A photocatalytic composite material, its preparation method and application

Abstract

The application provides a photocatalytic composite material and a preparation method and application thereof. The photocatalytic composite material comprises a carrier and a heterojunction loaded on the carrier, and the heterojunction is synthesized by a perylene diimide-urea polymer and a resorcinol-formaldehyde resin. The photocatalytic composite material can effectively control indoor pollutants. The results of a designed simulation indoor device show that 100% of urea can be controlled under sunlight irradiation, meanwhile, formaldehyde can be controlled below the national indoor formaldehyde standard value, and no secondary pollutants are generated. The application further provides a preparation method and application of the photocatalyst.

Description

Technical Field

[0001] This invention belongs to the field of air pollution control technology, specifically relating to a photocatalytic composite material, its preparation method, and its application. Background Technology

[0002] People spend most of their time indoors, making them susceptible to exposure to a wide variety of indoor air pollutants. Indoor pollutant exposure is linked to both acute and chronic health outcomes. Future population movements, climate change, changes in housing structures, and the use of new furniture can all influence human exposure to indoor air pollutants. Surveys show that in industrialized countries, people spend an average of more than 20 hours indoors per day. Even low concentrations of prolonged exposure to air pollutants can lead to serious illnesses such as leukemia. However, the health effects of indoor air pollution exposure are often overlooked. In recent years, extensive research has been conducted on indoor pollutant exposure. For example, some researchers have used models to assess the accumulation of pollutants in the indoor environment. The use of models provides a methodological framework for the routine assessment of indoor chemical exposure and for comparing the intake of indoor chemicals such as formaldehyde, benzene, and volatile organic carbon. These studies demonstrate the importance of the chemicals present in the indoor environment for human health. In addition to studying the relationship between indoor pollutants and human health, researchers are actively exploring strategies for controlling indoor pollutants, such as adsorption, catalytic combustion, and photocatalysis technologies.

[0003] Adsorption methods have poor degradation effects and pose potential secondary environmental pollution problems; catalytic combustion methods are not suitable for controlling indoor pollutants; while photocatalysis technology is an economical, environmentally friendly, and renewable method that has been widely used in the control of indoor pollutants. However, current technologies lack products based on photocatalysis technology for controlling indoor pollutants. Summary of the Invention

[0004] The present invention aims to at least solve one of the aforementioned technical problems existing in the prior art. To this end, the present invention provides a photocatalytic composite material that achieves 100% control of urea while simultaneously controlling formaldehyde below the national indoor formaldehyde standard value, without generating secondary pollutants.

[0005] The present invention also provides a method for preparing photocatalytic composite materials.

[0006] This invention also provides an application of photocatalytic composite materials in indoor air pollution control.

[0007] The present invention also provides a curtain.

[0008] A first aspect of the present invention provides a photocatalytic composite material comprising a support and a heterojunction loaded on the support, the heterojunction being synthesized from a perylene imide-urea polymer and a resorcinol-formaldehyde resin.

[0009] One of the technical solutions of the present invention concerning photocatalytic composite materials has at least the following beneficial effects:

[0010] The photocatalytic composite material of this invention can effectively control indoor pollutants. Research results from a simulated indoor device show that, under sunlight, it can achieve 100% control of urea while simultaneously keeping formaldehyde levels below the national indoor formaldehyde standard, with no secondary pollutants generated.

[0011] The photocatalytic composite material of this invention provides a new strategy and development direction for the future development of indoor air purification products.

[0012] The abbreviation for perylene imide-urea polymer is PDI-Urea.

[0013] Resorcinol-formaldehyde resin is abbreviated as RF.

[0014] The heterojunction formed by perylene imide-urea polymer and resorcinol-formaldehyde resin is abbreviated as PDI-Urea / RF.

[0015] According to some embodiments of the present invention, the carrier contains cellulose and hydroxyl groups.

[0016] This invention loads PDI-Urea / RF onto a carrier. On one hand, the cellulose in the modified carrier contains hydroxyl functional groups that are oxidized to carbonyl groups, making it easier and more abundant to load PDI-Urea / RF. Furthermore, PDI-Urea / RF is linked with the hydroxyl groups on PDI-Urea / RF to form carboxyl groups, resulting in a more stable structure. On the other hand, the PDI-Urea / RF loaded on cotton fabric stabilizes and promotes water oxidation performance, generating hydrogen peroxide (H2O2) under natural light. H2O2 easily decomposes into hydroxyl radicals, and pollutants in the air react with the hydroxyl radicals to produce substances such as water and carbon dioxide, exhibiting high degradation efficiency.

[0017] "Stable water oxidation performance" refers to the oxidation of water vapor in the air under natural light (occurring on the material surface) to produce H2O2, which is easily decomposed into hydroxyl radicals under light to degrade pollutants in the air.

[0018] According to some embodiments of the present invention, the carrier includes at least one of modified cotton fabric and modified nonwoven fabric.

[0019] According to some embodiments of the present invention, the method for preparing modified cotton fabric is as follows:

[0020] (1) Soak the cotton cloth in an alkaline solution;

[0021] (2) The modified cotton cloth is obtained by drying the soaked cotton cloth in an oven.

[0022] According to some embodiments of the present invention, the cotton fabric is selected from pure cotton products.

[0023] According to some embodiments of the present invention, the cotton fabric is selected from tie-dyed pure cotton fabric. This results in a higher load-bearing capacity.

[0024] According to some embodiments of the present invention, the method for preparing modified nonwoven fabric is as follows:

[0025] (1) Soak the non-woven fabric in an alkaline solution;

[0026] (2) The modified nonwoven fabric is obtained by drying the soaked nonwoven fabric in an oven.

[0027] Soaking cotton or nonwoven fabric in an alkaline solution oxidizes the hydroxyl functional groups in the cellulose of the cotton or nonwoven fabric into carbonyl groups, which then combine with the hydroxyl groups in PDI-Urea / RF to form carboxyl groups, thus stabilizing the loaded PDI-Urea / RF.

[0028] The time for soaking cotton or non-woven fabrics in an alkaline solution is 6 to 12 hours.

[0029] According to some embodiments of the present invention, the alkaline solution includes at least one of sodium hydroxide solution, sodium hypochlorite solution, and potassium hydroxide solution.

[0030] According to some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 0.5 wt% to 3.0 wt%.

[0031] According to some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 0.8 wt% to 3.0 wt%.

[0032] According to some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 1.0 wt% to 3.0 wt%.

[0033] According to some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 1.6 wt% to 3.0 wt%.

[0034] According to some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 0.8 wt%, 1.6 wt%, 2.4 wt%, or within a range consisting of any two of the above values.

[0035] The loading of the heterojunction in the photocatalytic composite material is within the above-mentioned range, thereby achieving good efficiency in photocatalytic degradation of pollutants.

[0036] A second aspect of the present invention provides a method for preparing the photocatalytic composite material, comprising the following steps: adding the perylene imide-urea polymer to a precursor solution formed by resorcinol, formaldehyde and ammonia, performing a hydrothermal reaction to obtain the heterojunction, impregnating the support in the solution of the heterojunction, and drying to obtain the photocatalytic composite material.

[0037] One technical solution of the present invention relating to the preparation method of photocatalytic composite materials has at least the following beneficial effects:

[0038] This invention involves immersing a carrier in a PDI-Urea / RF solution and drying it to obtain a photocatalytic composite material that can effectively control indoor pollutants. Research results show that the designed simulated indoor device achieves 100% control of urea under sunlight irradiation, while simultaneously keeping formaldehyde levels below the national indoor formaldehyde standard, with no secondary pollutants generated.

[0039] The preparation method of the present invention does not require expensive equipment and complex process control, the reaction conditions are not harsh, the raw materials are readily available, the production cost is low, and it is easy to industrialize.

[0040] According to some embodiments of the present invention, the molar ratio of the perylene imide-urea polymer, resorcinol, formaldehyde and ammonia is 1:113:57 to 226:57 to 339.

[0041] According to some embodiments of the present invention, the method for using the photocatalytic composite material includes the following steps:

[0042] S1: React urea, 3,4,9,10-polymethylenetetracarboxylic acid dianhydride and anhydrous zinc acetate in a solvent by heating;

[0043] S2: After cooling the product of step S1, acid is added, and the precipitate is collected after the reaction to obtain perylene imide-urea polymer;

[0044] S3: The perylene imide-urea polymer is added to a precursor solution formed by resorcinol, formaldehyde and ammonia, and after hydrothermal reaction, the heterojunction is obtained;

[0045] S4: The carrier is impregnated in the solution of the heterojunction and dried to obtain the photocatalytic composite material.

[0046] According to some embodiments of the present invention, in step S1, the molar ratio of urea, 3,4,9,10-polymethylenetetracarboxylic dianhydride and anhydrous zinc acetate is 1:0.5 to 3:0.5 to 3.

[0047] According to some embodiments of the present invention, in step S1, the solvent includes imidazole.

[0048] According to some embodiments of the present invention, in step S1, the temperature of the heating reaction is 120°C to 160°C; and / or, the heating reaction time is 3h to 7h.

[0049] In step S2, after adding acid, the pH of the solution is 3-6.

[0050] In step S2, the acid includes hydrochloric acid.

[0051] The purpose of adding hydrochloric acid is to lower the pH of the solution to acidity, thereby triggering self-assembly (the process by which molecules or ions spontaneously assemble into a system with a specific structure and function through non-covalent interactions without external intervention). When the pH decreases to acidity, the proton concentration in the solution increases, and functional groups in molecules undergo deprotonation reactions, which favors the self-assembly process. Therefore, by adding hydrochloric acid to lower the pH of the solution to acidity, the occurrence of non-covalent interactions between molecules can be promoted, thus triggering the self-assembly process.

[0052] In step S2, acid is added, and the reaction continues until no further precipitate is detected. The dark red precipitate is collected by vacuum filtration and washed repeatedly with distilled water until no chloride or silver ions are present in the washing solution. The collected precipitate is dried under vacuum. Then, the obtained material is washed repeatedly with DMSO until the washing solution becomes colorless, and the product is PDI-Urea. Washing the obtained material repeatedly with DMSO aims to remove the precursor solution, making the material purer. It can also be washed with organic substances such as acetone.

[0053] According to some embodiments of the present invention, in step S3, the molar ratio of resorcinol, formaldehyde and ammonia is 1:0.5 to 2:0.5 to 3.

[0054] According to some embodiments of the present invention, in step S3, the solvent of the precursor solution may be water.

[0055] According to some embodiments of the present invention, in step S3, the temperature of the hydrothermal reaction is 160°C to 280°C.

[0056] According to some embodiments of the present invention, in step S3, the hydrothermal reaction time is 12h to 24h.

[0057] According to some embodiments of the present invention, in step S3, after the hydrothermal reaction, the product is dried.

[0058] According to some embodiments of the present invention, the drying temperature is 60°C to 180°C.

[0059] According to some embodiments of the present invention, the drying time is 12h to 24h.

[0060] According to some embodiments of the present invention, in step S4, the carrier is impregnated in the solution of the heterojunction, wherein the solvent of the heterojunction solution may be water, and the photocatalytic composite material is obtained after drying.

[0061] Stirring can be performed during the soaking process.

[0062] According to some embodiments of the present invention, the stirring speed can be 600 rpm to 700 rpm.

[0063] According to some embodiments of the present invention, the stirring time can be from 10 min to 120 min.

[0064] Ultrasound can be used during the impregnation process.

[0065] According to some embodiments of the present invention, the ultrasound duration can be 60 min to 120 min.

[0066] According to some embodiments of the present invention, in step S4, the drying temperature is 60°C to 15°C.

[0067] According to some embodiments of the present invention, in step S4, the drying time is 12h to 24h.

[0068] A third aspect of the present invention provides the application of the aforementioned photocatalytic composite material in indoor air pollution control.

[0069] The present invention relates to a technical solution for the application of photocatalytic composite materials in indoor air pollution control, which has at least the following beneficial effects:

[0070] Because the photocatalytic composite material of this invention can effectively control indoor pollutants, the results of simulated indoor device studies show that under sunlight irradiation, it can achieve 100% control of urea and simultaneously control formaldehyde below the national indoor formaldehyde standard, without generating secondary pollutants. Therefore, the photocatalytic composite material has wide applications and diverse forms when used for indoor air pollution control.

[0071] When the photocatalytic composite material of the present invention is used for indoor air pollution control, it can be prepared into an air purification material, such as wallpaper, tiles, and window screens.

[0072] When the photocatalytic composite material of the present invention is used for indoor air pollution control, it can also be prepared into the form of filters and assembled into air purification devices, such as air purifiers, air conditioners, and fresh air systems.

[0073] The photocatalytic composite material of this invention can even be made into handicrafts and ornaments, which can play a role in indoor air pollution control while also having a decorative effect.

[0074] In summary, the photocatalytic composite material of this invention provides a new strategy and development direction for the future development of indoor air purification products.

[0075] A fourth aspect of the present invention provides a curtain comprising the photocatalytic composite material of the present invention.

[0076] The present invention relates to a technical solution for curtains, which has at least the following beneficial effects:

[0077] The curtain of the present invention, because it includes a photocatalytic composite material, possesses all the beneficial effects of a photocatalytic composite material. Specifically:

[0078] Because the photocatalytic composite material of this invention can effectively control indoor pollutants, the results of simulated indoor device studies show that under sunlight, it can achieve 100% control of urea and simultaneously keep formaldehyde below the national indoor formaldehyde standard, with no secondary pollutants generated. Therefore, the curtains of this invention can effectively control indoor air pollutants.

[0079] According to some embodiments of the present invention, since the photocatalytic composite material uses modified cotton or non-woven fabric as a carrier, it can be prepared into patterns with decorative effects in curtains.

[0080] According to some embodiments of the present invention, the area of ​​the carrier is 81 cm². 2 ~144cm 2 .

[0081] According to some embodiments of the present invention, the area of ​​the carrier is 81 cm². 2 100cm 2 144cm 2 Or, within the range of any two of the above values. Therefore, the curtains have better light transmission.

[0082] The carrier material is not limited to cotton or non-woven fabric. Any material with a certain strength that can be made into a window and can support the heterostructure of this invention can be used as a carrier. Attached Figure Description

[0083] Figure 1 This is a SEM image of the photocatalytic composite material prepared in Example 1 of the present invention.

[0084] Figure 2 This is a TEM image of the photocatalytic composite material prepared in Example 1 of the present invention.

[0085] Figure 3 This is the XRD pattern of PDI-Urea / RF prepared in Example 1 of this invention.

[0086] Figure 4 This is a SEM image of the PDI-Urea / RF prepared in Example 1 of this invention.

[0087] Figure 5 This is a graph showing the hydrogen peroxide performance produced by different PDI-Urea contents.

[0088] Figure 6 A diagram illustrating the mechanism by which the photocatalytic composite material prepared in this embodiment of the invention degrades pollutants.

[0089] Figure 7 The embodiments and comparative examples of this invention simulate indoor formaldehyde content degradation by photocatalysis.

[0090] Figure 8 The embodiments and comparative examples of this invention simulate the indoor photocatalytic degradation of urea content.

[0091] Figure 9 This is a physical image of the photocatalytic composite material prepared according to an embodiment of the present invention. Detailed Implementation

[0092] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0093] In some embodiments of the present invention, the present invention provides a photocatalytic composite material comprising a support and a heterojunction loaded on the support, the heterojunction being synthesized from perylene imide-urea polymer and resorcinol-formaldehyde resin.

[0094] It is understood that the photocatalytic composite material of this invention can effectively control indoor pollutants. Research results from the designed simulated indoor device show that, under sunlight, it can achieve 100% control of urea, while simultaneously keeping formaldehyde below the national indoor formaldehyde standard value, with no secondary pollutants generated.

[0095] It can also be understood that the photocatalytic composite material of the present invention provides a new strategy and development direction for the development of future indoor air purification products.

[0096] It should be noted that the abbreviation for perylene imide-urea polymer is PDI-Urea.

[0097] Resorcinol-formaldehyde resin is abbreviated as RF.

[0098] The heterojunction formed by perylene imide-urea polymer and resorcinol-formaldehyde resin is abbreviated as PDI-Urea / RF.

[0099] In some embodiments of the present invention, the carrier contains cellulose and hydroxyl groups.

[0100] This invention loads PDI-Urea / RF onto a carrier. On one hand, the cellulose in the modified carrier contains hydroxyl functional groups that are oxidized to carbonyl groups, making it easier and more abundant to load PDI-Urea / RF. Furthermore, PDI-Urea / RF is linked with the hydroxyl groups on PDI-Urea / RF to form carboxyl groups, resulting in a more stable structure. On the other hand, the PDI-Urea / RF loaded on cotton fabric stabilizes and promotes water oxidation performance, generating hydrogen peroxide (H2O2) under natural light. H2O2 easily decomposes into hydroxyl radicals, and pollutants in the air react with the hydroxyl radicals to produce substances such as water and carbon dioxide, exhibiting high degradation efficiency.

[0101] In some embodiments of the present invention, the carrier includes at least one of modified cotton fabric and modified nonwoven fabric.

[0102] In some embodiments of the present invention, the method for preparing the modified cotton fabric is as follows:

[0103] (1) Soak the cotton cloth in an alkaline solution;

[0104] (2) The modified cotton cloth is obtained by drying the soaked cotton cloth in an oven.

[0105] In some embodiments of the present invention, the cotton fabric is selected from pure cotton products.

[0106] In some embodiments of the present invention, the cotton fabric is selected from tie-dyed pure cotton fabric. This results in a higher load-bearing capacity.

[0107] In some embodiments of the present invention, the method for preparing the modified nonwoven fabric is as follows:

[0108] (1) Soak the non-woven fabric in an alkaline solution;

[0109] (2) The modified nonwoven fabric is obtained by drying the soaked nonwoven fabric in an oven.

[0110] It should be noted that soaking cotton or non-woven fabric in an alkaline solution oxidizes the hydroxyl functional groups in the cellulose of the cotton or non-woven fabric into carbonyl groups, which then combine with the hydroxyl groups in PDI-Urea / RF to form carboxyl groups, thus stabilizing the loaded PDI-Urea / RF.

[0111] The time for soaking cotton or non-woven fabrics in an alkaline solution is 6 to 12 hours.

[0112] In some embodiments of the present invention, the alkaline solution includes at least one of sodium hydroxide solution, sodium hypochlorite solution, and potassium hydroxide solution.

[0113] In some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 0.5 wt% to 3.0 wt%.

[0114] In some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 0.8 wt% to 3.0 wt%.

[0115] In some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 1.0 wt% to 3.0 wt%.

[0116] In some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 1.6 wt% to 3.0 wt%.

[0117] In some embodiments of the present invention, the loading of the heterojunction in the photocatalytic composite material is 0.8 wt%, 1.6 wt%, 2.4 wt%, or within the range of any two of the above values.

[0118] The loading of heterojunctions in the photocatalytic composite material is within the above range, thus exhibiting good efficiency in photocatalytic degradation of pollutants.

[0119] In other embodiments of the present invention, a method for preparing the photocatalytic composite material of the present invention is provided, comprising the following steps: adding the perylene imide-urea polymer to a precursor solution formed by resorcinol, formaldehyde, and ammonia; after hydrothermal reaction, obtaining the heterojunction; impregnating the support in the solution of the heterojunction; and drying to obtain the photocatalytic composite material. It can be understood that the present invention obtains a photocatalytic composite material that can effectively control indoor pollutants by immersing the support in a PDI-Urea / RF solution and drying it. Research results show that the designed simulated indoor device achieves 100% control of urea under sunlight irradiation, while simultaneously controlling formaldehyde below the national indoor formaldehyde standard value, with no secondary pollutants generated.

[0120] It can also be understood that the preparation method of the present invention does not require expensive equipment and complex process control, the reaction conditions are not harsh, the raw materials are readily available, the production cost is low, and it is easy to industrialize.

[0121] In some embodiments of the present invention, the molar ratio of perylene imide-urea polymer, resorcinol, formaldehyde and ammonia is 1:113:57 to 226:57 to 339.

[0122] The molecular weight of perylene imide-urea polymer (PDI-Urea) is 646.78 g / mol.

[0123] In some embodiments of the present invention, the preparation method of the photocatalytic composite material includes the following steps:

[0124] S1: React urea, 3,4,9,10-polymethylenetetracarboxylic acid dianhydride and anhydrous zinc acetate in a solvent by heating;

[0125] S2: After cooling the product of step S1, acid is added, and the precipitate is collected after the reaction to obtain perylene imide-urea polymer;

[0126] S3: Perylene imide-urea polymer is added to a precursor solution formed by resorcinol, formaldehyde and ammonia, and after hydrothermal reaction, a heterojunction is obtained;

[0127] S4: The support is impregnated in a solution of a heterojunction and dried to obtain the photocatalytic composite material of the present invention.

[0128] In some embodiments of the present invention, in step S1, the molar ratio of urea, 3,4,9,10-polymethylenetetracarboxylic dianhydride and anhydrous zinc acetate is 1:0.5 to 3:0.5 to 3.

[0129] In some embodiments of the present invention, in step S1, the solvent includes imidazole.

[0130] In some embodiments of the present invention, in step S1, the temperature of the heating reaction is 120°C to 160°C; and / or, the heating reaction time is 3h to 7h.

[0131] In some embodiments of the present invention, in step S2, after adding acid, the pH of the solution is 3-6.

[0132] In some embodiments of the present invention, in step S2, the acid includes hydrochloric acid.

[0133] In some embodiments of the present invention, in step S2, acid is added, and the reaction continues until no further precipitate is detected. The dark red precipitate is collected by vacuum filtration and washed repeatedly with distilled water until no chloride or silver ions are present in the washing solution. The collected precipitate is dried under vacuum. Then, the resulting material is washed repeatedly with DMSO until the washing solution becomes colorless, and the product is PDI-Urea.

[0134] In some embodiments of the present invention, in step S3, the molar ratio of resorcinol, formaldehyde and ammonia is 1:0.5 to 2:0.5 to 3.

[0135] In some embodiments of the present invention, in step S3, the molar ratio of resorcinol, formaldehyde and ammonia is 1:0.8 to 2:0.8 to 3.

[0136] In some embodiments of the present invention, in step S3, the solvent of the precursor solution may be water.

[0137] In some embodiments of the present invention, in step S3, the temperature of the hydrothermal reaction is 160°C to 280°C.

[0138] In some embodiments of the present invention, the hydrothermal reaction time in step S3 is 12h to 24h.

[0139] In some embodiments of the present invention, in step S3, after the hydrothermal reaction, the product is dried.

[0140] In some embodiments of the present invention, the drying temperature is 60°C to 180°C.

[0141] In some embodiments of the present invention, the drying time is 12h to 24h.

[0142] In some embodiments of the present invention, in step S4, the support is impregnated in a solution of the heterojunction, the solvent of which may be water, and after drying, the photocatalytic composite material of the present invention is obtained.

[0143] Stirring can be performed during the soaking process.

[0144] In some embodiments of the present invention, the stirring speed can be 600 rpm to 700 rpm.

[0145] In some embodiments of the present invention, the stirring time can be from 10 min to 120 min.

[0146] Ultrasound can be used during the impregnation process.

[0147] In some embodiments of the present invention, the ultrasound duration can be 60 min to 120 min.

[0148] In some embodiments of the present invention, in step S4, the drying temperature is 60°C to 15°C.

[0149] In some embodiments of the present invention, the drying time in step S4 is 12h to 24h.

[0150] In other embodiments of the present invention, the present invention provides the application of photocatalytic composite materials in indoor air pollution control.

[0151] It is understood that the photocatalytic composite material of this invention can effectively control indoor pollutants. Research results from a simulated indoor device show that, under sunlight, it can achieve 100% control of urea while simultaneously keeping formaldehyde levels below the national indoor formaldehyde standard, with no secondary pollutants generated. Therefore, the photocatalytic composite material has wide applications and diverse forms when used for indoor air pollution control.

[0152] When the photocatalytic composite material of the present invention is used for indoor air pollution control, it can be prepared into an air purification material, such as wallpaper, tiles, and window screens.

[0153] When the photocatalytic composite material of the present invention is used for indoor air pollution control, it can also be prepared into the form of filters and assembled into air purification devices, such as air purifiers, air conditioners, and fresh air systems.

[0154] The photocatalytic composite material of this invention can even be made into handicrafts and ornaments, which can play a role in indoor air pollution control while also having a decorative effect.

[0155] In summary, the photocatalytic composite material of this invention provides a new strategy and development direction for the future development of indoor air purification products.

[0156] In other embodiments of the present invention, a curtain is provided, comprising the photocatalytic composite material of the present invention.

[0157] It is understood that the curtain of the present invention, because it includes a photocatalytic composite material, possesses all the beneficial effects of a photocatalytic composite material. Specifically:

[0158] Because the photocatalytic composite material of this invention can effectively control indoor pollutants, the results of simulated indoor device studies show that under sunlight, it can achieve 100% control of urea and simultaneously keep formaldehyde below the national indoor formaldehyde standard, with no secondary pollutants generated. Therefore, the curtains of this invention can effectively control indoor air pollutants.

[0159] In some embodiments of the present invention, since the photocatalytic composite material uses modified cotton or non-woven fabric as a carrier, it can be prepared into patterns with decorative effects in curtains.

[0160] In some embodiments of the present invention, the area of ​​the carrier is 81 cm². 2 ~144cm 2 .

[0161] In some embodiments of the present invention, the area of ​​the carrier is 81 cm². 2 100cm 2 144cm 2 Or, within the range of any two of the above values. Therefore, the curtains have better light transmission.

[0162] The carrier material is not limited to cotton or non-woven fabric. Any material with a certain strength that can be made into a window and can support the heterostructure of this invention can be used as a carrier.

[0163] The technical solution of the present invention will be better understood below with reference to specific embodiments.

[0164] Example 1

[0165] This embodiment prepares a photocatalytic composite material, including modified cotton cloth and PDI-Urea / RF loaded on the modified cotton cloth, wherein PDI-Urea / RF accounts for 0.81% of the mass of the photocatalytic composite material.

[0166] The specific preparation method is as follows:

[0167] S1. Take a piece of cotton cloth with a length and width of 10cm, soak it in a 5% sodium hypochlorite solution, and store it at room temperature for 12 hours.

[0168] S2. Place the above cotton cloth in an oven to dry for 2 hours at a temperature of 10°C.

[0169] S3. Dissolve urea (0.12 g, 2.0 mmol), 3,4,9,10-polymethylenetetracarboxylic dianhydride (PDA) (0.78 g, 2.0 mmol), and anhydrous zinc acetate (0.37 g, 2.0 mmol) in 5.0 g imidazole in a 500 mL three-necked flask. Heat and stir the mixture at 140 °C for 5 h.

[0170] S4. Cool the reaction mixture to room temperature, then add 250 mL of 1 mol·L⁻¹ solution. -1 HCl. Stir the mixture until no further precipitate is detected. Collect the dark red precipitate by vacuum filtration and wash it repeatedly with distilled water until no chloride or silver ions are present in the washings.

[0171] S5. The collected precipitate was dried under vacuum. Then, the obtained material was washed repeatedly with DMSO until the washing liquid became colorless. Finally, 0.79 g of a deep red, highly insoluble product was obtained, with a yield of 87.8%, and it was named PDI-Urea.

[0172] S6. Take 0.096g of resorcinol powder and formaldehyde (0.135mL, 6mol·L⁻¹). -1 ), ammonia water (0.050 mL, 16 mol·L⁻¹) -1 Mix with deionized water, then add S5 to obtain 5 mg of PDI-Urea powder. After stirring for 30 min, transfer the mixture to a 20 mL Teflon-lined stainless steel autoclave and heat in a forced-air drying oven at 251 °C for 24 h, then air-cool to room temperature. Finally, filter to obtain PDI-Urea / RF and dry in a vacuum drying oven at 60 °C for 12 h.

[0173] S7. Weigh 10 mg of the PDI-Urea / RF powder prepared above, dissolve it in 50 mL of deionized water, add the modified cotton cloth (1222 mg) to the solution, stir for 60 min, then sonicate for 60 min, and finally dry at 100 °C for 2 h to obtain the final product.

[0174] The formula for calculating the loading rate is as follows: 10mg / (10mg+1222mg)×100%=0.81%.

[0175] The photocatalytic composite material prepared in Example 1 was subjected to SEM testing, and the results are as follows: Figure 1 As shown. The particulate matter adhering to the modified cotton fabric is PDI-Urea / RF.

[0176] The binding morphology of PDI-Urea / RF was further tested using TEM, and the results are as follows: Figure 2 As shown. Figure 2 In this mixture, the sheet-like substance is PDI-Urea, and the spherical substance is RF resin.

[0177] X-ray powder diffraction characterization was performed on the PDI-Urea and PDI-Urea / RF prepared in the examples, and the results are as follows: Figure 3 As shown.

[0178] Figure 3 These are XRD patterns of RF precursor solutions with different amounts of PDI-Urea added.

[0179] Figure 3 In the figure, 2.5 mg, 5 mg, 7.5 mg, and 10 mg are the amounts of PDI-Urea added to the RF precursor solution.

[0180] Studies have shown that adding different amounts of PDI-Urea has a certain impact on the generation of hydrogen peroxide during the synthesis of PDI-Urea / RF.

[0181] Figure 4 This is a SEM image of the PDI-Urea / RF prepared in Example 1 of this invention.

[0182] Figure 5 This is a graph showing the hydrogen peroxide performance produced by different PDI-Urea contents. (Example:) Figure 5 As shown, the best effect is achieved when the amount of PDI-Urea added is 5 mg (the mass ratio of resorcinol, one of the raw materials for RF preparation, to PDI-Urea is about 19:1).

[0183] Example 2

[0184] This embodiment prepares a photocatalytic composite material, including modified cotton cloth and PDI-Urea / RF loaded on the modified cotton cloth, wherein PDI-Urea / RF accounts for 1.61% of the mass of the photocatalytic composite material.

[0185] The specific preparation method is as follows:

[0186] S1. Take a piece of cotton cloth with a length and width of 10cm, soak it in a 5% sodium hypochlorite solution, and store it at room temperature for 12 hours.

[0187] S2. Place the above cotton cloth in an oven to dry for 2 hours at a temperature of 100℃.

[0188] S3. Dissolve urea (0.12 g, 2.0 mmol), 3,4,9,10-polymethylenetetracarboxylic dianhydride (PDA) (0.78 g, 2.0 mmol), and anhydrous zinc acetate (0.37 g, 2.0 mmol) in 5.0 g imidazole in a 500 mL three-necked flask. Heat and stir the mixture at 140 °C for 5 h.

[0189] S4. Cool the reaction mixture to room temperature, then add 250 mL of 1 mol·L⁻¹ solution. -1 HCl. Stir the mixture until no further precipitate is detected. Collect the dark red precipitate by vacuum filtration and wash it repeatedly with distilled water until no chloride or silver ions are present in the washings.

[0190] S5. The collected precipitate was dried under vacuum. Then, the obtained material was washed repeatedly with DMSO until the washing liquid became colorless. Finally, 0.79 g of a deep red, highly insoluble product was obtained, with a yield of 87.8%, and it was named PDI-Urea.

[0191] S6. Take 0.096g of resorcinol powder and formaldehyde (0.135mL, 6mol·L⁻¹). -1 ), ammonia water (0.050 mL, 16 mol / L) -1 Mix with deionized water, then add S5 to obtain 5 mg of PDI-Urea powder. After stirring for 30 min, transfer the mixture to a 20 mL Teflon-lined stainless steel autoclave and heat in a forced-air drying oven at 251 °C for 24 h, then air-cool to room temperature. Finally, filter to obtain PDI-Urea / RF and dry in a vacuum drying oven at 60 °C for 12 h.

[0192] S7. Weigh 20 mg of the PDI-Urea / RF powder prepared above, dissolve it in 50 mL of deionized water, add the modified cotton cloth (1223 mg) to the solution, stir for 60 min, then sonicate for 60 min, and finally dry at 100 °C for 2 h to obtain the final product.

[0193] The formula for calculating the loading rate is as follows: 20mg / (20mg+1223mg)×100%=1.61%.

[0194] Example 3

[0195] This embodiment prepares a photocatalytic composite material, including modified cotton cloth and PDI-Urea / RF loaded on the modified cotton cloth, wherein PDI-Urea / RF accounts for 2.52% of the mass of the photocatalytic composite material.

[0196] The specific preparation method is as follows:

[0197] S1. Take a piece of cotton cloth with a length and width of 10cm, soak it in a 5% sodium hypochlorite solution, and store it at room temperature for 12 hours.

[0198] S2. Place the above cotton cloth in an oven to dry for 2 hours at a temperature of 100℃.

[0199] S3. Dissolve urea (0.12 g, 2.0 mmol), 3,4,9,10-polymethylenetetracarboxylic dianhydride (PDA) (0.78 g, 2.0 mmol), and anhydrous zinc acetate (0.37 g, 2.0 mmol) in 5.0 g imidazole in a 500 mL three-necked flask. Heat and stir the mixture at 140 °C for 5 h.

[0200] S4. Cool the reaction mixture to room temperature, then add 250 mL of 1 mol·L⁻¹ solution. -1 HCl. Stir the mixture until no further precipitate is detected. Collect the dark red precipitate by vacuum filtration and wash it repeatedly with distilled water until no chloride or silver ions are present in the washings.

[0201] S5. The collected precipitate was dried under vacuum. Then, the obtained material was washed repeatedly with DMSO until the washing liquid became colorless. Finally, 0.79 g of a deep red, highly insoluble product was obtained, with a yield of 87.8%, and it was named PDI-Urea.

[0202] S6. Take 0.096g of resorcinol powder and formaldehyde (0.135mL, 6mol·L⁻¹). -1 ), ammonia water (0.050 mL, 16 mol·L⁻¹) -1 Mix with deionized water, then add S5 to obtain 5 mg of PDI-Urea powder. After stirring for 30 min, transfer the mixture to a 20 mL Teflon-lined stainless steel autoclave and heat in a forced-air drying oven at 251 °C for 24 h, then air-cool to room temperature. Finally, filter to obtain PDI-Urea / RF and dry in a vacuum drying oven at 60 °C for 12 h.

[0203] S7. Weigh 30 mg of the PDI-Urea / RF powder prepared above, dissolve it in 50 mL of deionized water, add the modified cotton cloth (1159 mg) to the solution, stir for 60 min, then sonicate for 60 min, and finally dry at 100 °C for 2 h to obtain the final product.

[0204] The formula for calculating the loading rate is as follows: 30mg / (30mg+1159mg)×100%=2.52%.

[0205] Example 4

[0206] This embodiment prepares a photocatalytic composite material, including modified cotton cloth and PDI-Urea / RF loaded on the modified cotton cloth, wherein PDI-Urea / RF accounts for 0.8% of the mass of the photocatalytic composite material.

[0207] The specific preparation method is as follows:

[0208] S1. Take a piece of cotton cloth with a length and width of 10cm, soak it in a 5% sodium hypochlorite solution, and store it at room temperature for 12 hours.

[0209] S2. Place the above cotton cloth in an oven to dry for 2 hours at a temperature of 100℃.

[0210] S3. Dissolve urea (0.12 g, 2.0 mmol), 3,4,9,10-polymethylenetetracarboxylic dianhydride (PDA) (0.78 g, 2.0 mmol), and anhydrous zinc acetate (0.37 g, 2.0 mmol) in 5.0 g imidazole in a 500 mL three-necked flask. Heat and stir the mixture at 140 °C for 5 h.

[0211] S4. Cool the reaction mixture to room temperature, then add 250 mL of 1 mol·L⁻¹ solution. -1 HCl. Stir the mixture until no further precipitate is detected. Collect the dark red precipitate by vacuum filtration and wash it repeatedly with distilled water until no chloride or silver ions are present in the washings.

[0212] S5. The collected precipitate was dried under vacuum. Then, the obtained material was washed repeatedly with DMSO until the washing liquid became colorless. Finally, 0.79 g of a deep red, highly insoluble product was obtained, with a yield of 87.8%, and it was named PDI-Urea.

[0213] S6. Take 0.096g of resorcinol powder and formaldehyde (0.135mL, 6mol·L⁻¹). -1 ), ammonia water (0.10 mL, 16 mol·L⁻¹) -1 Mix with deionized water, then add S5 to obtain 5 mg of PDI-Urea powder. After stirring for 30 min, transfer the mixture to a 20 mL Teflon-lined stainless steel autoclave and heat in a forced-air drying oven at 251 °C for 24 h, then air-cool to room temperature. Finally, filter to obtain PDI-Urea / RF and dry in a vacuum drying oven at 60 °C for 12 h.

[0214] S7. Weigh 10 mg of the PDI-Urea / RF powder prepared above, dissolve it in 50 mL of deionized water, add the modified cotton cloth (1219 mg) to the solution, stir for 60 min, then sonicate for 60 min, and finally dry at 100 °C for 2 h to obtain the final product.

[0215] The formula for calculating the loading rate is as follows: 10mg / (10mg+1219mg)×100%=0.81%.

[0216] Comparative Example 1

[0217] This comparative example prepared a photocatalytic composite material, and its preparation method and reagent dosage were basically the same as those in Example 1. The difference was that the cotton cloth in Comparative Example 1 did not have step S1.

[0218] The weight of the cotton cloth is 1271 mg.

[0219] The formula for calculating the loading rate is as follows: 10mg / (10mg+1271mg)×100%=0.78%.

[0220] Performance testing

[0221] The photocatalytic composite materials prepared in Examples 1-4 and Comparative Example 1 were subjected to formaldehyde and urea degradation tests.

[0222] Figure 6 This is a diagram illustrating the pollutant degradation mechanism in Examples 1-4 of this invention. From... Figure 6 It can be seen that water and oxygen in the air generate hydrogen peroxide on the surface of the composite material. Under light, hydrogen peroxide reacts with pollutants in the air and finally degrades them into organic matter such as carbon dioxide.

[0223] The steps of the pollutant degradation experiment are as follows: Prepare a 10cm×10cm×10cm cubic sealed box. Inject the prepared pollutant solution into the box by blowing argon gas, simulating indoor pollutant degradation. After adding light, extract the gas from the box, test for a certain period, and calculate the pollutant degradation concentration.

[0224] like Figure 7 The diagram shows a simulated indoor formaldehyde content degradation using photocatalytic degradation. The specific steps are as follows: 1 mol·L⁻¹ of formaldehyde in the device... -1 After the formaldehyde solution was purged with argon for 2 hours, 5 mL gas samples were taken every 15 minutes under dark conditions and fluorescent light. The formaldehyde concentration of the blank control group, Examples 1-4 and Comparative Example 1 was measured using an ultraviolet spectrophotometer, and the degradation rate was calculated.

[0225]

[0226] Where C0 represents the initial concentration, Ct This represents the concentration at time t.

[0227] Similarly, such as Figure 8 The diagram shows the simulated indoor photocatalytic degradation of urea content; 1 Mol·L⁻¹ urea was added to the device. -1 After the urea solution was purged with argon for 2 hours, 5 mL of gas samples were taken every 15 minutes under dark conditions and fluorescent light. The urea concentration of the blank control group, Examples 1-4 and Comparative Example 1 was measured using an ultraviolet spectrophotometer, and the degradation rate was calculated.

[0228]

[0229] Where C0 represents the initial concentration, C t This represents the concentration at time t.

[0230] The results are as follows Figure 7 , Figure 8 As shown in Table 1.

[0231] The photocatalytic composite material in Example 1 achieved a 57% degradation rate of formaldehyde in the air within one hour.

[0232] The degradation rate of urea in the air reached 100% within one hour.

[0233] The testing apparatus used in this invention is as follows: Figure 9 As shown, a 10cm x 10cm x 10cm cubic enclosed box is used to simulate an indoor spatial environment.

[0234] Table 1

[0235]

[0236] As can be seen from Examples 1 to 3 above, the loading of PDI-Urea / RF affects the catalytic performance of the photocatalytic composite material.

[0237] As seen in Example 4, increasing the amount of ammonia water will affect the performance of PDI-Urea / RF synthesis, resulting in less hydrogen peroxide production and thus affecting its degradation rate.

[0238] As seen in Comparative Example 1, the absence of step S1 results in less RF adhering to the product, thus affecting the efficiency of photocatalytic degradation of pollutants.

[0239] The present invention has been described in detail above with reference to the embodiments. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A window covering, comprising: The photocatalytic composite material comprises a carrier and a heterojunction loaded on the carrier; The carrier is modified cotton cloth or modified non-woven fabric, which is obtained by immersing cotton cloth or non-woven fabric in a basic solution, and the basic solution is sodium hypochlorite solution; The heterojunction is prepared by adding a perylene imide-urea polymer into a precursor solution formed by resorcinol, formaldehyde and ammonia, and then performing hydrothermal reaction to obtain the heterojunction; The loading amount of the heterojunction in the photocatalytic composite material is 0.5wt%-3.0wt%.

2. The window treatment of claim 1, wherein, The preparation method of the photocatalytic composite material comprises the following steps: immersing the carrier in a solution containing the heterojunction, and then drying to obtain the photocatalytic composite material.

3. The window treatment of claim 1, wherein, The molar ratio of the perylene imide-urea polymer, resorcinol, formaldehyde and ammonia is 1:113:57-226:57-339.

4. The window treatment of claim 1, wherein, The temperature of the hydrothermal reaction is 160°C-280°C.

5. The window treatment of claim 1, wherein, The time of the hydrothermal reaction is 12h-24h.

Images