CN112920357A - Porphyrin-based covalent organic framework material based on metal ion doping and preparation method and application thereof - Google Patents

Porphyrin-based covalent organic framework material based on metal ion doping and preparation method and application thereof Download PDF

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CN112920357A
CN112920357A CN202110110313.2A CN202110110313A CN112920357A CN 112920357 A CN112920357 A CN 112920357A CN 202110110313 A CN202110110313 A CN 202110110313A CN 112920357 A CN112920357 A CN 112920357A
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porphyrin
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贲腾
王婷
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Jilin University
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Abstract

The invention relates to a porphyrin-based covalent organic framework material doped with metal ions, a preparation method and application thereof, and belongs to the technical field of organic framework materials. Solves the problems that the adsorption and separation performance of the covalent organic framework material to carbon dioxide needs to be further improved and the cyclic usability of the covalent organic framework material is poor in the prior art. The repeating structural unit of the porphyrin-based covalent organic framework material based on metal ion doping is shown as a formula I. The porphyrin-based covalent organic framework material based on metal ion doping has high crystallinity, better specific surface area, permanent porosity, good thermal stability and chemical stability, and can absorb gasHas good effects in terms of attachment and separation, and can be recycled.
Figure DDA0002919039130000011

Description

Porphyrin-based covalent organic framework material based on metal ion doping and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic framework materials, and particularly relates to a metal ion doped porphyrin-based covalent organic framework material, a preparation method and application thereof, in particular to application of the metal ion doped porphyrin-based covalent organic framework material in gas adsorption separation.
Background
Carbon dioxide gas is a part of atmosphere (accounting for 0.03% -0.04% of the total volume of the atmosphere) and is abundant in nature, and the generation ways of the carbon dioxide gas are mainly as follows: organic matter (including animal and plant) can release carbon dioxide in the processes of decomposition, fermentation, decay and deterioration. ② carbon dioxide is also released in the combustion process of petroleum, paraffin, coal and natural gas. And thirdly, carbon dioxide is released during the production of chemical products from petroleum and coal. And fourthly, all excrement and humic acid can release carbon dioxide in the processes of fermentation and curing. All animals need to absorb oxygen and spit out carbon dioxide in the breathing process. Greenhouse gases such as carbon dioxide in the atmosphere can radiate long-wave radiation with longer wavelength to the ground after strongly absorbing the ground long-wave radiation, thereby playing a role in heat preservation on the ground. Since the industrial revolution, however, the concentration of greenhouse gases in the atmosphere has been sharply increased due to the emission of large amounts of greenhouse gases such as carbon dioxide by human activities, resulting in an increasing greenhouse effect. The increasing atmospheric greenhouse effect causes global warming, which creates a series of scientific unpredictable global climate problems today. International economic reports on climate change show that if humans maintain today's lifestyle, there is a 50% possible rise in global average air temperature of 4 ℃ by 2100 years. If the global air temperature rises by 4 ℃, glaciers in the south and north poles of the earth melt, the sea level rises, a plurality of island countries and coastal big cities with the most concentrated population in the world 40 face the danger of inundation, the life of tens of millions of people in the world faces crisis, even global ecological balance disorder is generated, and finally large-scale migration and conflict occur in the world. Therefore, the problem of global warming caused by the sharp rise of the concentration of carbon dioxide is not easy to solve, and in the prior art, methods for solving the problem mainly comprise physical/chemical adsorption, low-temperature distillation, temperature change/pressure change adsorption and membrane separation. Among them, the physical/chemical adsorption method is the most commonly used method for removing carbon dioxide.
Covalent organic framework materials (COFs) are an emerging class of porous crystalline materials, have periodic two-dimensional or three-dimensional network structures, and are formed by connecting organic structural units with dynamic covalent bonds. The material has the unique properties of ordered and controllable pore structure, permanent porosity, large specific surface area, post-modification of active groups, high thermal stability, high chemical stability and the like, so that the material has wide application in the fields of gas adsorption and storage, separation, catalysis, sensing, drug delivery, energy storage, photoelectricity and the like. However, in the prior art, the adsorption and separation performance of the covalent organic framework material on carbon dioxide needs to be further improved, and the cyclic usability of the covalent organic framework material is poor.
Disclosure of Invention
The invention aims to provide a porphyrin-based covalent organic framework material based on metal ion doping, and a preparation method and application thereof.
The technical scheme adopted by the invention for realizing the aim is as follows.
The invention provides a porphyrin-based covalent organic framework material based on metal ion doping, wherein a repeating structural unit is shown as a formula I:
Figure BDA0002919039110000031
the invention also provides a preparation method of the porphyrin-based covalent organic framework material based on metal ion doping, which comprises the following steps:
step one, preparing covalent organic framework material
Under the protection of inert atmosphere, uniformly mixing 5,10,15, 20-tetra (tetraaminophenyl) porphyrin, 2, 5-di (4-aminophenyl-1 yl) 1, 4-xylene, an organic solvent and an acetic acid aqueous solution, reacting for 25-75h at the temperature of 140 ℃, cooling to room temperature, washing, and drying in vacuum to obtain a covalent organic framework material;
the molar ratio of the 5,10,15, 20-tetra (tetraaminophenyl) porphyrin to the 2, 5-di (4-aminophenyl-1-yl) 1, 4-xylene is 1: 2;
step two, preparing a porphyrin-based covalent organic framework material based on metal ion doping
Under the protection of inert atmosphere, uniformly mixing the covalent organic framework material obtained in the step one, metal salt and an organic solvent, reacting for 8-72h at the temperature of 100 ℃ and 140 ℃, cooling to room temperature, filtering, washing and drying in vacuum to obtain the porphyrin-based covalent organic framework material doped based on metal ions;
the metal ion of the metal salt is Fe3+、Co2+、Ni2+、Cu2+、Pd2+、Zn2+The mass ratio of the covalent organic framework material to the metal salt is 1 (0.03-0.06).
Preferably, in the first step, 5,10,15, 20-tetra (tetraaminophenyl) porphyrin and 2, 5-bis (4-aminophenyl-1-yl) 1, 4-xylene are ground to be uniformly mixed, and then an organic solvent and an acetic acid aqueous solution are sequentially added to be uniformly mixed under the protection of an inert atmosphere.
Preferably, in the first step, the organic solvent is anhydrous n-butanol and o-dichlorobenzene in a volume ratio of 1:3 in a mixture of two or more.
Preferably, in the first step, the reaction temperature is 120 ℃ and the reaction time is 72 hours.
Preferably, in the first step, the amount of acetic acid is the amount of catalyst; more preferably 0.0012 equivalents.
Preferably, the step one, washing, is to soak in tetrahydrofuran for 12h, repeat for three times, and then soak in acetone for 12h, repeat for three times.
Preferably, in the second step, the metal salt is one or more of ferrous sulfate heptahydrate, cobalt acetate dihydrate, nickel nitrate hexahydrate, copper sulfate pentahydrate, zinc acetate dihydrate and palladium acetate.
Preferably, in the second step, the organic solvent is Dimethylformamide (DMF), methanol (CH)3OH) and Dichloromethane (DCM).
Preferably, in the second step, the reaction temperature is 80 ℃ and the reaction time is 12-24 h.
Preferably, in the second step, the washing is performed by soaking in deionized water for 12 hours, repeating for three times, then soaking in tetrahydrofuran for 12 hours, repeating for three times, then soaking in the organic solvent of the second step for 12 hours, repeating for three times, and finally soaking in acetone for 12 hours, repeating for three times.
Preferably, in the first step and the second step, the reaction is carried out under stirring, and the stirring speed is 800 r/min.
Preferably, in the first and second steps, the inert atmosphere is nitrogen or argon.
Preferably, in the first step and the second step, the drying temperature is 80 ℃ and the drying time is 4-8 h.
The invention also provides the porphyrin-based covalent organic framework material based on metal ion doping for adsorbing CO2、CH4、N2Or H2The use of (1).
The invention also provides the use of the porphyrin-based covalent organic framework material based on metal ion doping for separating N2And CO2Mixed gas of (2), CO2And CH4Mixed gas of (2), CO2And H2The use of one of the mixed gases of (1).
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the porphyrin-based covalent organic framework material based on metal ion doping provided by the invention adopts a four-node and two-node construction unit connection to obtain a two-dimensional microporous covalent organic framework, then different metal ions are doped into the covalent organic framework material to obtain the porphyrin-based covalent organic framework material based on metal ion doping, the operation is simple and easy, and the prepared porphyrin-based covalent organic framework material based on metal ion doping has high crystallinity, better specific surface area, permanent porosity, good thermal stability and chemical stability.
The porphyrin-based covalent organic framework material based on metal ion doping provided by the invention has good effects on gas adsorption and separation, and can be recycled.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction Pattern (PXRD) of the covalent organic framework material of example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the covalent organic framework material and the iron ion doped covalent organic framework material of example 1 of the present invention.
FIG. 3 is a Fourier Transform Infrared (FTIR) spectrum of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, 1, 2-bis (4, 4-aldehydiphenyl) acetylene and a covalent organic framework material according to example 1 of the present invention.
FIG. 4 is a Fourier Transform Infrared (FTIR) spectrum of a covalent organic framework material and iron ion doped covalent organic framework material of example 1 of the present invention.
FIG. 5 is a thermogravimetric analysis of the covalent organic framework material of example 1 of the present invention.
FIG. 6 is a thermogravimetric analysis of the iron ion doped covalent organic framework material of example 1 of the present invention.
FIG. 7 shows N at 77K for a covalent organic framework material according to example 1 of the present invention2Adsorption profile (a) and pore size distribution (b).
FIG. 8 shows the N at 77K of the iron ion doped covalent organic framework material prepared in example 1 of the present invention2Adsorption profile (a) and pore size distribution (b).
FIG. 9 shows a pair of CO covalent organic frameworks in example 1 of the present invention2、CH4、H2And N2Is at a temperature of 298K and a pressure of 1bar (a) and at a temperature of 273K and a pressure of 1bar (b).
FIG. 10 is a representation of the iron ion doped covalent organic framework material vs. CO prepared in example 12、CH4、H2And N2Is at a temperature of 298K and a pressure of 1bar (a) and at a temperature of 273K and a pressure of 1bar (b).
FIG. 11 shows the adsorption separation curve of the covalent organic framework material of example 1 of the present invention for a mixed gas, where (a) is N2And CO2And (b) is CO2And CH4And (c) is CO2And H2The temperature was 298K and the pressure was 1 bar.
FIG. 12 shows the adsorption separation curve of Fe ion doped covalent organic framework material on mixed gas in example 1 of the present invention, wherein (a) is N2And CO2And (b) is CO2And CH4And (c) is CO2And H2The temperature was 298K and the pressure was 1 bar.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and not to limit the claims to the invention.
The porphyrin-based covalent organic framework material based on metal ion doping has a repeating structural unit shown as a formula I:
Figure BDA0002919039110000071
the preparation method of the porphyrin-based covalent organic framework material based on metal ion doping comprises the following steps:
step one, preparing covalent organic framework material
Under the protection of inert atmosphere, uniformly mixing 5,10,15, 20-tetra (tetraaminophenyl) porphyrin, 2, 5-di (4-aminophenyl-1 yl) 1, 4-xylene, an organic solvent and an acetic acid aqueous solution, reacting for 25-75h at the temperature of 140 ℃, cooling to room temperature, washing, and drying in vacuum to obtain a covalent organic framework material;
step two, preparing a porphyrin-based covalent organic framework material based on metal ion doping
And (2) under the protection of inert atmosphere, uniformly mixing the covalent organic framework material obtained in the step one, metal salt and organic solvent, reacting for 8-72h at the temperature of 140 ℃, cooling to room temperature, filtering, washing and drying in vacuum to obtain the porphyrin-based covalent organic framework material based on metal ion doping.
The preparation method of the porphyrin-based covalent organic framework material based on metal ion doping has the following reaction equation:
Figure BDA0002919039110000081
in the above technical scheme, in the first step, the step of uniformly mixing 5,10,15, 20-tetra (tetraaminophenyl) porphyrin, 2, 5-bis (4-aminophenyl-1-yl) 1, 4-xylene, an organic solvent and an acetic acid aqueous solution is preferably performed by grinding 5,10,15, 20-tetra (tetraaminophenyl) porphyrin and 2, 5-bis (4-aminophenyl-1-yl) 1, 4-xylene until the mixture is uniform, and then sequentially adding the organic solvent and the acetic acid aqueous solution to be uniformly mixed under the protection of an inert atmosphere.
In the technical scheme, in the first step, the molar ratio of 5,10,15, 20-tetra (tetraaminophenyl) porphyrin to 2, 5-di (4-aminophenyl-1-yl) 1, 4-xylene is 1: 2; the organic solvent is preferably a mixture of anhydrous n-butyl alcohol and o-dichlorobenzene according to a volume ratio of 1: 3; acetic acid is used as a catalyst, preferably in an amount of 0.0012 equivalents (i.e., 0.0012:1 molar ratio to 5,10,15, 20-tetrakis (tetraaminophenyl) porphyrin).
According to the technical scheme, in the first step, the reaction temperature is preferably 120 ℃, and the time is preferably 72 hours; preferably, the reaction is carried out with stirring at a rate of 800 r/min.
In the above technical scheme, in the first step, the concentrations of 5,10,15, 20-tetra (tetraaminophenyl) porphyrin, 2.5-bis (4-aminophenyl-1 yl) 1, 4-xylene and acetic acid in the organic solvent are not particularly limited, and may serve as a solvent, for example, the concentration of 5,10,15, 20-tetra (tetraaminophenyl) porphyrin is 0.088mol/L, and the concentration of 2.5-bis (4-aminophenyl-1 yl) 1, 4-xylene is 0.044 mol/L.
In the above technical scheme, in the first step, the concentration of the acetic acid aqueous solution is not particularly limited, and is preferably 6 mol/L.
In the above technical solution, in the step one, the inert atmosphere is preferably nitrogen or argon.
In the technical scheme, in the first step, the drying temperature is preferably 80 ℃, and the drying time is preferably 4-8 h.
In the above technical scheme, in the step one, the washing is preferably performed by firstly soaking in tetrahydrofuran for 12h and then soaking in acetone for 12 h.
In the second step, the metal ion of the metal salt is Fe3+、Co2+、Ni2+、Cu2+、 Pd2+、Zn2+Preferably the metal salt is one or more of ferrous sulfate heptahydrate, cobalt acetate dihydrate, nickel nitrate hexahydrate, copper sulfate pentahydrate, zinc acetate dihydrate and palladium acetate; the organic solvent is preferably Dimethylformamide (DMF), methanol (CH)3One or more of OH) and Dichloromethane (DCM), and the dosage of the organic solvent is not particularly limited and can play a role of a solvent; the mass ratio of the covalent organic framework material to the metal salt is 1 (0.03-0.06).
In the technical scheme, in the second step, the reaction temperature is preferably 80 ℃, and the reaction time is preferably 12-24 h.
In the above technical scheme, in the second step, the reaction is preferably carried out under stirring, and the stirring speed is preferably 800 r/min.
In the above technical solution, in the second step, the inert atmosphere is preferably nitrogen or argon.
In the technical scheme, in the second step, the drying temperature is preferably 80 ℃, and the drying time is preferably 4-8 h.
In the above technical scheme, in the second step, the washing is preferably performed by soaking in deionized water for 12 hours, repeating for three times, then soaking in tetrahydrofuran for 12 hours, repeating for three times, then soaking in the organic solvent of the second step for 12 hours, repeating for three times, and finally soaking in acetone for 12 hours, repeating for three times.
The porphyrin-based covalent organic framework material based on metal ion doping can adsorb CO2、 CH4、N2Or H2The application is as follows.
The porphyrin-based covalent organic framework material based on metal ion doping can separate N2And CO2Mixed gas of (2), CO2And CH4Mixed gas of (2), CO2And H2The mixed gas of (1) is used.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified. In the present invention, room temperature is defined as 25 ℃.
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Preparation of porphyrin-based covalent organic framework material based on metal ion doping:
adding 2-di (4, 4-aldehyde phenyl) acetylene (20.6mg, 0.088mmol) and 5,10,15, 20-tetra (4-aminophenyl) porphyrin (29.6mg, 0.044mmol) into a mortar, grinding until the mixture is uniformly mixed (20min), adding the obtained mixture into a glass tube, charging nitrogen for 3 times, removing air in the tube, sequentially adding 0.25mL of anhydrous n-butyl alcohol, 0.75mL of o-dichlorobenzene and 0.2mL (6mol/L) of acetic acid aqueous solution into the glass tube under the protection of nitrogen, pumping out the gas in the tube to ensure that the tube is in a vacuum state, fusing to 15cm long by big fire (aiming at preventing the glass tube from being cracked during heating (if residual gas exists in the tube, the tube is easy to be cracked by high temperature), easily controlling the pressure and the volume of the tube to be consistent by 15cm long), cooling to room temperature, placing the tube in an oven at 120 ℃ for reaction for 72h, and cooling the obtained solid to room temperature, soaking in tetrahydrofuran for 12h, repeating for three times, soaking in acetone for 12h, repeating for three times, removing residual solvent and unreacted precursor, and vacuum-drying at 80 ℃ for 6h to obtain the covalent organic framework material.
And step two, weighing 0.06g of the covalent organic framework material prepared in the step one and 0.1g of ferrous sulfate heptahydrate, dissolving in 30mL of DMF, stirring at 80 ℃ (rotating speed of 800r/min) under the protection of nitrogen for 48h, cooling to room temperature, filtering, collecting precipitate, soaking in deionized water for 12h, repeating for three times, soaking in tetrahydrofuran for 12h, repeating for three times, soaking in DMF for 12h, repeating for three times, soaking in acetone for 12h, repeating for three times, and vacuum drying at 80 ℃ for 6h to obtain dark purple powder, namely the covalent organic framework material doped with iron ions.
The iron ion doped covalent organic framework material was obtained by Inductively Coupled Plasma (ICP) analysis with an iron ion incorporation of 1.69 wt%.
Example 2
Preparation of porphyrin-based covalent organic framework material based on metal ion doping:
step one, the same as the step one of the embodiment 1;
and step two, weighing 0.06g of the covalent organic framework material prepared in the step one and 0.1g of cobalt nitrate hexahydrate, dissolving in 30mL of methanol, stirring at 80 ℃ (rotating speed of 800r/min) under the protection of nitrogen, reacting for 12h, cooling to room temperature, filtering, collecting precipitate, soaking in deionized water for 12h, repeating for three times, soaking in tetrahydrofuran for 12h, repeating for three times, soaking in methanol for 12h, repeating for three times, soaking in acetone for 12h, repeating for three times, and vacuum-drying at 80 ℃ for 6h to obtain dark purple powder, namely the cobalt ion-doped covalent organic framework material.
The cobalt ion-doped covalent organic framework material was obtained by Inductively Coupled Plasma (ICP) analysis with a cobalt ion incorporation of 1.53 wt%.
Example 3
Preparation of porphyrin-based covalent organic framework material based on metal ion doping:
step one, the same as the step one of the embodiment 1;
and step two, weighing 0.06g of the covalent organic framework material prepared in the step one and 0.1g of nickel nitrate hexahydrate, dissolving in 30mL of dichloromethane, stirring at 80 ℃ (the rotating speed is 800r/min) under the protection of nitrogen, reacting for 12 hours, cooling to room temperature, filtering, collecting precipitates, sequentially soaking in deionized water for 12 hours, repeating for three times, then soaking in tetrahydrofuran for 12 hours, repeating for three times, then soaking in dichloromethane for 12 hours, repeating for three times, finally soaking in acetone for 12 hours, repeating for three times, and vacuum-drying at 80 ℃ for 6 hours to obtain dark purple powder, namely the nickel ion-doped covalent organic framework material.
The nickel ion-doped covalent organic framework material was obtained by Inductively Coupled Plasma (ICP) analysis with a nickel ion incorporation of 1.50 wt%.
Example 4
Preparation of porphyrin-based covalent organic framework material based on metal ion doping:
step one, the same as the step one of the embodiment 1;
and step two, weighing 0.06g of the covalent organic framework material prepared in the step one and 0.1g of copper sulfate pentahydrate, dissolving in 30mL of a mixed solvent of methanol and DCM (volume ratio is 1:1), stirring at 80 ℃ (rotation speed of 800r/min) under the protection of nitrogen, reacting for 12h, cooling to room temperature, filtering, collecting precipitate, soaking in deionized water for 12h, repeating for three times, then soaking in tetrahydrofuran for 12h, repeating for three times, soaking in DCM for 12h, repeating for three times, finally soaking in acetone for 12h, repeating for three times, and vacuum drying at 80 ℃ for 6h to obtain dark purple powder, namely the covalent organic framework material doped with copper ions.
The copper ion-doped covalent organic framework material was obtained by Inductively Coupled Plasma (ICP) analysis with a copper ion incorporation of 1.49 wt%.
Example 5
Preparation of porphyrin-based covalent organic framework material based on metal ion doping:
step one, the same as the step one of the embodiment 1;
and step two, weighing 0.06g of the covalent organic framework material prepared in the step one and 0.1g of zinc acetate dihydrate, dissolving in 20mL of DMF, stirring at 80 ℃ (rotating speed of 800r/min) under the protection of nitrogen, reacting for 12h, cooling to room temperature, filtering, collecting precipitates, sequentially soaking in deionized water for 12h, repeating for three times, then soaking in tetrahydrofuran for 12h, repeating for three times, then soaking in DMF for 12h, repeating for three times, finally soaking in acetone for 12h, repeating for three times, and vacuum drying at 80 ℃ for 6h to obtain dark purple powder, namely the covalent organic framework material doped with zinc ions.
The zinc ion doped covalent organic framework material was obtained by Inductively Coupled Plasma (ICP) analysis with a zinc ion incorporation of 1.62 wt%.
Example 6
Preparation of porphyrin-based covalent organic framework material based on metal ion doping:
step one, the same as the step one of the embodiment 1;
and step two, weighing 0.06g of the covalent organic framework material prepared in the step one and 0.1g of palladium acetate, dissolving in 30mL of dichloromethane, stirring at 80 ℃ (the rotating speed is 800r/min) under the protection of nitrogen, reacting for 12h, cooling to room temperature, filtering, collecting precipitates, sequentially soaking in deionized water for 12h, repeating for three times, soaking in tetrahydrofuran for 12h, repeating for three times, soaking in dichloromethane for 12h, repeating for three times, soaking in acetone for 12h, repeating for three times, and vacuum-drying at 80 ℃ for 6h to obtain dark purple powder, namely the covalent organic framework material doped with palladium ions.
The palladium ion-doped covalent organic framework material was analyzed by Inductively Coupled Plasma (ICP) to obtain a palladium ion incorporation of 1.61 wt%.
The covalent organic framework material and the iron-doped covalent organic framework material of example 1 were examined.
FIG. 1 is an X-ray diffraction Pattern (PXRD) of the covalent organic framework material of example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of a covalent organic framework material and an iron ion doped covalent organic framework material of example 1 of the present invention, wherein curve 1 is the X-ray diffraction pattern of the covalent organic framework material and curve 2 is the X-ray diffraction pattern of the iron ion doped covalent organic framework material; comparing curve 1 and curve 2, it can be seen that the covalent organic framework material of the present invention retains the framework integrity as well as crystallinity before and after incorporation of the metal ion.
FIG. 3 shows the results of example 1 of the present inventionFourier Transform Infrared (FTIR) spectra of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, 1, 2-bis (4, 4-carboxaldehyde phenyl) acetylene and a covalent organic framework material; wherein, the curve 1, the curve 2 and the curve 3 respectively represent 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin (N-H: 3000-3500 cm)-1Bimodal), 1, 2-bis (4, 4-carboxaldehyde phenyl) acetylene (C ═ O: 1725cm-1) And a covalent organic framework material (C ═ N: 1622cm-1) An infrared spectrum of (1).
Fig. 4 is a Fourier Transform Infrared (FTIR) spectrum of an iron ion doped covalent organic framework material of example 1 of the present invention. Curve 1 is the fourier transform infrared spectrum of the iron ion doped covalent organic framework material and curve 2 is the fourier transform infrared spectrum of the pure covalent organic framework material. As can be seen from fig. 4, the structure of the covalent organic framework material after doping with iron ions is not changed compared to the covalent organic framework material.
FIG. 5 is a thermogravimetric analysis of the covalent organic framework material of example 1 of the present invention. As can be seen from FIG. 5, the weight loss of the material is about 440 ℃, which indicates that the covalent organic framework material has good thermal stability.
FIG. 6 is a thermogravimetric analysis of the iron ion doped covalent organic framework material of example 1 of the present invention. As can be seen from fig. 6, the weight loss of 5 wt% of the material is around 350 ℃, which indicates that the thermal stability of the covalent organic framework material after being doped with iron ions can be maintained.
FIG. 7 shows N at 77K for a covalent organic framework material according to example 1 of the present invention2Adsorption profile (a) and pore size distribution (b). As can be seen from FIG. 7, (a) is a typical type I curve showing the microporous character of the material, and the specific surface area is 374.9cm2g-1And (b) the pore size is calculated according to the density functional theory to be 1.55nm and is basically consistent with the simulated pore size.
FIG. 8 shows the N at 77K of the iron ion doped covalent organic framework material prepared in example 1 of the present invention2Adsorption profile (a) and pore size distribution (b). As can be seen from FIG. 8, (a) is a typical type I curve showing the microporous character of the material, and the specific surface area is 220.3cm2g-1The pore size is 1.35nm according to the calculation of a density functional theory; compared with the covalent organic framework material, the covalent organic framework material doped with iron ions has small difference of pore diameter, and the reduction of the specific surface area is probably caused by residual iron ions in the pore canal and partial structural collapse of the surface of the material.
The covalent organic framework material obtained in example 1 and the iron-doped covalent organic framework material were subjected to gas (CO)2、CH4、H2、N2) And (5) performing adsorption test. The test method comprises the following steps: firstly, 60mg of covalent organic framework material (iron-doped covalent organic framework material) is weighed and filled into an adsorption tube, vacuum degassing is carried out for 8h at the temperature of 80 ℃, and then different gas adsorptions at the temperature of 298K and 273K are respectively tested at 1 bar. FIG. 9 shows a pair of CO covalent organic frameworks in example 1 of the present invention2、CH4、H2And N2Is at a temperature of 298K and a pressure of 1bar (a) and at a temperature of 273K and a pressure of 1bar (b). FIG. 10 is a representation of the iron ion doped covalent organic framework material vs. CO prepared in example 12、CH4、H2And N2Is at a temperature of 298K and a pressure of 1bar (a) and at a temperature of 273K and a pressure of 1bar (b).
The adsorption separation capacity of the covalent organic framework material and the iron-doped covalent organic framework material on the mixed gas was tested by a Breakthrough mass spectrometer. The test method comprises the following steps: firstly, the covalent organic framework material (iron-doped covalent organic framework material) is vacuumized and degassed at 80 ℃ for 8h, then the material is put into a penetrating column with the length of 10cm, and two mixed gases (respectively: CO)2And CH4、CO2And H2、CO2And N2The flow ratio is 1:1), and the balance is about 4 hours for testing. FIG. 11 shows the adsorption separation curve of the covalent organic framework material of example 1 of the present invention for a mixed gas, where (a) is N2And CO2And (b) is CO2And CH4And (c) is CO2And H2The temperature was 298K and the pressure was 1 bar. FIG. 12 is a graph showing the adsorptive separation of a mixed gas by the iron ion-doped covalent organic framework material of example 1 of the present invention,(a) is N2And CO2And (b) is CO2And CH4And (c) is CO2And H2The temperature was 298K and the pressure was 1 bar.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. The porphyrin-based covalent organic framework material based on metal ion doping is characterized in that a repeating structural unit is shown as a formula I:
Figure FDA0002919039100000011
2. the method for preparing a metal ion doped porphyrin based covalent organic framework material according to claim 1, comprising the following steps:
step one, preparing covalent organic framework material
Under the protection of inert atmosphere, uniformly mixing 5,10,15, 20-tetra (tetraaminophenyl) porphyrin, 2, 5-di (4-aminophenyl-1 yl) 1, 4-xylene, an organic solvent and an acetic acid aqueous solution, reacting for 25-75h at the temperature of 140 ℃, cooling to room temperature, washing, and drying in vacuum to obtain a covalent organic framework material;
the molar ratio of the 5,10,15, 20-tetra (tetraaminophenyl) porphyrin to the 2, 5-di (4-aminophenyl-1-yl) 1, 4-xylene is 1: 2;
step two, preparing a porphyrin-based covalent organic framework material based on metal ion doping
Under the protection of inert atmosphere, uniformly mixing the covalent organic framework material obtained in the step one, metal salt and an organic solvent, reacting for 8-72h at the temperature of 100 ℃ and 140 ℃, cooling to room temperature, filtering, washing and drying in vacuum to obtain the porphyrin-based covalent organic framework material doped based on metal ions;
the metal ion of the metal salt is Fe3+、Co2+、Ni2+、Cu2+、Pd2+、Zn2+The mass ratio of the covalent organic framework material to the metal salt is 1 (0.03-0.06).
3. The method according to claim 2, wherein in the first step, 5,10,15, 20-tetrakis (tetraaminophenyl) porphyrin and 2, 5-bis (4-aminophenyl-1-yl) 1, 4-xylene are ground to be uniformly mixed, and then an organic solvent and an aqueous acetic acid solution are sequentially added to be uniformly mixed under the protection of an inert atmosphere.
4. The method according to claim 2, wherein the amount of acetic acid used in the first step is a catalytic amount.
5. The method for preparing a porphyrin-based covalent organic framework material doped with metal ions according to claim 2, wherein in the second step, the metal salt is one or more of ferrous sulfate heptahydrate, cobalt acetate dihydrate, nickel nitrate hexahydrate, copper sulfate pentahydrate, zinc acetate dihydrate and palladium acetate.
6. The method for preparing a metal ion doped porphyrin based covalent organic framework material according to claim 2,
in the step one and the step two, the reaction is carried out under stirring, and the stirring speed is 800 r/min;
in the first step, the reaction temperature is 120 ℃, and the reaction time is 72 hours;
in the second step, the reaction temperature is 80 ℃, and the reaction time is 12-24 h.
7. The method for preparing a metal ion doped porphyrin based covalent organic framework material according to claim 2,
in the first step, the organic solvent is a mixture of anhydrous n-butyl alcohol and o-dichlorobenzene according to a volume ratio of 1: 3;
in the second step, the organic solvent is one or more of dimethylformamide, methanol and dichloromethane.
8. The method for preparing a metal ion doped porphyrin based covalent organic framework material according to claim 2,
the washing step I comprises the steps of soaking in tetrahydrofuran for 12 hours, repeating for three times, soaking in acetone for 12 hours, and repeating for three times;
in the second step, the washing is to soak in deionized water for 12 hours and repeat for three times, then soak in tetrahydrofuran for 12 hours and repeat for three times, then soak in the organic solvent of the second step for 12 hours and repeat for three times, and finally soak in acetone for 12 hours and repeat for three times.
In the step one and the step two, the drying temperature is 80 ℃, and the drying time is 4-8 h.
9. The method of claim 1, wherein the metal ion-doped porphyrin-based covalent organic framework material is used for adsorbing CO2、CH4、N2Or H2The use of (1).
10. The method of claim 1 for separating N based on metal ion doped porphyrin based covalent organic framework material2And CO2Mixed gas of (2), CO2And CH4Mixed gas of (2), CO2And H2The use of one of the mixed gases of (1).
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