Application of 4, 4-bipyridine cationic derivative cucurbituril host-guest in preparation of formaldehyde adsorption-degradation material

Abstract

The invention discloses an application of a 4, 4-bipyridine cationic derivative cucurbituril host-guest in preparation of a formaldehyde adsorption-degradation material, and the 4, 4-bipyridine cationic derivative cucurbituril host-guest is obtained by forming a supramolecular self-assembly structure in water by taking a 4, 4-bipyridine cationic derivative as a guest molecule and cucurbituril as a host molecule. The outer wall of the cucurbituril is used as a formaldehyde adsorption site, reactive oxygen species ROS is generated under the excitation of blue light or sunlight, and efficient adsorption and visible light driven degradation of formaldehyde are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of air purification materials, in particular to the application of cucurbitacin host-guest 4,4-bipyridyl cationic derivatives in the preparation of formaldehyde adsorption-degradation materials. Background Art

[0002] Formaldehyde (HCHO), a major indoor air pollutant, is widely sourced from wood-based panels, coatings, and furniture adhesives. Its release cycle can range from 3 to 15 years. It is highly volatile, toxic, and potentially carcinogenic. Long-term exposure to low-concentration formaldehyde can cause respiratory illnesses, immune system damage, and even leukemia. The World Health Organization (WHO) has classified it as a Class I carcinogen. Therefore, developing efficient and safe formaldehyde removal technologies is crucial for improving indoor air quality.

[0003] The current mainstream formaldehyde treatment technologies mainly include physical adsorption, catalytic oxidation and biodegradation. Physical adsorption materials (such as activated carbon and zeolite) rely on their pore structure to passively adsorb formaldehyde, but they have the disadvantages of low adsorption capacity, easy saturation and inability to decompose pollutants; although catalytic oxidation methods (such as photocatalytic TiO2 and precious metal catalysts) can degrade formaldehyde, they usually require high temperature, ultraviolet light or high humidity conditions, and nanocatalysts are prone to agglomeration and inactivation. In addition, formaldehyde molecules are small in size (dynamic diameter of about 0.45nm) and have weak polarity, making it difficult for traditional adsorbents to achieve efficient and selective capture, resulting in limited purification efficiency.

[0004] Cucurbitacin is a cyclic supramolecular entity formed by glycoluril units connected by methylene bridges. It can bind to formaldehyde molecules through hydrogen bonds and electrostatic interactions, demonstrating adsorption potential. However, existing research has focused on the host-guest inclusion complex in the cucurbitacin cavity, with insufficient research on the integration of its outer wall and catalytic function. Furthermore, adsorption alone cannot achieve formaldehyde degradation, and there are still problems such as difficulty in material regeneration and the risk of secondary pollution.

[0005] To address the above challenges, there is an urgent need to develop a composite material that has high adsorption capacity, selective capture and in situ degradation capabilities, break through the limitations of traditional technologies through the adsorption-catalysis synergistic mechanism, and provide innovative solutions for indoor formaldehyde pollution control. Summary of the Invention

[0006] The purpose of the present invention is to provide the application of a 4,4-bipyridyl cationic derivative cucurbitacin host-guest in the preparation of formaldehyde adsorption-degradation materials. The formaldehyde adsorption-degradation materials of the present invention can be made into liquids, solids, or loaded on fiber materials through an adsorption-catalysis synergistic mechanism, thereby achieving efficient and selective capture and light-driven degradation of formaldehyde, and are suitable for indoor formaldehyde pollution control.

[0007] The technical solution of the present invention:

[0008] The invention discloses an application of a 4,4-bipyridyl cationic derivative cucurbitacin host-guest in the preparation of formaldehyde adsorption-degradation materials. The 4,4-bipyridyl cationic derivative cucurbitacin host-guest is obtained by using a 4,4-bipyridyl cationic derivative as a guest molecule and a cucurbitacin as a host molecule to form a supramolecular self-assembly structure in water.

[0009] The aforementioned cucurbit ring is an eight-membered cucurbit ring, and the cucurbit ring structural formula is as follows:

[0010]

[0011] The aforementioned 4,4-bipyridyl cation derivative comprises a counter anion, pyridinium and an R substituent.

[0012] The aforementioned counter anion is chloride ion, bromide ion, fluoride ion or iodide ion;

[0013] The aforementioned pyridinium structural formula is as follows:

[0014]

[0015] The aforementioned R substituent is one or two of a phenyl group or a phenyl derivative; the aforementioned phenyl derivative is an electron-substituted phenyl group or an electron-withdrawing substituted phenyl group including a benzyl group, a benzyloxy group, a phenylcarboxyl group, or a halogen-substituted phenyl group; the structural formula of the aforementioned R substituent is as follows:

[0016]

[0017] 3. The aforementioned 4,4-bipyridyl cationic derivatives can also be connected by the R1 substituent as a linking group to connect two pyridiniums, wherein the R1 substituent is a heterocyclic ring or contains a heterocyclic aromatic group including thiophene, thiazolothiazole, benzothiadiazole, and 3,4-ethylenedioxythiophene; the structural formula of the R1 substituent is as follows:

[0018]

[0019] 4. The aforementioned 4,4-bipyridyl cationic derivative cucurbitacin host-guest can be made into liquid, solid or formaldehyde adsorption-degradation materials loaded on fiber materials.

[0020] The preparation method of the above-mentioned formaldehyde adsorption-degradation material is to add cucurbitacin and 4,4-bipyridyl cationic derivative into water in a molar ratio of 1-2:1, mix and stir evenly to obtain a clear solution, and then obtain a liquid cucurbitacin host-guest formaldehyde adsorption-degradation material.

[0021] The preparation method of the aforementioned formaldehyde adsorption-degradation material is to add cucurbitacin and 4,4-bipyridyl cationic derivative to water in a molar ratio of 1-2:1, mix and stir evenly to obtain a clear solution, thereby obtaining a liquid cucurbitacin host-guest formaldehyde adsorption-degradation material; then, the liquid cucurbitacin host-guest formaldehyde adsorption-degradation material is concentrated and dried using a rotary evaporator to obtain a solid formaldehyde adsorption-degradation material, that is, a solid cucurbitacin host-guest formaldehyde adsorption-degradation material is obtained.

[0022] The preparation of the above-mentioned formaldehyde adsorption-degradation material is to add cucurbitacin and 4,4-bipyridyl cationic derivative into water in a molar ratio of 1-2:1, mix and stir evenly to obtain a clear solution, thereby obtaining a liquid cucurbitacin host-guest formaldehyde adsorption-degradation material, then add fiber material to the liquid formaldehyde adsorption-degradation material so that the formaldehyde adsorption-degradation material is adsorbed on the fiber material, and dry the solvent in an oven to obtain the cucurbitacin host-guest formaldehyde adsorption-degradation fiber material.

[0023] The aforementioned plant fibers include cotton, linen or wood fibers; the aforementioned synthetic fibers include polyaramid fibers or polyurethane fibers.

[0024] A formaldehyde adsorption-degradation material comprises the aforementioned 4,4-bipyridyl cationic derivative cucurbitacin host-guest.

[0025] Beneficial effects of the present invention

[0026] 1. Experiments have confirmed that the cucurbit ring only has the function of adsorbing formaldehyde, but not the function of degrading formaldehyde. However, the 4,4-bipyridyl cationic derivative cucurbit ring host-guest of the present invention achieves efficient adsorption of formaldehyde and visible light-driven degradation through the synergistic effect of the cucurbit ring exine and the host-guest. The cucurbit ring exine serves as the formaldehyde adsorption site, and the 4,4-bipyridyl cationic derivative cucurbit ring host-guest serves as the adsorption-degradation material. Under blue light or sunlight, it is stimulated to produce reactive oxygen species (ROS), achieving efficient adsorption of formaldehyde and visible light-driven degradation.

[0027] 2. Self-assembly at room temperature and pressure, simple preparation, no need for complex processes and equipment.

[0028] 3. It can be made into liquid, solid or loaded on fiber materials to adapt to the needs of different scenarios. The loaded fiber materials can be directly used in masks, air filters, etc., which is convenient for practical application. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 H NMR spectrum of the host-guest assembly of a 4,4-bipyridyl cationic derivative (G1) and an eight-membered cucurbit ring (Q[8]);

[0030] Figure 2 H NMR spectrum of the host-guest assembly of a 4,4-bipyridyl cationic derivative (G2) and an eight-membered cucurbit ring (Q[8]);

[0031] Figure 3 H NMR spectrum of the host-guest assembly of a 4,4-bipyridyl cationic derivative (G3) and an eight-membered cucurbit ring (Q[8]);

[0032] Figure 4 The solid-gas adsorption curve of formaldehyde by G1-Q[8] changes with time;

[0033] Figure 5 The H NMR spectrum of formaldehyde degradation by G1-Q[8] under blue light and sunlight irradiation;

[0034] Figure 6 Fiber materials before and after loading G1-Q[8] (A: before loading G1-Q[8]; B: after loading G1-Q[8]);

[0035] Figure 7 This is a diagram of the formaldehyde testing process;

[0036] Figure 8 The UV-visible absorption spectra of formaldehyde adsorption-degradation (a: cucurbit ring-loaded host-guest fiber material; b: cucurbit ring-unloaded host-guest fiber material);

[0037] Figure 9 This is the H NMR spectrum of Q[8] for formaldehyde after solid-gas adsorption for 24 hours;

[0038] Figure 10 This is the H NMR spectrum of formaldehyde degradation by Q[8] under blue light irradiation. DETAILED DESCRIPTION

[0039] In order to enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific examples, but the examples are not intended to limit the present invention. The operating methods in the following examples where specific conditions are not specified are generally based on conventional conditions or conditions recommended by the manufacturer, and unspecified reagents are also conventional reagents.

[0040] Example 1

[0041] Preparation method of 4,4-bipyridyl cationic derivatives (G1)

[0042] The chemical formula of the 4,4-bipyridinium cation derivative is 4,4′-(thiazo[5,4-d]thiazol-2,5-bis(1-(4-iodophenyl)pyridin-1-ium)dichloride (C 26 H 16 I2N4S2 2+ 2Cl - ).

[0043]

[0044] Preparation: In a 100 mL Erlenmeyer flask, add 0.6 g of dithiooxamide and 1.2 mL of pyridine-4-carboxaldehyde to 30 mL of dry N,N-dimethylformamide. Stir the reaction mixture for 6 hours, reflux at 157°C, cool to room temperature, and filter. Collect the pale yellow precipitate (dipyridylthiazo[5,4-d]thiazole) and wash three times with water.

[0045]

[0046] 2,5-Bis(pyridin-4-yl)thiazolo[5,4-d]thiazole (700 mg, 2.36 mmol) and 2,4-dinitrochlorobenzene (7.18 g, 35.44 mmol) were added to 300 mL of ethanol. The mixture was stirred and reacted under reflux for 14 days. The mixture was cooled to room temperature, the solvent was evaporated to 10 mL under reduced pressure, and 40 mL of acetone was added. A solid was obtained by centrifugation. The crude product was washed with acetone (30 mL × 3) to obtain a brown solid of 1,1'-bis(2,4-dinitrophenyl)-2,5-bis(pyridinium-4-yl)thiazolo[5,4-d]thiazole dichloride (1.52 g, 92%). 1,1'-bis(2,4-dinitrophenyl)-2,5-di(pyridinium-4-yl)thiazolo[5,4-d]thiazole dichloride (130 mg, 0.19 mmol) and three equivalents of 4-iodoaniline were refluxed in 100 mL of ethanol for 24 hours. The mixture was cooled to room temperature and the solvent was evaporated to 5 mL under reduced pressure. The concentrated reaction mixture was mixed with 30 mL of acetone, centrifuged, decanted, and the solid was collected. The crude product was washed with acetone (25 mL × 3) to obtain 4,4'-(thiazolo[5,4-d]thiazole-2,5-di(1-(4-iodophenyl)pyridin-1-ium) dichloride (G1) with a yield of 60%.

[0047] Example 2

[0048] Preparation method of 4,4-bipyridyl cationic derivatives (G2)

[0049] 4,4-bipyridinium cation derivative, the chemical formula of which is 4,4′-(thiophene-2,5-bis(1-(4-methylphenyl)pyridin-1-ium) dichloride (C 28 H 24 N2S 2+ 2Cl - ),

[0050]

[0051] To a dry 100 mL Schlenk tube, 2,5-dibromothiophene (500 mg, 2.07 mmol), pyridine-4-boronic acid (761.5 mg, 6.20 mmol), tetrakistriphenylphosphine palladium (Pd(PPh3)4) (147 mg, 0.13 mmol), and potassium carbonate (K2CO3) (1425 mg, 10.31 mmol) were added. Under vacuum, 20 mL of 1,4-dioxane was added. The mixture was freeze-evacuated and thawed three times with liquid nitrogen, then filled with argon. The reaction was continued at 110°C for 48 hours. The reaction solution was cooled to room temperature, 50 mL of water was added, and the mixture was extracted three times with dichloromethane (20 mL x 3). The organic layer was separated, dried over anhydrous Na2SO4, concentrated, recrystallized from n-hexane, filtered, and dried in vacuum to yield a light yellow solid (251.6 mg, 51%).

[0052]

[0053] Based on references and combined with our own research, compound X2 was successfully synthesized. Compound X1 (200 mg, 0.84 mmol), 1-chloro-2,4-dinitrobenzene (1700 mg, 8.4 mmol), and 5 mL of acetonitrile were added to a dry 50 mL Schlenk tube and heated with stirring at 95°C for 48 hours. After the reaction, the precipitate was directly filtered, washed with acetonitrile, and dried to obtain the crude product. The solid was dissolved in a small amount of methanol, then recrystallized by adding diethyl ether, filtered, and dried in vacuo to obtain a red solid X2 (450 mg, 83%).

[0054]

[0055] Compound X2 (70 mg, 0.11 mmol), p-toluidine (35.4 mg, 0.33 mmol), and 15 mL of ethanol were added to a dry 50 mL Schlenk tube and heated at 90°C with stirring for 48 hours. After the reaction, the solution was concentrated under reduced pressure, acetone was added for recrystallization, filtered, and dried in vacuo to obtain a yellow solid 4,4′-(thiophene-2,5-bis(1-(4-methylphenyl)pyridin-1-ium) dichloride (C 28 H 24 N2S 2+ 2Cl - )(41.8 mg, 78%).

[0056] Example 3

[0057] Preparation method of 4,4-bipyridyl cationic derivatives (G3)

[0058] A 4,4-bipyridinium cation derivative, the chemical formula of which is 4,4′-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5,7-diyl)bis(1-(p-tolyl)pyridin-1-ium)C 30 H 26 N2O2S 2+ 2Cl -

[0059]

[0060] 2,5-Dibromo-3,4-vinyldioxythiophene (500 mg, 1.67 mmol), pyridine-4-boronic acid (614.6 mg, 5 mmol), tetrakistriphenylphosphine palladium (Pd(PPh3)4) (119 mg, 0.1 mmol), and potassium carbonate (K2CO3) (1154 mg, 8.35 mmol) were added to 1,4-dioxane (20 mL) and stirred at 110°C under argon for 48 h. Post-treatment gave an orange-yellow powder Y1 (202.5 mg, 43.57%).

[0061] Y1 (200 mg, 0.676 mmol), 1-chloro-2,4-dinitrobenzene (1369 mg, 6.76 mmol) and 5 mL of acetonitrile were heated at 95° C. with stirring for 48 hours. Post-treatment gave a brown powder Y2 (366.1 mg, 77.2%).

[0062] Compound Y2 (200 mg, 0.28 mmol), p-toluidine (93.4 mg, 0.87 mmol) and 15 mL of ethanol were heated and stirred at 90°C for 48 hours. Post-treatment gave a dark red solid powder of 4,4′-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5,7-diyl)bis(1-(p-tolyl)pyridin-1-ium)(C 30 H 26 N2O2S 2+ 2Cl - )(98.48 mg, 62.6%).

[0063] Example 4

[0064] 1. Host and guest molecular materials:

[0065] The host molecule is an eight-membered cucurbit ring (Q[8]); the guest molecule is a 4,4-bipyridyl cationic derivative (G1), whose chemical formula is 4,4′-(thiazo[5,4-d]thiazol-2,5-bis(1-(4-iodophenyl)pyridin-1-ium) dichloride (C 26 H 16 I2N4S2 2+ 2Cl - ), whose structural formula is as follows:

[0066]

[0067] Wherein: the counter anion X is a chloride ion; the substituent R is a 4-iodophenyl group; the substituent R1 is a thiazolothiazole;

[0068] 2. Preparation method:

[0069] The eight-membered cucurbit ring (Q[8]) and the 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2, mixed and stirred evenly to obtain a clear solution, which was then concentrated and dried using a rotary evaporator to obtain a solid formaldehyde adsorption-degradation material, namely G1-Q[8].

[0070] Example 5

[0071] 1. Host and guest molecular materials:

[0072] The host molecule is an eight-membered cucurbit ring (Q[8]); the guest molecule is a 4,4-bipyridyl cationic derivative (G2), whose chemical formula is 4,4′-(thiophene-2,5-di(1-(4-methylphenyl)pyridin-1-ium) dichloride

[0073]

[0074] (C 28 H 24 N2S 2+ 2Cl - ), whose structural formula is as follows:

[0075] Wherein: the counter anion X is a chloride ion; the substituent R is a benzyl group; the substituent R1 is a thiophene;

[0076] 2. Preparation method:

[0077] The eight-membered cucurbit ring (Q[8]) and the 4,4-bipyridyl cationic derivative (G2) were added to water at a molar ratio of 2:2, mixed and stirred evenly to obtain a clear solution, which was then concentrated and dried using a rotary evaporator to obtain a solid formaldehyde adsorption-degradation material, namely G2-Q[8].

[0078] Example 6

[0079] 1. Host and guest molecular materials:

[0080] The host molecule is an eight-membered cucurbit ring (Q[8]); the guest molecule is a 4,4-bipyridinium cation derivative (G3), whose chemical formula is 4,4′-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5,7-diyl)bis(1-(p-tolyl)pyridin-1-ium)C 30 H 26 N2O2S 2+ 2Cl- , its structural formula is as follows:

[0081]

[0082] Wherein: the counter anion X is a chloride ion; the substituent R is a benzyl group; the substituent R1 is 3,4-ethylenedioxythiophene;

[0083] 2. Preparation method:

[0084] The eight-membered cucurbit ring (Q[8]) and the 4,4-bipyridyl cationic derivative (G3) were added to water at a molar ratio of 2:2, mixed and stirred evenly to obtain a clear solution, which was then concentrated and dried using a rotary evaporator to obtain a solid formaldehyde adsorption-degradation material, namely G3-Q[8].

[0085] Example 7

[0086] Adsorption performance test:

[0087] Before the measurement, the G1-Q[8] solid was dried at 100°C for 24 hours to remove any vapor physically adsorbed on the surface. The G1-Q[8] solid material was placed in a closed formaldehyde gas environment and adsorbed at 25-35°C for 24 hours. The amount of formaldehyde adsorbed by G1-Q[8] was determined by proton nuclear magnetic resonance (PNR) before and after the adsorption process. 1 H NMR) spectrum changes. Figure 4 As shown, G1-Q[8] quickly reached adsorption saturation in 2 hours.

[0088] Example 8

[0089] Photocatalytic degradation test:

[0090] The G1-Q[8] solid adsorbed with formaldehyde was irradiated under sunlight / blue light for 24 hours. 1 HNMR monitoring of formaldehyde degradation before and after irradiation. Figure 5 As shown in the figure, under the same conditions, most formaldehyde can be converted into non-toxic formic acid under blue light irradiation, while the conversion rate is lower under sunlight irradiation.

[0091] Example 9

[0092] Preparation of Cucurbitacin Host-Guest Formaldehyde Adsorption-Degradation Fiber Material:

[0093] The eight-membered cucurbit ring (Q[8]) and the 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2, and the mixture was stirred to obtain a clear solution. Subsequently, the fiber substrate (the fiber substrate was cotton) was completely immersed in the G1-Q[8] composite solution for 60 minutes to ensure effective loading. Finally, the loaded sample was placed in a vacuum oven at 60°C and dried for 60 minutes. The functional material was stably immobilized by solvent evaporation, and finally a composite fiber material with both formaldehyde adsorption and photocatalytic degradation functions was obtained. Figure 6 .

[0094] like Figure 7 , place the formaldehyde solution (HCHO, 36%–38%) in a 125mL wide-mouth bottle and control the temperature on a constant temperature heating platform at 40±0.5℃. Fix the cucurbitacin host-guest formaldehyde adsorption-degradation fiber material in the center of the reactor, and set up a blank control group without catalyst loading. The reaction system adopts an airtight connection, and formaldehyde vapor is continuously introduced into the reaction system through a micro air pump, and the blue light source (440-450nm) is turned on simultaneously for formaldehyde adsorption-degradation test. Take 3.0mL of absorption liquid every 30 minutes, add 240μL of 1% (w / v) ammonium ferric sulfate solution as a color developer and shake it thoroughly, and let it stand in the dark for 15 minutes to complete the color reaction. Use a UV-visible spectrophotometer to measure the absorbance at a wavelength of 630nm. As Figure 8 As shown, the fiber material without the cucurbitacin host-guest loading can hardly adsorb and degrade formaldehyde. On the contrary, under the same conditions, the cucurbitacin host-guest formaldehyde adsorption-degradation fiber material can effectively adsorb and degrade formaldehyde.

[0095] Example 10

[0096] Preparation of Cucurbitacin Host-Guest Formaldehyde Adsorption-Degradation Fiber Material:

[0097] An eight-membered cucurbit ring (Q[8]) and a 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2 and stirred to obtain a clear solution. A fiber substrate (hemp) was then completely immersed in the G1-Q[8] composite solution for 60 minutes to ensure effective loading. Finally, the loaded sample was placed in a vacuum oven at 60°C and dried for 60 minutes. The solvent evaporated to achieve stable immobilization of the functional material, ultimately producing a composite fiber material with both formaldehyde adsorption and photocatalytic degradation functions.

[0098] Example 11

[0099] Preparation of Cucurbitacin Host-Guest Formaldehyde Adsorption-Degradation Fiber Material:

[0100] An eight-membered cucurbit ring (Q[8]) and a 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2 and stirred to obtain a clear solution. A fiber substrate (wood fiber) was then completely immersed in the G1-Q[8] composite solution for 60 minutes to ensure effective loading. Finally, the loaded sample was placed in a vacuum oven at 60°C and dried for 60 minutes. The solvent evaporated to achieve stable immobilization of the functional material, ultimately producing a composite fiber material with both formaldehyde adsorption and photocatalytic degradation functions.

[0101] Example 12

[0102] Preparation of Cucurbitacin Host-Guest Formaldehyde Adsorption-Degradation Fiber Material:

[0103] An eight-membered cucurbit ring (Q[8]) and a 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2 and mixed and stirred to obtain a clear solution. A fiber substrate (polyaramid fiber) was then completely immersed in the G1-Q[8] composite solution for 60 minutes to ensure effective loading. Finally, the loaded sample was placed in a 60°C vacuum oven and dried for 60 minutes. The solvent evaporated to achieve stable immobilization of the functional material, ultimately producing a composite fiber material with both formaldehyde adsorption and photocatalytic degradation functions.

[0104] Example 13

[0105] Preparation of Cucurbitacin Host-Guest Formaldehyde Adsorption-Degradation Fiber Material:

[0106] An eight-membered cucurbit ring (Q[8]) and a 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2 and mixed and stirred to obtain a clear solution. A fiber substrate (polyurethane fiber) was then completely immersed in the G1-Q[8] composite solution for 60 minutes to ensure effective loading. Finally, the loaded sample was placed in a vacuum oven at 60°C and dried for 60 minutes. The solvent evaporated to achieve stable immobilization of the functional material, ultimately producing a composite fiber material with both formaldehyde adsorption and photocatalytic degradation functions.

[0107] Example 14

[0108] Preparation of Cucurbitacin Host-Guest Formaldehyde Adsorption-Degradation Fiber Material:

[0109] An eight-membered cucurbit ring (Q[8]) and a 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2 and mixed and stirred to obtain a clear solution. A fiber substrate (including other plant fibers besides cotton, linen, or wood fibers) was then completely immersed in the G1-Q[8] composite solution for 60 minutes to ensure effective loading. Finally, the loaded sample was placed in a vacuum oven at 60°C and dried for 60 minutes to achieve stable immobilization of the functional material through solvent evaporation. Finally, a composite fiber material with both formaldehyde adsorption and photocatalytic degradation functions was prepared.

[0110] Example 15

[0111] Preparation of Cucurbitacin Host-Guest Formaldehyde Adsorption-Degradation Fiber Material:

[0112] An eight-membered cucurbit ring (Q[8]) and a 4,4-bipyridyl cationic derivative (G1) were added to water at a molar ratio of 3:2 and mixed and stirred to obtain a clear solution. A fiber substrate (which also includes other synthetic fibers besides polyaramid fibers or polyurethane fibers) was then completely immersed in the G1-Q[8] composite solution for 60 minutes to ensure effective loading. Finally, the loaded sample was placed in a vacuum oven at 60°C and dried for 60 minutes to achieve stable immobilization of the functional material through solvent evaporation. Finally, a composite fiber material with both formaldehyde adsorption and photocatalytic degradation functions was prepared.

[0113] Example 16

[0114] Cucurbitacin adsorption performance and photocatalytic degradation test:

[0115] Before the measurement, the Q[8] solid was dried at 100°C for 24 hours to remove any vapor physically adsorbed on the surface. The Q[8] solid material was placed in a closed formaldehyde gas environment and adsorbed at 25-35°C for 24 hours. The adsorption of formaldehyde by Q[8] was determined by proton nuclear magnetic resonance ( 1 H NMR) spectrum changes. Figure 9 As shown, after 24 hours, the molar ratio of formaldehyde to Q[8] was 0.56. The Q[8] solid adsorbed with formaldehyde was irradiated under blue light for 24 hours. 1 HNMR monitoring of formaldehyde degradation before and after irradiation. Figure 10 As shown, Q[8] cannot degrade formaldehyde under blue light irradiation.

Claims

1. Application of cucurbitacin host-guest derivatives of 4,4-bipyridyl cationic derivatives in the preparation of formaldehyde adsorption-degradation materials, characterized by: The 4,4-bipyridyl cationic derivative cucurbitacin host-guest is obtained by using a 4,4-bipyridyl cationic derivative as a guest molecule and a cucurbitacin as a host molecule to form a supramolecular self-assembled structure in water. The outer wall of the cucurbitacin is used as a formaldehyde adsorption site, and reactive oxygen species (ROS) are generated under blue light or sunlight, thereby achieving efficient adsorption of formaldehyde and visible light-driven degradation.

2. The use of the cucurbitacin host-guest 4,4-bipyridyl cationic derivative according to claim 1 in the preparation of formaldehyde adsorption-degradation materials, characterized in that: The melon ring is an eight-membered melon ring, and the melon ring structural formula is as follows: The 4,4-bipyridyl cation derivative comprises a counter anion, pyridinium and an R substituent.

3. The use of the cucurbitacin host-guest 4,4-bipyridyl cationic derivative according to claim 2 in the preparation of formaldehyde adsorption-degradation materials, characterized in that: The counter anion is chloride, bromide, fluoride or iodide; The pyridinium structural formula is as follows: The R substituent is one or two of a phenyl group or a phenyl derivative; the phenyl derivative is an electron-substituted phenyl group or an electron-withdrawing substituted phenyl group including a benzyl group, a benzyloxy group, a phenylcarboxyl group, or a halogen-substituted phenyl group; the structural formula of the R substituent is as follows:

4. The use of the cucurbitacin host-guest 4,4-bipyridyl cationic derivative according to claim 1 in the preparation of formaldehyde adsorption-degradation materials, characterized in that: The 4,4-bipyridyl cationic derivative can also connect two pyridiniums by using the R1 substituent as a linking group, wherein the R1 substituent is a heterocyclic ring or contains a heterocyclic aromatic group including thiophene, thiazolothiazole, benzothiadiazole, and 3,4-ethylenedioxythiophene; the structural formula of the R1 substituent is as follows:

5. Use of the cucurbitacin host-guest 4,4-bipyridyl cationic derivative according to any one of claims 1 to 4 in the preparation of formaldehyde adsorption-degradation materials, characterized in that: The cucurbitacin host-guest 4,4-bipyridyl cationic derivative can be made into a liquid, solid or formaldehyde adsorption-degradation material supported on a fiber material.

6. Use of the cucurbitacin host-guest derivative of a 4,4-bipyridyl cationic derivative according to claim 5 in the preparation of formaldehyde adsorption-degradation materials, characterized in that: The preparation method of the formaldehyde adsorption-degradation material is as follows: adding cucurbitacin and 4,4-bipyridyl cationic derivative into water in a molar ratio of 1-2:1, mixing and stirring uniformly to obtain a clear solution, thereby obtaining a liquid cucurbitacin host-guest formaldehyde adsorption-degradation material.

7. Use of the cucurbitacin host-guest 4,4-bipyridyl cationic derivative according to claim 5 in the preparation of formaldehyde adsorption-degradation materials, characterized in that: The preparation method of the formaldehyde adsorption-degradation material comprises the following steps: adding cucurbitacin and a 4,4-bipyridyl cationic derivative into water in a molar ratio of 1-2:1, uniformly mixing and stirring to obtain a clear solution, thereby obtaining a liquid cucurbitacin host-guest formaldehyde adsorption-degradation material; and concentrating and drying the liquid cucurbitacin host-guest formaldehyde adsorption-degradation material using a rotary evaporator to obtain a solid formaldehyde adsorption-degradation material, namely, obtaining a solid cucurbitacin host-guest formaldehyde adsorption-degradation material.

8. Use of the cucurbitacin host-guest derivative of a 4,4-bipyridyl cationic derivative according to claim 5 in the preparation of formaldehyde adsorption-degradation materials, characterized in that: The preparation of the formaldehyde adsorption-degradation material comprises adding cucurbitacin and a 4,4-bipyridyl cationic derivative to water in a molar ratio of 1-2:1, mixing and stirring uniformly to obtain a clear solution, thereby obtaining a liquid cucurbitacin host-guest formaldehyde adsorption-degradation material; then adding a fiber material to the liquid formaldehyde adsorption-degradation material, allowing the formaldehyde adsorption-degradation material to be adsorbed on the fiber material; and drying the solvent in an oven to obtain the cucurbitacin host-guest formaldehyde adsorption-degradation fiber material.

9. The method for preparing the formaldehyde adsorption-degradation material according to claim 8, characterized in that: The fiber material includes plant fiber or synthetic fiber. The plant fiber includes cotton, linen or wood fiber; the synthetic fiber includes polyaramid fiber or polyurethane fiber.

10. A formaldehyde adsorption-degradation material, characterized in that: The formaldehyde adsorption-degradation material includes the 4,4-bipyridyl cationic derivative cucurbitacin host-guest according to any one of claims 1 to 4.

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