Porous organic polymer material, preparation method thereof and application of porous organic polymer material in CO2 adsorption and photocatalytic preparation of H2O2

Abstract

The invention discloses a porous organic polymer material, a preparation method of the porous organic polymer material and application of the porous organic polymer material in CO2 adsorption and photocatalytic preparation of H2O2, and belongs to the technical field of organic framework materials. The porous organic polymer material is prepared by the following method: adding a compound A and benzo [1, 2-B: 3, 4-B ': 5, 6-B'] trithiophene-2, 5, 8-trialdehyde into a solvent, and uniformly mixing; then adding a catalyst, and carrying out polymerization reaction under the condition of inert gas to obtain a polymerization reaction product; and washing and drying the reaction product to obtain the porous organic polymer material. The porous organic polymer material prepared by the invention is novel in structure, not only has excellent photoinduced charge separation and transmission efficiency, shows better advantages in the aspect of photocatalytic preparation of H2O2, but also has excellent CO2 adsorption performance, thereby having important value and significance for further expansion and application of organic framework materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic framework materials, and specifically relates to porous organic polymer materials, a preparation method thereof, and applications in CO2 adsorption and photocatalytic preparation of H2O2. Background Art

[0002] The relationship between the structure and function of porous organic polymer materials has attracted extensive attention. Designing functional materials with unique structures, such as pore structures, compositions, active sites, etc., is of great significance for target applications. In terms of CO2 capture, adsorption based on porous materials has received increasing attention due to its high capture ability and easy operation. At the same time, H2O2 prepared with porous materials also has wide applications in fields such as organic synthesis, drinking water treatment, wastewater treatment, and medical and health. Therefore, developing new CO2 adsorption technologies and H2O2 preparation technologies is particularly important.

[0003] Porous organic framework materials are a class of crystalline porous organic polymer materials formed by covalent bonds of organic molecular precursors. These materials have excellent porosity, ordered channels, and excellent stability. Their building units are organic small molecules, which are widely sourced and diverse in types, enabling diverse building units and facilitating the regulation of the structure and function of target materials. Currently, many organic polymer materials with adjustable properties have met various requirements such as gas adsorption and separation, catalysis, and sewage treatment. Given the characteristics of these materials such as extremely high surface area, chemical diversity, and structural diversity, they are widely used in H2O2 production and CO2 adsorption.

[0004] The preparation of H2O2 and CO2 adsorption largely depends on the pore shape, structural configuration, and surface chemical properties of porous materials. Therefore, it is of great significance to design and synthesize porous organic polymer materials with high H2O2 production ability and high CO2 adsorption ability from these three aspects. Summary of the Invention

[0005] The present invention aims to expand the types of existing H2O2 materials and CO2 adsorption materials. The provided porous organic polymer materials have novel structures, high H2O2 yields, and good CO2 adsorption performance. To achieve the above invention objectives, the technical solutions adopted by the present invention are specifically as follows:

[0006] The present invention provides a preparation method of a porous organic polymer material, comprising the following steps:

[0007] Compound A and benzo[1,2-b:3,4-b':5,6-b'']terthiophene-2,5,8-tricarbaldehyde are added to a solvent and mixed evenly; then a catalyst is added, and a polymerization reaction is carried out under an inert gas condition to obtain a polymerization reaction product; then the reaction product is washed and dried to obtain a porous organic polymer material.

[0008] In the above preparation method, the compound A is 4,4',4'',4'''-(3a,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline or tetrakis(4-aminophenyl)porphyrin.

[0009] In the above preparation method, the molar ratio of the compound A to benzo[1,2-b:3,4-b':5,6-b'']terthiophene-2,5,8-tricarbaldehyde is selected from 3-6:4-8; preferably 3:4.

[0010] In the above preparation method, the solvent is selected from one of the mixed solutions of orthodichlorobenzene and n-butanol, dioxane and mesitylene, N-methylpyrrolidone and mesitylene, and dimethylacetamide and orthodichlorobenzene. In the mixed solution, the volume ratio of the two solvents is selected from 1:4-3:1; preferably 1:1.

[0011] In the above preparation method, the catalyst is selected from one of glacial acetic acid solution, isoquinoline, p-toluenesulfonic acid, and pyrrolidine; preferably glacial acetic acid solution; the concentration of the glacial acetic acid solution is selected from 1-9 mol / L; preferably 6 mol / L.

[0012] In the present invention, the amount of the catalyst used is subject to being able to catalyze the substrate to undergo a polymerization reaction, and no additional limitation is made.

[0013] In the above preparation method, the inert gas is selected from one of nitrogen and argon.

[0014] In the above preparation method, the conditions of the polymerization reaction are selected from: the reaction temperature is 100-150 °C, and the reaction time is 72-120 h.

[0015] In the above preparation method, the detergent used for washing is tetrahydrofuran or dichloromethane; its purpose is to wash away the substrate materials that did not participate in the reaction.

[0016] The present invention provides a porous organic polymer material prepared by the above method.

[0017] The present invention provides the application of the above porous organic polymer material in CO2 adsorption and / or photocatalytic preparation of H2O2.

[0018] The beneficial effects of the present invention are:

[0019] The present invention uses benzo[1,2-b:3,4-b':5,6-b'']terthiophene-2,5,8-tricarbaldehyde as a substrate, and through the polymerization reaction with 4,4',4'',4'''-(3a,1,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline or tetrakis(4-aminophenyl)porphyrin, two porous organic polymer materials with novel structures are prepared. The organic polymer materials have superior photoinduced charge separation and transfer efficiency, thus showing good advantages in the photocatalytic preparation of H2O2. At the same time, the organic polymer materials also have excellent CO2 adsorption performance. Therefore, the porous organic polymer materials prepared by the present invention can simultaneously possess the properties of CO2 adsorption and photocatalytic preparation of H2O2, which has important value and significance for the further expansion and application of organic framework materials. Description of the Drawings

[0020] Figure 1 It is the Fourier transform infrared spectroscopy (FT-IR) of 4,4',4'',4'''-(3a,1,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline (Py), benzo[1,2-b:3,4-b':5,6-b'']terthiophene-2,5,8-tricarbaldehyde (BTT) and aniline-based porous organic polymer material (BTT-Py);

[0021] Figure 2 It is the Fourier transform infrared spectroscopy (FT-IR) of tetrakis(4-aminophenyl)porphyrin (Tph), benzo[1,2-b:3,4-b':5,6-b'']terthiophene-2,5,8-tricarbaldehyde (BTT) and porphyrin-based porous organic polymer material (BTT-Tph);

[0022] Figure 3 It is the ultraviolet spectrum of aniline-based porous organic polymer material (BTT-Py);

[0023] Figure 4 It is the ultraviolet spectrum of porphyrin-based porous organic polymer material (BTT-Tph);

[0024] Figure 5 It is the nitrogen isothermal adsorption-desorption curve and pore size distribution diagram of aniline-based porous organic polymer material (BTT-Py);

[0025] Figure 6 It is the nitrogen isothermal adsorption-desorption curve and pore size distribution diagram of porphyrin-based porous organic polymer material (BTT-Tph);

[0026] Figure 7 It is the Mott-Schottky diagram of aniline-based porous organic polymer material (BTT-Py);

[0027] Figure 8 It is the Mott-Schottky diagram of porphyrin-based porous organic polymer material (BTT-Tph);

[0028] Figure 9 Energy band structure diagrams of aniline-based porous organic polymer material (BTT-Py) and porphyrin-based porous organic polymer material (BTT-Tph);

[0029] Figure 10 Transient photocurrent response tests of aniline-based porous organic polymer material (BTT-Py) and porphyrin-based porous organic polymer material (BTT-Tph);

[0030] Figure 11 Electrochemical impedance spectra of aniline-based porous organic polymer material (BTT-Py) and porphyrin-based porous organic polymer material (BTT-Tph);

[0031] Figure 12 Photocatalytic H2O2 production diagrams of aniline-based porous organic polymer material (BTT-Py) and porphyrin-based porous organic polymer material (BTT-Tph);

[0032] Figure 13 CO2 isothermal adsorption curves of aniline-based porous organic polymer material (BTT-Py) and porphyrin-based porous organic polymer material (BTT-Tph). Specific embodiments

[0033] In the present invention, the synthesis mechanism of the polymerization reaction between 4,4',4”,4”'-(3A1,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline (Py) and benzo[1,2-b:3,4-b':5,6-b']trithiophene-2,5,8-tricarbaldehyde compound (BTT) is as follows:

[0034]

[0035] In the present invention, the synthesis mechanism of the polymerization reaction between tetrakis(4-aminophenyl)porphyrin (Tph) and benzo[1,2-b:3,4-b':5,6-b']trithiophene-2,5,8-tricarbaldehyde compound (BTT) is as follows:

[0036]

[0037] The porous organic polymer material prepared in the present invention has a uniform layered structure, with a high specific surface area, small pore size, photocatalytic hydrogen peroxide production, and carbon dioxide adsorption capacity.

[0038] Other materials used in the present invention can be obtained through commercial channels without special declaration. Other terms used in the present invention generally have the meanings commonly understood by those of ordinary skill in the art unless otherwise specified. The present invention will be described in further detail below with reference to specific examples and data. The following examples are only for illustrating the present invention and do not limit the scope of the present invention in any way.

[0039] Example 1

[0040] To prepare an aniline-based porous organic polymer material, the steps are as follows:

[0041] Put 25.5 mg of 4,4',4”,4”'-(3A1,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline and 19.8 mg of benzo[1,2-b:3,4-b':5,6-b']terthiophene-2,5,8-tricarbaldehyde into a 10 mL ampoule bottle, add 2 mL of a mixed solution of o-dichlorobenzene and n-butanol (volume ratio 1:1), ultrasonicate for 10 min to mix evenly, and add 0.12 mL of acetic acid solution (concentration 6 mol / L) as a catalyst; then freeze-degas the ampoule bottle containing the mixed solution and fill it with nitrogen, cycle three times; seal the ampoule bottle with a flame torch, and then place the ampoule bottle in a constant temperature oven at 120 °C for 72 h of polymerization reaction to obtain a polymerization reaction product with a yield of 76%.

[0042] Centrifuge the obtained polymerization reaction product, wash it with tetrahydrofuran to remove the unreacted 4,4',4”,4”'-(3A1,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline and benzo[1,2-b:3,4-b':5,6-b']terthiophene-2,5,8-tricarbaldehyde, and dry it in a vacuum oven at 30 °C to obtain an aniline-based porous organic polymer material.

[0043] Example 2

[0044] To prepare a porphyrin-based porous organic polymer material, the steps are as follows:

[0045] Put 30.4 mg of tetrakis(4-aminophenyl)porphyrin and 19.8 mg of benzo[1,2-b:3,4-b':5,6-b']terthiophene-2,5,8-tricarbaldehyde into a 10 mL ampoule bottle; add 2 mL of a mixed solution of o-dichlorobenzene and n-butanol (volume ratio 1:1), ultrasonicate for 10 min to mix evenly, and add 0.12 mL of acetic acid solution (concentration 6 mol / L) as a catalyst; then freeze-degas the ampoule bottle containing the mixed solution and fill it with nitrogen, cycle three times; seal the ampoule bottle with a flame torch, and then place the ampoule bottle in a constant temperature oven at 120 °C for 72 h of polymerization reaction to obtain a polymerization reaction product with a yield of 62%.

[0046] The obtained polymerization product was centrifuged, washed with tetrahydrofuran, and the unreacted tetra(4-aminophenyl)porphyrin and benzo[1,2-b:3,4-b':5,6-b']terthiophene-2,5,8-tricarbaldehyde were washed away, and then dried in a vacuum oven at 30 °C to obtain the porphyrin-based porous organic polymer material.

[0047] I. Infrared and UV Characterizations

[0048] Figure 1 The infrared spectra (FT-IR) of 4,4',4”,4”'-(3A1,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline (Py), benzo[1,2-b:3,4-b':5,6-b']terthiophene-2,5,8-tricarbaldehyde (BTT) and aniline-based porous organic polymer material (BTT-Py) are shown. Figure 2 The infrared spectra (FT-IR) of tetra(4-aminophenyl)porphyrin (Tph), benzo[1,2-b:3,4-b':5,6-b']terthiophene-2,5,8-tricarbaldehyde (BTT) and porphyrin-based porous organic polymer material (BTT-Tph) are shown. Figure 3 The UV spectrum of the aniline-based porous organic polymer material (BTT-Py) is shown. Figure 4 The UV spectrum of the porphyrin-based porous organic polymer material (BTT-Tph) is shown.

[0049] It can be seen from Figure 1 that the vibration peak of the aldehyde group at 1655 cm -1 decreases, indicating a relatively high degree of polymerization of the condensation reaction. A vibration peak of C=N is formed at 1603 cm -1 , which also indicates the successful polymerization of the aniline organic polymer (BTT-Py). From Figure 3 , the UV adsorption curve of the aniline organic polymer solid sample can be obtained. By calculation and analysis, the band gap of the aniline organic polymer is 2.17 eV.

[0050] It can be seen from Figure 2 that the vibration peak of the aldehyde group at 1654 cm -1 decreases, indicating a relatively high degree of polymerization of the condensation reaction. A vibration peak of C=N is formed at 1605 cm -1 , which also indicates the polymerization of the porphyrin organic polymer (BTT-Tph). From Figure 4 , the UV adsorption curve of the porphyrin organic polymer solid sample can be obtained. By calculation and analysis, the band gap of the porphyrin organic polymer is 1.82 eV.

[0051] In summary, it can be seen from Figures 1 to 4It can be seen that the vibration peaks of the amino and aldehyde groups of the aniline organic polymer and the porphyrin organic polymer decay, and the vibration peak of C=N is successfully formed, indicating the successful synthesis of the two polymers.

[0052] II. Nitrogen Adsorption Test

[0053] The nitrogen adsorption test was carried out on the aniline organic polymer (BTT-Py) and the porphyrin organic polymer (BTT-Tph). This test was carried out at a temperature of 77K. The analytical instrument was a rapid specific surface and porosity analyzer, model ASAP2020plus HD88. Through the adsorption test, the adsorption and desorption capacity of the material can be understood, and key parameters such as its pore structure, specific surface area, and pore size distribution can be obtained, so as to deeply understand the gas storage capacity of the material.

[0054] The test results are as Figure 5 and Figure 6 shown:

[0055] The specific surface area of the aniline organic polymer (BTT-Py) calculated by the BET theory is 323.45m 2 / g. Through Figure 5 the peak of the pore size distribution diagram, its pore size distribution is 1.77nm.

[0056] The specific surface area of the porphyrin organic polymer (BTT-Tph) calculated by the BET theory is 253.21m 2 / g. Through Figure 6 the peak of the pore size distribution diagram, its pore size distribution is 1.12nm.

[0057] III. Electrochemical Property Characterization

[0058] The electrochemical properties of the aniline organic polymer (BTT-Py) and the porphyrin organic polymer (BTT-Tph) were systematically characterized. By measuring the electrode capacitance under different applied bias voltages, the energy band structure of the material was judged. This test was carried out on an electrochemical workstation CHI 660 at room temperature.

[0059] The test results are as Figure 7 and Figure 8 shown:

[0060] The flat band potentials of BTT-Py and BTT-Tph were determined to be -0.53 V and -0.46 V (vs. Ag / AgCl) respectively through Mott-Schottky plots. Based on the flat band potentials, the conduction band potentials of BTT-Py and BTT-Tph were calculated to be -0.33 V and -0.26 V (vs. normal hydrogen electrode) respectively. Then, through the formula (conduction band potential = valence band potential - band gap), the valence band potentials of BTT-Py and BTT-Tph were calculated to be 1.84 V and 1.56 V (vs. normal hydrogen electrode) respectively. Combining the above data, the energy band structures of the two porous organic polymers were finally obtained. As Figure 9 shown, the potentials of the conduction band and valence band of the two materials can be intuitively seen, so as to better analyze the energy level positions of the materials, and it can be judged that both materials are semiconductor materials with good performance.

[0061] IV. Transient photocurrent response test

[0062] Through the transient photocurrent response test, the photo-generated charge separation and migration abilities of BTT-Py and BTT-Tph were studied. Continuous photocurrent responses were observed for both samples during the on / off of the light source. This test was carried out on an electrochemical workstation CHI 660 at room temperature.

[0063] The test results are as Figure 10 shown:

[0064] The photocurrents of BTT-Py and BTT-Tph are relatively close, but the photocurrent of BTT-Py is slightly higher than that of BTT-Tph, indicating that the performance gap between BTT-Py and BTT-Tph in terms of photo-induced charge separation and transport efficiency is small.

[0065] V. Charge transport ability test

[0066] The electrochemical impedance spectroscopy (EIS) was used to evaluate the ease of charge migration of BTT-Py and BTT-Tph. This test was carried out on an electrochemical workstation CHI 660 at room temperature.

[0067] The test results are as Figure 11 shown:

[0068] Both BTT-Py and BTT-Tph have excellent charge transfer abilities. Relatively speaking, BTT-Py has a smaller semicircle diameter and a lower charge transfer resistance, indicating that the charge transfer process of this material is easier.

[0069] VI. Photocatalytic H2O2 production performance test

[0070] The performance tests of H2O2 production were carried out on aniline organic polymer (BTT-Py) and porphyrin organic polymer (BTT-Tph) respectively. The photocatalytic experiment was carried out in pure water at 25 °C, and the yield of H2O2 was determined by the iodometric method. The specific steps are as follows: The experiment was carried out in a 60 mL reactor. When testing the pure water system, 5 mg of porous organic polymer and 50 mL of pure water were added to the reactor. Oxygen was continuously introduced into the reactor and placed under a 300 W xenon lamp source (wavelength greater than 420 nm), and at the same time, circulating cooling water was applied to maintain the system temperature at 25 °C. After different reaction times, the filtrate was collected and the concentration of hydrogen peroxide in the system was determined by the iodometric method.

[0071] The test results are as Figure 12 shown:

[0072] The yield of H2O2 of aniline organic polymer (BTT-Py) is 1.1 mmol / g / h, and the H2O2 yield of porphyrin organic polymer (BTT-Tph) is 0.17 mmol / g / h.

[0073] VII. CO2 Adsorption Performance Test

[0074] Through the test of CO2 adsorption capacity, the CO2 adsorption capacities of BTT-Py and BTT-Tph were studied. This test was carried out at a temperature of 273 K. The analytical instrument is a rapid specific surface and porosity analyzer, model ASAP 2020plus HD88. Through this test, the absorption and storage capacities of the two materials for CO2 gas can be intuitively understood.

[0075] The test results are as Figure 13 shown:

[0076] At a temperature of 273 K, the CO2 adsorption capacity of BTT-Py material is 15.1 cm 3 / g, and the CO2 adsorption capacity of BTT-Tph material is 38.6 cm 3 / g. Both samples show excellent CO2 adsorption capacities.

[0077] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention in other forms. Any person skilled in the art may use the disclosed technical content to make changes or modifications into equivalent embodiments with equivalent changes. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the technical solution content of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A method for preparing a porous organic polymer material, characterized in that, It includes the following steps: Compound A and benzo[1,2-b:3,4-b':5,6-b'']terthiophene-2,5,8-tricarbaldehyde are added to a solvent and mixed evenly; then a catalyst is added, and a polymerization reaction is carried out under an inert gas condition to obtain a polymerization reaction product; then the reaction product is washed and dried to obtain a porous organic polymer material.

2. The preparation method according to claim 1, characterized in that, Compound A is 4,4',4'',4'''-(3a,5-dihydropyrene-1,3,6,8-tetrayl)tetraaniline or tetrakis(4-aminophenyl)porphyrin.

3. The preparation method according to claim 1, characterized in that, The molar ratio of Compound A to benzo [1,2-B:3,4-B':5,6-B'']terthiophene-2,5,8-tricarbaldehyde is selected from 3-6:4-8.

4. The preparation method according to claim 1, wherein The solvent is selected from one of the mixed solutions of o-dichlorobenzene and n-butanol, dioxane and mesitylene, N-methylpyrrolidone and mesitylene, and dimethylacetamide and o-dichlorobenzene.

5. The preparation method according to claim 1, characterized in that, The catalyst is selected from one of glacial acetic acid solution, isoquinoline, p-toluenesulfonic acid, and pyrrolidine.

6. The preparation method according to claim 1, characterized in that, The inert gas is selected from one of nitrogen and argon.

7. The preparation method according to claim 1, characterized in that, The conditions of the polymerization reaction are selected as follows: reaction temperature 100-150 °C, reaction time 72-120 h.

8. The preparation method according to claim 1, characterized in that, The detergent used for washing is tetrahydrofuran or dichloromethane; its purpose is to wash away the unreacted substrate materials.

9. A porous organic polymer material prepared by the method according to any one of claims 1-8.

10. Use of the porous organic polymer material according to claim 9 in CO2 adsorption and / or photocatalytic preparation of H2O2.

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