realized, and the effective extraction or removal of uranium can be realized.
In some embodiments of the invention, the kit further comprises a color chart. The semi-quantitative judgment of the uranium concentration can be carried out through the colorimetric card.
A qualitative uranium detection method comprises the following steps: and (3) mixing the hydrophilic amidoxime functional material with a solution to be detected, observing diffraction wavelength shift or observing color change, and judging whether uranium is contained.
A quantitative uranium detection method comprises the following steps: and mixing the hydrophilic amidoxime functional material with a solution to be detected, and judging the content of uranium in the solution to be detected according to the relation between the color variation and the content of uranium.
A uranium removal method, comprising the steps of: and mixing the hydrophilic amidoxime functional material with a solution to be detected.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic diagram of the preparation process of the HAPPCH material in the embodiment of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) test result chart of the product prepared by the embodiment of the invention; wherein, the picture A is a silicon dioxide microsphere; b is PCH; c is the outer surface of PPCH; d is the inner surface of PPCH;
FIG. 3 is a DLS test result graph in accordance with an embodiment of the present invention;
FIG. 4 is a diagram showing the results of the characterization of PPCH, APPCH and HAPPCH manufactured in the example of the present invention; wherein, the diagram A is a solid state13CNMR test result graph (curves a, b, c represent PPCH, APPCH and HAPPCH in order); graph B is a graph of FTIR test results (curves d, e, f represent PPCH, APPCH and HAPPCH in order); panel C shows HAPPCH at 1mM UO2 2+XPS wide scan spectra before and after 12h of adsorption in solution (curve g is after adsorption, curve h is before adsorption); panel D shows HAPPCH at 1mM UO2 2+EDS plot after 12h of adsorption in solution;
FIG. 5 is a graph of the adsorption capacity of HAPPCH material at different pH's in an example of the present invention;
FIG. 6 is a graph showing the adsorption capacities of the HAPPCH material in different salt environments in the example of the present invention;
FIG. 7 is a graph showing the results of the HAPPCH adsorption performance test in the example of the present invention; wherein, the graph A shows that the HAPPCH material adsorbs UO with different concentrations2 2+Subsequent optical image (starting UO represented by a to h in order)2 2+Concentrations of 0.01, 0.1, 0.5, 1, 3, 5, 8, 10 mM); panel B shows the ratio of HAPPCH to UO at an initial concentration of 5mM2 2+Adsorption kinetics curve of (a); FIG. C shows the adsorption capacity of the HAPPCH material prepared in the example of the present invention under the same conditions as different adsorbents in the related art; FIG. D shows HAPPCH produced by the present inventionMaterial pair UO2 2+Adsorption isotherms of (a); FIG. E shows HAPPCH material prepared in the example of the present invention at 5mM UO2 2+A cycle performance test result chart of (1);
FIG. 8 shows the detection performance of HAPPCH prepared according to the present invention; wherein, graph A shows HAPPCH and UO with different concentrations2 2 +Mixed optical patterns (a-l:0, 0.01, 0.1, 0.5, 1, 5, 10, 20, 30, 50, 80, 100. mu.M; sample solution volume: 1 mL); graph B is the diffraction spectrum corresponding to graph A; FIG. C is UO2 2+A detected calibration curve; FIG. D is a graph showing the results of a selectivity test of HAPPCH (the concentration of each ion was 20. mu.M);
FIG. 9 is a graph showing the results of the HAPPCH material in an actual water sample according to the present invention;
FIG. 10 is a schematic diagram of the process of reacting the HAPPCH material with uranium in an embodiment of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified. Acrylamide (AA), Acrylonitrile (AN), N '-methylenebisacrylamide (BisAA), ethyl orthosilicate (TEOS), polyethylene glycol diacrylate (PEGDA, Mw 700), N' -Tetramethylethylenediamine (TEMED), 2-hydroxy-2-methylpropenone (HMPP), and hydroxylamine hydrochloride (HAHC) were all obtained from alatin (shanghai, china). Uranyl acetate was purchased from the limited company of kusheng waffle chemicals, north of lake (wuhan, china). AG501-X8(D) mixed bed ion exchange resins were purchased from BioRad, Calif., USA. Other chemical reagents were of analytical grade.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the present invention, the meaning of "about" means plus or minus 2%, unless otherwise specified.
Examples
The present example prepares a hydrophilic amidoxime functionalized porous photonic crystal hydrogel (HAPPCH) material, and the preparation route of the material is shown in fig. 1, and the specific process is as follows:
1) by using
The method is used for preparing the monodisperse silicon dioxide nanometer microsphere, takes TEOS as a raw material, prepares according to the conventional parameters, and purifies.
2) Preparing a photonic crystal hydrogel pre-polymerization solution according to the following material ratio: 55% (w/v) of monodisperse silica microspheres, AA (10%, w/v), AN (20%, v/v), PEGDA (15%, v/v), HMPP (1%, v/v) and BisAA (1%, w/v), and the balance of water. The pre-polymer solution was shaken well to form a uniform suspension, then mixed with ion exchange resin and vortexed to form a photonic crystal array with a bright structural color. The resin was removed by low speed (3000rpm) centrifugation and the suspension was poured into a photopolymerization cell. The cell consisted of two slides separated by a spacer of 125 μm thickness.
3) The photonic crystal hydrogel pre-polymerization solution was photo-polymerized under ultraviolet rays having a wavelength of 365nm to produce a Photonic Crystal Hydrogel (PCH).
4) The prepared PCH was immersed in a hydrofluoric acid solution (2 wt%) to etch (etching) away the silica array to form a Porous Photonic Crystal Hydrogel (PPCH).
5) The PPCH is reacted with HAHC with the concentration of 20 wt% in water and methanol (neutralized by sodium hydroxide) with the volume ratio of 1:1 at 70 ℃ for 8h, and the reaction product is converted into amidoxime functionalized porous photonic crystal hydrogel (APPCH).
6) The APPCH is hydrolyzed (hydrosis) in a mixed solution containing 10% (v/v) TEMED and 0.1M sodium hydroxide for 1h to prepare Hydrophilic APPCH (HAPPCH).
In the embodiment of the invention, cyano-group is reacted with hydroxylamine to easily form amidoxime group, and the nitrile-group functionalized PCH is prepared for the first time by copolymerizing hydrogel pre-polymerization liquid containing AN, AA, PEGDA, BisAA and silicon dioxide microspheres. After etching to prepare PPCH, treatment with hydroxylamine is then carried out to convert the cyano group into an amidoxime group. Amidoxime functionalized porous photonic crystal hydrogel (APPCH) expands slightly in volume because the amidoxime group formed increases the hydrophilicity of the hydrogel. Meanwhile, due to the fact that the lattice spacing of the PC is increased due to hydrogel swelling, the structural color of the APPCH is changed from blue to green. Although amidoximation results in a slight improvement in hydrogel hydrophilicity, hydrogel hydrophilicity is still insufficient for efficient UO removal and detection2 2+. To further increase hydrophilicity, HAPPCH was obtained by hydrolysis of apppch in NaOH/TEMED solution. After the hydrolysis treatment, amide groups in the hydrogel network are partially converted into carboxyl groups, the osmotic pressure of the hydrogel is increased along with the increase of the number of the carboxyl groups, and the structural color of the hydrogel is gradually changed from green to red or even disappears.
Test examples
The test example tests the structure and properties of the materials prepared in the examples.
One, structure
The microstructure of the silica microspheres, PCH and PPCH films was characterized by scanning electron microscopy (SEM, Sigma HD, Carl-zeiss). The size and monodispersity of the silica microspheres was determined by dynamic light scattering (DLS, Zetasizer Nano ZS90, Malvern). Solid state13C Nuclear Magnetic Resonance (NMR) analysis was performed by NMR spectroscopy (AVANCE III HD 400MHz, Bruker). Attenuated Total reflectance Fourier transform Infrared (ATR-FTIR) Spectroscopy by Infrared Spectroscopy (Nicolet iS50, Thermo)And (5) obtaining the product.
The SEM results are shown in fig. 2. As can be seen from fig. 2A, the silica nanospheres have good monodispersity; as can be seen from fig. 2B, the nano-microspheres on the surface of PCH are in an ordered arrangement, and as can be seen from fig. 2C and 2D, the PPCH replicated by PCH also has a similar periodic structure with large micropores extending into the hydrogel.
The DLS test results are shown in fig. 3. As can be seen from FIG. 3, the silica microspheres had a polydispersity index (PDI) of 0.029 and a particle diameter (d) of 177.8 nm.
Solid state13The results of the CNMR test are shown in FIG. 4A. As can be seen from fig. 4A, the peak for the nitrile carbon of PPCH appeared at 118.8ppm and disappeared in APPCH, indicating that most of the nitrile groups were converted after amidoximation. At the same time, a new peak at 146.0ppm appeared, which is typical of the amidoxime carbon, thus indicating that the materials of the embodiments of the present invention carry an amidoxime group. In addition, a clear peak at 180.0ppm after hydrolysis in NaOH/TEMED solution, attributable to the carbon of the carboxylic acid group, indicates successful formation of the carboxylic acid group on the HAPPCH by the hydrolysis treatment.
The FTIR test results are shown in fig. 4B. As can be seen from FIG. 4B, the nitrile absorption band (2241.8 cm) in APPCH is comparable to that of PPCH-1) And (4) disappearing. Furthermore, at 1635.8cm-1A stretch band of-C-N-appears at 930cm-1A stretch band of-N-O is shown, which further indicates the conversion of the nitrile group to the amidoxime group. Furthermore, the absorption band of HAPPCH after hydrolysis is 1532.7cm-1The conversion is to 1557.3cm-1This should be attributed to the conversion of the amide moiety to the carboxyl group, these results provide strong evidence for the successful synthesis of HAPPCH.
Second, performance
1)UO2 2+And (3) testing the adsorption performance:
to verify whether HAPPCH can effectively enrich UO in water2 2+Unadsorbed and in 1mM UO were measured by X-ray photoelectron spectroscopy (XPS, k-alpha, Thermo)2 2+In solution adsorbs UO2 2+The HAPPCH of (a). Obtain rich UO2 2+Full scan XPS spectrum of HAPPCH (r). As shown in FIG. 4C, there are two distinct U4 f peaks, confirming the UO2 2+Fixation was successful on HAPPCH. X-ray energy spectra (EDS, X-MaxN, Oxford Instruments) are also used to explore HAPPCH and UO2 2+The interaction between them. As shown in fig. 4D, UO2 2+The treated HAPPCH sample showed a strong uranium peak, all of which confirm that HAPPCH is effective in adsorbing UO2 2+。
Due to the chemical structure of the adsorbent and UO2 2+The morphology depends on the pH of the solution, therefore, the pH value was investigated against HAPPCH against UO2 2+Influence of adsorption capacity. 5mM UO when the pH was increased from 2 to 52 2+In solution, the adsorption capacity of the HAPPCH material is from 1.10mmol g-1Gradually increased to 1.99mmol g-1. At the same time, the higher pH adsorption capacity decreased significantly (as shown in fig. 5). At lower pH values, some ligand groups may be protonated, thus, in a certain range (pH 2.0-5.0), the adsorption capacity increases with increasing pH. However, high pH values in this range will result in UO2 2+Formation of hydroxide, hence UO2 2+The adsorption rate of (2) is low. Overall, the optimal pH range for HAPPCH to achieve high adsorption capacity is 5.0.
High salt concentrations in sample solutions generally reduce adsorption capacity because strong ionic strength weakens chelating groups and UO2 2+The interaction between them. Nuclear effluents generally contain large amounts of electrolytes due to large amounts of concentrated HCl or HNO3For dissolving fuel rods, the strong acid must be treated with alkali before being discharged into the environment, which typically results in the formation of large amounts of NaCl and NaNO3. Thus, NaCl and NaNO were investigated separately3Effect on HAPPCH adsorption capacity (as shown in fig. 6). UO2 2+Adsorption capacity of (2) with NaNO3And a slight decrease in NaCl concentration, wherein the effect of NaCl is relatively higher than that of NaNO3This is because chloride ions have a certain coordination with uranyl ions. Salinity to UO2 2+The adsorption of (A) has almost no influence, demonstrating HAPPCH ligand and UO2 2+Has strong affinity between the two, and can remove UO from the practical water body2 2+。
The HAPPCH material prepared in the above example was added to a range of concentrations of UO2 2+And (5) carrying out an adsorption effect test in the solution. In the test process, the materials and the solution to be tested are placed on a shaking table at 25 ℃ and shaken for 12h, and the UO in the adsorbed solution is detected by inductively coupled plasma mass spectrometry (ICP-MS, ICAP-QC, Thermo)2 2+The concentration of (c). An optical image was taken with a camera (D5300, nikon) as shown in fig. 7A. As can be seen from FIG. 7A, the UO is adsorbed2 2+After that, the color of HAPPCH changes to yellow or even brown, indicating UO2 2+Enrichment on HAPPCH. While the volume of the HAPPCH shrinks dramatically due to the single UO2 2+And a plurality of ligands, the distance between ligand groups is greatly shortened.
The removal rate and adsorption capacity of the material prepared by the embodiment of the invention to uranium in an actual water body are calculated, and the results are shown in table 1. Wherein, the calculation formula of the removal rate is as follows:
the adsorption capacity is calculated as follows:
in the formula, CiAnd CeRespectively is UO in the solution before and after adsorption2 2+Concentration (mM), V represents the volume of the solution to be tested (mL), and m represents the mass of HAPPCH (g).
TABLE 1a)
a)The mass of the adsorbent is 0.05g, and the volume of the adsorption solution is 20 mL.
As can be seen from Table 1, HAPPCH vs. UO2 2+The extraction amount of (A) is dependent on the UO2 2+The concentration increased (as shown in table 1). Maximum adsorption Capacity (Q) of HAPPCHm) 2.52mmol g-1Much higher than some other sorbents reported in the related art (fig. 7C). UO2 2+UO at a concentration in the range of 0.01mM to 5mM2 2+The removal efficiency (η) of (a) is higher than 96.16%. Furthermore, UO after treatment with HAPPCH2 2+Can be reduced to 9.18nM below the highest concentration of uranium in drinking water prescribed by the United states Environmental Protection Agency (EPA). The above results indicate that HAPPCH is responsible for UO in water2 2+Is effective.
2) Adsorption kinetics, isotherms and adsorption regeneration
To study the HAPPCH vs UO2 2+The adsorption kinetics of (1) HAPPCH, 0.05g dry weight, was immersed in 20mL UO2 2+And (5mM) testing the adsorption effect at different times (0-180 min). Study of UO Using Langmuir and Freundlich models2 2+The adsorption isotherm at 298K was as shown in FIG. 7B, and it can be seen from FIG. 7B that UO in the supernatant was observed over time2 2+Gradually decreases in concentration. 91.8% UO2 2+Removed within 1 hour. As shown in fig. 7C, the adsorption equilibrium speed is superior to most related art adsorbents. The fast adsorption speed and the high adsorption capacity make the HAPPCH a potential material for treating uranium pollution.
The Langmuir isotherm adsorption equation is as follows:
in the formula, QLRepresents Langmuir monolayer adsorption capacity (mmol g)-1)，KLIndicating the Langmuir constant (L mmol) in relation to the affinity between the absorbate and the adsorbent material-1). In this exampleQL2.61mmol g-1，KL9.97L mmol-1。
The Freundlich isotherm adsorption equation is as follows:
in the formula, n and KFFreundlich constants, n and K, relating to adsorption strength and adsorption capacity, respectivelyF0.26 and 1.99, respectively.
To study the adsorption mechanism of the adsorbent, isothermal adsorption data (shown in FIG. 7D) were evaluated using Langmuir and Freundlich models, with a fitting correlation coefficient R for Langmuir in FIG. 7D2A fitting correlation coefficient R of 0.99, Freundlich2Is 0.90. Therefore, the Langmuir adsorption isotherm has a higher fitted correlation coefficient, calculated adsorption capacity (Q), than the Freundlich modelL，2.61mmol g-1) To the maximum experimental adsorption capacity (Q)m，2.52mmol g-1) Similarly. These results indicate that the Langmuir model is more suitable for interpreting UO2 2+Equilibrium adsorption on HAPPCH.
Evaluation of the removal of UO from HAPPCH by five cycles of regeneration and adsorption experiments using 1M HCl solution as eluent2 2+Due to the coordination between a plurality of ligands (amidoxime, carboxylate and amide) and uranyl ions, the coordination center of the ligand is occupied by proton in a strong acid solution, UO2 2+The ability to coordinate with the ligand is greatly impaired and the hydrogel is eluted therefrom. As shown in FIG. 7E, the HAPPCH maintained a high removal rate (greater than 94.09% of the initial adsorption capacity) even after 5 cycles, indicating that the material had a long useful life and was able to remove UO from water2 2+。
3)UO2 2+Test for detection Performance
The same size HAPPCH material was immersed in 1ml of different concentrations of UO2 2+In solution (pH 5), the reaction was carried out at room temperature for 1h, and then the diffraction spectrum of HAPPCH was recordedAnd an optical image. The diffraction spectra (NOVA, Ideoplastics, fixed angle of incidence of 90 ℃) of the HAPPCH film were measured using a fiber optic spectrometer.
By using the unique Bragg diffraction effect of HAPPCH, different concentrations of UO are used2 2+Solution, evaluation of HAPPCH versus UO2 2+The monitoring capability of (1). As shown in FIG. 8, the apparent change in color of the structure is readily discernible to the naked eye (as shown in FIG. 8A) and follows the UO2 2+The increase in concentration gradually blue-shifts the diffraction wavelength of HAPPCH (as shown in fig. 8B). HAPPCH allows sensitive detection of UO in the range of 10nM to 100. mu.M2 2+The minimum detection concentration was 10nM (FIG. 8C). According to the data of the United states environmental protection agency, the minimum detection concentration of HAPPCH is lower than that of UO in drinking water2 2+The level of toxicity of (a). In addition, the HAPPCH material can realize UO without other signal molecules2 2+Visual and field testing.
By recording HAPPCH for other common metal ions (including Fe)2+、Mg2+、Ba2+、Cu2+、Mn2+、Sn2+、Ca2+、Zn2+、K+、Hg2+And Na+) The wavelength shift value of HAPPCH was evaluated for UO2 2+The results are shown in FIG. 8D. It can be seen from FIG. 8D that the response of all other ions is much smaller than that of the UO2 2+Indicates HAPPCH versus UO2 2+High selectivity of detection.
4) Test of actual sample Effect
The effectiveness of HAPPCH was further assessed from real samples taken from environmental water surrounding the uranium tailing dam (hunan province, china). The sample was filtered through a 0.22 μm filter to remove solid impurities and the pH was adjusted to 5. After adding different concentrations of UO2 2+After that, the removal efficiency was recorded. As shown in FIG. 9, different UOs in the actual water samples2 2+The adsorption efficiency of the concentration is good and substantially in line with the results obtained in ultrapure water. It is thus shown that the material produced according to the inventive solution is believed to have a water-free effectExcept for UO2 2+Has great potential.
In summary, the invention provides a HAPPCH adsorbing material which can be used for UO2 2+Efficient removal and visual detection (as shown in fig. 10). The porous structure of HAPPCH imparts a high specific surface area and abundant adsorption sites to the adsorbent. In addition, the introduction of amidoxime group further improves the selectivity and adsorption capacity of HAPPCH. Compared with other adsorbents, the HAPPCH material not only has higher removal efficiency and adsorption capacity (2.52mmol g)-1) And for UO2 2+Showed good selectivity and sensitivity (10 nM). HAPPCH showed 94.09% recovery efficiency even after 5 regeneration cycles. The UO is also verified in dynamic experiments2 2+High-efficiency adsorption on the HAPPCH further verifies the practicability of the HAPPCH. The scheme of the invention has good application prospect in high-efficiency uranium removal and colorimetric detection.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A hydrophilic amidoxime functionalized material is characterized in that: the material is porous polymer hydrogel which is in a photonic crystal structure, and the polymer in the porous polymer hydrogel is provided with amidoxime groups, amido groups and carboxyl groups.
2. The hydrophilic amidoxime functionalized material according to claim 1, wherein: the polymer comprises the following structural units:
wherein n1, n2 and n3 are each independently a natural number.
3. The hydrophilic amidoxime functionalized material according to claim 1, wherein: the preparation raw materials of the material comprise the following components: the silicon dioxide nano-particle etching solution comprises monodisperse silicon dioxide microspheres, an etching agent, a gel pre-polymerization solution, hydroxylamine hydrochloride and N, N, N ', N' -tetramethyl ethylenediamine, wherein the gel pre-polymerization solution contains acrylamide, acrylonitrile, a cross-linking agent and a photoinitiator; preferably, the cross-linking agent comprises at least one of BisAA and PEGDA; more preferably, the photoinitiator is selected from HMPP.
4. The hydrophilic amidoxime functionalized material according to claim 3, wherein: the particle size of the monodisperse silicon dioxide microspheres is 100-500 nm; preferably 150-300 nm; more preferably 150 to 200 nm; most preferably about 177.8 nm; preferably, the cross-linking agent comprises BisAA, and the mass ratio of AA to BisAA in the gel pre-polymerization liquid is 5-15: 1; preferably, the crosslinking agent comprises PEGDA, the photoinitiator comprises HMPP, and the volume ratio of AN, PEGDA and HMPP in the gel pre-polymerization liquid is 15-25: 10-20: 1; more preferably, the total mass volume percentage concentration of the monodisperse silicon dioxide microspheres in the pre-polymerization solution is 30-60%; preferably 50-60%; more preferably 55%.
5. A preparation method of a hydrophilic amidoxime functional material is characterized in that: the method comprises the following steps:
s1, mixing the monodisperse silicon dioxide microspheres with the gel prepolymerization solution, and carrying out polymerization reaction under illumination;
s2, adding an etching agent to etch silicon dioxide;
s3, adding hydroxylamine hydrochloride to oximate;
s4, adding TEMED for hydrolysis to obtain;
wherein the gel pre-polymerization liquid contains acrylamide, acrylonitrile, a cross-linking agent and a photoinitiator.
6. The method for preparing the hydrophilic amidoxime functionalized material according to claim 5, wherein: step S1 further comprises a step of preparing a gel pre-polymerization solution, which specifically comprises mixing the raw materials with water, exchanging the mixture with ion exchange resin, and centrifuging to remove the resin; preferably, the polymerization is polymerization under ultraviolet light; preferably, the wavelength of the ultraviolet light is 360-370 nm; more preferably about 365 nm.
7. Use of a hydrophilic amidoxime functionalised material according to any one of claims 1 to 4 or a hydrophilic amidoxime functionalised material obtained according to claim 5 or 6 for uranium detection, extraction and/or removal.
8. A kit for uranium detection, extraction and/or removal, characterized by: the kit comprising a hydrophilic amidoxime functionalised material according to any one of claims 1 to 4 or a hydrophilic amidoxime functionalised material prepared according to claim 5 or 6; preferably, the kit further comprises a color comparison card.
9. A uranium detection method is characterized in that: the detection method is a quantitative detection method or a qualitative detection method;
if the method is a qualitative detection method, the method comprises the following steps: taking the hydrophilic amidoxime functional material as defined in any one of claims 1 to 4 or the hydrophilic amidoxime functional material prepared as defined in claim 5 or 6, mixing the hydrophilic amidoxime functional material with a solution to be detected, observing the diffraction wavelength shift or observing the color change, and judging whether uranium is contained;
if the method is a quantitative detection method, the method comprises the following steps: taking the hydrophilic amidoxime functional material as defined in any one of claims 1 to 4 or the hydrophilic amidoxime functional material prepared as defined in claim 5 or 6, mixing the hydrophilic amidoxime functional material with the solution to be detected, and determining the uranium content in the solution to be detected according to the relationship between the color variation and the uranium content.
10. A uranium removal method is characterized in that: the method comprises the following steps: taking the hydrophilic amidoxime functionalized material according to any one of claims 1 to 4 or the hydrophilic amidoxime functionalized material prepared according to claim 5 or 6, and mixing the hydrophilic amidoxime functionalized material with the solution to be detected.
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Application publication date: 20211217 |