CN110951107A - Controllable preparation of PI aerogel material and photocatalytic reduction of CO2In (1) - Google Patents

Controllable preparation of PI aerogel material and photocatalytic reduction of CO2In (1) Download PDF

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CN110951107A
CN110951107A CN201911274779.5A CN201911274779A CN110951107A CN 110951107 A CN110951107 A CN 110951107A CN 201911274779 A CN201911274779 A CN 201911274779A CN 110951107 A CN110951107 A CN 110951107A
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aerogel
reduction
photocatalytic
aerogel material
gel
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CN110951107B (en
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赵新富
伊希斌
张晶
刘本学
刘晓婵
沈晓冬
吴建华
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New Material Institute of Shandong Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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Abstract

The invention relates to controllable preparation of a PI aerogel material and CO photocatalytic reduction2The application of the preparation method aims at the current PI aerogel photocatalytic CO2The problems existing in the process firstly propose that PI aerogel materials with different energy band structures are prepared by adjusting the concentration and the polymerization degree of the polymer, and the prepared PI aerogel is used for carrying out photocatalytic reduction on CO2And (4) testing the performance to obtain high photocatalytic efficiency, and preferably selecting the PI catalyst with the optimal energy band structure. The PI aerogel is prepared by crosslinking DABA and BPDA with different concentrations and contents, so that the suitable photocatalytic reduction of CO is obtained2The optimum band structure of (3).

Description

Controllable preparation of PI aerogel material and photocatalytic reduction of CO2In (1)
Technical Field
The invention belongs to the field of preparation of organic aerogel materials, and particularly relates to a preparation method of a PI aerogel composite material and photocatalytic reduction of CO2Application is carried out.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, climate change caused by the "greenhouse effect" has become a global environmental problem. Greenhouse gas CO as a major contributor to global warming2It is mainly produced in the production process of petrochemical industry, ceramics, cement, fermentation, steel and electric power industry and other industries. (Angew. chem. int. Ed.2019,58,5492) is currently in CO2China is the second world's second largest country after the united states alone in terms of emissions. To mitigate the global warming effect, CO must be reduced2The discharge and the effective treatment and utilization are carried out. Introducing CO2The catalytic conversion is not only beneficial to eliminating the atmospheric greenhouse effect, but also can synthesize useful products such as formic acid, formaldehyde and the like, thereby realizing the circulation of carbon resources and the development of energy economy. (appl.surf.sci.2019,498,143899) currently the most promising application is photocatalytic conversion, since light energy does not cause environmental pollution. Thus, photocatalytic reduction of CO2The synthesis of organic chemicals has great significance for environmental protection and energy utilization. To achieve this transformation, many studies have been carried out, CO2Inert and thermodynamically unfavorable factors of (1) cause CO2The catalyst prepared by the traditional method has the problems of low conversion rate, more byproducts, low product selectivity and the like. (chem. rev.2014,114,1709) therefore, the development of a new high-efficiency catalyst was CO2One of the core problems of the catalytic conversion process route. Non-metallic polymer Polyimide (PI) gas with unique structure in a plurality of catalystsThe gel is used as a novel photocatalyst, and has the advantages that: the paint can absorb visible light, has good thermal stability and chemical stability, large specific surface area, no toxicity, rich raw material sources, simple preparation and forming process, no metal element, easy recovery and no secondary pollution to the environment.
The PI aerogel is an organic mesoporous material, has extremely high porosity and extremely large specific surface area, and the porosity of the PI aerogel can reach 99.8 percent. On the one hand, a high specific surface area and a porous structure are advantageous for providing more CO2Adsorption sites, promoting CO coupling2Adsorption of (3). (chem.eng.j.2019,368,618) on the other hand, the porous structure of the aerogel can reduce the reflection of light on the surface of the catalyst, prolong the propagation time of light in the catalyst, and increase the photon utilization rate of the catalyst, thereby improving the visible light absorption efficiency. Is suitable for reducing CO2The Conduction Band (CB) edge of the photocatalyst of (2) must be larger than the CO2The redox potential of the reduction is more negative (e.g., -0.61eV vs. sce for HCOOH product, -0.52eV vs. sce for CO product, etc.) and the VB edge should be more positive than the redox potential of water oxidation (in aqueous solution with pH 7.0 at 0.817eV vs. sce). PI polymer has large energy gap and catalyzes CO2Efficiency is still to be improved. The PI precursors are various in types, and PI with different energy band structures can be prepared by regulating and controlling experimental conditions. For example Chu topic group [19-21]Different precursors are utilized to synthesize PI, and the PI energy band structures prepared by different precursors are different, the polymerization degrees of the same precursors are different, the band gaps are different, and the efficiency of photocatalytic degradation of pollutants is different. It can be seen. However, the PI polymer has large forbidden band width and catalyzes CO2Efficiency is still to be improved.
Disclosure of Invention
Aiming at catalyzing CO by using current PI aerogel2In the aspect of problems, 3, 5-diaminobenzoic acid (DABA) and biphenyl tetracarboxylic dianhydride (BPDA) are selected as precursors for synthesizing PI, and PI aerogel with different band gaps is obtained by adjusting the concentration and polymerization degree of the precursors. Further reduction of CO by photocatalysis2Experiments show that the catalyst is suitable for catalyzing CO2The aerogel catalyst of (1) having an optimum band structure. The preparation method of the invention is simpleThe prepared aerogel material is light in weight and excellent in flexibility, and is expected to be made into appliances and used in industrial production.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a controllable preparation method of a PI aerogel material comprises the following steps:
3, 5-diaminobenzoic acid and biphenyl tetracarboxylic dianhydride are used as precursors of reaction, a sol-gel method is adopted to prepare PI wet gel in the presence of a cross-linking agent, and the PI wet gel is aged and dried to prepare the PI aerogel material.
The method utilizes the excellent molecular design and experimental controllability of the PI polymer to regulate and control the energy band structure of the PI, and obtains the high-efficiency catalytic reduction CO2The catalyst has important practical significance for solving the current greenhouse effect.
The type and the polymerization degree of the precursor can adjust the energy band structure of the finally synthesized PI, so that in some embodiments, the concentration of the precursor is 5-10 wt%, and the polymerization degree is 15-25, so as to obtain the high-efficiency catalytic reduction CO2The catalyst of (1).
In some embodiments, the crosslinker is 1,3, 5-tris (4-aminophenoxy) benzene (TAB).
In some examples, a dehydrating agent (acetic anhydride) and a catalyst (pyridine) are also added during the sol-gel process to prepare the PI wet gel.
In some embodiments, the aging comprises the specific steps of:
①, gelling and aging the PI wet gel for 12-14 h, and soaking the gel in 75% by volume of N-methylpyrrolidone ethanol solution for 24-28 h;
② soaking the wet aerogel in ① for 24-28 h in 25% N-methyl pyrrolidone by volume;
③, aging ② medium-humidity aerogel in an ethanol solution for 24-28 h, and repeating liquid changing for 3 times.
In some embodiments, the drying is ethanol supercritical drying, preferably, the specific conditions are: and carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 8.5-9.0 MPa.
The invention also provides a PI aerogel material prepared by any one of the methods.
The invention also provides a method for photocatalytic reduction of CO2The method for screening the PI aerogel material comprises the following steps:
the PI aerogel with different energy band structures is used for photocatalytic reduction of CO2In the process, the catalytic reduction CO is screened out according to the test result2The optimal band structure of PI aerogel.
In some embodiments, the photocatalytic reduction of CO2In the process, a continuous flow system reactor is adopted for carrying out reduction experiments, a 300W xenon lamp (with an additional optical filter of 420 nm) is used as a light source, and a mass spectrometer and a gas chromatograph are used for analyzing product components.
The invention also provides the application of the PI aerogel material in photocatalytic reduction of CO2The use of (1).
The invention has the beneficial effects that:
(1) the invention aims at the current PI aerogel photocatalytic CO2The problems existing in the process firstly propose that PI aerogel materials with different energy band structures are prepared by adjusting the concentration and the polymerization degree of the polymer, and the prepared PI aerogel is used for carrying out photocatalytic reduction on CO2Performance testing, after 6h of visible light irradiation, the CH of the PI aerogel with the band gap of 2.4eV4The yield was 0.69. mu. mol g-1h-1. The PI aerogel is prepared by crosslinking DABA and BPDA with different concentrations and contents, so that the suitable photocatalytic reduction of CO is obtained2The optimum band structure of (3).
(2) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is an optical photograph and an SEM photograph of a PI aerogel obtained in example 1; wherein, a is an optical picture of the PI aerogel, and b is an SEM picture of the PI aerogel.
FIG. 2 is a structural diagram of the band gap of PI aerogel obtained in example 1.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, the prior art PI aerogel catalysts have a band gap structure that is not suitable for catalytic reduction of CO2To a problem of (a).
The invention aims to provide a preparation method of PI aerogel with different energy band structures.
The invention also aims to provide a PI aerogel composite material.
The invention also aims to provide the PI aerogel as a photocatalyst for reducing CO2The use of (1).
In order to achieve the above purpose, the invention specifically discloses the following technical scheme:
the invention discloses a preparation method of PI aerogel with different energy band structures, which comprises the following steps:
s1, taking DABA and BPDA with different concentrations and different polymerization degrees as reaction precursors, adding a cross-linking agent, preparing PI wet gel by a sol-gel method, aging, and performing ethanol supercritical drying to obtain a PI aerogel material; the concentration of the precursor is 5-10 wt%, and the polymerization degree is 15-25;
s2, applying the prepared PI aerogel with different energy band structures to photocatalytic reduction of CO2In the process, a continuous flow system reactor is adopted for carrying out reduction experiments, a 300W xenon lamp (with an additional optical filter of 420 nm) is used as a light source, and a mass spectrometer and a gas chromatograph are used for analyzing product components. The suitable catalytic reduction CO is selected according to the test result2The optimal band structure of PI aerogel.
In a second aspect of the invention, a PI aerogel material prepared by the preparation method is disclosed.
In a third aspect of the invention, the PI aerogel composites are disclosed as CO2Application in photocatalysts;
in the invention, DABA and BPDA are used as precursors for synthesizing PI, and PI polymer aerogel with different energy band structures can be obtained by adjusting the proportion of DABA and BPDA, so that the adjustment of various band gaps is realized. Selecting prepared PI with different energy band structures for photocatalytic reduction of CO2And (4) obtaining high-efficiency photocatalytic efficiency through experiments, and further preferably selecting the PI aerogel with the optimal energy band structure.
In view of the above, in one embodiment of the present invention, a method for preparing PI aerogel composites with different energy band structures is provided, which includes the following steps:
s1, taking DABA and BPDA with different concentrations and different polymerization degrees as reaction precursors, adding a cross-linking agent, acetic anhydride and pyridine, preparing PI wet gel by using a chemical imide method, aging, and performing ethanol supercritical drying to obtain a PI aerogel material; the concentration of the precursor is 5-10 wt%, and the polymerization degree is 15-25;
s2, applying the prepared PI aerogel with different energy band structures to photocatalytic reduction of CO2In the process, a continuous flow system reactor is adopted for carrying out reduction experiments, a 300W xenon lamp (with an additional optical filter of 420 nm) is used as a light source, and a mass spectrometer and a gas chromatograph are used for analyzing product components. The suitable catalytic reduction CO is selected according to the test result2The optimal band structure of PI aerogel.
Wherein the content of the first and second substances,
in the step S1, the concentration of the precursor is 5-10 wt%;
in step S1, the polymerization degree of the wet gel is 15-25;
in step S1, the crosslinking agent is 1,3, 5-tris (4-aminophenoxy) benzene (TAB);
in step S1, the aging treatment specifically includes:
① gelling and aging the PI wet gel for 12h, and soaking the gel in 75% N-methylpyrrolidone (NMP) ethanol solution for 24 h;
② soaking wet aerogel ① in 25% NMP ethanol solution for 24 h;
③ the wet aerogel ② was aged in ethanol solution for 24h and the solution was changed 3 times.
In step S1, the ethanol supercritical drying method specifically includes the following conditions: carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 8.5-9.0 MPa;
in another embodiment of the invention, the PI aerogel material prepared by the preparation method is provided.
In yet another embodiment of the present invention, the PI aerogel composite is provided as CO2Application of a photocatalyst;
the present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
1. Preparation of PI aerogels
(1) Dissolving 1.704g of DABA monomer in 50mL of NMP, and stirring for dissolving to obtain a mixed solution; 2.273g of BPDA was then added to the solution and dissolved with stirring, 24.7mL of 0.066g of TAB was added rapidly, and after stirring well, 61.8mmol of 5.8mL of acetic anhydride and 61.8mmol of 5.0mL of pyridine were added in this order to give a PI wet gel.
(2) And (2) gelling and aging the PI wet gel obtained in the step (1) for 12h, soaking the gel in 75% NMP ethanol solution for 24h, then soaking the gel in 25% NMP ethanol solution for 24h, finally aging the gel in ethanol solution for 24h, and repeating the steps for 3 times. And carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 9.0MPa, and keeping the temperature for 2 hours to obtain the PI aerogel.
2. Photocatalytic reduction of CO by PI aerogel2Performance of
Photocatalytic CO using a continuous flow system reactor2Reduction experiment, using 300W xenon lamp (plus 420nm filter) as light source, by mass spectrometer and gas chromatograph analysis of product components. The test result shows that CH of the prepared PI aerogel is CH after the PI aerogel is irradiated for 6 hours by visible light4The yield was 0.69. mu. mol g-1h-1。
FIG. 1 is an optical photograph and an SEM photograph of the PI aerogel prepared in the present example; fig. 2 is a structure diagram of the band gap of the PI aerogel prepared in this example.
Example 2
1. Preparation of PI aerogels
(1) Dissolving 1.704g of DABA monomer in 33mL of NMP, and stirring for dissolving to obtain a mixed solution; 2.273g of BPDA was then added to the solution and dissolved with stirring, 16.6mL of 0.066g of TAB was added rapidly, and after stirring well, 61.8mmol of 4.0mL of acetic anhydride and 61.8mmol of 3.4mL of pyridine were added in this order to give a PI wet gel.
(2) And (2) gelling and aging the PI wet gel obtained in the step (1) for 12h, soaking the gel in 75% NMP ethanol solution for 24h, then soaking the gel in 25% NMP ethanol solution for 24h, finally aging the gel in ethanol solution for 24h, and repeating the steps for 3 times. And carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 9.0MPa, and keeping the temperature for 2 hours to obtain the PI aerogel.
2. Photocatalytic reduction of CO by PI aerogel2Performance of
Photocatalytic CO using a continuous flow system reactor2Reduction experiment, using 300W xenon lamp (plus 420nm filter) as light source, by mass spectrometer and gas chromatograph analysis of product components. And (4) characterizing the photocatalytic efficiency of the prepared PI aerogel through a test result.
Example 3
1. Preparation of PI aerogels
(1) Dissolving 1.704g of DABA monomer in 66mL of NMP, and stirring for dissolving to obtain a mixed solution; 2.273g of BPDA was then added to the solution and dissolved with stirring, and 33.2mL of 0.066g of TAB was added rapidly, after stirring well, 61.8mmol of 8.0mL of acetic anhydride and 61.8mmol of 6.8mL of pyridine were added in this order to give a PI wet gel.
(2) And (2) gelling and aging the PI wet gel obtained in the step (1) for 12h, soaking the gel in 75% NMP ethanol solution for 24h, then soaking the gel in 25% NMP ethanol solution for 24h, finally aging the gel in ethanol solution for 24h, and repeating the steps for 3 times. And carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 9.0MPa, and keeping the temperature for 2 hours to obtain the PI aerogel.
2. Photocatalytic reduction of CO by PI aerogel2Performance of
Photocatalytic CO using a continuous flow system reactor2Reduction experiment, using 300W xenon lamp (plus 420nm filter) as light source, by mass spectrometer and gas chromatograph analysis of product components. And (4) characterizing the photocatalytic efficiency of the prepared PI aerogel through a test result.
Example 4
1. Preparation of PI aerogels
(1) Dissolving 2.272g of DABA monomer in 50mL of NMP, and stirring for dissolving to obtain a mixed solution; 3.0304g of BPDA was then added to the solution and dissolved with stirring, and 24.7mL of 0.088g of TAB was added rapidly, followed by stirring to homogeneity and the addition of 82.4mmol of 5.8mL acetic anhydride followed by 82.4mmol of 5.0mL pyridine to give a PI wet gel.
(2) And (2) gelling and aging the PI wet gel obtained in the step (1) for 12h, soaking the gel in 75% NMP ethanol solution for 24h, then soaking the gel in 25% NMP ethanol solution for 24h, finally aging the gel in ethanol solution for 24h, and repeating the steps for 3 times. And carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 9.0MPa, and keeping the temperature for 2 hours to obtain the PI aerogel.
2. Photocatalytic reduction of CO by PI aerogel2Performance of
Photocatalytic CO using a continuous flow system reactor2Reduction experiment, using 300W xenon lamp (plus 420nm filter) as light source, by mass spectrometer and gas chromatograph analysis of product components. And (4) characterizing the photocatalytic efficiency of the prepared PI aerogel through a test result.
Example 5
1. Preparation of PI aerogels
(1) Dissolving 2.84g of DABA monomer in 50mL of NMP, and stirring for dissolving to obtain a mixed solution; 3.788g of BPDA was then added to the solution and dissolved with stirring, 24.7mL of 0.11g of TAB was added rapidly, and after stirring well, 103mmol of 5.8mL of acetic anhydride and 103mmol of 5.0mL of pyridine were added in this order to give a PI wet gel.
(2) And (2) gelling and aging the PI wet gel obtained in the step (1) for 12h, soaking the gel in 75% NMP ethanol solution for 24h, then soaking the gel in 25% NMP ethanol solution for 24h, finally aging the gel in ethanol solution for 24h, and repeating the steps for 3 times. And carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 9.0MPa, and keeping the temperature for 2 hours to obtain the PI aerogel.
2. Photocatalytic reduction of CO by PI aerogel2Performance of
Photocatalytic CO using a continuous flow system reactor2Reduction experiment, using 300W xenon lamp (plus 420nm filter) as light source, by mass spectrometer and gas chromatograph analysis of product components. And (4) characterizing the photocatalytic efficiency of the prepared PI aerogel through a test result.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.

Claims (10)

1. A controllable preparation method of a PI aerogel material is characterized by comprising the following steps:
3, 5-diaminobenzoic acid and biphenyl tetracarboxylic dianhydride are used as precursors of reaction, a sol-gel method is adopted to prepare PI wet gel in the presence of a cross-linking agent, and the PI wet gel is aged and dried to prepare the PI aerogel material.
2. The controllable preparation method of the PI aerogel material of claim 1, wherein the concentration of the precursor is 5-10 wt%.
3. The process for the controlled preparation of a PI aerogel material according to claim 1, wherein the cross-linking agent is 1,3, 5-tris (4-aminophenoxy) benzene.
4. The controllable preparation method of PI aerogel material as claimed in claim 1, wherein acetic anhydride and pyridine are added during the process of preparing PI wet gel by sol-gel method.
5. The controllable preparation method of the PI aerogel material as claimed in claim 1, wherein the aging comprises the following steps:
①, gelling and aging the PI wet gel for 12-14 h, and soaking the gel in 75% by volume of N-methylpyrrolidone ethanol solution for 24-28 h;
② soaking the wet aerogel in ① for 24-28 h in 25% N-methyl pyrrolidone by volume;
③, aging ② medium-humidity aerogel in an ethanol solution for 24-28 h, and repeating liquid changing for 3 times.
6. The controllable preparation method of the PI aerogel material as claimed in claim 1, wherein the drying is ethanol supercritical drying method, preferably, the specific conditions are as follows: and carrying out ethanol supercritical drying at the temperature of 275 ℃ and the pressure of 8.5-9.0 MPa.
7. A PI aerogel material prepared by the method of any one of claims 1-6.
8. Photocatalytic reduction of CO2The method for screening the PI aerogel material is characterized by comprising the following steps:
use of the PI aerogel with different energy band structures as defined in claim 7 for photocatalytic CO reduction2In the process, the catalytic reduction CO is screened out according to the test result2The optimal band structure of PI aerogel.
9. Photocatalytic reduction of CO as in claim 82The PI aerogel material screening method is characterized in that the CO is subjected to photocatalytic reduction2In the process, a continuous flow system reactor is adopted for carrying out reduction experiments, a 300W xenon lamp is used as a light source, and a mass spectrometer and a gas chromatograph are used for analyzing product components.
10. Use of the PI aerogel material of claim 7 in photocatalytic CO reduction2The use of (1).
CN201911274779.5A 2019-12-12 2019-12-12 Controllable preparation of PI aerogel material and photocatalytic reduction of CO 2 In (1) Active CN110951107B (en)

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