CN108311108B - Carbon-based calixarene crown ether hybrid material and preparation method and application thereof - Google Patents
Carbon-based calixarene crown ether hybrid material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon-based calixarene crown ether hybrid material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) adding concentrated nitric acid into a porous carbon ball to perform hydrothermal reaction, washing and drying to obtain a carboxylated carbon ball; (2) dissolving the amino calix [4] -crown-6 in an organic solvent, adding N, N-carbonyl diimidazole, stirring for 0.5-1.5 h, adding the carboxylated carbon spheres, continuously stirring for 8-15 h, and carrying out post-treatment to obtain the carbon-based calixarene crown ether hybrid material. The carbon-based calixarene crown ether hybrid material can be used as an adsorbent to adsorb and separate rubidium from an acidic water phase, has high selectivity, simple operation and high separation efficiency, and is suitable for industrial separation and recovery of rubidium.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a carbon-based calixarene crown ether hybrid material and a preparation method and application thereof.
Background
The extraction chromatography has the characteristics of high selectivity of solvent extraction, simplicity, multistage chromatography and the like, and has the advantages of small usage amount of organic reagents, simple process and compact equipment. Calix [4] -crown-6 is an organic compound and cannot be directly applied to a solid phase extraction method. It is an important idea to immobilize it on an inert carrier.
Scioto et al (G.Arena, A.Casnat, A.Contino, et al., Chemical Communications, (19) (1996)2277-]Crown-5 and cup [4]]Reacting the-crown-6 derivative with triethoxysilane under the catalysis of chloroplatinic acid to obtain the fixed extractant with the mass ratio of silanized calix arylcrown ether to silica gel of 1: 10. Tavlatides et al (l.l.tavlatides, j.s.lee, k.h.nam, et al, Tsinghua Science&Technology,11(2) (2006)233-]Crown-6 and cup [4]]-benzo-crown-6 silica gel adsorbent, N2The characterization result of the adsorption-desorption curve shows that the adsorbent has larger specific surface area and pore volume. Weyue et al (Y.Z.Wei, M.Kumagai, Y.Takashima, et al, Nuclear Technology 132(2000)1472-2P) for separating ln (iii), am (iii) and cm (iii) in HLLW. Subsequently, Zhang Anyu et al (Z. Chai, Separation Science and Technology,44(2009)2146-]arene-R14 and DtBuCH18C6 loaded on SiO2-P inside, preparing macroporous silicon-based (calixarene) crown ether supramolecular recognition material (Calix [4]]arene-R14/SiO2P and DtBuCH18C6/SiO2P) and proposes a SPEC extraction chromatography separation process, which is applied to the separation of cs (i) and sr (ii) in HLLW, and opens up a new field of applying the supramolecular recognition material to the separation of cs (i) in HLLW. Recently, He will turn Calix [4]]Co-loading with DBC to SiO2P, innovative proposing GPSC (group Partitioning of Strontium and silicon by Extraction chromatography) Extraction chromatography Separation procedure (A.Zhang, J.Li, D.ying, et al., Separation)&Purification Technology,127(2014) 39-45), achieves co-adsorptive separation of cs (i) and sr (ii) in HLLW: when HNO3The concentration is 3.0 mol.L-1Then, Calix [4]]@DBC/SiO2The partition coefficient of P to Cs (I) and Sr (II) is respectively up to 89.93cm3·g-1And 75.91cm3·g-1. Chenjing et al (R.Yi, G.Ye, D.Lv, et al, RSC Advances,5(68) (2015):55277-55284.) prepared calixarene-crosslinked temperature-controlled hydrogel microspheres by precipitation polymerization with high Cs (I) selectivity and 93.5% efficiency for separating trace Cs (I) from real seawater.
Rubidium is a precious rare alkali metal, has very active property, and is mainly added into solid ores such as lepidolite and caesium lutetium and salt lake brine. Rubidium has important application value in industrial fields such as national defense, aerospace, bioengineering and the like. Rubidium exists in mineral in the form of isomorphism instead of potassium atom, and rubidium exists with the accompanying alkali metal elements with very similar properties to potassium, sodium and the like in salt lake brine, which causes great difficulty in separating and purifying rubidium.
Separation materials and methods are key elements in separating rubidium. The separation materials most commonly used at present are crown ethers and phenols, and the common method is a solvent extraction method. However, the phenol extractant has the defects of high toxicity, long durability, difficult degradation, more organic solvents used in the solvent extraction method, large equipment volume, poor separation effect on low-concentration rubidium and the like.
In the prior art, a simple and feasible method for recovering and separating rubidium is still lacking.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a carbon-based calixarene crown ether hybrid material and a preparation method and application thereof, and the carbon-based calixarene crown ether hybrid material is prepared by connecting a calix [4] -crown-6 supermolecule compound to a carbon sphere in a chemical manner for the first time.
The technical scheme adopted by the invention is as follows:
a carbon-based calixarene crown ether hybrid material is shown in a structural formula I:
The invention also provides a preparation method of the carbon-based calixarene crown ether hybrid material, which comprises the following steps:
(1) adding concentrated nitric acid into a porous carbon ball to perform hydrothermal reaction, washing and drying to obtain a carboxylated carbon ball;
(2) dissolving amino calix [4] -crown-6 shown as a structural formula II in an organic solvent, adding N, N-Carbonyl Diimidazole (CDI), stirring for 0.5-1.5 h, adding a carboxylated carbon ball, continuously stirring for 8-20 h, and carrying out aftertreatment to obtain the carbon-based calixarene crown ether hybrid material;
n is an integer of 1 to 4.
Preferably, in the step (1), 8-15 mL of concentrated nitric acid is added into each gram of porous carbon spheres; if the adding amount of the nitric acid is too small, the carboxyl generated on the surface of the porous carbon sphere is less; when the amount of the nitric acid added is too large, the structure of the porous carbon sphere is unstable.
Preferably, in the step (1), the concentrated nitric acid is contacted with the porous carbon spheres through nitric acid vapor, so that the inner and outer surfaces of the carbon spheres can be contacted with the nitric acid, and the contact degree is uniform.
The porous carbon spheres are prepared by conventional means in the prior art, such as taking phenolic resin as a carbon source and F127 as a template.
The temperature of the hydrothermal reaction is 100-150 ℃, and the time of the hydrothermal reaction is 4-6 hours.
Preferably, in step (2), the organic solvent is Dimethylformamide (DMF) or acetonitrile.
Preferably, in the step (2), the amount ratio of the amino cup [4] -crown-6, the N, N-carbonyldiimidazole, the carboxylated carbon spheres and the organic solvent is 1 mol: 1.1-1.5 mol: 30-35 g: 4.5-6L.
The amino-cup [4] -crown-6 is prepared by the conventional means in the prior art.
In the step (2), N, N-carbonyl diimidazole is added into the system in batches to ensure that the raw materials can be fully and uniformly mixed and then react to generate CO2Can escape in time.
In order to obtain a product with higher purity, preferably, the post-treatment in step (2) comprises: and filtering the reaction product, washing precipitates with DMF (dimethyl formamide) to remove unreacted amino calix [4] crown-6, excessive N, N-carbonyl diimidazole and partial byproducts, washing DMF (dimethyl formamide) mixed in the porous carbon spheres with ethanol, washing ethanol with diethyl ether to facilitate drying, and drying in vacuum to obtain the carbon-based calixarene crown ether hybrid material.
The invention also provides an application of the carbon-based calixarene crown ether hybrid material, which comprises the following steps: the carbon-based calixarene crown ether hybrid material is mixed with a nitrate solution containing various metal ions, and rubidium ions in the nitrate solution are adsorbed and separated.
The nitrate solution contains Rb (I) and other metal ions, and the other metal ions comprise at least one of Na (I), K (I), Sr (II), Ba (II), Ru (III) and Fe (III).
The use amount of the carbon-based calixarene crown ether hybrid material can be adjusted according to requirements, preferably, each gram of the carbon-based calixarene crown ether hybrid material is mixed with 80-200 mL of nitrate solution, and within the range, the carbon-based calixarene crown ether hybrid material has good selectivity on rubidium and high separation efficiency.
Compared with the prior art, the invention has the following beneficial effects: the amino cup [4] -crown-6 is fixed on the porous carbon sphere by a chemical modification method for the first time, the structure is novel, the preparation method is simple and feasible, and rubidium in a water phase can be selectively separated. Generally, the rubidium exists with alkali metal elements with extremely similar properties such as potassium and sodium, and the like, which causes great difficulty in separation and purification of the rubidium, the carbon-based cup [4] -crown-6 hybrid material is used for separating the rubidium in a water phase, and has the advantages of acid resistance, alkali resistance, high Rb selectivity, high Rb recognition and the like.
Drawings
FIG. 1 is FT-IR infrared spectrum of porous carbon spheres, carboxylated carbon spheres, amino calix [4] -crown-6 and carbon-based calixarene crown ether hybrid material;
FIG. 2 is an SEM image of a carbon-based calixarene crown ether hybrid material prepared in example 1;
FIG. 3 is an isothermal adsorption-desorption curve of carbon spheres, carboxylated carbon spheres and carbon-based calixarene crown ether hybrid material;
FIG. 4 is a pore size distribution diagram of carbon spheres, carboxylated carbon spheres and carbon-based calixarene crown hybrid material;
FIG. 5 is a graph showing the relationship between the adsorption distribution coefficient of rubidium element separated from nitrate solution by using the carbon-based calixarene crown ether hybrid material prepared by the method of the present invention and the concentration of nitric acid.
Detailed Description
The porous carbon spheres used in the present invention are prepared by the following method:
dissolving 0.96g F127 in 15mL of deionized water; accurately weighing 0.6g of phenol, 2.1mL of formaldehyde and 15mL of 0.1 mol.L-1NaOH is evenly mixed and heated to 340 r.min at 70 DEG C-1Stirring at constant speed for 0.5h at the rotating speed to synthesize the low molecular weight phenolic resin; then pouring the dissolved F127 into phenolic resin, changing the temperature to 66 ℃, continuing stirring, adding 50mL of deionized water after 2h, continuing stirring for 16-18 h, observing whether a precipitate is generated, and stopping the reaction after the precipitate is generated(ii) a Standing for a period of time, precipitating and dissolving, uniformly diluting 17.7mL of dissolved liquid with 56mL of deionized water, and transferring into a high-pressure reaction kettle; and carrying out hydrothermal reaction at 130 ℃ for 24h, taking out, carrying out centrifugal separation, cleaning with deionized water, drying, grinding, putting into a tubular furnace, calcining at 700 ℃ for 3h under the protection of nitrogen, and fully grinding the fired black solid in a star-shaped ball mill to obtain the porous carbon ball.
Example 1
The synthetic schematic route of the carbon-based calixarene crown ether hybrid material of the embodiment is as follows:
the preparation method of this example includes:
(1) weighing 0.2g of porous carbon spheres, putting the porous carbon spheres into a 20mL reaction kettle lining, putting the 20mL lining filled with the porous carbon spheres into a 100mL reaction kettle lining, adding 2mL of concentrated nitric acid into the 100mL reaction kettle lining, sealing, reacting at 120 ℃ for 5 hours, wherein the concentrated nitric acid is in contact reaction with the porous carbon spheres in the form of nitric acid steam, cooling to room temperature, taking out a product, washing to be neutral by using deionized water, and drying to obtain the carboxylated carbon spheres.
(2) 3.382g (4.75mmol) of amino cup [4] of formula III was added to 25ml of DMF under Ar blanket]Crown-6, dissolved and to which 0.923g (5.7mmol) of N, N-carbonyldiimidazole are added, CDI is added in small portions, and CO produced2Escape within 5min and the mixture was stirred at room temperature for 1 h. 0.166g of carboxylated carbon spheres was added to the mixture, and the mixture was stirred for 18 hours. Filtering the mixture after the reaction to obtain precipitate, washing the precipitate with 20ml DMF twice, washing the precipitate with 20ml ethanol twice, washing the precipitate with 20ml diethyl ether twice, and vacuum drying at 50 deg.C for 8 hr to obtain 1.47g of the carbon-based calixarene crown ether hybrid material (i.e. carbon-based calix [4]]Crown-6), a carbon-based cup [4]]The structure of-crown-6) is shown as formula IV, and the yield is 65%.
Wherein, the porous carbon spheres, the carboxylated carbon spheres and the amino cups [4]]FT-IR infrared spectra of-crown-6 and carbon-based calixarene crown ether hybrid materials are shown in FIG. 1. Carbon-based cup [4]Crown-6 is a cup [4] formed by carboxyl and amino groups on carbon spheres]The amino group in crown-6 is amidated, thus forming a carbon-based cup [4]]Crown-6 will retain carbon spheres and cups [4]]Crown-6 infrared characteristic peak. In an amino cup [4]]In the spectrum of-crown-6, 3365cm-1Is an amino peak in the carbon-based cup [4] obtained after the amide reaction]None of crown-6, while in carbon-based cup [4]]1612cm in crown-6 spectrum-1Presents an N-H peak at 1712cm-1A C ═ O peak appears indicating amide bond formation. The infrared spectrum proves the carbon-based cup [4]]Crown-6 has been successfully prepared.
An SEM image of the carbon-based calixarene crown ether hybrid material prepared in this example is shown in fig. 2.
The BET characterization results of the porous carbon spheres, the carboxylated carbon spheres and the carbon-based calixarene crown ether hybrid material are shown in FIGS. 3-4, the BET data are shown in Table 1,
TABLE 1
Example 2
The preparation method of this example includes:
(1) weighing 0.2g of porous carbon spheres, putting the porous carbon spheres into a 20mL reaction kettle lining, putting the 20mL lining filled with the porous carbon spheres into a 100mL reaction kettle lining, adding 2mL of concentrated nitric acid into the 100mL reaction kettle lining, sealing, reacting at 120 ℃ for 5 hours, wherein the concentrated nitric acid is in contact reaction with the porous carbon spheres in the form of nitric acid steam, cooling to room temperature, taking out a product, washing to be neutral by using deionized water, and drying to obtain the carboxylated carbon spheres.
(2) 3.382g (4.75mmol) of amino cup [4] were added to 25ml of DMF under Ar protective gas]Crown-6, making it dissolve0.923g (5.7mmol) of N, N-carbonyldiimidazole are then added thereto, CDI is added in small portions, and CO produced2Escape within 5min and the mixture was stirred at room temperature for 1 h. 0.143g of carboxylated carbon spheres was added to the mixture, and the mixture was stirred for 12 hours. After the reaction is finished, filtering the mixture to obtain a precipitate, washing the precipitate twice by using 20ml of DMF, washing twice by using 20ml of ethanol, washing twice by using 20ml of diethyl ether, and drying for 8 hours in vacuum at the temperature of 50 ℃ to obtain 1.52g of the carbon-based calixarene crown ether hybrid material with the yield of 73%.
Example 3
The preparation method of this example includes:
(1) weighing 0.2g of porous carbon spheres, putting the porous carbon spheres into a 20mL reaction kettle lining, putting the 20mL lining filled with the porous carbon spheres into a 100mL reaction kettle lining, adding 3mL of concentrated nitric acid into the 100mL reaction kettle lining, sealing, reacting at 150 ℃ for 4 hours, wherein the concentrated nitric acid is in contact reaction with the porous carbon spheres in the form of nitric acid steam, cooling to room temperature, taking out a product, washing the product to be neutral by using deionized water, and drying to obtain the carboxylated carbon spheres.
(2) 3.382g (4.75mmol) of amino cup [4] were added to 25ml of DMF under Ar protective gas]Crown-6, dissolved and to which 0.839g (5.18mmol) of N, N-carbonyldiimidazole are added, CDI added in small portions, CO generated2Escape within 5min and the mixture was stirred at room temperature for 1 h. 0.155g of carboxylated carbon spheres was added to the mixture, and stirred for 15 hours. After the reaction is finished, filtering the mixture to obtain a precipitate, washing the precipitate twice by using 20ml of DMF, washing twice by using 20ml of ethanol and washing twice by using 20ml of diethyl ether, and drying for 8 hours in vacuum at the temperature of 50 ℃ to obtain 1.45g of the carbon-based calixarene crown ether hybrid material with the yield of 69.5 percent.
Example 4
The preparation method of this example includes:
(1) weighing 0.2g of porous carbon spheres, placing the porous carbon spheres into a 20mL reaction kettle lining, placing the 20mL lining filled with the porous carbon spheres into a 100mL reaction kettle lining, adding 1.6mL of concentrated nitric acid into the 100mL reaction kettle lining, sealing, reacting at 105 ℃ for 6 hours, wherein the concentrated nitric acid is in contact reaction with the porous carbon spheres in the form of nitric acid steam, cooling to room temperature, taking out a product, washing to be neutral with deionized water, and drying to obtain the carboxylated carbon spheres.
(2) 3.382g (4.75mmol) of amino cup [4] are added to 25ml of acetonitrile under Ar protective gas]Crown-6, dissolved and to which 1.15g (7.12mmol) of N, N-carbonyldiimidazole are added, CDI added in small portions, CO generated2Escape within 5min and the mixture was stirred at room temperature for 1 h. 0.143g of carboxylated carbon spheres was added to the mixture, and the mixture was stirred for 10 hours. After the reaction is finished, filtering the mixture to obtain a precipitate, washing the precipitate twice with 20ml of acetonitrile, washing twice with 20ml of ethanol, washing twice with 20ml of diethyl ether, and drying under vacuum at 50 ℃ for 4 hours to obtain 1.39g of the carbon-based calixarene crown ether hybrid material with the yield of 66.6%.
Examples 5 to 11
(1) Alkali metal salt NaNO3、KNO3、RbNO3(ii) a Alkaline earth metal salt Sr (NO)3)2、Ba(NO3)2(ii) a Transition metal salt Fe (NO)3)3(ii) a Dissolving 7 kinds of metal salts such as nitrate solution of noble metal Ru in nitric acid solution, adding deionized water to prepare nitrate solution containing multiple metal ions, wherein the concentration of nitric acid in the nitrate solution is 4.0M, and the concentration of each metal ion is 2.0 multiplied by 10-3M。
(2) Adding concentrated nitric acid and deionized water into the nitrate solution obtained in the step (1), adjusting the nitric acid concentration in the nitrate solution to be 0.5, 1.0, 2.0, 3.0, 4.0, 5.0 and 6.0M respectively, and adjusting the concentration of each metal ion to be 5.0 multiplied by 10-3M。
(3) And (3) contacting and mixing the salt solution containing 7 metal elements and different nitric acid concentrations obtained in the step (2) with the carbon-based calixarene crown ether hybrid material prepared in the example 1, wherein the dosage ratio during mixing is as follows: 0.1g of carbon-based calixarene crown ether hybrid material is corresponding to every 10mL of nitrate solution;
(4) and (3) carrying out an adsorption experiment on the mixed solution obtained in the step (3) on a DHG-9073BS-III type electric heating constant temperature air-blast drying oven, operating at the oscillation speed of 120rpm and the room temperature of 298K, keeping the adsorption for 180min, balancing the adsorption, and measuring the content of each element in different nitric acid water phases before and after adsorption by using ICP-OES.
The adsorption results of examples 5 to 11 are shown in FIG. 5, in which the abscissa in FIG. 5 is the nitric acid concentration value; the ordinate is the adsorption distribution coefficient KdIn units of cm3The graph shows that the adsorption distribution coefficient of rubidium is increased from 5.2cm to 4.0M when the concentration of nitric acid is increased from 0.5M3Increase in/g to 12.8cm3The adsorption distribution coefficient of rubidium is increased from 12.8cm when the concentration of nitric acid is increased from 4.0M to 6.0M3The/g is reduced to 8.1cm3(ii)/g, optimum adsorption acidity of 4.0M HNO3. The results show that HNO is present at 1.0M to 6.0M3Under the high acidity, the carbon-based calixarene crown ether hybrid material still has the performance of separating rubidium.
Claims (4)
1. The application of the carbon-based calixarene crown ether hybrid material is characterized in that the carbon-based calixarene crown ether hybrid material is mixed with a nitrate solution containing a plurality of metal ions, and rubidium ions in the nitrate solution are adsorbed and separated;
the nitrate solution contains Rb (I) and other metal ions, and the other metal ions comprise at least one of Na (I), K (I), Sr (II), Ba (II), Ru (III) and Fe (III);
mixing the carbon-based calixarene crown ether hybrid material per gram with 80-200 mL of nitrate solution;
the carbon-based calixarene crown ether hybrid material is shown as a structural formula I:
the preparation method of the carbon-based calixarene crown ether hybrid material comprises the following steps:
(1) adding concentrated nitric acid into a porous carbon ball to perform hydrothermal reaction, washing and drying to obtain a carboxylated carbon ball; adding 8-15 mL of concentrated nitric acid into each gram of porous carbon spheres;
(2) dissolving amino calix [4] -crown-6 shown as a structural formula II in an organic solvent, adding N, N-carbonyl diimidazole, stirring for 0.5-1.5 h, adding a carboxylated carbon sphere, continuously stirring for 8-20 h, and performing post-treatment to obtain the carbon-based calixarene crown ether hybrid material; the dosage ratio of the amino calix [4] -crown-6, the N, N-carbonyl diimidazole, the carboxylated carbon spheres and the organic solvent is 1 mol: 1.1-1.5 mol: 30-35 g: 4.5-6L;
n is an integer of 1 to 4.
2. The application of the carbon-based calixarene crown ether hybrid material as claimed in claim 1, wherein in the step (1), the concentrated nitric acid is contacted with the porous carbon spheres through nitric acid vapor.
3. The application of the carbon-based calixarene crown ether hybrid material as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 100-150 ℃ and the time of the hydrothermal reaction is 4-6 hours.
4. Use of carbon-based calixarene crown ether hybrid material according to claim 1, characterized in that the post-treatment in step (2) comprises: and filtering the reaction product, washing the precipitate with DMF, ethanol and diethyl ether in sequence, and drying in vacuum to obtain the carbon-based calixarene crown ether hybrid material.
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