CN117603464A - Copper (II) -calixarene complex monocrystal, and preparation method and application thereof - Google Patents
Copper (II) -calixarene complex monocrystal, and preparation method and application thereof Download PDFInfo
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- CN117603464A CN117603464A CN202311688539.6A CN202311688539A CN117603464A CN 117603464 A CN117603464 A CN 117603464A CN 202311688539 A CN202311688539 A CN 202311688539A CN 117603464 A CN117603464 A CN 117603464A
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 229910001427 strontium ion Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000002285 radioactive effect Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 15
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002901 radioactive waste Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 2
- 206010005949 Bone cancer Diseases 0.000 description 1
- 208000018084 Bone neoplasm Diseases 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 201000005787 hematologic cancer Diseases 0.000 description 1
- 208000024200 hematopoietic and lymphoid system neoplasm Diseases 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
Abstract
The invention belongs to the fields of coordination chemistry and extraction of pollutants in water, and relates to a copper (II) -calixarene complex monocrystal, a preparation method and application thereof. The copper (II) -calixarene complex monocrystal has a chemical formula as follows: [ (Cu) 2 L 2 )·2H 2 O] n Wherein l=5, 11,17, 23-tetra-tert-butyl-25, 26,27, 28-tetracarboxylic acid calix [4]]Aromatic hydrocarbons; belonging to monoclinic system, the space group isP21/c,a=22.468(5)Å,b=10.540(2)Å,c=20.861(4)Å,α=90.00°,β=91.80(3)°,γ=90.00°,V=4937.6(17)Å 3 . The copper (II) -calixarene complex monocrystal not only can exist stably in water, but also has high extraction efficiency, and the copper (II) -calixarene complex monocrystal has good application prospect when being used as an extraction material for extracting radioactive strontium ions in water.
Description
Technical Field
The invention belongs to the fields of coordination chemistry and extraction of pollutants in water, and particularly relates to a copper (II) -calixarene complex monocrystal capable of extracting radioactive strontium ions in water and a preparation method thereof.
Background
With the development of nuclear industry, radioactive waste is inevitably generated, and the radioactive waste mainly comprises alpha emitters (transuranics) and beta/gamma emitters with long service lives 99 Tc, 129 I, 135 Cs, 137 Cs, 90 Sr). Wherein, radioactive strontium ions are [ ] 90 Sr) is a long radiation period (t 1/2 = 28.6 years), high energy (0.546 MeV), beta radioisotope, consisting of 235 U or 239 Pu nuclear fission is generated. The strontium ions have good water solubility, can easily enter the water environment, have strong migration in the water body, are enriched through food chains, and threaten the environmental safety (Chemical Engineering Journal 435 (2022) 134906,1385-8947). Radioactive strontium ions are also very toxic and, due to their chemical nature similar to calcium ions, accumulate easily in human and animal bones, leading to blood and bone cancers. Therefore, there is an urgent need to develop a method for efficiently removing radioactive strontium ions.
For this purpose, a number of methods have been used to capture radioactive strontium ions from aqueous solutions. The extraction method has the advantages of low cost, simple operation, high efficiency and the like, and has wide application prospect for the adaptability of complex real systems and the applicability of large-scale operation. For extraction, the choice of extraction materials is particularly important, and in recent years, metal-organic frameworks (MOFs) are widely used for extracting radioactive contaminants in water, which have a large specific surface area, permanent porosity, adjustable chemical functions, fine adjustable pore structures, and in particular, various functional groups can reasonably be introduced into metal ligand modified microporous structures, thereby generating more active sites (Inorganic Chemistry,2022,61,9,3942-3950). The calixarene has adjustable cavity structure, excellent chemical stability, easy functionalization, low cost and other features, and may be used in synthesizing metal-organic frame. On the one hand, modification of the carboxyl group on the metal-organic framework can be well used for capturing radioactive strontium ions. On the other hand, calixarene itself has a large cavity that is more prone to capture radioactive strontium ions. Therefore, the metal-calixarene framework material with high extraction speed and large extraction capacity is designed and synthesized, so that the metal-calixarene framework material is more beneficial to extracting radioactive strontium ions in water. The method is used as a research target, and related literature reports are not available at present.
Disclosure of Invention
The invention aims to provide a copper (II) -calixarene complex with high extraction speed and large extraction capacity, which is used as a material for extracting radioactive strontium ions. Another object is to provide a method for its preparation.
In order to achieve the aim of the invention, the copper (II) -calixarene complex monocrystal is synthesized, and the chemical formula is as follows: [ (Cu) 2 L 2 )·2H 2 O] n Wherein l=5, 11,17, 23-tetra-tert-butyl-25, 26,27, 28-tetracarboxylic acid calix [4]]Aromatic hydrocarbons; belonging to monoclinic system, the space group is P21/c,α＝90.00°,β＝91.80(3)°,γ＝90.00°,/>
the preparation method of the copper (II) -calixarene complex monocrystal comprises the following steps: dissolving copper chloride dihydrate and 5,11,17, 23-tetra-tert-butyl-25, 26,27, 28-tetracarboxylcalix [4] arene in acetonitrile and distilled water, sealing in a reaction bottle, performing ultrasonic treatment at room temperature, placing in a constant-temperature oven, and then cooling to room temperature to obtain a blue transparent blocky crystal, namely the target product copper (II) -calixarene complex single crystal.
The molar ratio of the copper chloride dihydrate to the 5,11,17, 23-tetra-tert-butyl-25, 26,27, 28-tetracarboxycalix [4] arene is as follows: 1-4:1.
the complex can be used as an extraction material for extracting radioactive strontium ions in water.
The invention has the advantages that: the copper (II) -calixarene complex monocrystal not only can exist stably in water, but also has good stability and high extraction efficiency. And carboxyl is modified in the pore canal of the three-dimensional framework structure, which is favorable for acting with strontium ions, thereby rapidly extracting the strontium ions in the water body and realizing higher extraction capacity. The copper (II) -calixarene complex monocrystal can realize rapid extraction and balance of 5ppm strontium ions within 5 minutes, and the extraction efficiency is 82%. As the initial concentration of strontium ions increases, the copper (II) -calixarene complex monocrystal achieves 147.6mg g of maximum extraction capacity for strontium ion extraction -1 . In addition, anotherBesides, the preparation process is simple, the yield is high, and the method has good application prospect.
Drawings
FIG. 1 is a diagram showing the coordination environment of copper (II) in a copper (II) -calixarene complex single crystal according to the present invention;
FIG. 2 is a single crystal structure of the copper (II) -calixarene complex of the present invention;
FIG. 3 is a graph showing a single crystal simulated powder diffraction pattern, an experimental powder diffraction pattern, and a comparison of powder diffraction patterns after soaking in water (pH 10) for 24 hours of the copper (II) -calixarene complex of the present invention; 1 is a monocrystal simulated powder diffraction pattern, 2 is a powder diffraction pattern of the copper (II) calixarene complex of the invention, and 3 is a powder diffraction pattern of the copper (II) -calixarene complex of the invention after being soaked in water (with pH value of 10) for 24 hours.
FIG. 4 is a graph showing the kinetics of extraction of strontium ions (5 ppm) from water by the copper (II) -calixarene complex of the present invention.
FIG. 5 is an isothermal diagram of strontium ions in the extraction water of the copper (II) -calixarene complex according to the present invention.
Detailed Description
The invention is further illustrated by the following examples:
example 1: synthesis of copper (II) -calixarene complex single crystals
Copper chloride dihydrate (5.4 mg,0.032 mmol) was combined with 5,11,17, 23-tetra-tert-butyl-25, 26,27, 28-tetracarboxycup [4]]Aromatic hydrocarbon (7 mg,0.008 mmol) was dissolved in acetonitrile (4 mL) and distilled water (2 mL), sealed in a reaction flask, sonicated at room temperature, left in an oven at constant temperature of 90 ℃ for two days, and then cooled to room temperature to obtain a blue transparent bulk crystal having the molecular formula: [ (Cu) 2 L 2 )·2H 2 O] n Namely the copper (II) -calixarene complex monocrystal.
Single crystals of appropriate size were selected under a microscope and subjected to X-ray diffraction experiments at room temperature. On a Bruker Smart Apex-IICCD diffractometer, mo-K rays monochromatized by a graphite monochromator To->Diffraction data is collected in a manner. Data reduction was performed using the Bruker SAINT program. The diffraction data of the partial structure were subjected to absorption correction using the SADABS procedure. The crystal structure is synthesized and solved by a direct method and a difference Fourier synthesis method. All non-hydrogen atom coordinates and anisotropic parameters are corrected by a full matrix least square method, and the C-H atom positions are calculated and determined according to a theoretical mode. The coordination environment diagram of the copper metal in the complex is shown in figure 1; the crystal structure diagram of the complex is shown in figure 2; the detailed crystal measurement data are shown in Table 1.
Table 1 principal crystallographic data of the complexes
Example 2: the invention relates to a specific application of copper (II) -calixarene complex monocrystal in extracting strontium ions in water
The copper (II) -calixarene complex single crystal probe synthesized by the method is ground for 2 hours in an agate mortar, 7mg of ground sample is dispersed in 10mL of toluene solution to prepare an organic phase, the organic phase is added into 15mL of standard strontium ion solution, and the mixture is continuously stirred at room temperature and sampled at time intervals. The prepared samples were tested for concentration change by flame-atomic absorption. As shown in FIG. 4, the extraction was carried out rapidly to equilibrium within 5 minutes with an extraction efficiency of 82%. As shown in fig. 5, as the initial concentration increases, the extraction capacity increases. Saturated extraction at 60ppm initial concentration, maximum extraction capacity 147.6mg g -1 . This shows that the copper (II) -calixarene complex single crystal can rapidly extract strontium ions in water and realize larger extraction capacity.
Claims (2)
1. A first partCopper (II) -calixarene complex single crystals characterized by the chemical formula: [ (Cu) 2 L 2 )·2H 2 O] n Wherein L is 5,11,17, 23-tetra-tert-butyl-25, 26,27, 28-tetracarboxyl-cup [4]]Aromatic hydrocarbons; which belongs to monoclinic system and the space group isP21/c, a = 22.468(5) Å, b = 10.540(2) Å, c = 20.861(4) Å, α = 90.00°, β = 91.80(3)°, γ = 90.00°, V = 4937.6(17) Å 3 。
2. Use of a copper (II) -calixarene complex single crystal according to claim 1 as extraction material for extracting radioactive strontium ions in water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117816249A (en) * | 2024-03-04 | 2024-04-05 | 潍坊职业学院 | Lindqvist molybdenum polyacid-calix [4] arene inorganic-organic hybrid complex, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117816249A (en) * | 2024-03-04 | 2024-04-05 | 潍坊职业学院 | Lindqvist molybdenum polyacid-calix [4] arene inorganic-organic hybrid complex, and preparation method and application thereof |
| CN117816249B (en) * | 2024-03-04 | 2024-05-28 | 潍坊职业学院 | LINDQVIST type molybdenum polyacid-calix [4] arene inorganic-organic hybrid complex, and preparation method and application thereof |
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