CN113527707A - Normal-temperature rapid preparation method of copper-based MOF - Google Patents
Normal-temperature rapid preparation method of copper-based MOF Download PDFInfo
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- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 11
- BICXKAQZWLCDDX-UHFFFAOYSA-N copper dinitrate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O BICXKAQZWLCDDX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000010355 oscillation Effects 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000985 reactive dye Substances 0.000 abstract description 7
- 238000004043 dyeing Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 nitrate anions Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to the technical field of functional material preparation, in particular to a normal-temperature rapid preparation method of copper-based MOF, which comprises the following steps: step one, adding dimethyl imidazole into distilled water, and treating by ultrasonic waves to prepare a dimethyl imidazole water solution with the concentration of 0.1-0.2 mol/L; adding 0.2mol/L sodium hydroxide to adjust the pH value of the solution to 7-8 to obtain a solution A; step three, adding pentahydrate copper nitrate into distilled water, and performing ultrasonic treatment to obtain a copper nitrate aqueous solution with the concentration of 0.1-0.2mol/L, namely solution B; and step four, dropwise adding the solution B into the solution A according to the molar ratio of 1:1, carrying out oscillation reaction at room temperature for 15-30min, centrifuging and filtering a product after the reaction is finished, washing with distilled water, and drying to obtain the copper-based MOF. The operation method is simple and safe, green and environment-friendly, has short synthesis time, and is suitable for industrialization. The copper-based MOF prepared by the method has a good decolorizing effect on reactive dyes, and has a wide application prospect in the aspect of printing and dyeing wastewater treatment.
Description
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a normal-temperature rapid preparation method of copper-based MOF.
Background
With the wide use of reactive dyes in the printing and dyeing industry, a large amount of dye residual liquid with high chromaticity, high toxicity and high pollution is generated after dyeing, and the direct discharge can cause great water body pollution. For how to remove the reactive dye, various treatment means related to physics, chemistry, biology and the like are widely adopted, but the problems of serious secondary pollution, incomplete removal, complex process, large energy consumption and the like exist. Photocatalysis has attracted attention as an economical, efficient and environmentally friendly treatment means.
Metal-organic frameworks (MOFs) are a class of metal-framework porous coordination polymers composed of organic ligands and inorganic structural units (metal ions or metal clusters), have a topological three-dimensional network porous structure, and are formed by complexing ligands and metal ions. As a new material, the material has attracted extensive attention in the field of photocatalysis due to its high specific surface area, high porosity, abundant active sites, flexible chemical structure and high catalytic activity.
The preparation method of the copper-based MOF mainly comprises a common solution reaction method, a solvothermal method, an electrochemical method and the like. In the conventional solution reaction method, Cu2+ and a ligand are mixed in a specific solvent (water or an organic solvent), pH is adjusted as necessary, and the mixture is stirred or left to stand in an open system at a low temperature, and the solvent is evaporated as the reaction proceeds, thereby precipitating a product. The method has low cost, but the experimental period is about several days, the yield of the obtained product is low, and the crystal form is not complete. The solvothermal method is to mix Cu2+ with ligand in a specific high boiling point organic solvent (such as DMF), then put the mixture into a closed high pressure resistant reaction kettle, and generate pressure in the system under the heating condition to enable the reaction to proceed. The traditional heating method generally uses an oven, an oil bath and the like, has long reaction time and can be completed within half a day or even several days. The method is favorable for the growth of single crystals due to high temperature and high pressure, and modifies the size of the crystal form by controlling the temperature condition, but the product is easy to generate mechanical mixtures of different compound crystals, is difficult to separate, and simultaneously needs higher reaction temperature and longer reaction time, and has higher energy consumption. The electrochemical method is a method in which a ligand is dissolved in a specific solvent (water or an organic solvent) to form a solution, and a copper plate (cathode) and a metal electrode (anode) are used to form a precipitate under the action of an applied voltage. The method only needs normal temperature, has low cost and high synthesis speed, can realize continuous production, and can adjust the microcrystalline structure and the grain size by changing the voltage, the solution temperature, the solvent proportion and the like, but the formed film has uneven thickness. The synthesis of dense copper-based MOF films requires a strict control of the time, which is too short to complete the crystal layer and too long to damage the support. The method cannot be used for secondary growth by a solvothermal method subsequently, because the conditions such as low pH value, high temperature and the like are too severe for the film generated by an electrochemical method, the copper plate can be directly dissolved, and nitrate anions can also promote the oxidation of the copper plate.
In order to solve the problems, the method takes dimethyl imidazole and copper nitrate as raw materials, water as a medium, and the copper-based MOF is rapidly prepared at normal temperature, so that the prepared copper-based MOF has a good decolorizing effect on reactive dyes, and has a wide application prospect in the aspect of printing and dyeing wastewater treatment.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides the normal-temperature rapid preparation method of the copper-based MOF, which is simple and safe in operation method, green and environment-friendly, short in synthesis time and suitable for industrialization; the prepared copper-based MOF has a good decolorizing effect on reactive dyes and has a wide application prospect in the aspect of printing and dyeing wastewater treatment.
In order to achieve the purpose, the invention adopts the following technical scheme: a normal-temperature rapid preparation method of copper-based MOF specifically comprises the following steps:
step one, adding dimethyl imidazole into distilled water, and performing ultrasonic treatment on the dimethyl imidazole by using 30-50KHZ to prepare a dimethyl imidazole water solution with the concentration of 0.1-0.2 mol/L;
step two, adding 0.2mol/L sodium hydroxide into a dimethyl imidazole solution, adjusting the pH value of the solution to 7-8, and performing ultrasonic treatment by using 30-50KHZ to obtain a solution A;
step three, adding pentahydrate copper nitrate into distilled water, and carrying out ultrasonic treatment by using 30-50KHZ to prepare a copper nitrate aqueous solution with the concentration of 0.1-0.2mol/L, namely solution B;
and step four, dropwise adding the solution B into the solution A according to the molar ratio of 1:1, carrying out oscillation reaction at room temperature, centrifuging and filtering a product after the reaction is finished, cleaning with distilled water, and drying to obtain the copper-based MOF.
Preferably, in the first step, the concentration of the dimethyl imidazole aqueous solution is 0.16 mol/L.
Preferably, in the third step, the concentration of the copper nitrate aqueous solution is 0.16 mol/L.
Preferably, the ultrasonic treatment frequency in the first step, the second step and the third step is 40KHZ, and the ultrasonic treatment time is 10 min.
Preferably, in the fourth step, the dropping speed is 50-60 drops/min.
Preferably, in the fourth step, the reaction time is 15-30min under shaking at room temperature.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the conventional MOF preparation method, the reaction time of the method is shortened to be within 30min from several hours, so that the reaction time can be greatly shortened; meanwhile, the reaction is carried out at room temperature, no special production equipment is needed, the operation is convenient, and the energy is saved.
2. The invention takes water as a medium, does not adopt other organic solvents, can avoid the possible harm brought by the organic solvents, and is safe and environment-friendly.
3. The copper-based MOF prepared by the invention has a decolorization rate of more than 96 percent for 20min of common active dye treatment under the illumination condition, and has wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Example 1:
a normal-temperature rapid preparation method of copper-based MOF comprises the following specific steps:
the method comprises the following steps: adding dimethyl imidazole into distilled water, and treating with 40KHZ ultrasonic wave for 10min to obtain 0.16mol/L dimethyl imidazole aqueous solution;
step two: adding 0.2mol/L sodium hydroxide into a dimethyl imidazole aqueous solution, adjusting the pH value of the solution to 7, and performing ultrasonic treatment on the solution for 10min by using 40KHZ to obtain a solution A;
step three: adding copper nitrate pentahydrate into distilled water, and treating with 40KHZ ultrasonic wave for 10min to obtain 0.16mol/L copper nitrate aqueous solution, namely solution B;
step four: and dropwise adding the solution B into the solution A at the speed of 50 drops/min, oscillating and reacting at room temperature for 15min, centrifuging and filtering the product after the reaction is finished, cleaning with distilled water, and drying to obtain the copper-based MOF.
In order to investigate the decoloring performance of the prepared copper-based MOF on the active dye, 0.1g of copper-based MOF is added into 50mL of active red 3BS dye solution with the concentration of 50mg/L, and the decoloring rates of the active red 3BS dye are respectively 90.7% and 99.0% after the 1000W xenon lamp is irradiated for 10min and 20 min.
Example 2:
a normal-temperature rapid preparation method of copper-based MOF comprises the following specific steps:
the method comprises the following steps: adding dimethyl imidazole into distilled water, and treating with 40KHZ ultrasonic wave for 10min to obtain 0.16mol/L dimethyl imidazole aqueous solution;
step two: adding 0.2mol/L sodium hydroxide into a dimethyl imidazole aqueous solution, adjusting the pH value of the solution to 7.5, and carrying out ultrasonic treatment on the solution for 10min by using 40KHZ to obtain a solution A;
step three: adding copper nitrate pentahydrate into distilled water, and treating with 40KHZ ultrasonic wave for 10min to obtain 0.16mol/L copper nitrate aqueous solution, namely solution B;
step four: and dropwise adding the solution B into the solution A at a speed of 60 drops/min, oscillating and reacting at room temperature for 20min, centrifuging and filtering a product after the reaction is finished, cleaning with distilled water, and drying to obtain the copper-based MOF.
In order to investigate the decoloring performance of the prepared copper-based MOF on the reactive dye, 0.1g of copper-based MOF is added into 50mL of a reactive brilliant blue KN-R dye solution with the concentration of 50mg/L, and the decoloring rates of the reactive brilliant blue KN-R dye are respectively 92.5% and 96.4% after the 1000W xenon lamp is irradiated for 10min and 20 min.
Example 3:
a normal-temperature rapid preparation method of copper-based MOF comprises the following specific steps:
the method comprises the following steps: adding dimethyl imidazole into distilled water, and treating with 40KHZ ultrasonic wave for 10min to obtain 0.16mol/L dimethyl imidazole aqueous solution;
step two: adding 0.2mol/L sodium hydroxide into a dimethyl imidazole aqueous solution, adjusting the pH value of the solution to 8, and performing ultrasonic treatment on the solution for 10min by using 40KHZ to obtain a solution A;
step three: adding copper nitrate pentahydrate into distilled water, and treating with 40KHZ ultrasonic wave for 10min to obtain 0.16mol/L copper nitrate aqueous solution, namely solution B;
step four: and dropwise adding the solution B into the solution A at the speed of 50 drops/min, oscillating and reacting at room temperature for 30min, centrifuging and filtering the product after the reaction is finished, cleaning with distilled water, and drying to obtain the copper-based MOF.
In order to investigate the decoloring performance of the prepared copper-based MOF on the active dye, 0.1g of copper-based MOF is added into 50mL of 50mg/L active black KN-B dye solution, and the decoloring rates of the active black KN-B dye are respectively 99.2% and 99.5% after 1000W xenon lamp illumination for 10min and 20 min.
Example 4:
a normal-temperature rapid preparation method of copper-based MOF comprises the following specific steps:
the method comprises the following steps: adding dimethyl imidazole into distilled water, and treating with 30KHZ ultrasonic wave for 10min to obtain 0.1mol/L dimethyl imidazole aqueous solution;
step two: adding 0.2mol/L sodium hydroxide into a dimethyl imidazole aqueous solution, adjusting the pH value of the solution to 7, and performing ultrasonic treatment on the solution for 10min by using 30KHZ to obtain a solution A;
step three: adding copper nitrate pentahydrate into distilled water, and treating with 30KHZ ultrasonic wave for 10min to obtain 0.1mol/L copper nitrate aqueous solution, namely solution B;
step four: and dropwise adding the solution B into the solution A at the speed of 50 drops/min, oscillating and reacting at room temperature for 30min, centrifuging and filtering the product after the reaction is finished, cleaning with distilled water, and drying to obtain the copper-based MOF.
In order to investigate the decoloring performance of the prepared copper-based MOF on the active dye, 0.1g of copper-based MOF is added into 50mL of active black KN-B dye solution with the concentration of 50mg/L, and the decoloring rates of the active black KN-B dye are respectively 98.5% and 98.7% after the 1000W xenon lamp is irradiated for 10min and 20 min.
Example 5:
a normal-temperature rapid preparation method of copper-based MOF comprises the following specific steps:
the method comprises the following steps: adding dimethyl imidazole into distilled water, and treating with 50KHZ ultrasonic wave for 10min to obtain 0.2mol/L dimethyl imidazole aqueous solution;
step two: adding 0.2mol/L sodium hydroxide into a dimethyl imidazole aqueous solution, adjusting the pH value of the solution to 8, and performing ultrasonic treatment on the solution for 10min by using 30KHZ to obtain a solution A;
step three: adding copper nitrate pentahydrate into distilled water, and treating with 50KHZ ultrasonic wave for 10min to obtain 0.2mol/L copper nitrate aqueous solution, namely solution B;
step four: and dropwise adding the solution B into the solution A at the speed of 50 drops/min, oscillating and reacting at room temperature for 30min, centrifuging and filtering the product after the reaction is finished, cleaning with distilled water, and drying to obtain the copper-based MOF.
In order to investigate the decoloring performance of the prepared copper-based MOF on the active dye, 0.1g of copper-based MOF is added into 50mL of active black KN-B dye solution with the concentration of 50mg/L, and the decoloring rates of the active black KN-B dye are respectively 99.7% and 99.8% after the 1000W xenon lamp is irradiated for 10min and 20 min.
Experimental demonstration of the above examples 1, 2, 3, 4 and 5 shows that 50mL of different dyes with a concentration of 50mg/L are treated with 0.1g of copper-based MOF for different periods of time, and the dye decolorization ratios are as follows in Table 1:
table 1 experimental demonstration results
As can be seen from the above Table 1, the prepared copper-based MOF has decolorization rates of more than 90% after being treated for 10min, more than 96% after being treated for 20min and especially more than 98% for active black KN-B when being treated with active red 3BS, active brilliant blue KN-R and active black KN-B dye solutions with concentrations of 50mg/L under the irradiation of simulated visible light. The prepared copper-based MOF has very obvious photocatalytic decolorization effect on reactive dyes and can be rapidly decolorized in a short time.
The description and practice of the disclosure herein will be readily apparent to those skilled in the art from consideration of the specification and understanding, and may be modified and modified without departing from the principles of the disclosure. Therefore, modifications or improvements made without departing from the spirit of the invention should also be considered as the protection scope of the invention.
Claims (6)
1. A normal-temperature rapid preparation method of copper-based MOF is characterized by comprising the following steps:
step one, adding dimethyl imidazole into distilled water, and performing ultrasonic treatment on the dimethyl imidazole by using 30-50KHZ to prepare a dimethyl imidazole water solution with the concentration of 0.1-0.2 mol/L;
step two, adding 0.2mol/L sodium hydroxide into a dimethyl imidazole aqueous solution, adjusting the pH of the solution to 7-8, and performing ultrasonic treatment by using 30-50KHZ to obtain a solution A;
step three, adding pentahydrate copper nitrate into distilled water, and carrying out ultrasonic treatment by using 30-50KHZ to prepare a copper nitrate aqueous solution with the concentration of 0.1-0.2mol/L, namely solution B;
and step four, dropwise adding the solution B into the solution A according to the molar ratio of 1:1, carrying out oscillation reaction at room temperature, centrifuging and filtering a product after the reaction is finished, cleaning with distilled water, and drying to obtain the copper-based MOF.
2. The method for rapidly preparing copper-based MOF at normal temperature according to claim 1, wherein in the first step, the concentration of the dimethyl imidazole aqueous solution is 0.16 mol/L.
3. The method for rapidly preparing copper-based MOF at normal temperature according to claim 1, wherein in the third step, the concentration of the copper nitrate aqueous solution is 0.16 mol/L.
4. The method for rapidly preparing copper-based MOF at normal temperature according to claim 1, wherein the ultrasonic treatment frequency in the first step, the second step and the third step is 40KHZ, and the ultrasonic treatment time is 10 min.
5. The method for rapidly preparing copper-based MOF at normal temperature according to claim 1, 2 or 3, wherein in the fourth step, the dropping speed is 50-60 drops/min.
6. The method for rapidly preparing copper-based MOF at normal temperature according to claim 1, wherein in the fourth step, the oscillating reaction time at room temperature is 15-30 min.
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| US20090131643A1 (en) * | 2006-04-14 | 2009-05-21 | Zheng Ni | Rapid metal organic framework molecule synthesis method |
| US20170226040A1 (en) * | 2014-08-06 | 2017-08-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing an adsorbent from organometallic framework structures (mof) |
| CN110496603A (en) * | 2019-07-09 | 2019-11-26 | 东北大学 | A kind of synthetic method of copper-based flexibility MOF material |
| CN110483790A (en) * | 2019-07-25 | 2019-11-22 | 深圳大学 | A kind of copper base metal-organic frame nanosphere and the preparation method and application thereof |
| CN110387048A (en) * | 2019-08-19 | 2019-10-29 | 南京邮电大学 | A kind of metal organic frame two-dimensional nano piece and preparation method thereof |
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