CN113214480A - Synthesis method and adsorption application of cationic framework material - Google Patents

Synthesis method and adsorption application of cationic framework material Download PDF

Info

Publication number
CN113214480A
CN113214480A CN202110318261.8A CN202110318261A CN113214480A CN 113214480 A CN113214480 A CN 113214480A CN 202110318261 A CN202110318261 A CN 202110318261A CN 113214480 A CN113214480 A CN 113214480A
Authority
CN
China
Prior art keywords
imcop
cationic
framework material
reo
imidazole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110318261.8A
Other languages
Chinese (zh)
Other versions
CN113214480B (en
Inventor
梁汝萍
胡清华
邱建丁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanchang University
Original Assignee
Nanchang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanchang University filed Critical Nanchang University
Priority to CN202110318261.8A priority Critical patent/CN113214480B/en
Publication of CN113214480A publication Critical patent/CN113214480A/en
Application granted granted Critical
Publication of CN113214480B publication Critical patent/CN113214480B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a synthetic method and adsorption application of a cationic framework material, and belongs to the technical field of environmental protection. Firstly, a tripodia flexible ligand tri (4- (1H-imidazole-1-yl) phenyl) amine containing abundant imidazole groups is taken as a monomer to perform quaternization reaction with 1, 4-bis (bromomethyl) benzene to generate a cationic framework material (ImCOP) with positive charge imidazole groups. High density of positively charged imidazole groups with anionic ReO in ImCOP framework4 ‑Through the combination of electrostatic action, the ReO pair is greatly improved4 ‑The adsorption capacity of (c). The ImCOP skeleton is constructed by hydrophobic benzene ring and imidazole ring, so that the ImCOP is small in charge density to ReO4 ‑Has stronger affinity and selectivity than common competitive anions. The stability of the ImCOP prepared by the invention in strong acid and strong alkaliHigh qualitative rate of ReO4 ‑The method has the advantages of large adsorption capacity, fast kinetics, high selectivity and good application potential.

Description

Synthesis method and adsorption application of cationic framework material
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a synthesis method and adsorption application of a cationic framework material.
Background
In order to satisfy the growing energy and environmentThe protection requirement is that nuclear power is a very important choice, and with the vigorous development of the nuclear power industry, the nuclear power provides about 11% of the power all over the world. However, the safe disposal of large quantities of radionuclide waste generated in the nuclear industry is a very problematic issue. The waste radionuclides are generally classified into cationic ones and anionic ones, among which cationic ones have137Cs、90Sr、235U, etc., anionic radionuclides having99Tc、79Se、129I, and the like. At present, more cationic radionuclides are researched, and few anionic radionuclides are researched, especially for cationic radionuclides99Tc was less studied. Starting from the first nuclear reactor, it is estimated that a typical U or Pu fission reactor has produced about 400 metric tons in the last 70 years99Tc(Xiao,C.；Khayambashi,A.；Wang,S.Separation and remediation of 99TcO4 –from aqueous solutions, Chemistry of Materials,2019,31: 3863-. In addition, in the last decades, large amounts of radioactive waste have been released into the environment due to nuclear accidents and improper waste management, seriously threatening the ecological environment and human health. Therefore, radioactive waste treatment and pollution remediation are urgently needed to be solved.
The general strategy for nuclear waste disposal is to separate the solid waste from the liquid waste by gravity and then the nuclear waste is separated into two parts, high radioactive waste and low radioactive waste, for storage at the hanford base in the united states. The low volume high level waste is usually fixed in the form of borosilicate glass waste (known as the vitrification process) but is now in the process99Pertechnetate (TcO) during high temperature curing of Tc4 -) Tc, a radioactive gas which is easily converted into volatility2O7Precipitation, and therefore vitrification, is not suitable for removal99Tc. It is possible to capture and remove TcO4 -The methods of (1) mainly include ion exchange methods, extraction methods and precipitation methods (Katayev, E.A.; Kolesnikov, G.V.; Sessler, J.L. molecular registration of permethlate and perrhenate, Chemical Society Reviews,2009,31:1572-Has a high rate, thus99TcO4 -Removal is of great concern. The most common early studies were of different types of inorganic materials (e.g., nanoscale zero-valent iron, layered double hydroxides, porous carbon materials, etc.) (Li, J.; Zhu, L.; Xiao, C.; Chen, L.; Chai, Z.; Wang, S.Effeicient uptake of perrhenate/pertechnonate from aqueous solutions by the biofunctional-exchange resin, Radiochimica Acta 2018,106: 581-. Ion exchange resin materials were used in the mid-60 s to treat TcO in the Hanford region of the United states4 -Contamination, Bonnesen et al introduce long chain alkyl quaternary ammonium salts into strong base anion resins to increase TcO4 -Even for low concentrations of TcO4 -Also have good removability (Bonnesen, P.V.; Brown, G.M.; Alexandrites, S.D.; Bavoux, L.B.; Presley, D.J.; Patel, V.; Ober, R.; Moyer, B.A. development of Bifundamental Anion-Exchange Resins with Improved Selectivity and sonic Kinetics for Pertechnetiate: Batch-equivalent Experiments, Environmental Science&Technology,2000,34: 3761-. However, ion exchange resins have relatively long synthesis cycles, complex synthesis processes, and are less stable under extreme conditions (e.g., oxidation, irradiation, mechanical pressure, etc.), have slow adsorption kinetics during the exchange process, usually requiring several hours or even days, and inorganic exchange materials generally have poor adsorption properties, are unstable and easily soluble under extreme acid conditions, and have negative surface charges that are detrimental to TcO under alkaline conditions4 -And (4) anion exchange. Therefore, there is an urgent need to develop a novel material which is stable under extreme conditions, has a high adsorption capacity, good selectivity, and fast adsorption kinetics.
In recent years, a polymer network constructed of repetitive organic building blocks has been extensively studied, and exhibits superior hydrolytic stability even in highly acidic/alkaline solutions, which is a distinct advantage not possessed by inorganic materials. More importantly, these structural features are predictable and highly tunable, allowing the materials to be designed for specific tasks. Polymers having good stability under various types of extreme conditions (e.g., high acidity, alkalinity, salinity, etc.)Characteristically, this is due to the increased robustness of the covalent bond-based linkage of the building structure; many polymers are highly conjugated and stabilize radiation-generated radical intermediates, which is also an advantage not available with conventional polymeric anion exchange resins. Therefore, the invention designs and synthesizes imidazolyl cationic framework material (ImCOP), wherein the framework contains abundant positively charged imidazole groups and can react with perrhenate (ReO)4 -) Or pertechnetate (99TcO4 -) The anion generates electrostatic interaction, and the-NH-and ReO of the imidazole group in the framework4 -(ReO4 -Without radioactivity, and commonly used to replace radioactivity99TcO4 -Research is conducted) to form a high density hydrogen bonding network to enhance the ReO4 -The semi-rigid structure of the imidazolyl cationic framework material also improves the chemical stability of the imidazolyl cationic framework material. Up to now, the adsorption removal of ReO by imidazole-based cationic framework materials under strong acid/strong base conditions has not been shown4 -/99TcO4 -The report of (1).
Disclosure of Invention
The invention aims to provide a synthesis method and adsorption application of an imidazolyl cationic framework material with good stability, which has the characteristics of simple operation, environmental friendliness, economy and high efficiency, and meanwhile, an imidazolyl cationic framework material pair99TcO4 -/ReO4 -Has the advantages of high adsorption capacity, fast adsorption kinetics, high selectivity and high stability.
The invention is realized by the following technical scheme:
a tripodia flexible ligand tri (4- (1H-imidazole-1-yl) phenyl) amine containing abundant imidazolyl is taken as a monomer to perform quaternization reaction with 1, 4-bis (bromomethyl) benzene to generate a cationic framework material with positive charge imidazole groups, and the steps are as follows:
1) taking tris (4- (1H-imidazole-1-yl) phenyl) amine and 1, 4-bis (bromomethyl) benzene as reaction raw materials, adding N, N-dimethylformamide and acetonitrile into the reaction raw materials, and uniformly mixing to obtain a reaction mixed solution;
2) stirring and refluxing the reaction mixed solution in a nitrogen atmosphere, cooling to room temperature, and then removing a nitrogen source to obtain a reaction product solution;
3) and (3) carrying out suction filtration on the obtained reaction product solution, washing the precipitate with N, N-dimethylformamide and absolute ethyl alcohol, and drying the precipitate to obtain the imidazole-based cationic framework material ImCOP.
Further, the molar ratio of the tris (4- (1H-imidazol-1-yl) phenyl) amine to the 1, 4-bis (bromomethyl) benzene of step 1) is 1: (1-3).
The invention also provides an application of the cationic framework material in removal of perrhenate/pertechnetate, which comprises the following steps: and adding the cationic framework material into the solution to be treated containing the perrhenate, and oscillating at room temperature.
Further, the concentration range of the solution to be treated containing the perrhenate is 50-2000 mg/L.
Further, before oscillating at room temperature, a pH regulator is used for regulating the pH value to be 1-13; preferably, the pH is 7.
Further, the method comprises filtering the shaken mixture by a 0.22 μm membrane filter.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes tri (4- (1H-imidazole-1-yl) phenyl) amine as a monomer to perform quaternization reaction with 1, 4-bis (bromomethyl) benzene to synthesize the cationic framework material ImCOP with positive charge imidazole group.
(2) The imidazolyl cationic framework material ImCOP synthesized by the invention contains abundant functional groups such as imidazole, tertiary amine and the like, and can react with ReO4 -Selective binding, enhanced binding to ReO4 -The adsorption capacity of (c).
(3) The imidazole-based cationic framework material ImCOP synthesized by the invention contains hydrophobic benzene ring and imidazole group, forms a hydrophobic framework and has low charge density99TcO4 -/ReO4 -Has high selectivity.
(4) The tri (4- (1H-imidazole-1-yl) phenyl) amine used in the invention is a flexible tripodal ligand, so that the synthesized ImCOP is a semi-rigid structure and has high chemical stability under strong acid and strong alkali.
(5) The method for synthesizing the imidazolyl cationic framework material ImCOP is simple, convenient, low in cost, environment-friendly, economical and efficient, and is suitable for ReO4 -The adsorption capacity is high and the speed is high; in addition, the ImCOP has excellent cycle performance, is beneficial to the sustainable development of ecological environment, and is expected to be used for99TcO4 -And (4) removing.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of ImCOP, an imidazolyl cationic framework material.
Fig. 2 is an SEM image of ImCOP for an imidazolyl cationic framework material.
FIG. 3 is an infrared spectrum of Tipa, BBB and ImCOP.
FIG. 4 is an infrared spectrum of ImCOP in strong acid and strong base, an imidazolyl cationic frame material.
FIG. 5 shows ImCOP vs ReO for imidazolyl cationic framing material4 -Adsorption isotherm diagram of (1).
FIG. 6 shows ImCOP vs ReO for imidazolyl cationic framing material4 -Adsorption kinetics of (c).
FIG. 7 is ImCOP on imidazolyl cationic framing material in the presence of competing anions for ReO4 -Adsorption selectivity diagram of (1).
FIG. 8 shows ImCOP in excess NO for imidazolyl cationic framing material3 -For ReO under the condition4 -Adsorption selectivity diagram of (1).
FIG. 9 shows ImCOP in excess SO for imidazolyl cationic framing material4 2-For ReO under the condition4 -Adsorption selectivity diagram of (1).
Detailed Description
The technical solution of the present invention will be described clearly and completely with reference to the following examples, which are only a part of the examples of the present invention, but not all of them, which are conventional processes unless otherwise specified, and the raw materials which are commercially available from the public unless otherwise specified. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making creative efforts, fall within the protection scope of the present invention.
Example 1: preparation and characterization of imidazolyl cationic framework material ImCOP
0.4435g of tripodal flexible ligand tri (4- (1H-imidazole-1-yl) phenyl) amine (Tipa) containing abundant imidazole groups and 0.528g of 1, 4-bis (bromomethyl) benzene (BBB) are placed in a three-neck round-bottom flask, and then 15mL of N, N-Dimethylformamide (DMF) and 15mL of acetonitrile are added and mixed uniformly to obtain a reaction mixed solution; introducing nitrogen into the reaction mixed solution, stirring and refluxing for 3 days at 80 ℃ in the nitrogen atmosphere, cooling to room temperature, and removing the nitrogen source to obtain a reaction product solution; the reaction product solution was taken out and filtered, and the precipitate was washed with N, N-dimethylformamide and anhydrous ethanol, and dried under vacuum at 60 ℃ overnight to obtain an imidazolyl cationic framework material (ImCOP).
FIG. 1 is a schematic diagram of the synthesis process of ImCOP, an imidazolyl cationic framework material.
Fig. 2 is an SEM image of ImCOP for an imidazolyl cationic framework material. The appearance of ImCOP of the imidazolyl cationic type frame material was observed by a Scanning Electron Microscope (SEM), and from the SEM results, the ImCOP was a spherical structure with a diameter of about 2 μm.
FIG. 3 is an infrared spectrum of Tipa, BBB and ImCOP. Imidazole ring of tris (4- (1H-imidazol-1-yl) phenyl) amine (Tipa) at 1024cm-1Has a characteristic peak, and the characteristic peak moves to 1072cm after synthesizing the imCOP of the imidazolyl cationic framework material-1. Furthermore, 1, 4-bis (bromomethyl) benzene (BBB) was present at 567cm in the IR spectrum of ImCOP-1The C-Br bond at (A) disappears. The infrared spectrum result shows that the imidazolyl cationic framework material ImCOP is successfully synthesized by the method.
FIG. 4 is an infrared spectrum of ImCOP in strong acid and strong base, an imidazolyl cationic frame material. ImCOP was soaked in NaOH (1, 3M) and HNO, respectively3After 24h in the (1,3, 5M) solution, the IR spectrum was measured and, as can be seen from FIG. 4, the ImCOP was 1072cm-1Of imidazole ringsThe characteristic peak still exists, and the result shows that the ImCOP has good stability under strong acid and strong alkali conditions.
Example 2: imidazolyl cationic framework material ImCOP to ReO4 -Adsorption of (2)
(1) pH optimization
For ReO4 -The pH of the solution was optimized. 10mg of ImCOP, an imidazolyl cationic frame material, was added to 10mL of a solution containing 400mg/L of ReO4 -In solution of (2), with HNO3Or adjusting pH of the solution with NaOH (1,3,5,7,9,11,13), shaking on a shaker at room temperature for 24 hr, filtering with 0.22 μm membrane filter, and detecting residual ReO in the filtrate by inductively coupled plasma mass spectrometry4 -Concentration, calculation of ImCOP vs ReO for imidazolyl cationic frame material4 -The removal rate of (3). The results show that the imidazolyl cationic framework material ImCOP is against ReO in the pH value range of 3-134 -The adsorption removal efficiency of the catalyst is over 96 percent, and when the pH value of the solution is 7, the ImCOP (ImCOP) is applied to ReO4 -The removal efficiency of the method reaches more than 99 percent.
(2) ImCOP vs ReO4 -Adsorption capacity and adsorption kinetics behavior of
Dissolving sodium perrhenate in deionized water to prepare perrhenate solutions with different concentrations (50-2000mg/L), and adding HNO3Or NaOH is used for adjusting the pH value of the solution to be 7 and adding 10mL of ReO4 -Adding 10mg of imidazole-based cationic framework material ImCOP into the solution, oscillating the solution on a shaking table for 24 hours at room temperature, filtering the solution by using a 0.22 mu m membrane filter, and detecting residual ReO in the filtrate by using an inductively coupled plasma mass spectrometry4 -Concentration, calculation of ImCOP vs ReO for imidazolyl cationic frame material4 -The adsorption capacity of (c). Due to the larger driving force of the solid-liquid interface concentration gradient, the imidazolyl cationic framework material ImCOP is applied to ReO4 -Adsorption capacity with ReO4 -The concentration increases until the adsorption equilibrium is reached. FIG. 5 shows ImCOP vs ReO for imidazolyl cationic framing material4 -Adsorption isotherm diagram of (1). As can be seen in FIG. 5, the imidazolyl cationic frameworkMaterial ImCOP versus ReO4 -The maximum adsorption capacity of (a) was 1162 mg/g. FIG. 6 shows ImCOP vs ReO for imidazolyl cationic framing material4 -Adsorption kinetics of (c). As can be seen from FIG. 6, ImCOP vs ReO imidazole-based cationic framework material4 -The adsorption capacity of (2) is increased with the increase of the adsorption time, and when the adsorption time is 2min, the imidazole-based cationic framework material ImCOP is the adsorption capacity for ReO4 -The adsorption of (2) is saturated and the speed is very fast.
(3) ImCOP vs ReO4 -Selectivity of adsorption
10mg of ImCOP, an imidazolyl cationic type framework material, was added to 10mL of a solution containing 0.1mM of ReO4 -Adding coexisting anions (SO) commonly found in 0.1mM nuclear waste into the solution4 2-、NO3 -、PO4 3-、CO3 2-、Cl-) Shaking the solution and mixed solution at room temperature for 24 hr, filtering with 0.22 μm membrane filter, and detecting residual ReO in the filtrate by inductively coupled plasma mass spectrometry4 -Concentration, ImCOP vs ReO of imidazolyl cationic frame material was examined4 -Selectivity of adsorption. FIG. 7 is ImCOP on imidazolyl cationic framing material in the presence of competing anions for ReO4 -Adsorption selectivity diagram of (1). As can be seen in FIG. 7, ImCOP vs ReO4 -The adsorption removal rate of (3) is nearly 100%, and under the condition that other anions coexist, ImCOP is applied to ReO4 -The adsorption removal rate of (A) was about 96%, indicating that ImCOP was responsible for ReO4 -The selectivity of adsorption is high.
There is often a large excess of NO in nuclear waste3 -And SO4 2-. Study on excess NO3 -And SO4 2-Imidazolyl cationic framework material ImCOP to ReO under the condition4 -Selectivity of adsorption. 10mg of ImCOP, an imidazolyl cationic type framework material, was added to 10mL of a solution containing 0.1mM of ReO4 -Adding NaNO with different concentrations into the solution3(0.1mM, 1mM, 10mM, 100mM) or Na2SO4(0.1mM, 1mM, 10mM, 100mM, 600mM) solution, shaking the mixture at room temperature for 24h, filtering with a 0.22 μm membrane filter, and detecting residual ReO in the filtrate by inductively coupled plasma mass spectrometry4 -And (4) concentration. FIG. 8 shows ImCOP in excess NO for imidazolyl cationic framing material3 -For ReO under the condition4 -Adsorption selectivity diagram of (1). As can be seen from FIG. 8, when NO is present3 -：ReO4 -At molar ratios of 100:1 and 500:1, ImCOP to ReO of the imidazolyl cationic type framework material4 -The removal rates of (a) and (b) were 92.6% and 74.3%, respectively. FIG. 9 shows ImCOP in excess SO for imidazolyl cationic framing material4 2-For ReO under the condition4 -Adsorption selectivity diagram of (1). As can be seen from FIG. 9, when SO is present4 2-When the excess is 6000 times, the imidazole-based cationic framework material ImCOP is opposite to ReO4 -The removal rate of the catalyst can still reach 74 percent. Thus, the imidazolyl cationic framing material ImCOP vs ReO4 -Has good adsorption selectivity, probably because high-density aromatic substituent makes the ImCOP surface hydrophobic, and is more favorable for selectively adsorbing ReO with relatively low charge density4 -。
Example 3: cycling performance of ImCOP
150mg of ImCOP, an imidazolyl cationic framing material, was added to 150mL of ReO at pH 7 containing 28mg/L4 -In the solution (2), the mixture was shaken in a shaker at room temperature for 24 hours, 1mL of the mixture was filtered through a 0.22 μm membrane filter, and ReO remaining in the filtrate was detected by inductively coupled plasma mass spectrometry4 -Concentration, calculating ImCOP vs ReO4 -The removal rate of (3). Washing the residual mixed solution with deionized water, performing suction filtration, collecting precipitate, and vacuum drying at 60 ℃ overnight to obtain 135mg of the perrhenate-loaded imidazolyl cationic framework material ReO4And (3) grinding the ImCOP, dispersing the grinded ImCOP into 135mL of 3M KBr solution, shaking the dispersion at room temperature for 24h to elute, washing the obtained product with deionized water, carrying out suction filtration, and carrying out vacuum drying at 60 ℃ overnight to obtain the regenerated imidazole-based cationic framework material ImCOP for next use. ResultsShows that after 4 adsorption/desorption cycles, the imidazolyl cationic framework material ImCOP is applied to ReO4 -The removal efficiency of the imidazole-based cationic framework material still can reach more than 99 percent, which shows that the imidazole-based cationic framework material ImCOP has good recycling performance.
Therefore, the imidazolyl cationic framework material ImCOP prepared by the method has good stability in strong acid and strong alkali and ReO resistance4 -Has the advantages of high adsorption capacity, high adsorption speed, good selectivity and high recycling performance, and is expected to be used for removing pertechnetate.
The foregoing is only a preferred embodiment of the present invention and it should be noted that modifications and adaptations can be made by those skilled in the art without departing from the principle of the present invention and are intended to be included within the scope of the present invention.

Claims (7)

1. A method for synthesizing a cationic framework material, which is characterized by comprising the following steps:
1) taking tris (4- (1H-imidazole-1-yl) phenyl) amine and 1, 4-bis (bromomethyl) benzene as reaction raw materials, adding N, N-dimethylformamide and acetonitrile into the reaction raw materials, and uniformly mixing to obtain a reaction mixed solution;
2) stirring and refluxing the reaction mixed solution in a nitrogen atmosphere, cooling to room temperature, and then removing a nitrogen source to obtain a reaction product solution;
3) and (3) carrying out suction filtration on the obtained reaction product solution, washing the precipitate with N, N-dimethylformamide and absolute ethyl alcohol, and drying the precipitate to obtain the imidazole-based cationic framework material ImCOP.
2. The method for synthesizing a cationic type framework material according to claim 1, wherein the molar ratio of the tris (4- (1H-imidazol-1-yl) phenyl) amine to the 1, 4-bis (bromomethyl) benzene in step 1) is 1: (1-3).
3. Use of a cationic framework material obtained by the synthesis method according to claim 1 or 2 for the removal of perrhenate/pertechnetate.
4. Use of a cationic framework material for perrhenate/pertechnetate removal according to claim 3, characterized in that it is applied by adding said cationic framework material to the perrhenate-containing solution to be treated, oscillating at room temperature.
5. Use of a cationic framework material for perrhenate/pertechnetate removal according to claim 4, wherein the concentration of the solution to be treated containing perrhenate is in the range of 50-2000 mg/L.
6. Use of a cationic framework material for perrhenate/pertechnetate removal according to claim 4, wherein a pH adjusting agent is further used to adjust the pH to 1-13 before shaking at room temperature; preferably, the pH is 7.
7. The use of a cationic framework material for perrhenate/pertechnetate removal according to claim 4, further comprising filtering the shaken mixture through a 0.22 μm membrane filter.
CN202110318261.8A 2021-03-25 2021-03-25 Synthesis method and adsorption application of cationic framework material Active CN113214480B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110318261.8A CN113214480B (en) 2021-03-25 2021-03-25 Synthesis method and adsorption application of cationic framework material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110318261.8A CN113214480B (en) 2021-03-25 2021-03-25 Synthesis method and adsorption application of cationic framework material

Publications (2)

Publication Number Publication Date
CN113214480A true CN113214480A (en) 2021-08-06
CN113214480B CN113214480B (en) 2022-06-14

Family

ID=77084067

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110318261.8A Active CN113214480B (en) 2021-03-25 2021-03-25 Synthesis method and adsorption application of cationic framework material

Country Status (1)

Country Link
CN (1) CN113214480B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113996273A (en) * 2021-11-04 2022-02-01 辽宁大学 Polyion liquid adsorption film, preparation method thereof and application thereof in rhenium adsorption
CN114591244A (en) * 2022-03-24 2022-06-07 兰州大学 Material for separating technetium and preparation method thereof
CN115403767A (en) * 2022-08-24 2022-11-29 南昌大学 Preparation method of cationic organic polymer and application of cationic organic polymer to adsorption of perrhenate
CN115678032A (en) * 2022-11-24 2023-02-03 南昌大学 Preparation method and application of olefin-linked cationic three-dimensional covalent organic framework
CN115894912A (en) * 2022-11-24 2023-04-04 南昌大学 Perrhenate adsorption method based on three-dimensional covalent organic framework
CN116396493A (en) * 2023-04-13 2023-07-07 天津师范大学 Cationic metal-organic framework material, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107513164A (en) * 2016-06-16 2017-12-26 中国科学院福建物质结构研究所 For Cr VI Anionic recognition and the backbone chain type imidazolium ion polymer of separation
CN108102092A (en) * 2018-01-09 2018-06-01 苏州大学 cationic organic polymer and its preparation method and application
CN112111060A (en) * 2020-09-28 2020-12-22 潍坊光华精细化工有限公司 Porous organic framework material, preparation method thereof and application of porous organic framework material in selective separation of perrhenate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107513164A (en) * 2016-06-16 2017-12-26 中国科学院福建物质结构研究所 For Cr VI Anionic recognition and the backbone chain type imidazolium ion polymer of separation
CN108102092A (en) * 2018-01-09 2018-06-01 苏州大学 cationic organic polymer and its preparation method and application
CN112111060A (en) * 2020-09-28 2020-12-22 潍坊光华精细化工有限公司 Porous organic framework material, preparation method thereof and application of porous organic framework material in selective separation of perrhenate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANGXIN WANG ET AL: "A durable luminescent ionic polymer for rapid detection and efficient removal of toxic Cr2O72-", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113996273A (en) * 2021-11-04 2022-02-01 辽宁大学 Polyion liquid adsorption film, preparation method thereof and application thereof in rhenium adsorption
CN113996273B (en) * 2021-11-04 2023-11-10 辽宁大学 Polyion liquid adsorption film, preparation method thereof and application thereof in adsorption of rhenium
CN114591244A (en) * 2022-03-24 2022-06-07 兰州大学 Material for separating technetium and preparation method thereof
CN115403767A (en) * 2022-08-24 2022-11-29 南昌大学 Preparation method of cationic organic polymer and application of cationic organic polymer to adsorption of perrhenate
CN115403767B (en) * 2022-08-24 2023-10-03 南昌大学 Preparation method of cationic organic polymer and adsorption application of cationic organic polymer to perrhenate
CN115678032A (en) * 2022-11-24 2023-02-03 南昌大学 Preparation method and application of olefin-linked cationic three-dimensional covalent organic framework
CN115894912A (en) * 2022-11-24 2023-04-04 南昌大学 Perrhenate adsorption method based on three-dimensional covalent organic framework
CN115678032B (en) * 2022-11-24 2023-07-28 南昌大学 Preparation method and application of olefin-linked cationic three-dimensional covalent organic framework
CN115894912B (en) * 2022-11-24 2024-02-09 南昌大学 Perrhenate adsorption method based on three-dimensional covalent organic framework
CN116396493A (en) * 2023-04-13 2023-07-07 天津师范大学 Cationic metal-organic framework material, and preparation method and application thereof
CN116396493B (en) * 2023-04-13 2024-05-17 天津师范大学 Cationic metal-organic framework material, and preparation method and application thereof

Also Published As

Publication number Publication date
CN113214480B (en) 2022-06-14

Similar Documents

Publication Publication Date Title
CN113214480B (en) Synthesis method and adsorption application of cationic framework material
Tang et al. Amidoxime-based materials for uranium recovery and removal
CN108525648B (en) Aminated magnetic polyphosphazene adsorbent and method for preparing, separating and enriching uranium
CN109289803A (en) Polyamines base/amidoxime group modification polyfunctional group ion-exchange fibre method of preparation and use
EP3199650B1 (en) Rare earth element adsorption separation material
CN103285837A (en) Preparation method of adsorption material with high selectivity on different heavy metal ions
Huang et al. 2-Methylol-12-crown-4 ether immobilized PolyHIPEs toward recovery of lithium (i)
CN104774283A (en) Acrylic acid pyridine chelating resin as well as preparation method and application thereof
CN103406081A (en) Preparation method and applications of anion beta-cyclodextrin magnetic microsphere
Guo et al. Simultaneously efficient adsorption and highly selective separation of U (VI) and Th (IV) by surface-functionalized lignin nanoparticles: a novel pH-dependent process
Huang et al. Efficient and selective capture of uranium by polyethyleneimine-modified chitosan composite microspheres from radioactive nuclear waste
CN1935861A (en) N-methyl, N-carboxymethyl dithio amidocarbonic acid chelating resin and its preparing method
CN105664864B (en) A kind of preparation method of vascular plant Quito hole oxidation polymerization chelate adsorption and application
CN109482160A (en) Phosphate-based efficient uranium absorption agent of one kind and the preparation method and application thereof
CN101402033A (en) Chelate adsorption material and method of producing the same
CN114797795A (en) By using GMA/H 3 PO 4 Method for treating uranium-containing wastewater by using modified natural fibers
Qin et al. Innovative Amidoxime Nanofiber Membranes for Highly Effective Adsorption of Ga (III) from Waste Bayer Solution
EP1179367B1 (en) Use of a chelate-forming porous hollow fiber membrane and method for the recovery of germanium oxide with the same
CN101905146A (en) Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions
CN115403767B (en) Preparation method of cationic organic polymer and adsorption application of cationic organic polymer to perrhenate
CN114573827A (en) Synthesis and adsorption application of alkali-resistant halogen bond donor metal organic framework
Qin et al. Cross-linked amidoxime porous resin for selective gallium separation in Bayer solutions: Reaction mechanism and kinetic study
Li et al. Al-Doped chitosan nonwoven in a novel adsorption reactor with a cylindrical sleeve for dye removal: performance and mechanism of action
CN109317117B (en) Magnetic adsorbent, preparation method thereof and method for treating actinide waste liquid
CN115197435A (en) Polyion liquid @ metal organic framework composite material and removal method thereof 99 Application of Tc nuclide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant