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CN-121988393-A - Silsesquioxane porous material with near infrared photocatalytic effect and preparation method and application thereof

CN121988393ACN 121988393 ACN121988393 ACN 121988393ACN-121988393-A

Abstract

The invention provides a silsesquioxane porous material with a near infrared photocatalytic effect, and a preparation method and application thereof. The preparation method of the silsesquioxane porous material comprises the following steps of (1) reacting (3, 5-trimethylcyclohex-2-ene) malononitrile with a donor compound in a solvent A under the action of piperidine to obtain a D-A compound, (2) dissolving octavinyl silsesquioxane and the D-A compound obtained in the step (1) in the solvent B, adding a catalyst, stirring uniformly, reacting, cooling, filtering and washing after the reaction is finished to obtain a solid, performing Soxhlet extraction on the obtained solid, and then vacuum drying the obtained solid to obtain the silsesquioxane porous material with a near infrared photocatalysis effect. The silsesquioxane porous material prepared by the invention has the advantages of wide absorption of near infrared light, high efficient light absorption and conversion efficiency, high catalytic activity, high chemical stability and high water stability.

Inventors

  • LIU HONGZHI
  • WANG QINGZHENG

Assignees

  • 山东大学

Dates

Publication Date
20260508
Application Date
20251219

Claims (10)

  1. 1. A preparation method of a silsesquioxane porous material with a near infrared photocatalytic effect comprises the following steps: (1) Reacting (3, 5-trimethylcyclohex-2-ylene) malononitrile with a donor compound in a solvent A under the action of piperidine to obtain a D-A compound, wherein the donor compound has a structure shown in the following formula I-1, I-2 or I-3, and the D-A compound has a structure shown in the following formula DCI-1, DCI-2 or DCI-3; ; (2) Dissolving octavinyl silsesquioxane and the D-A compound obtained in the step (1) in a solvent B, adding a catalyst, stirring uniformly, reacting, cooling, filtering and washing after the reaction is finished to obtain a solid, carrying out soxhlet extraction on the obtained solid, and then carrying out vacuum drying on the obtained solid to obtain the silsesquioxane porous material with the near infrared photocatalysis effect.
  2. 2. The preparation method of the silsesquioxane porous material with the near infrared photocatalytic effect according to claim 1, wherein in the step (1), the solvent A is acetonitrile, toluene or ethanol, the ratio of the volume of the solvent A to the mole number of (3, 5-trimethylcyclohex-2-enyl) malononitrile is 15-25 mL:1mmol, and the ratio of the volume of piperidine to the mole number of (3, 5-trimethylcyclohex-2-enyl) malononitrile is 0.18-0.23 mL:1mmol.
  3. 3. The method for preparing a silsesquioxane porous material having a near infrared photocatalytic effect according to claim 1, wherein the molar ratio of the donor compound to (3, 5-trimethylcyclohex-2-ylene) malononitrile in step (1) is 1 to 1.5:1 to 1.5.
  4. 4. The method for preparing a silsesquioxane porous material with a near infrared photocatalytic effect according to claim 1, wherein the reaction temperature in the step (1) is 85-95 ℃, and the reaction time is 24-48 hours; After the reaction is completed, the method also comprises a post-treatment step, and specifically comprises the steps of naturally cooling the obtained reaction liquid to room temperature, filtering, washing with normal hexane, and recrystallizing the obtained solid in acetonitrile to obtain the D-A compound.
  5. 5. The method for preparing a porous silsesquioxane material with near infrared photocatalytic effect according to claim 1, wherein the molar ratio of octavinyl silsesquioxane to D-a compound in step (2) is 0.5-1:1, preferably 0.75-1:1.
  6. 6. The preparation method of the silsesquioxane porous material with the near infrared photocatalytic effect according to claim 1, wherein the solvent B is 1, 2-dichloroethane or o-dichlorobenzene, and the ratio of the volume of the solvent B to the mole number of octavinyl silsesquioxane is 30-80 mL/1 mmol; The catalyst is anhydrous AlCl 3 , and the molar ratio of the catalyst to octavinyl silsesquioxane is 1-1.8:1, preferably 1.25-1.5:1.
  7. 7. The method for preparing a silsesquioxane porous material with a near infrared photocatalytic effect according to claim 1, wherein in the step (2), when the solvent B is 1, 2-dichloroethane, the reaction temperature is 80-90 ℃, and when the solvent B is o-dichlorobenzene, the reaction temperature is 190-200 ℃, and the reaction time is 24-48 hours, preferably 30-48 hours; The washing step comprises the steps of washing the solid obtained after filtration with methanol, tetrahydrofuran, chloroform and acetone for 3-5 times in sequence; The Soxhlet extraction step comprises the steps of sequentially extracting the obtained solid in methanol and dichloromethane for 20-30 h respectively; The temperature of the vacuum drying is 70-100 ℃, preferably 80-90 ℃, and the time of the vacuum drying is 24-48 hours, preferably 24-30 hours.
  8. 8. A silsesquioxane porous material having a near infrared photocatalytic effect, which is prepared by the preparation method according to any one of claims 1 to 7.
  9. 9. The application of the silsesquioxane porous material with the near infrared catalytic effect as claimed in claim 8, which is used for catalyzing the generation of H 2 O 2 under near infrared illumination, is characterized in that the specific application method is as follows: Adding the silsesquioxane porous material with the near infrared photocatalysis effect into deionized water, uniformly dispersing by ultrasonic, carrying out photocatalysis reaction under the illumination of near infrared light, and filtering after the reaction is finished to obtain H 2 O 2 solution.
  10. 10. The use according to claim 9, characterized in that the ratio of the mass of the silsesquioxane porous material with near infrared photocatalytic effect to the volume of deionized water is 0.3-0.7mg:1ml; The near infrared light is provided by a near infrared lamp, and the wavelength lambda of the near infrared lamp is more than or equal to 800nm; the time of the photocatalytic reaction is 10-60 min, the photocatalytic reaction is carried out under the conditions of air atmosphere and stirring, and the stirring speed is 300-800 rpm.

Description

Silsesquioxane porous material with near infrared photocatalytic effect and preparation method and application thereof Technical Field The invention relates to a silsesquioxane porous material with a near infrared photocatalytic effect, and a preparation method and application thereof, and belongs to the technical field of photocatalysis. Background Hydrogen peroxide (H 2O2) is used as an important green oxidant, and is widely used in the fields of chemical synthesis, sewage treatment, medical treatment and health, etc. because of its high active oxygen content and the reaction products being only water and oxygen. However, most of the current H 2O2 is produced by an anthraquinone oxidation method, and the process is huge in energy consumption, and a large amount of wastewater, waste gas and solid waste are generated in the production process, so that a serious environmental burden is brought. Based on this, the conversion of H 2 O or O 2 to H 2O2 using solar energy in pure water is considered as a green, energy-saving, low-consumption and safe strategy. In the process of producing H 2O2 by photocatalysis, the method is carried out under the mild conditions of natural environment and pressure by taking sunlight as an energy source and taking green reactant as a substrate, and is expected to become an ideal method for replacing the traditional process. However, photocatalysts such as g-C 3N4（2.7eV）,TiO2 (3.2 eV) and ZnO (3.37 eV) which are widely used at present have wider band gaps and can only be activated by visible light and even ultraviolet rays. For example, chinese patent document CN119797281A provides a method for preparing hydrogen peroxide by ultra-low temperature photocatalysis, which comprises adding a photocatalysis material into water or solution, completely dispersing, regulating pH to obtain a reaction solution, adding O 2 into the reaction solution to be saturated, and starting a light source to perform photocatalysis reaction, wherein the photocatalysis material is semiconductor metal oxide, and the semiconductor metal oxide is at least one of TiO 2、CuO、ZnO、MgO、Co3O4 and CeO 2. In contrast, infrared light that accounts for a large portion (53%) of the solar spectrum remains unutilized. Therefore, the active development of a high-efficiency renewable near-infrared light-responsive photocatalyst is of great significance for fully exerting the effect of solar energy. The silsesquioxane hybrid porous Polymer (PCSs) has extremely high specific surface area, large porosity and strong thermochemical stability, so that the PCSs are more suitable to be used as high-efficiency photocatalysts, and the flexibility and the controllability of the structure of the PCSs further promote the exploration and the application of the PCSs in various photocatalytic reactions by researchers. In addition, the low solubility characteristic of PCSs provides convenience for the recovery and reuse of the catalyst, so that the economical efficiency of the PCSs in practical application is ensured. The donor (D) -acceptor (a) type PCSs are known for their unique structural characteristics, in which the photovoltaic units are arranged from the donor (D) unit and the acceptor (a) unit in such a way as to confer a specific interaction force, i.e. D-a interaction. However, the light absorption range of the currently studied silsesquioxane-based hybrid porous Polymers (PCSs) is still narrow, the photocatalytic production of H 2O2 cannot be stabilized under near infrared light conditions and the activity thereof needs to be further improved. In addition, the current photocatalyst generally requires the addition of a sacrificial agent when converting H 2 O or O 2 into H 2O2 by utilizing solar energy, which also increases the cost for producing H 2O2 by photocatalysis and also increases the pollution to the environment. Therefore, it is of great importance to develop PCSs materials that are highly active, stable, do not require a sacrificial agent, and can be catalyzed in near infrared light. For this purpose, the present invention is proposed. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a silsesquioxane porous material with a near infrared photocatalytic effect, and a preparation method and application thereof. The preparation method of the silsesquioxane porous material with the near infrared photocatalysis effect is simple, has low cost and has excellent catalytic activity under the irradiation of near infrared light. The technical scheme of the invention is as follows: A preparation method of a silsesquioxane porous material with a near infrared photocatalytic effect comprises the following steps: (1) Reacting (3, 5-trimethylcyclohex-2-ylene) malononitrile with a donor compound in a solvent A under the action of piperidine to obtain a D-A compound, wherein the donor compound has a structure shown in the following formula I-1, I-2 or I-3, and the D-A compound has a structure shown in