Application of copper-based metal-organic frameworks in formaldehyde adsorption and removal

Abstract

The application relates to the technical field of metal organic framework materials, and relates to application of a copper-based metal organic framework material in formaldehyde adsorption and removal. The chemical molecular formula of the copper-based organic framework material is [Cu2(Ad)2(SA)]*3DMA, Ad is an organic ligand adenine, and SA is an auxiliary ligand succinic acid; the copper-based organic framework material can adsorb and remove 0.87 mg / m<3> of formaldehyde within 3 hours, and can be regenerated and recycled after formaldehyde adsorption and removal. 3 ​

Description

Technical Field

[0001] This invention relates to the field of metal-organic framework materials technology, and specifically to the application of a copper-based metal-organic framework material in formaldehyde adsorption and removal. Technical Background

[0002] Formaldehyde, a significant air pollutant, primarily originates indoors from building materials, paints, furniture adhesives, and synthetic fiber carpets. Although indoor formaldehyde concentrations are typically kept at low levels (<20 ppm), its harm to human health cannot be ignored. Therefore, developing efficient formaldehyde removal technologies is of great practical importance.

[0003] Among existing volatile organic compound (VOC) removal technologies, adsorption has attracted much attention due to its high efficiency and cost-effectiveness. Metal-organic frameworks (MOFs), as a novel class of porous crystalline materials, possess high designability and tunability. Among them, amino (-NH2) functionalized MOFs exhibit excellent formaldehyde adsorption performance through the synergistic effect of covalent bonds (forming imine / Schiff bases) and non-covalent bonds (electrostatic interactions), providing a new solution for indoor formaldehyde pollution control. Summary of the Invention

[0004] The purpose of this invention is to provide an application of copper-based metal-organic framework materials in formaldehyde adsorption and removal.

[0005] This invention is achieved through the following technical solution:

[0006] Application of a copper-based organic framework material in formaldehyde adsorption and removal.

[0007] Furthermore, the chemical formula of the copper-based organic framework material is [Cu2(Ad)2(SA)]·3DMA, where Ad is the organic ligand adenine and SA is the auxiliary ligand succinic acid. The chemical structural formula of adenine is as follows:

[0008] The chemical structural formula of succinic acid is as follows:

[0009] .

[0010] Furthermore, the preparation method of the copper-based organic framework material includes the following steps:

[0011] Under sealed conditions, organic ligands adenine and succinic acid react with Cu(NO3)2·3H2O in a mixed solution of N,N-dimethylamide and deionized water via a solvothermal reaction to obtain crystals of a metal-organic framework.

[0012] Furthermore, the molar ratio of the organic ligand adenine, succinic acid, and Cu(NO3)2·3H2O is 1:1:2-4, and each 0.04 mmol of copper nitrate corresponds to 4 mL of N,N-dimethylformamide and 2.0 mL of deionized water; the solvothermal reaction is carried out at a temperature of 80 °C for 12–48 hours.

[0013] Furthermore, the copper-based organic framework material can be regenerated and recycled after formaldehyde adsorption and removal.

[0014] The present invention also provides a method for adsorbing and removing formaldehyde using the copper-based organic framework material, comprising the following steps: adding the copper-based organic framework material to a formaldehyde-air mixture, waiting for the formaldehyde gas concentration to stabilize, and then separating the copper-based organic framework material.

[0015] The present invention also provides a method for the adsorption and removal of formaldehyde by the copper-based organic framework material and its regeneration, comprising the following steps: placing the copper-based organic framework material after adsorption and removal of formaldehyde under the sun for 24 hours to achieve regeneration and recycling.

[0016] The present invention also provides a method for regenerating the copper-based organic framework material after adsorption and removal of formaldehyde, comprising the following steps: vacuum drying the copper-based organic framework material after adsorption and removal of formaldehyde to perform desorption, thereby achieving regeneration and recycling.

[0017] Furthermore, the drying temperature is 120-150℃.

[0018] Compared with the prior art, the present invention has the following technical effects:

[0019] The copper-based organic framework material of this invention exhibits good water stability and is resistant to acids, alkalis, and high temperatures. Furthermore, this copper-based organic framework material can be applied to formaldehyde adsorption and can be desorbed and recycled. Attached Figure Description

[0020] Figure 1 The adsorption curve of Cu-AD-SA material after static adsorption experiment with formaldehyde at an initial concentration of 1 mg / m3 in a 25L container at room temperature.

[0021] Figure 2 The adsorption curve of formaldehyde after static adsorption experiment of regenerated Cu-AD-SA material is shown.

[0022] Figure 3 This is a comparison chart of the formaldehyde adsorption effects of existing materials and the material obtained by this invention. Detailed Implementation

[0023] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to the following embodiments.

[0024] Example 1

[0025] Under sealed conditions, 0.01 mmol of the organic ligand adenine and 0.01 mmol of succinic acid were reacted with 0.04 mmol of Cu(NO3)2·3H2O in a mixed solution of 4 mL N,N-dimethylamide and 2 mL deionized water via a solvothermal reaction to obtain crystals of a metal-organic framework. The solvothermal reaction was carried out at a temperature of 80 °C for 12-48 hours.

[0026] The sample obtained in Example 1 was post-processed and dried to obtain an adsorbed sample for formaldehyde static adsorption testing.

[0027] Example 2

[0028] Step 1: Weigh 0.3183 g of the adsorbed sample and add it to a 25 L container (1 mg / m³). 3 In a container containing a mixture of formaldehyde and air.

[0029] Step 2: After the formaldehyde gas concentration stabilizes, begin the measurement.

[0030] Step 3: Measure the change in formaldehyde concentration inside the container using a formaldehyde detector.

[0031] Comparative Example 1

[0032] Step 1: Weigh 0.3183 g of activated carbon and add it to a 25 L container. This will give you 1 mg / m³ of activated carbon. 3 In a container containing a mixture of formaldehyde and air.

[0033] Step 2: After the formaldehyde gas concentration stabilizes, begin the measurement.

[0034] Step 3: Measure the change in formaldehyde concentration inside the container using a formaldehyde detector.

[0035] Example 3

[0036] Step 1: Weigh 0.3031 g of sample and add it to 25 L of water. This solution contains 1 mg / m³. 3 In a container containing a mixture of formaldehyde and air.

[0037] Step 2: After the formaldehyde gas concentration stabilizes, begin the measurement.

[0038] Step 3: Measure the change in formaldehyde concentration inside the container using a formaldehyde detector.

[0039] The adsorption curves obtained after static adsorption experiments in Examples 2-3 and Comparative Example 1 are shown below. Figure 1 As shown, this indicates that the Cu-AD-SA material can adsorb and remove 0.87 mg / m³ within 3 hours. 30.85 mg / m 3 Formaldehyde exhibits good trace static adsorption performance, superior to activated carbon (0.44 mg / m³). 3 This indicates that the material has good application prospects in the field of adsorbing and removing formaldehyde from the air.

[0040] After the adsorption test in Example 2, the sample was placed in the sun for 24 hours to dry, or vacuum dried at a temperature of 120-150 degrees Celsius to regenerate the material. The formaldehyde adsorption test was then repeated. The test conditions were the same as in Example 2, and the above operation was repeated twice.

[0041] The results obtained are as follows Figure 2 As shown, the regenerated material can adsorb and remove 0.71 mg / m³ within 3 hours. 3 0.84 mg / m 3 0.62 mg / m 3 The formaldehyde still exhibits good trace static adsorption performance, superior to activated carbon (0.44 mg / m³). 3 It has good application prospects in the field of adsorption and removal of formaldehyde from the air.

[0042] The same tests as in Example 2 were conducted on existing materials including activated carbon, CAU-10-NH3, CALF-20, Fe-BTC, Y-BTC, and Zn2atz2ipa. The formaldehyde adsorption effects of each material were compared, and the results are shown in [Figure 2]. Figure 3 This indicates that among the metal-organic framework materials that can be mass-produced, Cu-AD-SA has the best adsorption performance for formaldehyde, and its performance is superior to that of activated carbon, a commonly used formaldehyde adsorption material on the market.

Claims

1. The application of a copper-based organic framework material in formaldehyde adsorption and removal, characterized in that: The chemical formula of the copper-based organic framework material is [Cu2(Ad)2(SA)]·3DMA, where Ad is the organic ligand adenine and SA is the auxiliary ligand succinic acid. The chemical structural formula of adenine is as follows: The chemical structural formula of succinic acid is as follows: ； The copper-based organic framework material is used for trace static adsorption and removal of formaldehyde from the air at a formaldehyde concentration of 1 mg / m³. 3 ; The copper-based organic framework material can be regenerated and recycled after formaldehyde adsorption and removal.

2. The application of the copper-based organic framework material according to claim 1 in formaldehyde adsorption and removal, characterized in that: The preparation method of the copper-based organic framework material includes the following steps: Under sealed conditions, organic ligands adenine and succinic acid react with Cu(NO3)2·3H2O in a mixed solution of N,N-dimethylamide and deionized water via a solvothermal reaction to obtain crystals of a metal-organic framework.

3. The application of the copper-based organic framework material according to claim 2 in formaldehyde adsorption and removal, characterized in that: The molar ratio of the organic ligand adenine, succinic acid and Cu(NO3)2·3H2O is 1:1:2-4. Each 0.04 mmol of copper nitrate corresponds to 4 mL of N,N-dimethylformamide and 2.0 mL of deionized water. The solvothermal reaction is carried out at a temperature of 80 °C for 12–48 hours.

4. The application of the copper-based organic framework material according to claim 1 in formaldehyde adsorption and removal, characterized in that: The method for adsorbing and removing formaldehyde using the copper-based organic framework material includes the following steps: adding the copper-based organic framework material to a formaldehyde-air mixture, waiting for the formaldehyde gas concentration to stabilize, and then separating the copper-based organic framework material.

5. The application of the copper-based organic framework material according to claim 1 in formaldehyde adsorption and removal, characterized in that: The method for regenerating the copper-based organic framework material by adsorbing and removing formaldehyde includes the following steps: placing the copper-based organic framework material after adsorbing and removing formaldehyde under the sun for 24 hours to achieve regeneration and recycling.

6. The application of the copper-based organic framework material according to claim 1 in formaldehyde adsorption and removal, characterized in that: The method for regenerating copper-based organic framework materials by adsorbing and removing formaldehyde includes the following steps: vacuum drying the copper-based organic framework materials after adsorbing and removing formaldehyde to remove adsorption, thereby achieving regeneration and recycling.

7. The application of the copper-based organic framework material according to claim 6 in formaldehyde adsorption and removal, characterized in that: Drying temperature: 120-150℃.

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