CN109021246B - Temperature-responsive metal organic framework nanocrystal and preparation method and application thereof - Google Patents
Temperature-responsive metal organic framework nanocrystal and preparation method and application thereof Download PDFInfo
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- CN109021246B CN109021246B CN201810941155.3A CN201810941155A CN109021246B CN 109021246 B CN109021246 B CN 109021246B CN 201810941155 A CN201810941155 A CN 201810941155A CN 109021246 B CN109021246 B CN 109021246B
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a temperature-responsive metal organic framework nano crystal, a preparation method and application thereof. The MOFs nanocrystal has an excellent temperature control oil-water separation effect, and can be separated and recycled through temperature change after the reaction of a Pickering emulsion catalytic system.
Description
Technical Field
The invention belongs to the technical field of nano functional materials, and relates to preparation and catalytic application of Pickering emulsion based on temperature-responsive metal organic framework nanocrystals.
Background
Metal-Organic Frameworks (MOFs), which are Organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of Organic ligands and Metal ions or clusters through coordination bonds. Different types of MOFs materials have been prepared in the past years, and have important applications in the fields of hydrogen storage, gas adsorption and separation, sensors, drug slow release, catalytic reaction and the like. In the aspect of gas adsorption and separation, MOFs materials with excellent adsorption performance are synthesized to be used for hydrogen storage and adsorption and separation of toxic and harmful gases, and the increasingly serious environmental problem faced by some people can be solved. In the aspect of catalytic application, the composite MOFs material with high-efficiency catalytic function is constructed by mixing different metals, so that the catalytic efficiency is further improved. In addition, in the separation field, the prepared magnetic composite MOFs material can be used for adsorbing and separating toxic and harmful substances and heavy metals and extracting and separating target proteins in a complex system. Particularly in the biomedical field, due to controllable pore size, functional groups and good biocompatibility, the prepared nanoscale MOFs material is used for drug slow release and metabolism in living cells, real-time monitoring of activities of a living body and the like, and has great biological significance for people to know important life activities (such as functions of proteins and interactions among proteins) in the living body, an activation mechanism for regulating and controlling the proteins, protein regulation and control channels related to major diseases and the like. Therefore, the development of the MOFs with functional diversity and the composite MOFs material, and the application of the MOFs material in different fields can greatly promote the mutual development among disciplines.
Ultrafine solid particles can be used as oil-in-water or water-in-oil emulsifiers, and such emulsion systems are known as Pickering emulsions, the type of emulsion obtained depending on which phase preferentially wets the solid particles, usually one phase of the preferentially wetting solid particles being the external phase, also known as the continuous phase. If sometimes the solid particles are more wettable by the oil phase, the emulsion is of the W/O (water-in-oil) type; conversely, if the solid particles are more wettable by the aqueous phase, the emulsion is of the O/W (oil in water) type. The granular emulsifier is a key component in Pickering emulsion, and the solid powder used as the emulsifier comprises inorganic granular emulsifiers such as clay, silicon dioxide, metal hydroxide, graphite, carbon black and the like and organic granular emulsifiers. The Pickering emulsion has a plurality of application prospects, and particularly arouses great interest in the fields of drug slow release, Janus microsphere preparation, porous materials and the like.
Stimulus responsive polymers are a class of macromolecular systems with "smart" behavior. It can receive the stimulation signals of external environment, such as pH value, light, temperature, voltage, redox agent and gas, etc. to make the macromolecular conformation or state produce large change, so that it can affect its physicochemical properties, and can implement correspondent function. A large number of research results show that the stimulus-responsive polymer has wide application prospects in the fields of nano-material science, life science and clinical medicine, particularly has temperature responsiveness, is very easy to regulate and control, has no damage to a system, and has higher research significance.
Disclosure of Invention
In order to solve the defects of the prior art, one of the purposes of the invention is to provide a temperature-responsive metal organic framework nanocrystal, the MOFs nanocrystal is used as a particle emulsifier to prepare Pickering emulsion, so that the traditional oil-water-solid three-phase catalytic system of MOFs is converted into a Pickering emulsion catalytic system, the reaction interface is increased, the reaction efficiency is greatly improved, and meanwhile, the MOFs nanocrystal has an excellent temperature-control oil-water separation effect and can be separated and recycled through temperature change after the reaction of the Pickering emulsion catalytic system.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a temperature-responsive metal-organic framework nanocrystal comprises a metal-organic framework nanomaterial and a temperature-responsive polymer, wherein the temperature-responsive polymer is combined with the metal-organic framework nanomaterial through a thioether bond formed by a click chemistry method, and the metal-organic framework nanomaterial is a metal-organic framework material with a surface containing double bonds and obtained through chemical modification.
Another object of the present invention is to provide a method for preparing the temperature-responsive metal-organic framework nanocrystal, which comprises the steps of:
(1) taking a metal organic framework containing a primary amine group as a raw material, and modifying the primary amine group into a group containing a double bond to obtain a metal organic framework material with the surface containing the double bond;
(2) adding 2,2' - (thiocarbonylbis (sulfonamido)) bis (2-methylpropanoic acid) (CTA) into a temperature-responsive monomer to perform reversible addition-fragmentation chain transfer (RAFT) polymerization, and reducing trithiocarbonate groups into mercapto groups through aminolysis to obtain a temperature-responsive polymer with the terminal being a mercapto group;
(3) and (2) carrying out addition reaction of sulfydryl and double bonds on the temperature-responsive polymer with the tail end being sulfydryl and the metal organic framework material with the surface containing the double bonds by adopting a sulfydryl-alkene click chemical reaction so as to obtain the temperature-responsive metal organic framework nanocrystal.
The method for grafting the temperature-responsive polymer on the surface of the metal organic framework material also comprises an in-situ polymerization method, namely, the metal organic framework material with double bonds on the surface and the temperature-responsive monomer are directly subjected to free radical polymerization, however, the earlier experiments of the inventor of the invention find that the polymerization degree and the grafting density of the grafted temperature-responsive polymer are difficult to control through the in-situ polymerization method, so that the interface activity of the prepared temperature-responsive metal organic framework nanocrystal is not obviously changed along with the temperature, the temperature responsiveness is extremely poor, and the efficient temperature-controlled oil-water separation is difficult to realize.
The invention also aims to provide an application of the temperature-responsive metal organic framework nanocrystal in a Pickering emulsion system.
The fourth object of the present invention is to provide a catalyst, wherein the temperature-responsive metal-organic framework nanocrystals are used as a carrier to support metal palladium.
The fifth purpose of the invention is to provide the application of the catalyst in the heterogeneous catalysis of a Pickering emulsion system on dechlorination reaction.
The invention also aims to provide a catalytic dechlorination method, which comprises the steps of preparing a Pickering emulsion from an organic solvent, water, a chlorine-containing substrate, ammonium formate and the catalyst, and reacting the Pickering emulsion, wherein the chlorine-containing substrate is an organic matter directly connected with a benzene ring.
The invention has the beneficial effects that:
(1) the invention provides a temperature-responsive metal organic framework nanocrystal, which can be used as a particle emulsifier to prepare Pickering emulsion, so that traditional oil-water-solid three phases catalyzed by MOFs are converted into a Pickering emulsion catalysis system, a reaction interface is increased, the reaction efficiency is greatly improved, and meanwhile, the MOFs nanocrystal has an excellent temperature-control oil-water separation effect and can be separated and recycled through temperature change after the reaction of the Pickering emulsion catalysis system.
(2) The catalyst prepared by the temperature-responsive metal organic framework nanocrystal loaded with palladium has good catalytic performance and temperature-controlled oil-water separation effect when used for catalytic dechlorination, and the catalytic effect of the catalyst is almost unchanged after multiple times of separation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a synthetic route;
FIG. 2 shows UiO-66-NH2A TEM image of the nanocrystals;
FIG. 3 is a TEM image of UiO-66-Met nanocrystals;
FIG. 4 shows nuclear magnetic hydrogen spectra of PNIPAM-CTA and PNIPAM-SH;
FIG. 5 is a gel permeation chromatogram of PNIPAM-CTA and PNIPAM-SH;
FIG. 6 is a UV spectrum of PNIPAM-CTA and PNIPAM-SH;
FIG. 7 is a TEM image of UiO-66-S-PNIPAM nanocrystals;
FIG. 8 is a nuclear magnetic hydrogen spectrum of the synthetic process of UiO-66-S-PNIPAM;
FIG. 9 is an IR spectrum of UiO-66-S-PNIPAM;
FIG. 10 is a TEM image of Pd @ UiO-66-S-PNIPAM nanocrystals;
FIG. 11 is an EDS diagram of Pd @ UiO-66-S-PNIPAM nanocrystals;
FIG. 12 is a PXRD combination spectrum of synthetic nanocrystals;
FIG. 13 shows the photomicrographs of the emulsion and confocal microscope with different Pd @ UiO-66-S-PNIPAM contents;
FIG. 14 shows the photomicrographs of emulsions and confocal images with different oil-water ratios;
FIG. 15 is a photograph of the temperature response of an emulsion;
FIG. 16 is a model reaction equation for dechlorination;
FIG. 17 is a chart of gas phase monitoring for dechlorination reaction;
FIG. 18 is a nuclear magnetic hydrogen spectrum of the catalytic product;
FIG. 19 is the five cycle yield;
FIG. 20 is a five cycle powder;
FIG. 21 is a TEM image of catalyzed Pd @ UiO-66-S-PNIPAM nanocrystals;
FIG. 22 is an EDS plot of Pd @ UiO-66-S-PNIPAM nanocrystals after catalysis;
FIG. 23 is a nuclear magnetic hydrogen spectrum of nanocrystals prepared by in situ polymerization of example 12;
FIG. 24 is a gel permeation chromatogram of nanocrystals prepared by the in situ polymerization method of example 12;
FIG. 25 is a photograph of nanocrystals prepared by in situ polymerization in example 12 at different temperatures in an oil and water system.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the prior art does not have the defect of realizing the recovery and separation of the metal organic framework material by controlling the temperature change, and in order to solve the technical problems, the application provides a temperature-responsive metal organic framework nanocrystal and a preparation method and application thereof.
The application provides a temperature-responsive metal-organic framework nanocrystal, which comprises a metal-organic framework nanomaterial and a temperature-responsive polymer, wherein the temperature-responsive polymer is combined with the metal-organic framework nanomaterial through a thioether bond formed by a click chemical method, and the metal-organic framework nanomaterial is a metal-organic framework material with a surface containing double bonds and obtained by chemical modification.
The metal organic framework material is a metal organic framework with a primary amine group on the surface, such as UiO-66-NH2、UiO-67-NH2、NH2MIL-101 and the like. The temperature-responsive polymer is a polymer which can generate large transition of material chemical characteristics and conformational states by sensing external temperature change, such as poly-N-isopropylacrylamide (PNIPAM) and the like, and in the typical embodiment of the application, the metal organic framework material is UiO-66-NH2The temperature-responsive polymer is poly-N-isopropylacrylamide. The polymerization degree of the poly-N-isopropylacrylamide is 10-300. The number average molecular weight of the poly-N-isopropylacrylamide is 2000-5000 Da. The polymerization degree is an average value of the number of repeating units contained in a polymer macromolecular chain.
The application also provides a preparation method of the temperature-responsive metal organic framework nanocrystal, which comprises the following steps:
(1) taking a metal organic framework containing a primary amine group as a raw material, and modifying the primary amine group into a group containing a double bond to obtain a metal organic framework material with the surface containing the double bond;
(2) adding 2,2' - (thiocarbonylbis (sulfonamido)) bis (2-methylpropanoic acid) (CTA) into a temperature-responsive monomer to perform reversible addition-fragmentation chain transfer (RAFT) polymerization, and reducing trithiocarbonate groups into mercapto groups through aminolysis to obtain a temperature-responsive polymer with the terminal being a mercapto group;
(3) and (2) carrying out addition reaction of sulfydryl and double bonds on the temperature-responsive polymer with the tail end being sulfydryl and the metal organic framework material with the surface containing the double bonds by adopting a sulfydryl-alkene click chemical reaction so as to obtain the temperature-responsive metal organic framework nanocrystal.
In the preparation method of the typical temperature-responsive metal organic framework nanocrystal, the metal organic framework containing primary amine groups is UiO-66-NH2. The synthesis method refers to CN106928465A, 2-amino-1, 4-terephthalic acid, zirconium tetrachloride and acetic acid are dissolved in N, N-dimethylformamide, the temperature is kept constant at 120 ℃ for 24 hours, the temperature is reduced to room temperature, and the metal organic framework is obtained after centrifugal drying.
In one embodiment of the present application, in step (1), a metal organic framework containing a primary amine group is reacted with methacrylic anhydride such that the primary amine group reacts with methacrylic anhydride to form a peptide bond. The method comprises the following specific steps: mixing UiO-66-NH2Dissolving the crystal, methacrylic anhydride and triethylamine in chloroform, and heating and refluxing for 1-48 h at 25-88 ℃. Wherein, chloroform is dried, and triethylamine is steamed again, prevents impurity influence reaction efficiency. UiO-66-NH2The feeding ratio of the crystal, methacrylic anhydride, triethylamine and trichloromethane is 0.001: 0.008: 0.001: 25, mol: mol: mol: and (mL).
The temperature-responsive monomer described herein is an organic substance capable of obtaining a temperature-responsive polymer by double bond polymerization, such as N-isopropylacrylamide (NIPAM), and in one embodiment of the present disclosure, in step (2), RAFT polymerization conditions are as follows: and heating to 70-75 ℃ under the inert gas atmosphere, and reacting for 24-36 h. The inert gas is a gas capable of preventing oxidation of oxygen, such as nitrogen, argon, etc. The reaction is simple as follows:
in one embodiment of the present application, in the step (2), the step of aminolysis is: and (3) reacting the polymer subjected to RAFT polymerization with ethanolamine and tributylphosphine at room temperature in an inert gas atmosphere. The room temperature is 15-35 ℃. In order to mix the polymer after RAFT polymerization with ethanolamine and tributylphosphine uniformly and accelerate the reaction rate, the aminolysis reaction needs to be carried out in a solvent, and the solvent is preferably 1, 4-dioxane. The reaction is simple as follows:
in one embodiment of the present application, in step (3), the reaction conditions are: adding ultraviolet initiator to react under the irradiation of ultraviolet light. The ultraviolet light initiator is preferably 2, 2-dimethoxy-2-phenylacetophenone, and the ultraviolet light has a wavelength of 365 nm. The reaction is simple as follows:
the application also provides an application of the temperature-responsive metal organic framework nanocrystal in a Pickering emulsion system.
The application also provides a catalyst, which takes the temperature-responsive metal organic framework nano crystal as a carrier to load metal palladium.
One embodiment of the present application for supporting metallic palladium using temperature-responsive metal-organic framework nanocrystals as a carrier is to impregnate the temperature-responsive metal-organic framework nanocrystals with a palladium acetate solution, remove the solvent, and then reduce divalent palladium under the action of a reducing agent. Wherein the content of the metal palladium in the catalyst is 3-4% by mass. The reaction is simple as follows:
the application also provides an application of the catalyst in catalysis of a Pickering emulsion system to dechlorination reaction.
The application also provides a catalytic dechlorination method, which comprises the steps of preparing a Pickering emulsion from an organic solvent, water, a chlorine-containing substrate, ammonium formate and the catalyst, and reacting, wherein the chlorine-containing substrate is an organic matter directly connected with a benzene ring. The reaction is simple as follows:
in one embodiment of the present application, the Pickering emulsion has a solid content of 1 to 2 wt%. The Pickering emulsion with solid content is stable in state, wherein the Pickering emulsion is most stable when the solid content is 2 wt%. Meanwhile, when the volume ratio of the oil phase to the water phase in the Pickering emulsion is 3:1, the formed Pickering emulsion is more stable.
The reaction temperature for dechlorination was room temperature. The molar ratio of the chlorine-containing substrate to the ammonium formate is 1: 10.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
For convenience of description, the abbreviations for each crystal and polymer are as described in table 1 below:
TABLE 1
Example 1 Metal organic framework UiO-66-NH2Synthesis of (2)
Weighing zirconium tetrachloride (93.2mg, 0.4mmol), placing in a 25mL conical flask, adding N, N-dimethylformamide (16mL), then adding acetic acid (1200mg, 20mmol), ultrasonically oscillating for 30min to completely dissolve, then adding organic ligand 2-amino terephthalic acid (72.5mg, 0.4mmol), ultrasonically oscillating for 30min, placing in a 20mL high-temperature autoclave, keeping the temperature at 120 ℃ for 24h, cooling to 20 ℃ after 10h to obtain a light yellow nanoscale crystal (120mg), centrifuging, and drying; wherein the ratio of the added amounts of the organic ligand 2-aminoterephthalic acid, zirconium tetrachloride, acetic acid and N, N-dimethylformamide solvent is 0.4 mmol: 0.4 mmol: 20 mmol: 1.6 mL; washing the obtained UiO-66-NH2 crystal powder with DMF for 4-5 times, then washing with fresh chloroform for 4-5 times, then placing in chloroform, stirring and soaking at room temperatureSoaking for 3d, changing fresh chloroform every 24h, and centrifugally drying; keeping the dried crystal at 100 deg.C for 3 hr, taking out, and keeping the shape of octahedron of about 200nm as shown in FIG. 2; two peaks clearly separated between 5 and 10 degrees, the appearance of a peak around 25 degrees, proved to be UiO-66-NH2See fig. 12.
Example 2 Synthesis of UiO-66-Met nanocrystals
Weighing UiO-66-NH2The crystals (0.6g, 0.002mol), 2.356mL (2.45g, 0.016mol) of methacrylic anhydride, 0.279mL (0.002mol) of triethylamine and 50mL of chloroform solution were added into a 100mL round-bottomed flask, wherein chloroform was dried and triethylamine was redistilled, heated under reflux at 55 ℃ for 24h, and a drying device was added to a condenser tube. After the reaction is finished, carrying out centrifugal treatment after natural cooling, then washing for 6 times by using fresh trichloromethane, carrying out vacuum drying for 5 hours at the temperature of 100 ℃, and marking the treated product as UiO-66-Met, wherein the yield is 90%, the shape of the octahedron is about 200nm, and the figure is 3; there are two distinct peaks seen between 5 and 10 degrees, respectively, and the appearance of the peak around 25 degrees demonstrates that the post-modified framework is not damaged, see fig. 12.
Example 3 preparation of PNIPAM-CTA
Under the protection of nitrogen, NIPAM (6.1224g, 53nmol) is placed in a three-necked bottle, 16mL of 1, 4-dioxane is added as a solvent, RFAT reagent CTA (2,2' - (thiocarbonylbis (sulfonamido)) bis (2-methylpropanoic acid)) (0.299g,1.06mmol) azobisisobutyronitrile (AIBN, 0.0087g, 0.053nmol) is added, the mixture is heated and stirred for 24 hours at 70 ℃, an ice water bath is used for stopping the reaction, 80mL of ether is used for dissolving and precipitating, yellow precipitate is just started to be separated out, suction filtration is carried out, vacuum drying is carried out, and 5.3698g of yellow powder is obtained and is marked as PNIPAM-CTA, the yield is 82.62%, and the nuclear magnetic hydrogen spectrum is shown in figure 4; the GPC measurement gave a number average molecular weight of 4748Da, a calculated degree of polymerization of 42, and a GPC curve as shown in FIG. 5.
Example 4 preparation of PNIPAM-SH
PNIPAM-CTA (5.00g,1.009mol) was weighed into a three-necked flask under nitrogen, 16mL of 1, 4-dioxane was added as solvent, ethanolamine (1.209mL,10.09mmol) and tributylphosphine (530.6. mu.L, 1.009mmol) were added, the mixture was reacted at room temperature for 2h, precipitated with 80mL of ether and dried in vacuo to give a brownish red gum, designated PNIPAM-SH, of about 5.6 g. The nuclear magnetic hydrogen spectrum is shown in figure 4, the GPC obtained number average molecular weight is 2395Da, the calculated polymerization degree is 21, the GPC curve is shown in figure 5, and nuclear magnetism before and after reduction has polymer peaks; the ultraviolet pattern is shown in FIG. 6, and the 310nm peak disappears and the 250nm peak is enhanced after reduction, thus proving that the reduction is complete.
Example 5 preparation of UiO-66-S-PNIPAM
Weighing PNIPAM-SH (3.7g,1.5mmol), placing in a 20mL beaker, adding 10mL tetrahydrofuran to dissolve completely, then adding UiO-66-Met (0.3g,1mmol), 2, 2-dimethoxy-2-phenylacetophenone (30mg), stirring for 0.5 hour at 25 ℃ with ultrasonic oscillation, then illuminating for 1.5 hours under a 365nm ultraviolet lamp, centrifuging, washing three times, and drying for 3 hours in vacuum at 60 ℃ until the nuclear magnetic yield is about 50%. The powder was unchanged, see FIG. 12, electron microscopy, see FIG. 6, dimensions around 200nm, octahedron, nuclear magnetic assembly, see FIG. 8, the appearance of the peaks of the polymer, the reduction of the double bonds, which is evidence of the attachment of a moiety, and the infrared, see FIGS. 9, 2950 and 2840cm-1The presence of a peak evidences the presence of the methyl methylene group of the polymer.
Example 6 preparation of Pd @ UiO-66-S-PNIPAM
Weighing 60mg of palladium acetate, dissolving the palladium acetate in 30mL of toluene, taking UiO-66-S-PNIPAM (100mg) for standby, and stirring at room temperature for 6 hours; after 6h, washing with fresh toluene for 3 times, drying and waiting for reduction; weighing 20mg NaBH4Dissolving in 20mL of secondary water, soaking the MOF loaded with divalent palladium in the secondary water for 0.5h, washing with fresh secondary water for 3 times after reduction, and drying for later use to obtain palladium-loaded crystals for later use, wherein a layer of palladium particles is loaded on the surface of the crystals, and the crystal lattice of the palladium is 0.24nm as shown in a TEM (transmission electron microscope) shown in figure 10; EDS is shown in figure 11, palladium content is 3.5% measured by ICP in the presence of palladium element, and the general reaction equation of examples 1-6 is shown in figure 1.
Example 7 preparation of Pickering emulsion from MOFs particles
Weighing 15mg, 30mg, 60mg and 90mg of Pd @ UiO-66-S-PNIPAM crystal, putting the Pd @ UiO-66-S-PNIPAM crystal into a toluene/water (2mL/1mL) solution, emulsifying for 1min under the condition that the rotating speed of a high-speed homogenizer is 5000r/min, and standing for 30min to obtain pickering emulsions with the mass fractions of 0.5 wt%, 1.0 wt%, 2.0 wt% and 3.0 wt% as shown in figure 13.
Weighing 60mg of Pd @ UiO-66-S-PNIPAM crystal, putting the Pd @ UiO-66-S-PNIPAM crystal into a solution of toluene/water (2.4mL/0.6mL, 2.25mL/0.75mL, 2mL/1mL and 1.5mL/1.5mL), emulsifying for 1min under the condition that the rotating speed of a high-speed homogenizer is 5000r/min, standing for 30min, and obtaining emulsions with mass fractions of 2.0 wt% and Pickering emulsions under different states under different oil-water ratios, wherein the emulsions form the most stable emulsion as shown in figure 14 and 2.25mL/0.75 mL.
Example 8 confocal characterization
In the process of preparing pickering emulsion, a fluorescein dye is added into the water phase, a drop of stable emulsion is dropped on a glass slide by using a laser confocal microscope, 20% of excitation light source with 488nm is used for shooting, and as shown in figures 13 and 14, the stable emulsion is oil-in-water emulsion seen from confocal, and the ratio of toluene to water is 3:1, the emulsion with the mass fraction of 2 percent is most stable; as the mass fraction increases, the emulsion particle size decreases gradually, and 0.5% of the emulsion is the least stable and will agglomerate into large droplets. The viscosity of the emulsion is slightly better at 1%, better at 2%, and too high at 3%, which is not suitable for a reaction system.
Example 9 catalytic dechlorination
Preparing an emulsion with the mass fraction of 2.0 wt% in toluene (2.25 mL)/water (0.75mL), Pd @ UiO-66-S-PNIPAM (60 mg); m-chloroacetophenone (0.25mmol), ammonium formate (2.5mmol), reacting at 25 ℃, monitoring the reaction in a gas phase, completely reacting for 2.5 hours, wherein the reaction equation is shown in figure 16, the temperature is increased to 45 ℃ and maintained for 5min for demulsification, the catalyst is moved to an oil phase, the temperature of an ice water bath is maintained for 10min and the catalyst is returned to a water phase, standing at room temperature for half an hour, the catalyst is settled at the bottom of the water phase, oil and water are separated, the demulsification process is shown in figure 15, the product is in the oil phase, the product is shown in figure 18 for nuclear magnetism, the gas phase yield is 99.5%, the monitoring yield is shown in figure 17, the catalyst is recovered, five catalytic cycles are carried out, the yield is basically unchanged in figure 19, the powder is shown in figure 20, the powder.
Example 10 Hot filtration
After the reaction is carried out for 1.5, the temperature is raised, the emulsion is broken, the temperature of the catalyst is reduced, the catalyst is dropped to a water phase, the catalyst is filtered and removed, the reaction is continued, the yield is not increased, and the heterogeneous catalysis characteristic of the catalyst is proved, which is shown in figure 17.
Example 11 catalytic dechlorination
Preparing an emulsion with the mass fraction of 2.0 wt% in toluene (2.25 mL)/water (0.75mL), Pd @ UiO-66-SH-PNIPAM (60 mg); chlorinated substrate (0.25mmol), ammonium formate (2.5mmol), reaction at 25 ℃ and gas phase monitoring of the reaction, the yield results are shown in Table 2. The results show that: different positions of the same substituent (such as o-chlorophenol, m-chlorophenol and p-chlorophenol) have little influence on dechlorination; different substituted substrates (such as p-chlorophenol, p-chloroaniline, p-chloroanisole, 4-chloro-methyl benzoate and 4-chloro-ethyl benzoate), the (phenol and aniline) with electron donating group effect on dechlorination reaction is obviously better than the (anisole and lipid) substrate with electron withdrawing group; fused-ring substrates (e.g., 4-chloro-biphenyl, 1-chloro-naphthalene) have a reduced reaction efficiency for dechlorination; in view of the effect of polychlorinated substrates (e.g., 2, 4-dichloro-phenol, 2,4, 6-trichlorophenol) on dechlorination, the reaction efficiency is reduced compared to monochloro-substituted substrates, with the greater the number of chlorines, the longer the reaction time.
TABLE 2 Table of yields of various chlorine-containing substrates
Example 12
Under the protection of nitrogen, UiO-66-Met (0.3g,1mmol), NIPAM (6.1224g, 53nmol), potassium persulfate (9mg, about 1.25 mol%), 20mL of isopropanol were put into a three-necked flask, heated and stirred at 70 ℃ for 72h, centrifuged, washed three times with THF, and dried for later use. The nuclear magnetic hydrogen spectrum is shown in figure 23, the proton peak content corresponding to the polymer is very low, the GPC spectrum is shown in figure 24, the number average molecular weight is only 1300Da, the molecular weight distribution is very wide (PDI is 2.16), the state of the particles in an oil-water two-phase (the lower layer is a water phase, and the upper layer is a toluene phase) at different temperatures is shown in figure 25, and the phase inversion does not occur when the temperature is raised to 45 ℃.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (12)
1. A preparation method of a temperature-responsive metal organic framework nanocrystal is characterized by comprising the following steps:
(1) taking a metal organic framework containing a primary amine group as a raw material, and modifying the primary amine group into a group containing a double bond to obtain a metal organic framework material with the surface containing the double bond;
(2) adding 2,2' - (thiocarbonylbis (sulfonamido)) bis (2-methylpropanoic acid) into the temperature-responsive monomer to perform reversible addition-fragmentation chain transfer polymerization, and reducing trithiocarbonate groups into sulfydryl through aminolysis to obtain a temperature-responsive polymer with a sulfydryl terminal;
(3) and (2) carrying out addition reaction of sulfydryl and double bonds on the temperature-responsive polymer with the tail end being sulfydryl and the metal organic framework material with the surface containing the double bonds by adopting a sulfydryl-alkene click chemical reaction so as to obtain the temperature-responsive metal organic framework nanocrystal.
2. The method for preparing a temperature-responsive metal organic framework nanocrystal according to claim 1, wherein in the step (2), the polymerization conditions are as follows: and heating to 70-75 ℃ under the inert gas atmosphere, and reacting for 24-36 h.
3. The method for preparing a temperature-responsive metal organic framework nanocrystal according to claim 1, wherein in the step (2), the aminolysis step comprises: and reacting the polymerized polymer with ethanolamine and tributyl phosphine at room temperature in an inert gas atmosphere.
4. The method for preparing a temperature-responsive metal organic framework nanocrystal according to claim 1, wherein in the step (3), the reaction conditions are as follows: adding ultraviolet initiator to react under the irradiation of ultraviolet light.
5. The temperature-responsive metal-organic framework nanocrystal prepared by the preparation method of any one of claims 1 to 4, comprising a metal-organic framework nanomaterial and a temperature-responsive polymer, wherein the temperature-responsive polymer is bonded to the metal-organic framework nanomaterial by a thioether bond formed by a click chemistry method, and the metal-organic framework nanomaterial is a metal-organic framework material obtained by chemical modification and having a double bond on the surface; the metal organic framework material is UiO-66-NH2The temperature-responsive polymer is poly-N-isopropylacrylamide.
6. Use of the temperature-responsive metal-organic framework nanocrystals of claim 5 in a Pickering emulsion system.
7. A catalyst comprising the temperature-responsive metal-organic framework nanocrystal of claim 5 as a carrier supporting metallic palladium.
8. The catalyst of claim 7, wherein the metallic palladium is supported by immersing the temperature-responsive metal-organic framework nanocrystals in a palladium acetate solution, removing the solvent, and then reducing the divalent palladium by a reducing agent.
9. The catalyst according to claim 7, wherein the metal palladium is present in an amount of 3 to 4% by mass.
10. Use of the catalyst of any one of claims 7 to 9 in catalysis of dechlorination reactions in a Pickering emulsion system.
11. A catalytic dechlorination method is characterized in that an organic solvent, water, a chlorine-containing substrate, ammonium formate and the catalyst according to any one of claims 7 to 9 are prepared into Pickering emulsion to react, wherein the chlorine-containing substrate is an organic matter formed by directly connecting chlorine and a benzene ring.
12. The process as claimed in claim 11, wherein the Pickering emulsion has a solids content of 1 to 2 wt.%.
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| CN106928465A (en) * | 2017-03-02 | 2017-07-07 | 山东师范大学 | A kind of pH response types metal organic frame nanocrystal and preparation method and application |
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