WO2021051849A1 - Cationic metal-organic framework membrane material and preparation method and application - Google Patents

Cationic metal-organic framework membrane material and preparation method and application Download PDF

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WO2021051849A1
WO2021051849A1 PCT/CN2020/091870 CN2020091870W WO2021051849A1 WO 2021051849 A1 WO2021051849 A1 WO 2021051849A1 CN 2020091870 W CN2020091870 W CN 2020091870W WO 2021051849 A1 WO2021051849 A1 WO 2021051849A1
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uio
organic framework
nme
membrane material
membrane
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马继平
吴阁格
李爽
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青岛理工大学
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/14—Chemical modification with acids, their salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride

Definitions

  • the invention belongs to the technical field of metal organic framework materials, and relates to a cationic metal organic framework membrane material and a preparation method and application.
  • Metal-organic frameworks are a class of nanoporous materials formed by organic-inorganic hybridization, and are currently one of the research hotspots and frontiers in the field of new materials.
  • the metal-organic framework material is mainly composed of a three-dimensional network structure crystal formed by the coordination bonding of an aromatic acid or a base containing a multidentate organic ligand containing nitrogen and oxygen and an inorganic metal center. Because MOFs materials combine inorganic and organic components, they have many advantages compared to traditional porous materials, such as multiple types, strong functions, large porosity and specific surface area, strong pore size controllability, and certain Biocompatibility.
  • the Chinese patent with application number 201611242102.X discloses a method for preparing a hydroxyl-modified MOF film with high removal of heavy metal ions in the blood. The method adopts a pre-irradiation or co-irradiation method to graft the MOF material with double bonds on the high A hydroxyl-modified MOF film is obtained on the surface of the molecular base material.
  • the inventors of the present invention have discovered that the preparation process of this method is relatively complicated, and the loading amount of MOF is not high.
  • Ionic metal-organic frameworks are new types of MOFs reported in recent years, and research on their preparation and application is still in its infancy. Compared with traditional ion exchange materials, ionic MOFs have faster adsorption speed, better selectivity and larger adsorption capacity, and some MOFs materials have better acid and alkali resistance than some inorganic or organic ion exchangers.
  • UiO-66 is a kind of MOFs material with metal Zr as the metal center. It is composed of inorganic metal unit Zr 6 O 4 (OH) 4 and coordinated with the carboxyl oxygen in the ligand.
  • Zr 6 octahedral core is coordinated with 12 terephthalic acid ligands to form two types of tetrahedral and octahedral cages. It has a large specific surface area, good thermal and chemical stability.
  • the purpose of the present invention is to provide a cationic metal-organic framework membrane material and its preparation method and application.
  • This type of cationic metal-organic framework membrane material can adsorb and enrich phenoxycarboxylic acid herbicides and simultaneously carry out pentavalent arsenic Adsorption removal.
  • a cationic metal organic framework membrane material the cationic metal organic framework membrane material UiO-66-NMe 3 + ⁇ Cl - membrane is a mixed matrix membrane formed by a polymer matrix and an ionic metal organic framework material , the ionic material is a metal organic framework UiO-66-NMe 3 + ⁇ Cl - , the UiO-66-NMe 3 + ⁇ Cl - as UiO-66-NH 2 portions or all of the -NH 2 group The group is methylated to form a -NMe 3 + group.
  • a method for preparing cationic metal organic framework membrane material is to disperse polymer and UiO-66-NH 2 into a solvent and mix uniformly, spread the uniformly mixed liquid and remove the solvent to obtain UiO-66-NH 2 film, using methyl trifluoromethanesulfonate and UiO-66-NH 2 film reactor, such that a quaternary amino UiO-66-NH 2 film amination, then quaternized UiO-66-NH 2 As for the film UiO-66-NMe 3 + ⁇ Cl - film is obtained by soaking in hydrochloric acid solution.
  • the present invention provides a cationic metal organic framework membrane material based on UiO-66-NMe 3 + ⁇ Cl - .
  • the membrane material can effectively treat phenoxycarboxylic acid herbicides and pentavalent arsenic in water. Selective adsorption, but also easy to separate from the aqueous solution.
  • Figure 1 is a scanning electron microscope (SEM) image of Example 1 of the present invention.
  • A is a UiO-66-NH 2 film
  • B is a UiO-66-NH 2 film
  • C is a UiO-66-NMe modified by a quaternary amine group. 3 + ⁇ Cl - ion exchange membrane
  • D is UiO-66-NMe 3 + ⁇ Cl - ion exchange membrane modified by quaternary amine group;
  • Figure 2 is the infrared spectrum of the membrane material prepared in Example 1 of the present invention, a is a pure PVDF membrane, b is a UiO-66-NH 2 membrane, and c is a UiO-66-NMe 3 + modified by a quaternary amine group. Cl - ion exchange membrane;
  • Figure 3 is an X-ray diffraction diagram of the membrane material prepared in Example 1 of the present invention, a is a UiO-66-NH 2 membrane, and b is a UiO-66-NMe 3 + ⁇ Cl - ion exchange membrane modified by a quaternary amino group;
  • Figure 4 is the XPS analysis diagram of the UiO-66-NMe 3 + ⁇ Cl - film prepared in Example 1 of the present invention, a is the total element diagram, b is the high-resolution diagram of Zr 3d, c is the high-resolution diagram of C1s, and d It is a high-resolution image of N1s.
  • a typical embodiment of the present invention provides a cationic metal-organic framework membrane material.
  • the cationic metal-organic framework membrane material UiO-66-NMe 3 + ⁇ Cl - membrane is a polymer matrix and ionic metal organic framework material mixed matrix membrane is formed, the ionic material is a metal organic framework UiO-66-NMe 3 + ⁇ Cl - , the UiO-66-NMe 3 + ⁇ Cl - as the UiO-66-NH 2 of Part or all of the -NH 2 groups are methylated to form -NMe 3 + groups.
  • the mixed matrix membrane is a new type of composite membrane material for the preparation of MOFs membrane material, which is to embed MOFs crystal particles in a polymer substrate such as polysulfone, polytetrafluoroethylene, polyvinylidene fluoride, etc. It not only retains the porous structure, high specific surface area and selectivity of MOF, but also has high permeability and mechanical strength.
  • the polymer of the present invention for example, polysulfone, polytetrafluoroethylene, polyvinylidene fluoride and the like.
  • the polymer matrix is polyvinylidene fluoride.
  • the present invention has found through research that the bonding strength of UiO-66-NMe 3 + ⁇ Cl - and polyvinylidene fluoride is better, thereby increasing the performance of the membrane material.
  • Another embodiment of the present invention provides a method for preparing a cationic metal-organic framework membrane material.
  • the polymer and UiO-66-NH 2 are dispersed in a solvent and mixed uniformly, and the uniformly mixed liquid is flattened and removed the solvent to obtain UiO-66-NH 2 film, using methyl trifluoromethanesulfonate and UiO-66-NH 2 film reactor, such that a quaternary amino UiO-66-NH 2 film amination, then quaternized UiO
  • the -66-NH 2 membrane is soaked in the hydrochloric acid solution to obtain the UiO-66-NMe 3 + ⁇ Cl - membrane.
  • polymers in this embodiment is polysulfone, polytetrafluoroethylene, polyvinylidene fluoride, and the like.
  • polyvinylidene fluoride When polyvinylidene fluoride is selected, it can form a better film with UiO-66-NH 2 and increase the bonding strength between the metal organic framework material and the polymer matrix, which is beneficial to the quaternary amine of UiO-66-NH 2 ⁇ modification.
  • the mass ratio of the polymer to UiO-66-NH 2 is 1:1 to 1.5.
  • the mass ratio is 1:1.5.
  • the time for the reaction between methyl triflate and the UiO-66-NH 2 film is 10 to 14 hours.
  • the addition ratio of methyl trifluoromethanesulfonate to UiO-66-NH 2 is 8-9:6, ⁇ L:mg.
  • the addition ratio is 4:3, ⁇ L:mg.
  • the time for the immersion treatment is 10 to 14 hours.
  • the solvent for preparing the UiO-66-NH 2 membrane is one or two of acetone and N,N-dimethylformamide.
  • UiO-66-NH 2 film is: 2 acetone and the dispersion obtained UiO-66-NH UiO-66 -NH 2 dispersion, the polymer was dissolved in N, N- Dimethylformamide obtains the polymer solution, mix the polymer solution with the UiO-66-NH 2 dispersion evenly, heat to remove the acetone, spread the acetone-removed liquid on the plate, and heat the N,N-dimethyl UiO-66-NH 2 membrane is obtained by removal of methyl formamide.
  • ultrasonic dispersion in order to make UiO-66-NH 2 uniformly dispersed, ultrasonic dispersion is used.
  • the ultrasonic dispersion time is 8-12 min (for example, 10 min).
  • ultrasonic dispersion in order to mix the polymer solution and the UiO-66-NH 2 dispersion uniformly, ultrasonic dispersion is used, and the ultrasonic dispersion time is 13-17 min (for example, 15 min).
  • acetone in order to remove acetone more quickly, acetone is removed by rotary evaporation.
  • the acetone-removed liquid in order to improve the film-forming properties, is spread on the plate and heated to 65-75° C. to volatilize N,N-dimethylformamide.
  • the concentration of the polymer in the polymer solution is 3 to 7%.
  • the concentration is 5%.
  • the concentration is the mass concentration (mass percentage).
  • UiO-66-NH 2 membrane preparation UiO-66-NMe 3 + ⁇ Cl - film process to: UiO-66-NH 2 film is taken up in dichloromethane, trifluoroacetic acid methyl ester obtained UiO-66-NMe 3 + ⁇ CF 3 SO 3 - film, the UiO-66-NMe 3 + ⁇ CF 3 SO 3 - hydrochloric acid solution film is placed, soaking obtained UiO-66-NMe 3 + ⁇ Cl - film.
  • the dichloromethane after the reaction of methyl triflate is replaced multiple times. To remove unreacted methyl trifluoromethanesulfonate. The replacement interval is 11 ⁇ 13h.
  • water washing is performed after soaking.
  • the UiO-66-NH 2 described in the present invention can be synthesized by itself, or by purchasing commercially available products (named NH 2 -UiO-66 or NH 2 -UIO-66(Zr), etc., CAS number 1260119-00- 3) Obtained.
  • the invention provides a preparation method of UiO-66-NH 2 which is obtained by solvothermal reaction of zirconium tetrachloride and aminoterephthalic acid.
  • the solvothermal reaction refers to heating the organic solvent system in a closed system to make the system in a high temperature and high pressure state for reaction.
  • the solvent of the solvothermal reaction is N,N-dimethylformamide.
  • the solvothermal reaction conditions are 115-125°C for 46-50 hours.
  • the solvothermal reaction is followed by washing with N,N-dimethylformamide and ethanol. After washing with N,N-dimethylformamide, drying, and then soaking and cleaning with ethanol.
  • the present invention provides a preparation method with better effect, and the steps are as follows:
  • Step 1 Preparation of metal organic framework material UiO-66-NH 2 :
  • step (1-1) Reacting the mixture prepared in step (1-1) at 120°C in a solvothermal reactor for 48 hours;
  • (2-1) Disperse the prepared UiO-66-NH 2 in acetone, ultrasonically disperse for 10 minutes, dissolve polyvinylidene fluoride (PVDF) in DMF, and add the PVDF-dissolved DMF solution to UiO-66-NH 2 in the acetone solution, ultrasonically mix well for 15 minutes;
  • PVDF polyvinylidene fluoride
  • step (2-2) Use the rotary evaporation method to volatilize the acetone from the mixed solution prepared in step (2-1), and then spread the remaining mixed solution dropwise on the glass plate; place the glass plate in an oven at 70°C Heating to volatilize the solvent to prepare UiO-66-NH 2 film.
  • Step 3 Preparation of cationic UiO-66-NMe 3 + ⁇ Cl - metal organic framework membrane
  • the third embodiment of the present invention provides an application of the above-mentioned cationic metal organic framework membrane material in the enrichment and separation of phenoxycarboxylic acid herbicides in water.
  • the specific application method is as follows: the cationic metal organic framework membrane material is placed in water containing phenoxycarboxylic acid herbicides for adsorption, and after adsorption for a set time, the eluent is used for elution, and the eluate is subjected to UPLC- MS/MS performs detection.
  • the eluent is 1% methanol ammonia solution.
  • the fourth embodiment of the present invention provides an application of the cationic metal organic framework membrane material in the adsorption and removal of pentavalent arsenic from water.
  • the specific application method is: placing the cationic metal-organic framework membrane material in water containing pentavalent arsenic for adsorption removal, and after adsorption for a set time, the adsorbed water is detected by ICP-MS.
  • Step 1 Preparation of metal organic framework material NH 2 -UiO-66.
  • step (1-1) React the mixture prepared in step (1-1) at 120°C in a solvothermal reactor for 48 hours.
  • Step 2 Preparation of UiO-66-NH 2 mixed matrix membrane.
  • step (2-2) Use the rotary evaporation method to volatilize the acetone from the mixed solution prepared in step (2-1), and then spread the remaining mixed solution dropwise on the glass plate; place the glass plate in an oven at 70°C Heating to volatilize the solvent to prepare UiO-66-NH 2 film.
  • Step 3 Preparation of cationic UiO-66-NMe 3 + ⁇ Cl - metal organic framework membrane.
  • FIG. 1 The morphology characterization is shown in Figure 1. From Figures 1A and 1B, it can be seen that the MOF crystals with an octahedral structure are bridged together. The diameter of the MOF crystals is about 100nm. In Figure 1C and Figure 1D, the configuration of the UiO-66-NMe 3 + ⁇ Cl - ion exchange membrane MOF crystals modified by the quaternary amino group did not change significantly, indicating that the modification step did not affect the framework structure of the MOF .
  • the UiO-66-NMe 3 + ⁇ Cl - film modified by the quaternary amino group has an absorption peak of 1280 cm -1 near 1254 cm -1 , indicating that a new CN stretching vibration has appeared, and the absorption peak of 1072 cm -1 is derived from the quaternary
  • the above results prove that the synthesized membrane is a UiO-66MOF material with quaternary amino anion exchange groups.
  • the UiO-66-NMe 3 + ⁇ Cl - ion exchange membrane was subjected to XPS analysis to determine its surface chemical composition. The results are shown in Figure 4.
  • Figure 4a the characteristic peaks of C 1s, Zr 3d, O 1s, N 1s, Cl 2p, and F 1s d are located at 286.1, 182.8, 531.6, 399.6, 196.8, and 688.1 eV, respectively.
  • the high-resolution spectrum of Zr 3d in Figure 4b shows that the binding energy positions of the Zr 3d 3/2 and Zr 3d 5/2 peaks are around 185.0 eV and 182.7 eV, respectively, which are consistent with the UiO-66 reported in the previous literature.
  • the peaks of C 1s binding energy at 288.5eV, 285.4eV, 284.5eV correspond to CO, CC, and C-NMe 3 groups, respectively.
  • the N 1s XPS binding energy peaks are located at 399.0 and 400.4eV, respectively, with the nitrogen in the Ph-NMe 3 and CN groups.
  • Example 2 The UiO-66-NMe 3 + ⁇ Cl - membrane material obtained in Example 1 is used for the adsorption and enrichment of phenoxycarboxylic acid herbicides in water, the spiked concentration is 0.2 ⁇ g/L, and the adsorption time is 30 minutes , Using 5mL1% methanol ammonia solution for elution, the elution time is 30min, the eluate is dried with nitrogen and then reconstituted, detected by UPLC-MS/MS, six phenoxycarboxylic acid herbicides2, 4-dichlorophenoxybutyric acid, 2,4-dichlorophenoxypropionic acid, dimethyltetrachloride, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4 The recovery rates of 5-trichlorophenoxypropionic acid are 76%, 83%, 86%, 78%, 86%, 81%, respectively.
  • Example 3 The UiO-66-NMe 3 + ⁇ Cl - film material obtained in Example 1 is used for the adsorption and removal of pentavalent arsenic in water.
  • the initial solubility is 20mg/L
  • the adsorption time is 1 hour
  • the removal rate is 90% by ICP-MS detection.

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Abstract

Provided are a cationic metal-organic framework membrane material and a preparation method and an application. The preparation method comprises: dispersing a polymer and UiO-66-NH2 into a solvent and mixing uniformly, laying the uniformly mixed liquid and removing the solvent to obtain a UiO-66-NH2 membrane, using methyl trifluoromethanesulfonate to react with the UiO-66-NH2 membrane to implement quaternary amination of the amino group of the UiO-66-NH2 membrane, and then soaking the UiO-66-NMe3 +CF3SO3 - membrane after quaternary amination in a hydrochloric acid solution to obtain a UiO-66-NMe3 +Cl- membrane. The provided cationic metal-organic framework membrane material retains the highly efficient selective adsorption properties of the metal-organic framework material, also facilitates separation from an aqueous solution, and has a good application prospect for the removal and enrichment of anionic pollutants in water.

Description

一种阳离子型金属有机骨架膜材料及制备方法与应用Cationic metal organic framework membrane material and preparation method and application 技术领域Technical field
本发明属于金属有机骨架材料技术领域，涉及一种阳离子型金属有机骨架膜材料及制备方法与应用。The invention belongs to the technical field of metal organic framework materials, and relates to a cationic metal organic framework membrane material and a preparation method and application.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。Disclosure of the background information is only intended to increase the understanding of the overall background of the present invention, and is not necessarily regarded as an acknowledgement or any form of suggestion that the information constitutes the prior art known to those of ordinary skill in the art.
金属-有机骨架材料(metal-organic frameworks,MOFs)是一类有机-无机杂化形成的纳米多孔材料，目前是新材料领域的研究热点与前沿之一。金属-有机骨架材料主要由含有氮、氧的多齿有机配体的芳香酸或碱与无机金属中心配位键合而形成的立体网络结构晶体。由于MOFs材料将无机组分与有机组分结合在一起，故相较于传统多孔材料具有很多优点，如种类多、功能强、孔隙率和比表面积大、孔尺寸可调控性强及具有一定的生物相容性。Metal-organic frameworks (MOFs) are a class of nanoporous materials formed by organic-inorganic hybridization, and are currently one of the research hotspots and frontiers in the field of new materials. The metal-organic framework material is mainly composed of a three-dimensional network structure crystal formed by the coordination bonding of an aromatic acid or a base containing a multidentate organic ligand containing nitrogen and oxygen and an inorganic metal center. Because MOFs materials combine inorganic and organic components, they have many advantages compared to traditional porous materials, such as multiple types, strong functions, large porosity and specific surface area, strong pore size controllability, and certain Biocompatibility.
然而MOFs材料的固体粉末分散在水中时，很难进行固液分离。基于MOFs制备的膜材料既保留了MOFs的高效选择吸附性，且极大地缩短了MOFs从水相中分离的时间。申请号为201611242102.X的中国专利公开了一种对血液中重金属离子高清除的羟基修饰MOF膜的制备方法，该方法采用预辐射或共辐照方法将带双键的MOF材料接枝在高分子基底材料表面得到羟基修饰MOF膜。然而，本发明的发明人研究发现，该方法制备过程较为复杂，且MOF的负载量不高。However, when the solid powder of MOFs material is dispersed in water, it is difficult to carry out solid-liquid separation. Membrane materials prepared based on MOFs not only retain the high-efficiency selective adsorption of MOFs, but also greatly shorten the separation time of MOFs from the aqueous phase. The Chinese patent with application number 201611242102.X discloses a method for preparing a hydroxyl-modified MOF film with high removal of heavy metal ions in the blood. The method adopts a pre-irradiation or co-irradiation method to graft the MOF material with double bonds on the high A hydroxyl-modified MOF film is obtained on the surface of the molecular base material. However, the inventors of the present invention have discovered that the preparation process of this method is relatively complicated, and the loading amount of MOF is not high.
由于MOFs的带电金属中心与有机配体的相互结合，使其往往呈现电中性，限制了其在水环境中的应用，也限制了其作为吸附剂是对强极性化合物的选择吸附性。离子型金属有机骨架材料(Ionic metal-organic frameworks,iMOFs)是最近几年报道的新型MOFs材料，对其制备及应用研究目前尚处于起步阶段。离子型MOFs材料相比传统的离子交换材料吸附速度快、选择性好、吸附容量大，且某些MOFs材料比一些无机或有机离子交换剂有更好的耐酸碱性。Due to the mutual combination of the charged metal center of MOFs and the organic ligands, they tend to be neutral, which limits their application in water environments and also limits their selective adsorption of strongly polar compounds as adsorbents. Ionic metal-organic frameworks (iMOFs) are new types of MOFs reported in recent years, and research on their preparation and application is still in its infancy. Compared with traditional ion exchange materials, ionic MOFs have faster adsorption speed, better selectivity and larger adsorption capacity, and some MOFs materials have better acid and alkali resistance than some inorganic or organic ion exchangers.
UiO-66是一种以金属Zr为金属中心的MOFs材料，由无机金属单元Zr 6O 4(OH) 4，与配体中羧基氧的配位作用。一个Zr 6八面体核与12个对苯二甲酸配体配位，形成四面体和八面体两种类型的孔笼。具有大的比表面积、良好的热稳定性和化学稳定性。 UiO-66 is a kind of MOFs material with metal Zr as the metal center. It is composed of inorganic metal unit Zr 6 O 4 (OH) 4 and coordinated with the carboxyl oxygen in the ligand. A Zr 6 octahedral core is coordinated with 12 terephthalic acid ligands to form two types of tetrahedral and octahedral cages. It has a large specific surface area, good thermal and chemical stability.
发明内容Summary of the invention
本发明的目的是提供一种阳离子型金属有机骨架膜材料及制备方法与应用，该类阳离 子型金属有机骨架膜材料能够对苯氧羧酸类除草剂进行吸附富集，同时对五价砷进行吸附去除。The purpose of the present invention is to provide a cationic metal-organic framework membrane material and its preparation method and application. This type of cationic metal-organic framework membrane material can adsorb and enrich phenoxycarboxylic acid herbicides and simultaneously carry out pentavalent arsenic Adsorption removal.
为了实现上述目的，本发明的技术方案为：In order to achieve the above objective, the technical solution of the present invention is as follows:
一方面，一种阳离子型金属有机骨架膜材料，所述阳离子型金属有机骨架膜材料UiO-66-NMe 3 +·Cl -膜，是聚合物基体与离子型金属有机骨架材料形成的混合基质膜，所述离子型金属有机骨架材料为UiO-66-NMe 3 +·Cl -，所述UiO-66-NMe 3 +·Cl -为UiO-66-NH 2中的部分或全部的-NH 2基团甲基化形成-NMe 3 +基团。 On the one hand, a cationic metal organic framework membrane material, the cationic metal organic framework membrane material UiO-66-NMe 3 + ·Cl - membrane is a mixed matrix membrane formed by a polymer matrix and an ionic metal organic framework material , the ionic material is a metal organic framework UiO-66-NMe 3 + · Cl - , the UiO-66-NMe 3 + · Cl - as UiO-66-NH 2 portions or all of the -NH 2 group The group is methylated to form a -NMe 3 + group.
另一方面，一种阳离子型金属有机骨架膜材料的制备方法，将聚合物与UiO-66-NH 2分散至溶剂中混合均匀，将混合均匀的液体平铺并去除溶剂获得UiO-66-NH 2膜，采用三氟甲磺酸甲酯与UiO-66-NH 2膜进行反应，使得UiO-66-NH 2膜的氨基季胺化，再将季胺化的UiO-66-NH 2膜至于盐酸溶液中浸泡处理获得UiO-66-NMe 3 +·Cl -膜。 On the other hand, a method for preparing cationic metal organic framework membrane material is to disperse polymer and UiO-66-NH 2 into a solvent and mix uniformly, spread the uniformly mixed liquid and remove the solvent to obtain UiO-66-NH 2 film, using methyl trifluoromethanesulfonate and UiO-66-NH 2 film reactor, such that a quaternary amino UiO-66-NH 2 film amination, then quaternized UiO-66-NH 2 As for the film UiO-66-NMe 3 + ·Cl - film is obtained by soaking in hydrochloric acid solution.
第三方面，一种上述阳离子型金属有机骨架膜材料在富集分离水中苯氧羧酸类除草剂的应用。In the third aspect, an application of the above-mentioned cationic metal organic framework membrane material in the enrichment and separation of phenoxycarboxylic acid herbicides in water.
第四方面，一种上述阳离子型金属有机骨架膜材料在吸附去除水中五价砷的应用。In the fourth aspect, an application of the above-mentioned cationic metal organic framework membrane material in the adsorption and removal of pentavalent arsenic from water.
本发明的有益效果为：The beneficial effects of the present invention are:
本发明提供了一种基于UiO-66-NMe 3 +·Cl -的阳离子型金属有机骨架膜材料，经过实验表明，该膜材料能够对水中的苯氧羧酸类除草剂和五价砷进行高效选择性吸附，同时也方便从水溶液中分离。 The present invention provides a cationic metal organic framework membrane material based on UiO-66-NMe 3 + ·Cl - . Experiments show that the membrane material can effectively treat phenoxycarboxylic acid herbicides and pentavalent arsenic in water. Selective adsorption, but also easy to separate from the aqueous solution.
附图说明Description of the drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The drawings of the specification forming a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments and descriptions of the present invention are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1为本发明实施例1的扫描电镜(SEM)图，A为UiO-66-NH 2膜，B为UiO-66-NH 2膜，C为季胺基改性后的UiO-66-NMe 3 +·Cl -离子交换膜，D为季胺基改性后的UiO-66-NMe 3 +·Cl -离子交换膜； Figure 1 is a scanning electron microscope (SEM) image of Example 1 of the present invention. A is a UiO-66-NH 2 film, B is a UiO-66-NH 2 film, and C is a UiO-66-NMe modified by a quaternary amine group. 3 + ·Cl - ion exchange membrane, D is UiO-66-NMe 3 + ·Cl - ion exchange membrane modified by quaternary amine group;
图2为本发明实施例1制备的膜材料的红外光谱图，a为纯PVDF膜，b为UiO-66-NH 2膜，c为季胺基改性后的UiO-66-NMe 3 +·Cl -离子交换膜； Figure 2 is the infrared spectrum of the membrane material prepared in Example 1 of the present invention, a is a pure PVDF membrane, b is a UiO-66-NH 2 membrane, and c is a UiO-66-NMe 3 + modified by a quaternary amine group. Cl - ion exchange membrane;
图3为本发明实施例1制备的膜材料的X射线衍射图，a为UiO-66-NH 2膜，b为季氨基改性后的UiO-66-NMe 3 +·Cl -离子交换膜； Figure 3 is an X-ray diffraction diagram of the membrane material prepared in Example 1 of the present invention, a is a UiO-66-NH 2 membrane, and b is a UiO-66-NMe 3 + ·Cl - ion exchange membrane modified by a quaternary amino group;
图4为本发明实施例1制备的UiO-66-NMe 3 +·Cl -膜的XPS分析图，a为总元素图，b为Zr 3d的高分辨图，c为C1s的高分辨图，d为N1s的高分辨图。 Figure 4 is the XPS analysis diagram of the UiO-66-NMe 3 + ·Cl - film prepared in Example 1 of the present invention, a is the total element diagram, b is the high-resolution diagram of Zr 3d, c is the high-resolution diagram of C1s, and d It is a high-resolution image of N1s.
具体实施方式detailed description
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed descriptions are all exemplary and are intended to provide further descriptions of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terms used here are only for describing specific embodiments, and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should also be understood that when the terms "comprising" and/or "including" are used in this specification, they indicate There are features, steps, operations, devices, components, and/or combinations thereof.
本发明的一种典型实施方式，提供了一种阳离子型金属有机骨架膜材料，所述阳离子型金属有机骨架膜材料UiO-66-NMe 3 +·Cl -膜，是聚合物基体与离子型金属有机骨架材料形成的混合基质膜，所述离子型金属有机骨架材料为UiO-66-NMe 3 +·Cl -，所述UiO-66-NMe 3 +·Cl -为UiO-66-NH 2中的部分或全部的-NH 2基团甲基化形成-NMe 3 +基团。 A typical embodiment of the present invention provides a cationic metal-organic framework membrane material. The cationic metal-organic framework membrane material UiO-66-NMe 3 + ·Cl - membrane is a polymer matrix and ionic metal organic framework material mixed matrix membrane is formed, the ionic material is a metal organic framework UiO-66-NMe 3 + · Cl - , the UiO-66-NMe 3 + · Cl - as the UiO-66-NH 2 of Part or all of the -NH 2 groups are methylated to form -NMe 3 + groups.
混合基质膜是制备MOFs膜材料的一种新型的复合膜材料，是将MOFs晶体微粒嵌入如含有聚砜、聚四氟乙烯、聚偏二氟乙烯等聚合物基底中。既保留了MOF的多孔结构、高比表面积和选择性，又具有较高的渗透性和机械强度。The mixed matrix membrane is a new type of composite membrane material for the preparation of MOFs membrane material, which is to embed MOFs crystal particles in a polymer substrate such as polysulfone, polytetrafluoroethylene, polyvinylidene fluoride, etc. It not only retains the porous structure, high specific surface area and selectivity of MOF, but also has high permeability and mechanical strength.
本发明所述的聚合物，例如聚砜、聚四氟乙烯、聚偏二氟乙烯等。为了提高离子型金属有机骨架材料与聚合物基体的结合强度，该实施方式的一些实施例中，聚合物基体为聚偏二氟乙烯。本发明经研究发现，UiO-66-NMe 3 +·Cl -与聚偏二氟乙烯的结合强度更好，从而增加膜材料性能。 The polymer of the present invention, for example, polysulfone, polytetrafluoroethylene, polyvinylidene fluoride and the like. In order to improve the bonding strength between the ionic metal organic framework material and the polymer matrix, in some examples of this embodiment, the polymer matrix is polyvinylidene fluoride. The present invention has found through research that the bonding strength of UiO-66-NMe 3 + ·Cl - and polyvinylidene fluoride is better, thereby increasing the performance of the membrane material.
本发明的另一种实施方式，提供了一种阳离子型金属有机骨架膜材料的制备方法，将聚合物与UiO-66-NH 2分散至溶剂中混合均匀，将混合均匀的液体平铺并去除溶剂获得UiO-66-NH 2膜，采用三氟甲磺酸甲酯与UiO-66-NH 2膜进行反应，使得UiO-66-NH 2膜的氨基季胺化，再将季胺化的UiO-66-NH 2膜至于盐酸溶液中浸泡处理获得UiO-66-NMe 3 +·Cl -膜。 Another embodiment of the present invention provides a method for preparing a cationic metal-organic framework membrane material. The polymer and UiO-66-NH 2 are dispersed in a solvent and mixed uniformly, and the uniformly mixed liquid is flattened and removed the solvent to obtain UiO-66-NH 2 film, using methyl trifluoromethanesulfonate and UiO-66-NH 2 film reactor, such that a quaternary amino UiO-66-NH 2 film amination, then quaternized UiO The -66-NH 2 membrane is soaked in the hydrochloric acid solution to obtain the UiO-66-NMe 3 + ·Cl - membrane.
该实施方式对聚合物的选择聚砜、聚四氟乙烯、聚偏二氟乙烯等。当选择聚偏二氟乙烯时，能够与UiO-66-NH 2更好的成膜，增加金属有机骨架材料与聚合物基体之间的结合强度，从而有利于UiO-66-NH 2的季胺化改性。 The selection of polymers in this embodiment is polysulfone, polytetrafluoroethylene, polyvinylidene fluoride, and the like. When polyvinylidene fluoride is selected, it can form a better film with UiO-66-NH 2 and increase the bonding strength between the metal organic framework material and the polymer matrix, which is beneficial to the quaternary amine of UiO-66-NH 2化modification.
该实施方式的一些实施例中，聚合物与UiO-66-NH 2的质量比为1:1～1.5。例如质量比为1:1.5。 In some examples of this embodiment, the mass ratio of the polymer to UiO-66-NH 2 is 1:1 to 1.5. For example, the mass ratio is 1:1.5.
该实施方式的一些实施例中，三氟甲磺酸甲酯与UiO-66-NH 2膜进行反应的时间为10～14h。 In some examples of this embodiment, the time for the reaction between methyl triflate and the UiO-66-NH 2 film is 10 to 14 hours.
该实施方式的一些实施例中，三氟甲磺酸甲酯与UiO-66-NH 2的添加比为8～9:6，μL：mg。例如添加比4:3，μL：mg。 In some examples of this embodiment, the addition ratio of methyl trifluoromethanesulfonate to UiO-66-NH 2 is 8-9:6, μL:mg. For example, the addition ratio is 4:3, μL:mg.
该实施方式的一些实施例中，浸泡处理的时间为10～14h。In some examples of this embodiment, the time for the immersion treatment is 10 to 14 hours.
该实施方式的一些实施例中，制备UiO-66-NH 2膜的溶剂为丙酮、N,N-二甲基甲酰胺中的一种或两种。 In some examples of this embodiment, the solvent for preparing the UiO-66-NH 2 membrane is one or two of acetone and N,N-dimethylformamide.
该实施方式的一些实施例中，制备UiO-66-NH 2膜的过程为：采用丙酮将UiO-66-NH 2分散获得UiO-66-NH 2分散液，将聚合物溶解于N,N-二甲基甲酰胺获得聚合物溶液，将聚合物溶液与UiO-66-NH 2分散液混合均匀，加热将丙酮去除，将去除丙酮的液体平铺在板上，加热将N,N-二甲基甲酰胺去除获得UiO-66-NH 2膜。 Some embodiments of the embodiment, during the preparation of UiO-66-NH 2 film is: 2 acetone and the dispersion obtained UiO-66-NH UiO-66 -NH 2 dispersion, the polymer was dissolved in N, N- Dimethylformamide obtains the polymer solution, mix the polymer solution with the UiO-66-NH 2 dispersion evenly, heat to remove the acetone, spread the acetone-removed liquid on the plate, and heat the N,N-dimethyl UiO-66-NH 2 membrane is obtained by removal of methyl formamide.
在一种或多种实施例中，为了使UiO-66-NH 2分散均匀，采用超声分散。超声分散时间为8～12min(例如10min)。 In one or more embodiments, in order to make UiO-66-NH 2 uniformly dispersed, ultrasonic dispersion is used. The ultrasonic dispersion time is 8-12 min (for example, 10 min).
在一种或多种实施例中，为了使将聚合物溶液与UiO-66-NH 2分散液混合均匀，采用超声分散，超声分散时间为13～17min(例如15min)。 In one or more embodiments, in order to mix the polymer solution and the UiO-66-NH 2 dispersion uniformly, ultrasonic dispersion is used, and the ultrasonic dispersion time is 13-17 min (for example, 15 min).
在一种或多种实施例中，为了将丙酮更快去除，采用旋转蒸发将丙酮去除。In one or more embodiments, in order to remove acetone more quickly, acetone is removed by rotary evaporation.
在一种或多种实施例中，为了提高成膜性，将去除丙酮的液体平铺在板上，加热至65～75℃，使N,N-二甲基甲酰胺挥发。In one or more embodiments, in order to improve the film-forming properties, the acetone-removed liquid is spread on the plate and heated to 65-75° C. to volatilize N,N-dimethylformamide.
在一种或多种实施例中，聚合物溶液中聚合物的浓度为3～7％。例如浓度为5％。浓度为质量浓度(质量百分数)。In one or more embodiments, the concentration of the polymer in the polymer solution is 3 to 7%. For example, the concentration is 5%. The concentration is the mass concentration (mass percentage).
该实施方式的一些实施例中，UiO-66-NH 2膜制备UiO-66-NMe 3 +·Cl -膜的过程为：将UiO-66-NH 2膜置于二氯甲烷中，添加三氟甲磺酸甲酯反应获得UiO-66-NMe 3 +·CF 3SO 3 -膜，将UiO-66-NMe 3 +·CF 3SO 3 -膜置于盐酸溶液中，浸泡获得UiO-66-NMe 3 +·Cl -膜。 Some embodiments of the embodiment, UiO-66-NH 2 membrane preparation UiO-66-NMe 3 + · Cl - film process to: UiO-66-NH 2 film is taken up in dichloromethane, trifluoroacetic acid methyl ester obtained UiO-66-NMe 3 + · CF 3 SO 3 - film, the UiO-66-NMe 3 + · CF 3 SO 3 - hydrochloric acid solution film is placed, soaking obtained UiO-66-NMe 3 + ·Cl - film.
在一种或多种实施例中，三氟甲磺酸甲酯反应后的二氯甲烷进行多次置换。以去除未反应的三氟甲磺酸甲酯。置换的间隔时间为11～13h。In one or more embodiments, the dichloromethane after the reaction of methyl triflate is replaced multiple times. To remove unreacted methyl trifluoromethanesulfonate. The replacement interval is 11~13h.
在一种或多种实施例中，浸泡后进行水洗。In one or more embodiments, water washing is performed after soaking.
本发明中所述的UiO-66-NH 2可以自行合成，也通过购买市售产品(名称为NH 2-UiO-66或NH 2-UIO-66(Zr)等，CAS号为1260119-00-3)获得。 The UiO-66-NH 2 described in the present invention can be synthesized by itself, or by purchasing commercially available products (named NH 2 -UiO-66 or NH 2 -UIO-66(Zr), etc., CAS number 1260119-00- 3) Obtained.
本发明提供了一种UiO-66-NH 2的制备方法：将四氯化锆与氨基对苯二甲酸进行溶剂热反应获得。 The invention provides a preparation method of UiO-66-NH 2 which is obtained by solvothermal reaction of zirconium tetrachloride and aminoterephthalic acid.
所述溶剂热反应是指在密闭体系中，对有机溶剂体系进行加热，使体系处于高温高压状态，进行反应。The solvothermal reaction refers to heating the organic solvent system in a closed system to make the system in a high temperature and high pressure state for reaction.
在一种或多种实施例中，溶剂热反应的溶剂为N,N-二甲基甲酰胺。In one or more embodiments, the solvent of the solvothermal reaction is N,N-dimethylformamide.
在一种或多种实施例中，溶剂热反应的条件为115～125℃反应46～50h。In one or more embodiments, the solvothermal reaction conditions are 115-125°C for 46-50 hours.
在一种或多种实施例中，溶剂热反应后依次采用N,N-二甲基甲酰胺和乙醇进行洗涤。 采用N,N-二甲基甲酰胺洗涤后进行干燥后，再采用乙醇进行浸泡清洗。In one or more embodiments, the solvothermal reaction is followed by washing with N,N-dimethylformamide and ethanol. After washing with N,N-dimethylformamide, drying, and then soaking and cleaning with ethanol.
为了更好的获得阳离子型金属有机骨架膜材料，本发明提供了一种效果较优的制备方法，步骤如下：In order to better obtain the cationic metal-organic framework membrane material, the present invention provides a preparation method with better effect, and the steps are as follows:
步骤一：制备金属有机骨架材料UiO-66-NH 2： Step 1: Preparation of metal organic framework material UiO-66-NH 2 :
(1-1)将四氯化锆和的氨基对苯二甲酸溶于N,N-二甲基甲酰胺(DMF)溶液中充分搅拌溶解；(1-1) Dissolve zirconium tetrachloride and aminoterephthalic acid in N,N-dimethylformamide (DMF) solution and stir to dissolve;
(1-2)将步骤(1-1)中制得的混合物在溶剂热反应釜内120℃条件下反应48h；(1-2) Reacting the mixture prepared in step (1-1) at 120°C in a solvothermal reactor for 48 hours;
(1-3)将溶剂热反应釜冷却至室温，所的产物用DMF洗涤数次，在100℃条件下干燥12h，再将材料于乙醇中浸泡洗涤数次，于70℃干燥12h，制得金属有机骨架材料UiO-66-NH 2备用； (1-3) Cool the solvothermal reaction kettle to room temperature, wash the product with DMF several times, dry at 100°C for 12h, then soak the material in ethanol for washing several times, dry at 70°C for 12h, and prepare The metal organic framework material UiO-66-NH 2 is spare;
步骤二：制备UiO-66-NH 2混合基质膜 Step 2: Preparation of UiO-66-NH 2 mixed matrix membrane
(2-1)将制得的UiO-66-NH 2分散在丙酮中，超声分散10min，聚偏二氟乙烯(PVDF)溶解于DMF中，将溶有PVDF的DMF溶液加入UiO-66-NH 2的丙酮溶液中，超声充分混合15min； (2-1) Disperse the prepared UiO-66-NH 2 in acetone, ultrasonically disperse for 10 minutes, dissolve polyvinylidene fluoride (PVDF) in DMF, and add the PVDF-dissolved DMF solution to UiO-66-NH 2 in the acetone solution, ultrasonically mix well for 15 minutes;
(2-2)将步骤(2-1)中制得的混合溶液采用旋转蒸发法使丙酮挥发，再将剩余的混合溶液逐滴平铺在玻璃板上；将玻璃板置于70℃烘箱中加热使溶剂挥发，制得UiO-66-NH 2膜。 (2-2) Use the rotary evaporation method to volatilize the acetone from the mixed solution prepared in step (2-1), and then spread the remaining mixed solution dropwise on the glass plate; place the glass plate in an oven at 70°C Heating to volatilize the solvent to prepare UiO-66-NH 2 film.
步骤三：制备阳离子型UiO-66-NMe 3 +·Cl -金属有机骨架膜 Step 3: Preparation of cationic UiO-66-NMe 3 + ·Cl - metal organic framework membrane
(3-1)将制得的NH 2-UiO-66膜置于二氯甲烷中，向其中滴加三氟甲磺酸甲酯，反应12小时，所得产物为UiO-66-NMe 3 +·CF 3SO 3 -膜。 (3-1) Put the prepared NH 2 -UiO-66 membrane in dichloromethane, add methyl trifluoromethanesulfonate dropwise to it, and react for 12 hours. The resulting product is UiO-66-NMe 3 + · CF 3 SO 3 - film.
(3-2)每隔12小时置换一次二氯甲烷，以去除未反应的三氟甲磺酸甲酯。(3-2) Dichloromethane was replaced every 12 hours to remove unreacted methyl triflate.
(3-3)将UiO-66-NMe 3 +·CF 3SO 3 -膜与二氯甲烷分离，再将UiO-66-NMe 3 +·CF 3SO 3 -膜置于盐酸溶液中，浸泡12小时，使其形成具有离子交换基团的UiO-66-NMe 3 +·Cl -膜。 (3-3) The UiO-66-NMe 3 + · CF 3 SO 3 - separation membrane with dichloromethane, then UiO-66-NMe 3 + · CF 3 SO 3 - hydrochloric acid solution film is placed, soaking 12 After hours, it forms a UiO-66-NMe 3 + ·Cl - membrane with ion exchange groups.
(3-4)将UiO-66-NMe 3 +·Cl -膜用超纯水洗涤数次，直至洗涤液呈中性。 (3-4) Wash the UiO-66-NMe 3 + ·Cl - membrane several times with ultrapure water until the washing solution is neutral.
本发明的第三种实施方式，提供了一种上述阳离子型金属有机骨架膜材料在富集分离水中苯氧羧酸类除草剂的应用。The third embodiment of the present invention provides an application of the above-mentioned cationic metal organic framework membrane material in the enrichment and separation of phenoxycarboxylic acid herbicides in water.
具体的应用方法为：将阳离子型金属有机骨架膜材料放置在含有苯氧羧酸类除草剂的水中进行吸附，吸附设定时间后，采用洗脱剂进行洗脱，对洗脱液进行UPLC-MS/MS进行检测。洗脱剂为1％的甲醇氨水溶液。The specific application method is as follows: the cationic metal organic framework membrane material is placed in water containing phenoxycarboxylic acid herbicides for adsorption, and after adsorption for a set time, the eluent is used for elution, and the eluate is subjected to UPLC- MS/MS performs detection. The eluent is 1% methanol ammonia solution.
本发明的第四种实施方式，提供了一种上述阳离子型金属有机骨架膜材料在吸附去除水中五价砷的应用。The fourth embodiment of the present invention provides an application of the cationic metal organic framework membrane material in the adsorption and removal of pentavalent arsenic from water.
具体的应用方法为：将阳离子型金属有机骨架膜材料放置在含有五价砷的水中进行吸附去除，吸附设定时间后，通过ICP-MS对吸附后水进行检测。The specific application method is: placing the cationic metal-organic framework membrane material in water containing pentavalent arsenic for adsorption removal, and after adsorption for a set time, the adsorbed water is detected by ICP-MS.
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的 实施例详细说明本发明的技术方案。In order to enable those skilled in the art to understand the technical solutions of the present invention more clearly, the technical solutions of the present invention will be described in detail below in conjunction with specific embodiments.
实施例1Example 1
步骤一：制备金属有机骨架材料NH 2-UiO-66。 Step 1: Preparation of metal organic framework material NH 2 -UiO-66.
(1-1)将0.23g的四氯化锆和0.16g的氨基对苯二甲酸溶于50mLN,N-二甲基甲酰胺(DMF)溶液中充分搅拌溶解。(1-1) Dissolve 0.23 g of zirconium tetrachloride and 0.16 g of aminoterephthalic acid in 50 mL of N,N-dimethylformamide (DMF) solution and fully stir to dissolve them.
(1-2)将步骤(1-1)中制得的混合物在溶剂热反应釜内120℃条件下反应48h。(1-2) React the mixture prepared in step (1-1) at 120°C in a solvothermal reactor for 48 hours.
(1-3)将溶剂热反应釜冷却至室温，所的产物用DMF洗涤数次，在100℃条件下干燥12h，再将材料于乙醇中浸泡洗涤数次，于70℃干燥12h，制得金属有机骨架材料UiO-66-NH 2备用。 (1-3) Cool the solvothermal reaction kettle to room temperature, wash the product with DMF several times, dry at 100°C for 12h, then soak the material in ethanol for washing several times, dry at 70°C for 12h, and prepare The metal organic framework material UiO-66-NH 2 is reserved.
步骤二：制备UiO-66-NH 2混合基质膜。 Step 2: Preparation of UiO-66-NH 2 mixed matrix membrane.
(2-1)将40mg制得的UiO-66-NH 2分散在丙酮中，超声分散10min，40mg聚偏二氟乙烯(PVDF)溶解于DMF中，将溶有PVDF的DMF溶液加入UiO-66-NH 2的丙酮溶液中，超声充分混合15min。 (2-1) Disperse 40 mg of UiO-66-NH 2 prepared in acetone, disperse ultrasonically for 10 minutes, dissolve 40 mg of polyvinylidene fluoride (PVDF) in DMF, and add the PVDF-dissolved DMF solution to UiO-66 -NH 2 in acetone solution, ultrasonically mix well for 15 minutes.
(2-2)将步骤(2-1)中制得的混合溶液采用旋转蒸发法使丙酮挥发，再将剩余的混合溶液逐滴平铺在玻璃板上；将玻璃板置于70℃烘箱中加热使溶剂挥发，制得UiO-66-NH 2膜。 (2-2) Use the rotary evaporation method to volatilize the acetone from the mixed solution prepared in step (2-1), and then spread the remaining mixed solution dropwise on the glass plate; place the glass plate in an oven at 70°C Heating to volatilize the solvent to prepare UiO-66-NH 2 film.
步骤三：制备阳离子型UiO-66-NMe 3 +·Cl -金属有机骨架膜。 Step 3: Preparation of cationic UiO-66-NMe 3 + ·Cl - metal organic framework membrane.
(3-1)将制得的UiO-66-NH 2膜置于二氯甲烷中，向其中滴加60μL的三氟甲磺酸甲酯，反应12小时，所得产物为UiO-66-NMe 3 +·CF 3SO 3 -膜。 (3-1) Put the prepared UiO-66-NH 2 membrane in dichloromethane, add 60 μL of methyl trifluoromethanesulfonate dropwise to it, and react for 12 hours. The resulting product is UiO-66-NMe 3 + · CF 3 SO 3 - membrane.
(3-2)每隔12小时置换一次二氯甲烷，以去除未反应的三氟甲磺酸甲酯。(3-2) Dichloromethane was replaced every 12 hours to remove unreacted methyl triflate.
(3-3)将UiO-66-NMe 3 +·CF 3SO 3 -膜与二氯甲烷分离，再将UiO-66-NMe 3 +·CF 3SO 3 -膜置于盐酸(0.1mol/L)溶液中，浸泡12小时，使其形成具有离子交换基团的UiO-66-NMe 3 +·Cl -膜。 (3-3) The UiO-66-NMe 3 + · CF 3 SO 3 - separation membrane with dichloromethane, then UiO-66-NMe 3 + · CF 3 SO 3 - membrane is placed (0.1mol / L hydrochloric acid ) Soak in the solution for 12 hours to form a UiO-66-NMe 3 + ·Cl - membrane with ion exchange groups.
(3-4)将UiO-66-NMe 3 +·Cl -膜用超纯水洗涤数次，直至洗涤液呈中性。 (3-4) Wash the UiO-66-NMe 3 + ·Cl - membrane several times with ultrapure water until the washing solution is neutral.
对制备过程中各膜材料进行如下表征：The following characterization of each membrane material during the preparation process:
形貌表征如图1所示，由图1A和图1B可以看到八面体结构的MOF晶体桥联在一起，MOF晶体的直径大约为100nm。图1C、图1D中，季氨基改性后的UiO-66-NMe 3 +·Cl -离子交换膜MOF晶体的构型并未发生明显变化，说明改性步骤并未对MOF的骨架结构造成影响。 The morphology characterization is shown in Figure 1. From Figures 1A and 1B, it can be seen that the MOF crystals with an octahedral structure are bridged together. The diameter of the MOF crystals is about 100nm. In Figure 1C and Figure 1D, the configuration of the UiO-66-NMe 3 + ·Cl - ion exchange membrane MOF crystals modified by the quaternary amino group did not change significantly, indicating that the modification step did not affect the framework structure of the MOF .
红外光谱分析如图2所示，1496cm -1和1655cm -1的吸收峰表明-O-C-O-键的存在，1386cm -1和1571cm -1的吸收峰是由于C＝C键的伸缩振动，1254cm -1and 967cm -1的吸收峰来自于C-N伸缩振动，证明骨架结构中的氨基对苯二甲酸配体的存在。季氨基改性后的UiO-66-NMe 3 +·Cl -膜在1254cm -1附近出现1280cm -1的吸收峰，表明出现了新的C-N伸缩振动，而1072cm -1的吸收峰是来自于季氨基，以上结果证明合成的膜是一种存在季氨基阴离子交换基团的UiO-66MOF材料。 IR spectrum shown in Figure 2, 1496cm -1 and an absorption peak of 1655cm -1 indicating the presence -OCO- bond, 1386cm -1 to 1571cm -1 and an absorption peak due to stretching vibration of C = C bond, 1254cm -1 The absorption peak of and 967cm -1 comes from the CN stretching vibration, which proves the existence of aminoterephthalic acid ligand in the skeleton structure. The UiO-66-NMe 3 + ·Cl - film modified by the quaternary amino group has an absorption peak of 1280 cm -1 near 1254 cm -1 , indicating that a new CN stretching vibration has appeared, and the absorption peak of 1072 cm -1 is derived from the quaternary The above results prove that the synthesized membrane is a UiO-66MOF material with quaternary amino anion exchange groups.
XRD分析如图3所示，在2θ＝7.4、8.6、25.8°的峰是UiO-66系列的特征峰，季氨基改性后的UiO-66-NMe 3 +·Cl -离子交换膜与UiO-66-NH 2膜具有这些吸收峰的存在，说明改性步骤并未对MOF的晶体结构造成影响。 XRD analysis shown in Figure 3, the peak of 2θ = 7.4,8.6,25.8 ° is a characteristic peak of UiO-66 series, UiO-66-NMe the quaternary amino modified 3 + · Cl - ion exchange membrane and UiO- The 66-NH 2 film has these absorption peaks, indicating that the modification step did not affect the crystal structure of MOF.
对UiO-66-NMe 3 +·Cl -离子交换膜进行XPS分析，确定其表面化学组成，结果如图4所示。图4a中，C 1s,Zr 3d,O 1s,N 1s,Cl 2p,F 1s d的特征峰分别位于286.1,182.8,531.6,399.6,196.8,688.1eV。图4b中Zr 3d的高分辨图谱表明Zr 3d 3/2和Zr 3d 5/2峰的结合能位置分别在185.0eV和182.7eV左右，与之前文献报道中的UiO-66一致。图4c中C 1s结合能位于288.5eV,285.4eV,284.5eV的峰分别对应C-O,C-C,C-NMe 3基团。此外图4d中N 1s XPS结合能位于399.0和400.4eV的峰分别Ph-NMe 3和C-N基团中的氮。 The UiO-66-NMe 3 + ·Cl - ion exchange membrane was subjected to XPS analysis to determine its surface chemical composition. The results are shown in Figure 4. In Figure 4a, the characteristic peaks of C 1s, Zr 3d, O 1s, N 1s, Cl 2p, and F 1s d are located at 286.1, 182.8, 531.6, 399.6, 196.8, and 688.1 eV, respectively. The high-resolution spectrum of Zr 3d in Figure 4b shows that the binding energy positions of the Zr 3d 3/2 and Zr 3d 5/2 peaks are around 185.0 eV and 182.7 eV, respectively, which are consistent with the UiO-66 reported in the previous literature. In Figure 4c, the peaks of C 1s binding energy at 288.5eV, 285.4eV, 284.5eV correspond to CO, CC, and C-NMe 3 groups, respectively. In addition, in Figure 4d, the N 1s XPS binding energy peaks are located at 399.0 and 400.4eV, respectively, with the nitrogen in the Ph-NMe 3 and CN groups.
综上所述，季氨基改性的阳离子型UiO-66MOFs材料已成功制备。In summary, the cationic UiO-66MOFs materials modified by quaternary amino groups have been successfully prepared.
实施例2：将实施例1得到的UiO-66-NMe 3 +·Cl -膜材料用于水中苯氧羧酸类除草剂的吸附富集，加标浓度为0.2μg/L，吸附时间30分钟，采用5mL1％的甲醇氨水溶液进行洗脱，洗脱时间为30min，将洗脱液用氮气吹干后复溶，通过UPLC-MS/MS进行检测，六种苯氧羧酸类除草剂2,4-二氯苯氧丁酸、2,4-二氯苯氧丙酸、二甲四氯、2,4-二氯苯氧乙酸、2,4,5-三氯苯氧乙酸、2,4,5-三氯苯氧丙酸的回收率分别为76％、83％、86％、78％、86％、81％。 Example 2: The UiO-66-NMe 3 + ·Cl - membrane material obtained in Example 1 is used for the adsorption and enrichment of phenoxycarboxylic acid herbicides in water, the spiked concentration is 0.2 μg/L, and the adsorption time is 30 minutes , Using 5mL1% methanol ammonia solution for elution, the elution time is 30min, the eluate is dried with nitrogen and then reconstituted, detected by UPLC-MS/MS, six phenoxycarboxylic acid herbicides2, 4-dichlorophenoxybutyric acid, 2,4-dichlorophenoxypropionic acid, dimethyltetrachloride, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4 The recovery rates of 5-trichlorophenoxypropionic acid are 76%, 83%, 86%, 78%, 86%, 81%, respectively.
实施例3：将实施例1得到的UiO-66-NMe 3 +·Cl -膜材料用于水中五价砷的吸附去除。初始溶度为20mg/L，吸附时间为1小时，通过ICP-MS进行检测，去除率达到90％。 Example 3: The UiO-66-NMe 3 + ·Cl - film material obtained in Example 1 is used for the adsorption and removal of pentavalent arsenic in water. The initial solubility is 20mg/L, the adsorption time is 1 hour, and the removal rate is 90% by ICP-MS detection.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

  1. 一种阳离子型金属有机骨架膜材料，其特征是，所述阳离子型金属有机骨架膜材料UiO-66-NMe 3 +·Cl -膜，是聚合物基体与离子型金属有机骨架材料形成的混合基质膜，所述离子型金属有机骨架材料为UiO-66-NMe 3 +·Cl -，所述UiO-66-NMe 3 +·Cl -为UiO-66-NH 2中的部分或全部的-NH 2基团甲基化形成-NMe 3 +基团。 A cationic metal organic framework membrane material, characterized in that the cationic metal organic framework membrane material UiO-66-NMe 3 + ·Cl - membrane is a mixed matrix formed by a polymer matrix and an ionic metal organic framework material membrane, the ionic material is a metal organic framework UiO-66-NMe 3 + · Cl - , the UiO-66-NMe 3 + · Cl - as part of UiO-66-NH 2 or all of -NH 2 The group is methylated to form a -NMe 3 + group.
  2. 如权利要求1所述的阳离子型金属有机骨架膜材料，其特征是，聚合物基体为聚偏二氟乙烯。The cationic metal organic framework membrane material of claim 1, wherein the polymer matrix is polyvinylidene fluoride.
  3. 一种阳离子型金属有机骨架膜材料的制备方法，其特征是，将聚合物与UiO-66-NH 2分散至溶剂中混合均匀，将混合均匀的液体平铺并去除溶剂获得UiO-66-NH 2膜，采用三氟甲磺酸甲酯与UiO-66-NH 2膜进行反应，使得UiO-66-NH 2膜的氨基季胺化，再将季胺化的UiO-66-NH 2膜至于盐酸溶液中浸泡处理获得UiO-66-NMe 3 +·Cl -膜。 A method for preparing cationic metal-organic framework membrane material, which is characterized in that the polymer and UiO-66-NH 2 are dispersed in a solvent and mixed uniformly, the uniformly mixed liquid is laid flat and the solvent is removed to obtain UiO-66-NH 2 film, using methyl trifluoromethanesulfonate and UiO-66-NH 2 film reactor, such that a quaternary amino UiO-66-NH 2 film amination, then quaternized UiO-66-NH 2 As for the film UiO-66-NMe 3 + ·Cl - film is obtained by soaking in hydrochloric acid solution.
  4. 如权利要求3所述的阳离子型金属有机骨架膜材料的制备方法，其特征是，聚合物为聚偏二氟乙烯。The method for preparing cationic metal organic framework membrane material according to claim 3, wherein the polymer is polyvinylidene fluoride.
  5. 如权利要求3所述的阳离子型金属有机骨架膜材料的制备方法，其特征是，聚合物与UiO-66-NH 2的质量比为1:1～1.5。 The method for preparing cationic metal-organic framework membrane material according to claim 3, wherein the mass ratio of polymer to UiO-66-NH 2 is 1:1 to 1.5.
  6. 如权利要求3所述的阳离子型金属有机骨架膜材料的制备方法，其特征是，三氟甲磺酸甲酯与UiO-66-NH 2的添加比为8～9:6，μL：mg。 The method for preparing cationic metal-organic framework membrane material according to claim 3, characterized in that the addition ratio of methyl trifluoromethanesulfonate to UiO-66-NH 2 is 8-9:6, μL:mg.
  7. 如权利要求3所述的阳离子型金属有机骨架膜材料的制备方法，其特征是，制备UiO-66-NH 2膜的过程为：采用丙酮将UiO-66-NH 2分散获得UiO-66-NH 2分散液，将聚合物溶解于N,N-二甲基甲酰胺获得聚合物溶液，将聚合物溶液与UiO-66-NH 2分散液混合均匀，加热将丙酮去除，将去除丙酮的液体平铺在板上，加热将N,N-二甲基甲酰胺去除获得UiO-66-NH 2膜。 The method for preparing cationic metal-organic framework membrane material according to claim 3, characterized in that the process of preparing UiO-66-NH 2 membrane is: dispersing UiO-66-NH 2 with acetone to obtain UiO-66-NH 2 Dispersion solution, dissolve the polymer in N,N-dimethylformamide to obtain a polymer solution, mix the polymer solution with the UiO-66-NH 2 dispersion evenly, heat to remove the acetone, and make the acetone-removed liquid level Spread on a plate, heat to remove N,N-dimethylformamide to obtain UiO-66-NH 2 film.
  8. 如权利要求3所述的阳离子型金属有机骨架膜材料的制备方法，其特征是，UiO-66-NH 2膜制备UiO-66-NMe 3 +·Cl -膜的过程为：将UiO-66-NH 2膜置于二氯甲烷中，添加三氟甲磺酸甲酯反应获得UiO-66-NMe 3 +·CF 3SO 3 -膜，将UiO-66-NMe 3 +·CF 3SO 3 -膜置于盐酸溶液中，浸泡获得UiO-66-NMe 3 +·Cl -膜。 The method for preparing cationic metal-organic framework membrane material according to claim 3, characterized in that the process of preparing UiO-66-NMe 3 + ·Cl - membrane from UiO-66-NH 2 membrane is: UiO-66- NH 2 film is taken up in dichloromethane, was added methyl trifluoromethanesulfonate obtained by reacting UiO-66-NMe 3 + · CF 3 SO 3 - film, the UiO-66-NMe 3 + · CF 3 SO 3 - film Place it in a hydrochloric acid solution and soak to obtain a UiO-66-NMe 3 + ·Cl - film.
  9. 一种权利要求1或2所述的阳离子型金属有机骨架膜材料或权利要求3～8任一所述的制备方法获得的阳离子型金属有机骨架膜材料在富集分离水中苯氧羧酸类除草剂的应用。A cationic metal-organic framework membrane material according to claim 1 or 2 or a cationic metal-organic framework membrane material obtained by a preparation method according to any one of claims 3 to 8 in the enrichment and separation of water with phenoxycarboxylic acids for weeding The application of the agent.
  10. 一种权利要求1或2所述的阳离子型金属有机骨架膜材料或权利要求3～8任一所述的制备方法获得的阳离子型金属有机骨架膜材料在吸附去除水中五价砷的应用。An application of the cationic metal-organic framework membrane material of claim 1 or 2 or the cationic metal-organic framework membrane material obtained by the preparation method of any one of claims 3 to 8 in the adsorption and removal of pentavalent arsenic from water.
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