CN114163653A - Preparation method of pore liquid supersaturated metal organic framework - Google Patents
Preparation method of pore liquid supersaturated metal organic framework Download PDFInfo
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Abstract
The invention discloses a preparation method of a pore liquid supersaturated metal organic framework. The preparation method of the liquid super-saturated metal organic framework in the hole comprises the following steps: the liquid to be packaged, the molecular size of which is matched with the aperture of the metal organic framework, and the hydrothermally stable metal organic framework material are subjected to in-hole matching combination, the combination of liquid molecules and the metal organic framework is promoted by utilizing the polar action between a surfactant and the molecules of the liquid to be packaged, the aperture matching effect is fully exerted, the obtained in-hole liquid supersaturated metal organic framework has good stability and ultrahigh in-hole liquid molecule retention rate, and the molar ratio of the liquid molecules to the metal organic framework can reach the theoretical upper limit. The preparation method is simple and convenient to operate, short in reaction time and easy to popularize, and meanwhile, the mild reaction conditions do not obviously influence the structure of the metal organic framework, so that the secondary structure preservation rate is high.
Description
Technical Field
The invention relates to the field of preparation of functionalized nano composite materials, in particular to a preparation method of a pore liquid supersaturated metal organic framework.
Background
The liquid material has the characteristics of good dispersibility, full contact between active sites and a target object and the like, has unique advantages in the separation field and the catalysis field, such as mild reaction, high selectivity and the like, but often faces the problems of poisoning inactivation, volatilization decomposition and the like in the actual use process.
The metal organic framework is a unique porous material, and has the characteristics of high porosity, specific surface area, secondary structure convenient to design, functionalization and the like, so that the metal organic framework is widely applied to the fields of catalysis, separation, adsorption and the like. In addition, the metal-organic framework is a good carrier, and is usually used for encapsulating some active components to obtain a composite material so as to achieve the purposes of protecting the active components and strengthening the active components synergistically. Generally, two packaging ideas exist, one is a one-pot method, namely, active components are packaged together in the process of preparing the metal organic framework, but the method has a narrow application range, and one method is usually only suitable for a specific metal organic framework-active component composite material; the other method is a post-treatment method, namely, the existing metal organic framework is further modified, so that the method has the advantages of wide application range and no influence on the physicochemical properties of the metal organic framework and the active component, but has the defect of low retention rate of the active component in pores.
Disclosure of Invention
In order to overcome the defect of low retention rate of active components in pores in the prior aftertreatment technology, the invention provides a preparation method of a supersaturated metal-organic framework of a liquid in pores.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a pore liquid supersaturated metal organic framework comprises the steps of carrying out pore matching combination on liquid to be packaged, the molecular size of which is matched with the pore diameter of the metal organic framework, and a hydrothermally stable metal organic framework material, promoting the combination of liquid molecules and the metal organic framework by utilizing the polar action between a surface active agent and liquid molecules to be packaged, and fully playing the pore matching effect. The liquid super-saturated metal organic framework in the pores is prepared according to the following method:
selecting liquid to be packaged, the molecular size of which is matched with the aperture of the metal organic framework, preparing 50ml of methanol solution, adding a proper amount of the metal organic framework, carrying out ultrasonic treatment for a certain time at room temperature, adding a proper amount of surfactant, adding a sealing film, stirring for a certain time at room temperature, then placing the mixture in a water bath kettle, continuously stirring until the methanol is completely evaporated, placing the obtained solid on a filter membrane for vacuum filtration, sequentially adding a detergent for quick suction washing, weighing after each suction washing until the weight change of certain two times is less than 0.5%, and finally drying.
According to the invention, the liquid to be packaged, the molecular size of which is matched with the aperture of the metal organic framework, and the hydrothermally stable metal organic framework material are subjected to in-hole matching combination, so that the aperture matching effect is fully exerted, the ultrahigh in-hole liquid molecule retention rate is realized, the molar ratio of the liquid molecules to the metal organic framework can reach the theoretical upper limit, the preparation method is simple, the conditions are mild, and the secondary structure and the crystal characteristics of the metal organic framework are retained. The specific synthesis steps are as follows:
the ZIF-8 powder was previously dried in an 80 degree oven overnight to remove moisture from the channels. Selecting liquid to be packaged, the molecular size of which is matched with the aperture of the metal organic framework, preparing 50ml of methanol solution, adding a proper amount of the metal organic framework, carrying out ultrasonic treatment for a certain time at room temperature, adding a proper amount of surfactant, adding a sealing film, stirring for a certain time at room temperature, then placing the mixture in a water bath kettle, continuously stirring until the methanol is completely evaporated, placing the obtained solid on a filter membrane for vacuum filtration, sequentially adding 5ml of detergent, carrying out quick suction washing, weighing after each suction washing until the weight change of certain two times is less than 0.5%, and finally placing the mixture in an 80-DEG oven for drying for 12 hours.
In the invention, firstly, the metal organic framework is selected to be matched with the molecular size of liquid to be encapsulated in pore diameter, and the size of the encapsulated molecules is close to (matched with) the pore diameter of the MOF, so that the result is influenced if the size is too large or too small; secondly, the surfactant needs to form a polar effect with the liquid molecules to be sealed, the current test result in the invention is that for organic amine molecules, the effect of selecting a nonionic surfactant (i.e. PVP) is better, and for ionic liquid, the effect of selecting an ionic surfactant (e.g. cetyl trimethyl ammonium bromide) is better, and the surfactant is supposed to have a main effect of facilitating the combination of the liquid molecules and MOF cages; thirdly, a special cleaning process is used, weighing and washing are carried out for multiple times, liquid molecules which are combined with the surfactant and on the outer layer are accurately washed away, and only molecules in pores are left. The invention gives full play to the aperture matching effect, realizes the ultrahigh retention rate of liquid molecules in the pores,
preferably, the selected liquid to be encapsulated includes, but is not limited to, triethylene tetramine, tetraethylene pentamine, 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim)]BF4) At least one of (1). The minimum diameter of the van der waals surface of the liquid molecule to be encapsulated needs to be close to and smaller than the pore size of the metal-organic framework.
Further preferably, the concentration of the prepared liquid methanol solution to be packaged is 0.01-0.05M.
Preferably, the metal organic framework material includes, but is not limited to, at least one of ZIF-11, ZIF-8, MOF-EIA, and HKUST-1. The metal organic framework materials used in the present invention can be obtained by commercial sources or prepared by reference to the existing literature.
Further preferably, the mass ratio of the liquid to be encapsulated to the metal organic framework is 1: 2 to 3.5. The mass of the added metal organic framework is 0.1-1 g.
Still further preferably, the ultrasonic treatment time is 10-30 min, and the time is not suitable to be too long.
Preferably, the surfactant includes, but is not limited to, at least one of polyvinylpyrrolidone (PVP, average molecular weight 15000, nonionic surfactant), cetyltrimethylammonium bromide (cationic surfactant).
Further preferably, the surfactant is added in an amount of 0.1 to 2 mol times based on the metal-organic skeleton.
Still more preferably, the mixture is stirred at 10 to 35 ℃ for 6 to 10 hours with the sealing film. Placing the mixture into a water bath kettle at the temperature of 40-60 (most preferably 50 ℃) for continuous stirring until the methanol is completely evaporated,
preferably, the added detergent is one or more of ultrapure water, ethanol, and N, N-Dimethylformamide (DMF).
Further preferably, the detergent is a mixture of a plurality of compounds, wherein the volume ratio of the mixture of the detergent to the compound is 1: 1 to 3.
Preferably, the vacuum degree of vacuum filtration is 0.08-0.1 MPa.
Preferably, the conditions of drying: and drying in an oven at 70-90 ℃ for 10-14 hours, preferably in an oven at 80 ℃ for 12 hours.
Compared with the prior art, the invention has the following advantages:
according to the invention, the metal organic framework material is used as an adsorbent carrier, the liquid is used as an active component, the ionic liquid is loaded into the pore canal of the metal organic framework material through the aperture matching effect, the aperture matching effect is fully exerted, the ultrahigh retention rate of liquid molecules in the pore is realized, and the molar ratio of the liquid molecules to the metal organic framework can reach the theoretical upper limit.
The liquid to be packaged, the molecular size of which is matched with the aperture of the metal organic framework, and the hydrothermally stable metal organic framework material are subjected to in-hole matching combination, so that the aperture matching effect is fully exerted, the obtained in-hole liquid supersaturated metal organic framework has good stability and ultrahigh in-hole liquid molecule retention rate, and the molar ratio of the liquid molecules to the metal organic framework can reach the theoretical upper limit. The preparation method is simple and convenient to operate, short in reaction time and easy to popularize, and meanwhile, the mild reaction conditions do not obviously influence the structure of the metal organic framework, so that the secondary structure preservation rate is high.
Drawings
FIG. 1 is a thermogram of a medium pore triethylenetetramine supersaturated ZIF-8 material of example 1.
Detailed Description
The invention is further illustrated by the following specific examples. The scope of the invention is not limited to the following examples.
Example 1
0.292g of triethylene tetramine (the minimum diameter of the van der Waals surface is 3.1 angstroms, the maximum length of the molecule is 11.2 angstroms, and the relative molecular mass is 146.23) is prepared into 0.04M and 50ml of methanol solution, 0.843g of ZIF-8 (the aperture is 3.4 angstroms, the cage diameter is 11.6 angstroms, and the relative molecular mass is 842.71) is added into the methanol solution, ultrasonic treatment is carried out at the room temperature of 25 ℃ for 30min, 4.5g of PVP (the average molecular weight is 15000) is added, a sealing film is added to be stirred for 6h at the room temperature of 25 ℃, then the mixture is placed into a water bath kettle at the temperature of 50 ℃ to be continuously stirred until the methanol is completely evaporated, the obtained solid is placed on a filter membrane to be subjected to vacuum filtration (the vacuum degree is 0.09MPa), 5ml of detergent (mixed with water and ethanol 1: 1) is added in sequence to be quickly pumped and washed, and then weighed after each time, until the weight change of two times is less than 0.5%, and finally the mixture is placed into an oven to be dried for 12 h at the temperature of 80 ℃.
Retention in the pores was determined by thermogravimetric analysis:
detecting the supersaturated ZIF-8 of the triethylene tetramine in the holes prepared in the step 1 by adopting a thermogravimetric differential thermal coupling thermal analyzer (SDT Q600), pretreating for 30min at 80 ℃ in a nitrogen atmosphere to remove water and oxygen, then heating to 800 ℃ at 10 ℃/min, and obtaining a result shown in a figure 1, wherein only one weightless platform exists before 500 ℃, and the fact that the triethylene tetramine is not attached to the surface of the ZIF-8 and the triethylene tetramine is in the holes is proved; weight loss of 16% at 500 ℃, and the mol ratio of triethylene tetramine molecules to ZIF-8 in the holes is proved to be 1.1: 1. almost every cage has one triethylene tetramine, and the retention rate is as high as 110%.
Example 2
0.468g of tetraethylenepentamine (Van der Waals surface minimum diameter 3.0 angstroms, maximum molecular length 14.3 angstroms, relative molecular mass 189.3) is prepared into 0.05M of 50ml of methanol solution, 1.259g of ZIF-11 (aperture 3.0 angstroms, cage diameter 14.6 angstroms, relative molecular mass 1258.84) is added into the methanol solution, ultrasonic treatment is carried out for 30min at room temperature and 25 ℃, 6g of PVP (average molecular weight 15000) is added, a sealing film is added to be stirred for 8h at room temperature and 25 ℃, then the mixture is placed into a 50 ℃ water bath kettle to be continuously stirred until the methanol is completely evaporated, the obtained solid is placed on a filter membrane to be subjected to vacuum filtration (the vacuum degree is 0.09MPa), 5ml of detergent (mixed with water and ethanol 1: 1) is added in sequence to be rapidly pumped and washed, and weighed after each time of pumping, until the weight change of two times is less than 0.5%, and finally the mixture is placed into an oven to be dried for 12 h at 80 ℃.
By adopting the method of the embodiment 1 for detection, all tetraethylenepentamine molecules of the finally obtained composite material are positioned in a ZIF-11 cage, and the weight loss is 13.6% at 500 ℃, so that the mol ratio of the tetraethylenepentamine to the ZIF-11 is proved to be 1.05: 1, almost every cage contains one tetraethylenepentamine, and the retention rate is as high as 105%.
Example 3
0.113g of [ Bmim ]]BF4(Van der Waals surface minimum diameter 4.1 angstroms, molecular maximum length 10 angstroms, relative molecular mass 226.02) to prepare 0.01M, 50ml of methanol solution, adding 0.315g of MOF-EIA (aperture 3.0 angstroms, cage diameter 14.6 angstroms, relative molecular mass 1027.02), carrying out ultrasonic treatment at room temperature 25 ℃ for 10min, adding 0.364g of cetyl trimethyl ammonium bromide, adding a sealing film, stirring at room temperature 25 ℃ for 10h, then placing in a 50 ℃ water bath, continuously stirring until methanol is completely evaporated, placing the obtained solid on a filter membrane, carrying out vacuum filtration (vacuum degree is 0.1MPa), sequentially adding 5ml of DMF, carrying out rapid suction and washing, weighing after each suction and washing until the weight change of two times is less than 0.5%, and finally placing in an 80 ℃ oven to dry for 12 hours.
The composite material obtained by the detection method of example 1 has all [ Bmim]BF4The molecules are all positioned in MOF-EIA cages, the weight loss is 17.3 percent at 500 ℃, and the results prove that [ Bmim [ -]BF4Molar ratio to MOF-EIA 0.95: 1, there is one [ Bmim ] in almost every cage]BF4The retention rate is as high as 95 percent.
Claims (10)
1. A preparation method of a pore liquid supersaturated metal organic framework is characterized by comprising the following steps:
selecting liquid to be packaged, the molecular size of which is matched with the aperture of the metal organic framework, preparing a methanol solution of the liquid to be packaged, adding the metal organic framework into the methanol solution, carrying out ultrasonic treatment, adding a surfactant, adding a sealing film, stirring, then placing the mixture into a water bath kettle, continuously stirring until the methanol is completely evaporated, placing the obtained solid on a filter membrane for vacuum filtration, sequentially adding a detergent for quick suction washing, and finally drying to obtain the liquid supersaturated metal organic framework in the pores.
2. The method for preparing an intra-pore liquid supersaturated metal-organic framework according to claim 1, wherein the liquid to be encapsulated is at least one of triethylene tetramine, tetraethylene pentamine and 1-butyl-3-methylimidazolium tetrafluoroborate.
3. The method for preparing a pore liquid supersaturated metal-organic framework according to claim 1, wherein the concentration of the liquid to be encapsulated in the methanol solution of the liquid to be encapsulated is 0.01-0.05M;
the mass ratio of the liquid to be packaged to the metal organic framework is 1: 2 to 3.5.
4. The method for preparing a liquid supersaturated metal-organic framework within a pore according to claim 1, wherein the metal-organic framework is at least one of ZIF-11, ZIF-8, MOF-EIA and HKUST-1.
5. The method for preparing a liquid supersaturated metal-organic framework in a pore according to claim 1, wherein the time of ultrasonic treatment is 10-30 min.
6. The method of claim 1, wherein the surfactant is at least one of polyvinylpyrrolidone and cetyltrimethylammonium bromide.
7. The method for preparing a supersaturated metal organic framework for a liquid in a pore according to claim 1, wherein the surfactant is added in an amount of 0.1 to 2 molar times the metal organic framework.
8. The method for preparing a supersaturated metal organic framework for a liquid in a pore according to claim 1, wherein the stirring time at 10-35 ℃ with the sealing film is 6-10 h.
9. The method for preparing a supersaturated metal organic framework for a liquid in a pore according to claim 1, wherein the mixture is placed in a water bath kettle at a temperature of 40-60 ℃ and stirred continuously until the methanol is completely evaporated.
10. The method for preparing a liquid supersaturated metal-organic framework in a pore according to claim 1, wherein the detergent is one or more of ultrapure water, ethanol and N, N-dimethylformamide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130280151A1 (en) * | 2012-04-23 | 2013-10-24 | Ut-Battelle, Llc | Ionic liquid-functionalized mesoporous sorbents and their use in the capture of polluting gases |
| CN108114695A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | The zeolitic imidazolate framework material of solid-loaded ionic-liquid and its application in cage |
| CN108786755A (en) * | 2018-05-30 | 2018-11-13 | 浙江大学 | A kind of metal organic frame-porous polymer composite material and preparation method of organic amine load and application |
| WO2019156635A1 (en) * | 2018-02-08 | 2019-08-15 | Nanyang Technological University | Graphene frameworks membranes for separation of immiscible liquids |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130280151A1 (en) * | 2012-04-23 | 2013-10-24 | Ut-Battelle, Llc | Ionic liquid-functionalized mesoporous sorbents and their use in the capture of polluting gases |
| CN108114695A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | The zeolitic imidazolate framework material of solid-loaded ionic-liquid and its application in cage |
| WO2019156635A1 (en) * | 2018-02-08 | 2019-08-15 | Nanyang Technological University | Graphene frameworks membranes for separation of immiscible liquids |
| CN108786755A (en) * | 2018-05-30 | 2018-11-13 | 浙江大学 | A kind of metal organic frame-porous polymer composite material and preparation method of organic amine load and application |
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