CN112933984A

CN112933984A - GYSNs (gysan) -filled polyurethane hybrid film and preparation method thereof

Info

Publication number: CN112933984A
Application number: CN202110130024.9A
Authority: CN
Inventors: 彭平; 兰永强
Original assignee: Sanming University
Current assignee: Sanming University
Priority date: 2021-01-29
Filing date: 2021-01-29
Publication date: 2021-06-11
Anticipated expiration: 2041-01-29
Also published as: CN112933984B

Abstract

The invention provides a GYSNs filled polyurethane hybrid film and a preparation method thereof. The preparation method of the hybrid membrane comprises the following steps: mixing and stirring graphene oxide, polyvinylpyrrolidone and a first solvent, then adding ammonia water and ethyl orthosilicate, centrifuging and washing to obtain GO @ SiO₂. Mixing GO @ SiO₂Mixing the suspension with a second solvent, and adding formaldehyde, resorcinol, ethylenediamine and ethyl orthosilicate to obtain GO @ SiO₂@PB/SiO₂。GO@SiO₂@PB/SiO₂Carbonizing, soaking and washing to obtain GYSNs. The synthesized GYSNs were added as fillers to the PU matrix to prepare PU/GYSNs films. The invention fills GYSNs into the PU matrix, and can effectively reduce the film thicknessSwelling and improving the desulfurization capability of the polyurethane membrane, and the prepared PU/GYSNs membrane has high thiophene separation capability while keeping high permeation flux.

Description

GYSNs (gysan) -filled polyurethane hybrid film and preparation method thereof

Technical Field

The invention relates to the technical field of pervaporation membranes, and particularly relates to a GYSNs (GYSNs-rich and high-molecular-weight polyurethanes) filled polyurethane hybrid membrane and a preparation method thereof.

Background

The gasoline desulfurization industry is currently receiving high attention from countries throughout the world. The removal of sulfur components in gasoline can improve the service life of the engine and reduce environmental pollution. Pervaporation is a membrane separation technique that is commonly used for the separation of small molecule liquids. Compared with the traditional hydrodesulfurization, the pervaporation method can remove organic sulfur compounds in the gasoline under the condition of keeping the octane number of the gasoline. In addition, pervaporation operates at normal temperature and pressure, and does not require hydrogen and a catalyst, thereby greatly reducing the operating cost.

Pervaporation separation efficiency is related to the affinity of the membrane material for the sulfide. Polydimethylsiloxane (PDMS), polyvinyl alcohol (PEG), Polyurethane (PU), and polyether block polyamide (Pebax) are common pervaporation desulfurization materials. PU is a polymer containing various functional groups and has good mechanical, chemical and thermal properties. The main problem limiting the wide application of PU is that the swelling degree is high when the PU is contacted with a liquid phase, which can cause the selectivity of the PU membrane to be reduced. Current approaches to this problem mainly include polymer crosslinking and the addition of fillers.

According to the facilitated transfer mechanism, the membrane binds/releases specific molecules through a reversible acid-base or complexation reaction, thereby significantly improving the transport characteristics and separation efficiency of the membrane. A plurality of two-dimensional nanosheets, such as molybdenum disulfide (MoS)₂) Zeolite imidazolate framework materials (ZIF-8), graphene and derivatives thereof and the like have been successfully added to polymer matrices to provide transfer-promoting sites for molecules to be separated so as to improve pervaporation performance. For conventional two-dimensional materials, the loading of carriers is typically low due to the limited number of functional groups on the nanoscale surface. In addition, graphene nanoplatelets and their derivatives are generally prepared by a modified Hummer method, which inevitably results in structural defects. It is necessary to rationally design and develop a novel two-dimensional material to improve the desulfurization performance of the pervaporation membrane.

Disclosure of Invention

The invention aims to provide a preparation method of GYSNs filled polyurethane hybrid membrane, which is simple, easy to operate and suitable for industrial production.

The invention also aims to provide a GYSNs-filled polyurethane hybrid membrane, and the synthesized GYSNs are added into a polyurethane matrix, so that the obtained hybrid membrane has high thiophene separation capacity while high permeation flux is ensured.

The technical problem to be solved by the invention is realized by adopting the following technical scheme.

The invention provides a preparation method of a GYSNs filled polyurethane hybrid film, which is characterized by comprising the following steps:

s1, synthesizing GYSNs, including:

s11, mixing and stirring Graphene Oxide (GO), polyvinylpyrrolidone and a first solvent, then adding ammonia water and ethyl orthosilicate, stirring for 5-7 h at 25-35 ℃, centrifuging and washing to obtain GO @ SiO₂；

S12, mixing the GO @ SiO₂Dispersing in 25-35 mL of deionized water to obtain GO @ SiO₂Suspension of GO @ SiO₂Mixing the suspension with the second solvent, adding formaldehyde, resorcinol, ethylenediamine and ethyl orthosilicate, stirring for 23-25 h at 35-45 ℃, and centrifuging to obtain GO @ SiO₂@PB/SiO₂；

S13, mixing the GO @ SiO₂@PB/SiO₂Drying at 55-65 ℃ for 10-14 h, introducing inert gas, carbonizing at 780-820 ℃ for 3.5-4.5 h, soaking, and washing to obtain GYSNs;

s2, preparing PU/GYSNs films: dispersing GYSNs in a Tetrahydrofuran (THF) solvent, stirring for 20-40 min, adding polyurethane, continuously stirring for 22-24 h, standing and degassing for 20-40 min to obtain a membrane casting solution, and pouring the membrane casting solution into a culture dish at room temperature until the solvent is completely volatilized to obtain the PU/GYSNs membrane.

The invention provides a GYSNs filled polyurethane hybrid film which is prepared according to the preparation method.

The GYSNs filled polyurethane hybrid film and the preparation method thereof have the beneficial effects that:

PU is a polymer containing various functional groups and has good mechanical, chemical and thermal properties. The invention adds the self-made graphene yolk shell structure (GYSNs) as a filler into a PU matrix, thereby preparing the PU/GYSNs film. The GYSNs have the advantages of large specific surface area, large pore volume, good dispersibility and the like, and can effectively reduce the swelling of the membrane and improve the desulfurization capacity of the polyurethane membrane, so that the prepared PU/GYSNs membrane has high thiophene separation capacity while maintaining high permeation flux.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is an FTIR spectrum of GYSNs of example 4 of the present invention;

FIG. 2 is an X-ray diffraction pattern of GYSNs of example 4 of the present invention;

FIG. 3 is SEM images of GYSNs and PU/GYSNs films of example 4 of the invention;

FIG. 4 is an AFM image of the PU film of comparative example 1 and the PU/GYSNs film of example 4 of the present invention;

FIG. 5 is a TGA profile and a DTGA profile of PU/GYSNs films and PU films;

FIG. 6 is a DSC plot of PU/GYSNs films and PU films;

FIG. 7 is a graph showing the effect of GYSNs content on PU/GYSNs membrane separation performance;

FIG. 8 is a diagram showing the influence of sulfur content in feed liquid on the separation performance of PU/GYSNs membranes;

FIG. 9 is a graph of the effect of operating temperature on permeate flux and enrichment factor;

FIG. 10 is a graph of the effect of operating temperature on permeate flux of thiophene and n-octane;

FIG. 11 is a graph of the effect of operating temperature on permeability and selectivity;

FIG. 12 is a graph of the operational stability of PU/GYSNs films.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The GYSNs-filled polyurethane hybrid film and the preparation method thereof according to the embodiment of the present invention will be specifically described below.

The preparation method of the GYSNs filled polyurethane hybrid film provided by the embodiment of the invention is characterized by comprising the following steps:

s1, synthesizing GYSNs, including:

s11, mixing and stirring graphene oxide, polyvinylpyrrolidone and a first solvent, then adding ammonia water and ethyl orthosilicate, stirring for 5-7 h at 25-35 ℃, centrifuging and washing to obtain GO @ SiO₂。

Further, in a preferred embodiment of the present invention, the mass ratio of the graphene oxide to the polyvinylpyrrolidone is 1: 9.5-10.5, and the first solvent is a mixed solution of deionized water and ethanol at a volume ratio of 1: 7.5-8.5.

Further, in a preferred embodiment of the invention, the volume ratio of the ammonia water to the tetraethoxysilane is 1-2: 1.

S12, mixing the GO @ SiO₂Dispersing in 25-35 ml of deionized water to obtain GO @ SiO₂Suspension of GO @ SiO₂Mixing the suspension with the second solvent, adding formaldehyde, resorcinol, ethylenediamine and ethyl orthosilicate, stirring for 23-25 h at 35-45 ℃, and centrifuging to obtain GO @ SiO₂@PB/SiO₂. By this step, the resulting benzoxazine (PB) can be assembled in SiO₂In the last step, the GO @ SiO with a three-layer structure is formed₂@PB/SiO₂。

Further, in a preferred embodiment of the present invention, the second solvent is a mixed solution of deionized water and ethanol at a volume ratio of 1: 1.5-2.5, wherein GO @ SiO is₂The volume ratio of the suspension to the deionized water to the ethanol is 1: 5.5-6.5: 2.5-3.5.

Further, in a preferred embodiment of the invention, the volume ratio of the formaldehyde, the ethylenediamine and the tetraethoxysilane is 1: 1-1.5: 1.5-2.5, and the mass volume ratio of the resorcinol and the tetraethoxysilane is 1: 2.5-3.5.

S13, mixing the GO @ SiO₂@PB/SiO₂Drying at 55-65 ℃ for 10-14 h, introducing inert gas, carbonizing at 780-820 ℃ for 3.5-4.5 h, soaking, and washing to obtain GYSNs. In the graphene yolk shell nano structure synthesized by the method, the graphene is encapsulated in the hollow porous carbon nanosheet, so that the inherent defects of the graphene are overcome. The GYSNs have the advantages of large specific surface area, large pore volume, good dispersibility and the like.

Further, in the preferred embodiment of the present invention, the GO @ SiO₂@PB/SiO₂After carbonization, the mixture is soaked in HF solution with the mass fraction of 9-11% and repeatedly washed by deionized water.

S2, preparing PU/GYSNs films: dispersing GYSNs in a THF solvent, stirring for 20-40 min, adding polyurethane, continuously stirring for 22-24 h, standing and degassing for 20-40 min to obtain a membrane casting solution, and pouring the membrane casting solution into a culture dish at room temperature until the solvent is completely volatilized to obtain the PU/GYSNs membrane. PU is a polymer containing various functional groups and has good mechanical, chemical and thermal properties. According to the invention, GYSNs are used as fillers and added into the PU matrix, so that the swelling of the film can be effectively reduced and the desulfurization capability of the PU film can be effectively improved.

Further, in a preferred embodiment of the present invention, in the casting solution, the mass ratio of the polyurethane to the THF solvent is 1:14 to 16. The GYSNs and the polyurethane can be completely dissolved in the proportion, so that the subsequent preparation of the hybrid film is facilitated.

Further, in a preferred embodiment of the present invention, the polyurethane is dried at 55-65 ℃ for 23-25 hours in advance.

Further, in the preferred embodiment of the present invention, the mass percentage of the GYSNs in the PU/GYSNs film is 0.01 to 1 wt.%.

The invention also provides a GYSNs filled polyurethane hybrid film which is prepared according to the preparation method. The invention adds the self-made graphene yolk shell structure (GYSNs) as a filler into a PU matrix, thereby preparing the PU/GYSNs film. The GYSNs have the advantages of large specific surface area, large pore volume, good dispersibility and the like, and can effectively reduce the swelling of the membrane and improve the desulfurization capacity of the polyurethane membrane, so that the prepared PU/GYSNs membrane has high thiophene separation capacity while maintaining high permeation flux.

The hybrid membrane is adopted to separate n-octane solution, the separated product is gaseous, and the solution obtained after condensation and collection of the product is the separated thiophene solution. The thiophene solution can be used for measuring the solubility of the thiophene solution by gas chromatography.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

The GYSNs filled polyurethane hybrid film provided by the embodiment is prepared according to the following method:

(1) synthesis of GYSNs: firstly, 30mg of Graphene Oxide (GO) and 0.3g of polyvinylpyrrolidone are respectively added into a mixed solution consisting of 120mL of ethanol and 15mL of deionized water, and stirred for 10 min. An additional 6mL of aqueous ammonia and 4mL of tetraethylorthosilicate were added and stirring continued at 30 ℃ for 6 hours. The resulting suspension was then centrifuged and washed with deionized water. Finally, the prepared GO @ SiO₂Dispersed in 30mL of deionized water. Taking 10mL of the GO @ SiO₂The suspension was added to a mixture of 60mL of deionized water and 30mL of ethanol. After further addition of 0.3mL of formaldehyde, 0.2g of resorcinol, 0.3mL of ethylenediamine and 0.6mL of ethyl orthosilicate, the mixture was stirred at 40 ℃ for 24 hours. The resulting Polybenzoxazine (PB) is assembled on SiO₂On top of that, GO @ SiO is formed₂@PB/SiO₂And (4) a three-layer structure. Intermediate GO @ SiO was collected by centrifugation₂@PB/SiO₂And dried at 60 ℃ for 12 h. Finally, at 800 ℃ and N₂Carbonizing for 4h under the atmosphere condition, soaking for 24h by using 10% HF solution, and then repeatedly cleaning by using deionized water to obtain the GYSNs.

(2) PU polymer particle pretreatment: the PU polymer particles were dried at 60 ℃ for 24 hours.

Preparing a casting solution: firstly, dispersing a certain amount of GYSNs in a THF solvent, stirring for 30min, adding PU, and continuously stirring for 24 hours at room temperature to completely dissolve the GYSNs to obtain a casting solution. Wherein, in the casting solution, the mass ratio of PU to THF solvent is 1:15, and the content of GYSNs is 0.2 wt.%. Standing and degassing for 30min, pouring the membrane casting solution into a culture dish, and completely volatilizing the solvent at room temperature to obtain the PU/GYSNs membrane.

The PU/GYSNs film prepared in the embodiment is used for measuring pervaporation performance in an n-octane solution with the thiophene content of 1312ppm at the temperature of 30 ℃, and the permeation flux of the PU/GYSNs film is 1086 g.m^-2·h^-1The enrichment factor was 3.20.

Example 2

The difference between the GYSNs filled polyurethane hybrid film and the GYSNs filled polyurethane hybrid film in the embodiment 1 is that the content of GYSNs in the PU/GYSNs film is 0.4 wt.%.

The PU/GYSNs film prepared in the embodiment is used for measuring the pervaporation performance in an n-octane solution with the thiophene content of 1312ppm at the temperature of 30 ℃, and the permeation flux is 1128 g.m^-2·h^-1The enrichment factor was 3.57.

Example 3

The difference between the GYSNs filled polyurethane hybrid film and the GYSNs filled polyurethane hybrid film in the embodiment 1 is that the content of GYSNs in the PU/GYSNs film is 0.6 wt.%.

The PU/GYSNs film prepared in the embodiment is used for measuring the pervaporation performance in an n-octane solution with the thiophene content of 1312ppm at the temperature of 30 ℃, and the permeation flux is 1275 g.m^-2·h^-1The enrichment factor was 3.82.

Example 4

The difference between the GYSNs filled polyurethane hybrid film and the GYSNs filled polyurethane hybrid film in the embodiment 1 is that the content of GYSNs in the PU/GYSNs film is 0.8 wt.%.

The PU/GYSNs film prepared in the embodiment is used for measuring the pervaporation performance in an n-octane solution with the thiophene content of 1312ppm at the temperature of 30 ℃, and the permeation flux is 1411 g.m^-2·h^-1The enrichment factor was 4.33.

Example 5

The difference between the GYSNs filled polyurethane hybrid film and the GYSNs filled polyurethane hybrid film in the embodiment 1 is that the content of GYSNs in the PU/GYSNs film is 1 wt.%.

The PU/GYSNs film prepared in the embodiment is used for measuring the pervaporation performance in an n-octane solution with the thiophene content of 1312ppm at the temperature of 30 ℃, and the permeation flux is 1707 g.m^-2·h^-1The enrichment factor was 3.97.

Comparative example 1

In this comparative example, a PU film was provided, which is different from example 1 in that the content of GYSNs in the PU film was 0 wt.%.

The PU film prepared by the comparative example has pervaporation performance measured in normal octane solution with the thiophene content of 1312ppm at 30 ℃, and the permeation flux is 829.8 g.m^-2·h^-1The enrichment factor was 2.56.

FIG. 1 shows FTIR spectra of GYSNs provided in example 4 of the present invention, wherein 470cm^-1、809cm^-1And 1107cm^-1The absorption peaks appeared at this point correspond to the bending vibration of the Si — O bond and the symmetric and asymmetric stretching vibration, respectively, and it can be seen from fig. 1 that GYSNs have typical characteristic peaks of the Si — O structure. Furthermore, no distinct characteristic absorption peak of GO appears in the figure, indicating that the silica completely covers the GO surface.

FIG. 2 shows the X-ray diffraction pattern of GYSNs provided in example 4 of the present invention, and it can be seen from FIG. 2 that there is a SiO in the region of 23 °₂Typical characteristic peak of (A), indicating SiO₂Successfully coated on the surface of GO to form a target product GYSNs, and simultaneously can prove that SiO is₂Coated on the GO in an amorphous state. In addition, a small characteristic peak of graphene (100) is found around 43 °, indicating that a small amount of graphene exists in the form of a thin layer.

Fig. 3 is SEM images of GYSNs and PU/GYSNs films provided in embodiment 4 of the present invention, in which fig. 3a is an SEM image of GYSNs, fig. 3b is a surface topography view of the PU/GYSNs film, fig. 3c is a cross-sectional view of the PU/GYSNs film, and fig. 3d is a cross-sectional enlarged view of the PU/GYSNs film. From fig. 3a it can be seen that the diameters of GYSNs are around 100nm and no significant agglomeration occurs. As can be seen from fig. 3b, fig. 3c and fig. 3d, after addition of GYSNs, the film surface remained smooth and the GYSNs were uniformly dispersed in the PU matrix film. As shown in fig. 3d, no interfacial voids were observed in the PU matrix.

As shown in fig. 4, the surface roughness has an important influence on the wettability of the hybrid film, and high surface roughness can effectively improve the wettability of the hybrid film. Therefore, the surface roughness of the PU/GYSNs film was measured using an Atomic Force Microscope (AFM). FIG. 4a is an AFM image of the three-dimensional surface of the PU film provided in comparative example 1 of the present invention, and FIG. 4b is an AFM image of the three-dimensional surface of the PU/GYSNs film provided in example 4 of the present invention. The brightest areas in fig. 4 are the highest points on the film surface, while the dark areas are the valleys or holes in the film. The surface roughness parameters of the film were calculated based on the scan size of 1 μm × 1 μm. The average roughness of the PU film and the PU/GYSNs film is 3.61nm and 4.06nm respectively. The surface area of the PU/GYSNs film is larger than that of the PU film, and the permeation flux is increased due to the increase of the surface area of the film.

The thermal stability of the PU/GYSNs film and the PU film is characterized by TGA and DTGA as shown in FIG. 5, wherein FIG. 5a is the TGA curve of the PU/GYSNs film and the PU film, and FIG. 5b is the DTGA curve of the PU/GYSNs film and the PU film. As can be seen in FIG. 5a, both the PU film and the PU/GYSNs film decomposed at a temperature of 285 deg.C, which is well above the operating temperature (40-70 deg.C) for pervaporation gasoline desulfurization.

The thermal stability of the PU/GYSNs film and the PU film was characterized by DSC as shown in fig. 6, and the exothermic peak was slightly decreased as the GYSNs content was increased as shown in fig. 6. However, no substantial effect of the incorporation of GYSNs on PU segment mobility was observed.

As shown in FIG. 7, the effect of GYSNs content on PU/GYSNs membrane separation performance was tested at 30 ℃. Wherein 1 is a variation trend line of permeation flux, and 2 is a variation trend line of enrichment factor. As can be seen from fig. 7, the addition of GYSNs succeeded in improving the desulfurization efficiency of the hybrid membrane compared to the PU membrane. With the increase of GYSNs content, the permeation flux is continuously increased, and the enrichment factor is increased and then reduced. When the addition amount of GYSNs is 0.8 wt.%, the enrichment factor reaches a maximum of 4.32, and the corresponding permeation flux is 1411 g.m^-2·h^-1. GYSNs can provide more free volume for the permeation of thiophene and n-octane, thereby improving permeation flux, and GYSNs provide transfer sites for thiophene molecules through pi-pi complexation,thereby improving the separation efficiency of thiophene. When the content of GYSNs is too large, agglomeration phenomenon begins to occur, so that overlapping of transmission sites is promoted, and enrichment factors are reduced.

As shown in FIG. 8, the PU/GYSNs film with GYSNs content of 0.8 wt.% is used as the separation membrane to test the influence of the sulfur content in the feed liquid on the separation performance of the PU/GYSNs film. Wherein 1 is the variation trend line of the total flux, and 2 is the variation trend line of the enrichment factor. As can be seen from fig. 8, as the sulfur content in the feed solution increases, the permeation flux increases, while the enrichment factor decreases. Since the increase in the thiophene content increases the swelling phenomenon of the PU/GYSNs film and the pores between PU segments, while increasing the diffusion rates of n-octane and thiophene, it results in an increase in permeation flux and a decrease in selectivity.

As shown in fig. 9, 10 and 11, the influence of the operating temperature on the separation performance of the PU/GYSNs film was tested using the PU/GYSNs film having a GYSNs content of 0.8 wt.% as the separation film. Fig. 9 is a graph showing the influence of the operating temperature on the permeation flux and the enrichment factor, wherein 1 is a variation trend line of the permeation flux, and 2 is a variation trend line of the enrichment factor. Fig. 10 is a graph showing the effect of the operating temperature on the permeation flux of thiophene and n-octane, where 1 is the permeation flux change trend line of n-octane and 2 is the permeation flux change trend line of thiophene. FIG. 11 is a graph of the effect of operating temperature on permeability and selectivity. As can be seen from fig. 9 and 10, when the temperature of the feed liquid is increased from 30 ℃ to 70 ℃, the permeation flux of thiophene and n-octane is simultaneously increased, and the enrichment factor is decreased. The higher working temperature increases the thermal movement of molecules and the movement rate of PU molecular chains, increasing permeability, and the high temperature increases the saturated vapor pressure of thiophene and n-octane on the upstream side, resulting in increased permeability. At the same time, the increase in temperature provides additional energy for desorption of molecules from the active sites of GYSNs, resulting in rapid transport of the molecules to be separated. As can be seen from fig. 11, the permeability of thiophene and n-octane is decreasing. The thiophene permeability decreases at a lower rate than n-octane, resulting in increased selectivity.

As shown in fig. 12, PU/GYSNs membranes having a GYSNs content of 0.8 wt.% were tested for operational stability at 30 ℃, where 1 is the variation trend line of permeation flux and 2 is the variation trend line of enrichment factor. As can be seen from fig. 12, both the permeation flux and the enrichment factor remained stable over 168 h. The high thermal stability, mechanical strength and excellent resistance to swelling allow the PU/GYSNs membrane to have long term operational stability required for osmotic separation.

The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims

1. A preparation method of GYSNs filled polyurethane hybrid film is characterized by comprising the following steps:

s1, synthesizing GYSNs, including:

s11, mixing and stirring graphene oxide, polyvinylpyrrolidone and a first solvent, then adding ammonia water and ethyl orthosilicate, stirring for 5-7 h at 25-35 ℃, centrifuging and washing to obtain GO @ SiO₂；

s2, preparing PU/GYSNs films: dispersing GYSNs in a tetrahydrofuran solvent, stirring for 20-40 min, adding polyurethane, continuously stirring for 22-24 h, standing and degassing for 20-40 min to obtain a membrane casting solution, and pouring the membrane casting solution into a culture dish at room temperature until the solvent is completely volatilized to obtain the PU/GYSNs membrane.

2. The preparation method according to claim 1, wherein the mass ratio of the graphene oxide to the polyvinylpyrrolidone is 1: 9.5-10.5, and the first solvent is a mixed solution of deionized water and ethanol in a volume ratio of 1: 7.5-8.5.

3. The preparation method according to claim 1, wherein the volume ratio of the ammonia water to the tetraethoxysilane is 1-2: 1.

4. The preparation method of claim 1, wherein the second solvent is a mixed solution of deionized water and ethanol in a volume ratio of 1: 1.5-2.5, and wherein the GO @ SiO is₂The volume ratio of the suspension to the deionized water to the ethanol is 1: 5.5-6.5: 2.5-3.5.

5. The preparation method according to claim 1, wherein the volume ratio of the formaldehyde to the ethylenediamine to the ethyl orthosilicate is 1: 1-1.5: 1.5-2.5, and the mass volume ratio of the resorcinol to the ethyl orthosilicate is 1: 2.5-3.5.

6. The method of claim 1, wherein in step S13, the GO @ SiO is₂@PB/SiO₂After carbonization, the mixture is soaked in HF solution with the mass fraction of 9-11% and repeatedly washed by deionized water.

7. The preparation method according to claim 1, wherein the mass ratio of the polyurethane to the tetrahydrofuran solvent in the casting solution is 1:14 to 16.

8. The method according to claim 1, wherein the polyurethane is dried at 55 to 65 ℃ for 23 to 25 hours in advance.

9. The method of claim 1, wherein the GYSNs is present in the PU/GYSNs film in an amount of 0.01 to 1 wt.%.

10. The GYSNs-filled polyurethane hybrid film is characterized by being prepared according to the preparation method of any one of claims 1-9.