CN109876776B - Indium-based MOF micro-nano powder and room-temperature preparation method and application thereof - Google Patents
Indium-based MOF micro-nano powder and room-temperature preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a metal organic framework material, in particular to indium-based MOF micro-nano powder and a preparation method and application thereof, wherein the indium-based MOF micro-nano powder is prepared by taking indium nitrate and carboxylic acid as reaction raw materials, adding water or salt or water and salt into the reaction raw materials, and reacting at 15-45 ℃, especially preferably at room temperature. The room temperature mild preparation technology of the indium-based MOF micro-nano powder has important significance for simplifying operation, enriching the types of classical MOFs, developing the application field of the MOFs and realizing industrial application.
Description
Technical Field
The invention relates to a Metal Organic Framework (MOF) material, in particular to an indium MOF material prepared by a simple method universally at normal temperature.
Background
Metal Organic Framework (MOF) materials have attracted much attention due to the advantages of adjustable pore size, functional pores, and the like. Although MOFs are various, only a few micro-nano powder materials (such as ZIFs, MILs and other series) of classical MOFs are currently applied to the field of photocatalysis, because most MOFs exist in a bulk crystal form, which limits the application and development of MOFs. Most of the MOFs are reported to be prepared by a hydrothermal method or a solvothermal method, which limits the development and industrial application of the MOFs.
Disclosure of Invention
The invention aims to solve the technical problems that the existing methods for preparing indium-based MOF are mostly hydrothermal methods, solvothermal methods and high-temperature water bath methods, and the invention aims to regulate and control experimental parameters, develop a room-temperature universal preparation technology of indium-based MOF micro-nano powder and reduce energy consumption. The invention simplifies the preparation method of the indium-based Metal Organic Framework (MOF) material, reduces the energy consumption in the preparation process of the indium-based MOF, and develops a universal preparation method to realize the room-temperature preparation of various indium-based MOF micro-nano powders. Specifically, in order to solve the above technical problems, the present invention provides the following technical solutions:
indium-based MOF micro-nano powder is prepared by taking indium nitrate and carboxylic acid as reaction raw materials, adding water or salt or water and salt into the reaction raw materials, and reacting at 15-45 ℃ (preferably room temperature).
For the indium-based MOF micro-nano powder, the carboxylic acid is preferably selected from polycarboxylic acid, and the polycarboxylic acid is preferably more than one of dicarboxylic acid, tricarboxylic acid and tetracarboxylic acid; more preferably, the polycarboxylic acid is selected from one or more of terephthalic acid, 2-aminobenzoic acid, 2-nitroterephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 1 ' -cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1,2,3,4,5, 6-cyclohexanehexocarboxylic acid, 4 ' -diphenyletherdicarboxylic acid, 2, 5-thiophenedicarboxylic acid, fumaric acid, 1,2,3, 4-butanetetracarboxylic acid, trimesic acid, 1 ' -ferrocenedicarboxylic acid, and still more preferably, the polycarboxylic acid is selected from fumaric acid, 1, 4-naphthalenedicarboxylic acid, trimesic acid, 2, 5-thiophenedicarboxylic acid, 4 ' -phenylenedicarboxylic acid, 1 ' -cyclobutanedioic acid, 1-cyclohexanedicarboxylic acid, and mixtures thereof, 1, 6-cyclohexanedicarboxylic acid, 1,2,3,4,5, 6-cyclohexanehexacarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid, 1, 1' -ferrocenedicarboxylic acid; the salt is selected from one or more of sodium formate, sodium acetate, sodium propionate or sodium fluoride, preferably from one or more of sodium formate, sodium propionate or sodium fluoride; further preferably selected from sodium fluoride.
For the indium-based MOF micro-nano powder, preferably, an organic solvent is further added into the reaction raw materials for reaction; preferably, the organic solvent is selected from an alcohol solvent or an amide solvent; more preferably, the solvent is at least one selected from the group consisting of methanol, ethanol, propanol, butanol, N-dimethylamide acetamide and N, N-dimethylformamide, and still more preferably N, N-dimethylformamide.
The indium-based MOF micro-nano powder is preferably obtained by a method comprising the following steps: adding water into indium nitrate to form an indium nitrate aqueous solution, adding the indium nitrate aqueous solution into a carboxylic acid organic solvent solution, and preparing at 15-30 ℃.
For the indium-based MOF micro-nano powder, preferably, a salt is added into an organic solvent solution of carboxylic acid.
The invention also provides a preparation method of the indium-based MOF micro-nano powder, which is characterized by comprising the following preparation steps:
1) preparing a carboxylic acid solution: dissolving a carboxylic acid in an organic solvent (preferably N, N-dimethylformamide) to form a carboxylic acid reaction solution;
2) preparing an indium nitrate solution;
3) adding the indium nitrate solution obtained in the step 2) into the carboxylic acid solution obtained in the step 1), reacting at 15-45 ℃, preferably 15-30 ℃, and separating and drying to obtain an indium-based MOF micro/nano material;
wherein, in step 1), salt is added to form a carboxylic acid reaction solution; and/or adding water in the step 2) to form an indium nitrate aqueous solution.
For the production method according to the present invention, it is preferable that an organic solvent and a salt are added in step 1) to form a carboxylic acid reaction solution, and water is added in step 2) to form an indium nitrate aqueous solution.
For the production method according to the present invention, it is preferable that an organic solvent is added in step 1) without adding a salt to form a carboxylic acid reaction solution, and water is added in step 2) to form an indium nitrate aqueous solution.
For the preparation method according to the present invention, it is preferable that an organic solvent is added and a salt is added to form a carboxylic acid reaction solution in step 1), and an organic solvent is added to form an indium nitrate solution in step 2).
For the preparation method of the present invention, it is preferable that in the step 1), when the carboxylic acid solution is formed, the mass ratio of the carboxylic acid to the salt is 2:45-100, preferably 2:45-60, in terms of mmol of the carboxylic acid and mg of the salt;
step 2) when an indium nitrate solution is formed, the ratio of indium nitrate to water in mmol to water in mL is 2:5-2: 10; or the ratio of the indium nitrate to the organic solvent is 2:5-2:10 according to mmol and mL.
For the preparation method of the present invention, it is preferable that in the step 1), the carboxylic acid solution is formed by using the carboxylic acid and the organic solvent in a ratio of 2:20 to 2:30, preferably 2:25 to 2:30 in terms of mmol and mL of the organic solvent.
For the preparation method of the present invention, preferably, the indium-based MOF material is MIL-68(In) or amino MIL-68 (In).
The invention also provides indium-based MOF micro-nano powder obtained by any one of the preparation methods.
The invention also provides application of the indium-based MOF micro-nano powder in an adsorbent or a photocatalytic product.
Aiming at the problems that the existing methods for preparing indium-based MOF are mostly hydrothermal methods, solvothermal methods and high-temperature water bath methods, the invention develops a mild preparation technology for indium-based MOF micro-nano powder with the temperature being as low as room temperature, not only greatly simplifies the operation, but also reduces the particle size of the prepared MOF material, improves the specific surface area, can improve the adsorbability, and has important significance for enriching the types of classical MOF, developing the application field of the MOF material and realizing industrial application. Therefore, the method provides a universal preparation technology for preparing the indium-based MOF micro-nano powder with a specific morphology at room temperature, and has the advantages of simple operation, low energy consumption and no need of a special reactor.
Drawings
Fig. 1 is an XRD pattern of MIL-68 micro-nano powder prepared under different conditions of examples 1, 3,4,5,6, and 7;
FIG. 2 NH prepared in examples 8, 9 and 102-XRD pattern of MIL-68 micro-nano powder;
fig. 3a is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 11 and a corresponding ligand;
fig. 3b is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 12 and a corresponding ligand;
fig. 3c is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 13 and a corresponding ligand;
fig. 3d is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 14 and a corresponding ligand;
fig. 3e is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 15 and a corresponding ligand;
fig. 3f is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 16 and a corresponding ligand;
fig. 3g is an XRD chart of the indium-based MOF micro-nano powder prepared in example 17 and a corresponding ligand;
fig. 3h is an XRD chart of the indium-based MOF micro-nano powder prepared in example 18 and a corresponding ligand;
fig. 3i is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 19 and a corresponding ligand;
fig. 3j is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 20 and a corresponding ligand;
fig. 3k is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 21 and a corresponding ligand;
fig. 3l is an XRD pattern of the indium-based MOF micro-nano powder prepared in example 22 and a corresponding ligand;
FIG. 4a is an SEM image (magnification 10k) of the MIL-68(In) micro-nano material prepared In example 1(5ml water);
FIG. 4b is an SEM (magnification of 10k) image of the MIL-68(In) micro-nano material prepared In example 2(10ml water);
FIG. 5a is SEM image (magnification 10k) of rod-shaped MIL-68(In) micro-nano material prepared In example 4 (reaction at 25 ℃ for 24 hours, 50mg NaAc) by electron microscope;
FIG. 5b is an SEM image (magnification 10k) of the rod-shaped MIL-68(In) micro-nano material prepared In example 4A (reaction at 90 ℃ for 2 hours, 50mg NaAc);
FIG. 6a is an SEM image (magnification is 5k) of the rod-shaped MIL-68(In) micro-nano material prepared In example 6(50mg NaF);
FIG. 6b is an SEM image (magnification is 5k) of the rod-shaped MIL-68(In) micro-nano material prepared In example 6A (100mg NaF);
FIG. 7a is an SEM (magnification of 10k) of the rod-shaped MIL-68 micro-nano material prepared in example 7;
FIG. 7b is a bar of NH prepared in example 102SEM image (magnification of 10k) of MIL-68 micro-nano material;
FIG. 8a is an SEM image (magnification 10k) of the indium-based MOF micro-nano powder prepared in example 11 (2-nitroterephthalic acid);
FIG. 8b is an SEM image (magnification is 10k) of the indium-based MOF micro-nano powder prepared in example 12(2, 5-dihydroxyterephthalic acid);
FIG. 8c is an SEM image (magnification 10k) of the indium-based MOF micro-nano powder prepared in example 13(1, 4-naphthalenedicarboxylic acid);
FIG. 8d is an SEM image (magnification 10k) of the indium-based MOF micro-nano powder prepared in example 14(1,2,3,4,5, 6-cyclohexanehexacarboxylic acid);
FIG. 8e is an SEM image (magnification is 30k) of the indium-based MOF micro-nano powder prepared in example 15(1, 4-cyclohexanedicarboxylic acid);
FIG. 8f is an SEM image (magnification 10k) of the indium-based MOF micro-nano powder prepared in example 16(1, 1' -cyclobutane dicarboxylic acid);
FIG. 8g is an SEM image (magnification 10k) of the indium-based MOF micro-nano powder prepared in example 17(4, 4' -diphenyl ether dicarboxylic acid);
FIG. 8h is an SEM image (magnification 10k) of the indium-based MOF micro-nano powder prepared in example 18(2, 5-thiophenedicarboxylic acid);
FIG. 8i is an SEM image (50 k magnification) of the indium-based MOF micro-nano powder prepared in example 19(1,2,3, 4-butanetetracarboxylic acid);
FIG. 8j is an SEM image (20 k magnification) of the indium-based MOF micro-nano powder prepared in example 20(1, 1' -ferrocene dicarboxylic acid);
fig. 8k is an SEM image (magnification 5k) of the indium-based MOF micro-nano powder prepared in example 21 (fumaric acid);
FIG. 8l is an SEM image (magnification 10k) of the indium-based MOF micro-nano powder prepared in example 22 (trimesic acid).
Detailed Description
MIL-68(In) is taken as a classic MOF, and the micro-nano powder of the MIL-68(In) is usually obtained under the high-temperature condition of 90 ℃ by taking N, N-Dimethylformamide (DMF) as a reaction solvent. Most of the existing methods for preparing indium-based MOF are hydrothermal method, solvothermal method and high-temperature water bath method, so that the development of the mild preparation technology of indium-based MOF micro-nano powder is a problem to be solved urgently, and the method has important significance for simplifying operation, enriching the types of classical MOF, developing the application field of the indium-based MOF micro-nano powder and realizing industrial application.
The inventor finds that In a reaction system of MIL-68(In) micro-nano powder, indium nitrate organic solvent solution or aqueous solution is added into carboxylic acid solution, particularly organic solvent solution such as DMF of carboxylic acid, so that the reaction temperature can be reduced to room temperature, and the obtained micro-nano powder has a uniform rod-shaped structure. In addition, the inventor finds that In the reaction system of the MIL-68(In) micro-nano powder, the reaction temperature can be reduced to room temperature by adding sodium formate, sodium acetate, sodium propionate, sodium fluoride and other salts into a carboxylic acid organic solvent solution. By adopting the method, the aminated MIL-68 (NH) can be successfully prepared at room temperature2-MIL-68). Then, we apply this method to room temperature preparation of other indium-based MOF micro-nano powders, and found that organic ligands such as 2-nitroterephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 1,2,3,4,5, 6-cyclohexanehexocarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1 ' -cyclobutanedicarboxylic acid, 4 ' -diphenyletherdicarboxylic acid, 2, 5-thiophenedicarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid, 1 ' -ferrocenedicarboxylic acid, fumaric acid, and trimesic acid can be reacted with indiumForming MOF micro-nano powder with regular and uniform appearance, in particular to indium-based MOF micro-nano powder prepared by mixing organic ligands such as fumaric acid, 1, 4-naphthalenedicarboxylic acid, trimesic acid, 2, 5-thiophenedicarboxylic acid, 4 ' -phenylate dicarboxylic acid, 1,1 ' -cyclobutane diacid, 1, 6-cyclohexanedicarboxylic acid, 1,2,3,4,5, 6-cyclohexanehexocarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid and 1,1 ' -ferrocenedicarboxylic acid with indium at room temperature.
In particular, the 2 schemes for the preparation of indium-based MOF materials of the prior art that are most similar to the present invention are as follows:
1. preparing indium-based MOF by a hydrothermal method or a solvothermal method under the conditions of high temperature and high pressure;
2. preparing indium-based MOF micro-nano powder by a water bath method under the condition of high temperature (90 ℃).
After the research, the inventor designs and develops a universal scheme for preparing various indium-based MOF micro/nano powder at room temperature or normal temperature of 15-45 ℃ and preferably 20-25 ℃ for the first time, and the key means is as follows:
(1) indium nitrate and terephthalic acid are used as reactants, DMF is used as a main solvent, and rod-shaped MIL-68 micro-nano powder with reduced particle size, increased specific surface area and greatly improved adsorbability can be prepared at room temperature by adding water independently, such as adding in the form of indium nitrate aqueous solution, adding salt independently, and adding salt and indium nitrate aqueous solution simultaneously;
(2) indium nitrate and 2-amino terephthalic acid are used as reactants, DMF is used as a main solvent, and rod-shaped NH with small particle size, large specific surface area and excellent adsorbability can be prepared at room temperature by adding an indium nitrate aqueous solution independently, adding a salt independently, and adding the salt and the indium nitrate aqueous solution simultaneously2-MIL-68 micro-nano powder;
(3) DMF is used as a main solvent, 10 organic ligands of fumaric acid, 1, 4-naphthalenedicarboxylic acid, trimesic acid, 2, 5-thiophenedicarboxylic acid, 4 ' -phenylenedicarboxylic acid, 1,1 ' -cyclobutane diacid, 1, 6-cyclohexanedicarboxylic acid, 1,2,3,4,5, 6-cyclohexanehexocarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid and 1,1 ' -ferrocenedicarboxylic acid can react with indium nitrate at room temperature to obtain indium-based MOF micro-nano powder with small particle size, large specific surface area and excellent adsorbability of specific morphology by adding water and salt.
The room temperature general method for preparing indium-based MOF micro-nano powder is specifically described by the following embodiments.
Wherein, the types of SEM instruments used in the SEM photographs of the indium-based MOF micro-nano powder used in examples 1 to 22 are: SU8020 field emission scanning electron microscope.
The instrument model for measuring the XRD of the indium-based MOF micro-nano powder is as follows: the testing conditions of the powder X-ray diffractometer model DX-2700B of Dandonghao are as follows: cu target, scan interval: 0.02 °, scan range: 5-50 degrees.
Examples
Example 1:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), and stirring for 10min for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting at the temperature of 25 ℃ for 24h, centrifuging, washing with ethanol for 2 times, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an electron micrograph of the material is shown In figure 4a (the magnification of the electron micrograph is 10k), and an XRD (X-ray diffraction) diagram of the material is shown In figure 1. In fig. 1, standard MIL-68 refers to the XRD structure of known standard MIL-68, and it can be seen from fig. 1 that the example of the present invention successfully prepared indium-based MIL-68 having the characteristic peaks of XRD diffraction of the standard.
Example 2:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 20mL of N, N-Dimethylformamide (DMF), and stirring for 10min for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 10mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing with ethanol for 2 times, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an electron micrograph of the material is shown In figure 4B (the magnification of the electron micrograph is 10 k).
As can be seen from fig. 4b and 4a, the more water is added in the method of the present invention, the more non-uniform the morphology of the material.
After repeated research, the inventor shows that when the indium nitrate aqueous solution is prepared, the added water is not too much, so that the prepared material has an undesirable shape, and particularly when the water amount required by 2mmol of indium nitrate is not more than 10mL, and when the water amount exceeds the ideal value, the shape defect exceeds the ideal value, and the shape defect is deteriorated.
Example 3:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium formate to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5ml DMF to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an XRD (X-ray diffraction) pattern of the rod-shaped MIL-68(In) micro-nano material is shown In figure 1. In fig. 1, standard MIL-68 refers to the XRD structure of known standard MIL-68, and it can be seen from fig. 1 that the example of the present invention successfully prepared indium-based MIL-68 having the characteristic peaks of XRD diffraction of the standard.
Example 4:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium acetate to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of DMF to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing with ethanol for 2 times, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an electron microscope photo of the micro-nano material is shown In figure 5a (the magnification of the electron microscope photo is 10k), and an XRD (X-ray diffraction) graph is shown In figure 1. In fig. 1, standard MIL-68 refers to the XRD structure of known standard MIL-68, and it can be seen from fig. 1 that the example of the present invention successfully prepared indium-based MIL-68 having the characteristic peaks of XRD diffraction of the standard.
Example 4A:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium acetate to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of DMF to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 2h at the temperature of 90 ℃, centrifuging, washing with ethanol for 2 times, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an electron micrograph of the micro-nano material is shown In figure 5B (the magnification of the electron micrograph is 10 k).
After comparing fig. 5a with fig. 5b, it can be seen that the micro-nano material prepared by the reaction at the temperature of 90 ℃ can be prepared at room temperature by the method of the present invention, and the particle size of the micro-nano material is at least half of that of the micro-nano material prepared by the reaction at the temperature of 90 ℃; wherein, the particle size of the micro-nano material in fig. 5a is 250nm to 1500 nm; the micro-nano material in fig. 5b has a particle size of 500nm 3000 nm.
Example 5:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium propionate to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of DMF to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an XRD (X-ray diffraction) pattern of the rod-shaped MIL-68(In) micro-nano material is shown In figure 1. In fig. 1, standard MIL-68 refers to the XRD structure of known standard MIL-68, and it can be seen from fig. 1 that the example of the present invention successfully prepared indium-based MIL-68 having the characteristic peaks of XRD diffraction of the standard.
Example 6:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5ml DMF to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting at the temperature of 25 ℃ for 24h, centrifuging, washing with ethanol for 2 times, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an electron micrograph of the rod-shaped MIL-68(In) micro-nano material is shown In figure 6a (the magnification of the electron micrograph is 5k), and an XRD (XRD) diagram of the rod-shaped MIL-68(In) micro-nano material is shown In figure 1.
Example 6A:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 100mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5ml DMF to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing with ethanol for 2 times, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an electron micrograph of the rod-shaped MIL-68(In) micro-nano material is shown In figure 6B (the magnification of the electron micrograph is 5 k).
As can be seen from FIGS. 6a and 6b, the addition amount of NaF does not substantially affect the morphology of the prepared MIL-68(In) micro-nano material.
Example 7:
(1) preparation of solution A: dissolving 2mmol of terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting at the temperature of 25 ℃ for 24h, centrifuging, washing with ethanol for 2 times, and drying to obtain a rod-shaped MIL-68(In) micro-nano material, wherein an electron micrograph of the rod-shaped MIL-68(In) micro-nano material is shown In figure 7a (the magnification of the electron micrograph is 10k), and an XRD (XRD) diagram of the rod-shaped MIL-68(In) micro-nano material is shown In figure 1. In fig. 1, standard MIL-68 refers to the XRD structure of known standard MIL-68, and it can be seen from fig. 1 that the example of the present invention successfully prepared indium-based MIL-68 having the characteristic peaks of XRD diffraction of the standard.
Example 8:
(1) preparation of solution A: dissolving 2mmol of 2-amino terephthalic acid in 25mL of N, N-Dimethylformamide (DMF), and stirring for 10min for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 40 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain rod-shaped NH2-MIL-68(In) micro-nano material; the XRD pattern is shown in FIG. 2. In fig. 2, the standard MIL-68 refers to the XRD structure of the known standard MIL-68, and it can be seen from fig. 2 that the indium-based MIL-68 having the characteristic peaks of XRD diffraction of the standard was successfully prepared in the example of the present invention.
Example 9:
(1) preparation of solution A: dissolving 2mmol of 2-aminoterephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of DMF to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 40 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain rod-shaped NH2-MIL-68(In) micro-nano material; the XRD pattern is shown in FIG. 2. In fig. 2, the standard MIL-68 refers to the XRD structure of the known standard MIL-68, and it can be seen from fig. 2 that the indium-based MIL-68 having the characteristic peaks of XRD diffraction of the standard was successfully prepared in the example of the present invention.
Example 10:
(1) preparation of solution A: dissolving 2mmol of 2-aminoterephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 40 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain rod-shaped NH2-MIL-68(In) micro-nano material, wherein SEM image thereof is shown In fig. 7 b; the XRD pattern is shown in FIG. 2. In FIG. 2, standard MIL-68 refers to the XRD structure of known standard MIL-68, and as can be seen from FIG. 2, examples of the present invention successfully prepared a standardIndium base MIL-68 of XRD diffraction characteristic peak of the standard product.
Example 11:
(1) preparation of solution A: dissolving 2mmol of 2-nitroterephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-101), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 a; the XRD pattern is shown in figure 3 a.
Example 12:
(1) preparation of solution A: dissolving 2mmol of 2, 5-dihydroxyterephthalic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-102), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8B; the XRD pattern is shown in FIG. 3 b.
Example 13:
(1) preparation of solution A: dissolving 2mmol of 1, 4-naphthalenedicarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride thereto for use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing with ethanol for 2 times, and drying to obtain indium-based MOF micro-nano powder (named BUC-103), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in FIG. 8 c; the XRD pattern is shown in FIG. 3 c.
Example 14:
(1) preparation of solution A: dissolving 2mmol of 1,2,3,4,5, 6-cyclohexane-hexacarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-104), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 d; the XRD pattern is shown in figure 3 d.
Example 15:
(1) preparation of solution A: dissolving 2mmol of 1, 4-cyclohexanedicarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing with ethanol for 2 times, and drying to obtain indium-based MOF micro-nano powder (named BUC-105), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in FIG. 8 e; the XRD pattern is shown in figure 3 e.
Example 16:
(1) preparation of solution A: dissolving 2mmol of 1, 1' -cyclobutanedicarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-106), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 f; the XRD pattern is shown in FIG. 3 f.
Example 17:
(1) preparation of solution A: dissolving 2mmol of 4, 4' -diphenyl ether dicarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-107), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in fig. 8 g; the XRD pattern is shown in figure 3 g.
Example 18:
(1) preparation of solution A: dissolving 2mmol of 2, 5-thiophenedicarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride thereto for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-108), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 h; the XRD pattern is shown in FIG. 3 h.
Example 19:
(1) preparation of solution A: dissolving 2mmol of 1,2,3, 4-butanetetracarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-109), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 i; the XRD pattern is shown in FIG. 3 i.
Example 20:
(1) preparation of solution A: dissolving 2mmol of 1, 1' -ferrocenedicarboxylic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride to the solution for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-110), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 j; the XRD pattern is shown in FIG. 3 j.
Example 21:
(1) preparation of solution A: dissolving 2mmol fumaric acid in 25mL N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg sodium fluoride;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting for 24h at the temperature of 25 ℃, centrifuging, washing for 2 times by using ethanol, and drying to obtain indium-based MOF micro-nano powder (named as BUC-111), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 k; the XRD pattern is shown in FIG. 3 k.
Example 22:
(1) preparation of solution A: dissolving 2mmol of trimesic acid in 25mL of N, N-Dimethylformamide (DMF), stirring for 10min, and adding 50mg of sodium fluoride for later use;
(2) preparation of solution B: dissolving 2mmol of indium nitrate in 5mL of water to form a uniform solution;
(3) pouring the solution B into the solution A, continuously stirring and reacting (pairing) at the temperature of 25 ℃ for 24h, centrifuging, washing with ethanol for 2 times, and drying to obtain indium-based MOF micro-nano powder (named as BUC-112), wherein an electron microscope photo of the indium-based MOF micro-nano powder is shown in figure 8 l; the XRD pattern is shown in FIG. 3 l.
The indium-based MOFs in examples 11-22 differ in morphology, which can be attributed to the different coordination patterns of the different carboxylic acid ligands to indium.
Fig. 3a to 3l show XRD diffraction patterns of the acids used in examples 11 to 22 and XRD diffraction patterns of the prepared indium-based MOF micro-nano powders, respectively, which shows that the indium-based MOF micro-nano powders having typical XRD diffraction characteristic peaks are successfully prepared by the examples of the present invention.
Fig. 8a to 8l are SEM images of the indium-based MOF micro/nano powders prepared in examples 11 to 22, and it can be seen from these images that the prepared indium-based MOF micro/nano powders have rod-like structures and can be used as a material with excellent adsorbability.
As can be seen from fig. 8 a-8 l, 8a, 8c,8e,8g,8k are rod-like structures; 8d,8f,8h,8j,8l are sheet-shaped structures; 8i is a spheroidal particle; 8b are irregular in appearance.
Claims (23)
1. A preparation method of indium-based MOF micro-nano powder is characterized in that indium nitrate and carboxylic acid are used as reaction raw materials, water or salt or water and salt are added into the reaction raw materials, and the indium-based MOF micro-nano powder is prepared by reaction at 15-45 ℃, and the preparation method specifically comprises the following preparation steps:
1) preparing a carboxylic acid solution: dissolving carboxylic acid in an organic solvent to form a carboxylic acid reaction solution;
2) preparing an indium nitrate solution;
3) adding the indium nitrate solution obtained in the step 2) into the carboxylic acid solution obtained in the step 1), reacting at 15-45 ℃, and separating and drying to obtain an indium-based MOF micro/nano material;
wherein, in step 1), salt is added to form a carboxylic acid reaction solution; and/or adding water in the step 2) to form an indium nitrate aqueous solution;
wherein the carboxylic acid is a polycarboxylic acid, and the polycarboxylic acid is specifically selected from any one or two or more of terephthalic acid, 2-aminobenzoic acid, 2-nitroterephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 1 ' -cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1,2,3,4,5, 6-cyclohexanehexacarboxylic acid, 4 ' -diphenyletherdicarboxylic acid, 2, 5-thiophenedicarboxylic acid, fumaric acid, 1,2,3, 4-butanetetracarboxylic acid, trimesic acid, and 1,1 ' -ferrocenedicarboxylic acid; the salt is selected from one or more of sodium formate, sodium acetate, sodium propionate and sodium fluoride.
2. The production method according to claim 1, wherein the polycarboxylic acid is selected from fumaric acid, 1, 4-naphthalenedicarboxylic acid, trimesic acid, 2, 5-thiophenedicarboxylic acid, 4 ' -phenylenedicarboxylic acid, 1,1 ' -cyclobutanedioic acid, 1, 6-cyclohexanedicarboxylic acid, 1,2,3,4,5, 6-cyclohexanehexocarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid, 1,1 ' -ferrocenedicarboxylic acid.
3. The method according to claim 2, wherein the salt is one or more selected from sodium formate, sodium propionate and sodium fluoride.
4. The method of claim 2, wherein the salt is selected from sodium fluoride.
5. The process according to claim 1, which is obtained by a process comprising: adding water into indium nitrate to form an indium nitrate aqueous solution, adding the indium nitrate aqueous solution into the dicarboxylic acid organic solvent solution obtained in the step 1), and preparing at 15-30 ℃.
6. The production method according to claim 5, wherein a salt is added to the organic solvent solution of the dicarboxylic acid.
7. The method of claim 1 wherein the carboxylic acid reaction solution is formed by adding an organic solvent and a salt in step 1) and the aqueous indium nitrate solution is formed by adding water in step 2).
8. The production method according to claim 1, wherein an organic solvent is added without adding a salt to form a carboxylic acid reaction solution in step 1), and water is added to form an indium nitrate aqueous solution in step 2).
9. The production method according to claim 1, wherein an organic solvent is added and a salt is added to form a carboxylic acid reaction solution in step 1), and an organic solvent is added to form an indium nitrate solution in step 2).
10. The production method according to claim 1, wherein the reaction temperature in the step 3) is 15 to 30 ℃.
11. The production process according to claim 1, wherein in the step 1), the carboxylic acid solution is formed in a ratio of 2:45 to 100 in terms of mmol of carboxylic acid, mg of salt, and carboxylic acid and salt;
and 2) when the indium nitrate solution is formed, the ratio of the indium nitrate to the water is 2:5-2:10 according to mmol and mL.
12. The production method according to claim 9, wherein in the step 1), the carboxylic acid solution is formed in a ratio of 2:45 to 100 in terms of mmol of carboxylic acid, mg of salt, and carboxylic acid and salt;
and 2) when the indium nitrate solution is formed in the step 2), the ratio of the indium nitrate to the organic solvent is 2:5-2:10 according to mmol and mL.
13. The production method according to claim 11, wherein in step 1), the ratio of the carboxylic acid to the salt is 2:45 to 60.
14. The production method according to claim 12, wherein in step 1), the ratio of the carboxylic acid to the salt is 2:45 to 60.
15. The production process according to claim 1, wherein in the step 1), the carboxylic acid solution is formed by using the carboxylic acid and the organic solvent in a ratio of 2:20 to 2:30 in terms of mmol of the carboxylic acid and mL of the organic solvent.
16. The production method according to claim 15, wherein in step 1), the carboxylic acid and the organic solvent are used in a ratio of 2:25 to 2: 30.
17. The method of claim 1, wherein the indium-based MOF material is MIL-68(In), or amino MIL-68 (In).
18. The method according to any one of claims 5 to 9 or any one of claims 11 to 16, wherein the organic solvent of step 1) or step 2) is selected from an alcohol solvent or an amide solvent.
19. The method according to claim 18, wherein the organic solvent is one or more selected from the group consisting of methanol, ethanol, propanol, butanol, N-dimethylamide acetamide and N, N-dimethylformamide.
20. The method according to claim 19, wherein the organic solvent is N, N-dimethylformamide.
21. Indium-based MOF micro-nano powder obtained by the preparation method of any one of claims 1 to 20.
22. The indium-based MOF micro-nano powder of claim 21 which is MIL-68(In), or amino MIL-68 (In).
23. Use of the indium-based MOF micro-nano powder of claim 21 or 22 in an adsorbent or a photocatalytic product.
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| CN110305330B (en) * | 2019-06-27 | 2021-11-23 | 华南理工大学 | To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof |
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| CN110841715A (en) * | 2019-11-20 | 2020-02-28 | 江苏师范大学 | Synthesis method of MIL-68(In) MOFs hollow rod |
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| CN114349971B (en) * | 2021-12-22 | 2022-12-06 | 广州特种承压设备检测研究院 | Metal organic framework material and preparation method and application thereof |
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