CN109261203B - Covalent triazine organic polymer photocatalyst capable of efficiently producing methane, and preparation and application thereof - Google Patents
Covalent triazine organic polymer photocatalyst capable of efficiently producing methane, and preparation and application thereof Download PDFInfo
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 60
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000004298 light response Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 101710205482 Nuclear factor 1 A-type Proteins 0.000 description 4
- 101710170464 Nuclear factor 1 B-type Proteins 0.000 description 4
- 102100022162 Nuclear factor 1 C-type Human genes 0.000 description 4
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- 101710140810 Nuclear factor 1 X-type Proteins 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013311 covalent triazine framework Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000000696 methanogenic effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 108010018842 CTF-1 transcription factor Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
Abstract
The invention discloses a covalent triazine organic polymer photocatalyst capable of efficiently producing methane, and a preparation method and application thereof, belonging to the technical field of preparation of photocatalytic materials. The catalyst has good visible light response, can efficiently realize the photocatalytic reduction of carbon dioxide into methane by visible light, and has the advantages of simple and convenient annealing method, low production cost and good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to a covalent triazine organic polymer photocatalyst capable of efficiently producing methane, and preparation and application thereof.
Background
The mass combustion of fossil fuels results in atmospheric CO2The concentration is continuously increased, which causes a series of environmental problems such as global warming and the like, CO2The emission reduction and conversion technology become the current research focus. The semiconductor photocatalysis technology can utilize inexhaustible solar energy in the nature to convert CO into CO2Reducing the carbon-containing fuel into methane and other carbon-containing fuels, realizing the carbon cycle in the nature, and being an effective method for solving the problems of greenhouse effect, energy shortage and the like. However, CO2The molecules have a very stable linear structure and require extremely high activation energy and appropriate catalysts to convert them into available carbon resources. Therefore, the development of novel efficient visible light catalytic reduction CO2Is CH4Are the hot spots of current research.
Among the novel photocatalysts that have been reported, covalent triazine organic polymers (CTFs) are a class of organic polymers composed of triazinesThe organic polymer formed by connecting organic functional groups on the ring has visible light response and proper energy band structure. Meanwhile, as a nitrogen-rich covalent organic framework, CTFs have good CO2Adsorption capacity, which is beneficial to converting the carbon into available carbon resources. However, CTFs still have the problems of poor light absorption capacity, high photocarrier recombination rate and the like, and further application of CTFs in the field of photocatalysis is restricted. Research shows that the annealed photocatalytic semiconductor material can reduce surface defects and remove ammonia (NH) adsorbed on the surface3) More pores can be formed, so that the specific surface area is increased, more active sites are exposed, and the photocatalytic activity of the photocatalyst can be improved.
Disclosure of Invention
The invention aims to provide a covalent triazine organic polymer photocatalyst capable of efficiently producing methane, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a covalent triazine organic polymer photocatalyst capable of efficiently producing methane is synthesized by mixing a rodlike silicon dioxide serving as a template with a covalent triazine organic polymer and adopting an annealing method. The catalyst has good visible light response and can be used for the reaction of photocatalytic reduction of carbon dioxide into methane.
The preparation method of the covalent triazine organic polymer photocatalyst comprises the following steps:
(1) preparation of covalent triazine organic polymers:
slowly adding 40 mL of trifluoromethanesulfonic acid into 5.12 g of terephthalonitrile at the temperature of 0 ℃, replacing an oil bath, heating to 30 ℃, standing for 3 days, stirring the obtained solid, washing and filtering with 160 mL of dichloromethane with 100-; refluxing the obtained solid precipitate with methanol at 80-100 deg.C for 10-30 h, refluxing with dichloromethane at 60-80 deg.C for 10-30 h, collecting solid, and vacuum drying at 80 deg.C for 12 h to obtain covalent triazine organic polymer;
(2) preparation of rod-shaped silica:
adding 0.7-0.8 g of triblock copolymer F127 and 1.8-2.0 g of hexadecyl trimethyl ammonium bromide into 180 mL of ammonia water solution with the concentration of 0.9-1wt.%, dropwise adding 6-8 mL of ethyl orthosilicate under the stirring condition, fully reacting for 2-4 h, washing with water, refluxing in a mixed solution of hydrochloric acid and ethanol for 2-4 h, and adding water into the obtained solid to prepare a suspension with the concentration of 25-30 mg/mL; then adding 60 mL of the suspension into 1200 mL of 5 mg/mL polyetherimide solution, reacting for 2-4 h at 90 ℃, washing the obtained solid for several times after cooling to room temperature, drying in vacuum, and calcining for 2-4 h at 550 ℃ to obtain rod-shaped silicon dioxide;
(3) preparation of covalent triazine organic polymer photocatalyst:
respectively weighing 0.1-0.2 g of rod-shaped silicon dioxide and 0.3-0.4 g of covalent triazine organic polymer, mixing the rod-shaped silicon dioxide and the covalent triazine organic polymer in 10-20 mL of distilled water, and heating and evaporating to dryness under the condition of oil bath at 70-90 ℃; grinding the obtained solid, placing the ground solid in a tube furnace, and carrying out heat treatment for 1-2 h at the temperature of 400-550 ℃ in a nitrogen atmosphere; after cooling to room temperature, placing the solid sample in 10wt.% hydrofluoric acid solution, stirring for 4 h at 65-85 ℃, washing with water, centrifuging for several times, and drying at 60 ℃; and refluxing the dried sample with methanol at 80-100 ℃ for 10-30 h, collecting the solid, and drying at 60 ℃ for 12 h to obtain the covalent triazine organic polymer photocatalyst.
The covalent triazine organic polymer photocatalyst is applied to efficient visible light photocatalytic reduction of carbon dioxide into methane.
The invention has the following remarkable advantages:
(1) the covalent triazine organic polymer is annealed for the first time to prepare the covalent triazine organic polymer visible light photocatalyst capable of efficiently producing methane;
(2) the preparation method is simple and convenient, has low production cost and good application prospect;
(3) the photocatalyst obtained by the invention has good catalytic activity, can realize the photocatalytic reduction of carbon dioxide into methane by visible light, and has good practical value and application prospect.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of a covalent triazine organic polymer and a covalent triazine organic polymer photocatalyst obtained in examples 1-4;
FIG. 2 is a graph of the UV-VIS diffuse reflectance spectra of covalent triazine organic polymers and the covalent triazine organic polymer photocatalysts obtained in examples 1-4;
FIG. 3 is a graph comparing the visible light photocatalytic reduction of carbon dioxide to methane for covalent triazine organic polymer photocatalysts obtained in examples 1-4.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Preparation of covalent triazine organic polymers: slowly adding 40 mL of trifluoromethanesulfonic acid into 5.12 g of terephthalonitrile at the temperature of 0 ℃, changing an oil bath, heating to 30 ℃, standing for 3 days, stirring the obtained solid, washing and filtering with 160 mL of dichloromethane, washing with ammonia water for several times, adding 200 mL of ammonia water, fully stirring for 12 hours, washing with water, centrifuging to neutrality, and washing with methanol for one time; the resulting solid precipitate was refluxed with methanol at 90 ℃ for 10 h, then with dichloromethane at 70 ℃ for 10 h, the solid was collected and dried under vacuum at 80 ℃ for 12 h to give the covalent triazine organic polymer, which was designated as CTF-1.
Preparation of rod-shaped silica: adding 0.738 g of triblock copolymer F127 and 1.8 g of hexadecyl trimethyl ammonium bromide into 180 mL of ammonia water solution with the concentration of 0.9wt.%, dropwise adding 6 mL of ethyl orthosilicate under the stirring condition, fully reacting for 4 hours, then washing with water for several times, refluxing for 4 hours in a mixed solution of hydrochloric acid and ethanol (1: 20, v/v), and adding water into the obtained solid to prepare a suspension with the concentration of 25 mg/mL; and then adding 60 mL of the suspension into 1200 mL of 5 mg/mL polyetherimide solution, reacting for 4 h at 90 ℃, cooling to room temperature, washing the obtained solid with water for a plurality of times, drying in vacuum, and calcining for 2 h at 550 ℃ to obtain the rod-shaped silicon dioxide.
Example 1 preparation of a covalent triazine organic polymer photocatalyst with high efficiency for methane production
Respectively weighing 0.1 g of rod-shaped silicon dioxide and 0.3 g of covalent triazine organic polymer, mixing the rod-shaped silicon dioxide and the covalent triazine organic polymer in 20 mL of distilled water, and heating the mixture under the condition of oil bath at 90 ℃ until the water is evaporated to dryness; grinding the obtained solid, placing the ground solid in a tube furnace, and carrying out heat treatment for 2 h at 400 ℃ in a nitrogen atmosphere; after cooling to room temperature, placing the solid sample in 10wt.% hydrofluoric acid solution, stirring for 4 h at 85 ℃, washing with water, centrifuging for several times, and drying at 60 ℃; and refluxing the dried sample with methanol at 90 ℃ for 10 h, collecting the solid, and drying at 60 ℃ for 12 h to obtain the covalent triazine organic polymer photocatalyst capable of efficiently producing methane, which is recorded as CTF-400.
Example 2 preparation of a covalent triazine organic Polymer photocatalyst with high efficiency for methane production
Respectively weighing 0.1 g of rod-shaped silicon dioxide and 0.3 g of covalent triazine organic polymer, mixing the rod-shaped silicon dioxide and the covalent triazine organic polymer in 20 mL of distilled water, and heating the mixture under the condition of oil bath at 90 ℃ until the water is evaporated to dryness; grinding the obtained solid, placing the ground solid in a tube furnace, and carrying out heat treatment for 2 h at 450 ℃ in a nitrogen atmosphere; after cooling to room temperature, placing the solid sample in 10wt.% hydrofluoric acid solution, stirring for 4 h at 85 ℃, washing with water, centrifuging for several times, and drying at 60 ℃; and refluxing the dried sample with methanol at 90 ℃ for 10 h, collecting the solid, and drying at 60 ℃ for 12 h to obtain the covalent triazine organic polymer photocatalyst capable of efficiently producing methane, which is recorded as CTF-450.
Example 3 preparation of a highly efficient methanogenic covalent triazine organic polymer photocatalyst
Respectively weighing 0.1 g of rod-shaped silicon dioxide and 0.3 g of covalent triazine organic polymer, mixing the rod-shaped silicon dioxide and the covalent triazine organic polymer in 20 mL of distilled water, and heating the mixture under the condition of oil bath at 90 ℃ until the water is evaporated to dryness; grinding the obtained solid, placing the ground solid in a tube furnace, and carrying out heat treatment for 2 h at 500 ℃ in a nitrogen atmosphere; after cooling to room temperature, placing the solid sample in 10wt.% hydrofluoric acid solution, stirring for 4 h at 85 ℃, washing with water, centrifuging for several times, and drying at 60 ℃; and refluxing the dried sample with methanol at 90 ℃ for 10 h, collecting the solid, and drying at 60 ℃ for 12 h to obtain the covalent triazine organic polymer photocatalyst capable of efficiently producing methane, which is recorded as CTF-500.
Example 4 preparation of a covalent triazine organic Polymer photocatalyst with high efficiency for methane production
Respectively weighing 0.1 g of rod-shaped silicon dioxide and 0.3 g of covalent triazine organic polymer, mixing the rod-shaped silicon dioxide and the covalent triazine organic polymer in 20 mL of distilled water, and heating the mixture under the condition of oil bath at 90 ℃ until the water is evaporated to dryness; grinding the obtained solid, placing the ground solid in a tube furnace, and carrying out heat treatment for 2 h at 550 ℃ in a nitrogen atmosphere; after cooling to room temperature, placing the solid sample in 10wt.% hydrofluoric acid solution, stirring for 4 h at 85 ℃, washing with water, centrifuging for several times, and drying at 60 ℃; and refluxing the dried sample with methanol at 90 ℃ for 10 h, collecting the solid, and drying at 60 ℃ for 12 h to obtain the covalent triazine organic polymer photocatalyst capable of efficiently producing methane, which is recorded as CTF-550.
Performance testing
FIG. 1 is a Fourier transform infrared spectrum of a covalent triazine organic polymer and the covalent triazine organic polymer photocatalyst obtained in examples 1-4. As can be seen from the figure, the photocatalyst samples obtained in examples 1-4 exhibited characteristic absorption peaks substantially consistent with the parent sample, indicating that the annealed covalent triazine organic polymer did not alter its triazine host framework structure.
FIG. 2 is a graph of the UV-Vis diffuse reflectance spectra of covalent triazine organic polymers and the covalent triazine organic polymer photocatalysts obtained in examples 1-4. It can be found from the figure that, compared with the parent sample, the annealed photocatalyst sample has a new absorption band in the visible light range, so that the light absorption range of the catalyst is widened, and the light absorption performance of the catalyst is improved.
The catalyst dosage is 10 mg, a 300W xenon lamp is used as a light source, and the light source is filtered by an optical filter to ensure incident lightThe reaction system is triethylamine and water, the reaction device is vacuumized and is introduced with carbon dioxide, and activity test of visible light photocatalytic reduction of carbon dioxide into methane is carried out. FIG. 3 is a graph comparing the visible light photocatalytic reduction of carbon dioxide to methane for covalent triazine organic polymers and the covalent triazine organic polymers obtained in examples 1-4. As can be seen from FIG. 3, the activity of the precursor sample was low, while the methanogenic activity of the photocatalyst sample obtained by annealing was improved to various degrees, wherein the photocatalyst sample CTF-450 obtained by annealing at 450 ℃ exhibited the highest visible light photocatalytic reduction of CO2Is the activity of methane.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. The application of a covalent triazine organic polymer photocatalyst in visible light photocatalytic reduction of carbon dioxide to methane is characterized in that: the covalent triazine organic polymer photocatalyst is synthesized by mixing rod-shaped silicon dioxide serving as a template with a covalent triazine organic polymer and adopting an annealing method; the preparation method of the covalent triazine organic polymer photocatalyst comprises the following steps:
(1) preparation of covalent triazine organic polymers:
slowly adding 40 mL of trifluoromethanesulfonic acid into 5.12 g of terephthalonitrile at the temperature of 0 ℃, replacing an oil bath, heating to 30 ℃, standing for 3 days, stirring the obtained solid, washing and filtering with 160 mL of dichloromethane with 100-; refluxing the obtained solid precipitate with methanol at 80-100 deg.C for 10-30 h, refluxing with dichloromethane at 60-80 deg.C for 10-30 h, collecting solid, and vacuum drying at 80 deg.C for 12 h to obtain covalent triazine organic polymer;
(2) preparation of rod-shaped silica:
adding 0.7-0.8 g of triblock copolymer F127 and 1.8-2.0 g of hexadecyl trimethyl ammonium bromide into 180 mL of ammonia water solution with the concentration of 0.9-1wt.%, dropwise adding 6-8 mL of ethyl orthosilicate under the stirring condition, fully reacting for 2-4 h, washing with water, refluxing in a mixed solution of hydrochloric acid and ethanol for 2-4 h, and adding water into the obtained solid to prepare a suspension with the concentration of 25-30 mg/mL; then adding 60 mL of the suspension into 1200 mL of 5 mg/mL polyetherimide solution, reacting for 2-4 h at 90 ℃, cooling to room temperature, washing the obtained solid with water, drying in vacuum, and calcining for 2-4 h at 550 ℃ to obtain rod-shaped silicon dioxide;
(3) preparation of covalent triazine organic polymer photocatalyst:
respectively weighing 0.1-0.2 g of rod-shaped silicon dioxide and 0.3-0.4 g of covalent triazine organic polymer, mixing the rod-shaped silicon dioxide and the covalent triazine organic polymer in 10-20 mL of distilled water, and heating and evaporating to dryness under the condition of oil bath at 70-90 ℃; grinding the obtained solid, placing the ground solid in a tube furnace, and carrying out heat treatment for 1-2 h at the temperature of 400-550 ℃ in a nitrogen atmosphere; after cooling to room temperature, placing the solid sample in 10wt.% hydrofluoric acid solution, stirring for 4 h at 65-85 ℃, washing with water, centrifuging, and drying at 60 ℃; and refluxing the dried sample with methanol at 80-100 ℃ for 10-30 h, collecting the solid, and drying at 60 ℃ for 12 h to obtain the covalent triazine organic polymer photocatalyst.
2. Use according to claim 1, characterized in that: the volume ratio of the hydrochloric acid to the ethanol in the mixed solution in the step (2) is 1: 20.
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| CN103240119A (en) * | 2013-05-13 | 2013-08-14 | 福州大学 | Chirality graphite phase carbon nitride polymer semiconductor photocatalyst |
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| WO2018110817A1 (en) * | 2016-12-15 | 2018-06-21 | 국민대학교산학협력단 | Covalently bonded triazine structure-based heterogeneous carbonylation catalyst, and method for manufacture lactone using same |
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| CN104607231A (en) * | 2015-02-16 | 2015-05-13 | 江苏理工学院 | Carbon nitride photocatalyst with three-dimensional ordered macroporous structure and preparation method of carbon nitride photocatalyst |
| CN106732723A (en) * | 2015-02-16 | 2017-05-31 | 江苏理工学院 | The preparation method of the carbon nitride photocatalyst with three-dimensional ordered macroporous structure |
| CN105126908A (en) * | 2015-08-24 | 2015-12-09 | 福州大学 | Sulfur-doped covalent triazine organic polymer visible photocatalyst, and preparation method and application thereof |
| WO2018110817A1 (en) * | 2016-12-15 | 2018-06-21 | 국민대학교산학협력단 | Covalently bonded triazine structure-based heterogeneous carbonylation catalyst, and method for manufacture lactone using same |
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