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

Abstract

The invention relates to the technical field of metal organic framework materials, in particular 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, 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 regeneration and cyclic utilization can be achieved after formaldehyde adsorption and removal.

Description

Technical Field

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

[0002] Formaldehyde is one of the important pollutants in the atmospheric environment, and its indoor sources mainly include building decoration materials, coatings, furniture adhesives and synthetic fiber carpets. Although the indoor formaldehyde concentration is usually maintained at a low level (<20 ppm), its harm to human health cannot be ignored. Therefore, the development of efficient formaldehyde removal technology is of great practical significance.

[0003] Among the existing volatile organic compound (VOCs) removal technologies, the adsorption method has attracted much attention due to its high efficiency and economy. Metal-Organic Frameworks (MOFs), as a new type of porous crystalline materials, are highly designable and controllable. Among them, amino (-NH2) functionalized MOFs materials show excellent formaldehyde adsorption performance through the synergistic effect of covalent bonds (forming imines / 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 the present invention is to provide an application of a copper-based metal organic framework material in the adsorption and removal of formaldehyde.

[0005] The present invention is achieved through the following technical solutions: Application of a copper-based organic framework material in formaldehyde adsorption and removal.

[0006] Furthermore, the chemical formula of the copper-based organic framework material is [Cu2(Ad)2(SA)]·3DMA, where Ad is an organic ligand adenine and SA is an auxiliary ligand succinic acid, wherein the chemical structure of adenine is as follows: The chemical structure of succinic acid is as follows: .

[0007] Furthermore, the method for preparing the copper-based organic framework material comprises the following steps: Under sealed conditions, organic ligands adenine and succinic acid reacted with Cu(NO3)2·3H2O in a mixed solution of N,N-dimethylamide and deionized water to obtain metal-organic framework crystals via solvothermal reaction.

[0008] Furthermore, the molar ratio of the organic ligand adenine, succinic acid and Cu(NO3)2·3H2O is 1:1:2-4, and every 0.04 mmol of copper nitrate corresponds to 4 mL of N,N-dimethylformamide and 2.0 mL of deionized water; the temperature of the solvent thermal reaction is 80°C, and the reaction time is 12 to 48 hours.

[0009] Furthermore, the copper-based organic framework material can be regenerated and recycled after formaldehyde is adsorbed and removed.

[0010] The present invention also provides a method for removing formaldehyde by adsorption of 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.

[0011] The present invention also provides a method for regenerating the copper-based organic framework material after removing formaldehyde by adsorption, comprising the following steps: placing the copper-based organic framework material after the formaldehyde is adsorbed and removed under the sun for 24 hours to achieve regeneration and recycling.

[0012] 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.

[0013] Furthermore, the drying temperature is 120-150°C.

[0014] Compared with the prior art, the present invention has the following technical effects: The copper-based organic framework material of the present invention has good water stability, and is resistant to acid, alkali and high temperature. In addition, the copper-based organic framework material can be applied to formaldehyde adsorption and can be desorbed and recycled. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is the adsorption curve of Cu-AD-SA material after the static adsorption experiment of formaldehyde with an initial concentration of 1 mg / m3 in a 25L container at room temperature; Figure 2 It is the adsorption curve diagram of the regenerated Cu-AD-SA material after the static adsorption experiment of formaldehyde; Figure 3 The figure is a comparison chart of the formaldehyde adsorption effects of the existing material and the material obtained by the present invention. DETAILED DESCRIPTION

[0016] The present invention will be further described below in conjunction with examples, but the present invention is not limited to the following examples.

[0017] Example 1 Under sealed conditions, 0.01 mmol of 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 of N,N-dimethylamide and 2 mL of deionized water to obtain metal-organic framework crystals via a solvothermal reaction. The solvothermal reaction temperature was 80°C and the reaction time was 12-48 hours.

[0018] The sample obtained in Example 1 was post-treated and dried to obtain an adsorption sample for formaldehyde static adsorption test.

[0019] Example 2 Step 1: Weigh 0.3183 g of adsorption sample and add it to 25 L of 1 mg / m 3 In a container of formaldehyde-air mixture.

[0020] Step 2: Wait for the formaldehyde gas concentration to stabilize and then start measuring.

[0021] Step 3: Use a formaldehyde detector to measure the concentration change of formaldehyde in the container.

[0022] Comparative Example 1 Step 1: Weigh 0.3183 g of activated carbon and add it to 25 L to obtain 1 mg / m 3 In a container of formaldehyde-air mixture.

[0023] Step 2: Wait for the formaldehyde gas concentration to stabilize and then start measuring.

[0024] Step 3: Use a formaldehyde detector to measure the concentration change of formaldehyde in the container.

[0025] Example 3 Step 1: Weigh 0.3031 g of sample and add it to 25 L to obtain 1 mg / m 3 In a container of formaldehyde-air mixture.

[0026] Step 2: Wait for the formaldehyde gas concentration to stabilize and then start measuring.

[0027] Step 3: Use a formaldehyde detector to measure the concentration change of formaldehyde in the container.

[0028] The adsorption curves obtained after the static adsorption experiments of Examples 2-3 and Comparative Example 1 are as follows: Figure 1 It shows that the Cu-AD-SA material can adsorb and remove 0.87 mg / m 3 , 0.85 mg / m 3 It has good trace static adsorption performance for formaldehyde, which is better than activated carbon (0.44 mg / m 3), indicating that this material has good application prospects in the field of adsorption and removal of formaldehyde in the air.

[0029] The sample after the adsorption test in Example 2 was placed in the sun for 24 hours, or vacuum dried for desorption at a drying temperature of 120-150 degrees Celsius to achieve material regeneration, and then the formaldehyde adsorption test was repeated. The test conditions were the same as in Example 2, and the above operation was repeated twice.

[0030] The results are as follows Figure 2 As shown in the figure, it shows that the regenerated materials can remove 0.71 mg / m 3 , 0.84 mg / m 3 , 0.62 mg / m 3 It still has good trace static adsorption performance of formaldehyde, which is better than activated carbon (0.44mg / m 3 ), has good application prospects in the field of adsorption and removal of formaldehyde in the air.

[0031] The materials activated carbon, CAU-10-NH3, CALF-20, Fe-BTC, Y-BTC, and Zn2atz2ipa in the prior art were tested in the same manner as in Example 2 to compare the formaldehyde adsorption effects of the above materials. The results are shown in FIG. Figure 3 , indicating that among the metal-organic framework materials that can be prepared in large quantities, Cu-AD-SA has the best formaldehyde adsorption performance, and its performance is better than activated carbon, a commonly used formaldehyde adsorption material on the market.

Claims

1. Application of a copper-based organic framework material in formaldehyde adsorption and removal.

2. The use of the copper-based organic framework material in formaldehyde adsorption removal according to claim 1, characterized in that: The chemical formula of the copper-based organic framework material is [Cu2(Ad)2(SA)]·3DMA, where Ad is an organic ligand adenine and SA is an auxiliary ligand succinic acid, wherein the chemical structure of adenine is as follows: The chemical structure of succinic acid is as follows: 。 3. The use of the copper-based organic framework material in formaldehyde adsorption and removal according to claim 1, characterized in that: The preparation method of the copper-based organic framework material comprises the following steps: Under sealed conditions, organic ligands adenine and succinic acid reacted with Cu(NO3)2·3H2O in a mixed solution of N,N-dimethylamide and deionized water to obtain metal-organic framework crystals via solvothermal reaction.

4. The use of the copper-based organic framework material in formaldehyde adsorption removal according to claim 3, 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 temperature of the solvent thermal reaction is 80°C, and the reaction time is 12 to 48 hours.

5. The use of the copper-based organic framework material in formaldehyde adsorption and removal according to claim 1, characterized in that: The copper-based organic framework material can be regenerated and recycled after formaldehyde is adsorbed and removed.

6. The use of the copper-based organic framework material in formaldehyde adsorption removal according to claim 1, characterized in that: The method for removing formaldehyde by adsorption of the copper-based organic framework material comprises the following steps: adding the copper-based organic framework material into a formaldehyde-air mixed gas, waiting for the formaldehyde gas concentration to stabilize, and then separating the copper-based organic framework material.

7. The use of the copper-based organic framework material in formaldehyde adsorption removal according to claim 1, characterized in that: The method for regenerating a copper-based organic framework material by removing formaldehyde through adsorption comprises the following steps: placing the copper-based organic framework material after the formaldehyde has been removed through adsorption under the sun for 24 hours to achieve regeneration and recycling.

8. The use of the copper-based organic framework material in formaldehyde adsorption and removal according to claim 1, characterized in that: The method for regenerating a copper-based organic framework material by removing formaldehyde through adsorption comprises the following steps: vacuum drying the copper-based organic framework material after the formaldehyde has been adsorbed and removed for desorption to achieve regeneration and recycling.

9. The use of the copper-based organic framework material in formaldehyde adsorption and removal according to claim 8, characterized in that: Drying temperature 120-150℃.

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