CN113351167A - Ion type skeleton structure porous adsorption material and preparation method and application thereof - Google Patents
Ion type skeleton structure porous adsorption material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 74
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- 235000020188 drinking water Nutrition 0.000 claims abstract description 21
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 20
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- 125000000129 anionic group Chemical group 0.000 claims description 25
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- 238000000034 method Methods 0.000 claims description 23
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 15
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
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- 238000005406 washing Methods 0.000 claims description 12
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- 229960000643 adenine Drugs 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
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- 238000004729 solvothermal method Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 abstract description 40
- 239000000126 substance Substances 0.000 abstract description 18
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 abstract description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 36
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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
- 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]
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- 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
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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
- C02F2101/36—Organic compounds containing halogen
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Abstract
The invention discloses an ionic framework structure porous adsorption material and a preparation method and application thereof. The porous adsorption materials with the two ionic framework structures can efficiently adsorb and remove perfluoroalkyl substances and heavy metal ion pollutants in water, and mainly remove the perfluoroalkyl substances and the heavy metal ion pollutantsThe perfluoroalkyl substances are perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), and the heavy metal ions mainly removed are Hg2+、As2+、Cd2+And Pb2+. The ionic skeleton structure porous adsorbent material prepared by the invention is used for treating drinking water, so that the quality of the drinking water meets the set standard and requirement of domestic drinking water.
Description
Technical Field
The invention belongs to the field of preparation of adsorbents for removing pollutants in water, and particularly relates to an ionic type skeleton structure porous adsorption material capable of efficiently removing perfluoroalkyl pollutants and heavy metal ions in water and a preparation method thereof.
Background
Water body pollution can be divided into: organic pollution, heavy metal pollution and microbial pollution. Among a great variety of organic pollutants, perfluoroalkyl substances (PFASs) as a novel persistent organic pollutant are always difficult to treat wastewater due to the characteristics of remarkable thermal and chemical stability, high surface activity, biological enrichment, high toxicity, difficult degradation and the like. Currently, a large number of drinking water sources have been contaminated with PFASs to varying degrees. Because the traditional purification process of the water works cannot effectively remove the PFASs in the water, the PFASs exposure risk of the public is extremely high. The environmental pollution problem caused by PFASs has already posed a great threat to aquatic ecosystems and human health. Therefore, the economic and efficient removal of PFASs substances in tap water has very important scientific value and practical significance.
In addition, heavy metal ions Hg2+、As2+、Cd2+、Pb2+And the like are also commonly found in various industrial and agricultural wastewater, once the wastewater enters natural water, serious harm is caused to aquatic ecosystems and production and living of people, once people drink water with excessive heavy metal or eat aquatic products such as fishes and shrimps polluted by heavy metal, serious kidney and cardiovascular and cerebrovascular injury can be caused, and the long-term existence of the heavy metal in the body also increases carcinogenic risk.
Disclosure of Invention
The invention aims to provide an ionic framework porous material capable of efficiently removing perfluoroalkyl pollutants and heavy metal ions in water and a preparation method thereof, so as to overcome the problems existing in the treatment process of the perfluoroalkyl pollutants, the heavy metal ions and the like in drinking water, and develop a porous adsorption material containing an ionic framework structure.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an ionic framework structure porous adsorption material is provided, wherein the ionic framework structure porous adsorption material is a porous adsorption material with an anionic framework structure or a porous adsorption material with a cationic framework structure;
when the ionic framework structure porous adsorption material is a porous adsorption material with an anionic framework structure, the method comprises the following steps:
step 1.1: dissolving adenine, zinc acetate and biphenyldicarboxylic acid in a reaction solvent A to obtain a mixed solution A1;
step 1.2: adding a catalyst into the mixed solution A1 obtained in the step 1.1 to obtain mixed solution B1;
step 1.3: carrying out a solvothermal reaction on the mixed solution B1 obtained in the step 1.2, and reacting for 2-3 days at 100-150 ℃ to obtain a mixed solution C1;
step 1.4: filtering the mixed solution C1 obtained in the step 1.3, and collecting a white product;
step 1.5: fully soaking and washing the white product obtained in the step 1.4 by using N, N-dimethylformamide and methanol respectively to obtain a product;
step 1.6: vacuum drying the product obtained in the step 1.5 at the temperature of 80-100 ℃ for 1-2 days to obtain the organic porous adsorption material with the anionic skeleton structure;
when the ionic framework structure porous adsorption material is a porous adsorption material with a cationic framework structure, the method comprises the following steps:
step 2.1: dissolving zirconium chloride in a reaction solvent B to obtain a mixed solution A2;
step 2.2: adding 2, 5-thiophenedicarboxylic acid into the mixed solution A2 obtained in the step 2.1, and fully dissolving to obtain mixed solution B2;
step 2.3: adding formic acid into the mixed solution B2 obtained in the step 2.2 to obtain a mixed solution C2;
step 2.4: reacting the mixed solution C2 obtained in the step 2.3 at 110-130 ℃ for 2-3 days to obtain a mixed solution D;
step 2.5: filtering the mixed solution D obtained in the step 2.4, collecting white precipitates, washing with N, N-Dimethylformamide (DMF) and ethanol respectively, and removing unreacted organic solvent;
step 2.6: and (3) drying the material obtained in the step (2.5) at 100-140 ℃ for 1 day in vacuum to obtain the cationic skeleton organic porous adsorbent material.
Further, the molar ratio of adenine, zinc acetate and biphenyldicarboxylic acid described in step 1.1 is 1:3: 2.
Further, the reaction solvent a described in step 1.1 is a mixture of N, N-dimethylformamide and water, and the volume ratio of N, N-dimethylformamide to water is 9: 1.
Further, the ratio of the molar amount of the raw material adenine to the volume of the reaction solvent a in step 1.1 is: n isAdenine:VReaction solvent A＝0.25mmol:30mL。
Further, the catalyst in the step 1.2 is nitric acid, the mass concentration of the nitric acid is 68%, and the volume ratio of the N, N-dimethylformamide to the water to the nitric acid is 225:25: 1.
Further, the molar ratio of zirconium chloride to 2, 5-thiophenedicarboxylic acid is 1.5: 1.
Further, in step 2.1, the reaction solvent B is a mixture of N-methylpyrrolidone and N, N-dimethylformamide, and the volume ratio of N-methylpyrrolidone to N, N-dimethylformamide is 1:1, and the ratio of the molar amount of zirconium chloride to the volume of the reaction solvent B is: n isZirconium chloride:VReaction solvent B＝3mmol:80mL。
Further, the volume ratio of the formic acid in the step 2.3 to the N-methylpyrrolidone and the N, N-dimethylformamide in the reaction solvent B is 1:6: 6.
The ionic framework structure porous adsorption material is prepared by the preparation method of the ionic framework structure porous adsorption material.
An application of an ionic skeleton structure porous adsorption material in removing perfluoroalkyl pollutants and heavy metal ions in drinking water.
Compared with the prior art, the invention has the following beneficial technical effects:
the porous adsorption material with the anionic and cationic framework structures has the capability of efficiently and deeply removing perfluoroalkyl substances and heavy metal ion pollutants, and is characterized in that a large number of ionic adsorption sites are loaded on the surface of pore channels of the porous adsorption material with the ionic framework structures, and the ionic adsorption sites can be bonded with the perfluoroalkyl substances and the heavy metal ions, so that the adsorption material has high-efficiency selective adsorption capability on the perfluoroalkyl substances and the heavy metal ion pollutants in water, and the purpose of greatly reducing the perfluoroalkyl substances and the heavy metal ion pollutants in the water body is finally realized.
The porous adsorption material with the ionic framework structure, which is obtained by the invention, not only has high selectivity and high adsorption capacity, but also has good physical and chemical stability, so that the porous adsorption material is easy to recycle, thereby providing a premise and a basis for meeting the requirements of industrial application.
The synthesis process of the porous adsorption material with the ion framework structure is simple and controllable, and the prepared porous adsorption material is stable in physical and chemical properties and has good tolerance to water, acid and alkali environments, so that the porous adsorption material can be used in potential industrial application.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a powder X-ray diffraction (PXRD) pattern of a porous adsorbing material Bio-MOF-1 with an anionic framework structure prepared in example 1;
FIG. 2 shows N of the porous adsorbent Bio-MOF-1 having an anionic skeleton structure prepared in example 12Adsorption-desorption isotherm diagram;
FIG. 3 is a pore size distribution diagram of the porous adsorption material Bio-MOF-1 with an anionic skeleton structure prepared in example 1;
FIG. 4 is a scanning electron microscope image of the porous adsorbent material Bio-MOF-1 having an anionic skeleton structure prepared in example 1;
FIG. 5 is a graph showing the adsorption kinetics of the porous adsorption material Bio-MOF-1 with an anionic framework structure prepared in example 1 on PFOS and PFOA in a simulated water sample under different pH conditions;
FIG. 6 is a graph showing the adsorption kinetics of the porous adsorption material Bio-MOF-1 with an anionic framework structure prepared in example 1 on four heavy metal ions in a simulated water sample.
Detailed Description
The present invention will be described in further detail below:
the invention provides an ion type skeleton porous adsorption material which is excellent in performance, efficient, reliable and easy to carry out practical application aiming at perfluoroalkyl substances and heavy metal ion pollutants in water, and comprises a porous adsorption material with an anionic skeleton structure and a porous adsorption material with a cationic skeleton structure.
The structure of the porous adsorption material with the anionic skeleton structure is shown as the formula (I):
the structure of the porous adsorption material with the cationic skeleton structure is shown as the formula (II):
the invention provides a preparation method of a porous adsorption material with an anionic or cationic skeleton structure, which has simple process and good adsorption effect.
The preparation method of the porous adsorption material with the anion framework structure comprises the following steps:
step 1.1: dissolving adenine, zinc acetate and biphenyldicarboxylic acid in a reaction solvent A to obtain a mixed solution A1, wherein the molar ratio of adenine, zinc acetate and biphenyldicarboxylic acid is 1:3:2, and the reaction solvent A is N, N-Dimethylformamide (DMF) and water in a volume ratio of 9: 1;
step 1.2: adding catalyst nitric acid into the mixed solution A1 obtained in the step 1.1 to obtain a mixed solution B1, wherein the mass concentration of the catalyst nitric acid is 68%, and the volume ratio of the catalyst nitric acid to the solvent is as follows: the volume ratio of N, N-Dimethylformamide (DMF), water and nitric acid is 225:25: 1;
step 1.3: carrying out a solvothermal reaction on the mixed solution B1 obtained in the step 1.2, and reacting for 2-3 days at 100-150 ℃ to obtain a mixed solution C1;
step 1.4: filtering the mixed solution C1 obtained in the step 1.3, and collecting a white product;
step 1.5: fully soaking and washing the white product obtained in the step 1.4 by using N, N-dimethylformamide and methanol respectively to obtain a product;
step 1.6: vacuum drying the product obtained in the step 1.5 at 80-100 ℃ for 1 day to obtain an organic porous adsorption material Bio-MOF-1 with an anionic framework structure;
the preparation method of the porous adsorption material with the cation framework structure comprises the following steps:
step 2.1: dissolving zirconium chloride in a reaction solvent B to obtain a mixed solution A2, wherein the reaction solvent B is a mixture of N-methylpyrrolidone and N, N-dimethylformamide, the volume ratio of the N-methylpyrrolidone to the N, N-dimethylformamide is 1:1, and the volume ratio of the molar weight of the zirconium chloride to the volume of the reaction solvent B is as follows: n isZirconium chloride:VReaction solvent B＝3mmol:80mL。
Step 2.2: adding 2, 5-thiophenedicarboxylic acid into the mixed solution A2 obtained in the step 2.1, and fully dissolving to obtain a mixed solution B2, wherein the molar ratio of the raw material zirconium chloride to the 2, 5-thiophenedicarboxylic acid is 3: 2;
step 2.3: adding formic acid into the mixed solution B2 obtained in the step 2.2 to obtain a mixed solution C2, wherein the concentration of the formic acid is 98%, and the volume ratio of the added formic acid to the solvents of the N-methylpyrrolidone and the N, N-dimethylformamide is 1:6
Step 2.4: reacting the mixed solution C2 obtained in the step 2.3 at 110-130 ℃ for 2-3 days to obtain a mixed solution D;
step 2.5: filtering the mixed solution D obtained in the step 2.4, collecting white precipitates, washing with N, N-Dimethylformamide (DMF) and ethanol respectively, and removing unreacted organic solvent;
step 2.6: and (3) drying the material obtained in the step (2.5) at 100-140 ℃ for 1 day in vacuum to obtain the cationic skeleton organic porous adsorbent material DUT-67.
The porous material adsorbent with the anionic or cationic skeleton structure can efficiently adsorb perfluoroalkyl pollutants and heavy metal ion pollutants in water, and is used for adsorbing and treating the perfluoroalkyl pollutants and the heavy metal ion pollutants in the water, and the method comprises the following operation process steps:
adding the prepared porous material adsorbent with an anionic or cationic framework structure into a simulated water sample containing perfluoroalkyl substances and heavy metal ions with different pollutant types and concentrations, wherein the pH value of the water sample containing the perfluoroalkyl substances and the heavy metal ions is adjusted to be within a range of 3-7, the temperature of the water sample is within a range of 5-50 ℃, immediately starting stirring and timing, the stirring speed is 100-600 rpm, taking out a small amount of water sample from a container at intervals, measuring the contents of the perfluoroalkyl substances and the heavy metal ions in the water sample by using High Performance Liquid Chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS), and judging the time for the adsorbent to reach equilibrium according to the concentration change conditions of each component in the water sample taken at different times. And separating the adsorbent from the simulated water sample after the adsorption reaches the balance, recovering the adsorbent, and fully eluting the adsorbent by using the eluent, thereby realizing the cyclic recovery and reutilization of the adsorbent.
Wherein the perfluoroalkyl substances are mainly perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS); the concentration of the perfluorooctanoic acid (PFOA) and the perfluorooctane sulfonate (PFOS) is 200 ng/L-800 ng/L, and the heavy metal ions are mainly Hg2+、As2+、Cd2+、Pb2+And the concentration of the heavy metal ions is 5mg/L-15 mg/L.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Example 1
Dissolving 0.25mmol of adenine, 0.75mmol of zinc acetate and 0.50mmol of biphenyldicarboxylic acid in a mixed solution prepared by 27mL of N, N-Dimethylformamide (DMF) and 3mL of water, adding 0.12mL of nitric acid serving as a catalyst into the solution system after the raw materials are fully dissolved, transferring the mixed solution into a polytetrafluoroethylene reaction kettle core for sealing, placing the reaction kettle into a stainless steel reaction kettle, placing the reaction kettle at 130 ℃ for heating for 3 days, centrifuging to collect products, washing the products with N, N-Dimethylformamide (DMF) and methanol respectively, and then drying in vacuum at 90 ℃ for 1 day to obtain Bio-MOF-1 with an anionic framework structure.
Bio-MOF-1 having an anionic skeleton structure prepared by the present embodiment was characterized, and the results were as follows:
FIG. 1 is an XRD spectrum of Bio-MOF-1 prepared in example 1, and the XRD spectrum of the Bio-MOF-1 can be seen to have a sharp diffraction peak, which indicates that the material has good crystallization performance;
FIG. 2 shows N of Bio-MOF-1 prepared in example 12Adsorption-desorption isotherm diagram, generalThe specific surface area of the material is 1018m according to the over-isotherm2/g；
FIG. 3 shows the pore size and pore size distribution of Bio-MOF-1 prepared in example 1, from which it can be seen that the average pore size of Bio-MOF-1 is 1.36nm, which is a typical microporous structure material;
FIG. 4 is a scanning electron micrograph of Bio-MOF-1 prepared in example 1, and it can be seen that the crystals of Bio-MOF-1 are quadrangular prism-like rod-shaped materials;
based on the above characteristics, we tested the water treatment capacity of the Bio-MOF-1 porous adsorbent material prepared in example 1, and the results are shown in FIG. 5, FIG. 6 and Table 1:
FIG. 5 is a graph showing the adsorption kinetics of PFOS and PFOA in a water body under different pH conditions of the Bio-MOF-1 porous adsorbent material prepared in example 1, and the graph shows that the Bio-MOF-1 shows good adsorption performance for PFOA and PFOS under different pH conditions;
FIG. 6 is a graph showing the adsorption kinetics of Bio-MOF-1 prepared in example 1 on four heavy metal ions in a water body, and it can be seen that the Bio-MOF-1 can be used for detecting Hg in a water sample under different pH conditions2+、As2+、Cd2+And Pb2+The ions exhibit good adsorption properties;
table 1 shows the conventional index and limit values of drinking water quality and the pairs of Bio-MOF-1 prepared in example 1 containing PFOA, PFOS and Hg2+、As2+、Cd2+、Pb2+The concentration change condition of the content of each component in the water after the water sample adsorption treatment is simulated;
as can be understood from FIG. 5 and Table 1, when the water sample contains PFOA and PFOS at concentrations of 500ng/L, the Bio-MOF-1 porous adsorbing material prepared in example 1 can effectively adsorb PFOA and PFOS in the water sample, so that the concentrations of PFOA and PFOS in the water sample are respectively reduced from 500ng/L to 8ng/L and 6ng/L, thereby meeting the upper limits of the concentrations of PFOA and PFOS in drinking water specified by mechanisms such as European Food Safety Agency (EFSA);
as can be understood from FIG. 6 and Table 1, when Hg is present in a water sample2+、As2+、Cd2+And Pb2+When the concentration of the metal ions is 10mg/L, the Bio-MOF-1 adsorbent prepared in example 1 can effectively adsorb the heavy metal ions in the water sample, so that Hg in the treated water sample can be effectively adsorbed2+、As2+、Cd2+And Pb2+The concentration of the heavy metal ions is respectively reduced from 10mg/L to 0.0005mg/L, 0.007mg/L, 0.004mg/L and 0.007mg/L, which meets the national limit requirements on the concentration of the related heavy metal ions in the drinking water.
As a result, it was found that PFOA, PFOS and Hg were contained in the pairs of Bio-MOF-1 porous adsorbents prepared in example 12+、As2+、Cd2+And Pb2+When the simulated water sample of the heavy metal ion pollutants is subjected to adsorption treatment, the Bio-MOF-1 adsorbent material shows a good effect of removing the perfluorinated substances and the heavy metal ion pollutants in the water sample.
TABLE 1 Drinking water quality conventional index and Limit and concentration Change of Each component before and after simulated Water sample treatment
Example 2
Dissolving 0.25mmol of adenine, 0.75mmol of zinc acetate and 0.50mmol of biphenyldicarboxylic acid in a mixed solution prepared by 27mL of N, N-dimethylformamide and 3mL of water, adding 0.12mL of nitric acid serving as a catalyst into the solution system after the raw materials are fully dissolved, transferring the mixed solution into a polytetrafluoroethylene reaction kettle core, sealing, placing the reaction kettle in a stainless steel reaction kettle, heating for 3 days at 100 ℃, centrifuging, collecting products, washing with N, N-Dimethylformamide (DMF) and methanol respectively, and then drying for 1 day in vacuum at 80 ℃ to obtain Bio-MOF-1 with an anionic framework structure.
The Bio-MOF-1 having an anionic skeleton structure obtained in the present embodiment was subjected to a water treatment ability test, and the results showed that when the Bio-MOF-1 porous adsorbent prepared as described above was used for the treatment of a sample containing PFOA, PFOS and Hg2+、As2+、Cd2+And Pb2+Of heavy metal ionsWhen a simulated water sample is subjected to adsorption treatment, the Bio-MOF-1 shows remarkable capacity of removing pollutants in water. When the concentrations of PFOA and PFOS in the water sample are both 200ng/L, Bio-MOF-1 can effectively adsorb PFOA and PFOS in the water sample, so that the concentrations of PFOA and PFOS in the water sample are respectively reduced from 200ng/L to 3ng/L and 2ng/L, thereby meeting the upper limit of the concentrations allowed for PFOA and PFOS in drinking water specified by mechanisms such as European Food Safety Agency (EFSA) and the like; when Hg exists in the water sample2+、As2+、Cd2+And Pb2+When the concentration of the ions is 5mg/L, the Bio-MOF-1 adsorbent can effectively adsorb the heavy metal ions in a water sample, and Hg in the water sample treated by the adsorbent2+、As2+、Cd2+And Pb2+The concentration of the heavy metal ions is respectively reduced from 5mg/L to 0.0004mg/L, 0.005mg/L, 0.003mg/L and 0.006mg/L, which meets the national limit requirements on the concentration of the relevant heavy metal ions in the drinking water.
Example 3
Dissolving 0.25mmol of adenine, 0.75mmol of zinc acetate and 0.50mmol of biphenyldicarboxylic acid in a mixed solution prepared by 27mL of N, N-dimethylformamide and 3mL of water, adding 0.12mL of nitric acid serving as a catalyst into the solution system after the raw materials are fully dissolved, transferring the mixed solution into a polytetrafluoroethylene reaction kettle core, sealing, placing the reaction kettle in a stainless steel reaction kettle, heating the reaction kettle at 150 ℃ for 2 days, centrifuging, collecting products, washing the products with N, N-Dimethylformamide (DMF) and methanol respectively, and then drying the products in vacuum at 100 ℃ for 1 day to obtain Bio-MOF-1 with an anionic framework structure.
The Bio-MOF-1 having an anionic skeleton structure obtained in the present embodiment was subjected to a water treatment ability test, and the results showed that when the Bio-MOF-1 porous adsorbent prepared as described above was used for the treatment of a sample containing PFOA, PFOS and Hg2+、As2+、Cd2+And Pb2+When a simulated water sample of the heavy metal ions is subjected to adsorption treatment, the Bio-MOF-1 shows remarkable capacity of removing pollutants in water. When the concentrations of PFOA and PFOS in the water sample are both 800ng/L, Bio-MOF-1 can effectively adsorb PFOA and PFOS in the water sample, so that PFOA and PF in the water sampleThe concentration of OS is respectively reduced from 800ng/L to 8ng/L and 7ng/L, thereby meeting the upper limit of the concentration allowed by PFOA and PFOS in drinking water specified by mechanisms such as European Food Safety Agency (EFSA); when Hg exists in the water sample2+、As2+、Cd2+And Pb2+When the concentration of the ions is 15mg/L, the Bio-MOF-1 adsorbent can effectively adsorb the heavy metal ions in a water sample, and Hg in the water sample treated by the adsorbent2+、As2+、Cd2 +And Pb2+The concentration of the water is respectively reduced from 15mg/L to 0.0009mg/L, 0.008mg/L, 0.005mg/L and 0.008mg/L, which meets the national limit requirements on the concentration of related heavy metal ions in the drinking water.
Example 4
Dissolving 6.0mmol of zirconium chloride in 160mL of mixed solvent consisting of N, N-dimethylformamide and N-methylpyrrolidone, wherein the volume ratio of the N, N-dimethylformamide to the N-methylpyrrolidone is 1:1, then adding 4.0mmol of 2, 5-thiophenedicarboxylic acid into the system, continuing to add 26.6mL of 98% formic acid after full dissolution, fully mixing the reaction system, heating the obtained mixture at 110 ℃ for 3 days, filtering, collecting white precipitate, washing with N, N-Dimethylformamide (DMF) and ethanol, and drying in vacuum at 100 ℃ for 1 day to obtain DUT-67 with a cationic framework structure.
The DUT-67 having a cationic skeleton structure prepared by the present embodiment was subjected to a water treatment ability test, and the results showed that when the DUT-67 porous adsorbent prepared as described above was used for treating a sample containing PFOA, PFOS and Hg2+、As2+、Cd2+And Pb2+When the simulated water sample of the heavy metal ions is subjected to adsorption treatment, the DUT-67 shows remarkable capability of removing pollutants in water. When the concentrations of PFOA and PFOS in the water sample are both 500ng/L, the DUT-67 can effectively adsorb the PFOA and PFOS in the water sample, so that the concentrations of the PFOA and the PFOS in the water sample are respectively reduced from 500ng/L to 7ng/L and 5ng/L, thereby meeting the upper limit of the concentrations of the PFOA and the PFOS in drinking water specified by mechanisms such as European Food Safety Agency (EFSA) and the like; when Hg exists in the water sample2+、As2+、Cd2+And Pb2+When the ion concentration of the metal ions is 10mg/L, the DUT-67 adsorbent can effectively adsorb the heavy metal ions in a water sample, and Hg in the water sample treated by the adsorbent2+、As2+、Cd2+And Pb2+The concentration of (A) is respectively reduced from 10mg/L to 0.0005mg/L, 0.006mg/L, 0.003mg/L and 0.006mg/L, which meets the national limit requirements on the concentration of related heavy metal ions in the drinking water.
Example 5
Dissolving 6.0mmol of zirconium chloride in 160mL of mixed solvent consisting of N, N-dimethylformamide and N-methylpyrrolidone, wherein the volume ratio of the N, N-dimethylformamide to the N-methylpyrrolidone is 1:1, then adding 4.0mmol of 2, 5-thiophenedicarboxylic acid into the system, continuing to add 26.6mL of 98% formic acid after full dissolution, fully mixing the reaction system, heating the obtained mixture at 120 ℃ for 3 days, filtering, collecting white precipitate, washing with N, N-Dimethylformamide (DMF) and ethanol, and drying in vacuum at 120 ℃ for 1 day to obtain DUT-67 with a cationic framework structure.
The DUT-67 having a cationic skeleton structure prepared by the present embodiment was subjected to a water treatment ability test, and the results showed that when the DUT-67 porous adsorbent prepared as described above was used for treating a sample containing PFOA, PFOS and Hg2+、As2+、Cd2+And Pb2+When the simulated water sample of the heavy metal ions is subjected to adsorption treatment, the DUT-67 shows remarkable capability of removing pollutants in water. When the concentrations of PFOA and PFOS in the water sample are both 200ng/L, the DUT-67 can effectively adsorb the PFOA and PFOS in the water sample, so that the concentrations of the PFOA and the PFOS in the water sample are respectively reduced from 200ng/L to 4ng/L and 3ng/L, thereby meeting the upper limit of the concentrations of the PFOA and the PFOS in drinking water specified by mechanisms such as European Food Safety Agency (EFSA) and the like; when Hg exists in the water sample2+、As2+、Cd2+And Pb2+When the ion concentration of the metal ions is 5mg/L, the DUT-67 adsorbent can effectively adsorb the heavy metal ions in a water sample, and Hg in the water sample treated by the adsorbent2+、As2+、Cd2+And Pb2+In a concentration of5mg/L is respectively reduced to 0.0004mg/L, 0.003mg/L, 0.002mg/L and 0.004mg/L, which meets the national limit requirements on the concentration of the related heavy metal ions in the drinking water.
Example 6
Dissolving 6.0mmol of zirconium chloride in 160mL of mixed solvent consisting of N, N-dimethylformamide and N-methylpyrrolidone, wherein the volume ratio of the N, N-dimethylformamide to the N-methylpyrrolidone is 1:1, then adding 4.0mmol of 2, 5-thiophenedicarboxylic acid into the system, continuing to add 26.6mL of 98% formic acid after full dissolution, fully mixing the reaction system, heating the obtained mixture at 130 ℃ for 2 days, filtering, collecting white precipitate, washing with N, N-Dimethylformamide (DMF) and ethanol, and drying in vacuum at 140 ℃ for 1 day to obtain DUT-67 with a cationic framework structure.
The DUT-67 having a cationic skeleton structure prepared by the present embodiment was subjected to a water treatment ability test, and the results showed that when the DUT-67 porous adsorbent prepared as described above was used for treating a sample containing PFOA, PFOS and Hg2+、As2+、Cd2+And Pb2+When the simulated water sample of the heavy metal ions is subjected to adsorption treatment, the DUT-67 shows remarkable capability of removing pollutants in water. When the concentrations of PFOA and PFOS in the water sample are both 800ng/L, the DUT-67 can effectively adsorb the PFOA and PFOS in the water sample, so that the concentrations of the PFOA and the PFOS in the water sample are respectively reduced from 800ng/L to 9ng/L and 6ng/L, thereby meeting the upper limit of the concentrations of the PFOA and the PFOS in drinking water specified by mechanisms such as European Food Safety Agency (EFSA) and the like; when Hg exists in the water sample2+、As2+、Cd2+And Pb2+When the ion concentration of the metal ions is 15mg/L, the DUT-67 adsorbent can effectively adsorb the heavy metal ions in a water sample, and Hg in the water sample treated by the adsorbent2+、As2+、Cd2+And Pb2+The concentration of the heavy metal ions is respectively reduced from 15mg/L to 0.0008mg/L, 0.009mg/L, 0.005mg/L and 0.009mg/L, which meets the national limit requirements on the concentration of the relevant heavy metal ions in the drinking water.
The embodiments described above are merely preferred embodiments of the present invention, and should not be considered as limitations of the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (10)
1. A preparation method of an ionic skeleton structure porous adsorption material is characterized by comprising the following steps: the ionic type skeleton structure porous adsorption material is a porous adsorption material with an anionic skeleton structure or a porous adsorption material with a cationic skeleton structure;
when the ionic framework structure porous adsorption material is a porous adsorption material with an anionic framework structure, the method comprises the following steps:
step 1.1: dissolving adenine, zinc acetate and biphenyldicarboxylic acid in a reaction solvent A to obtain a mixed solution A1;
step 1.2: adding a catalyst into the mixed solution A1 obtained in the step 1.1 to obtain mixed solution B1;
step 1.3: carrying out a solvothermal reaction on the mixed solution B1 obtained in the step 1.2, and reacting for 2-3 days at 100-150 ℃ to obtain a mixed solution C1;
step 1.4: filtering the mixed solution C1 obtained in the step 1.3, and collecting a white product;
step 1.5: fully soaking and washing the white product obtained in the step 1.4 by using N, N-dimethylformamide and methanol respectively to obtain a product;
step 1.6: vacuum drying the product obtained in the step 1.5 at the temperature of 80-100 ℃ for 1-2 days to obtain the organic porous adsorption material with the anionic skeleton structure;
when the ionic framework structure porous adsorption material is a porous adsorption material with a cationic framework structure, the method comprises the following steps:
step 2.1: dissolving zirconium chloride in a reaction solvent B to obtain a mixed solution A2;
step 2.2: adding 2, 5-thiophenedicarboxylic acid into the mixed solution A2 obtained in the step 2.1, and fully dissolving to obtain mixed solution B2;
step 2.3: adding formic acid into the mixed solution B2 obtained in the step 2.2 to obtain a mixed solution C2;
step 2.4: reacting the mixed solution C2 obtained in the step 2.3 at 110-130 ℃ for 2-3 days to obtain a mixed solution D;
step 2.5: filtering the mixed solution D obtained in the step 2.4, collecting white precipitates, washing with N, N-Dimethylformamide (DMF) and ethanol respectively, and removing unreacted organic solvent;
step 2.6: and (3) drying the material obtained in the step (2.5) at 100-140 ℃ for 1 day in vacuum to obtain the cationic skeleton organic porous adsorbent material.
2. The method for preparing the ionic skeleton structure porous adsorption material according to claim 1, wherein the method comprises the following steps: the molar ratio of adenine, zinc acetate and biphenyldicarboxylic acid described in step 1.1 is 1:3: 2.
3. The method for preparing the ionic skeleton structure porous adsorption material according to claim 1, wherein the method comprises the following steps: the reaction solvent A in the step 1.1 is a mixture of N, N-dimethylformamide and water, and the volume ratio of the N, N-dimethylformamide to the water is 9: 1.
4. The method for preparing the ionic skeleton structure porous adsorption material according to claim 3, wherein the method comprises the following steps: the volume ratio of the molar weight of the raw material adenine to the reaction solvent A in the step 1.1 is as follows: n isAdenine:VReaction solvent A＝0.25mmol:30mL。
5. The method for preparing the ionic skeleton structure porous adsorption material according to claim 3, wherein the method comprises the following steps: the catalyst in the step 1.2 is nitric acid, the mass concentration of the nitric acid is 68%, and the volume ratio of the N, N-dimethylformamide to the water to the nitric acid is 225:25: 1.
6. The method for preparing the ionic skeleton structure porous adsorption material according to claim 1, wherein the method comprises the following steps: the molar ratio of zirconium chloride to 2, 5-thiophenedicarboxylic acid is 1.5: 1.
7. The method for preparing the ionic skeleton structure porous adsorption material according to claim 1, wherein the method comprises the following steps: the reaction solvent B in the step 2.1 is a mixture of N-methylpyrrolidone and N, N-dimethylformamide, the volume ratio of the N-methylpyrrolidone to the N, N-dimethylformamide is 1:1, and the volume ratio of the molar amount of the zirconium chloride to the reaction solvent B is as follows: n isZirconium chloride:VReaction solvent B＝3mmol:80mL。
8. The method for preparing the ionic skeleton structure porous adsorption material according to claim 7, wherein the method comprises the following steps: and 2.3, the volume ratio of the formic acid to the N-methyl pyrrolidone and the N, N-dimethylformamide in the reaction solvent B is 1:6: 6.
9. An ionic framework structure porous adsorption material, which is characterized by being prepared by the preparation method of the ionic framework structure porous adsorption material according to any one of claims 1 to 8.
10. Use of the ionic porous adsorption material with a framework structure according to claim 9 for removing perfluoroalkyl pollutants and heavy metal ions in drinking water.
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