CN115304779A - MIL-101 (Cr) and preparation method thereof - Google Patents
MIL-101 (Cr) and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of MIL-101 (Cr), which comprises the following steps: (1) Adding malic acid powder into deionized water to prepare malic acid solution; (2) Mixing and stirring uniformly the chromium nitrate nonahydrate and the terephthalic acid with the malic acid solution to obtain a mixed solution, and putting the mixed solution into a reaction kettle to carry out hydrothermal reaction to obtain the MIL-101 (Cr). Compared with the traditional mineralizers, such as hydrofluoric acid, nitric acid and the like, the mineralizer adopted by the invention is malic acid, and has the advantages of no toxicity, environmental protection and lower price. The prepared MIL-101 (Cr) material can reduce the harm in the experiment and protect the health of experimenters when ensuring good water absorption performance. The MIL-101 (Cr) material of the invention has regular grain shape and narrow size distribution range. The MIL-101 (Cr) material is in a regular octahedron shape, and the size of the material is distributed between 200 and 600 nanometers.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials, and particularly relates to MIL-101 (Cr) and a preparation method thereof.
Background
Metal Organic Frameworks (MOFs) are crystalline porous materials constructed by self-assembly of Metal ions and Organic ligands, and have the properties of porosity, adjustable pore size, large specific surface area, abundant adsorption sites and the like, so that the Metal Organic Frameworks are widely applied to the fields of chemical adsorption, electrocatalysis, component detection and the like. MIL-101 (Cr) material is synthesized in French Ferey preparation room and 2005 by hydrothermal reaction with hydrofluoric acid at 220 deg.C for the first time in small scale (5 mL). Its nomenclature is also proposed by professor frerey, the structure of MIL = materials institute Lavoisier is similar to the enhanced MTN zeolite topology. MIL-101 (Cr) has two different types of inner cages with diameters respectively equal to the diameter of the pore size window and extremely high specific surface area (BET specific surface area reaches 4000 m) 2 In terms of/g). MIL-101 (Cr) has a terminal water molecule attached to the octahedral Cr (III) building block, and this water molecule is removable under high vacuum conditions, thus creating a potential Lewis acid site. MIL-101 (Cr) and its ligand-modified derivatives exhibit significant stability to water, which makes it most suitable for use in humid or aqueous environments. Currently, MIL-101 (Cr) has evolved into one of the most important typical materials of MOFs.
Based on the unique and outstanding properties of MIL-101 (Cr), such as excellent hydrolytic stability, large specific surface area and pore size, low synthesis cost, the existence of functional metal sites and various post-modification possibilities, and the like, MIL-101 (Cr) is a good candidate material for industrial application as well as a hotspot of research of scientists. The traditional MIL-101 (Cr) adopts a high-temperature high-pressure hydrothermal synthesis method, and hydrofluoric acid, nitric acid, perfluorobenzoic acid, acetic acid, sodium acetate and the like are usually added into the synthesis reaction of the MIL-101 (Cr) as mineralizers, so that the crystallization process of the MIL-101 (Cr) is influenced. Generally, the addition of mineralizers results in better MIL-101 (Cr) crystals. However, the prior mineralizers are often associated with several disadvantages: 1. the mineralizer has high toxicity and strong corrosivity; 2. the price is high; 3. the obtained product has irregular grain shape and size and the like. Therefore, a preparation method with non-toxic production and good product property is developed, and the preparation method has obvious practical significance for large-scale commercial production and application of MIL-101 (Cr).
Disclosure of Invention
The invention aims to provide a preparation method of MIL-101 (Cr) aiming at the technical problems in the background technology.
The technical scheme adopted by the invention is as follows:
a preparation method of MIL-101 (Cr) comprises the following steps:
(1) Adding malic acid powder into deionized water to prepare malic acid solution;
(2) Mixing and stirring uniformly the chromium nitrate nonahydrate and the terephthalic acid with the malic acid solution to obtain a mixed solution, and putting the mixed solution into a reaction kettle to carry out hydrothermal reaction to obtain the MIL-101 (Cr).
More preferably, the malic acid is L-malic acid, and the concentration of the malic acid solution is in the range of 0.01 to 0.03mol/L.
The malic acid comprises L-malic acid and R-malic acid, wherein L-malic acid is an acidic substance existing in nature, and has mature extraction and synthesis technology and low cost. Too high or too low a concentration of malic acid solution can adversely affect the crystallization of the material; too low a level of crystallization is incomplete and too high a level inhibits crystallization due to low pH.
Further preferably, the mass ratio of the chromium nitrate nonahydrate to the terephthalic acid is 1: (0.2-0.6).
It is preferred that this ratio is for the convenience of subsequent purification procedures, and purification beyond this ratio is more difficult; secondly, within this ratio range, the yield of the reaction is relatively high.
More preferably, the mass of the malic acid is 1 to 1.5 percent of the total mass of the chromium nitrate nonahydrate and the terephthalic acid. The mineralizer with the proportion range can ensure that the MIL-101 (Cr) prepared by the hydrothermal reaction has the optimal crystallization effect.
Further preferably, the temperature of the hydrothermal reaction is 160-220 ℃, and the heat preservation reaction time is 6-12h.
When the reaction temperature is lower than 160 ℃, crystallization cannot be carried out, and when the reaction temperature is higher than 220 ℃, crystallization is destroyed.
Further preferably, the hydrothermal reaction kettle takes polytetrafluoroethylene as an inner liner; the temperature of the mixed solution in the reaction kettle is increased from room temperature to reaction temperature, and the temperature increasing speed is 5-10 ℃/min.
Acid is adopted as a mineralizer, and the acid corrosion is generally strong. Therefore, polytetrafluoroethylene is selected as the inner lining of the hydrothermal reaction kettle to avoid influencing the normal operation of the reaction. Because the reaction kettle is provided with the lining, the temperature inside and outside the reaction kettle can be ensured to be consistent by the slow temperature rise speed, thereby avoiding the lack of reaction time.
Further preferably, the preparation method of MIL-101 (Cr) further comprises purification treatment; the treatment method comprises the steps of carrying out suction filtration on MIL-101 (Cr) obtained after heat preservation reaction, and then putting the substance obtained by suction filtration into an organic solvent for purification; after repeated purification for many times, removing the organic solvent by using deionized water; and finally, drying and grinding the obtained substance to obtain the MIL-101 (Cr).
More preferably, the organic solvent is an N, N-dimethylformamide solvent.
Since the solvent serves to remove the reaction substance that is not combined into a crystal structure, it is necessary to make the solvent dissolve the reaction substance and to make the solvent dissolve the reaction substance very easily, which would otherwise cause the crystal structure that has been synthesized to be destroyed. Through test optimization, the N, N-dimethylformamide solvent is selected in the invention.
Further preferably, when the N, N-dimethylformamide solvent is used for purification, the mixture is heated in an oil bath at the temperature of between 50 and 70 ℃ and stirred for 1 to 5 hours; the mass ratio of the substance obtained by suction filtration to the solvent is 1: (30-60). At a temperature of 50-70 ℃, the N, N-dimethylformamide solvent can rapidly dissolve the ligand and can not cause the damage of the crystal structure.
The invention also provides the MIL-101 (Cr) prepared by the method.
The present invention is based on the following principlesTreating: 1) The mineralizer acts to activate the crystal lattice by forming a solid solution with the reactant, and the reaction capability is enhanced; forming eutectic mixture with the reactant to make the system generate liquid phase at lower temperature and accelerate the dissolution of diffusion to solid phase; form some kind of active intermediate with the reactant, or through the polarization of mineralizer ion, promote its lattice distortion and activation, etc. In the synthesis process, malic acid is used as a mineralizer and plays a role in accelerating the crystallization process of the compound. During the reaction, H is ionized in aqueous solution + And carboxylate ion promoted Cr 3+ Binding of ions to the ligand terephthalic acid. 2) The adsorptivity of the porous material MIL-101 (Cr) depends on its specific surface area and pore volume. The water absorption principle is that unsaturated sites absorb water molecules after heat treatment, the water molecules are aggregated to form water clusters, and the water clusters are combined with a cage-shaped structure to perform capillary condensation absorption. The physical adsorption mode enables the material to release the moisture stored in the pore channel under the condition of low heat exposure (50-80 ℃). The above process is repeated to achieve the effect of cycle work. In the invention, the synthesized MIL-101 (Cr) is octahedral particles with the size of micropores (b and c)<2 nm) and mesopores (2-50 nm).
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the traditional mineralizers, such as hydrofluoric acid, nitric acid and the like, the mineralizer adopted by the invention is malic acid, and has the advantages of no toxicity, environmental protection and lower price. The prepared MIL-101 (Cr) material can reduce the harm in the experiment and protect the health of experimenters when ensuring good water absorption performance.
(2) The MIL-101 (Cr) material of the invention has regular grain shape and narrow size distribution range. The MIL-101 (Cr) material is in a regular octahedron shape, and the size of the material is distributed between 200 and 600 nanometers.
(3) The MIL-101 (Cr) synthesized by the method not only has higher specific surface area and pore volume, but also has excellent water absorption capacity. Due to the recyclable physical adsorption effect, no toxicity and stability, the material is an excellent candidate material for producing drinking water in humid air.
Drawings
FIG. 1 is an SEM photograph of MIL-101 (Cr) in example 1;
FIG. 2 is N of MIL-101 (Cr) in example 1 2 Isothermal adsorption profile.
FIG. 3 is an SEM photograph of MIL-101 (Cr) in example 2;
FIG. 4 shows N of MIL-101 (Cr) in example 2 2 Isothermal adsorption curve diagram;
FIG. 5 is an SEM photograph of MIL-101 (Cr) in comparative example 1;
FIG. 6 is N of MIL-101 (Cr) in comparative example 1 2 Isothermal adsorption graph;
FIG. 7 is an SEM image of MIL-101 (Cr) in comparative example 2;
FIG. 8 is N of MIL-101 (Cr) in comparative example 2 2 Isothermal adsorption profile.
Detailed Description
In order to facilitate an understanding of the invention, the invention is described more fully and in detail below, but the scope of the invention is not limited to the following specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of MIL-101 (Cr) comprises the following steps of preparing raw materials of 4.0g of chromium nitrate nonahydrate, 1.66g of terephthalic acid and 50ml of malic acid solution, wherein the concentration of the malic acid solution is 0.01mol/L.
The synthesis method of the MIL-101 (Cr) material comprises the following steps: 0.67g malic acid was added to 500ml deionized water and stirred magnetically until the powder was completely dissolved. 4.0g of chromium nitrate nonahydrate and 1.66g of terephthalic acid were added to an empty beaker, and 50ml of the prepared malic acid solution was measured in a measuring cylinder and poured into the beaker. And magnetically stirring the mixture for 30min, pouring the mixture into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a stainless steel hydrothermal reaction kettle, and screwing a kettle cover. Then placing the mixture into a forced air drying oven, wherein the reaction temperature rise program is as follows: heating to 220 deg.C from room temperature, maintaining for 8h, and controlling the heating rate at 10 deg.C/min. After the reaction is finished. Cooling the reaction kettle to room temperature along with the furnace, and taking out to obtain a primary product. Purifying the obtained product, wherein the purification process comprises the following steps: and (3) carrying out suction filtration on the obtained primary product, adding the primary product into a three-neck flask containing an N, N-dimethylformamide solvent, carrying out oil bath heating at the temperature of 50 ℃, and stirring for 4 hours. After three times of purification, the N, N-dimethylformamide is changed into deionized water, and the mixture is stirred for 1 hour. And (3) putting the obtained purified product into a drying oven, drying at 70 ℃ for 1h, taking out and grinding to obtain the MIL-101 (Cr) powder in the embodiment.
FIG. 1 shows the SEM image of MIL-101 (Cr) synthesized in this example, from which it can be seen that the synthesized material has regular octahedron shape and mainly has size distribution in the 200-500nm interval, indicating that the synthesized material has relatively uniform size under the guidance of the experimental method.
N in the present example 2 The isothermal adsorption curve is shown in fig. 2.
The BET test results of this example are shown in table 1. Under the guidance of the experimental method, the specific surface area of the synthetic material is 2247m 2 G, average pore diameter of 3.2nm and pore volume of 1.78cm 3 (ii) in terms of/g. The example 1 indicates that the synthesized material has excellent adsorption and desorption capacity.
TABLE 1
| Concentration (mol/L) | Specific surface area (m) 2 /g) | Aperture (nm) | Pore volume (cm) 3 g -1 ) |
| 0.01 | 2247 | 3.2 | 1.78 |
Example 2:
a preparation method of MIL-101 (Cr) comprises the following steps of preparing raw materials of 4.0g of chromium nitrate nonahydrate, 1.66g of terephthalic acid and 50ml of malic acid solution, wherein the concentration of the malic acid solution is 0.02mol/L.
The synthesis method of the MIL-101 (Cr) material comprises the following steps: 0.67g of malic acid is added into 500ml of deionized water, and the mixture is magnetically stirred until the powder is completely dissolved for later use. 4.0g of chromium nitrate nonahydrate and 1.66g of terephthalic acid were added to an empty beaker, and 50ml of the prepared malic acid solution was measured out by a measuring cylinder and poured into the beaker. And magnetically stirring the mixture for 30min, pouring the mixture into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a stainless steel hydrothermal reaction kettle, and screwing a kettle cover. Then placing the mixture into a forced air drying oven, wherein the reaction temperature rise program is as follows: heating to 220 deg.C from room temperature, maintaining for 8h, and controlling the heating rate at 10 deg.C/min. After the reaction is finished. Cooling the reaction kettle to room temperature along with the furnace, and taking out to obtain a primary product. Purifying the obtained product, wherein the purification process comprises the following steps: and (3) carrying out suction filtration on the obtained primary product, adding the primary product into a three-neck flask containing an N, N-dimethylformamide solvent, carrying out oil bath heating at the temperature of 50 ℃, and stirring for 4 hours. After three times of purification, the N, N-dimethylformamide is changed into deionized water, and the mixture is stirred for 1 hour. And (3) putting the obtained purified product into a drying oven, drying at 70 ℃ for 1h, taking out and grinding to obtain the MIL-101 (Cr) powder in the embodiment.
FIG. 3 shows the SEM image of MIL-101 (Cr) synthesized in this example, from which it can be seen that the synthesized material has regular octahedron shape and mainly has size distribution in the 200-500nm interval, indicating that the synthesized material has relatively uniform size under the guidance of the experimental method.
N in the present example 2 The isothermal adsorption curve is shown in fig. 4.
The BET test of this exampleThe results are shown in Table 2. Under the guidance of the experimental method, the specific surface area of the synthetic material is 1715m 2 G, average pore diameter of 4.2nm, pore volume of 1.80cm 3 (ii) in terms of/g. The example 2 indicates that the synthesized material has excellent adsorption and desorption capacity.
TABLE 2
| Concentration (mol/L) | Specific surface area (m) 2 /g) | Pore size (nm) | Pore volume (cm) 3 g -1 ) |
| 0.02 | 1715 | 4.2 | 1.80 |
Comparative example 1:
in this comparative example, the concentration of the mineralizer in the raw material was changed to 0.04mol/L, and the other conditions were the same as in example 1.
FIG. 5 shows the MIL-101 (Cr) SEM image synthesized in this example, from which it can be seen that the morphology of the synthesized material is a mixture of regular octahedron and spheres with a size less than 200nm, indicating that the crystallization process of the material is affected under the guidance of this experimental method.
N in the present example 2 The isothermal adsorption curve is shown in fig. 6.
The BET test results of this example are shown in table 3. Under the guidance of this experimental method, the specific surface area of the synthetic material was 1069m 2 G, average pore diameter of 3.4nm and pore volume of 0.90cm 3 (ii) in terms of/g. Showing that the comparative example directs the adsorption and desorption capacity of the synthesized material to be decreased.
TABLE 3
| Concentration (mol/L) | Specific surface area (m) 2 /g) | Pore size (nm) | Pore volume (cm) 3 g -1 ) |
| 0.04 | 1069 | 3.4 | 0.90 |
Comparative example 2
In this comparative example, MIL-101 (Cr) was synthesized using hydrofluoric acid as a mineralizer.
Firstly, 4.0g of chromium nitrate nonahydrate and 1.66g of terephthalic acid are weighed and added into an empty beaker; 50ml of deionized water is measured by a measuring cylinder, 0.5ml of hydrofluoric acid solution (40 wt%) is dripped into the measuring cylinder, the concentration of the obtained acid solution is 0.05mol/L, and the prepared acid solution is poured into a beaker. And magnetically stirring the mixture for 30min, pouring the mixture into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a stainless steel hydrothermal reaction kettle, and screwing a kettle cover. Then placing the mixture into a forced air drying oven, wherein the reaction temperature rise program is as follows: heating to 220 ℃ from room temperature, keeping the temperature for 8h, and controlling the heating rate to be 10 ℃/min. After the reaction is finished. Cooling the reaction kettle to room temperature along with the furnace, and taking out to obtain a primary product. Purifying the obtained product, wherein the purification process comprises the following steps: and (3) carrying out suction filtration on the obtained primary product, adding the primary product into a three-neck flask containing an N, N-dimethylformamide solvent, carrying out oil bath heating at the temperature of 50 ℃, and stirring for 4 hours. After three times of purification, the N, N-dimethylformamide is changed into deionized water, and the mixture is stirred for 1 hour. And (3) putting the obtained purified product into a drying oven, drying at 70 ℃ for 1h, taking out and grinding to obtain the MIL-101 (Cr) powder in the embodiment.
FIG. 7 is an SEM image of MIL-101 (Cr) synthesized in the example, from which it can be seen that the synthesized material has a regular octahedral shape with sizes mainly distributed in the 200-500nm interval, indicating that the synthesized material has relatively uniform sizes under the guidance of the experimental method.
N in the present example 2 The isothermal adsorption curve is shown in fig. 8.
The BET test results of this example are shown in table 4. Under the guidance of the experimental method, the specific surface area of the synthetic material is 1438m 2 G, average pore diameter of 2.3nm, pore volume of 0.84cm 3 (ii) in terms of/g. It is shown that the use of hydrofluoric acid as a mineralizer not only results in the generation of toxic substances during the preparation of MIL-101 (Cr), but also the quality of the MIL-101 (Cr) prepared by the mineralizer is not as good as the synthesized material in example 1 in terms of adsorption and desorption.
TABLE 4
| HF(mol/L) | Specific surface area (m) 2 /g) | Aperture (nm) | Pore volume (cm) 3 g -1 ) |
| 0.05 | 1438 | 2.3 | 0.84 |
The above is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described examples. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A preparation method of MIL-101 (Cr) is characterized by comprising the following steps:
(1) Adding malic acid powder into deionized water to prepare malic acid solution;
(2) Mixing and stirring chromium nitrate nonahydrate, terephthalic acid and the malic acid solution uniformly to obtain a mixed solution, and putting the mixed solution into a reaction kettle for hydrothermal reaction to obtain MIL-101 (Cr).
2. The method according to claim 1, wherein the malic acid is L-malic acid, and the concentration of the malic acid solution is in the range of 0.01 to 0.03mol/L.
3. The production method according to claim 2, wherein the mass ratio of the chromium nitrate nonahydrate to the terephthalic acid is 1: (0.2-0.6).
4. The preparation method according to claim 3, wherein the mass of the malic acid is 1-1.5% of the total mass of the chromium nitrate nonahydrate and the terephthalic acid.
5. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction is 160-220 ℃ and the reaction time is 6-12h.
6. The preparation method according to claim 5, characterized in that the hydrothermal reaction kettle is lined with polytetrafluoroethylene; the temperature of the mixed solution in the reaction kettle is increased from room temperature to reaction temperature, and the temperature increasing speed is 5-10 ℃/min.
7. The method according to claim 1, further comprising a purification treatment; the treatment method comprises the steps of carrying out suction filtration on MIL-101 (Cr) obtained after heat preservation reaction, and then putting a substance obtained by suction filtration into an organic solvent for purification; after repeated purification for many times, removing the organic solvent by using deionized water; and finally, drying and grinding the obtained substance to obtain the MIL-101 (Cr).
8. The method according to claim 7, wherein the organic solvent is an N, N-dimethylformamide solvent.
9. The preparation method according to claim 8, wherein in the purification with the N, N-dimethylformamide solvent, the mixture is heated in an oil bath at 50 to 70 ℃ and stirred for 1 to 5 hours; and (3) performing suction filtration to obtain a substance and solvent mass ratio of 1: (30-60).
10. MIL-101 (Cr) prepared by the method of any one of claims 1-9.
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