CN115010938B - Covalent organic framework material and preparation method and application thereof - Google Patents
Covalent organic framework material and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a covalent organic framework material and a preparation method and application thereof. The side chain of the covalent organic framework material disclosed by the invention has a phosphate group, the phosphate group has moderate dissociation and proton accepting capability, and a wide hydrogen bond network system is easy to construct, so that the covalent organic framework material has excellent proton conductivity; the preparation method of the covalent organic framework material has the advantages of simple synthesis, high yield, mild preparation process and no pollution; the covalent organic framework material can be widely applied to the field of proton conduction.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a covalent organic framework material as well as a preparation method and application thereof.
Background
With the growth of population and the rapid development of industry, the demand of human beings for fossil energy is increasing, and the problem of increasingly serious environmental pollution is brought along. Therefore, it is very urgent to develop renewable, green and clean energy to adjust a single energy structure. Among many clean energy sources, proton Exchange Membrane Fuel Cells (PEMFCs) are receiving attention from researchers due to their characteristics of high conversion efficiency, high portability, and ultra-low emission. The PEMFCs are formed by respectively placing redox reaction pairs on two sides of electrodes for reaction, and directly converting chemical energy contained in hydrogen and oxygen into electric energy in an electrochemical mode. In the electrochemical reaction process, hydrogen in the anode is oxidized to form hydrogen ions, then the hydrogen ions flow to the cathode through a proton exchange membrane in the form of hydrogen ions, and finally the hydrogen ions react with oxygen to generate electric energy, and the product discharged in the whole process is only water. The proton transfer rate of the proton exchange membrane has a decisive influence on the overall performance of the fuel cell, and therefore, the development of materials with high proton conductivity is becoming one of the focuses of research.
Covalent organic framework materials (COFs) are used as a class of crystalline organic porous polymers formed by light elements such as C, O, S, N, H and B through covalent bonds, and the COFs have wide attention in the field of ion conduction due to the prededesibility, high specific surface area, stable and highly ordered pore channels and unique molecular structures of the structures. The ionic COFs proton conductive material constructed by the ionic groups has the following two advantages: (1) The ionic COFs proton conductive material can utilize the electrostatic interaction force of ionic groups to construct a special pore structure and environment, so that an unimpeded proton transmission channel can be realized more easily; (2) Some special acidic ionic groups are introduced into the COFs structure, so that the proton carrier concentration of the ionic COFs proton conducting material is improved, and the ionic COFs proton conducting material is promoted to have higher intrinsic proton conductivity. In recent years, ionic COFs proton conductive materials constructed based on acidic ionic groups have been developed successively, especially COFs with sulfonic acid and acetic acid ionic groups. However, the COFs of the existing sulfonic acid and acetic acid ionic groups still have the problems of low proton transfer rate, high cost and the like, so that a new covalent organic framework material needs to be developed.
Disclosure of Invention
In order to overcome the problems of the prior art, it is an object of the present invention to provide a covalent organic framework material; the other purpose of the invention is to provide a preparation method of the covalent organic framework material; it is a further object of the present invention to provide the use of such covalent organic framework materials.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a covalent organic framework material, wherein the structure of the covalent organic framework material is shown as a formula (I);
in the formula (I), n is selected from positive integers from 1 to 6.
Preferably, in the formula (I), n is selected from a positive integer of 2-4; further preferably, in the formula (I), n is 3.
Preferably, the structure of the covalent organic framework material is shown as a formula (II);
in a second aspect, the present invention provides a method for preparing a covalent organic framework material according to the first aspect of the present invention, comprising the steps of:
mixing a compound shown in a formula (VI) with a compound shown in a formula (VII) and reacting to obtain the covalent organic framework material;
in the formula (VI), n is selected from positive integers of 1-6.
Preferably, the reaction further comprises adding a catalyst to participate in the reaction.
Preferably, the catalyst comprises an acid; further preferably, the catalyst comprises at least one of formic acid, acetic acid, p-toluenesulfonic acid and caproic acid; still further preferably, the catalyst is acetic acid; still more preferably, the catalyst is acetic acid at a concentration of 5mol/L to 7 mol/L.
Preferably, the molar ratio of the compound shown in the formula (VI) to the compound shown in the formula (VII) is (1-2): 1; further preferably, the molar ratio of the compound represented by the formula (VI) to the compound represented by the formula (VII) is (1.3-1.7): 1.
preferably, the reaction temperature is 100-140 ℃; further preferably, the temperature of the reaction is 110 ℃ to 130 ℃.
Preferably, the reaction time is 120h-216h; further preferably, the reaction time is 144h-192h.
Preferably, the solvent for the reaction comprises at least one of halogenated aromatic hydrocarbon solvent and alcohol solvent; further preferably, the solvent of the reaction comprises at least one of o-dichlorobenzene, m-dichlorobenzene, n-butanol, ethanol, methanol and propanol; still more preferably, the solvent for the reaction is a mixed solvent of o-dichlorobenzene and n-butanol; more preferably, the solvent of the reaction is o-dichlorobenzene and n-butanol in a volume ratio of (7-10): 1, and a mixed solvent.
Preferably, after the reaction is finished, the method further comprises the step of performing Soxhlet extraction on the covalent organic framework material.
Preferably, the solvent for the soxhlet extraction is tetrahydrofuran.
Preferably, the compound shown in the formula (VI) is prepared by a compound shown in the formula (V) through hydrolysis reaction;
wherein R is 1 Selected from C1-C6 alkyl; n is selected from a positive integer from 1 to 6.
Preferably, the hydrolysis reaction further comprises adding at least one of trimethyl bromosilane and hydrochloric acid to participate in the reaction; further preferably, the hydrolysis reaction further comprises adding trimethyl bromosilane for reaction.
Preferably, the molar ratio of the compound represented by the formula (V) to the trimethylbromosilane is 1: (5-15); further preferably, the molar ratio of the compound represented by the formula (v) to the trimethylbromosilane is 1: (8 to 12).
Preferably, the reaction temperature of the hydrolysis reaction is 15 ℃ to 60 ℃.
Preferably, the reaction time of the hydrolysis reaction is 12-72 h.
Preferably, the compound shown in the formula (V) is prepared by mixing a compound shown in a formula (III) and a compound shown in a formula (IV) and reacting;
in the formula (IV), R 1 Selected from C1-C6 alkyl; n is selected from a positive integer from 1 to 6; x is selected from halogen.
Preferably, in the formula (IV), X is selected from Br, cl or I; more preferably, in the formula (IV), X is Br.
Preferably, said R is 1 Selected from C1-C3 alkyl; further preferably, said R 1 Is ethyl.
Preferably, in the formula (IV), the formula (V) or the formula (VI), n is selected from a positive integer of 2-4; further preferably, in the formula (IV), the formula (V) or the formula (VI), n is 3.
Preferably, the molar ratio of the compound represented by the formula (III) to the compound represented by the formula (IV) is 1: (1-3); further preferably, the molar ratio of the compound represented by the formula (iii) to the compound represented by the formula (iv) is 1: (2-2.5).
Preferably, the reaction temperature is 90-130 ℃; further preferably, the temperature of the reaction is 90 ℃ to 110 ℃.
Preferably, the reaction time is 12-36 h; more preferably, the reaction time is 12 to 24 hours.
In a third aspect the present invention provides the use of a covalent organic framework material according to the first aspect of the present invention in the field of proton conduction.
Preferably, the proton conducting area comprises a fuel cell.
The invention has the beneficial effects that:
the side chain of the covalent organic framework material disclosed by the application has a phosphate group, the phosphate group has moderate dissociation and proton accepting capability, and a wide hydrogen bond network system is easy to construct, so that the covalent organic framework material has excellent proton conductivity; the preparation method of the covalent organic framework material has the advantages of simple synthesis, high yield, mild preparation process and no pollution; the covalent organic framework material can be widely applied to the field of proton conduction.
Drawings
FIG. 1 is an infrared spectrum of the covalent organic framework material prepared in example 1.
Fig. 2 is a solid nmr carbon spectrum of the covalent organic framework material prepared in example 1.
FIG. 3 is an X-ray diffraction pattern of the covalent organic framework material prepared in example 1.
FIG. 4 is a schematic representation of carbon dioxide adsorption stripping of the covalent organic framework material prepared in example 1.
FIG. 5 is a transmission electron microscopy characterization result graph of the covalent organic framework material prepared in example 1.
FIG. 6 is a scanning electron micrograph of a covalent organic framework material prepared according to example 1.
FIG. 7 is a thermogravimetric analysis of the covalent organic framework material prepared in example 1.
Fig. 8 is a contact angle test chart of the covalent organic framework material prepared in example 1.
FIG. 9 is a plot of the AC impedance of the covalent organic framework material prepared in example 1.
Detailed Description
The following examples are included to further illustrate the practice of the invention, but are not intended to limit the practice or protection of the invention. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available through commercial purchase.
Example 1
The specific preparation procedure of the covalent organic framework material of this example is as follows.
1) Synthesis of monomer TBB: 2, 5-dihydroxy-terephthalaldehyde (1660mg, 10.0mmol) and anhydrous K were weighed and mixed 2 CO 3 (5520mg, 40mmol) in a 250mL two-necked flask. After adding ultra-dry acetonitrile (40 mL) and carrying out ultrasonic mixing uniformly, freezing for 15 minutes by using liquid nitrogen, vacuumizing for 10 minutes, introducing argon into the device for 5 minutes, unfreezing by using tap water at room temperature, reciprocating twice, and then refluxing for 1 hour at 100 ℃ under the argon atmosphere. Cooling to room temperature, adding diethyl (3-bromopropyl) phosphonate (5410mg, 21mmol) at liquid nitrogen temperature, repeating the above pumping and ventilating operation twice, refluxing at 100 deg.C under argon atmosphere for 24h, detecting reaction progress by TLC spot plate, cooling to room temperature after reaction, adding acetic acid solution (6 mol. L -1 ) Neutralizing the reaction system, adding DCM for extraction for three times, collecting an organic phase, performing reduced pressure spin drying on the organic phase, and separating and purifying a product through column chromatography, wherein a developing solvent is a mixed solvent of DCM and methanol (the volume ratio is 50. Finally dried in a vacuum oven at 80 ℃ overnight to give the product TBB as a yellow oil (91% yield), the reaction is as follows;
2) Synthesis of DPPA: TBB (4750mg, 9.1mmol) was added to a 250mL round-bottomed flask under an argon atmosphere, and super-dry DCM (50 mL) was added and dissolved with stirring, followed by slow addition of trimethylbromosilane (13920mg, 91mmol) to the system via syringe (50 mL) at 0 ℃. After the addition, the temperature was slowly returned to room temperature and stirred at room temperature for 48 hours. After the reaction is finished, filtering to remove a small amount of black insoluble substances, collecting filtrate, carrying out spin drying to obtain a solid crude product, carrying out recrystallization purification on the product through methanol and water, and finally drying in a vacuum oven at 80 ℃ overnight to obtain a yellow solid product DPPA (yield is 91%), wherein the reaction formula is as follows;
3) Synthesis of TPB-DPPA-COF: a mixed solvent (1 mL, volume ratio of 9) of 1,3, 5-tris (4-aminophenyl) benzene (TPB, 7.1mg, 0.02mmol), DPPA (14.3mg, 0.03mmol), o-dichlorobenzene (o-DCB) and n-butanol (n-BuOH) (1 mL, height 102.0 mm) was weighed in a 10mL ampoule (outer diameter 17.75mm, height 102.0 mm), after ultrasonic mixing uniformly for 3 minutes, acetic acid (0.1mL, 6 mol. L-1) was added as a catalyst, the ampoule was frozen for 5 minutes using liquid nitrogen, then the ampoule was evacuated for 5 minutes, and then thawed three times to completely remove the air in the reaction apparatus. The ampoule bottle was sintered and sealed with a flame spray gun, and then heated in an oven at 120 ℃ for 7 days. After the system is cooled to room temperature, carrying out vacuum filtration on reaction liquid to obtain a filter cake, repeatedly washing the filter cake with DMF and DCM, carrying out Soxhlet extraction on the filter cake with THF for 24h to remove low molecular weight compounds, then collecting solids, and carrying out vacuum drying at 120 ℃ for 12h to obtain dark brown solid powder TPB-DPPA-COF (15.3 mg, yield 84%) with the following reaction formula;
performance test
FIG. 1 is an infrared spectrum of the covalent organic framework material prepared in example 1. Wherein the infrared spectrum testing equipment IS Nicolet IS50-Nicolet Continuum of Thermo Fisher Scientific. As can be seen from fig. 1: in TPB-DPPA-COF, the stretching vibration peak of C = O basically disappears, which reveals that the polymerization reaction is relatively complete and is 1643cm -1 A strong absorption peak is shown indicating the formation of imine bonds C = N. In addition phosphoric acid and ethers in DPPAThe characteristic absorption peak of the bond still remains in the product TPB-DPPA-COF, indicating that the phosphate side chain group is well incorporated into the TPB-DPPA-COF structure. The synthesis gives the expected product.
Fig. 2 is a solid nmr carbon spectrum of the covalent organic framework material prepared in example 1. The apparatus is a JEOL ECZ-400R/M1 type solid nuclear magnetic resonance spectrometer, the probe is a 3.2mm solid probe, the test mode is cross polarization magic angle spinning, and the frequency is 16kHz. As can be seen from fig. 2: in the TPB-DPPA-COF spectrum, the peak at 153.5ppm can be assigned as the characteristic peak of the carbon in imine bond C = N, and the peaks at 13.4, 24.2 and 70.1ppm are respectively assigned as the characteristic peak of the carbon in alkyl chain, which indicates the integrity of the TPB-DPPA-COF structure, and in the lower field, we do not observe the characteristic peak of the aldehyde carbon, which indicates that the condensation reaction is full and the degree of polymerization is very high.
FIG. 3 is an X-ray diffraction pattern of the covalent organic framework material prepared in example 1. Wherein, the testing instrument is a MiniFlex600 diffractometer of Japan science company. The test range is 2.4-45 degrees, and the step size is 0.02 degrees. As can be seen from fig. 3: TPB-DPPA-COF shows stronger diffraction peaks, and the diffraction signal peaks at the peak positions of 3.10 degrees, 5.15 degrees, 5.74 degrees, 7.65 degrees and 9.85 degrees respectively correspond to the crystal faces of (100), (110), (200), (210) and (310) in a simulated AA stacking structure (simulated AA stacking), so that TPB-DPPA-COF is a better crystalline material.
FIG. 4 is a schematic representation of carbon dioxide adsorption stripping of the covalent organic framework material prepared in example 1. Wherein the test instrument is BELSORP-max, the test temperature is 195K, and the 195K condition is realized by respectively using a mixture of dry ice and isopropanol. The samples were subjected to vacuum treatment at 120 ℃ for 48h before testing. The specific surface area of the porous material can be obtained by carbon dioxide adsorption. As can be seen from fig. 4: the desorption curve of the TPB-DPPA-COF has very obvious hysteresis, which shows that the TPB-DPPA-COF has stronger chemical adsorption effect on carbon dioxide, and the specific surface area of the TPB-DPPA-COF can be calculated to be 6.2m through a BET model 2 ·g -1 。
FIG. 5 is a transmission electron microscopy characterization plot of the covalent organic framework material prepared in example 1. Wherein, fig. 5 (a) is a small-magnification transmission electron micrograph of the covalent organic framework material prepared in example 1, the lower right inset of fig. 5 (a) is a Selected Area Electron Diffraction (SAED) micrograph, fig. 5 (b) is a large-magnification transmission electron micrograph of the covalent organic framework material prepared in example 1, and the upper right inset of fig. 5 (b) is a partial enlarged micrograph. The test instrument is a Japanese JEOL company, the model is a JEM-2100F type high-resolution field emission transmission electron microscope, the more microscopic appearance of the sample is characterized, and the test condition is that the acceleration voltage is 200kV. As can be seen from fig. 5 (b): TPB-DPPA-COF is formed by stacking two-dimensional layered planar structures, large light and dark stripe areas can be observed, the distance between TPB-DPPA-COF layers can be calculated to be 0.35nm according to the width between the stripes, and in addition, a diffraction ring which is clearly visible in a selected area electron diffraction pattern (SAED) shows that the TPB-DPPA-COF has the structural characteristic of long-range order.
FIG. 6 is a scanning electron micrograph of a covalent organic framework material prepared according to example 1. Wherein, FIG. 6 (a) is a small-magnification scanning electron micrograph of the covalent organic framework material prepared in example 1; FIG. 6 (b) is a high magnification scanning electron micrograph of the covalent organic framework material prepared in example 1. The testing instrument is a Japanese JEOL company, and the model is JSM-7900F type high-resolution scanning electron microscope to characterize the surface topography of the sample. The test condition is that the accelerating voltage is about 5 kV. As can be seen from FIG. 6, TPB-DPPA-COF is a bulk structure formed by stacking of relatively uniform-sized flakes, which are about 200nm to 300nm in size.
FIG. 7 is a thermogravimetric analysis of the covalent organic framework material prepared in example 1. Wherein the instrument is a German Nasicon company and the model thereof is a TG209F1 type TG thermogravimetric analyzer. The test conditions are that the gas environment is nitrogen, the temperature range is 30-850 ℃, and the heating rate is5 ℃ per minute -1 . As can be seen from FIG. 7, weight loss of TPB-DPPA-COF begins to occur until the temperature rises to 177 ℃, the quality gradually decreases, and the weight of TPB-DPPA-COF is kept at 95% when the temperature reaches 285 ℃, so that the TPB-DPPA-COF has better thermal stability.
Fig. 8 is a contact angle test chart of the covalent organic framework material prepared in example 1. Wherein the testing instrument is a Guangzhou Berotu DSA-X type surface tension instrument, and the testing sample is a TPB-BPTA-COF sheet. As can be seen from FIG. 8, TPB-DPPA-COF has a low water contact angle of 37 degrees, and due to the introduction of alkyl phosphate into the COF skeleton, TPB-DPPA-COF shows excellent hydrophilicity, and provides a very good way for water molecules to enter the TPB-DPPA-COF structure of the material.
FIG. 9 is a plot of the AC impedance of the covalent organic framework material prepared in example 1. Wherein the testing instrument is a British Solartron 1255B type frequency response analyzer, the temperature and the humidity are controlled by a Japanese Espec SH-221 type high-low temperature test box, the testing frequency range is 1 Hz-1 MHz, and the amplitude is50 mV. As can be seen from fig. 9: at 90 ℃ and 98% RH, a semicircular arc having a large radius was exhibited in the high frequency region, and then a straight line having a certain slope was exhibited in the low frequency region, and the resistance R was 205. Omega. As a result of extending the straight line in the opposite direction to intersect the X-axis. Then, the proton conductivity of the TPB-DPPA-COF is 4.96 multiplied by 10 under the condition that the proton conductivity is calculated by a formula through the conductivity -4 S·cm -1 。
The phosphate side chain is introduced to the skeleton of the covalent organic framework material, so that the covalent organic framework material has excellent proton conductivity; the covalent organic framework material disclosed by the application is simple in preparation method and high in yield; the covalent organic framework material disclosed by the application has excellent proton conductivity, and can be applied to the field of proton conduction as a proton conduction material, particularly applied to a fuel cell.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are intended to be included in the scope of the present invention.
Claims (10)
1. A covalent organic framework material, characterized by: the structure of the covalent organic framework material is shown as a formula (I);
in the formula (I), n is selected from positive integers of 1-6.
2. The covalent organic framework material of claim 1, characterized in that: the structure of the covalent organic framework material is shown as a formula (II);
3. the method of preparing a covalent organic framework material according to claim 1 or 2, characterized in that: the method comprises the following steps:
mixing a compound shown in a formula (VI) with a compound shown in a formula (VII) and reacting to obtain the covalent organic framework material;
in the formula (VI), n is selected from a positive integer of 1-6.
4. The production method according to claim 3, characterized in that: the compound shown in the formula (VI) is prepared by a compound shown in the formula (V) through hydrolysis reaction;
wherein R is 1 Selected from C1-C6 alkyl; n is selected from a positive integer from 1 to 6.
5. The method of manufacturing according to claim 4, characterized in that: the compound shown in the formula (V) is prepared by mixing a compound shown in a formula (III) and a compound shown in a formula (IV) and reacting;
in the formula (IV), R 1 Selected from C1-C6 alkyl; n is selected from a positive integer from 1 to 6; x is selected from halogen.
6. The production method according to claim 3, characterized in that: the reaction also comprises adding a catalyst to participate in the reaction.
7. The production method according to claim 3, characterized in that: the molar ratio of the compound shown in the formula (VI) to the compound shown in the formula (VII) is (1-2): 1.
8. the production method according to claim 3, characterized in that: the reaction temperature is 100-140 ℃; the reaction time is 120-216 h.
9. The production method according to claim 3, characterized in that: the solvent for the reaction comprises at least one of halogenated aromatic hydrocarbon solvent and alcohol solvent.
10. Use of the covalent organic framework material of claim 1 or 2 in the field of proton conduction.
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