Porphyrin-benzobisthiadiazole covalent organic framework material as well as preparation method and application thereof
By introducing porphyrin-benzobisthiadiazole groups into covalent organic frame materials, the D-A system is formed, and the problem of easy recombination of photogenerated electrons and holes is solved, efficient charge separation and transmission of the material is achieved, photothermal performance is improved, and its applications in photothermal, electrochemical catalysis and energy storage are expanded.
Patent Information
- Application Number
- CN202510425971.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-07
- Publication Date
- 2025-08-08
AI Technical Summary
Photogenerated electrons and holes in existing covalent organic framework materials are prone to recombination during transmission, resulting in the need of higher incident light energy to excite electrons, limiting their application.
The covalent organic framework material of porphyrin-benzobisthiadiazolyl was synthesized by SchiffBase reaction. By introducing porphyrin as donor and benzobisthiadiazolyl as acceptor in COFs, a D-A system was formed, and the imine bonds were used to improve the charge separation and transport capabilities.
It effectively reduces the incident light energy required to excite electrons, improves the photothermal performance of the material, and has potential application value for photothermal, electrochemical catalysis and energy storage.
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Figure CN120441793A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of porous polymers, and in particular relates to a porphyrin-benzobisthiadiazolyl-based covalent organic framework material, a preparation method thereof, and an application thereof. Background Art
[0002] Covalent organic frameworks (COFs) are a class of crystalline porous polymer materials composed of light elements (such as carbon, hydrogen, oxygen, nitrogen, and sulfur). Their organic building blocks are precisely self-assembled through covalent bonds. COFs offer advantages such as diverse frameworks, ordered pore structures, good modifiability, excellent thermal stability, and large specific surface areas. They have been widely used in sensing, catalysis, optoelectronics, and environmental applications.
[0003] Research has shown that porphyrin is a cyclic tetrapyrrole derivative with unique photophysical properties, exhibiting excellent absorption in the ultraviolet-visible-near-infrared region. By introducing porphyrin groups into COFs, a conjugated network can be constructed that facilitates the transport of photogenerated electrons and holes, accelerating reaction kinetics and improving the photothermal performance of the material. In the COF structure, the porphyrin groups are arranged in parallel to form stacked two-dimensional layers, with their π orbitals overlapping and generating p-electron channels through strong electrophilic interactions. This channel promotes the efficient transport of photoinduced charge carriers under visible light irradiation. However, the electrons and holes generated in COFs are prone to recombination during transport, hindering their application. Thiadiazole groups have strong electron-withdrawing ability, and their introduction into the COF backbone can effectively reduce the recombination of photogenerated carriers. Existing patent CN116284633A utilizes porphyrin and benzothiadiazole to synthesize COFs. However, the electron-withdrawing properties of a single thiadiazole group are weak, resulting in a wide band gap in the resulting COFs, requiring higher incident light energies to excite electrons. Therefore, there is still a need to develop a new covalent organic framework material. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a porphyrin-benzobisthiadiazolyl-based covalent organic framework material and its preparation method and application, which solves the problem that photogenerated electrons and holes in the covalent organic framework material are easily recombine during transmission.
[0005] The present invention provides a porphyrin-benzobisthiadiazolyl covalent organic framework material, the structural formula of which is shown below:
[0006] Denoted as Por-COFs.
[0007] The present invention also provides a method for preparing a porphyrin-benzobisthiadiazolyl covalent organic framework material, comprising the following steps:
[0008] 4,4-(Benzo[c][1,2,5]bithiadiazole-4,7-diyl)benzaldehyde and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin are mixed in a molar ratio of 4:1-1:1, and then glacial acetic acid, o-dichlorobenzene and n-butanol are added, mixed evenly, and then degassed to react, and then washed, filtered and vacuum dried to obtain a porphyrin-benzobithiadiazole-based covalent organic framework material.
[0009] Furthermore, the preparation method of the 4,4-(benzo[c][1,2,5]bisthiadiazole-4,7-diyl)benzaldehyde is as follows: after mixing 4,7-dibromobenzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) and 4-formylphenylboronic acid pinacol ester in a molar ratio of 1:1-1:8, 50-200 mg of tetrakistriphenylphosphine palladium, 1-10 mL of saturated potassium carbonate aqueous solution and 10-20 mL of 1,4-dioxane are added in sequence, the mixture is heated to 40-150° C. and refluxed with stirring for 24-96 hours, and the product is post-treated to obtain the product.
[0010] Preferably, the volume ratio of the glacial acetic acid, o-dichlorobenzene and n-butanol is 1:2:8-1:8:2.
[0011] Preferably, the mass volume ratio of the 4,4-(benzo[c][1,2,5]bithiadiazole-4,7-diyl)benzaldehyde to glacial acetic acid is 1:1-1:10.
[0012] Preferably, the process parameters of the reaction are: heating in a vacuum oven at 80-150° C. for 72-180 hours.
[0013] Preferably, the washing process conditions are: washing with acetone and n-hexane in sequence at room temperature for several times.
[0014] Preferably, the process parameters of the vacuum drying are: vacuum drying temperature is 60-80° C., and vacuum drying time is 10-24 h.
[0015] The above reaction equation is as follows:
[0016]
[0017] The present invention also provides a porphyrin-benzobisthiadiazolyl-based covalent organic framework material for use in the fields of photothermal, electrochemical catalysis, and energy storage.
[0018] Beneficial effects
[0019] The present invention is a porphyrin-benzobisthiadiazole-based covalent organic framework material synthesized based on the SchiffBase reaction. Aromatic compounds containing aldehyde groups and amino groups undergo condensation in an acidic environment to form a porphyrin-benzobisthiadiazole covalent organic framework material connected by imine bonds. The material is composed of porphyrin as a donor (D) and benzobisthiadiazole as an acceptor (A). The DA system has efficient charge separation and charge transfer capabilities, effectively reducing the incident light energy required to excite electrons, and improving the photothermal performance of the material. It has potential application value in the fields of photothermal, electrochemical catalysis, and energy storage. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 The monomer 4,4-(benzo[c][1,2,5]bisthiadiazole-4,7-diyl)dibenzaldehyde of Example 1 1 H-NMR spectrum.
[0021] Figure 2 This is the XRD pattern of the porphyrin-benzobisthiadiazolyl-based covalent organic framework material synthesized in Example 1.
[0022] Figure 3 This is the FTIR spectrum of the porphyrin-benzobisthiadiazolyl-based covalent organic framework material synthesized in Example 1.
[0023] Figure 4 The porphyrin-benzobisthiadiazolyl covalent organic framework material synthesized in Example 1 13 C-NMR spectrum.
[0024] Figure 5 This is the N2 adsorption-desorption curve of the porphyrin-benzobisthiadiazolyl-based covalent organic framework material synthesized in Example 1 at 77.4K.
[0025] Figure 6 This is the UV-visible diffuse reflectance image of the porphyrin-benzobisthiadiazolyl-based covalent organic framework material synthesized in Example 1.
[0026] Figure 7 This is a calculated band gap diagram of the porphyrin-benzobisthiadiazolyl-based covalent organic framework material synthesized in Example 1.
[0027] Figure 8 This is the Mott-Schottky and band structure diagram of the porphyrin-benzobisthiadiazolyl-based covalent organic framework material synthesized in Example 1.
[0028] Figure 9 This is a photothermal temperature curve of the porphyrin-benzobisthiadiazolyl-based covalent organic framework material synthesized in Example 1. DETAILED DESCRIPTION
[0029] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.
[0030] The drugs and instruments used in the embodiments of the present invention are:
[0031] Drugs: 4,7-dibromobenzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) (Shanghai Aladdin Biochemical Technology Co., Ltd.), 4-formylphenylboronic acid pinacol ester (Shanghai Aladdin Biochemical Technology Co., Ltd.), phenylphosphine palladium (Shanghai Aladdin Biochemical Technology Co., Ltd.), 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin (Jilin Zhongke Science and Technology Co., Ltd.), n-butanol (Shanghai Aladdin Biochemical Technology Co., Ltd.), o-dichlorobenzene (Sinopharm Chemical Reagent Co., Ltd.), glacial acetic acid (Shanghai Yien Chemical Technology Co., Ltd.), acetone (Sinopharm Chemical Reagent Co., Ltd.), n-hexane (Sinopharm Chemical Reagent Co., Ltd.).
[0032] Instruments: nuclear magnetic resonance spectrometer (AVANCE300), X-ray diffractometer (Bruker D8 ADVANCE), Fourier transform infrared spectrometer (Nicolet 670 spectrometer), solid-state nuclear magnetic resonance (AVANCE400), nitrogen adsorption and desorption test (Micromeritics ASAP2460), ultraviolet-visible spectrophotometer (UV-2600i, Shimadzu, Japan), simulated sunlight (Oriel Newport 69911, United States), infrared camera (FOTRIC 220s).
[0033] Example 1
[0034] 0.568 mmol of 4,7-dibromobenzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) and 3.408 mmol of 4-formylphenylboronic acid pinacol ester were mixed in a 100 mL Schlenk tube. 130 mg of tetrakistriphenylphosphine palladium, 4 mL of saturated aqueous potassium carbonate, and 16 mL of 1,4-dioxane were added sequentially and mixed thoroughly. The mixture was degassed three times, purged with nitrogen, and sealed. The mixture was heated to 100°C and refluxed for 72 hours. After cooling to room temperature, the reaction mixture was poured into water and the solid was collected by centrifugation. The product was washed with methanol and acetone, and the washings were collected. After drying over anhydrous sodium sulfate, the organic solvent was removed by rotary evaporation. The product was then purified by silica gel column chromatography using ethyl acetate as the mobile phase to obtain a light red solid, 4,4-(benzo[c][1,2,5]bisthiadiazole-4,7-diyl)benzaldehyde.
[0035] 4,4-(Benzo[c][1,2,5]bithiadiazole-4,7-diyl)benzaldehyde (16.7 mg, 0.04 mmol) and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin (16.1 mg, 0.02 mmol) were mixed in a 10 mL Schlenk tube. 0.3 M glacial acetic acid (100 μL), o-dichlorobenzene (500 μL), and n-butanol (500 μL) were added. After sonication, the mixture was completely dissolved, degassed three times, and sealed in a 120°C oven for 120 h. After completion of the reaction, the mixture was filtered, washed with acetone and then n-hexane, filtered, and dried under vacuum at 60°C for 10 h to obtain porphyrin-benzobithiadiazole-based covalent organic frameworks, designated Por-COFs.
[0036] The monomer 4,4-(benzo[c][1,2,5]bisthiadiazole-4,7-diyl)dibenzaldehyde obtained in this example 1 The H-NMR test results are as follows Figure 1 As shown, the single peak at 10.8 ppm corresponds to the protons of the aldehyde groups at both ends, and the two double peaks at 7.75-8.1 ppm correspond to the protons of the benzene rings connected to the two ends of the benzobisthiadiazole group. The peak area ratio of the above signals is 1:2:2.
[0037] The XRD test results of Por-COFs obtained in this example are as follows: Figure 2 As shown, strong peaks are shown at 3.4° and 6.2° (±0.2, 2θ), proving the successful formation of the covalent organic framework structure.
[0038] The FTIR test results of Por-COFs obtained in this example are as follows Figure 3 As shown, 3340cm -1The characteristic vibration band of the NH group of 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin is 1680 cm -1 The band at 1560 cm is attributed to the characteristic vibration band of C=O group of 4,4-(benzo[c][1,2,5]bisthiadiazole-4,7-diyl)dibenzaldehyde. -1 The generation of characteristic vibration bands of the C=N group of the covalent organic framework indicated that Por-COFs were successfully synthesized.
[0039] The Por-COFs obtained in this example 13 The C-NMR test results are as follows Figure 4 As shown in the figure, the peak at a chemical shift of 152 ppm is the C peak in the chemical environment of porphyrin, proving the presence of the porphyrin group; the peak at a chemical shift of 131 ppm is the C peak in the chemical environment of benzobisthiadiazole, proving the presence of the benzobisthiadiazole group. These results confirm the successful synthesis of Por-COFs.
[0040] The N2 adsorption-desorption curve test results of Por-COFs obtained in this example are as follows Figure 4 As shown in the figure, from the N2 adsorption-desorption curve at 77.4K, it can be seen that when the adsorption isoline is in the low relative pressure region (P / P0<0.001), the gas adsorption has a relatively rapid growth stage. This is due to the effect of micropore filling, indicating that there is a certain micropore structure in Por-COFs. The desorption curve is not completely closed with the adsorption curve. This is because some N2 remains in the pores of the sample Por-COFs and cannot be completely desorbed.
[0041] The solid ultraviolet diffuse reflectance image of Por-COFs obtained in this example is as follows Figure 6 As shown, the material exhibits significant broadband light absorption characteristics in the wavelength range of 200-750nm, and has excellent light capture ability and visible light response characteristics.
[0042] The band gap data of Por-COFs obtained in this example are as follows Figure 7 As shown, the optical direct band gap value of the material can be obtained by solid UV testing and the Kubelka-Munk formula to be 1.69 eV.
[0043] The Mott-Schottky and band structure diagrams of Por-COFs obtained in this example are shown in Figure 2. Figure 8 As shown, the conduction band CB = -0.17 V and the valence band VB = 1.52 V were calculated by Mott-Schottky test combined with the band gap value. This result proves that the introduction of DA structure can synthesize narrow band gap polymers and reveals the band structure of the material.
[0044] The photothermal temperature curve of Por-COFs obtained in this example is shown in FIG. Figure 9 As shown, the intensity is 1kW·m -2 The material was irradiated with simulated sunlight and the temperature was recorded with an infrared camera. The results showed that the surface temperature of Por-COFs could reach above 100°C within 1200s, proving that Por-COFs have good photothermal properties.
Claims
1. A porphyrin-benzobisthiadiazolyl-based covalent organic framework material, characterized by: Its structural formula is shown below:
2. A method for preparing a porphyrin-benzobisthiadiazolyl covalent organic framework material, comprising the following steps: 4,4-(Benzo[c][1,2,5]bithiadiazole-4,7-diyl)benzaldehyde and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin are mixed in a molar ratio of 4:1-1:1, and then glacial acetic acid, o-dichlorobenzene and n-butanol are added, mixed evenly, and then degassed to react, and then washed, filtered and vacuum dried to obtain a porphyrin-benzobithiadiazole-based covalent organic framework material.
3. The preparation method according to claim 2, wherein: The preparation method of the 4,4-(benzo[c][1,2,5]bisthiadiazole-4,7-diyl)benzaldehyde comprises: mixing 4,7-dibromobenzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) and 4-formylphenylboronic acid pinacol ester in a molar ratio of 1:1-1:8, adding 50-200 mg of tetrakistriphenylphosphine palladium, 1-10 mL of saturated potassium carbonate aqueous solution and 10-20 mL of 1,4-dioxane in sequence, heating to 40-150° C., reflux stirring and reacting for 24-96 hours, and post-treating the product to obtain the product.
4. The preparation method according to claim 2, wherein: The volume ratio of the glacial acetic acid, o-dichlorobenzene and n-butanol is 1:2:8-1:8:
2.
5. The preparation method according to claim 2, wherein: The mass volume ratio of the 4,4-(benzo[c][1,2,5]bithiadiazole-4,7-diyl)benzaldehyde to glacial acetic acid is 1:1-1:
10.
6. The preparation method according to claim 2, wherein: The process parameters of the reaction are: heating in a vacuum oven at 80-150° C. for 72-180 hours.
7. The preparation method according to claim 2, characterized in that: The washing process conditions are: washing with acetone and n-hexane in sequence at room temperature for several times.
8. The preparation method according to claim 2, wherein: The process parameters of the vacuum drying are: vacuum drying temperature is 60-80° C., and vacuum drying time is 10-24 hours.
9. An application of the porphyrin-benzobisthiadiazole-based covalent organic framework material according to claim 1 in the fields of photothermal, electrochemical catalysis, and energy storage.