An amorphous composite material, its preparation method, and its application in carbon capture.

Abstract

This invention provides an amorphous composite material, its preparation method, and its application in carbon capture, belonging to the technical fields of composite material preparation, carbon capture, and mixed matrix membrane preparation. The invention prepares an amorphous composite material based on a steric hindrance-driven amorphization method. In the amorphous composite material, TpPa is integrated on the amino groups of Cu(BDC-NH2) nanosheets. The growth process of the TpPa is affected by the steric hindrance of adjacent TpPa, leading to lattice stress. The densely packed TpPa exerts stress on the Cu(BDC-NH2) surface, causing the material lattice to collapse, resulting in the amorphous composite material. The amorphous composite material can be used as a filler to prepare mixed matrix membranes. The preparation process of the mixed matrix membrane is simple, the reaction is controllable, the raw materials are inexpensive and readily available, and the conditions are mild, making it well-suited for carbon capture, especially in the separation of CO2 / CH4 mixed gases.

Description

Technical Field

[0001] This invention belongs to the technical field of composite material preparation, carbon capture and mixed matrix membrane preparation, specifically relating to an amorphous composite material, its preparation method and its application in carbon capture. Background Technology

[0002] Rising atmospheric CO2 concentrations lead to severe consequences such as global warming and ecological damage, necessitating measures to limit CO2 emissions. However, CO2 emissions are unavoidable during production processes, and CO2 is an abundant C1 resource with broad application prospects in industries such as chemicals, food, agriculture, and oil and gas extraction. Therefore, CO2 separation and capture can not only effectively address the greenhouse effect but also fully utilize resources, achieve resource recycling, and contribute to improving socio-economic benefits, thus possessing broad development prospects.

[0003] The choice of CO2 separation process depends on various factors, including purity, recovery rate, and cost. Among these, membrane separation is considered one of the most promising CO2 separation technologies due to its high efficiency, low energy consumption, and low cost. Mixed matrix membranes (MMMs) are composed of dispersed fillers and continuous polymeric matrices, and the choice of filler determines the upper limit of membrane performance. The orientation of common fillers, such as anisotropic crystalline fillers, significantly affects the CO2 transport process, although amorphization can be used to avoid this orientation limitation. Currently, amorphization methods are mainly top-down strategies, such as pressure-induced, thermally-induced, and radiation-induced amorphization. However, these methods require extreme conditions such as high temperature and high pressure, and may even damage the chemical structure of the material itself during amorphization, thus negating the purpose of amorphization. Therefore, it is necessary to develop a new amorphous composite material and use it as a filler in the preparation of carbon capture materials. Summary of the Invention

[0004] To address some shortcomings in existing technologies, this invention provides an amorphous composite material, its preparation method, and its application in carbon capture. This invention prepares an amorphous composite material Cu(BDC-NH2)@TpPa based on a steric hindrance-driven amorphization method. In this amorphous composite material, TpPa is integrated on the amino groups of Cu(BDC-NH2) nanosheets. The growth process of TpPa is affected by the steric hindrance of adjacent TpPa, leading to lattice stress. The densely packed TpPa exerts stress on the surface of Cu(BDC-NH2), causing the material's lattice to collapse, resulting in the amorphous composite material. This amorphous composite material can be used as a filler to prepare mixed matrix membranes. The preparation process of these mixed matrix membranes is simple, the reaction is controllable, the raw materials are inexpensive and readily available, and the conditions are mild. It has excellent applications in carbon capture, especially in the separation of CO2 / CH4 mixed gases.

[0005] To achieve the above-mentioned technical effects, the present invention employs the following technical means:

[0006] The present invention first provides an amorphous composite material, which is obtained by combining TpPa and Cu(BDC-NH2), wherein TpPa is integrated on the amino groups of Cu(BDC-NH2) nanosheets; the amorphous composite material has a sheet-like structure.

[0007] The present invention also provides a method for preparing the above-mentioned amorphous composite material, comprising the following steps:

[0008] (1) Add copper nitrate trihydrate and 2,5-diaminoterephthalic acid to a solvent, and then add triethylamine to obtain solution A; sonicate solution A at room temperature to obtain suspension B, and then centrifuge, wash and dry to obtain Cu(BDC-NH2);

[0009] (2) Cu(BDC-NH2) and trialdehyde phloroglucinol were added to a 1,4-dioxane solution to obtain a mixture C. The mixture C was then sonicated and heated at a certain temperature. After the reaction was completed, acetic acid solution and p-phenylenediamine were added to react 1. After the reaction was completed, a mixture D was obtained.

[0010] (3) The mixture D is repeatedly frozen-pumped-thawed in a cycle. After the treatment, the mixture D is degassed and vacuum sealed. Then it is heated to react at a certain temperature. After the reaction is completed, it is washed and dried to obtain the amorphous composite material.

[0011] Preferably, in step (1), the ratio of copper nitrate trihydrate, 2,5-diaminoterephthalic acid, and triethylamine is: 0.5~1 mol: 0.5~1 mol: 0.2~2 mL;

[0012] The solvent includes a mixed solution of DMF, ethanol and water, wherein the volume ratio of DMF, ethanol and water in the mixed solution is 32 mL: 2 mL: 2 mL;

[0013] The ultrasonic treatment time is 5-10 hours.

[0014] Preferably, in step (2), the ratio of 1,4-dioxane, Cu(BDC-NH2), trialdehyde phloroglucinol, acetic acid and p-phenylenediamine is 2~8 mL: 1~30 mg: 1~60 mg: 0.1~10 mL: 1~60 mg;

[0015] The concentration of the acetic acid is 1~10 mol / L;

[0016] The heating reaction is carried out at 50-120°C for 0.5-10 h.

[0017] Preferably, in step (3), the heating reaction is carried out at 80~150℃ for 48~96h.

[0018] The present invention also provides the application of the above-mentioned amorphous composite material in the preparation of carbon capture materials.

[0019] Preferably, the carbon capture material comprises a mixed matrix membrane, and the carbon capture comprises the separation of a CO2 / CH4 mixed gas.

[0020] The present invention also provides a carbon capture material, wherein the carbon capture material uses the above-mentioned amorphous composite material as a filler and polyether polyimide block Pebax as a polymer matrix; the carbon capture material is formed by physical blending of the filler and the polymer matrix at room temperature; the thickness of the carbon capture material is 100-130 μm; and the filler accounts for 1% to 7% of the mass percentage of the carbon capture material.

[0021] The present invention also provides a method for preparing the above-mentioned carbon capture material, which specifically includes the following steps:

[0022] (1) Dissolve the polyether polyimide block Pebax in a mixed solution of ethanol and water to obtain a polyether polyimide block Pebax solution;

[0023] (2) The above amorphous Cu(BDC-NH2)@TpPa material was physically blended with the polyether polyimide block Pebax solution and stirred at room temperature to obtain the casting solution;

[0024] (3) Casting and drying the casting liquid to obtain the carbon capture material.

[0025] Preferably, in the carbon capture material, amorphous Cu(BDC-NH2)@TpPa material accounts for 1% to 7% of the mass percentage of the carbon capture material.

[0026] The present invention also provides the application of the above-mentioned carbon capture materials in carbon capture.

[0027] Preferably, the application includes: separation of CO2 / CH4 mixed gases.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] (1) The present invention provides a novel amorphous composite material Cu(BDC-NH2)@TpPa. Unlike the prior art, the amorphous material of the present invention is prepared by a bottom-up method. This method can effectively avoid the harsh amorphization conditions of the prior art and avoid the orientation problem of the crystal filler in the film.

[0030] (2) In this invention, the prepared amorphous composite material Cu(BDC-NH2)@TpPa is used as a filler and physically blended with the polyether-polyimide block copolymer Pebax to form a unique isotropic mixed matrix membrane. This mixed matrix membrane allows the filler to avoid orientation limitations within the membrane, thereby improving CO2 permeability. Furthermore, the amorphous composite material Cu(BDC-NH2)@TpPa increases Lewis basic sites and open metal sites on the mixed matrix membrane, which is beneficial for preferential CO2 transport. Therefore, the amorphous composite material of this invention effectively improves the selectivity and separation performance of CO2 / CH4 within the membrane.

[0031] (3) The mixed matrix membrane based on polyether-polyamide block copolymer (Pebax) of the present invention constructs an efficient CO2 transport pathway within the membrane, improving the permeation-selectivity performance of the mixed matrix membrane and overcoming the trade-off effect, exhibiting high permeability and high separation factor. The preparation process of the mixed matrix membrane is simple, the reaction is controllable, the raw materials are inexpensive and readily available, and the conditions are mild, which can promote the complementary advantages of the filler and the polymer matrix. The research results show that the mixed matrix membrane of the present invention has the highest permeation selectivity for CO2 / CH4 mixed gas with a CO2 flux of 815.9±19.7 barrer and a CO2 / CH4 selectivity of 20.3±0.4, which has good application in carbon capture, especially in the separation of CO2 / CH4 mixed gas. Attached Figure Description

[0032] Figure 1 This is a transmission electron microscope (TEM) image of Cu(BDC-NH2)@TpPa (scale bar is 200 nm).

[0033] Figure 2 This is the PXRD pattern of Cu(BDC-NH2)@TpPa.

[0034] Figure 3 This is a scanning electron microscope cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-1 mixed matrix film.

[0035] Figure 4 This is a scanning electron microscope cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-3 mixed matrix film.

[0036] Figure 5 This is a scanning electron microscope cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-5 mixed matrix film.

[0037] Figure 6 This is a scanning electron microscope cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-7 mixed matrix film.

[0038] Figure 7 This is a scanning electron microscope cross-sectional image of a pure Pebax membrane. Detailed Implementation

[0039] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited thereto. Experimental methods in the embodiments that do not specify specific conditions are performed under conventional conditions; reagents and materials used, unless otherwise specified, are commercially available.

[0040] Example 1: Preparation of amorphous composite materials

[0041] (1) 0.75 mmol of copper nitrate trihydrate and 0.75 mmol of 2,5-diaminoterephthalic acid were mixed in a solvent consisting of 32 mL of DMF, 2 mL of ethanol and 2 mL of water. The mixture was stirred until homogeneous and 0.8 mL of triethylamine was added to the solution, which quickly turned dark green, to obtain solution A. Solution A was sonicated at room temperature for 8 h to obtain a green suspension B. The suspension was then centrifuged and washed three times with ethanol to obtain a solid. Finally, the solid was dried overnight under vacuum at 60°C to obtain Cu(BDC-NH2).

[0042] (2) Add 30 mg of Cu(BDC-NH2) and 16 mg of trialdehyde phloroglucinol to 4 mL of 1,4-dioxane solvent to obtain mixture C. Then, sonicate mixture C for 20 minutes and heat it at 80°C for 2 hours. After the reaction is complete, add 0.3 mL of 6 M acetic acid solution and 16 mg of p-phenylenediamine to mixture C and react for another hour to obtain mixed solution D.

[0043] (3) The mixed solution D was subjected to three freeze-pump-thaw cycles, then the mixed solution D was degassed and vacuum sealed, and heated at 120°C for 72 h. After the reaction was completed, it was washed with 1,4-dioxane and acetone, and then vacuum dried at 120°C for 12 h to obtain the amorphous composite material Cu(BDC-NH2)@TpPa.

[0044] Figure 1 This is a transmission electron microscope (TEM) image of Cu(BDC-NH2)@TpPa, from... Figure 1 As can be seen, Cu(BDC-NH2)@TpPa exhibits a plate-like morphology; the aldehyde group of TpPa and the amino group of Cu(BDC-NH2) generate CN bonds through a Schiff base reaction, and then generate C=N bonds through irreversible enolization, so that TpPa and Cu(BDC-NH2) can be successfully complexed.

[0045] Figure 2 The image shows the PXRD pattern of Cu(BDC-NH2)@TpPa. As can be seen from the image, all the diffraction peaks of Cu(BDC-NH2)@TpPa have disappeared, which indicates that Cu(BDC-NH2)@TpPa has been successfully amorphized.

[0046] Example 2: Preparation of amorphous composite materials

[0047] (1) 0.75 mmol of copper nitrate trihydrate and 0.75 mmol of 2,5-diaminoterephthalic acid were mixed in a solvent consisting of 32 mL of DMF, 2 mL of ethanol and 2 mL of water. The mixture was stirred until homogeneous and 0.8 mL of triethylamine was added to the solution, which quickly turned dark green, to obtain solution A. Solution A was sonicated at room temperature for 10 h to obtain a green suspension B. The suspension was then centrifuged and washed three times with ethanol to obtain a solid. Finally, the solid was dried overnight under vacuum at 60°C to obtain Cu(BDC-NH2).

[0048] (2) Mixture C was obtained by adding 30 mg of Cu(BDC-NH2) and 16 mg of trialdehyde phloroglucinol to an appropriate amount of 1,4-dioxane solvent. Mixture C was then sonicated for 20 minutes and heated at 80°C for 2 hours. After the reaction was completed, 0.5 mL of 3 M acetic acid solution and 20 mg of p-phenylenediamine were added to mixture C and reacted for another hour to obtain mixed solution D.

[0049] (3) The mixed solution D was subjected to three freeze-pump-thaw cycles, then the mixed solution D was degassed and vacuum sealed, and heated at 120°C for 72 h. After the reaction was completed, it was washed with 1,4-dioxane and acetone, and then vacuum dried at 120°C for 12 h to obtain the amorphous composite material Cu(BDC-NH2)@TpPa.

[0050] Example 3: Preparation of carbon capture materials containing amorphous composite materials

[0051] Weigh 0.645 g of Pebax® 1657 and dissolve it in 10 mL of a 7:3 mixture of ethanol and water. Heat and stir in an 80°C water bath for 2 h to ensure that all Pebax particles are dissolved, thus preparing a 6 wt% Pebax matrix solution for later use.

[0052] 0.0065 g of Cu(BDC-NH2)@TpPa prepared in Example 1 was physically blended with 6 wt% Pebax matrix solution and stirred at room temperature for 4 h to obtain a casting solution. The casting solution was poured onto a clean petri dish for casting. It was dried at room temperature (25°C) for 48 h, and then vacuum dried at 40°C in a vacuum drying oven to remove residual solvent from the surface of the mixed matrix membrane, thus obtaining the carbon capture material containing the amorphous composite material, namely the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane. Since the weight percentage of Cu(BDC-NH2)@TpPa in the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane is 1%, it is named Pebax / Cu(BDC-NH2)@TpPa-1 mixed matrix membrane.

[0053] The thickness of the Pebax / Cu(BDC-NH2)@TpPa-1 hybrid matrix membrane was measured to be 106 μm. Figure 3 Here is a scanning electron microscope (SEM) cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-1 mixed matrix film. Figure 3 It can be seen that after introducing Cu(BDC-NH2)@TpPa into the Pebax matrix, the cross-sectional view of the mixed matrix membrane becomes rough, which proves the introduction of the filler. Furthermore, Cu(BDC-NH2)@TpPa is uniformly distributed in the mixed matrix membrane and there is no agglomeration.

[0054] This embodiment also tests the performance of the prepared Pebax / Cu(BDC-NH2)@TpPa-1 hybrid matrix membrane. The test steps are as follows:

[0055] (1) The prepared Pebax / Cu(BDC-NH2)@TpPa-1 mixed matrix membrane was used for CO2 / CH4 mixed gas separation test;

[0056] (2) A mixture of 80 vol% CH4 and 20 vol% CO2 was used as the feed gas. Then, the dried Pebax / Cu(BDC-NH2)@TpPa-1 mixed matrix membrane was wetted with deionized water so that the volume of the Pebax / Cu(BDC-NH2)@TpPa-1 mixed matrix membrane after wetting was about twice the original volume. The membrane was then placed in a membrane pool for permeability testing.

[0057] (3) A circular stainless steel tank was placed in an oven to study the Pebax / Cu(BDC-NH2)@TpPa-1 mixed matrix membrane (12.56 cm⁻¹). 2 The separation performance of the central part;

[0058] (4) Test the gas permeability of MMMs under different loads:

[0059] The feed gas was introduced upstream of the membrane at a controlled flow rate of 50 mL / min and a pressure range of 0.2–0.8 MPa. The permeabilities of CO2 and CH4 were calculated based on the purge gas flow rate and composition. The effects of H2 back diffusion and concentration polarization on data analysis were negligible because the volume of the feed gas was much larger than that of the purge gas (H2), and H2 back diffusion did not alter the composition of the feed gas. Therefore, H2 was suitable as the purge gas downstream of the membrane, with a flow rate controlled at 30 mL / min. The content of each component in the permeate gas was determined using a gas chromatograph (GC 2014C).

[0060] Test results show that its CO2 flux is 682.2 Barrer (1 Barrer = 10⁻⁶). -10 cm 3 cm / cm 2 (s cmHg), CO2 / CH4 selectivity was 20.46.

[0061] Example 4: Preparation of carbon capture materials containing amorphous composite materials

[0062] 0.0199 g of Cu(BDC-NH2)@TpPa prepared in Example 1 was physically blended with 6 wt% Pebax matrix solution and stirred at room temperature for 4 h to obtain a casting solution. The casting solution was poured onto a clean petri dish for casting. It was dried at room temperature (25°C) for 48 h, and then vacuum dried at 40°C in a vacuum drying oven to remove residual solvent from the surface of the mixed matrix membrane, thus obtaining the carbon capture material containing the amorphous composite material, namely the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane. Since the weight percentage of Cu(BDC-NH2)@TpPa in the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane is 3%, it is named Pebax / Cu(BDC-NH2)@TpPa-3 mixed matrix membrane.

[0063] The thickness of the Pebax / Cu(BDC-NH2)@TpPa-3 mixed matrix membrane was measured to be 113 μm. Figure 4 Here is a scanning electron microscope (SEM) cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-3 mixed matrix film. Figure 4 It can be seen that after introducing Cu(BDC-NH2)@TpPa into the Pebax matrix, the cross-sectional view of the mixed matrix membrane becomes rough, which proves the introduction of the filler. Furthermore, Cu(BDC-NH2)@TpPa is uniformly distributed in the mixed matrix membrane and there is no agglomeration.

[0064] The performance of the Pebax / Cu(BDC-NH2)@TpPa-3 mixed matrix membrane was tested using the method described in Example 3. The CO2 flux was 815.9±19.7 Barrer and the CO2 / CH4 selectivity was 20.3±0.4.

[0065] Example 5: Preparation of carbon capture materials containing amorphous composite materials

[0066] 0.0339 g of Cu(BDC-NH2)@TpPa prepared in Example 1 was physically blended with 6 wt% Pebax matrix solution and stirred at room temperature for 4 h to obtain a casting solution. The casting solution was poured onto a clean petri dish for casting. It was dried at room temperature (25°C) for 48 h, and then vacuum dried at 40°C in a vacuum drying oven to remove residual solvent from the surface of the mixed matrix membrane, thus obtaining the carbon capture material containing the amorphous composite material, namely the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane. Since the weight percentage of Cu(BDC-NH2)@TpPa in the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane is 5%, it is named Pebax / Cu(BDC-NH2)@TpPa-5 mixed matrix membrane.

[0067] The thickness of the Pebax / Cu(BDC-NH2)@TpPa-5 mixed matrix membrane was measured to be 112 μm. Figure 5 Here is a scanning electron microscope (SEM) cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-5 mixed matrix film. Figure 5 It can be seen that after introducing Cu(BDC-NH2)@TpPa into the Pebax matrix, the cross-sectional view of the mixed matrix membrane becomes rough, which proves the introduction of the filler. Furthermore, Cu(BDC-NH2)@TpPa is uniformly distributed in the mixed matrix membrane and there is no agglomeration.

[0068] The performance of the Pebax / Cu(BDC-NH2)@TpPa-5 mixed matrix membrane was tested using the method described in Example 3. The CO2 flux was 737.1±7.4 Barrer and the CO2 / CH4 selectivity was 20.6±0.8.

[0069] Example 5: Preparation of carbon capture materials containing amorphous composite materials

[0070] 0.0485 g of Cu(BDC-NH2)@TpPa prepared in Example 1 was physically blended with 6 wt% Pebax matrix solution and stirred at room temperature for 4 h to obtain a casting solution. The casting solution was poured onto a clean petri dish for casting. It was dried at room temperature (25°C) for 48 h, and then vacuum dried at 40°C in a vacuum drying oven to remove residual solvent from the surface of the mixed matrix membrane, thus obtaining the carbon capture material containing the amorphous composite material, namely the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane. Since the weight percentage of Cu(BDC-NH2)@TpPa in the Pebax / Cu(BDC-NH2)@TpPa mixed matrix membrane is 7%, it is named Pebax / Cu(BDC-NH2)@TpPa-7 mixed matrix membrane.

[0071] The thickness of the Pebax / Cu(BDC-NH2)@TpPa-5 mixed matrix membrane was measured to be 117 μm. Figure 6 Here is a scanning electron microscope (SEM) cross-sectional image of the Pebax / Cu(BDC-NH2)@TpPa-7 mixed matrix film. Figure 6 It can be seen that after introducing Cu(BDC-NH2)@TpPa into the Pebax matrix, the cross-sectional view of the mixed matrix membrane becomes rough, which proves the introduction of the filler. Furthermore, Cu(BDC-NH2)@TpPa is uniformly distributed in the mixed matrix membrane and there is no agglomeration.

[0072] The performance of the Pebax / Cu(BDC-NH2)@TpPa-7 mixed matrix membrane was tested using the method described in Example 3. The CO2 flux was 658.1±4.4 Barrer and the CO2 / CH4 selectivity was 18.1±0.8.

[0073] Comparative Example 1:

[0074] As a comparison, 0.537 g of Pebax particles were weighed and dissolved in a 70% ethanol / 30% water mixture. After stirring at 80°C for 2 h, the resulting casting solution was poured onto a clean ultraflat petri dish for casting. The mixture was dried at room temperature (25°C) for 48 h and then placed in a 40°C vacuum oven for 24 h to remove residual solvent, resulting in a Pebax film with a thickness of 102 μm.

[0075] Figure 7 This is a scanning electron microscope (SEM) cross-sectional image of the prepared pure Pebax film. (From...) Figure 7 As can be seen, the cross-section of the pure Pebax membrane exhibits the typical morphology of a smooth, dense, and defect-free polymer membrane. At 25°C and 2 bar, the Pebax membrane was used for the separation of a CO2 / CH4 mixture with a CO2 volume fraction of 20% (CO2 to CH4 volume ratio of 2:8). The measured CO2 flux was 280 barrer, and the CO2 / CH4 selectivity was 25.

[0076] In summary, this invention prepares an amorphous composite material Cu(BDC-NH2)@TpPa based on a steric hindrance-driven amorphization method. In the amorphous composite material, TpPa is integrated on the amino groups of Cu(BDC-NH2) nanosheets. The growth process of TpPa is affected by the steric hindrance of neighboring TpPa, resulting in lattice stress. The densely packed TpPa exerts stress on the surface of Cu(BDC-NH2), causing the material lattice to collapse, thus obtaining the amorphous composite material. The amorphous composite material can be used as a filler to prepare mixed matrix membranes. The preparation process of the mixed matrix membrane is simple, the reaction is controllable, the raw materials are inexpensive and readily available, and the conditions are mild. It has good applications in carbon capture, especially in the separation of CO2 / CH4 mixed gases.

[0077] The embodiments described above are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Any obvious improvements, substitutions or modifications that can be made by those skilled in the art without departing from the essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A method of preparing an amorphized composite material, characterized by, The method comprises the following steps: (1) adding copper nitrate trihydrate and 2,5-diamino terephthalic acid into a solvent, then adding triethylamine into the solvent to obtain solution A; ultrasonically treating solution A at room temperature to obtain suspension B, then centrifuging, washing and drying suspension B to obtain Cu(BDC-NH2); (2) adding Cu(BDC-NH2) and triformylphloroglucin into a 1,4-dioxane solution to obtain mixture C, then ultrasonically treating mixture C and heating mixture C at 50-120 ℃ to react, adding acetic acid solution and p-phenylenediamine after the reaction is completed, and then reacting again to obtain mixture D; (3) repeatedly processing mixture D through freezing-pumping-thawing cycles, degassing and vacuum sealing mixture D after the processing is completed, and then heating mixture D at 80-150 ℃ to react, and washing and drying mixture D after the reaction is completed to obtain the amorphous composite material.

2. The method of claim 1, wherein the amorphous composite material is prepared by a method comprising: In step (1), the amount of copper nitrate trihydrate, 2,5-diamino terephthalic acid and triethylamine is in the range of 0.5-1 mol, 0.5-1 mol and 0.2-2 mL respectively; The solvent comprises a mixed solution of DMF, ethanol and water, and the volume ratio of DMF, ethanol and water in the mixed solution is 32 mL:2 mL:2 mL; The ultrasonic treatment time is 5-10 h.

3. The method of claim 1, wherein the amorphous composite material is prepared by a method comprising: In step (2), the amount of 1,4-dioxane, Cu(BDC-NH2), triformylphloroglucin, acetic acid and p-phenylenediamine is in the range of 2-8 mL, 1-30 mg, 1-60 mg, 0.1-10 mL and 1-60 mg respectively; The concentration of acetic acid is 1-10 mol / L; The heating reaction condition is that the reaction is carried out at 50-120 ℃ for 0.5-10 h.

4. The method of claim 1, wherein the amorphous composite material is prepared by a method comprising: In step (3), the heating reaction condition is that the reaction is carried out at 80-150 ℃ for 48-96 h.

5. The amorphous composite prepared according to the method of any one of claims 1 to 4, characterized in that, The amorphous composite material is obtained by compounding TpPa and Cu(BDC-NH2), the TpPa is integrated on the amino group of Cu(BDC-NH2) nanosheet, and the amorphous composite material has a sheet structure.

6. The use of the amorphous composite material in claim 5 in the preparation of a carbon capture material.

7. Use according to claim 6, characterized in that, The carbon capture material comprises a mixed matrix membrane, and the carbon The carbon capture comprises the separation of a CO2 / CH4 mixed gas.

8. A carbon capture material, characterized in that, The carbon capture material uses the amorphous composite material in claim 5 as a filler and polyether polyimide block Pebax as a polymer matrix; the carbon capture material is formed by physically blending the filler and the polymer matrix at room temperature; the thickness of the carbon capture material is 100-130 μm; and the mass percentage of the filler in the carbon capture material is 1%-7%.

9. The use of the carbon capture material in claim 8 in carbon capture.

10. Use according to claim 9, characterized in that, The use comprises the separation of a CO2 / CH4 mixed gas.

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