CN112403446A - Conjugated microporous polymer and preparation method and application thereof - Google Patents
Conjugated microporous polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a conjugated microporous polymer, wherein a porous molecular structure of the conjugated microporous polymer comprises alkynyl and a rigid ring structure which are alternately connected, the alkynyl is ethynyl or conjugated alkynyl, the rigid ring structure comprises an aromatic ring and/or an aromatic hetero-shell, and at least one amidoxime group is also connected to the rigid ring structure. The invention relates to a preparation method of a conjugated microporous polymer. The invention also relates to a uranium adsorbent containing the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method. The invention further relates to the application and the using method of the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a conjugated microporous polymer and a preparation method and application thereof.
Background
Uranium is the most important fuel resource in the current nuclear energy technical field, and the reserve quantity of the uranium is related to whether the stable and healthy development of the national nuclear industry can be maintained. A large amount of uranium resources are contained in natural water bodies such as seawater, saline water lakes, salt lakes and the like, the average concentrations are 3 mug/L, 56 mug/L and 480 mug/L respectively, and the research on the enrichment and separation technology of uranium in the water bodies is an important guarantee for realizing green and sustainable development of nuclear energy.
Various methods including a solvent extraction method, a coprecipitation method, an electrochemical method, an ion exchange method, an adsorption method and the like are proposed for enrichment and separation of uranium in an aqueous solution. In contrast, the adsorption method has the advantages of high selectivity, low energy consumption, relatively simple and easily-controlled treatment process, and the like, and is considered to be one of the most potential methods in the field of uranium enrichment and separation, and has been paid attention to by researchers for a long time. The ideal uranium adsorbent should have good porosity and strong coordination and chelation capacity to uranium, thereby realizing the basic function of enrichment and separation of uranium. In addition, in order to be used stably and continuously in a complex aqueous environment, the water-soluble organic silicon material also needs to have certain mechanical strength, good chemical and irradiation stability, anti-biological pollution and recycling use. However, at present, the conventional adsorbent is mainly in the form of a composite material, and atoms or functional groups having coordination chelation on uranium are introduced as functional layers on the surface of a porous substrate (including metal oxides, carbon materials, mesoporous materials and the like) by various methods (including doping, grafting, coating and the like). Such adsorbents generally have problems of poor stability and poor cyclability, and the introduced functional layer is gradually lost in the long-term use process, thereby causing the reduction of the adsorption performance. Although the functional layer loss problem faced by the composite material can be solved to a certain extent by adopting the high polymer material, the adsorption efficiency and the service life of the composite material are limited due to poor porosity and irradiation stability.
Organic porous materials, including covalent organic framework materials (COFs), Conjugated Microporous Polymers (CMPs), porous aromatic framework materials (PAFs) and metal-organic framework Materials (MOFs), are porous high molecular materials with high specific surface area and rich pore environments. Functionalized MOFs or CMPs polymers are used for uranium adsorption, the MOFs stability is weaker than that of the CMPs, and therefore the functionalized CMPs polymers are concerned for uranium adsorption. However, in practical application, natural water is a relatively complex aqueous environment, and various ions often exist, while the specific adsorption capacity of the existing functionalized CMPs polymer material to uranium is poor. Therefore, no effective adsorption material exists at present for enrichment and separation of uranium in natural water.
Disclosure of Invention
Based on the above, there is a need to provide a conjugated microporous polymer, a preparation method and an application thereof, which can realize effective enrichment and separation of uranium in natural water.
In one aspect of the invention, a conjugated microporous polymer is provided, wherein a porous molecular structure of the conjugated microporous polymer comprises alkynyl groups and rigid ring structures which are alternately connected, the alkynyl groups are ethynyl groups or conjugated alkynyl groups, the rigid ring structures comprise aromatic rings and/or aromatic hetero-shells, and at least one amidoxime group is further connected to the rigid ring structures.
In one aspect of the present invention, a method for preparing the conjugated microporous polymer is provided, which comprises the following steps:
carrying out sonogashira-securina coupling reaction on a first monomer and a second monomer to obtain a cyano-containing conjugated microporous polymer precursor; and
carrying out amidoximation reaction on the precursor to convert cyano into amidoxime group;
wherein the molecular structure of the first monomer comprises the rigid ring structure and at least two non-fluorine halogen substituents, the molecular structure of the second monomer comprises the rigid ring structure and at least two of the alkynyl groups, and at least one of the first monomer and the second monomer further comprises at least one cyano group.
In one aspect of the invention, the uranium adsorbent comprises the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method.
In one aspect of the invention, the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method is used as a uranium adsorbent.
In one aspect of the present invention, a method for using the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method as a uranium adsorbent is further provided, and the conjugated microporous polymer is immersed in an alkaline solution for deprotonation before being used as a uranium adsorbent to adsorb uranium.
Drawings
FIG. 1 is a Fourier infrared spectrum of CMP-p1CN and CMP-p1AO prepared in example 1 of the present invention;
FIG. 2 is a nitrogen adsorption desorption isotherm of CMP-p1CN and CMP-p1AO prepared in example 1 of the present invention;
FIG. 3 shows the adsorption performance of CMP-p1CN and CMP-p1AO prepared in example 1 of the present invention in aqueous solutions of uranium of different pH;
FIG. 4 is an adsorption thermodynamic isotherm and fitted curve of CMP-p1AO prepared in example 1 of the present invention;
FIG. 5 is a histogram of the cyclic performance of CMP-p1AO prepared in example 1 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:
the term "alkyl" refers to a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Suitable examples of "straight chain alkyl, branched alkyl having 1 to 6C atoms" include, but are not limited to: methyl (Me, -CH)3) Ethyl (Et-CH)2CH3) 1-propyl (n-Pr, n-propyl, -CH)2CH2CH3) 2-propyl (i-Pr, i-propyl, -CH (CH)3)2) 1-butyl (n-Bu, n-butyl, -CH)2CH2CH2CH3) 2-methyl-1-propyl (i-Bu, i-butyl, -CH)2CH(CH3)2) 2-butyl (s-Bu, s-butyl, -CH (CH)3)CH2CH3) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH)3)3) 1-pentyl (n-pentyl, -CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH3) CH2CH2CH3), 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3)、1-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3. Phrases comprising this term, such as "straight chain alkyl" means that the molecular chain constituting the alkyl group has only one chain, "branched alkyl" means that the molecular chain constituting the alkyl group has one main chain and at least one branch, and "substituted alkyl" means that one or more hydrogen atoms in the alkyl group are replaced by other atoms, which may be substituents selected from defined or suitable substituents. It is to be understood that the term "substituted" includes the following implied conditions: such substitution should be consistent with the permissible valences of the substituted atoms and substituents and the substitution results in stable compounds. The term "substituted" in the present invention means not only that a hydrogen atom on a carbon atom is substituted but also that a carbon atom on an aromatic ring is substituted with a hetero atom. The heteroatom may be N, O, S.
The term "alkoxy" refers to a group having an-O-alkyl group, i.e., an alkyl group as defined above attached to the parent core structure via an oxygen atom. Suitable examples include, but are not limited to: methoxy (-O-CH)3or-OMe), ethoxy (-O-CH)2CH3or-OEt) and tert-butoxy (-O-C (CH)3)3or-OtBu).
The term "halogen" refers to F, Cl, Br or I, and "non-fluorine halogen" refers to Cl, Br or I.
The embodiment of the invention provides a conjugated microporous polymer, wherein a porous molecular structure of the conjugated microporous polymer comprises alkynyl and a rigid ring structure which are alternately connected, the alkynyl is ethynyl or conjugated alkynyl, the rigid ring structure comprises an aromatic ring and/or an aromatic hetero-shell, and at least one amidoxime group is further connected to the rigid ring structure.
The Conjugated Microporous Polymer (CMP) is a random microporous reticular high-molecular material prepared by coupling reaction of two polysubstituted aromatic hydrocarbon monomers and having a large pi-bond conjugated system in the polymer system. This conjugated system is the result of alternating connection of single and multiple carbon-carbon bonds within the polymer, i.e., a large conjugated system is present throughout the polymer resulting from the overlap of the p or d orbitals of atoms within the polymer. The large conjugated system of the conjugated microporous polymer can disperse energy in the conjugated system when being irradiated, and all chemical bonds participating in conjugation are shared, so that the possibility of aging failure caused by irradiation breakage of single chemical bonds is reduced. CMP has its natural advantages as a uranium adsorbent, since uranium is itself radioactive. Moreover, the large conjugated system not only provides good mechanical, chemical and irradiation stability for CMP, but also hinders the bending and folding of polymer molecular chains to a certain extent by a rigid conjugated structure, and provides good porous property for CMP. Due to these properties, CMP is very suitable for uranium adsorption. However, in order to realize enrichment and separation of uranium in natural water, a modifying group with a specific adsorption effect on uranium is also needed. The inventor of the invention finds that amidoxime groups have specific selective adsorption on uranium. However, how to combine CMP with amidoxime groups is a technical difficulty in the art. The inventor firstly obtains a cyano-containing conjugated microporous polymer precursor through sonogashira-securinega original coupling reaction, and the precursor is subjected to hydroxylamination reaction to convert the cyano-group into an amidoxime group, so that the conjugated microporous polymer is simply and efficiently prepared. The conjugated microporous polymer has the general characteristics of the conjugated microporous polymer, such as good mechanical property, chemical stability, irradiation stability and porosity, and has specific selective adsorption on uranium due to the amidoxime group contained in the structure, so that enrichment and separation of uranium in natural water bodies with complex environments, such as seawater, saline lakes, salt lakes and the like, can be realized; in addition, due to the existence of alkynyl in the structure of the conjugated microporous polymer, rigid ring structures are easier to be coplanar, the conjugation effect of the conjugated microporous polymer is further improved, and the irradiation resistance is stronger. Therefore, the conjugated microporous polymer provided by the embodiment of the invention has more efficient adsorption performance and excellent recycling performance when being used as a uranium adsorbent.
The ethynyl group or the conjugated alkynyl group may form conjugation with the rigid ring structure, enhancing the radiation resistance of the conjugated microporous polymer. Preferably, the conjugated alkynyl group is a diacetylene.
The aromatic ring may include one or more of benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, and fluorene.
The heteroaromatic ring may include one or more of pyridine, pyrimidine, triazine, quinoline, isoquinoline, carbazole, thiophene, benzothiophene, furan, benzofuran, thiazole, pyrrole, pyrazole, pyrazine, triazole, phenanthroline, and naphthyridine.
In one embodiment, the rigid ring structure is selected from one or more of the following structural formulas:
x is independently selected from CR, N, O or S at each occurrence;
each occurrence of R is independently selected from hydrogen, D, non-fluorine halogen, ethynyl, conjugated alkynyl, cyano, straight, branched or substituted alkyl having 1 to 6C atoms, straight alkoxy, straight thioalkoxy, keto, alkoxycarbonyl having 2 to 6C atoms, silyl, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, and at least one R is selected from amidoxime groups.
In one embodiment, in the rigid ring structure, R, which is ortho to the amidoxime group, is selected from amino or hydroxyl, preferably amino. The inventor of the invention finds out for the first time that amino or hydroxyl has an ortho-group synergistic effect and can synergistically promote coordination adsorption of amidoxime groups and uranium.
In one embodiment, in the rigid ring structure, the ring carbon atom adjacent to the ring carbon atom to which the amidoxime group is attached is replaced with a heteroatom containing a lone pair of electrons. That is, in the rigid ring structure, X adjacent to X to which the amidoxime group is attached is substituted with a heteroatom which is N, O or S. The conjugated microporous polymer containing the heteroatom has better adsorption performance.
In one embodiment, the conjugated microporous polymer has a plurality of repeating pore structural units comprising 4 to 12 of the rigid ring structures. Such as a pore building block of the formula:
preferably, the higher the density of amidoxime groups contained in the conjugated microporous polymer is, the better the adsorption performance is.
The embodiment of the invention also provides a preparation method of the conjugated microporous polymer, which comprises the following steps:
s10, performing sonogashira-suffruticosa coupling reaction on the first monomer and the second monomer to obtain a cyano-containing conjugated microporous polymer precursor; and
s20, carrying out amidoximation reaction on the precursor to convert a cyano group into an amidoxime group;
wherein the molecular structure of the first monomer comprises the rigid ring structure and at least two non-fluorine halogen substituents, the molecular structure of the second monomer comprises the rigid ring structure and at least two of the alkynyl groups, and at least one of the first monomer and the second monomer further comprises at least one cyano group.
The first monomer may be selected from one or more of the following structural formulae:
the second monomer may be selected from one or more of the following structural formulae:
wherein, X1Each occurrence is independently selected from CR1Or N;
X2each occurrence is independently selected from CR2Or N;
R1、R2each occurrence is independently selected from hydrogen, D, non-fluorine halogen, ethynyl, conjugated alkynyl, cyano, straight, branched or substituted alkyl having 1 to 6C atoms, straight alkoxy, straight thioalkoxy, keto, alkoxycarbonyl having 2 to 6C atoms, silyl, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, amino, and at least two R' s1Selected from non-fluorine halogen, at least two R2Selected from ethynyl or conjugated alkynyl, at least one R1Or at least one R2Selected from cyano groups. Preferably, the more R1And/or R2The amidoxime group is selected from a cyano group, and the higher the density of the amidoxime group contained in the conjugated microporous polymer is, the better the adsorption performance is.
The traditional composite material adsorbent usually adopts a post-modification strategy to introduce functional components, uncertainty exists in introduction effect and material functionalization degree, high functionalization degree is difficult to obtain usually, and high adsorption capacity is not easy to obtain. The preparation method of the conjugated microporous polymer provided by the embodiment of the invention adopts a strategy of pre-introducing cyano groups on monomers and constructing a porous framework through a coupling polymerization reaction. The cyano group on the precursor of the conjugated microporous polymer can not react and can not be lost in the polymerization process. After the cyano-containing conjugated microporous polymer is obtained, amidoxime conversion rate of nearly 100% is obtained by amidoxime treatment reaction with high conversion rate. The preparation method of the conjugated microporous polymer provided by the embodiment of the invention can adjust the position and number density of the introduced functionalized functional group amidoxime group according to requirements, can meet actual requirements, and can enable the conjugated microporous polymer material to obtain higher adsorption capacity.
In a preferred embodiment, the molecular structure of the first monomer comprises at least three non-fluorine halogen substituents, and/or the molecular structure of the second monomer comprises at least three said alkynyl groups. The conjugated microporous polymer formed by the first monomer and/or the second monomer with the characteristics can have better porosity and adsorption capacity.
In some embodiments, the first monomer may be selected from one or more of the following structural formulae:
wherein x is a non-fluoro halogen;
the second monomer may be selected from one or more of the following structural formulae:
the non-fluorine halogen element and the ethynyl group in the first monomer and the second monomer can be interchanged, that is, the first monomer can also be an aromatic hydrocarbon substituted by two or more ethynyl groups and contain at least one cyano group, and the second monomer can also be an aromatic hydrocarbon substituted by two or more non-fluorine halogen elements.
In step S10, the sonogashira-securinega coupling reaction may be catalyzed by a palladium catalyst and a copper-containing co-catalyst. The palladium catalyst may be at least one selected from palladium-containing catalysts such as tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, palladium acetate, tris (dibenzylideneacetone) dipalladium, palladium carbon and the like. The copper-containing cocatalyst may be at least one selected from cuprous salts such as cuprous chloride and cuprous iodide.
The molar ratio of the palladium catalyst, the copper-containing cocatalyst and the monomer is 1: (0.8-2): (20-100), wherein the monomer is the total amount of the first monomer and the second monomer.
The solvent used in the sonogashira-securinega coupling reaction is a first solvent, and the first solvent can be a mixed solvent of N, N-dimethylformamide and triethylamine. The volume ratio of the N, N-dimethylformamide to the triethylamine is 1 (0.1-0.5). The adding amount of the first solvent is 20 mL-50 mL per 1mmol of the monomer.
The reaction temperature of the sonogashira-securinega coupling reaction is 60-90 ℃, and the reaction time is 12-72 h.
And (3) ultrasonically washing the reactant after the sonogashira-securinega conjugation reaction in N, N-dimethylformamide, dichloromethane and methanol in sequence to remove other impurities such as raw materials.
In step S20, the amidoximation reaction may be performed by converting the cyano group in the precursor into an amidoxime group using a hydroxylamine reagent. The hydroxylamine reagent may be hydroxylamine hydrochloride or an aqueous hydroxylamine solution. When the hydroxylamine reagent is hydroxylamine hydrochloride, an auxiliary agent is further added in the amidoximation reaction. The auxiliary agent can be a basic auxiliary agent, including but not limited to triethylamine, ammonia water, sodium hydroxide, potassium hydroxide, to neutralize the acidic components in hydroxylamine hydrochloride.
The adding amount of the hydroxylamine reagent can be adjusted according to the cyano content in the precursor, and the molar ratio of the cyano in the precursor to the hydroxylamine in the hydroxylamine reagent is 1 (1.2-3).
The solvent used in the amidoximation reaction is a second solvent, and the second solvent can be a mixed solvent prepared from one or more of water, methanol, ethanol and N, N-dimethylformamide. The second solvent may be added in an amount of 20mL to 250mL per 1g of the cyano group-containing precursor.
The reaction temperature of the amidoximation reaction is 70-90 ℃, and the reaction time is 4-36 h.
The invention also provides a uranium adsorbent, which comprises the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method.
The invention further provides the application of the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method as a uranium adsorbent.
In one embodiment, the uranium adsorbent is used for enrichment and separation of uranium in neutral and/or weakly alkaline natural water.
In one embodiment, the natural water bodies include seawater water bodies, salt water lake water bodies, and salt lake water bodies.
The invention further provides a use method of the conjugated microporous polymer or the conjugated microporous polymer obtained by the preparation method as a uranium adsorbent, and the conjugated microporous polymer is immersed in an alkaline solution for deprotonation before being used as the uranium adsorbent to adsorb uranium.
In one embodiment, the alkaline solution has OH-The molar concentration of the catalyst is 0.015-0.6 mol/L, and the deprotonation time is 1-12 h.
The following are specific examples. The present invention is intended to be further described in detail to assist those skilled in the art and researchers to further understand the present invention, and the technical conditions and the like do not limit the present invention. Any modification made within the scope of the claims of the present invention is within the scope of the claims of the present invention. The reagents used in the following examples are all commercially available.
EXAMPLE 1 preparation of conjugated microporous Polymer CMP-p1AO
1mmol of 1,3, 5-triacetylbenzene (150mg) and 1mmol of 2, 5-dibromobenzonitrile (261mg) were taken in a 50mL Schlenk tube. To a Schlenk tube were added 0.05mmol of bis (triphenylphosphine) palladium dichloride (35mg) catalyst and 0.075mmol of cuprous iodide (15mg) co-catalyst. Uniformly mixing 20mL of N, N-dimethylformamide and 6mL of triethylamine, adding a Stirling tube, connecting and sealing a reaction system, vacuumizing, backfilling with argon for protection, repeating for three times, and then protecting for 10min under the argon atmosphere. Subsequently, the reaction system was warmed to 80 ℃ and reacted for 72 hours. And filtering after the reaction is finished to obtain a crude product, ultrasonically washing and filtering in N, N-dimethylformamide, dichloromethane and methanol in sequence, and drying in a vacuum oven at 50 ℃ overnight to obtain a cyano-containing conjugated microporous polymer precursor CMP-p1 CN.
400mg of CMP-p1CN was placed in a 25mL Schlenk tube, 10mL of methanol was added and dispersed by sonication. Then, 3.6mmol of hydroxylamine hydrochloride (243mg) and 3.6mmol of triethylamine (360mg) were added thereto, and the mixture was reacted at 70 ℃ for 4 hours with magnetic stirring. And after the reaction is finished, cooling the system to room temperature, filtering to obtain a solid crude product, washing with deionized water for 3 times, and drying in a vacuum oven at 50 ℃ overnight to obtain the amidoxime group-containing conjugated microporous polymer CMP-p1 AO.
Fourier infrared spectrum and nitrogen adsorption and desorption characterization are carried out on the synthesized conjugated microporous polymer CMP-p1AO and a cyano-containing precursor CMP-p1CN thereof. FIG. 1 shows Fourier transform infrared spectra of CMP-p1CN and CMP-p1AO, 2233cm on CMP-p1AO common line-1The complete disappearance of the characteristic peak at the cyano-carbon-nitrogen triple bond proves the high conversion rate of the amidoximation reaction; 1668cm-1And 952cm-1The generation of amidoxime groups is evidenced by the appearance of peaks characteristic of amidoxime groups C ═ N double bonds and N-O bonds. FIG. 2 is a nitrogen adsorption-desorption isotherm of CMP-p1CN and CMP-p1AO, and the experiment shows that the specific surface areas of CMP-p1CN and CMP-p1AO are 956m respectively2(iv) g and 548m2Per g, pore volume 0.72cm3G and 0.44cm3Per g, good porosity of CMP-p1AO was demonstrated.
And (3) testing the adsorption performance:
1. adsorption of uranium in aqueous solution by CMP-p1AO
(1) Adsorption of uranium in aqueous solutions with different pH values by CMP-p1AO
Preparing 20mg/L uranyl nitrate solution, and adjusting the pH of the solution to 4, 5, 6, 7, 8, 9 and 10 by using sodium hydroxide. Taking a certain amount of the solution, adding CMP-p1AO, fixing the solid-to-liquid ratio to be 100mg/L, and adsorbing for 24 h. Thereafter, CMP-p1AO was filtered off, and the adsorption capacity of CMP-p1AO for uranium under the above pH conditions was determined by measuring the residual uranium concentration in the aqueous solution. The uranium concentration in the solution before and after adsorption is measured by a spectrophotometer and an azoarsenic III color development method, or is directly measured by an inductively coupled plasma emission spectrometer (ICP-OES). Fig. 3 shows the adsorption performance of CMP-p1CN and CMP-p1AO in aqueous solutions of uranium with different pH values, and CMP-p1AO shows a higher adsorption capacity and obtains the maximum adsorption capacity at pH 6.
(2) Saturated adsorption Capacity of CMP-p1AO
Uranium sample solutions with concentrations of 10mg/L, 20mg/L, 50mg/L, 100mg/L, 160mg/L and 200mg/L were prepared, and the pH was adjusted to 6 with sodium hydroxide. Taking a certain amount of the solution, adding CMP-p1AO, fixing the solid-to-liquid ratio to be 250mg/L, and adsorbing for 4 h. Then, the CMP-p1AO was filtered, the adsorption capacity of CMP-p1AO to uranium in the above solution was measured by measuring the residual uranium concentration in the aqueous solution, and the saturated adsorption capacity was calculated by drawing an adsorption thermodynamic isotherm and fitting it with an adsorption isotherm model. FIG. 4 shows the adsorption thermodynamic isotherm and the fitted curve of CMP-p1 AO. The maximum experimental adsorption capacity of CMP-p1AO for uranium is 386mg/g, according to the fitting result, the adsorption process is more consistent with a Langmuir adsorption isotherm model, the theoretical saturated adsorption capacity is calculated to be 521mg/g, and the CMP-p1AO has higher adsorption capacity.
(3) Cyclic utilization of CMP-p1AO
A20 mg/L uranium sample solution was prepared and the pH adjusted to 6 with sodium hydroxide. Taking a certain amount of the solution, adding CMP-p1AO, fixing the solid-to-liquid ratio to be 100mg/L, and adsorbing for 2 h. And then filtering the CMP-p1AO, washing the uranium adsorbent by using a mixed solution of 0.1mol/L sodium carbonate and 0.01mol/L hydrogen peroxide as an eluent, wherein the solid-liquid ratio is 400mg/L, eluting for 1h, repeating for several times, and measuring the uranium concentration in the residual solution and the eluent after adsorption is finished so as to determine the recycling performance of the CMP-p1 AO. FIG. 5 shows the recycling performance of CMP-p1AO, and after 5 times of recycling, the removal rate of the CMP-p1AO to uranium is kept above 80%, the elution rate is kept above 90%, and the good recycling performance is achieved.
2. Adsorption of CMP-p1AO on uranium in seawater
(1) Adsorption performance of CMP-p1AO in uranium-added seawater
Uranyl nitrate was added to seawater to prepare uranium-added seawater having a uranium concentration of 8mg/L, and the pH was adjusted to the original pH of seawater with sodium hydroxide. Taking a certain amount of the solution, adding CMP-p1AO, fixing the solid-to-liquid ratio to be 100mg/L, and adsorbing for 24 h. Thereafter, CMP-p1AO was filtered off, and the adsorption capacity of CMP-p1AO for uranium under the above pH conditions was measured by measuring the residual uranium concentration in the uranium-added seawater. The concentration of uranium in seawater added with uranium before and after adsorption was measured with an inductively coupled plasma emission spectrometer (ICP-OES). The adsorption capacity of the CMP-p1AO to uranium under the conditions can reach 79 mg/g.
(2) Adsorption performance of CMP-p1AO in natural seawater
5mg of CMP-p1AO was dispersed in 25L of natural seawater and shaken on a shaker for 30 days. And then filtering out the CMP-p1AO, dissolving the solution by using a small amount of aqua regia, diluting the solution by a certain multiple, and measuring the uranium concentration in the diluted solution by using an inductively coupled plasma mass spectrometer (ICP-MS). The adsorption capacity of CMP-p1AO to uranium under the above conditions can reach 4.64mg/g, and CMP-p1AO can realize enrichment and separation of uranium in natural seawater.
Example 2CMP-mAO-NH2Preparation of
1mmol of 1,2, 4-triethylenebenzene, 0.6mmol of 2-amino-3, 5-dibromobenzonitrile and 0.6mmol of 4-amino-3, 5-dibromobenzonitrile are taken up in a 50mL Schlenk tube. 0.04mmol of tetrakis (triphenylphosphine) palladium catalyst and 0.05mmol of cuprous chloride cocatalyst were added to a Schlenk's tube. Uniformly mixing 25mL of N, N-dimethylformamide and 5mL of triethylamine, adding a Stirling tube, linking and sealing a reaction system, vacuumizing, backfilling with nitrogen for protection, repeating for three times, and then protecting for 10min in a nitrogen atmosphere. Subsequently, the reaction system was warmed to 85 ℃ and reacted for 24 hours. Filtering to obtain a crude product after the reaction is finished, sequentially carrying out ultrasonic washing in N, N-dimethylformamide, dichloromethane and methanol, filtering, and drying in a vacuum oven at 50 ℃ overnight to obtain a cyano-containing conjugated microporous polymer precursor CMP-mCN-NH2。
Taking 400mg of CMP-mCN-NH2Placed in a 50mL Schlenk tube, 30mL of methanol was added and dispersed by sonication. Then, an aqueous hydroxylamine solution containing 2mmol of hydroxylamine was added thereto, and the mixture was reacted at 80 ℃ for 12 hours with magnetic stirring. After the reaction is finished, cooling the system to room temperature, filtering to obtain a solid crude product, washing with deionized water for 3 times, placing in a vacuum oven at 50 ℃ for drying overnight to obtain the amidoxime group-containing conjugated microporous polymer adsorbent CMP-mAO-NH2。
CMP-mAO-NH was tested in accordance with the CMP-p1AO adsorption Performance test method in example 12The results are as follows: CMP-mAO-NH2The maximum adsorption capacity of the experiment is 418mg/g, the calculated saturated adsorption capacity is 541mg/g, the maximum adsorption capacity is obtained when the pH value is 6, the adsorption capacity can reach 113mg/g in the uranium solution with the concentration of 20mg/L and the pH value is 6, the removal rate and the elution rate are respectively kept above 85 percent and 90 percent after repeated use for 5 times, and the adsorption capacity can reach 84mg/g in 8mg/L uranium added seawater.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The conjugated microporous polymer is characterized in that a porous molecular structure of the conjugated microporous polymer comprises alkynyl groups and rigid ring structures which are alternately connected, wherein the alkynyl groups are ethynyl groups or conjugated alkynyl groups, the rigid ring structures comprise aromatic rings and/or aromatic hetero-rings, and at least one amidoxime group is further connected to the rigid ring structures.
2. The conjugated microporous polymer of claim 1, wherein the rigid ring structure is selected from one or more of the following structural formulas:
x is independently selected from CR, N, O or S at each occurrence;
each occurrence of R is independently selected from hydrogen, D, non-fluorine halogen, ethynyl, conjugated alkynyl, cyano, straight, branched or substituted alkyl having 1 to 6C atoms, straight alkoxy, straight thioalkoxy, keto, alkoxycarbonyl having 2 to 6C atoms, silyl, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, and at least one R is selected from amidoxime groups.
3. The conjugated microporous polymer according to claim 2, wherein R, ortho to the amidoxime group in the rigid ring structure, is selected from amino or hydroxyl.
4. The conjugated microporous polymer according to claim 2, wherein in the rigid ring structure, X adjacent to X to which the amidoxime group is attached is substituted with a heteroatom which is N, O or S.
5. A method for preparing the conjugated microporous polymer according to any one of claims 1 to 4, comprising the steps of:
carrying out sonogashira-securina coupling reaction on a first monomer and a second monomer to obtain a cyano-containing conjugated microporous polymer precursor; and
carrying out amidoximation reaction on the precursor to convert cyano into amidoxime group;
wherein the molecular structure of the first monomer comprises the rigid ring structure and at least two non-fluorine halogen substituents, the molecular structure of the second monomer comprises the rigid ring structure and at least two of the alkynyl groups, and at least one of the first monomer and the second monomer further comprises at least one cyano group.
6. The method of claim 5, wherein the molecular structure of the first monomer comprises at least three non-fluorine halogen substituents and/or the molecular structure of the second monomer comprises at least three said alkynyl groups.
7. The method of claim 5, wherein the first monomer is selected from one or more of the following formulas:
wherein x is a non-fluoro halogen;
the second monomer is selected from one or more of the following structural formulas:
8. a uranium adsorbent comprising the conjugated microporous polymer according to any one of claims 1 to 4 or the conjugated microporous polymer obtained by the preparation method according to any one of claims 5 to 7.
9. Use of the conjugated microporous polymer according to any one of claims 1 to 4 or the conjugated microporous polymer obtained by the preparation method according to any one of claims 5 to 7 as a uranium adsorbent, wherein the uranium adsorbent is used for enrichment and separation of uranium in neutral and/or weakly alkaline natural water.
10. Use of the conjugated microporous polymer according to any one of claims 1 to 4 or obtained by the preparation method according to any one of claims 5 to 7 as a uranium adsorbent, wherein the conjugated microporous polymer is immersed in an alkaline solution for deprotonation before being used as a uranium adsorbent to adsorb uranium.
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