CN112225903A - Metal organic framework material capable of selectively adsorbing dye in wastewater and preparation method and application thereof - Google Patents
Metal organic framework material capable of selectively adsorbing dye in wastewater and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 31
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000975 dye Substances 0.000 claims abstract description 32
- PGQDZMBBEMPQQC-UHFFFAOYSA-N 4,5-dipyridin-4-yl-1,2,3-benzothiadiazole Chemical compound N1=CC=C(C=C1)C=1C=CC2=C(N=NS2)C=1C1=CC=NC=C1 PGQDZMBBEMPQQC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 111
- 239000000243 solution Substances 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- -1 transition metal salt Chemical class 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000004753 textile Substances 0.000 description 3
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 2
- 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 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- 239000000835 fiber Substances 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 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 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
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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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pyridine Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a metal organic framework material capable of selectively adsorbing dye in wastewater and a preparation method and application thereof, wherein the metal organic framework material is prepared by utilizing N and metal coordination on pyridine and assisting different polyacid molecules, and because lone pair electrons on N-S-N in bis (4-pyridyl) benzothiadiazole of the metal organic framework material have electrostatic adsorption effect on the dye and selective adsorption capacity on different dyes, tests show that the adsorption rate of the adsorbent prepared by the invention on the dye can reach more than 75% at most, the adsorption effect is good, and the synthesis process is simple.
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to a metal organic framework material capable of selectively adsorbing dye in wastewater, and a preparation method and application thereof.
Background
With the rapid development of science and technology, in order to meet the demands of customers on fashion color, the textile industry uses more and more diversified dyes, which causes the living environment to be more and more polluted, since the textile industry is one of the most used chemical industries in the world, the waste water discharged in the process also contains more or less pollution sources which cannot be treated, after all, the principle of dye molecule design is based on the premise that the dye molecule is expected not to fall off from the fiber easily, therefore, most of the dye molecules are not easy to be separated, and the combination of a plurality of dyes is also the production mode of the mainstream textile industry, so that a plurality of dyes exist in the discharged wastewater, if the different dye molecules in the wastewater cannot be effectively decomposed or removed, the dye molecules discharged with the wastewater may in turn cause environmental deterioration due to natural circulation.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a metal organic framework material capable of selectively adsorbing dye in wastewater, a preparation method and application thereof, and the prepared metal organic framework material can selectively and efficiently adsorb dye.
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of a metal organic framework material capable of selectively adsorbing dyes in wastewater comprises the following steps:
(1) mixing 250-310 mg of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 360-380 mg of 4-pyridineboronic acid, 160-180 mg of tetrakis (triphenylphosphine) palladium and 294mg of potassium acetate to form a mixture A; mixing 30ml of deionized water, 10ml of ethanol and 10-20 ml of 1, 4-dioxane to form a mixed solution B; injecting the mixed solution B into the mixture A under the protective atmosphere at 80-100 ℃ for reaction, and naturally cooling to room temperature after the reaction is finished;
(2) extracting a reaction product in the step (1) by using a mixture of deionized water and dichloromethane, cleaning impurities by using methanol, and then air-drying to obtain khaki bis (4-pyridyl) benzothiadiazole;
(3) methanol solution containing 0.02-0.035 mmol of bis (4-pyridyl) benzothiadiazole, methanol solution containing 0.045-0.06 mmol of transition metal salt, methanol solution containing 0.050mmol of 1,2, 4-benzenetricarboxylic acid, 1, 4-naphthalene dicarboxylic acid or NO2-1,4-H2And mixing methanol solutions of bdc to form a mixed solution C, heating the mixed solution C to 140-160 ℃ within 6 hours, preserving heat for 48-56 hours, cooling to room temperature, cleaning generated crystals, and filtering the solution to obtain the metal organic framework material.
Further, the protective atmosphere is argon or nitrogen.
Further, the transition metal salt is Co (NO)3)2、Zn(NO3)2、Mn(ClO4)2Or Ni (NO)3)2。
Further, in the step (3), after the mixed solution C is heated to 150 ℃ at a constant rate within 6 hours and is kept warm for 48-56 hours, the mixed solution C is cooled to room temperature at a constant rate within 36 hours.
Further, the crystals generated in the step (3) are washed by a methanol solution, and the solution is filtered to obtain the metal organic framework material.
An application of a metal organic framework material capable of selectively adsorbing dye in wastewater as a dye adsorbent in wastewater treatment.
The invention has the following beneficial effects:
the metal organic framework material is prepared by utilizing N and metal coordination on pyridine and assisting different polyacid molecules, and because lone pair electrons on N-S-N in bis (4-pyridyl) benzothiadiazole of the metal organic framework material have electrostatic adsorption effect on dyes and have selective adsorption capacity on different dyes, tests show that the adsorption rate of the adsorbent prepared by the invention on the dyes can reach more than 75% at most, the adsorption effect is good, and the synthesis process is simple.
Drawings
FIG. 1 is a graph showing the change of adsorption rate with time of the metal organic framework material prepared in example 1 of the present invention
FIG. 2 is a graph showing the change of adsorption rate with time of the metal organic framework material prepared in example 2 of the present invention
FIG. 3 is a graph showing the change of adsorption rate with time of the metal organic framework material prepared in example 3 of the present invention
FIG. 4 is a graph showing the change of the adsorption rate of the metal organic framework material prepared in example 4 of the present invention with time
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1
(1) 250mg of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 360mg of 4-pyridineboronic acid, 160mg of tetrakis (triphenylphosphine) palladium and 294mg of potassium acetate were mixed to form mixture A. 30ml of deionized water, 10ml of ethanol and 10ml of 1, 4-dioxane were mixed to form a mixed solution B. And injecting the mixed solution B into the mixture A under an argon atmosphere at 80 ℃ to react, and naturally cooling to room temperature after the reaction is finished.
(2) And (3) extracting a reaction product in the last step by using a mixture of deionized water and dichloromethane, washing impurities by using methanol, and then air-drying to obtain the khaki bis (4-pyridyl) benzothiadiazole.
(3) A solution of 0.02mmol of bis (4-pyridyl) benzothiadiazole (BTD-bpy) in methanol containing 0.045mmol of Co (NO)3)2The solution C is heated to 140 ℃ at a constant rate within 6 hours and kept warm for 48 hours, then cooled from 150 ℃ to room temperature at a constant rate within 36 hours, the generated crystals are transferred to a new methanol solution, and after the solution is washed with methanol and filtered off, a dark red metal organic framework material [ Co ] is obtained2(BTD-bpy)2(Hbtc)2]·3MeOH。
The reaction formula of the preparation and synthesis process is as follows:
example 2
(1) 280mg of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 365mg of 4-pyridineboronic acid, 180mg of tetrakis (triphenylphosphine) palladium and 294mg of potassium acetate were mixed to form mixture A. 30ml of deionized water, 10ml of ethanol and 20ml of 1, 4-dioxane were mixed to form a mixed solution B. And (3) injecting the mixed solution B into the mixture A under an argon atmosphere at 90 ℃ to react, and naturally cooling to room temperature after the reaction is finished.
(2) And (3) extracting a reaction product in the last step by using a mixture of deionized water and dichloromethane, washing impurities by using methanol, and then air-drying to obtain the khaki bis (4-pyridyl) benzothiadiazole.
(3) A methanol solution containing 0.03mmol of bis (4-pyridyl) benzothiadiazole (BTD-bpy) and 0.050mmol of Zn (NO)3)2Mixing methanol solution containing 0.050mmol of 1, 4-naphthalene dicarboxylic acid to obtain mixed solution C, heating the mixed solution C to 150 deg.C at constant rate within 6 hr, keeping the temperature for 52 hr, cooling from 150 deg.C to room temperature at constant rate within 36 hr, transferring the generated crystal into new methanol solution, washing with methanol, and filtering to obtain yellowish metal organic framework material [ Zn ]4(BTD-bpy)2(1,4-ndc)4]·MeOH·H2O(3·MeOH·H2O)。
Example 3
(1) 295mg of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 370mg of 4-pyridineboronic acid, 165mg of tetrakis (triphenylphosphine) palladium and 294mg of potassium acetate were mixed to form mixture A. 30ml of deionized water, 10ml of ethanol and 20ml of 1, 4-dioxane were mixed to form a mixed solution B. And (3) injecting the mixed solution B into the mixture A under an argon atmosphere at 90 ℃ to react, and naturally cooling to room temperature after the reaction is finished.
(2) And (3) extracting a reaction product in the last step by using a mixture of deionized water and dichloromethane, washing impurities by using methanol, and then air-drying to obtain the khaki bis (4-pyridyl) benzothiadiazole.
(3) A methanol solution containing 0.035mmol of bis (4-pyridyl) benzothiadiazole (BTD-bpy) and 0.055mmol of Mn (ClO)4)2The methanol solution of (2) is mixed with a methanol solution containing 0.050mmol of 1, 4-naphthalenedicarboxylic acid to form a mixed solution C, the mixed solution C is heated to 155 ℃ at a constant rate within 6 hours and kept at the temperature for 54 hours, then the mixed solution C is cooled from 155 ℃ to room temperature at a constant rate within 36 hours, the generated crystals are transferred to a new methanol solution, the solution is washed by methanol and filtered, and then a light yellow metal organic framework material, Mn, is obtained5(BTD-bpy)2(1,4-ndc)5(MeOH)2。
Example 4
(1) 310mg of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 380mg of 4-pyridineboronic acid, 175mg of tetrakis (triphenylphosphine) palladium and 294mg of potassium acetate were mixed to form mixture A. 30ml of deionized water, 10ml of ethanol and 20ml of 1, 4-dioxane were mixed to form a mixed solution B. And (3) injecting the mixed solution B into the mixture A under an argon atmosphere at 100 ℃ to react, and naturally cooling to room temperature after the reaction is finished.
(2) And (3) extracting a reaction product in the last step by using a mixture of deionized water and dichloromethane, washing impurities by using methanol, and then air-drying to obtain the khaki bis (4-pyridyl) benzothiadiazole.
(3) A solution of 0.035mmol of bis (4-pyridyl) benzothiadiazole (BTD-bpy) in methanol and 0.060mmol of Ni (NO)3)2Contains 0.050mmol of NO2-1,4-H2Mixing methanol solutions of bdc to form a mixed solution C, heating the solution C to 160 ℃ at a constant rate within 6 hours, keeping the temperature for 56 hours, cooling the solution C to room temperature from 155 ℃ at a constant rate within 36 hours, transferring the generated crystal into a new methanol solution, cleaning the solution by using methanol, and filtering the solution to obtain a light yellow metal organic framework material, [ Ni (BTD-bpy) (NO) ]2-1,4-bdc)(MeOH)]·MeOH·H2O(5·MeOH·H2O)。
Six solutions of acid orange, methylene blue, malachite green, rhodamine B, methyl orange and methyl blue with solute mass fractions of 0.002% are selected to be used for dye adsorption experiments, 10mg of the metal organic framework material prepared in each example is taken and respectively put into the six dye solutions, and the curves of the adsorption rate of the metal organic framework material prepared in the examples 1,2, 3 and 4 along with time change are respectively shown in the figure 1, the figure 2, the figure 3 and the figure 4. It can be seen that the adsorbents prepared in the embodiments have adsorption effects on dyes, the adsorbents in different embodiments have different adsorption capacities on different dyes, the adsorption rate of the adsorbent prepared in embodiment 1 on acid orange is the highest and can reach 75%, and the adsorption rate of the adsorbent prepared in embodiment 4 on methyl blue is the highest and can reach 73%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (7)
1. A preparation method of a metal organic framework material capable of selectively adsorbing dyes in wastewater is characterized by comprising the following steps:
(1) mixing 250-310 mg of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 360-380 mg of 4-pyridineboronic acid, 160-180 mg of tetrakis (triphenylphosphine) palladium and 294mg of potassium acetate to form a mixture A; mixing 30ml of deionized water, 10ml of ethanol and 10-20 ml of 1, 4-dioxane to form a mixed solution B; injecting the mixed solution B into the mixture A under the protective atmosphere at 80-100 ℃ for reaction, and naturally cooling to room temperature after the reaction is finished;
(2) extracting a reaction product in the step (1) by using a mixture of deionized water and dichloromethane, cleaning impurities by using methanol, and then air-drying to obtain khaki bis (4-pyridyl) benzothiadiazole;
(3) methanol solution containing 0.02-0.035 mmol of bis (4-pyridyl) benzothiadiazole, methanol solution containing 0.045-0.06 mmol of transition metal salt,containing 0.050mmol of 1,2, 4-benzenetricarboxylic acid, 1, 4-naphthalene dicarboxylic acid or NO2-1,4-H2And mixing methanol solutions of bdc to form a mixed solution C, heating the mixed solution C to 140-160 ℃ within 6 hours, preserving heat for 48-56 hours, cooling to room temperature, cleaning generated crystals, and filtering the solution to obtain the metal organic framework material.
2. The method according to claim 1, wherein the protective atmosphere is argon or nitrogen.
3. The method of claim 1, wherein the transition metal salt is Co (NO)3)2、Zn(NO3)2、Mn(ClO4)2Or Ni (NO)3)2。
4. The method for preparing a metal organic framework material capable of selectively adsorbing dyes in wastewater according to claim 1, wherein in the step (3), the mixed solution C is heated to 150 ℃ at a constant rate within 6 hours, is kept at the temperature for 48-56 hours, and then is cooled to room temperature at a constant rate within 36 hours.
5. The method for preparing a metal organic framework material capable of selectively adsorbing dyes in wastewater according to claim 1, wherein the crystals formed in the step (3) are washed with a methanol solution and the solution is filtered to obtain the metal organic framework material.
6. A metal organic framework material capable of selectively adsorbing dyes in wastewater, prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the metal organic framework material according to claim 6 for selectively adsorbing dyes in wastewater as a dye adsorbent in wastewater treatment.
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