Preparation method and application of MOF-801 / GO composite adsorbent for CO2 / N2 adsorption separation
By adding graphene oxide (GO) to MOF-801 material to synthesize the adsorbent of MOF-801/GO composite material, the problem of insufficient carbon dioxide capture and N2 separation efficiency in the prior art is solved, and a high stability and efficient CO2/N2 adsorption and separation effect is achieved.
Patent Information
- Application Number
- CN202411856621.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-17
- Publication Date
- 2025-04-04
AI Technical Summary
Existing carbon dioxide capture technology has shortcomings in efficient separation of CO2 and N2, especially in terms of stability and cycling performance.
By adding graphene oxide (GO) to the MOF-801 material, the adsorbent of high-stability MOF-801/GO composite material is synthesized in situ by using the rich oxygen-containing functional groups of GO and the good gas adsorption and separation performance of MOF-801 to improve the adsorption and separation effect of CO2/N2.
It achieves higher CO2 adsorption efficiency and better CO2/N2 separation performance, while improving the physical stability and cycling performance of the material.
Smart Images
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Abstract
Description
[Technical field]
[0001] The present invention belongs to the technical field of adsorption materials, and in particular relates to research on a MOF-801 / GO composite material adsorbent for CO2 / N2 adsorption and separation. [Background technology]
[0002] With the development of industrialization, carbon dioxide emissions are still increasing significantly, reaching an unprecedented level. As the main component of greenhouse gases, carbon dioxide has caused many environmental problems such as global warming and climate change. If urgent action is not taken to reduce the emission of carbon dioxide gas, the atmosphere will eventually exceed the global temperature mark of 1.5°C per year, eventually bringing about a variety of natural disasters. Therefore, finding efficient carbon dioxide capture and storage technology has become one of the urgent needs. Over the years, people have explored a variety of technologies for capturing carbon dioxide. Among the various new technologies that have emerged one after another, adsorption is the most promising technology, among which solid material adsorption technology is considered to be one of the most attractive technologies. In recent years, many solid materials such as zeolite, activated carbon, molecular sieves, activated alumina, polymer resins and porous metal organic frameworks (MOFs) have been used for carbon dioxide capture and storage.
[0003] MOFs materials are a type of functional materials assembled by metal nodes and organic ligands through coordination bonds. They are widely studied because of their large specific surface area, adjustable pore size, large porosity, high stability and easy modification, and are used in many fields including gas separation and storage. Zr-MOF has been studied because of its high water stability. MOF-801 is a type of Zr-MOF, composed of fumaric acid and zirconium clusters, with good thermal stability, can withstand high temperatures of 400°C, and has chemical stability against erosion by small molecules such as water and DMF, and has good gas adsorption and separation performance.
[0004] Graphene oxide (GO) is composed of two-dimensional covalent bonds and carbon atoms, with abundant oxygen-containing functional groups on the basal plane and edges. It is the best starting material for forming uniform and stable composite materials, which can effectively improve the performance of composite materials. In particular, graphene oxide and MOFs-based composite materials have been widely studied due to their unique properties.
[0005] The present invention synthesizes a highly stable MOF-801 / GO composite material in situ by adding graphene oxide (GO) to the material MOF-801. Compared with the MOF-801 adsorbent, the composite adsorbent has more stable physical properties, higher adsorption efficiency and better cycle performance. [Summary of the invention]
[0006] [Technical issues to be solved]
[0007] The purpose of the present invention is to provide a preparation method and application of a MOF / GO composite adsorbent for CO2 / N2 adsorption separation.
[0008] To achieve the above object, the present invention provides the following technical solutions:
[0009] Synthesis of Graphene Oxide (GO):
[0010] First, add 4g of graphite to a three-necked flask containing 90mL of concentrated H2SO4 and stir continuously for 30min at 4℃. Then slowly add 2g of anhydrous NaNO3 and 12g of KMnO4 and stir vigorously for 150min. Transfer the three-necked flask to a 35℃ water bath, continue stirring, and slowly add 190ml of ultrapure water. After the temperature rises to 90℃, add 35ml of 30% H2O2 solution and 280ml of ultrapure water, keep warm for 10 minutes, and end the oxidation process. After the mixed solution is transferred to a beaker and allowed to stand for 24h, pour out the supernatant, retain the precipitate, and wash the precipitate with 1% hydrochloric acid aqueous solution until no precipitate is produced when BaCl2 solution is added to the supernatant. Wash the synthesized GO with deionized water until the pH value of GO is close to 7. After GO is placed in a blast drying oven and dried at 35℃, the graphene oxide product is obtained.
[0011] Synthesis of MOF-801:
[0012] First, add 1.75g of fumaric acid, 3.5g of zirconium tetrachloride and 20mL of formic acid into 80mL of deionized water and stir to dissolve for 30min. Pour the mixed solution into a single-necked flask and reflux at 100°C for 16 hours to obtain the product. Cool the sample to about 25°C, filter out the solvent, and soak and wash the precipitate in deionized water and ethanol for 3 days. Centrifuge the sample twice a day to remove the solvent and replace it with fresh solvent. After drying to remove the solvent ethanol at room temperature, dry it in a drying oven at 100°C for 12 hours under a vacuum environment to obtain MOF-801.
[0013] Synthesis of MOF-801 / GO:
[0014] First, 80 ml of deionized water was added to the graphene oxide powder and ultrasonically treated for 2 hours to obtain a graphene oxide suspension. 1.75 g of fumaric acid, 3.5 g of zirconium tetrachloride and 20 mL of formic acid were added to the suspension and stirred to dissolve for 30 minutes. The mixed solution was placed in a single-necked flask and refluxed at 100 ° C for 16 hours to obtain the product. The sample was cooled to about 25 ° C, the solvent was filtered out, and the precipitate was immersed in deionized water and ethanol for 3 days. The sample was centrifuged twice a day to remove the solvent and replace it with fresh solvent. After drying to remove the solvent ethanol at room temperature, it was dried in a drying oven at 100 ° C for 12 hours under a vacuum environment to obtain MOF-801 / GO (n), where n represents the mass (g) of GO added when preparing the composite material.
[0015] Adsorption scheme:
[0016] At 273K and 298K, the specific surface area, pore volume, pore size and CO2 and N2 adsorption performance of the adsorbent material were tested using a physical adsorption analyzer. At 298K, the separation coefficient of the adsorbent for CO2 and N2 was tested using a penetration analyzer.
[0017] Compared with the prior art, the advantages and beneficial effects of the present invention are:
[0018] The MOF-801 and GO selected in the technical solution of the present invention are used to synthesize a composite material. MOF-801 has good hydrothermal stability, and GO has abundant oxygen-containing functional groups, which can provide binding sites and adsorption sites.
[0019] The sample MOF-801 / GO in the technical solution of the present invention has high CO2 adsorption performance and has a certain specific surface area and micropore volume.
[0020] The MOF-801 / GO in the technical solution of the present invention has good CO2 / N2 separation performance.
Brief Description of the Drawings
[0021] Figure 1 TEM characterization image of GO prepared in Examples 1 and 2 (a) and SEM characterization images of MOF-801 and MOF-801 / GO (b, c, d).
[0022] Figure 2 CO2 adsorption isotherms of MOF-801 and MOF-801 / GO prepared in Examples 1 and 2 at 298K and 273K (a, b).
[0023] Figure 3 Pore size distribution diagrams (a, b, c) of MOF-801 and MOF-801 / GO prepared in Examples 1 and 2.
[0024] Figure 4 These are the penetration curves of MOF-801 / GO (0.05) and MOF-801 / GO (0.10) prepared in Examples 1 and 2 (a, b). [Specific implementation method]
[0025] Embodiment 1:
[0026] Synthesis of Graphene Oxide (GO):
[0027] First, add 4g of graphite to a three-necked flask containing 90mL of concentrated H2SO4 and stir continuously for 30min at 4℃. Then slowly add 2g of anhydrous NaNO3 and 12g of KMnO4 and stir vigorously for 150min. Transfer the three-necked flask to a 35℃ water bath, continue stirring, and slowly add 190ml of ultrapure water. After the temperature rises to 90℃, add 35ml of 30% H2O2 solution and 280ml of ultrapure water, keep warm for 10 minutes, and end the oxidation process. After the mixed solution is transferred to a beaker and allowed to stand for 24h, pour out the supernatant, retain the precipitate, and wash the precipitate with 1% hydrochloric acid aqueous solution until no precipitate is produced when BaCl2 solution is added to the supernatant. Wash the synthesized GO with deionized water until the pH value of GO is close to 7. After GO is placed in a blast drying oven and dried at 35℃, the graphene oxide product is obtained.
[0028] Synthesis of MOF-801:
[0029] First, add 1.75g of fumaric acid, 3.5g of zirconium tetrachloride and 20mL of formic acid into 80mL of deionized water and stir to dissolve for 30min. Pour the mixed solution into a single-necked flask and reflux at 100°C for 16 hours to obtain the product. Cool the sample to about 25°C, filter out the solvent, and soak and wash the precipitate in deionized water and ethanol for 3 days. Centrifuge the sample twice a day to remove the solvent and replace it with fresh solvent. After drying to remove the solvent ethanol at room temperature, dry it in a drying oven at 100°C for 12 hours under a vacuum environment to obtain MOF-801.
[0030] Synthesis of MOF-801 / GO(0.05):
[0031] First, 80 ml of deionized water was added to 0.05 g of graphene oxide powder and ultrasonically treated for 2 h to obtain a graphene oxide suspension. 1.75 g of fumaric acid, 3.5 g of zirconium tetrachloride and 20 mL of formic acid were added to the suspension and stirred to dissolve for 30 min. The mixed solution was placed in a single-necked flask and refluxed at 100 ° C for 16 hours to obtain the product. The sample was cooled to about 25 ° C, the solvent was filtered out, and the precipitate was immersed in deionized water and ethanol for 3 days. The sample was centrifuged twice a day to remove the solvent and replace it with fresh solvent. After drying to remove the solvent ethanol at room temperature, it was dried in a drying oven at 100 ° C for 12 hours under a vacuum environment to obtain MOF-801 / GO (0.05).
[0032] Adsorption scheme:
[0033] At 273K and 298K, the specific surface area, pore volume, pore size and CO2 and N2 adsorption performance of the adsorbent material were tested using an adsorption analyzer. At 298K, the separation coefficient of the adsorbent was tested using a penetration analyzer. Results: At 273K, the CO2 adsorption capacity of MOF-801 / GO (0.05) was 81.5 cm 3 / g, at 298K, the CO2 adsorption capacity of MOF-801 / GO(0.05) is 52.8cm 3 / g, the separation coefficient of CO2 to N2 is 14.86.
[0034] Embodiment 2:
[0035] Synthesis of Graphene Oxide (GO):
[0036] First, add 4g of graphite to a three-necked flask containing 90mL of concentrated H2SO4 and stir continuously for 30min at 4℃. Then slowly add 2g of anhydrous NaNO3 and 12g of KMnO4 and stir vigorously for 150min. Transfer the three-necked flask to a 35℃ water bath, continue stirring, and slowly add 190ml of ultrapure water. After the temperature rises to 90℃, add 35ml of 30% H2O2 solution and 280ml of ultrapure water, keep warm for 10 minutes, and end the oxidation process. After the mixed solution is transferred to a beaker and allowed to stand for 24h, pour out the supernatant, retain the precipitate, and wash the precipitate with 1% hydrochloric acid aqueous solution until no precipitate is produced when BaCl2 solution is added to the supernatant. Wash the synthesized GO with deionized water until the pH value of GO is close to 7. After GO is placed in a blast drying oven and dried at 35℃, the graphene oxide product is obtained.
[0037] Synthesis of MOF-801:
[0038] First, add 1.75g of fumaric acid, 3.5g of zirconium tetrachloride and 20mL of formic acid into 80mL of deionized water and stir to dissolve for 30min. Pour the mixed solution into a single-necked flask and reflux at 100°C for 16 hours to obtain the product. Cool the sample to about 25°C, filter out the solvent, and soak and wash the precipitate in deionized water and ethanol for 3 days. Centrifuge the sample twice a day to remove the solvent and replace it with fresh solvent. After drying to remove the solvent ethanol at room temperature, dry it in a drying oven at 100°C for 12 hours under a vacuum environment to obtain MOF-801.
[0039] Synthesis of MOF-801 / GO(0.10):
[0040] First, 80 ml of deionized water was added to 0.10 g of graphene oxide powder and ultrasonically treated for 2 h to obtain a graphene oxide suspension. 1.75 g of fumaric acid, 3.5 g of zirconium tetrachloride and 20 mL of formic acid were added to the suspension and stirred to dissolve for 30 min. The mixed solution was placed in a single-necked flask and refluxed at 100 ° C for 16 hours to obtain the product. The sample was cooled to about 25 ° C, the solvent was filtered out, and the precipitate was immersed in deionized water and ethanol for 3 days. The sample was centrifuged twice a day to remove the solvent and replace it with fresh solvent. After drying to remove the solvent ethanol at room temperature, it was dried in a drying oven at 100 ° C for 12 hours under a vacuum environment to obtain MOF-801 / GO (0.10).
[0041] Adsorption scheme:
[0042] At 273K and 298K, the specific surface area, pore volume, pore size and CO2 and N2 adsorption performance of the adsorbent material were tested using an adsorption analyzer. At 298K, the separation coefficient of the adsorbent was tested using a penetration analyzer. Results: At 273K, the CO2 adsorption capacity of MOF-801 / GO (0.10) was 84.1 cm 3 / g, at 298K, the CO2 adsorption capacity of MOF-801 / GO(0.10) is 62.7 cm 3 / g, the separation coefficient of CO2 to N2 is 18.14.
Claims
1. A method for preparing a MOF-801 / GO composite material adsorbent for CO2 / N2 adsorption separation, characterized in that Deionized water is added to graphene oxide powder and ultrasonic treatment is performed to obtain a graphene oxide suspension. Fumaric acid, zirconium tetrachloride and formic acid are added to the suspension and stirred. The mixture was placed in a single-necked flask and heated under reflux to obtain the product. The sample was cooled, the solvent was filtered off, and the precipitate was immersed in water and ethanol respectively. The sample was centrifuged every 12 hours to remove the solvent and replace it with fresh solvent. After drying at room temperature to remove the solvent ethanol, the mixture was dried in a drying oven under vacuum to obtain MOF-801 / GO(n), where n represents the mass (g) of GO added when preparing the composite material.
2. The method according to claim 1, characterized in that 80 ml of deionized water was added to the graphene oxide powder and ultrasonically treated for 2 h to obtain a graphene oxide suspension. 1.75 g of fumaric acid, 3.5 g of zirconium tetrachloride and 20 mL of formic acid were added to the suspension and stirred for 30 min to dissolve. The mixed solution was poured into a single-necked flask and refluxed at 100°C for 16 hours to obtain the product. The sample was cooled to about 25°C, the solvent was filtered off, and the precipitate was immersed in water and ethanol for 3 days. The sample was centrifuged twice a day to remove the solvent and replace it with fresh solvent. After drying at room temperature to remove the solvent ethanol, the mixture was dried in a drying oven at 100° C. for 12 h under a vacuum environment to obtain MOF-801 / GO(n), where n represents the mass (g) of GO added when preparing the composite material.
3. The method according to claim 1 and 2, characterized in that The mass of GO added when preparing the composite material is 0.05g and 0.10g.