Synthetic method of modified mesoporous material
Through the synthesis method of modified mesoporous materials, the existing heterogeneous catalysts have been solved in the insufficient catalytic performance and low recycling rate during the conversion and fixation of carbon dioxide, and the excellent catalytic performance and high recycling rate of cinnamic acid are achieved in catalytic phenylacetylene and carbon dioxide.
Patent Information
- Application Number
- CN202411980258.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-05-13
AI Technical Summary
The existing heterogeneous catalysts have problems of insufficient catalytic performance and low recycling rate during carbon dioxide conversion and fixation.
Using the synthesis method of modified mesoporous materials, an intermediate was obtained by reacting parabenophenol and dicyandiamide in acetonitrile, and then reacting with phenol and formaldehyde to form a phenolic resin precursor. After the addition of template agent F127 and the reduction of silver nitrate, a modified mesoporous material with excellent catalytic properties was prepared.
The prepared modified mesoporous materials exhibit excellent catalytic properties in the catalytic phenylacetylene and carbon dioxide synthesis of cinnamic acid, and have high recycling rates.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of nanomaterials, and in particular to a method for synthesizing a modified mesoporous material. Background Art
[0002] The main energy source of modern society is still fossil fuels. The energy generated by the combustion of fossil fuels accounts for 85% of the total energy demand, but the combustion of fossil fuels produces a large amount of CO2, which causes the greenhouse effect. At the same time, CO2, as an important C1 resource, has important applications in industrial synthesis.
[0003] Converting carbon dioxide into various value-added compounds through chemical reactions is one of the important ways to meet the requirements of green chemistry and achieve carbon dioxide conversion. Heterogeneous catalysts are often used in the conversion and fixation of carbon dioxide because they are green and environmentally friendly and easy to recycle. Ordered mesoporous phenolic resin polymers have become excellent heterogeneous catalyst carriers because of their advantages such as many mesoporous channels, large specific surface area, and adjustable pore size.
[0004] The invention provides a method for synthesizing a modified mesoporous material, which is used for synthesizing a heterogeneous catalyst for a carbon conversion reaction. Summary of the invention
[0005] In view of the above technical problems, the present invention provides a method for synthesizing a modified mesoporous material.
[0006] Technical solution: A method for synthesizing a modified mesoporous material comprises the following steps: S1: dissolve p-bromophenol and dicyandiamide in acetonitrile, add an acid binding agent, and heat under reflux for 20-30h to obtain an intermediate; the structure of the intermediate is as follows: ; S2: Add phenol and the intermediate into a reaction vessel, heat to 40-45°C to melt, add sodium hydroxide solution, dropwise add formaldehyde solution, raise the reaction temperature to 70-75°C and reflux for 2-3h to obtain a phenolic resin precursor; S3: Add dilute hydrochloric acid to the reaction solution to adjust the pH to neutral, remove water by rotary evaporation, dissolve with ethanol, add template F127 and heat to dissolve, mix and stir at room temperature for 0.5-1h, pour on a glass plate and evaporate at room temperature for 8-10h, then transfer to an oven and cure at 110-130°C for 24-48h to obtain ordered mesoporous phenolic resin. S4: immersing the ordered mesoporous phenolic resin in a silver nitrate solution for 20-30 hours, taking it out and adding it into methanol for dispersion reduction for 4-6 hours, taking it out and drying it at 80-90° C. to obtain the modified mesoporous material.
[0007] Furthermore, the molar ratio of p-bromophenol to dicyandiamide in S1 is 1:1.
[0008] Furthermore, the acid binding agent in S1 is sodium hydroxide, sodium carbonate or sodium bicarbonate.
[0009] Furthermore, the molar ratio of phenol, intermediate and formaldehyde in S2 is 1:0.1-0.5:2-6.
[0010] Furthermore, the mass fraction of the sodium hydroxide solution in S2 is 8-15%, and the added amount is 1.5-2 times the mass of phenol.
[0011] Furthermore, the amount of template F127 added in S3 is 2-3 times the mass of phenol.
[0012] Further, the silver nitrate in S4 is 0.02-0.3 mol / L.
[0013] Beneficial effects: The invention provides a method for synthesizing a modified mesoporous material. The prepared modified mesoporous material can be used as a catalytic synthesis of cinnamic acid from phenylacetylene and carbon dioxide, has excellent catalytic performance, and has a high recycling rate. DETAILED DESCRIPTION
[0014] The present invention is described in detail below.
[0015] Embodiment 1: A method for synthesizing a modified mesoporous material comprises the following steps: S1: p-Bromophenol (10 g, 57.8 mmol) and dicyandiamide (4.86 g, 57.8 mmol) were dissolved in acetonitrile (250 mL), sodium hydroxide (5 g, 125 mmol) was added, and the mixture was heated under reflux for 24 h to react. After filtration and concentration, the intermediate (9.8 g, 55.63 mmol) was obtained by column chromatography purification with a purity of 99.3% and a yield of 96.24%. The reaction formula is as follows: ; S2: Add phenol (1 g, 10.63 mmol) and the intermediate (187 mg, 1.06 mmol) into a reaction container, heat to 40°C to melt, add 1.5 g of 10% sodium hydroxide solution, dropwise add 3.0 g of 37% formaldehyde solution, raise the reaction temperature to 70°C and reflux for 2 h to obtain a phenolic resin precursor; S3: 1 mol / L dilute hydrochloric acid was added dropwise to the reaction solution to adjust the pH to neutral, water was removed by rotary evaporation, and 150 mL of ethanol was used to dissolve the solution. 2.5 g of template F127 was added and heated to dissolve the solution. The mixture was stirred at room temperature for 40 min, poured onto a glass plate and evaporated at room temperature for 8 h, and then transferred to an oven and cured at 120 ° C for 36 h to obtain an ordered mesoporous phenolic resin. S4: Immerse the ordered mesoporous phenolic resin in a silver nitrate solution for 25 hours, take it out and add it into 50 mL of methanol for dispersion reduction for 5 hours, take it out and dry it at 85° C. to obtain the modified mesoporous material.
[0016] Embodiment 2: A method for synthesizing a modified mesoporous material comprises the following steps: S1: Same as Example 1; S2: Add phenol (1 g, 10.63 mmol) and the intermediate (935 mg, 3.18 mmol) into a reaction container, heat to 40°C to melt, add 1.5 g of 10% sodium hydroxide solution, dropwise add 3.9 g of 37% formaldehyde solution, raise the reaction temperature to 70°C and reflux for 2 h to obtain a phenolic resin precursor; S3: 1 mol / L dilute hydrochloric acid was added dropwise to the reaction solution to adjust the pH to neutral, water was removed by rotary evaporation, and 150 mL of ethanol was used to dissolve the solution. 3.25 g of template F127 was added thereto and heated to dissolve the solution. The mixture was stirred at room temperature for 40 min, poured onto a glass plate and evaporated at room temperature for 8 h, and then transferred to an oven and cured at 120°C for 36 h to obtain an ordered mesoporous phenolic resin. S4: Immerse the ordered mesoporous phenolic resin in a silver nitrate solution for 25 hours, take it out and add it into 50 mL of methanol for dispersion reduction for 5 hours, take it out and dry it at 85° C. to obtain the modified mesoporous material.
[0017] Embodiment 3: A method for synthesizing a modified mesoporous material comprises the following steps: S1: Same as Example 1; S2: Add phenol (1 g, 10.63 mmol) and the intermediate (374 mg, 5.3 mmol) into a reaction container, heat to 40°C to melt, add 1.5 g of 10% sodium hydroxide solution, dropwise add 4.5 g of 37% formaldehyde solution, raise the reaction temperature to 70°C and reflux for 2 h to obtain a phenolic resin precursor; S3: 1 mol / L dilute hydrochloric acid was added dropwise to the reaction solution to adjust the pH to neutral, water was removed by rotary evaporation, and 150 mL of ethanol was used to dissolve the solution. 3.75 g of template F127 was added thereto and heated to dissolve the mixture. The mixture was mixed and stirred at room temperature for 40 min, poured onto a glass plate and evaporated at room temperature for 8 h, and then transferred to an oven and cured at 120°C for 36 h to obtain an ordered mesoporous phenolic resin. S4: Immerse the ordered mesoporous phenolic resin in a silver nitrate solution for 25 hours, take it out and add it into 50 mL of methanol for dispersion reduction for 5 hours, take it out and dry it at 85° C. to obtain the modified mesoporous material.
[0018] Test example 1-3: Add phenylacetylene (1.0 eq) as reactant and 3% of the modified mesoporous material prepared in Example 1-3 as a catalyst, and 3.0 eq of cesium carbonate into the reactor. The reaction solvent is DMSO. The reaction is carried out at 50° C. under 1 atm carbon dioxide pressure for 24 h. After the reaction, the product cinnamic acid is purified.
[0019] Comparative Examples 1-3: Add phenylacetylene (1.0 eq) as a reactant and 3% of the ordered mesoporous phenolic resin obtained in step S3 of Example 1-3 as a catalyst, and 3.0 eq of cesium carbonate into the reactor. The reaction solvent is DMSO. The reaction is carried out at 50° C. under a carbon dioxide pressure of 1 atm for 24 h. After the reaction, the product cinnamic acid is purified.
[0020] Blank example: Add reactants phenylacetylene (1.0 eq) and 3.0 eq of cesium carbonate into the reactor, use DMSO as the reaction solvent, and react at 50°C under 1 atm carbon dioxide pressure for 24 h. After the reaction, cinnamic acid is obtained by purification.
[0021] After the experiment, the reaction yield of preparing cinnamic acid was analyzed. The results showed that no product was detected in Comparative Examples 1-3 and the blank case, and the reaction did not proceed. The reaction yields of Test Examples 1-3 were 83%, 91%, and 94%, respectively. The catalyst was recovered and the reaction was carried out again, and the yield did not decrease significantly.
[0022] Although the present invention has been disclosed as above in terms of preferred embodiments, they are not intended to limit the present invention. Anyone skilled in the art can make various changes or modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection defined by the claims of this application.
Claims
1. A method for synthesizing a modified mesoporous material, characterized in that: The following steps are involved: S1: dissolve p-bromophenol and dicyandiamide in acetonitrile, add an acid binding agent, and heat under reflux for 20-30h to obtain an intermediate; the structure of the intermediate is as follows: ； S2: Add phenol and the intermediate into a reaction vessel, heat to 40-45°C to melt, add sodium hydroxide solution, dropwise add formaldehyde solution, raise the reaction temperature to 70-75°C and reflux for 2-3h to obtain a phenolic resin precursor; S3: Add dilute hydrochloric acid to the reaction solution to adjust the pH to neutral, remove water by rotary evaporation, dissolve with ethanol, add template F127 and heat to dissolve, mix and stir at room temperature for 0.5-1h, pour on a glass plate and evaporate at room temperature for 8-10h, then transfer to an oven and cure at 110-130°C for 24-48h to obtain ordered mesoporous phenolic resin. S4: immersing the ordered mesoporous phenolic resin in a silver nitrate solution for 20-30 hours, taking it out and adding it into methanol for dispersion reduction for 4-6 hours, taking it out and drying it at 80-90° C. to obtain the modified mesoporous material.
2. The method for synthesizing a modified mesoporous material according to claim 1, characterized in that: The molar ratio of p-bromophenol to dicyandiamide in S1 is 1:
1.
3. A method for synthesizing a modified mesoporous material according to claim 1 or 2, characterized in that: The acid binding agent in S1 is sodium hydroxide, sodium carbonate or sodium bicarbonate.
4. The method for synthesizing a modified mesoporous material according to claim 3, characterized in that: The molar ratio of phenol, intermediate and formaldehyde in S2 is 1:0.1-0.5:2-6.
5. The method for synthesizing a modified mesoporous material according to claim 4, characterized in that: The mass fraction of the sodium hydroxide solution in S2 is 8-15%, and the added amount is 1.5-2 times the mass of phenol.
6. A method for synthesizing a modified mesoporous material according to claim 4 or 5, characterized in that: The amount of template F127 added in S3 is 2-3 times the mass of phenol.
7. The method for synthesizing a modified mesoporous material according to claim 6, characterized in that: The silver nitrate in S4 is 0.02-0.3 mol / L.