CN109467711B - Cd coordination polymer iodine vapor load material and preparation method and application thereof - Google Patents
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Abstract
Novel CdCoordination polymer iodine vapor load material, preparation method and application thereof, and space group of novel Cd coordination polymer iodine vapor load material isP2 1 By reacting with 2- (pyridin-4-yl) -1H-benzo [ d]Imidazole-5-carboxylic acid as ligand and Cd2+The soluble salt is prepared by reaction; the chemical formula is as follows: [ Cd (pbica)2]·2DMF·2C2H5OH, asymmetric cell containing one Cd2+Ionic, two 2- (pyridin-4-yl) -1H-benzo [ d]Imidazole-5-carboxylic acid molecules. Experimental results show that the novel Cd coordination polymer prepared by the method disclosed by the invention becomes I due to the characteristics of high absorption capacity, rapid adsorption and the like2The fields of capture, storage and the like of the radioactive element I of the capture technology candidate have good application prospects.
Description
Technical Field
The invention belongs to the technical field of complex preparation, and particularly relates to a Cd coordination polymer iodine vapor load material, and a preparation method and application thereof.
Background
Nuclear power is a clean and reliable energy source and can meet the increasing global energy demand. Therefore, proper management of nuclear waste has become a major safety issue in nuclear power production. As is well known in the art,129i and131i is an important radioisotope in nuclear waste.129I is a dangerous species, with a relatively long half-life (1.57 x 107 years), and is bioaccumulating and must therefore be captured and reliably stored by effective means. Although it is not limited to131I is a short-lived (half-life of 8.02 days) radionuclide, but due to its high volatility, it has a direct effect on the metabolic processes of the human body,131immediate capture of I is still necessary. At present I2Trapping techniques rely primarily on natural or synthetic zeolites, e.g. Ag0Faujasite or mordenite zeolites, and other adsorbents such as Ag +Impregnated silica and alumina, activated carbon or graphene aerogels and powders all have a certain absorption I2The ability of the cell to perform. However, their main disadvantage is the expensive and/or inefficient recoverability. Recently, several Metal Organic Frameworks (MOFs) have been discovered to have the ability to adsorb large amounts of iodine rapidly, and thus are I2Capture technology candidates.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a cadmium coordination polymer iodine vapor load material, a preparation method and application thereof, and solves the problem of the existing capture I2Expensive materials and inefficient recovery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a Cd coordination polymer iodine vapor load material is prepared by reacting 2- (pyridin-4-yl) -1H-benzo [ d]Imidazole-5-carboxylic acid as ligand and Cd2+The soluble salt is prepared to obtain the chemical general formula [ Cd (pbica)2]·2DMF·2C2H5An OH Cd coordination polymer iodine vapor load material;
wherein the repeating unit is an asymmetric unit containing one Cd2+Two pbica; DMF is N, N-dimethylformamide; pbica is 2- (pyridin-4-yl) -1H-benzo [ d]Imidazole-5-carboxylic acid ions.
The Cd is binuclear [ Cd ]2(COO)4N4]Two identical Cd1 are hexacoordinated and are bound by pbica -Ligands are linked into a binuclear structure, with two Cd' s2+From 4 different pbica -4 oxygen atoms (. eta.) of ligands1-η2）-μ2Coordinative and 4 different pbica -2 nitrogen atoms of the ligand pass through (. eta.)1）-μ1Coordinately coordinated to pbica -In particular, adopt(η 1 -η 1 )-μ 2 (pbica -A)And (η) 1 )-(η 1 -η 2 -μ 2 )-μ 3 (pbica-B) coordination mode, pbica -With Cd2+Three-dimensional structures are formed by two coordination modes, binuclear units are connected by eight pbica ligands, and point symbols (4) are connected by a 3D frame forming an acs network with 6 connections9.66) Connected, 3D framework with 1D channels along the a-axis), and has an aperture of 14.6272 x 14.6272 a2。
The pbica adopts(η 1 -η 1 )-μ 2 (pbica -A)And (η) 1 )-(η 1 -η 2 -μ 2 )-μ 3 (pbica-B) coordination mode, pbica -With Cd2+Two coordination modes are connected to form a three-dimensional structure, namely binuclear [ Cd ]2(COO)4N4]By eight pbica ligands, by forming a 3D framework with 6 linked acs networks and point symbols (4)9.66) And (4) connecting.
A preparation method of a Cd coordination polymer iodine vapor load material comprises the following steps:
1) weigh 0.05 mmol of Cd2+Is dissolved in CH3Transferring the solution into a reaction kettle in the mixed solution of OH and DMF;
2) weighing 0.1 mmol of Hpbica (2- (pyridin-4-yl) -1H-benzo [ d ] imidazole-5-carboxylic acid), and adding into the reaction kettle in the step 1);
3) and sealing the reaction kettle, keeping the temperature constant at 373K for 72h, slowly cooling to room temperature, filtering, and washing to obtain a light yellow transparent blocky crystal, namely the Cd coordination polymer.
The Cd coordination polymer iodine vapor load material space group isP2 1 。
The Cd2+The soluble salt of (a) is cadmium nitrate.
The Cd coordination polymer crystal is monoclinic system, and the space group isP21/cThe unit cell parameter is a = 8.70955 (15) a; b =23.1334 (4) a; c =17.9071 (3) a; β =97.1938 (16)O；V =3579.55 (11) Å3；Z = 4。
The Cd coordination polymer iodine vapor load material has potential application in the fields of radioactive element iodine vapor rapid capture, release, storage and the like.
The invention has the beneficial effects that:
the invention discloses a preparation method and application of a Cd coordination polymer iodine vapor load material, which utilizes Hpbica (2- (pyridine-4-yl) -1H-benzo [ d ]]Imidazole-5-carboxylic acid) as ligand with Cd2+The coordination polymer of Cd is prepared by the soluble salt, the repeating unit of the coordination polymer is an asymmetric unit, and the asymmetric unit contains one Cd2+Two hpdica molecules; the ultraviolet spectrometer test shows that the polymer has the function of rapidly capturing and releasing iodine vapor, and the capturing amount of the iodine vapor is large.
The invention discloses a preparation method and application of a Cd coordination polymer iodine vapor load material, firstly Hpbica (2- (pyridine-4-yl) -1H-benzo [ d ]]Imidazole-5-carboxylic acid) is dissolved in a mixed solution of N, N-dimethylformamide and ethanol, and then Cd is added2+The Cd coordination polymer is finally obtained through sealing reaction of the soluble salt, the process is simple, the cost is low, and the ultraviolet spectrometer test at room temperature shows that the Cd coordination polymer has the function of rapidly capturing and releasing iodine vapor and has larger adsorption capacity.
Drawings
FIG. 1 is a complex [ Cd (pbica) ]2]·2DMF·2C2H5The structure diagram of the metal ion coordination mode of OH;
FIG. 2 is a complex [ Cd (pbica)2]·2DMF·2C2H5The structure of the ligand coordination mode of OH;
FIG. 3 is a complex [ Cd (pbica)2]·2DMF·2C2H5A three-dimensional structure diagram of OH;
FIG. 4 is a complex [ Cd (pbica)2]·2DMF·2C2H56-connected acs topological diagram of OH;
FIG. 5 is a complex [ Cd (pbica)2]·2DMF·2C2H5Powder diffractogram of OH;
FIG. 6 is a complex [ Cd (pbica)2]·2DMF·2C2H5Thermogravimetric analysis of OH;
FIG. 7 is a complex [ Cd (pbica) ]2]·2DMF·2C2H5OH carbon dioxide is attached to the drawing;
FIG. 8 is a complex [ Cd (pbica) ]2]·2DMF·2C2H5OH Crystal immersion I2A photograph showing a color change when in vapor;
FIG. 9 is a complex [ Cd (pbica) ]2]·2DMF·2C2H5OH crystals (30 mg) when immersed in ethanol (3 mL) I2A photograph of the color change during release;
FIG. 10 is the complex [ Cd (pbica)2]·2DMF·2C2H5OH crystals (30 mg) immersed in ethanol (3 mL) I2Graph of UV/vis absorption spectra over time for the release process;
FIG. 11310 nm Abs vs. time plot (298K);
FIG. 12 is a graph (298K) showing the amount of iodine vapor released as a function of time;
FIG. 13I2TG plots for capture and acetone replacement;
FIG. 14 Complex [ Cd (pbica)2]·2DMF·2C2H5Asymmetric unit diagram of OH.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
A method for preparing a Cd coordination polymer iodine vapor load material comprises the following steps:
1) weighing Cd (NO)3)2·4H2O (0.05 mmol, 15.4 mg) was dissolved in CH3Transferring the solution into a 12 mL reaction kettle in a mixed solution of OH/DMF (v/v,1: 9);
2) weighing (0.1 mmol, 23.9 mg) Hpbica (2- (pyridin-4-yl) -1H-benzo [ d ] imidazole-5-carboxylic acid) and adding to the reaction kettle of step 1);
3) and sealing the reaction kettle, keeping the temperature constant at 373K for 72h, slowly cooling to room temperature, filtering, and washing to obtain a light yellow transparent blocky crystal, namely the Cd coordination polymer.
The invention uses 2- (pyridine-4-yl) -1H-benzo [ d ] imidazole-5-carboxylic acid as ligand to prepare cadmium coordination polymer with cadmium nitrate by a solvothermal method, the appearance of the coordination polymer is light yellow transparent blocky crystal, the coordination polymer is tasteless and insoluble in organic solvent and water, and the coordination polymer has the advantages of simple process, low cost, good repeatability and the like.
The chemical formula of the Cd coordination polymer prepared by the invention is as follows: [ Cd (pbica)2]·2DMF·2C2H5OH, the basic structural unit of the polymer, i.e. the repeat unit, has the formula C36H42N8CdO8. The cell is an asymmetric cell (FIG. 14) containing one Cd2+Ionic, two 2- (pyridin-4-yl) -1H-benzo [ d]Imidazole-5-carboxylic acid molecules.
The prepared Cd coordination polymer crystal is monochromized by a graphite monochromator on a Bruke smart APEXII CCD diffractometer
Rays, scanned in an omega-theta fashion. At 298K, diffraction points were collected. The modified structure analysis of F2 via full matrix least squares was done with the SHELXL =2014 software package. The molecular formula of the polymer is C36H42N8CdO8The relative molecular weight is 827.1788 g/mol, the crystal is monoclinic system, and the space group isP21/cThe unit cell parameter is a = 8.70955 (15) a; b =23.1334 (4) a; c =17.9071 (3) a; β =97.1938 (16)O；V =3579.55 (11) Å3；Z = 4。
Referring to FIGS. 1 and 2, the coordination pattern of the complex metal ion shown in FIGS. 1 and 2 contains 2 Cd 2+8 pbica -An anionic molecule. As shown in fig. 1, two phasesCd in the same way2+Is hexa-coordinated and passes through pbica -Ligands are linked into a binuclear structure, with two Cd' s2+From 4 different pbica -4 oxygen atoms on the ligand are coordinated in a bridging chelate coordination mode and 4 different pbica -The 2 nitrogen atoms of the ligand are coordinated by means of a bridging coordination (FIG. 1). For pbica -In particular, adopt(η 1 -η 1 )-μ 2 (pbica -A)And (η) 1 )-(η 1 -η 2 -μ 2 )-μ 3 (pbica-B) coordination mode (FIG. 2). pbica -With Cd2+The three-dimensional structure is formed by two coordination modes (figure 3). The binuclear units are linked by eight pbica ligands, by forming a binuclear unit having 6 linkages, (4)9.66) The acs network 3D framework of the topology (fig. 4). Having a 1D channel along the a-axis (FIG. 3) with an aperture of 14.6272X 14.6272-A2. Comparing the powder diffraction data obtained from the fresh coordination polymer powder sample obtained in figure 3 with the powder diffraction data obtained from the powder sample and the single crystal after being dried for one week, the diffraction peak of the obtained iodine vapor trapping coordination polymer is consistent with the peak simulated by the single crystal diffraction data, which shows that the purity of the obtained coordination polymer powder sample is higher, and the experimental reproducibility and the stability of the sample are also proved (figure 5).
The thermal stability of the iodine vapor trapping coordination polymer was obtained by thermogravimetric analysis of fig. 6. The three-dimensional framework of the obtained fluorescent coordination polymer single crystal sample can be stabilized to 350 ℃ through a thermogravimetric analysis curve, then the collapse of the framework occurs, and finally the residual mass is a calcination final product CdO which is consistent with the molecular formula obtained through single crystal diffraction analysis. The prepared material has good thermal stability and is a new material with practical application value.
The 500 mg of the removed sample of desolvation was placed in I of 298k2In the vapor saturated chamber, the color of the crystals changed from colorless to yellow, then brown, and finally black (fig. 8). When the iodine vapor trapping compound is soaked in absolute ethyl alcoholThey underwent visually detectable color change as shown in the figure (fig. 9), the color of the ethanol solution gradually increased from colorless to yellow, and the crystal color changed from brown to pale yellow. The UV/Vis spectra were measured at room temperature, as shown in FIG. 10. 30mg of the crystals are immersed in 3ml of ethanol, I2The absorbance in ethanol increased with time, the release rate of iodine subsequently slowed, and the maximum adsorbed amount was 25.32 g.g−1(FIG. 11) due to I in ethanol2The concentration increased with time as shown in figure 12. TGA measurements showed complete adsorption I2The latter molecular formula is [ Cd (pbica) 2]2I (FIG. 13).
Claims (7)
1. The Cd coordination polymer iodine vapor load material is characterized in that 2- (pyridine-4-yl) -1H-benzo [ d ] is prepared by]Imidazole-5-carboxylic acid as ligand and Cd2+The soluble salt is prepared to obtain the chemical general formula [ Cd (pbica)2]·2DMF·2C2H5An OH Cd coordination polymer iodine vapor load material;
wherein the repeating unit is an asymmetric unit containing one Cd2+Two pbica; DMF is N, N-dimethylformamide; c2H5OH is ethanol; pbica is 2- (pyridin-4-yl) -1H-benzo [ d]Imidazole-5-carboxylic acid ion;
the Cd coordination polymer crystal is monoclinic system, and the space group isP21/cThe unit cell parameter is a = 8.70955 (15) a; b =23.1334 (4) a; c =17.9071 (3) a; β =97.1938 (16)O；V =3579.55 (11) Å3；Z = 4。
2. A Cd coordination polymer iodine vapor loading material as defined in claim 1 wherein said Cd is binuclear [ Cd ]2(COO)4N4]Two identical Cd1 are hexacoordinated and are bound by pbica -Ligands are linked into a binuclear structure; two of Cd2+From 4 different pbica -4 oxygen atoms (. eta.) of ligands1-η2）-μ2Coordinative and 4 different pbica -2 nitrogen atoms of the ligand pass through (. eta.)1）-μ1Coordinately coordinated to pbica -In particular, adopt(η 1 -η 1 )-μ 2 (pbica -A)And (η) 1 )-(η 1 -η 2 -μ 2 )-μ 3 (pbica-B) coordination mode, pbica -With Cd2+The three-dimensional structure is formed by connecting two coordination modes; the binuclear units are linked by eight pbica ligands to form a binuclear unit with 6 linkages, (4)9.66) A topological acs network 3D framework with 1D regular nanopores along the a-axis with an pore diameter of 14.6272 x 14.6272A2。
3. A Cd coordination polymer iodine vapor load material as defined in claim 1 wherein said pbica is selected from(η 1 -η 1 )-μ 2 (pbica -A)And (η) 1 )-(η 1 -η 2 -μ 2 )-μ 3 (pbica-B) coordination mode, pbica -With Cd2+Two coordination modes are connected to form a three-dimensional structure, namely binuclear [ Cd ]2(COO)4N4]By eight pbica ligands to form a linker having 6 linkages, (4)9.66) Acs network 3D framework of topology.
4. A preparation method of a Cd coordination polymer iodine vapor load material is characterized by comprising the following steps:
1) weigh 0.05 mmol of Cd2+Is dissolved in CH3Transferring the solution into a reaction kettle in the mixed solution of OH and DMF;
2) weighing 0.1 mmol of Hpbica (2- (pyridin-4-yl) -1H-benzo [ d ] imidazole-5-carboxylic acid), and adding into the reaction kettle in the step 1);
3) and sealing the reaction kettle, keeping the temperature constant at 373K for 72h, slowly cooling to room temperature, filtering, and washing to obtain a light yellow transparent blocky crystal, namely the Cd coordination polymer.
5. The method for preparing Cd coordination polymer iodine vapor load material according to claim 1, wherein the space group of Cd coordination polymer iodine vapor load material isP2 1 。
6. The method for preparing a Cd coordination polymer iodine vapor load material as claimed in claim 1, wherein the Cd coordination polymer iodine vapor load material is characterized in that the Cd coordination polymer iodine vapor load material is prepared from Cd2+The soluble salt of (a) is cadmium nitrate.
7. The Cd coordination polymer iodine vapor load material as claimed in claim 1, wherein the Cd coordination polymer iodine vapor load material has potential application in the fields of rapid capture, release and storage of radioactive elemental iodine vapor.
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