Formaldehyde-removing graphene oxide hydrogel-loaded material and preparation method thereof

Abstract

The present invention discloses a formaldehyde-removing graphene oxide hydrogel loading material and a preparation method thereof. The formaldehyde-removing graphene oxide hydrogel loading material comprises: a reduced graphene oxide hydrogel; a compound represented by formula I and / or formula II, wherein the compound represented by formula I and / or formula II is loaded on the reduced graphene oxide hydrogel; wherein R1 is selected from C3 to C 12 Alkylene; R2 is selected from H, Cl, or Br. The graphene oxide hydrogel-loaded material of the present invention can efficiently and rapidly capture and adsorb formaldehyde from the air, reacting with it to form a stable compound that is harmless to humans. Furthermore, the graphene oxide hydrogel-loaded material is a solid hydrogel and can be placed in a corner of a room without requiring any construction process. Furthermore, the graphene oxide hydrogel-loaded material is easy to use and, after prolonged storage, releases no substances other than water evaporation, making it safe and pollution-free.

Description

Technical Field

[0001] The present invention belongs to the technical field of air purification composite materials, and in particular relates to a formaldehyde-removing graphene oxide hydrogel-loaded material and a preparation method thereof. Background Art

[0002] Formaldehyde is a colorless, water-soluble gas that is highly volatile and has a pungent odor. Indoor formaldehyde primarily originates from building materials, furniture, artificial boards, various adhesives and coatings, and synthetic textiles. Urea-formaldehyde resin, commonly used as an adhesive in the production of various artificial boards and furniture, may be the largest source of formaldehyde emissions. Indoor formaldehyde pollution poses the most direct and significant threat to human health. However, current formaldehyde removal products on the market either have unsatisfactory removal effects or leave residues, causing secondary pollution. Therefore, developing an efficient and environmentally friendly formaldehyde removal material is a technical challenge that urgently needs to be addressed in this field. Summary of the Invention

[0003] The present invention aims to solve, at least to a certain extent, one of the technical problems in the related art. To this end, the purpose of the present invention is to provide a formaldehyde-removing graphene oxide hydrogel-loaded material and a preparation method thereof. The graphene oxide hydrogel-loaded material of the present invention can efficiently and quickly capture and adsorb formaldehyde in the air, and react with it to form a stable compound that is harmless to humans. In addition, the graphene oxide hydrogel-loaded material is a solid hydrogel and only needs to be placed in a corner of the room, without any construction process requirements. At the same time, the graphene oxide hydrogel-loaded material is easy to use and does not release any substances other than water evaporation after being placed for a long time. It is safe, harmless and pollution-free.

[0004] In one aspect of the present invention, the present invention provides a formaldehyde-removing graphene oxide hydrogel loading material. According to an embodiment of the present invention, the formaldehyde-removing graphene oxide hydrogel loading material comprises:

[0005] reduced graphene oxide hydrogel;

[0006] A compound represented by Formula I and / or Formula II, wherein the compound represented by Formula I and / or Formula II is supported on the reduced graphene oxide hydrogel;

[0007]

[0008]

[0009] Wherein, R1 is selected from C3~C 12 Alkylene; R2 is selected from H, Cl or Br.

[0010] The formaldehyde-removing graphene oxide hydrogel-loaded material according to an embodiment of the present invention can efficiently and rapidly capture and adsorb formaldehyde from the air, reacting with it to form a stable compound without secondary release. Specifically, the aldehyde-amine condenses to form a Schiff base. Furthermore, the graphene oxide hydrogel-loaded material is a solid hydrogel and can be placed in a corner of a room without requiring any construction process. Furthermore, the graphene oxide hydrogel-loaded material is easy to use and, after prolonged storage, releases no substances other than water evaporation, making it safe, harmless, and pollution-free.

[0011] In addition, the formaldehyde removal graphene oxide hydrogel loading material according to the above embodiment of the present invention may also have the following additional technical features:

[0012] In some embodiments of the present invention, the compound represented by formula I is:

[0013] In some embodiments of the present invention, the compound represented by formula II is selected from

[0014]

[0015] At least one of .

[0016] In some embodiments of the present invention, based on the mass of the reduced graphene oxide hydrogel being 1 g, the loading amount of the compound represented by Formula I and / or Formula II on the reduced graphene oxide hydrogel is 0.2-0.45 g.

[0017] In some embodiments of the present invention, the reduced graphene oxide hydrogel is bound to the compound represented by Formula I and / or Formula II through covalent bonds between graphene sheets.

[0018] In another aspect of the present invention, a method for preparing the above-mentioned formaldehyde-removing graphene oxide hydrogel-supported material is provided. According to an embodiment of the present invention, the method comprises:

[0019] (1) preparing a compound represented by Formula I or Formula II to form a hydrosol;

[0020] (2) preparing reduced graphene oxide hydrogel;

[0021] (3) immersing the reduced graphene oxide hydrogel in the hydrosol so that the compound represented by Formula I and / or Formula II is loaded on the reduced graphene oxide hydrogel, and washing the reduced graphene oxide hydrogel to obtain the formaldehyde-removing graphene oxide hydrogel loaded material.

[0022] According to the method for preparing the above-mentioned formaldehyde-removing graphene oxide hydrogel-loaded material according to an embodiment of the present invention, the graphene oxide hydrogel-loaded material prepared by this method can efficiently and quickly capture and adsorb formaldehyde in the air, and react with it to form a stable compound that is harmless to humans. In addition, the graphene oxide hydrogel-loaded material is a solid hydrogel and can be placed in a corner of the room without any construction process requirements. At the same time, the graphene oxide hydrogel-loaded material is easy to use and does not release any substances other than water evaporation after being placed for a long time. It is safe, harmless and pollution-free. The preparation process is simple and easy to implement.

[0023] In addition, the method according to the above embodiment of the present invention may also have the following additional technical features:

[0024] In some embodiments of the present invention, step (1) comprises: (1-1) mixing a compound represented by Formula III or Formula IV, a compound represented by Formula V, and a solvent, subjecting the resulting mixture to reflux reaction under an inert atmosphere, and centrifuging, washing, and drying the reaction product to obtain the compound represented by Formula I or Formula II; (1-2) mixing the compound represented by Formula I and / or Formula II with water to form the hydrosol;

[0025]

[0026]

[0027] Wherein, R1 is selected from C3~C 12 Alkylene; R2 is selected from H, Cl or Br.

[0028] In some embodiments of the present invention, in step (1-1), the molar ratio of the compound represented by formula III or formula IV to the compound represented by formula V is 1:(2-3); and / or the temperature of the reflux reaction is 80-90 degrees Celsius, and the time is 6-48 hours.

[0029] In some embodiments of the present invention, in step (1-2), the concentration of the compound represented by Formula I and / or Formula II in the hydrosol is 0.2-2.0 mg / mL.

[0030] In some embodiments of the present invention, it is characterized in that step (2) includes: placing the graphene oxide dispersion under high temperature and high pressure for reaction, and washing it to obtain the reduced graphene oxide hydrogel.

[0031] In some embodiments of the present invention, in step (2), the reaction temperature is 150-170 degrees Celsius, the reaction pressure is 300 kPa-500 kPa, and the reaction time is 6-24 hours; and / or the solvent of the graphene oxide dispersion is water, and the concentration of graphene oxide in the graphene oxide dispersion is 0.8-1.2 mg / mL.

[0032] In some embodiments of the present invention, in step (3), the culture time is 20-48 hours.

[0033] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0035] Figure 1 This is an electron microscope image of the formaldehyde-removing graphene oxide hydrogel-loaded material of Example 1 of the present invention. DETAILED DESCRIPTION

[0036] The following describes embodiments of the present invention in detail, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and are not to be construed as limiting the present invention.

[0037] In one aspect, the present invention provides a formaldehyde-removing graphene oxide hydrogel-supported material. According to an embodiment of the present invention, the formaldehyde-removing graphene oxide hydrogel-supported material comprises: a reduced graphene oxide hydrogel; a compound represented by Formula I and / or Formula II, wherein the compound represented by Formula I and / or Formula II is supported on the reduced graphene oxide hydrogel;

[0038]

[0039] Wherein, R1 is selected from C3~C 12 Alkylene; R2 is selected from H, Cl, or Br. Thus, the graphene oxide hydrogel-supported material of the present invention can efficiently and rapidly capture and adsorb formaldehyde from the air, reacting with it to form a harmless, stable compound. Specifically, the aldehyde-amine condenses to form a Schiff base. Furthermore, the graphene oxide hydrogel-supported material is a solid hydrogel and can be placed in a corner of a room without requiring any construction process. Furthermore, the graphene oxide hydrogel-supported material is easy to use and, after prolonged storage, releases no substances other than water evaporation, making it safe and pollution-free.

[0040] As some specific examples, the compound represented by formula I can be

[0041] The compound of this structure loaded on the reduced graphene oxide hydrogel can further efficiently and quickly capture and adsorb formaldehyde in the air, and react with it to form a stable compound that is harmless to humans.

[0042] As some specific examples, the compound represented by formula II can be:

[0043] The compound with the above structure loaded on the reduced graphene oxide hydrogel can further efficiently and quickly capture and adsorb formaldehyde in the air, and react with it to form a stable compound that is harmless to humans.

[0044] In an embodiment of the present invention, the three-dimensional reduced graphene oxide hydrogel is combined with the compound represented by Formula I and / or Formula II through covalent bonds between graphene sheets, as shown in the following equation.

[0045]

[0046] According to some specific embodiments of the present invention, based on the mass of the reduced graphene oxide hydrogel being 1 g, the loading amount of the compound represented by Formula I and / or Formula II on the reduced graphene oxide hydrogel is 0.2-0.45 g (for example, it can be 0.2 / 0.25 / 0.3 / 0.35 / 0.4 / 0.45 g). By limiting the loading amount of the compound represented by Formula I and / or Formula II to the above range, it is further ensured that the graphene oxide hydrogel loading material can efficiently and quickly capture and adsorb formaldehyde in the air, and react with it to form a stable compound that is harmless to humans.

[0047] In another aspect of the present invention, the present invention provides a method for preparing the above-mentioned formaldehyde removal graphene oxide hydrogel loading material. Figure 1 , the method comprising:

[0048] S100: preparing a compound represented by Formula I or Formula II to form a hydrosol;

[0049] Step S100 includes:

[0050] S110: Mix the compound represented by Formula III or Formula IV, the compound represented by Formula V, and a solvent (e.g., isopropanol), and reflux the mixture under an inert atmosphere (e.g., a nitrogen atmosphere). Centrifuge the reaction product, collect the solid product, and then wash it (e.g., with a large amount of ethanol) and dry it to obtain the compound represented by Formula I or Formula II.

[0051]

[0052] Wherein, R1 is selected from C3~C 12 Alkylene; R2 is selected from H, Cl or Br.

[0053] According to some specific embodiments of the present invention, the molar ratio of the compound represented by formula III or formula IV to the compound represented by formula V is 1:(2-3), preferably 1:(2.3-2.7), thereby allowing the compound represented by formula III or formula IV to fully react with the compound represented by formula V.

[0054] According to some further specific embodiments of the present invention, the reflux reaction temperature is 80-90 degrees Celsius and the time is 6-48 hours, so that the compound represented by formula III or formula IV can fully react with the compound represented by formula V.

[0055] S120: Mixing the compound represented by Formula I and / or Formula II with water to form the hydrosol. Preferably, the concentration of the compound represented by Formula I and / or Formula II is 0.2-2.0 mg / mL, thereby further facilitating the loading of the compound represented by Formula I and / or Formula II in the hydrosol onto the reduced graphene oxide hydrogel.

[0056] S200: preparation of reduced graphene oxide hydrogel;

[0057] In this step, the graphene oxide dispersion is subjected to a high temperature and high pressure reaction (for example, by sealing the graphene oxide dispersion in a polytetrafluoroethylene-lined autoclave for high temperature and high pressure reaction). The hydrothermally formed reduced graphene oxide hydrogel is thoroughly washed with water to obtain a pure reduced graphene oxide hydrogel. Specifically, the reaction temperature is 150-170 degrees Celsius, the reaction pressure is 300kPa-500kPa, and the reaction time is 6-24 hours, thereby ensuring that the graphene oxide dispersion fully reacts to form a three-dimensional reduced graphene oxide hydrogel.

[0058] Furthermore, the solvent of the graphene oxide dispersion is water, and the concentration of graphene oxide in the graphene oxide dispersion is 0.8-1.2 mg / mL.

[0059] It should be noted that the specific order of steps S100 and S200 is not particularly limited. Step S100 may be performed first and then S200, or step S200 may be performed first and then S100, or S100 and S200 may be performed simultaneously.

[0060] S300: Immersing the reduced graphene oxide hydrogel in the hydrosol so that the compound represented by Formula I and / or Formula II is loaded on the reduced graphene oxide hydrogel, and washing to obtain the formaldehyde-removing graphene oxide hydrogel loaded material.

[0061] According to some specific embodiments of the present invention, the culture time is 20-48 hours, thereby further ensuring that the compound represented by Formula I and / or Formula II is fully loaded on the reduced graphene oxide hydrogel.

[0062] As a specific example, the washing steps are as follows: the formed graphene oxide hydrogel-loaded material is washed three times with distilled water, using 100 mL of water in each step. The mass loading of the compound represented by Formula I and / or Formula II in the graphene oxide hydrogel-loaded material is calculated by measuring the concentration of the hydrosol before and after incubation and in the waste washing solution. The concentration of the hydrosol is determined by ultraviolet spectroscopy based on a standard curve generated based on the hydrosol. The loading efficiency is calculated by calculating the mass ratio of the compound represented by Formula I and / or Formula II loaded on the reduced graphene oxide hydrogel to the compound represented by Formula I and / or Formula II present in the hydrosol.

[0063] The following embodiments of the present invention are described in detail. It should be noted that the following embodiments are illustrative and are intended only to explain the present invention and are not to be construed as limiting the present invention. In addition, unless otherwise expressly stated, all reagents used in the following embodiments are commercially available or can be synthesized according to methods described herein or known methods. Reaction conditions not listed are also readily available to those skilled in the art.

[0064] Example 1

[0065] This embodiment provides a method for preparing a formaldehyde-removing graphene oxide hydrogel-loaded material, comprising:

[0066] 1. Preparation of PBI-NH2

[0067] 5.0 mmol of PDA and 12.9 mmol of 1,6-hexanediamine were mixed in 10 mL of isopropanol to produce a red mixture. The red mixture was refluxed at 85°C under an N2 atmosphere for 6 hours. The reaction product was then cooled and centrifuged to collect the dark red solid product. The red solid product was then washed three times with a large amount of ethanol. After vacuum drying, a red powder, PBI-NH2, was obtained. The PBI-NH2 solid powder was dissolved in distilled water to prepare a 1 mg / mL aqueous sol.

[0068]

[0069] 2. Preparation of 3D Reduced Graphene Oxide Hydrogel and PBI-NH2-rGO

[0070] First, a three-dimensional reduced graphene oxide hydrogel was synthesized by hydrothermal reduction of graphene oxide. Specifically, 40 mL of graphene oxide dispersion (1.0 mg / mL) was sealed in a polytetrafluoroethylene-lined autoclave. The autoclave was then heated to 160°C and kept at this temperature for 6 hours. The hydrothermally formed reduced graphene oxide hydrogel was thoroughly rinsed with water.

[0071] The reduced graphene oxide hydrogel and 10 mL of a 1 mg / mL PBI-NH2 solution (i.e., a hydrosol) were then incubated for 24 hours to prepare PBI-NH2-rGO, as shown in the following equation. The formed PBI-NH2-rGO was then washed three times with distilled water, using 100 mL of water in each step. By measuring the concentration of the PBI-NH2 solution before and after incubation and in the discarded washing solution, the mass loading of PBI-NH2 in PBI-NH2-rGO was calculated to be 9.23 mg rGO. The PBI-NH2 concentration was determined by ultraviolet spectroscopy based on a standard curve generated from a PBI-NH2 aqueous solution. By calculating the mass ratio of the PBI-NH2 molecules loaded on the reduced graphene oxide hydrogel to the PBI-NH2 molecules present in the incubation solution, the loading efficiency was calculated to be 92.3%.

[0072]

[0073] PBI-NH2-rGO was tested by electron microscopy, and the test results are as follows Figure 1 As shown, from Figure 1 It can be seen that PBI-NH2 was successfully loaded on the reduced graphene oxide hydrogel.

[0074] Example 2

[0075] 5.0 mmol of 1,4,5,8-naphthalenetetracarboxylic anhydride and 11 mmol of 1,5-pentanediamine were mixed in 10 mL of isopropanol to obtain a mixture. The mixture was refluxed at 85°C under an N2 atmosphere for 6 hours. The reaction product was then cooled and centrifuged to collect the dark solid product, which was then washed three times with copious amounts of ethanol. After vacuum drying, a powdered PBI-NH2 was obtained. The PBI-NH2 solid powder was dissolved in distilled water to prepare a 0.4 mg / mL aqueous sol.

[0076]

[0077] The other steps are the same as those in Example 1.

[0078] The mass loading of PBI-NH2 in PBI-NH2-rGO was calculated to be 9.35 mg rGO.

[0079] Example 3

[0080] 5.0 mmol of 3,4,9,10-tetracarboxylic anhydride and 14 mmol of 1,5-pentanediamine were mixed in 10 mL of isopropanol to obtain a mixture. The mixture was refluxed at 85°C under an N2 atmosphere for 6 hours. The reaction product was then cooled and centrifuged to collect the dark solid product, which was then washed three times with copious amounts of ethanol. After vacuum drying, a powdered PBI-NH2 was obtained. The PBI-NH2 solid powder was dissolved in distilled water to prepare a 0.8 mg / mL aqueous sol.

[0081] The other steps are the same as those in Example 1.

[0082] The mass loading of PBI-NH2 in PBI-NH2-rGO was calculated to be 9.28 mg rGO.

[0083] Example 4

[0084] 5.0 mmol of 1,7-dibromo-3,4,9,10-perylenetetracarboxylic dianhydride and 12.5 mmol of propylenediamine were mixed in 10 mL of isopropanol to obtain a mixture. The mixture was refluxed at 85°C under a nitrogen atmosphere for 6 hours. The reaction product was then cooled and centrifuged to collect the dark solid product, which was then washed three times with a large amount of ethanol. After vacuum drying, a powdered PBI-NH2 was obtained. The PBI-NH2 solid powder was dissolved in distilled water to prepare a 1.4 mg / mL aqueous sol.

[0085]

[0086] The other steps are the same as those in Example 1.

[0087] The mass loading of PBI-NH2 in PBI-NH2-rGO was calculated to be 9.46 mg rGO.

[0088] Example 5

[0089] 5.0 mmol of tetrachloroperylene anhydride and 12.5 mmol of propylenediamine were mixed in 10 mL of isopropanol to obtain a mixture. The mixture was refluxed at 85°C under an N2 atmosphere for 6 hours. The reaction product was then cooled and centrifuged to collect the dark solid product, which was then washed three times with a large amount of ethanol. After vacuum drying, a powdered PBI-NH2 was obtained. The PBI-NH2 solid powder was dissolved in distilled water to prepare a 1.8 mg / mL aqueous sol.

[0090]

[0091] The other steps are the same as those in Example 1.

[0092] The mass loading of PBI-NH2 in PBI-NH2-rGO was calculated to be 9.15 mg rGO.

[0093] Example 6

[0094] 5.0 mmol of 3,4,9,10-tetracarboxylic anhydride and 12.5 mmol of decanediamine were mixed in 10 mL of isopropanol to obtain a mixture. The mixture was refluxed at 85°C under a nitrogen atmosphere for 6 hours. The reaction product was then cooled and centrifuged to collect the dark solid product. The solid product was then washed three times with copious amounts of ethanol. After vacuum drying, powdered PBI-NH2 was obtained.

[0095] PBI-NH2 solid powder was dissolved in distilled water to prepare a 1 mg / mL aqueous sol.

[0096]

[0097] The other steps are the same as those in Example 1.

[0098] The mass loading of PBI-NH2 in PBI-NH2-rGO was calculated to be 9.26 mg rGO.

[0099] Example 7

[0100] 5.0 mmol of 3,4,9,10-tetracarboxylic anhydride and 12.5 mmol of 1,12-diaminododecane were mixed in 10 mL of isopropanol to obtain a mixture. The mixture was refluxed at 85°C under an N2 atmosphere for 6 hours. The reaction product was then cooled and centrifuged to collect the dark solid product, which was then washed three times with a large amount of ethanol. After vacuum drying, a powdered PBI-NH2 was obtained. The PBI-NH2 solid powder was dissolved in distilled water to prepare a 1 mg / mL aqueous sol.

[0101]

[0102] The other steps are the same as those in Example 1.

[0103] The mass loading of PBI-NH2 in PBI-NH2-rGO was calculated to be 9.36 mg rGO.

[0104] Formaldehyde removal experiment:

[0105] Test method: Two air test chambers (A is a blank chamber, B is a sample chamber) are used to test the concentration of gaseous pollutants removed by the purification product. The test conditions are carried out at normal temperature and pressure.

[0106] Preparation of release source: Roll 5 layers of 425px1000px medical absorbent gauze on 2 glass rods with a diameter of 5m and a length of 30mm, fix them with cotton thread and place them upright in a 500mL reagent bottle, fill it with 200mL of formaldehyde with a pollutant concentration of 0.2%. The analytical pure containers are labeled A1 and B1. After the gauze is completely wetted, it can be put into use.

[0107] Experimental steps: The formaldehyde-removing graphene oxide hydrogel load material of Examples 1-7 is prepared into a 2cm*2cm*2cm square hydrogel and placed in the test chamber B. The containers containing the prepared pollutant release sources A1 and B1 are placed in the blank test chamber A and the sample test chamber B respectively, and the doors are closed immediately. Turn on the fans of the blank test chamber A and the sample test chamber B, stir for 1 minute, and mix the air in the chamber with the pollutants released by the release source. Then turn off the fans at the same time, sample the air in the blank chamber, and measure the pollutant concentration in the air in the blank chamber as the initial concentration, which is recorded as C0. After 24 hours, the concentration of air pollutants in the two chambers is sampled and analyzed and tested, which is the concentration value of chambers A and B in a certain period of time, recorded as C A with C B .

[0108] Sampling and analysis of sampling results

[0109] Sampling method: The air outlet is connected to the inlet of the air sampler or test instrument outside the cabin, and a certain flow passes through the absorption tube, sampling tube or test instrument to collect the air sample in the cabin. The sampling and analysis shall be in accordance with the method specified in GB / T18883.

[0110] Absorption liquid sampling: Depending on the pollutant, connect a bubble absorption tube filled with 5L or 1mL of absorption liquid to the sampling port on the test chamber wall. Sample 10L of gas at a flow rate of 0.5L / min or 1.10L / min, respectively. Immediately seal the sampling port of the test chamber with a rubber cap after sampling. Analyze samples at room temperature within 24 hours.

[0111] The measurement results of Examples 1-7 are shown in Table 1.

[0112] Table 1

[0113] <![CDATA[C A (ppm)]]> <![CDATA[C B (ppm)]]> <![CDATA[Formaldehyde removal rate (C A -C B ) / C A * 100%]]> Example 1 0.205 0.012 94.14％ Example 2 0.212 0.015 92.92％ Example 3 0.208 0.013 93.75％ Example 4 0.212 0.013 93.9％ Example 5 0.218 0.012 94.5％ Example 6 0.220 0.011 95.0％ Example 7 0.221 0.015 93.2％

[0114] It can be seen from the above table that the formaldehyde-removing graphene oxide hydrogel-loaded materials prepared in Examples 1-7 can effectively remove formaldehyde.

[0115] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0116] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A formaldehyde-removing graphene oxide hydrogel loading material, characterized in that: include: reduced graphene oxide hydrogel; Compounds represented by Formula I and / or Formula II and / or Formula VI, wherein the compounds represented by Formula I and / or Formula II and / or Formula VI are supported on the reduced graphene oxide hydrogel; Formula I Formula II Formula VI Wherein, R1 is selected from C3~C 12 Alkylene; R2 is selected from H, Cl or Br; Based on the mass of the reduced graphene oxide hydrogel being 1 g, the loading amount of the compound represented by Formula I and / or Formula II and / or Formula VI on the reduced graphene oxide hydrogel is 0.2-0.45 g.

2. The formaldehyde-removing graphene oxide hydrogel loading material according to claim 1, wherein The compound represented by formula I is: .

3. The formaldehyde-removing graphene oxide hydrogel loading material according to claim 1, wherein The compound represented by formula II is selected from 、 、 、 and At least one of .

4. The formaldehyde-removing graphene oxide hydrogel supported material according to any one of claims 1 to 3, characterized in that: The reduced graphene oxide hydrogel is combined with the compound represented by formula I and / or formula II and / or formula VI through covalent bonds between graphene sheets.

5. A method for preparing the formaldehyde-removing graphene oxide hydrogel-loaded material according to any one of claims 1 to 4, characterized in that: include: (1) preparing a compound represented by Formula I, Formula II and / or Formula VI to form a hydrosol; (2) Preparation of reduced graphene oxide hydrogel; (3) Immersing the reduced graphene oxide hydrogel in the aqueous sol so that the compound represented by Formula I and / or Formula II and / or Formula VI is loaded on the reduced graphene oxide hydrogel, and washing the reduced graphene oxide hydrogel to obtain the formaldehyde-removing graphene oxide hydrogel loaded material.

6. The method according to claim 5, characterized in that Step (1) includes: (1-1) mixing a compound represented by Formula III or Formula IV, a compound represented by Formula V, and a solvent, subjecting the resulting mixture to reflux reaction under an inert atmosphere, and centrifuging, washing, and drying the reaction product to obtain the compound represented by Formula I or Formula II and / or Formula VI; (1-2) mixing the compound represented by Formula I and / or Formula II and / or Formula VI with water to form the hydrosol; Formula III Formula IV Formula V Wherein, R1 is selected from C3~C 12 Alkylene; R2 is selected from H, Cl or Br.

7. The method according to claim 6, characterized in that In step (1-1), the molar ratio of the compound represented by formula III or formula IV to the compound represented by formula V is 1:(2-3); And / or, the reflux reaction temperature is 80-90 degrees Celsius and the time is 6-48 hours; And / or, in step (1-2), in the hydrosol, the concentration of the compound represented by Formula I and / or Formula II and / or Formula VI is 0.2-2.0 mg / mL.

8. The method according to claim 5, characterized in that Step (2) includes: placing the graphene oxide dispersion under high temperature and high pressure for reaction, and washing it to obtain the reduced graphene oxide hydrogel; And / or, in step (3), the reduced graphene oxide hydrogel is immersed in the hydrosol for 20-48 hours.

9. The method according to claim 8, characterized in that In step (2), the reaction temperature is 150-170 degrees Celsius, the reaction pressure is 300 kPa-500 kPa, and the reaction time is 6-24 hours; And / or, the solvent of the graphene oxide dispersion is water, and the concentration of graphene oxide in the graphene oxide dispersion is 0.8-1.2 mg / mL.

Images