CN112341632A - Bivalent copper ion coordination polymer and preparation method and application thereof - Google Patents
Bivalent copper ion coordination polymer and preparation method and application thereof Download PDFInfo
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- CN112341632A CN112341632A CN202011227726.0A CN202011227726A CN112341632A CN 112341632 A CN112341632 A CN 112341632A CN 202011227726 A CN202011227726 A CN 202011227726A CN 112341632 A CN112341632 A CN 112341632A
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 52
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 52
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229940126062 Compound A Drugs 0.000 claims abstract description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims abstract description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 3
- 229940012189 methyl orange Drugs 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- RBAVYOXHMMFCHU-UHFFFAOYSA-N 5-methyl-4-oxo-1-phenylpyridazine-3-carboxylic acid Chemical compound N1=C(C(O)=O)C(=O)C(C)=CN1C1=CC=CC=C1 RBAVYOXHMMFCHU-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000975 dye Substances 0.000 claims description 9
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
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- 239000000446 fuel Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention discloses a divalent copper ion coordination polymer and a preparation method and application thereof. The preparation method comprises the steps of mixing a compound A, 1,3-BIP, HPDC, sodium hydroxide, N' -dimethylformamide and water, reacting the mixture at a constant temperature of 70-90 ℃ for 70-74 hours to obtain a reaction product, cooling and crystallizing the reaction product, washing, filtering and drying the crystallized product in sequence to obtain the divalent copper ion coordination polymer, wherein the coordination polymer takes copper (II) as a central ion and adopts NO to pass through3 ‑The ions are connected with adjacent Cu (II) ions to form a one-dimensional chain, and a one-dimensional ring is formed by bridging 1,3-BIP, so that a three-dimensional supermolecular network structure is formed by the hydrogen bond action among molecules. The coordination polymer of the invention has photocatalytic degradation effect on rhodamine B, methyl orange and methyl blue.In addition, the preparation method has the advantages of simple process, convenient operation, high yield, good reproducibility and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation development, and particularly relates to a divalent copper ion coordination polymer and a preparation method and application thereof.
Background
The coordination polymer is a coordination polymer which is formed by connecting an organic ligand and a metal ion through a coordination bond and has a highly regular infinite network structure. The compound has abundant and diversified topological structures, and is concerned by scientific researchers due to the potential application in the aspects of photoluminescence, electroluminescence, fluorescent probes, magnetism, adsorption, catalysis, medicines and the like.
Organic pollutants such as colored dyes and the like have high toxicity and carcinogenicity, are difficult to degrade in natural water areas, and when the fuels are gathered and exposed in water for a long time, the fuels can seriously pollute the water body, destroy the ecological environment and cause serious influence on the human health. The metal organic coordination polymer is a novel photocatalytic material and is widely applied to degradation of organic pollutants and dyes, and mainly has narrow band gap energy because the metal organic coordination polymer is a material formed by a multifunctional organic ligand and inorganic metal ions or metal clusters through strong coordination bonds, so that ultraviolet and visible light can be effectively absorbed, and organic dye molecules are catalytically degraded. Compared with other wastewater treatment methods, the photocatalytic oxidation method not only has the advantages of environmental friendliness, practicability, convenience and the like, but also can degrade organic dye molecules into small molecular substances, even mineralize into CO2And water molecules.
At present, the Cu (II) coordination polymer with novel structure and specific function has great challenge, and the metal ions and organic ligands determine the structure of the coordination polymer; meanwhile, reaction conditions such as reaction temperature, pH value, counter ion in the solution and the like have a great influence on the formation of the coordination polymer. In addition to Cu2+Binding to ligandsThe coordination polymer obtained has low productivity and low repeatability.
Disclosure of Invention
The invention aims at providing a bivalent copper ion coordination polymer.
The invention also aims to provide a preparation method of the divalent copper ion coordination polymer, and aims to solve the problems of low yield, low repeatability and excessive influence on reaction conditions in the existing preparation method of the divalent copper ion coordination polymer.
The invention also aims to provide the application of the divalent copper ion coordination polymer in photocatalytic degradation of water body dye.
The invention is realized by the following steps that: { [ Cu (1,3-BIP) (PDC) (NO)3)]·2H2O}nWherein, the 1,3-BIP is 1,3- (imidazolyl) propane, and the HPDC is 5-methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid;
the coordination polymer takes copper (II) as a central ion and passes through NO3 -The ions are connected with adjacent Cu (II) ions to form a one-dimensional chain, and a one-dimensional ring is formed by bridging 1,3-BIP, so that a three-dimensional supermolecular network structure is formed by the hydrogen bond action among molecules.
The invention further discloses a preparation method of the divalent copper ion coordination polymer, which comprises the following steps:
(1) mixing the compound A, 1,3- (imidazolyl) propane, methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, sodium hydroxide, N' -dimethylformamide and water, and reacting the mixture at the constant temperature of 80-100 ℃ for 70-74 hours to obtain a reaction product; wherein the molar ratio of the compound A, the 1,3- (imidazolyl) propane, the methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, the N, N' -dimethylformamide and the water is 1: 1: 0.75-1: 2-4: 4.5-5; the compound A is any one of copper nitrate trihydrate, copper chloride and copper acetate;
(2) and cooling and crystallizing the reaction product, and washing, filtering and drying the crystallized product in sequence to obtain the divalent copper ion coordination polymer.
Preferably, in step (1), the molar ratio of compound a, 1,3- (imidazolyl) propane, methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, N' -dimethylformamide and water is 1: 1: 0.75: 3: 4.5;
in the step (2), the washing is washing with deionized water, the filtering is decompression filtering, and the drying is constant temperature drying in an oven at 80 ℃ for 2-4 hours.
Preferably, in the step (1), the mixture is placed in a sealed high-pressure reaction kettle for reaction, and the temperature in the reaction kettle is controlled to rise to 90 ℃ at a temperature rise rate of 10 ℃ per hour.
Preferably, in step (1), the mixture is reacted at constant temperature for 72 hours.
The invention further discloses application of the divalent copper ion coordination polymer in photocatalytic degradation of dyes in water bodies.
Preferably, the dyes are rhodamine B, methyl orange and methyl blue.
The invention overcomes the defects of the prior art and provides a cupric ion coordination polymer and a preparation method and application thereof, the invention mixes copper nitrate trihydrate, 1,3- (imidazolyl) propane, methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, N' -dimethylformamide, sodium hydroxide, DMF and water, and the mixture reacts for 72 hours at the constant temperature of 80 ℃ to obtain a reaction product; and naturally cooling and crystallizing the reaction product, and washing, filtering and drying the crystallized product in sequence to obtain the divalent copper ion coordination polymer. In the reaction process of the invention, DMF is organic solvent molecule N, N' -dimethylformamide, and the structure of the DMF is shown as the following formula 1:
the chemical expression of the obtained divalent copper ion coordination polymer is as follows: { [ Cu (1,3-BIP) (PDC) (NO)3)]·2H2O}n(ii) a The structures of 1,3-BIP and HPDC are shown in the following formulas 2 and 3The following steps:
the divalent copper ion coordination polymer takes copper (II) as a central ion and passes through NO3 -The ions are connected with adjacent Cu (II) ions to form a one-dimensional chain, and a one-dimensional ring is formed by bridging 1,3-BIP, so that a three-dimensional supermolecular network structure is formed by the hydrogen bond action among molecules. The coordination polymer crystal belongs to an orthorhombic system, the space group is P2(1)/c, the unit cell parameter is
α＝γ＝90.00゜，β＝125.445(5)゜，
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) the coordination polymer has good thermal stability, and the formation of the coordination polymer is beneficial to the degradation of an organic solvent rhodamine B, so that the environmental pollution is reduced.
(2) The invention can prepare the divalent copper ion coordination polymer with photocatalytic degradation capability by adopting one-pot solvothermal reaction, and the preparation method has the advantages of simple process, convenient operation, high yield, good reproducibility and the like.
Drawings
FIG. 1 is a single-molecule diagram of copper in a divalent copper ion-coordination polymer prepared according to an example of the present invention;
FIG. 2 is a three-dimensional supramolecular structure of a cupric ion coordination polymer prepared in accordance with an embodiment of the present invention;
FIG. 3 is an IR chart of a divalent copper ion-complexing polymer 4 prepared according to an example of the present invention;
FIG. 4 is an XRD pattern of a cupric ion coordination polymer 4 prepared according to an embodiment of the present invention;
FIG. 5 is an ultraviolet-visible absorption spectrum of a photocatalytic degradation RhB solution using coordination polymer 4 as a catalyst;
FIG. 6 shows variation of RhB concentration with reaction time; wherein, the line A in the figure indicates the blank experimental condition, and the line B indicates the experimental condition of the regio-polymer 4 catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1)0.15mmol of copper nitrate trihydrate, 0.1mmol of 5-methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, 1.5mL of 1,3- (imidazolyl) propane, 3mL of N, N' -dimethylformamide and 6mL of water were mixed, and 0.3 mol. L.-1Adjusting the pH value to 4.14 by using sodium hydroxide, and carrying out solvothermal reaction on the mixture at the temperature of 80 ℃ for 72 hours;
(2) naturally cooling and crystallizing the reaction product, washing the crystal with deionized water, filtering under reduced pressure to obtain a blue needle crystal, and placing the blue needle crystal in an oven at 80 ℃ for 3 hours to obtain the divalent copper ion coordination polymer 1, wherein the yield is about 78.5%.
Example 2
(1)0.15mmol of copper nitrate trihydrate, 0.1mmol of 5-methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, 1.5mL of 1,3- (imidazolyl) propane, 3mL of N, N' -dimethylformamide and 6mL of water were mixed, and 0.3 mol. L.-1Adjusting the pH value to 4.64 by using sodium hydroxide, placing the mixture into a sealed high-pressure reaction kettle, heating to 90 ℃ at a heating rate of 10 ℃ per hour, and carrying out solvothermal reaction for 72 hours;
(2) and naturally cooling and crystallizing the reaction product, washing the crystal by deionized water, filtering under reduced pressure to obtain a blue needle crystal, and placing the blue needle crystal in an oven at the temperature of 80 ℃ for 3 hours to obtain the divalent copper ion coordination polymer 2, wherein the yield is about 74.6%.
Example 3
(1)0.15mmol of copper nitrate trihydrate, 0.1mmol of 5-methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, 1.5mL of 1,3- (imidazolyl) propane, 3mL of N, N' -dimethylformamide and 6mL of water were mixed, and 0.3 mol. L.-1Adjusting the pH value to 5.14 by using sodium hydroxide, placing the mixture into a sealed high-pressure reaction kettle, heating to 100 ℃ at a heating rate of 10 ℃ per hour, and carrying out solvothermal reaction for 72 hours;
(2) naturally cooling and crystallizing the reaction product, washing the crystal with deionized water, filtering under reduced pressure to obtain a blue needle crystal, and placing the blue needle crystal in an oven at 80 ℃ for 3 hours to obtain the divalent copper ion coordination polymer 3, wherein the yield is about 78.9%.
Example 4
(1)0.15mmol of copper nitrate trihydrate, 0.1mmol of 5-methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, 1.5mL of 1,3- (imidazolyl) propane, 3mL of N, N' -dimethylformamide and 6.5mL of water were mixed, and 0.3 mol. L.-1Adjusting pH to 5.69 with sodium hydroxide, sealing in a reaction kettle, heating to 80 deg.C at a rate of 10 deg.C per hour, and maintaining the temperature for 72 hr;
(2) and (3) cooling to room temperature at the rate of 10 ℃ per hour to obtain blue needle crystals, washing the crystals with deionized water, filtering under reduced pressure to obtain blue needle crystals, and placing the blue needle crystals in an oven at the temperature of 80 ℃ for keeping the temperature for 3 hours to obtain the divalent copper ion coordination polymer 4, wherein the yield is about 81.5%.
Effect example 1
The cupric ion coordination polymer 4 prepared in example 4 was further characterized as follows:
(1) crystal structure determination of coordination polymers
X-ray diffraction experiments were carried out at room temperature under a microscope using single crystals of suitable dimensions 0.250X 0.200X 0.150 mm. Collecting diffraction data on Bruker-Apex II X-ray single crystal diffractometer, and monochromating Mo-K alpha rays with a graphite monochromator
Diffraction points were collected in an omega-2 theta scan. All data are corrected by factor and empirical absorption, and the crystal structure adopts a processThe order is solved by direct methods and the hydrogen atoms are determined by differential fourier synthesis and fixing at the calculated optimal positions. The whole non-hydrogen atoms and their anisotropic thermal parameters were corrected by a full matrix least squares method using the SHELX-97 program. The detailed crystal measurement data are shown in Table 1, the important bond length and bond angle data are shown in Table 2, and the crystal structure is shown in FIGS. 1 and 2.
TABLE 1 Main crystallographic data for divalent copper ion complexing Polymer 4
TABLE 2 bond length of divalent copper ion complexing Polymer 4 of interest
Angle of harmony key (°)
(2) FIG. 3 is an IR spectrum of coordination polymer 4, and the data collected by the infrared spectrum of the sample is 400-4000 cm-1From FIG. 3, it can be seen that the coordination polymer was found to be 3411cm in size by using KBr pellets-1The strong and wide absorption peak is shown, which indicates that the compound contains lattice water molecules. 1558-1504 cm-1Peaks in the range of COO-Asymmetrical and symmetrical telescopic vibration. 3083cm-1The absorption peak is the stretching vibration peak of the C-H bond of the benzene ring. 1517 cm to 1556cm-1The peak in the range is a stretching vibration peak of C ═ C bond on the benzene ring.
(3) Characterization of phase purity of coordination polymers
The powder XRD characterization of the coordination polymer shows that it has a reliable phase purity, providing assurance for its use as a catalyst, see FIG. 4 (instrument model: Bruker/D8 Advance).
Effect example 2
Dissolving 10mg of rhodamine B in a 1000mL volumetric flask, measuring 250mL, placing in a conical flask, dispersing 30mg of divalent copper ion coordination polymer 4 in 250mL of 10mg/L rhodamine B solution, absorbing 3mL of supernatant by using a syringe provided with a filter head after ultrasonic treatment for 5min, measuring the absorbance of the solution, and recording the characteristic absorption peak of the rhodamine B obtained at the moment. The mixture was placed under 300W mercury lamp with stirring to promote degradation of rhodamine B. 3mL of the supernatant was aspirated every 20min with a syringe equipped with a filter head, and the change in the characteristic absorbance peak (554nm) for rhodamine B was recorded. After the rhodamine B system is irradiated for 20min by a xenon lamp, the absorbance of the rhodamine B system is reduced by 17 percent; when the mercury lamp irradiation time was 240min, the absorbance decreased by 82% (fig. 5, 6).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A divalent copper ion coordination polymer, characterized in that the coordination polymer has the chemical formula: { [ Cu (1,3-BIP) (PDC) (NO)3)]·2H2O}nWherein, the 1,3-BIP is 1,3- (imidazolyl) propane, and the HPDC is 5-methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid;
the coordination polymer takes copper (II) as a central ion and passes through NO3 -The ions are connected with adjacent Cu (II) ions to form a one-dimensional chain, and a one-dimensional ring is formed by bridging 1,3-BIP, so that a three-dimensional supermolecular network structure is formed by the hydrogen bond action among molecules.
2. The method for preparing a cupric ion coordination polymer according to claim 1, comprising the steps of:
(1) mixing the compound A, 1,3- (imidazolyl) propane, methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, sodium hydroxide, N' -dimethylformamide and water, and reacting the mixture at the constant temperature of 80-100 ℃ for 70-74 hours to obtain a reaction product; wherein the molar ratio of the compound A, the 1,3- (imidazolyl) propane, the methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, the N, N' -dimethylformamide and the water is 1: 1: 0.75-1: 2-4: 4.5-5; the compound A is any one of copper nitrate trihydrate, copper chloride and copper acetate;
(2) and cooling and crystallizing the reaction product, and washing, filtering and drying the crystallized product in sequence to obtain the divalent copper ion coordination polymer.
3. The method for producing a divalent copper ion-complexing polymer according to claim 2, characterized in that in step (1), the molar ratio of compound a, 1,3- (imidazolyl) propane, methyl-4-oxo-1-phenyl-1, 4-dihydropyridazine-3-carboxylic acid, N' -dimethylformamide and water is 1: 1: 0.75: 3: 4.5;
in the step (2), the washing is washing with deionized water, the filtering is decompression filtering, and the drying is constant temperature drying in an oven at 80 ℃ for 2-4 hours.
4. The method for preparing a cupric ion complex polymer according to claim 2, wherein in the step (1), the mixture is placed in a sealed autoclave to perform the reaction, and the temperature in the autoclave is controlled to be increased to 90 ℃ at a rate of 10 ℃ per hour.
5. The method for producing a divalent copper ion-coordinating polymer according to claim 2, wherein in the step (1), the mixture is reacted at a constant temperature for 72 hours.
6. Use of the divalent copper ion coordination polymer of claim 1 in a dye for photocatalytic degradation of a body of water.
7. The use of claim 6, wherein the dyes are rhodamine B, methyl orange and methyl blue.
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