TW202323259A - Metal organic frameworks material and method for preparing the same, and adsorption device employing the same - Google Patents

Abstract

A metal organic frameworks material and a method for preparing the same, and an adsorption device employing are provided. The metal organic frameworks material includes a first ligand, a second ligand, and a metal ion, wherein the first ligand is 3,5-pyridinedicarboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, or 2,5-furandicarboxylic acid; the second ligand is isophthalic acid, or 5-hydroxyisophthalic acid; and the metal ion is an aluminum ion, a chromium ion, or a zirconium ion. The first ligand and the second ligand are coordinated to the metal ion.

Description

Metal-organic framework material, preparation method thereof, and adsorption device comprising same

The disclosure relates to a metal organic framework material, a method for preparing the metal organic framework material, and an adsorption device comprising the metal organic framework material.

Moisture adsorbents are currently widely used in adsorption dryers in compressed air systems. After the outside air passes through the air compressor, the humidity will be higher than 80% relative humidity (RH). It is necessary to remove most of the moisture in the compressed air through a refrigeration dryer, and then remove the moisture in the compressed air through an adsorption dryer. small amount of residual moisture. After the compressed air is treated by a refrigerated dryer, the humidity will drop below about 30% RH, and then a small amount of residual moisture in the compressed air will be removed by an adsorption dryer. Therefore, the adsorbent to be suitable for the aforementioned equipment must still have a high water vapor adsorption rate in a low relative humidity environment, which is of great benefit to the volume, construction cost, and operating efficiency of the equipment.

Although the traditional water vapor adsorbent 4A zeolite has a good water vapor adsorption rate in a low-humidity environment, its high hydrophilicity increases the difficulty of water vapor desorption. Generally speaking, 4A zeolite needs to be desorbed at a temperature of 140~160°C or higher to desorb water vapor. However, high temperature desorption will not only consume a lot of energy during the regeneration of the adsorbent, but also increase the inconvenience of use. Under this consideration, there is a demand for adsorbents that desorb at low temperatures and can be used in low-humidity environments.

However, the current adsorbents are limited to the current situation that the adsorption capacity is small under low humidity and the desorption temperature needs to be higher than 140°C, which increases the equipment construction cost and operation cost, and causes the equipment to consume a lot of energy, resulting in high energy consumption. Although the industry has proposed a water vapor adsorbent that can desorb water vapor below 100°C, the key synthetic raw materials are expensive, which limits the application of the water vapor adsorbent. Furthermore, if the water vapor desorption temperature and rate of the water vapor adsorbent can be further reduced under the premise of maintaining a low humidity water vapor adsorption rate, the practicability of the water vapor adsorbent can be greatly improved.

Therefore, the industry urgently needs a novel metal-organic framework material to solve the problems encountered by previous technologies.

According to an embodiment of the present disclosure, the present disclosure provides a metal organic framework material. The metal organic framework material may include a first ligand, a second ligand, and a metal ion, wherein the first ligand is 3,5-pyridinedicarboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, or 2,5-furandicarboxylic acid; the second ligand is isophthalic acid or 5-hydroxyisophthalic acid; and the metal ion is aluminum ion, chromium ion, or zirconium ion. The first ligand and the second ligand coordinate with the metal ion.

According to some embodiments of the present disclosure, the present disclosure provides a method for preparing a metal organic framework material. The preparation method of the metal organic framework material includes the following steps. First, a composition is provided, wherein the composition includes a first ligand, a second ligand, a metal compound, and a solvent, wherein the first ligand is 3,5-pyridinedicarboxylic acid, 1H-pyrrole -2,5-dicarboxylic acid, or 2,5-furandicarboxylic acid; the second ligand is isophthalic acid, or 5-hydroxyisophthalic acid; and, the metal compound is an aluminum salt, a chromium salt, or a zirconium salt . Next, a heating step is performed on the composition to react the first ligand and the second ligand with the metal compound to obtain the metal organic framework material of the present disclosure.

According to other embodiments of the present disclosure, the present disclosure provides an adsorption device. The adsorption device includes a carrier; and an adsorption material is placed on the carrier. The adsorption material is the metal organic framework material described in this disclosure.

The metal organic framework material of the present disclosure, its preparation method, and the adsorption device comprising the metal organic framework material are described in detail below. It should be understood that the following description provides many different embodiments or examples for implementing different aspects of the present disclosure. The specific elements and arrangements described below are merely for describing the present disclosure. Of course, these are only examples rather than limitations of the present disclosure. Furthermore, repeated reference numerals or designations may be used in different embodiments. These repetitions are only for the purpose of simply and clearly describing the present disclosure, and do not represent any relationship between the different embodiments and/or structures discussed. In this disclosure, the word "about" means that the specified amount can be increased or decreased by an amount that a person skilled in the art would recognize as a normal and reasonable size.

Embodiments of the present disclosure provide a metal organic framework material, a preparation method thereof, and an adsorption device comprising the metal organic framework material.

In the preparation process of metal organic framework materials, the present disclosure uses two different ligands to carry out coordination reaction with metal ions to prepare complex ligand metal organic framework materials with porous properties. The metal organic framework material described in this disclosure can further reduce the water vapor desorption temperature and rate of the water vapor adsorbent under the premise of maintaining a low humidity water vapor adsorption rate, so that the metal organic framework material can be reduced in desorption. The energy consumption required for water vapor. In addition, through the selection of specific ligands and the adjustment of the ratio between the two ligands, the preparation cost of the metal-organic framework materials described in the present disclosure can be further reduced, increasing the practicability and competitiveness of the metal-organic framework materials.

The metal organic framework material described in this disclosure has a fast moisture absorption effect under low humidity, and can quickly desorb water vapor under low temperature conditions. The "low humidity condition" defined here refers to a temperature of 25°C with a relative humidity of 15-30%RH, and the "lower temperature condition" refers to a temperature of 60°C to 80°C. The metal-organic framework material described in this disclosure can be further configured on a carrier as an adsorption device for an adsorption dryer to achieve the purpose of rapid moisture absorption in a low-humidity environment.

According to an embodiment of the present disclosure, the present disclosure provides a metal organic framework material. The metal organic framework material includes a first ligand, a second ligand, and metal ions. According to an embodiment of the present disclosure, the first ligand may be 3,5-pyridinedicarboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, or 2,5-furandicarboxylic acid. The second ligand can be isophthalic acid, or 5-hydroxyisophthalic acid. And, the metal ion may be aluminum ion, chromium ion, or zirconium ion. The first ligand and the second ligand coordinate with the metal ion. According to an embodiment of the present disclosure, the metal organic framework material may be composed of a first ligand, a second ligand, and a metal ion, and the first ligand and the second ligand coordinate with the metal ion.

According to an embodiment of the present disclosure, the molar ratio between the first ligand and the second ligand may be about 1:9 to 9:1, such as 1:9 to 7:3, 3:7 to 1:9, or 3:7 to 7:3. If the molar ratio of the first ligand to the second ligand is lower than 1:9, the resulting metal organic framework material has a poor water vapor adsorption rate in a low humidity environment. If the molar ratio of the first ligand to the second ligand is higher than 9:1, the obtained metal organic framework material has a poor water vapor desorption rate under lower temperature conditions. According to an embodiment of the present disclosure, the ratio of the mole number of the metal ion to the total number of moles of the first ligand and the second ligand may be about 1:2 to 2:1, such as 3:5, 2:3 , 3:4, 4:5, 1:1, 5:4, 4:3, 3:2, or 5:3.

According to an embodiment of the present disclosure, the metal-organic framework material has a nitrogen-to-aluminum ratio greater than zero. If 100% primary ligand is used, the nitrogen to aluminum ratio is up to 0.34. According to an embodiment of the present disclosure, the nitrogen-to-aluminum ratio of the MOF material may be greater than 0 and less than 0.34 (eg, 0.01 to 0.33, or 0.03 to 0.32). If the nitrogen-to-aluminum ratio of the metal-organic framework material is lower, the resulting metal-organic framework material has a poorer water vapor adsorption rate in a low-humidity environment. If the nitrogen-to-aluminum ratio of the metal-organic framework material is higher, the resulting metal-organic framework material has a poorer water vapor desorption rate under lower temperature conditions.

According to an embodiment of the present disclosure, the present disclosure provides a method for preparing the above metal organic framework material. The preparation method of the metal organic framework material includes the following steps. First, a composition is provided. According to an embodiment of the present disclosure, the composition includes a first ligand, a second ligand, a metal compound, and a solvent, wherein the first ligand is 3,5-pyridinedicarboxylic acid, 1H-pyrrole-2 , 5-dicarboxylic acid, 2,5-furandicarboxylic acid, or a combination of the above, and the second ligand is isophthalic acid, 5-hydroxyisophthalic acid, or a combination of the above. Next, a heating step is performed on the composition to make the first ligand and the second ligand react with the metal compound to obtain the metal organic framework material described in Claim 1.

According to an embodiment of the present disclosure, the molar ratio between the first ligand and the second ligand is 1:9 to 9:1. According to an embodiment of the present disclosure, the molar ratio of the metal compound to the total molar ratio of the first ligand and the second ligand is 1:2 to 2:1.

According to an embodiment of the present disclosure, the first ligand is selected from the group consisting of 3,5-pyridinedicarboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, and 2,5-furandicarboxylic acid; and, the first ligand The diligand is selected from the group consisting of isophthalic acid and 5-hydroxyisophthalic acid.

According to an embodiment of the present disclosure, the metal compound may be an aluminum salt, a chromium salt, or a zirconium salt. According to an embodiment of the present disclosure, the aluminum salt can be aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum phosphate, or a combination thereof; the chromium salt can be chromium nitrate, chromium phosphate, or a combination of the above; and the zirconium salt can be Zirconium nitrate, zirconium phosphate, zirconium oxychloride, or a combination of the above. According to an embodiment of the present disclosure, the metal compound is selected from the group consisting of aluminum salts, chromium salts, and zirconium salts. According to an embodiment of the present disclosure, the metal compound is selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum phosphate, chromium nitrate, chromium phosphate, zirconium nitrate, zirconium phosphate, and zirconium oxychloride.

According to an embodiment of the present disclosure, the initial concentration of the metal compound in the composition may be between 0.15 mol/L and 0.66 mol/L (for example, 0.2 mol/L, 0.25 mol/L, 0.3 mol/L, 0.4 mol /L, 0.5 mol/L, or 0.6 mol/L), based on the volume of the solvent.

According to an embodiment of the present disclosure, the temperature of the heating step may be about 100°C to 150°C, for example, 110°C to 140°C. In addition, the time of the heating step can be 1 hour to 66 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, 12 hours, 30 hours, 50 hours, or 60 hours.

According to an embodiment of the present disclosure, the solvent includes an organic solvent, water, or a combination thereof. According to some embodiments of the present disclosure, the solvent may be an organic solvent. According to some embodiments of the present disclosure, the solvent may be water. According to some embodiments of the present disclosure, the solvent may be composed of water and an organic solvent, wherein the weight ratio of the organic solvent to water may be between 1:99 and 99:1 (for example: 1:99 to 1:29, 1: 99 to 1:1, 10:90 to 2:1, or 1:1 to 99:1). For example, the weight ratio of organic solvent to water can be 4:1, 2:1, 1:1, 1:2, 1:4, or 1:8. The organic solvent described in this disclosure may be N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, or a combination thereof. According to some embodiments of the present disclosure, the solvent is selected from the group consisting of water, N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylacetamide .

According to an embodiment of the present disclosure, the composition may consist of a first ligand, a second ligand, a metal compound, and an organic solvent. According to an embodiment of the present disclosure, the composition may be composed of a first ligand, a second ligand, a metal compound, and water.

According to an embodiment of the present disclosure, when the solvent is water, the composition further includes an alkali metal hydroxide. In other words, the composition may consist of the first ligand, the second ligand, the metal compound, water, and alkali metal hydroxide. The alkali metal hydroxide can be lithium hydroxide, sodium hydroxide, potassium hydroxide, or a combination thereof. According to an embodiment of the present disclosure, the alkali metal hydroxide is selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide.

According to an embodiment of the present disclosure, when the solvent is water, the composition further includes an alkali metal hydroxide and an aluminate, wherein the aluminate is different from the metal compound. In other words, the composition may consist of the first ligand, the second ligand, the metal compound, water, alkali metal hydroxide, and aluminate. The aluminate is lithium aluminate, sodium aluminate, potassium aluminate, magnesium aluminate, calcium aluminate, or a combination thereof. In addition, the initial concentration of the aluminate in the composition is between about 0.01 mol/L to 0.20 mol/L (eg, about 0.05 mol/L to 0.15 mol/L), based on the volume of water.

According to an embodiment of the present disclosure, when the solvent is water, the composition further includes an alkali metal hydroxide. In other words, the composition may consist of the first ligand, the second ligand, the metal compound, water, and alkali metal hydroxide.

According to an embodiment of the present disclosure, when the solvent is water, the purpose of adding alkali metal hydroxide is to neutralize the first ligand (such as 3,5-pyridinedicarboxylic acid) and the second ligand (such as isophthalic acid) to maintain the composition (aqueous solution) close to neutral (ie the pH of the composition is between 6-8), forming a water-soluble composition. Based on the above, the molar ratio of the alkali metal hydroxide to the total number of the first ligand and the second ligand may be about 1.8 to 2.2, for example, 2. Therefore, when the ratio of the total number of moles of the alkali metal hydroxide to the first ligand and the second ligand, the alkali metal hydroxide cannot completely neutralize the first ligand and the second ligand in the composition. As a result, the obtained metal organic framework material has a poor adsorption rate for water, and even the metal organic framework material cannot be obtained.

According to an embodiment of the present disclosure, when the solvent is water, adding aluminate or alcohol to the composition can inhibit the generation of crystalline by-products when the first ligand and the second ligand react with the metal compound, so as to avoid Crystalline by-products affect the water absorption of the resulting metal-organic framework materials.

According to an embodiment of the present disclosure, when the solvent is composed of water and an organic solution, and the weight ratio of the organic solution to water is 1:29 to 1:99, the composition further includes alkali metal hydroxides, aluminates, and/or alcohol. According to certain embodiments of the present disclosure, when the weight ratio of the organic solution to water is 1:29 to 1:99, if the composition does not contain alkali metal hydroxides, aluminates, and/or alcohols, the obtained Metal-organic framework materials have a poor water adsorption rate, and even metal-organic framework materials cannot be obtained.

，其中W ₁為吸附材料吸濕後的重量，以及W ₀為吸附材料完全脫附水之後所得到的重量。根據本揭露實施例，該吸附裝置100在80℃的環境放置60分鐘後其水氣脫附率可達95%至100%。在此，本揭露所述水氣脫附率可由下式所決定：

，其中W ₀為吸附材料完全脫附水之後所得到的重量、W ₂為吸附材料飽和吸水後所得到的重量，以及W ₃為吸附材料進行水氣脫附後的重量。 According to an embodiment of the present disclosure, please refer to FIG. 1 , the present disclosure provides an adsorption device 100 . The adsorption device 100 includes a carrier 120 and an adsorption material 140 . The adsorption material 140 can be disposed on the carrier 120 . According to an embodiment of the present disclosure, the adsorption material may be the metal organic framework material described in the present disclosure. According to an embodiment of the present disclosure, the adsorption device 100 can achieve saturated adsorption of metal-organic framework materials in an environment of 5%RH-80%RH (relative humidity) and 25°C, for example, the adsorption rate of water vapor at a relative humidity of 15%RH can reach 28% to 31%. Here, the water vapor adsorption rate in this disclosure can be determined by the following formula:

, where W ₁ is the weight of the absorbent material after absorbing moisture, and W ₀ is the weight obtained after the absorbent material has completely desorbed water. According to an embodiment of the present disclosure, the water vapor desorption rate of the adsorption device 100 can reach 95% to 100% after being placed in an environment of 80° C. for 60 minutes. Here, the moisture desorption rate described in this disclosure can be determined by the following formula:

, where W ₀ is the weight obtained after the adsorption material completely desorbs water, W ₂ is the weight obtained after the adsorption material is saturated with water absorption, and W ₃ is the weight of the adsorption material after desorption of water vapor.

According to an embodiment of the present disclosure, the adsorption material can be used in an adsorption dryer, such as a high-pressure air dryer or a plastic dryer, in addition to being applicable in a low-humidity environment. Moreover, the adsorbent material can also be used as an adsorbent to remove specific polar harmful small molecules or gases.

In order to make the above and other purposes, features, and advantages of the present disclosure more obvious and understandable, the following special examples and comparative examples are described in detail as follows:

Metal Organic Framework Materials

Example 1 First, aluminum sulfate (Al(SO ₄ ) ₃ ‧16H ₂ O) (3.4 mmol), 3,5-pyridine-3,5-dicarboxylic acid (8.1 mmol), m-benzene Diformic acid (isophthalic acid) (0.9mmol), sodium hydroxide (18mmol) and 25ml of water were added to a reaction flask, wherein the molar ratio of 3,5-pyridinedicarboxylic acid to isophthalic acid was 9:1 . Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into a powder to obtain the metal organic framework material (1).

Example 2 The method described in Example 1 was carried out, except that the molar ratio of 3,5-pyridinedicarboxylic acid to isophthalic acid was decreased from 9:1 to 7:3 to obtain metal organic framework material (2).

Example 3 The method described in Example 1 was carried out, except that the molar ratio of 3,5-pyridinedicarboxylic acid to isophthalic acid was decreased from 9:1 to 1:1, to obtain metal organic framework material (3).

Example 4 The method described in Example 1 was carried out, except that the molar ratio of 3,5-pyridinedicarboxylic acid to isophthalic acid was decreased from 9:1 to 3:7 to obtain metal organic framework material (4).

Example 5 The method described in Example 1 was carried out, except that the molar ratio of 3,5-pyridinedicarboxylic acid to isophthalic acid was decreased from 9:1 to 1:9 to obtain metal organic framework material (5).

Comparative Example 1 First, aluminum sulfate (Al(SO ₄ ) ₃ ‧16H ₂ O) (3.4mmol), 3,5-pyridine-3,5-dicarboxylic acid (9mmol), sodium hydroxide (18 mmol ) and 25 ml of water were added to a reaction flask. Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol ) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into a powder to obtain the metal-organic framework material (6).

Comparative Example 2 First, aluminum sulfate (Al(SO ₄ ) ₃ ‧16H ₂ O) (3.4mmol), isophthalic acid (9mmol), sodium hydroxide (18mmol) and 25ml of water were added to a in the reaction vial. Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol ) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into a powder to obtain the MOF (7).

Nitrogen-aluminum ratio measurement The metal organic framework materials (1)-(7) described in Examples 2, 4 and Comparative Examples 1 and 2 were combined with a transmission electron microscope ( transmission electron microscope, TEM) to carry out element identification, and calculate the ratio of nitrogen to aluminum in metal organic framework materials, and the results are shown in Table 1.

Table 1 Nitrogen to Aluminum Ratio (N/Al) Metal Organic Framework Materials (2) 0.06 Metal Organic Framework Materials (4) 0.17 Metal Organic Framework Materials (6) 0.34 Metal Organic Framework Materials (7) 0

It can be seen from Table 1 that the nitrogen-to-aluminum ratio of MOFs synthesized with different molar ratios of 3,5-pyridinedicarboxylic acid and isophthalic acid is linear. When the amount of 3,5-pyridinedicarboxylic acid is larger, , the higher the nitrogen-to-aluminum ratio of the metal-organic framework material of the obtained metal-organic framework material.

Water vapor adsorption rate measurement The metal-organic framework materials (1)-(7) described in Examples 1-5 and Comparative Examples 1 and 2 were dried in a vacuum environment at 80° C. for 2 hours to completely desorb water from the metal-organic framework materials. Next, place the metal organic framework material in a constant temperature and humidity machine, and place it at 25°C and different relative humidity for 120 minutes to allow the metal organic framework material to absorb water vapor, and measure the water vapor adsorption rate of the metal organic framework material , and the results are shown in Table 2.

Table 2 Ligand Water adsorption ratio (%) 15%RH 20%RH 30%RH 80%RH Metal Organic Framework Materials (1) 3,5-pyridinedicarboxylic acid/isophthalic acid (9/1) - - 31 - Metal Organic Framework Materials (2) 3,5-pyridinedicarboxylic acid/isophthalic acid (7/3) 30 31 31 33 Metal Organic Framework Materials (3) 3,5-pyridinedicarboxylic acid/isophthalic acid (1/1) 29 30 31 33 Metal Organic Framework Materials (4) 3,5-pyridinedicarboxylic acid/isophthalic acid (3/7) 28 30 31 36 Metal Organic Framework Materials (5) 3,5-pyridinedicarboxylic acid/isophthalic acid (1/9) - - 26 - Metal Organic Framework Materials (6) 3,5-Pyridinedicarboxylic acid 29 30 31 34 Metal Organic Framework Materials (7) Isophthalic acid 8 27 28 35

It can be seen from Table 2 that the metal organic framework materials described in Examples 1-5 (with different proportions of ligands (3,5-pyridinedicarboxylic acid and isophthalic acid)) were exposed to high humidity (80%RH) And low humidity (15-30%RH) can maintain a high water vapor adsorption rate. In addition, when only isophthalic acid is used as the ligand of the MOF, it can be observed that the moisture adsorption rate of the obtained MOF under low humidity (15%RH) is poor.

Water vapor desorption rate measurement The metal organic framework materials (2)-(4) and (6) described in Examples 2-4 and Comparative Example 1 were adsorbed to saturation at 25° C. and 80% RH. Next, put the metal organic framework material in an oven at 60°C, 70°C, and 80°C, measure the weight of the metal organic framework material at different times, and convert the water vapor adsorption rate, the results are shown in Figures 2-4 respectively Show.

It can be seen from Figures 2-4 that when moisture is desorbed at 60°C, the metal organic framework material described in Comparative Example 1 (that is, the metal organic framework material using only 3,5-pyridinedicarboxylic acid as a ligand) After standing for 120 minutes, the water vapor desorption rate is only about 34%. The moisture desorption rate of the metal organic framework material described in Example 2 can reach about 73% after being placed for 120 minutes, and the metal organic framework material described in Examples 3 and 4 can even achieve complete desorption of water vapor after being placed for 120 minutes attached. In addition, when moisture desorption is performed at 80°C, the moisture desorption rate of the metal organic framework material in this disclosure can reach 95% to 100% after standing for 60 minutes, while the metal organic framework material described in Comparative Example 1 After standing for 60 minutes, the water vapor desorption rate only reached about 85%. Based on the above, it can be seen from Table 2 and Figures 2-4 that the composite ligand metal-organic framework material formed by using isophthalic acid and 3,5-pyridinedicarboxylic acid can maintain the water vapor adsorption rate. Under this condition, the temperature required for water vapor desorption is lowered and the rate of water vapor desorption is increased. In addition, since the raw material cost of 3,5-pyridinedicarboxylic acid is more than 90 times that of isophthalic acid, the metal-organic framework material (6) (that is, a metal that only uses 3,5-pyridinedicarboxylic acid as a ligand Compared with organic framework materials), the preparation cost of metal organic framework materials described in the present disclosure can be greatly reduced.

Comparative Example 3 First, aluminum sulfate (Al(SO ₄ ) ₃ ‧16H ₂ O) (3.4mmol), 3,5-pyridine-3,5-dicarboxylic acid (4.5mmol), ortho-benzene Diformic acid (o-phthalic acid) (4.5mmol), sodium hydroxide (18mmol) and 25 ml of water were added to a reaction flask, wherein the molar ratio of 3,5-pyridinedicarboxylic acid to phthalic acid was 1 :1. Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into powder to obtain metal organic framework material (8).

Comparative Example 4 First, aluminum sulfate (Al(SO ₄ ) ₃ ‧16H ₂ O) (3.4mmol), 3,5-pyridine-3,5-dicarboxylic acid (4.5mmol), p-benzene Dicarboxylic acid (terephthalic acid) (4.5mmol), sodium hydroxide (18mmol) and 25ml of water were added to a reaction flask, wherein the molar ratio of 3,5-pyridinedicarboxylic acid to phthalic acid was 1:1 . Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol ) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into a powder to obtain the metal-organic framework material (9).

Comparative Example 5 First, aluminum sulfate (Al(SO ₄ ) ₃ ‧16H ₂ O) (3.4mmol), 2,6-pyridine-2,6-dicarboxylic acid (4.5mmol), m-benzene Dicarboxylic acid (isophthalic acid) (4.5mmol), sodium hydroxide (18mmol) and 25ml of water were added to a reaction flask, wherein the molar ratio of 3,5-pyridinedicarboxylic acid to phthalic acid was 1:1 . Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol ) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into a powder to obtain the metal organic framework material (10).

Next, the metal-organic framework materials (8)-(10) described in Comparative Examples 3-5 were dried in a vacuum environment at 80° C. for 2 hours, so as to completely desorb water from the metal-organic framework materials. Next, the metal organic framework material was placed in a constant temperature and humidity machine, and placed at 25°C and 30% RH for 120 minutes to allow the metal organic framework material to absorb water vapor, and the water vapor adsorption rate of the metal organic framework material was measured. The results are shown in Table 2.

Table 2 Water adsorption ratio (%) (30% RH) Metal Organic Framework Materials (3) 31 Metal Organic Framework Materials (8) 10 Metal Organic Framework Materials (9) 11 Metal Organic Framework Materials (10) 6

It can be seen from Table 2 that when isophthalic acid is replaced by phthalic acid or terephthalic acid, the obtained metal organic framework material has a poor water vapor adsorption rate at 30% RH. In addition, when 3,5-pyridinedicarboxylic acid was replaced by 2,6-pyridinedicarboxylic acid, the resulting metal-organic framework material had a poor water vapor adsorption rate at 30% RH.

From the foregoing examples, it can be known that the composite ligand metal-organic framework material described in this disclosure can reduce the temperature required for water vapor desorption and increase the water vapor desorption rate under the premise of maintaining the water vapor adsorption rate, to achieve The effect of rapid moisture absorption in low humidity environment and rapid desorption at low temperature.

Example 6 First, zirconium oxychloride (ZrOCl ₂ ‧8H ₂ O) (6.75mmol), 3,5-pyridine-3,5-dicarboxylic acid (4.5mmol), isophthalic acid (isophthalic acid) (4.5mmol), sodium hydroxide (18mmol) and 25 ml of water were added to a reaction flask, wherein the molar ratio of 3,5-pyridinedicarboxylic acid to phthalic acid was 1:1. Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol ) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into a powder to obtain the metal organic framework material (11).

Example 7 First, chromium nitrate (Cr(NO ₃ ) ₃ ‧9H ₂ O) (3.4mmol), 3,5-pyridine-3,5-dicarboxylic acid (4.5mmol), m-benzene Dicarboxylic acid (isophthalic acid) (4.5mmol), sodium hydroxide (18mmol) and 25ml of water were added to a reaction flask, wherein the molar ratio of 3,5-pyridinedicarboxylic acid to phthalic acid was 1:1 . Next, sodium aluminate aqueous solution (NaAlO ₂ ) (2.3 mmol ) was added into the reaction flask to obtain a composition. Next, the obtained composition was uniformly stirred and reacted at 125° C. for 20 hours. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The above precipitate was washed with water and filtered to obtain a solid. Then, the obtained solid was dried overnight in an oven at a drying temperature of about 80°C. After drying, the solid was ground into a powder to obtain the metal-organic framework material (12).

Next, the organic framework materials (11) and (12) described in Examples 6-7 were dried in a vacuum environment at 80° C. for 2 hours, so as to completely desorb water from the metal organic framework materials. Next, the metal organic framework material was placed in a constant temperature and humidity machine, and placed at 25°C and 30% RH for 120 minutes to allow the metal organic framework material to absorb water vapor, and the water vapor adsorption rate of the metal organic framework material was measured. The results are shown in Table 3.

table 3 Water adsorption ratio (%) (30% RH) Metal Organic Framework Materials (11) 9.63 Metal Organic Framework Materials (12) 11.04

Although the disclosure has been disclosed above with several embodiments, it is not intended to limit the disclosure, and anyone with ordinary knowledge in the technical field may make any changes and modifications without departing from the spirit and scope of the disclosure. , so the scope of protection of this disclosure should be defined by the appended claims.

100: adsorption device 120: carrier 140: Adsorbent material

Figure 1 is a schematic diagram of the adsorption device described in the embodiment of the present disclosure; Figure 2 is a graph showing the relationship between the moisture desorption rate and time at 60°C for the metal-organic framework materials described in Examples 2-4 and Comparative Example 1 of the present disclosure; Figure 3 is a graph showing the relationship between the moisture desorption rate and time at 70°C for the metal organic framework materials described in Examples 2-4 and Comparative Example 1 of the present disclosure; and FIG. 4 is a graph showing the relationship between the water vapor desorption rate and time at 80° C. of the metal-organic framework materials described in Examples 2-4 and Comparative Example 1 of the present disclosure.

100: adsorption device

120: carrier

140: Adsorbent material

Claims (24)

A metal organic framework material comprising: A first ligand, wherein the first ligand is 3,5-pyridinedicarboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, or 2,5-furandicarboxylic acid; A second ligand, wherein the second ligand is isophthalic acid, or 5-hydroxyisophthalic acid; and A metal ion, wherein the metal ion is aluminum ion, chromium ion, or zirconium ion, wherein the first ligand and the second ligand coordinate with the metal ion. The metal organic framework material according to claim 1, wherein the molar ratio of the first ligand and the second ligand is 1:9 to 9:1. The metal organic framework material according to claim 1, wherein the molar ratio of the metal ion to the total molar ratio of the first ligand and the second ligand is 1:2 to 2:1. The metal organic framework material according to claim 1, wherein the nitrogen to aluminum ratio of the metal organic framework material is greater than 0 and less than 0.34. A method for preparing a metal organic framework material, comprising: A composition is provided, wherein the composition includes a first ligand, a second ligand, a metal compound, and a solvent, wherein the first ligand is 3,5-pyridinedicarboxylic acid, 1H-pyrrole-2 , 5-dicarboxylic acid, 2,5-furandicarboxylic acid, or a combination of the above, and the second ligand system isophthalic acid, 5-hydroxyisophthalic acid, or a combination of the above; and A heating step is performed on the composition to react the first ligand and the second ligand with the metal compound to obtain the metal organic framework material described in Claim 1. The method for preparing a metal-organic framework material according to claim 5, wherein the molar ratio between the first ligand and the second ligand is 1:9 to 9:1. The method for preparing a metal organic framework material according to claim 5, wherein the ratio of the mole number of the metal ion to the total number of moles of the first ligand and the second ligand is 1:2 to 2:1. The method for preparing a metal organic framework material according to claim 5, wherein the metal compound is an aluminum salt, a chromium salt, or a zirconium salt. The method for preparing metal-organic framework materials according to claim 5, wherein the metal compound is aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum phosphate, chromium nitrate, chromium phosphate, zirconium nitrate, zirconium phosphate, or zirconium oxychloride. The method for preparing a metal organic framework material according to claim 5, wherein the initial concentration of the metal compound in the composition is between about 0.05 mol/L and 0.20 mol/L. The method for preparing a metal organic framework material according to claim 5, wherein the solvent includes an organic solvent, water, or a combination thereof. The preparation method of the metal organic framework material as described in claim 11, wherein the organic solvent includes N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylformamide Amide, or a combination of the above. According to the preparation method of the metal organic framework material described in claim 11, when the solvent is water, the composition further includes an alkali metal hydroxide. The method for preparing a metal organic framework material as claimed in item 13, wherein the alkali metal hydroxide comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, or the above-mentioned combination. The method for preparing a metal organic framework material according to claim 13, wherein the molar ratio of the alkali metal hydroxide to the total number of the first ligand and the second ligand is 3 to 1. The method for preparing a metal organic framework material as claimed in claim 5, wherein the composition further includes an aluminate. The preparation method of the metal organic framework material as described in claim item 16, wherein the aluminate comprises lithium aluminate (lithium aluminate), sodium aluminate (sodium aluminate), potassium aluminate (potassium aluminate), magnesium aluminate (magnesium aluminum), calcium aluminate, or a combination of the above. The method for preparing a metal-organic framework material according to claim 16, wherein the initial concentration of the aluminate in the composition is between about 0.05 mol/L and 0.20 mol/L. The method for preparing a metal organic framework material according to claim 5, wherein the composition further includes alcohol. The method for preparing a metal organic framework material as claimed in claim 5, wherein the temperature of the heating step is between about 100°C and 150°C. The preparation method of the metal organic framework material as claimed in claim 5, wherein the time of the heating step is about 1 hour to 66 hours. An adsorption device comprising: a carrier; and An adsorption material is placed on the carrier, wherein the adsorption material is a metal organic framework material as described in item 1 of the claim. The adsorption device as claimed in claim 22, wherein the adsorption rate of the adsorption device for water can reach 28% to 31% after being placed in an environment of 15% RH and 25°C for 120 minutes. The adsorption device according to claim 22, wherein the desorption rate of the adsorption device for water can reach 95% to 100% after being placed in an environment of 80°C for 60 minutes.

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