CN116273162B - Composite photocatalytic material and preparation method thereof - Google Patents
Composite photocatalytic material and preparation method thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002071 nanotube Substances 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005917 acylation reaction Methods 0.000 claims abstract description 11
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims abstract description 11
- OUYSIVYIKXCLTF-UHFFFAOYSA-N [C].S1C=CC=C1 Chemical compound [C].S1C=CC=C1 OUYSIVYIKXCLTF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 13
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 abstract description 7
- 229960004989 tetracycline hydrochloride Drugs 0.000 abstract description 7
- 238000001782 photodegradation Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 12
- 239000004098 Tetracycline Substances 0.000 description 11
- 235000019364 tetracycline Nutrition 0.000 description 11
- 150000003522 tetracyclines Chemical class 0.000 description 11
- 229960002180 tetracycline Drugs 0.000 description 8
- 229930101283 tetracycline Natural products 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229940040944 tetracyclines Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 amino carbon nano tube Chemical compound 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- B01J31/0215—Sulfur-containing compounds
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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
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to the technical field of photocatalysis, in particular to a composite photocatalytic material and a preparation method thereof. The photocatalytic material is formed by loading thiophene-carbon nitride on a carbon bromide nano tube, wherein the carbon bromide nano tube is formed by an acylation reaction of an aminated carbon nano tube and 2-bromoisobutyryl bromide, and the thiophene-carbon nitride is formed by thermal copolymerization of urea and 2-thiophenecarboxaldehyde on the surface of the carbon bromide nano tube. The composite photocatalytic material prepared by the invention can realize the photodegradation rate of 94.1% for 30mg/L tetracycline hydrochloride, and the photodegradation rate of the carbon nitride prepared directly by urea under the same condition for the tetracycline hydrochloride is only 18.5%.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a composite photocatalytic material and a preparation method thereof.
Background
Tetracyclines have been widely used for the prevention and treatment of bacterial infections in humans and animals, however, more than 70% of tetracyclines are excreted and released into the environment through human and animal feces and urine, resulting in serious water and soil pollution, and the high hydrophilicity and low volatility of tetracyclines further exacerbate pollution, and in recent years, photocatalysis has become a promising advanced technology for the removal of antibiotics in water due to their energy saving, low cost, high efficiency, etc.
Carbon Nitride (CN) has been widely used for photocatalysis, however, original CN still has defects of insufficient optical absorption, rapid charge recombination, lack of active sites, and the like, resulting in limited photocatalytic activity. Because of its inherent conjugated electron system, the charge separation in CN is uncontrolled and will therefore result in a higher photon-generated carrier recombination rate. Accordingly, there have been many efforts to improve the separation efficiency between photogenerated electrons and holes, in which the construction of the donor-acceptor (D-a) configuration induces an internal electric field that will promote the generation of free holes and electrons, and the difference in electron affinity will enhance intramolecular charge transfer, thereby driving electrons on the donor unit to the acceptor unit. Thus, holes and electrons are effectively separated on the donor unit and the acceptor unit, facilitating separation of photogenerated carriers.
Chinese patent CN201910909857.8 discloses a D-a photocatalyst based on carbon nitride nanotubes, and preparation method and application thereof. In this system, g-C 3 N 4 The carbon ring acts as an electron donor, and the D-A type carbon nitride-based photocatalyst is successfully constructed by using a supermolecule self-assembly method. However, the radicals playing an important role in the photocatalytic degradation process mainly come from the reduction of electrons on the LUMO of CN, and the introduction of electron acceptors leads to a decrease in LUMO energy in CN, which is detrimental to the production of active species.
Disclosure of Invention
In view of the above, the present invention provides a composite photocatalytic material and a preparation method thereof, so as to solve the above-mentioned problems.
Based on the above object, the present invention provides a composite photocatalytic material, wherein the photocatalytic material is formed by loading thiophene-carbon nitride with carbon bromide nanotubes, the carbon bromide nanotubes are formed by acylation reaction of aminated carbon nanotubes and 2-bromoisobutyryl bromide, and the thiophene-carbon nitride is formed by thermal copolymerization of urea and 2-thiophenecarboxaldehyde on the surface of the carbon bromide nanotubes.
Preferably, the amino group content of the aminated carbon nanotube is 0.3-0.8wt%.
Preferably, the inner diameter of the aminated carbon nano tube is 2-4nm, the length is 50-100 mu m, and the specific surface area is 200-500m 2 /g。
The invention further provides a preparation method of the composite photocatalytic material, which comprises the following steps:
s1: adding an aminated carbon nano tube, 2-bromoisobutyryl bromide and triethylamine into N, N-dimethylformamide, carrying out an acylation reaction in ice water bath, washing after the reaction is finished, and drying to obtain a brominated carbon nano tube;
s2: mixing 2-thiophenecarboxaldehyde, urea and carbon bromide nano tube, placing in an alumina crucible, calcining under the atmosphere of argon, cooling after calcining, washing and drying to obtain the composite photocatalytic material.
Preferably, the mass ratio of the aminated carbon nanotube, the 2-bromoisobutyryl bromide, the triethylamine and the N, N-dimethylformamide in the step S1 is 20-50:5-15:10-50:300-500.
Preferably, the acylation reaction in the step S1 is carried out for 10-18h.
Preferably, in the step S2, the mass ratio of the 2-thiophenecarboxaldehyde, the urea and the brominated carbon nano tube is 0.1-0.3:1-2.5:10-15.
Preferably, the calcining conditions in the step S2 are as follows: heating to 550-600 ℃ at a heating rate of 2 ℃/min, and calcining for 5-6h.
The invention has the beneficial effects that:
according to the invention, the thiophene-carbon nitride structure is generated on the carbon bromide nano tube in situ, so that the compactness of the thiophene-carbon nitride and the carbon bromide nano tube on the space structure is promoted, the electron transfer is facilitated, the electron donor of a thiophene group and the electron acceptor of a bromine atom are built outside a molecule of the carbon nitride, and the imine bond and the carbon nano tube are taken as bridges, so that the simultaneous electron transfer inside and outside the molecule is realized, and the separation of electron and hole is accelerated.
The invention realizes the high-efficiency degradation of 30mg/L tetracycline hydrochloride under visible light, adopts a 20nm cut-off filter to degrade the tetracycline solution for 60min under a 50W Xe lamp, can realize the photodegradation rate of 94.1% for 30mg/L tetracycline hydrochloride, and the photodegradation rate of the tetracycline hydrochloride by carbon nitride prepared directly from urea under the same condition is only 18.5%.
Drawings
FIG. 1 is a graph showing the performance of the products of examples 1-3, comparative examples 1-4 in degrading tetracycline according to the present invention.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1
S1: adding 20g of an aminated carbon nano tube, 5g of 2-bromoisobutyryl bromide and 10g of triethylamine into 300g of N, N-dimethylformamide, carrying out an acylation reaction in an ice water bath for 10 hours, washing after the reaction is finished, and drying to obtain the brominated carbon nano tube;
s2: mixing 0.1g of 2-thiophenecarboxaldehyde, 1g of urea and 10g of carbon bromide nano tube, placing into an alumina crucible, calcining under the atmosphere of argon, heating to 550 ℃ at the heating rate of 2 ℃/min, calcining for 5 hours, cooling after the calcining is finished, washing and drying to obtain the composite photocatalytic material.
Example 2
S1: adding 35g of an aminated carbon nano tube, 10g of 2-bromoisobutyryl bromide and 25g of triethylamine into 400g of N, N-dimethylformamide, and carrying out an acylation reaction in an ice water bath for 14h, washing and drying after the reaction is finished to obtain the brominated carbon nano tube;
s2: mixing 0.2g of 2-thiophenecarboxaldehyde, 1.8g of urea and 12g of carbon bromide nano tube, placing into an alumina crucible, calcining under the atmosphere of argon, heating to 570 ℃ at the heating rate of 2 ℃/min, calcining for 5.5h, cooling after the calcining is finished, washing and drying to obtain the composite photocatalytic material.
Example 3
S1: adding 50g of amino carbon nano tube, 15g of 2-bromo isobutyryl bromide and 50g of triethylamine into 500g of N, N-dimethylformamide, and carrying out acylation reaction in ice water bath for 18h, washing and drying after the reaction is finished to obtain brominated carbon nano tube;
s2: mixing 0.3g of 2-thiophenecarboxaldehyde, 2.5g of urea and 15g of carbon bromide nano tube, placing into an alumina crucible, calcining under the atmosphere of argon, heating to 600 ℃ at the heating rate of 2 ℃/min, calcining for 6 hours, cooling after the calcining is finished, washing and drying to obtain the composite photocatalytic material.
Comparative example 1
S1: adding 35g of an aminated carbon nano tube, 10g of 2-bromoisobutyryl bromide and 25g of triethylamine into 400g of N, N-dimethylformamide, and carrying out an acylation reaction in an ice water bath for 14h, washing and drying after the reaction is finished to obtain the brominated carbon nano tube;
s2: mixing 1.8g of urea and 12g of carbon bromide nano tube, placing the mixture into an alumina crucible, calcining the mixture in an argon atmosphere, heating the mixture to 570 ℃ at a heating rate of 2 ℃/min, calcining the mixture for 5.5 hours, cooling the mixture after the calcining is finished, and washing and drying the mixture to obtain the composite photocatalytic material.
Comparative example 2
Mixing 0.2g of 2-thiophenecarboxaldehyde, 1.8g of urea and 12g of aminated carbon nano tube, placing into an alumina crucible, calcining under the atmosphere of argon, heating to 570 ℃ at the heating rate of 2 ℃/min, calcining for 5.5h, cooling after the calcining is finished, washing and drying to obtain the composite photocatalytic material.
Comparative example 3
S2: mixing 1.8g of urea and 12g of aminated carbon nanotubes, placing the mixture into an alumina crucible, calcining the mixture in an argon atmosphere, heating the mixture to 570 ℃ at a heating rate of 2 ℃/min, calcining the mixture for 5.5 hours, cooling the mixture after the calcining is finished, and washing and drying the mixture to obtain the composite photocatalytic material.
Comparative example 4
And (3) placing 1.8g of urea into an alumina crucible, calcining under the atmosphere of argon, heating to 570 ℃ at the heating rate of 2 ℃/min, calcining for 5.5 hours, cooling after the calcining is finished, and washing and drying to obtain the composite photocatalytic material.
Photocatalytic degradation of tetracycline experiments: 10mg of the catalyst sample was dispersed in a tetracycline solution (20 mL,30 mg/L), and the mixed suspension was continuously stirred under dark conditions for half an hour to reach adsorption-desorption equilibrium, and the tetracycline solution was degraded under a 50W Xe lamp with a 20nm cut-off filter for 60min, and the tetracycline concentration was measured with a Hach DR420 ultraviolet-visible spectrophotometer.
Specific surface area data were obtained by nitrogen adsorption analyzer.
The degradation efficiency (DE,%) of the prepared catalyst was obtained by the following formula:
TABLE 1 physical Properties and catalytic Properties of examples 1-3, comparative examples 1-4
Data analysis: as can be seen from FIG. 1 and Table 1, the electron donor built in the carbon nitride molecule and the molecular acceptor built outside the molecule have obvious improvement effect on the performance of photocatalytic degradation of tetracycline, the 20nm cut-off filter is adopted to degrade the tetracycline solution for 60min under a 50W Xe lamp, the photodegradation rate of 94.1% for 30mg/L tetracycline hydrochloride can be realized, and the photodegradation rate of the carbon nitride prepared directly from urea on the tetracycline hydrochloride under the same condition is only 18.5%.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention (including the claims) is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (8)
1. The composite photocatalytic material is characterized in that the photocatalytic material is formed by loading thiophene-carbon nitride on a carbon bromide nano tube, the carbon bromide nano tube is formed by acylation reaction of an aminated carbon nano tube and 2-bromoisobutyryl bromide, and the thiophene-carbon nitride is formed by thermal copolymerization of urea and 2-thiophenecarboxaldehyde on the surface of the carbon bromide nano tube.
2. The composite photocatalytic material according to claim 1, wherein the amino group content of the aminated carbon nanotube is 0.3 to 0.8wt%.
3. The composite photocatalytic material according to claim 1, wherein the aminated carbon nanotube has an inner diameter of 2 to 4nm, a length of 50 to 100 μm and a specific surface area of 200 to 500m 2 /g。
4. A method of preparing a composite photocatalytic material according to any one of claims 1-3, characterized in that the preparation method comprises the steps of:
s1: adding an aminated carbon nano tube, 2-bromoisobutyryl bromide and triethylamine into N, N-dimethylformamide, carrying out an acylation reaction in ice water bath, washing after the reaction is finished, and drying to obtain a brominated carbon nano tube;
s2: mixing 2-thiophenecarboxaldehyde, urea and carbon bromide nano tube, placing in an alumina crucible, calcining under the atmosphere of argon, cooling after calcining, washing and drying to obtain the composite photocatalytic material.
5. The method for preparing a composite photocatalytic material according to claim 4, wherein in the step S1, the mass ratio of the aminated carbon nanotube, the 2-bromoisobutyryl bromide, the triethylamine and the N, N-dimethylformamide is 20-50:5-15:10-50:300-500.
6. The method for preparing a composite photocatalytic material according to claim 4, wherein the time for the acylation reaction in the step S1 is 10 to 18 hours.
7. The method for preparing a composite photocatalytic material according to claim 4, wherein the mass ratio of 2-thiophenecarboxaldehyde, urea and brominated carbon nanotubes in step S2 is 0.1-0.3:1-2.5:10-15.
8. The method for preparing a composite photocatalytic material according to claim 4, wherein the calcining conditions in step S2 are: heating to 550-600 ℃ at a heating rate of 2 ℃/min, and calcining for 5-6h.
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