CN114713293A - Polyacrylonitrile nanofiber membrane loaded with composite photocatalyst as well as preparation method and application of polyacrylonitrile nanofiber membrane - Google Patents
Polyacrylonitrile nanofiber membrane loaded with composite photocatalyst as well as preparation method and application of polyacrylonitrile nanofiber membrane Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 73
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 72
- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 239000002121 nanofiber Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002086 nanomaterial Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 19
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 claims description 91
- 239000013310 covalent-organic framework Substances 0.000 claims description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 239000002105 nanoparticle Substances 0.000 claims description 41
- 238000009987 spinning Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 230000001699 photocatalysis Effects 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000001523 electrospinning Methods 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000010041 electrostatic spinning Methods 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
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- 239000011888 foil Substances 0.000 description 6
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a polyacrylonitrile nanofiber membrane loaded with a composite photocatalyst as well as a preparation method and application thereof. The polyacrylonitrile nano-fiber membrane loaded with the composite photocatalyst comprises polyacrylonitrile and the composite photocatalyst, wherein the composite photocatalyst is a ternary heterostructure and is prepared from an organic covalent skeleton nano material and graphite carbon nitride (g-C)3N4) Compounding with silver-doped nano titanium dioxideAnd (4) synthesizing. The polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst has a very good application prospect in removing difficultly-degradable pollutants.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a polyacrylonitrile nanofiber membrane loaded with a composite photocatalyst as well as a preparation method and application of the polyacrylonitrile nanofiber membrane.
Background
Energy crisis and environmental pollution are increasingly attracting global attention, and high energy conversion rate and environmental protection are receiving more and more attention. At present, the photocatalysis technology is widely applied to the fields of conversion of solar energy into hydrogen energy, degradation of organic pollutants, reduction of carbon dioxide, immobilization of nitrogen and the like. Photocatalytic technology is considered one of the most promising technological approaches to alleviate energy and pollution problems.
Titanium dioxide (TiO)2) As an n-type semiconductor material, the catalyst has the advantages of low price, stable chemical properties and the like, and is the most widely researched and applied catalyst. But TiO 22The band gap of the solar cell is wide, and can only absorb ultraviolet rays with the wavelength of less than 380nm and can not absorb light energy outside the ultraviolet region, because the sunlight only contains about 5 percent of ultraviolet light, thereby greatly limiting the utilization of natural sunlight. In addition, due to TiO2The presence of strong redox groups, which may result in a high probability of electron-hole pair recombination after the transition, may reduce the catalytic ability. Graphite phase carbon nitride (g-C)3N4) The material has the advantages of good chemical stability, low cost, easy obtainment, environmental friendliness, proper band gap, unique physical and chemical properties and controllable electronic structure, the band gap of the carbon nitride is about 2.7eV, the material responds to visible light, and the material has great development potential in the field of photocatalysis. However, g-C3N4The specific surface area of the material is small, the utilization rate of visible light is low, and the photoproduction electron-hole recombination rate is high.
Through g-C3N4With TiO2The heterostructure photocatalyst is compositely constructed, so that the oxidation-reduction reaction on the surface of the catalyst can be promoted, and the photocatalytic activity is obviously improved. However, the semiconductor heterostructures have the defects of slow electron transfer, easy recombination of electron holes and the like, and the improvement of the photoelectric conversion efficiency is limited. Therefore, the speed of electron transfer between the heterostructure interfaces is increased, the electron-hole recombination is reduced, and the photoelectric conversion efficiency can be further improved.
In addition, most of high-efficiency photocatalysts are nano-sized powder particles, but in order to weaken the surface energy of the nano-sized powder, the nano-sized powder is easy to agglomerate and become larger particles, and in the catalytic reaction process, the large-particle photocatalyst is deposited at the bottom of a reactor and cannot be fully contacted with light, so that the photocatalytic efficiency is seriously influenced; meanwhile, the nano powder after the photocatalytic reaction is finished also faces the problem of secondary pollution caused by difficult recovery, and further hinders the application of the photocatalyst in the industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polyacrylonitrile nanofiber membrane loaded with a composite photocatalyst as well as a preparation method and application thereof. According to the invention, the photo-generated electron-hole pairs are effectively separated by forming the heterostructure and the pi-pi conjugated system between the composite materials, so that the visible light response is increased, the photocatalytic performance is improved, and the composite visible light photocatalytic system is constructed. Meanwhile, polyacrylonitrile is used as a carrier to prepare the nanofiber membrane embedded in the photocatalytic system.
The invention is realized by the following technical scheme.
In one aspect, the present invention provides a polyacrylonitrile nanofiber membrane supporting a composite photocatalyst, wherein the polyacrylonitrile nanofiber membrane comprises Polyacrylonitrile (PAN) and the composite photocatalyst; wherein the composite photocatalyst consists of organic covalent skeleton nano material (COF) and graphite carbon nitride (g-C)3N4) And silver-doped nano titanium dioxide.
Preferably, the polyacrylonitrile has an average molecular weight of 20000-;
preferably, the composite photocatalyst is prepared by a method comprising the steps of:
(1) ag doped TiO2Preparing nano particles: mixing Ti (SO)4)2Adding into 0.8-2.0M sulfuric acid solution, stirring to dissolve, and adding AgNO3Transferring the mixture to a reaction kettle, sealing the reaction kettle, preserving the heat for 8 to 15 hours at the temperature of 240-350 ℃, collecting the precipitate, washing the precipitate with distilled water, and drying the precipitate to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2；
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): adding melamine into hydrochloric acid, and stirring to form pasteFreeze-drying the mixture at-80 to-50 ℃ for 12 to 24 hours, calcining the paste at 550 to 700 ℃ for 2 to 6 hours, and naturally cooling to room temperature to obtain g-C3N4；
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: g-C prepared in the step (2)3N4And the Ag-TiO prepared in the step (1)2The nano particles are ball-milled and mixed evenly and react for 1-5 h in an autoclave with the temperature of 300-3N4/Ag-TiO2A catalyst;
(4) preparing a composite photocatalyst: covalent organic framework nano material (COF) and g-C prepared in the step (3)3N4/Ag-TiO2Adding into ethanol, mixing with ultrasound for 30-60min, heating to 50-70 deg.C, reacting for 4-8h, centrifuging, collecting solid, and drying to obtain covalent organic framework nanometer material (COF) modified g-C3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF。
Preferably, in step (1), the AgNO is3With Ti (SO)4)2Is 0.05 to 0.2:1, more preferably 0.1: 1;
preferably, in step (1), the sulfuric acid solution is mixed with Ti (SO)4)2The ratio of (B) is 300-700ml:0.1 mol; further preferably 400ml:0.1 mol;
preferably, in step (1), the sulfuric acid solution is a 0.8-1.0M sulfuric acid solution;
preferably, in the step (1), after sealing, the temperature is kept at 260-280 ℃ for 8-10 h;
preferably, in the step (1), the distilled water washing is performed 5 to 8 times;
preferably, in step (2), the melamine and hydrochloric acid are used in a ratio of 10g:50ml to 80ml, more preferably 10g to 60 mml;
preferably, in the step (2), the freeze-drying is carried out at-80 to-60 ℃ for 12 to 18 hours;
preferably, in step (2), the calcination is carried out at 550-600 ℃ for 2-4 hours;
preferably, in step (3), said g-C3N4With Ag-TiO2The mass ratio of the nano particles is 2-6: 1, and more preferably 4: 1;
preferably, in the step (3), the reaction is carried out in an autoclave at 400 ℃ and 300 ℃ for 1 to 3 hours;
preferably, in step (4), the COF is reacted with g-C3N4/Ag-TiO2Is 1-5:10, further preferably 3: 10;
preferably, in the step (4), heating to 50-60 ℃ for reaction for 4-5 h;
preferably, in step (4), the covalent organic framework nanomaterial (COF) is prepared by a method comprising:
under the protection of nitrogen, cyanuric chloride, anhydrous piperazine and potassium carbonate in a molar ratio of 1:1.5:3 are added into 1, 4-dioxane, wherein the use amount of the 1, 4-dioxane is 4 times of the molar amount of the anhydrous piperazine, the temperature is increased to 110 ℃ under the stirring condition for reaction for 48 hours, after the reaction is finished, the solid is collected by filtration, the obtained solid product is washed by dichloromethane, ethanol and water in sequence until the filtrate is colorless, then the solid is collected, and the solid is dried in vacuum at 50 ℃ for 8 hours, so that the covalent organic framework nano material (COF) is obtained, and the structure is shown in figure 1.
On the other hand, the invention provides a preparation method of the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst, which comprises the following steps:
s1: adding polyacrylonitrile into N, N-Dimethylformamide (DMF), and mechanically stirring at 50-80 deg.C for 2-4h to obtain spinning solution A;
s2: mixing the composite photocatalyst g-C3N4/Ag-TiO2Adding @ COF into the spinning solution A prepared in the step S1, and ultrasonically dispersing for 1-3h at room temperature to obtain a spinning solution B;
s3: and (4) injecting the spinning solution B prepared in the step (S2) into an injector, adjusting electrostatic spinning parameters to perform electrospinning, and drying the collected fiber membrane in a blast oven at 40-60 ℃ for 8-12h to finally obtain the polyacrylonitrile nano-fiber membrane loaded with the composite photocatalyst.
Preferably, in step S1, the polyacrylonitrile has an average molecular weight of 20000 + 40000, and further preferably of 20000 + 30000;
preferably, in step S1, the mass ratio of polyacrylonitrile to DMF is 7-15:100, further preferably 7-8: 100;
preferably, in step S2, the g-C3N4/Ag-TiO2The amount of addition of @ COF is 20 to 40%, further preferably 30% by mass of the polyacrylonitrile used in step S1;
preferably, in step S3, the electrospinning parameters are: the voltage is 12-25kV, the distance between the needle head of the injector for spinning and the receiving device is 10-20cm, the rotating speed of the roller collector is 70-150rpm, and the feeding speed is 0.8-1.5 ml/h; further preferably, the electrospinning parameters are: the voltage was 18kV, the distance between the syringe needle and the receiving device was 12cm, the rotational speed of the drum collector was 100rpm, and the feed rate was 1.0 ml/h.
Preferably, in step S2, the composite photocatalyst g-C3N4/Ag-TiO2@ COF is prepared by a process comprising the steps of:
(1) ag doped TiO2Preparing nano particles: mixing Ti (SO)4)2Adding into 0.8-2.0M sulfuric acid solution, stirring to dissolve, and adding AgNO3Transferring the mixture to a reaction kettle, sealing the reaction kettle, preserving the heat for 8 to 15 hours at the temperature of 240-350 ℃, collecting the precipitate, washing the precipitate with distilled water, and drying the precipitate to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2；
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): adding melamine into hydrochloric acid, stirring to form a pasty mixture, freeze-drying at-80 to-50 ℃ for 12 to 24 hours, calcining the pasty mixture at 550 to 700 ℃ for 2 to 6 hours, and naturally cooling to room temperature to obtain g-C3N4；
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: g-C prepared in the step (2)3N4And the Ag-TiO prepared in the step (1)2Mixing the nano particles by ball millingUniformly reacting in an autoclave at 500 ℃ for 1-5 h to obtain g-C3N4/Ag-TiO2A catalyst;
(4) preparing a composite photocatalyst: covalent organic framework nano material (COF) and g-C prepared in the step (3)3N4/Ag-TiO2Adding into ethanol, mixing with ultrasound for 30-60min, heating to 50-70 deg.C, reacting for 4-8 hr, centrifuging, collecting solid, and drying to obtain g-C modified by covalent organic framework nanometer material (COF)3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF。
Preferably, in step (1), the AgNO is3With Ti (SO)4)2Is 0.05 to 0.2:1, more preferably 0.1: 1;
preferably, in step (1), the sulfuric acid solution is mixed with Ti (SO)4)2The ratio of (B) is 300-700ml:0.1 mol; further preferably 400ml:0.1 mol;
preferably, in step (1), the sulfuric acid solution is a 0.8-1.0M sulfuric acid solution;
preferably, in the step (1), after sealing, the temperature is kept at 260-280 ℃ for 8-10 h;
preferably, in the step (1), the distilled water washing is performed 5 to 8 times;
preferably, in step (2), the ratio of the amount of melamine to the amount of hydrochloric acid is 10g:50ml to 80ml, more preferably 10g to 60 mml;
preferably, in the step (2), the freeze-drying is carried out at-80 to-60 ℃ for 12 to 18 hours;
preferably, in step (2), the calcination is performed at 550-600 ℃ for 2-4 hours;
preferably, in step (3), said g-C3N4With Ag-TiO2The mass ratio of the nano particles is 2-6: 1, and more preferably 4: 1;
preferably, in the step (3), the reaction is carried out in an autoclave at 400 ℃ and 300 ℃ for 1 to 3 hours;
preferably, in step (4), the COF is reacted with g-C3N4/Ag-TiO2Is 1-5:10, further preferably 3: 10;
preferably, in the step (4), heating to 50-60 ℃ for reaction for 4-5 h;
preferably, in step (4), the covalent organic framework nanomaterial (COF) is prepared by a method comprising:
under the protection of nitrogen, cyanuric chloride, anhydrous piperazine and potassium carbonate in a molar ratio of 1:1.5:3 are added into 1, 4-dioxane, wherein the use amount of the 1, 4-dioxane is 4 times of the molar amount of the anhydrous piperazine, the temperature is increased to 110 ℃ under the stirring condition for reaction for 48 hours, after the reaction is finished, the solid is collected by filtration, the obtained solid product is washed by dichloromethane, ethanol and water in sequence until the filtrate is colorless, then the solid is collected, and the solid is dried in vacuum at 50 ℃ for 8 hours, so that the covalent organic framework nano material (COF) is obtained, and the structure is shown in figure 1.
In another aspect, the invention provides the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst or the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst prepared by the preparation method, as a photocatalytic material, and the application of the photocatalytic material in sewage treatment.
Compared with the prior art, the invention has at least the following beneficial effects:
in the semiconductor heterostructure, after photo-generated electrons and holes are separated due to illumination, the photo-generated electrons and the holes can migrate due to the difference of the positions of a valence band and a conduction band of a semiconductor, so that the electrons and the holes are respectively positioned on the surfaces of different semiconductors, recombination of the photo-generated electrons and the holes is further inhibited, and the separation efficiency of the photo-generated electrons and the holes can be obviously improved. However, due to the interface action between the contact interfaces, the transfer of the photogenerated carriers between the two interfaces needs to exceed a large energy barrier, and further recombination of photogenerated electrons and holes occurs at the interfaces, which limits the improvement of the separation efficiency of the photogenerated electron/hole pairs.
In a covalent organic framework nano material (COF), periodic polymer sheets with topological structures are generally formed by aromatic structures through covalent bonds, the sheets form a laminated stacking structure through the driving of pi-pi interaction force, and the transmission of charge carriers and photoexcited electrons is enhanced by the 2D crystal characteristics of the composite photocatalytic material due to the pi-pi conjugation between the layers.
On the other hand, the COF has a special structure, so that a conjugation effect is formed between the COF and a cyano group on a polyacrylonitrile molecular chain, so that the adhesion performance between the composite photocatalyst and polyacrylonitrile and the dispersibility of the composite photocatalyst in polyacrylonitrile are enhanced, the agglomeration condition of the nano-scale photocatalyst is improved, and the photocatalytic efficiency is improved.
Drawings
FIG. 1 is a structural view of a COF prepared by the present invention;
FIG. 2 shows g-C prepared in example 13N4/Ag-TiO2Transmission Electron Microscope (TEM) pictures of the catalyst;
FIG. 3 is g-C prepared in example 13N4/Ag-TiO2High power transmission electron microscopy (HRTEM) pictures of the catalyst;
FIG. 4 is a high power transmission electron micrograph of COF used in example 1;
FIG. 5 is g-C prepared in example 13N4/Ag-TiO2TEM photograph of @ COF;
FIG. 6 shows Ag-TiO compound prepared in example 22、g-C3N4、g-C3N4/Ag-TiO2And g-C3N4/Ag-TiO2X-ray diffraction patterns for @ COF;
FIG. 7 shows Ag-TiO compound prepared in example 22、g-C3N4/Ag-TiO2And g-C3N4/Ag-TiO2Ultraviolet-visible diffuse reflectance spectra for @ COF (UV-Vis DRS);
FIG. 8 is a transmission electron micrograph of a polyacrylonitrile nanofiber membrane supporting a composite photocatalyst in example 2;
fig. 9 is a graph showing the change of the methylene blue concentration with time when the polyacrylonitrile fiber membranes prepared in example 2, comparative example 1 and comparative example 2 degrade the methylene blue solution.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are merely illustrative of the present invention and do not limit the scope of the present invention in any way.
The raw materials and reagent materials used in the following examples are all commercially available products unless otherwise specified. Wherein, the purchase conditions of part of the reagents are as follows:
melamine: suzhou Rongteng chemical Co., Ltd;
anhydrous piperazine: shandong Yinhong chemical Co., Ltd;
polyacrylonitrile: hoshin plastics materials Co., Ltd, Dongguan, Japan;
titanium sulfate: chemical agents of the national drug group, ltd.
In the following examples and comparative examples, the covalent organic framework nanomaterials (COFs) used were prepared by the following methods:
respectively weighing 12.6g of melamine, 12.9g of anhydrous piperazine and 41.4g of potassium carbonate, adding the melamine, the anhydrous piperazine and the potassium carbonate into 0.6mol of 1, 4-dioxane, transferring the mixture into a reaction device, heating to 110 ℃ under the protection of nitrogen and stirring for reaction for 48 hours, filtering and collecting a solid after the reaction is finished, and washing the obtained solid product with dichloromethane, ethanol and water in sequence until the filtrate is colorless. And then collecting the solid, and drying the solid for 8 hours at 50 ℃ in vacuum to obtain the covalent organic framework nano material.
Example 1
(1) Ag doped TiO2Preparing nano particles: 0.1mol of Ti (SO)4)2Adding into 300ml of 0.8M sulfuric acid solution, stirring for dissolving, and adding 0.005mol of AgNO3Transferring to a reaction kettle, sealing, keeping the temperature at 260 ℃ for 8h, collecting the precipitate, washing with distilled water for 5 times, and drying to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2。
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): 10g of melamine are added to 50ml of hydrochloric acid and stirredForming a paste mixture, freeze-drying at-80 deg.C for 12h, calcining at 550 deg.C for 2h, and naturally cooling to room temperature to obtain g-C3N4。
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: 2g of g-C prepared in the above step (2)3N4With 1g of Ag-TiO prepared in step (1) above2The nano particles are ball-milled and mixed evenly and react for 1h in a high-pressure kettle at the temperature of 300 ℃ to obtain g-C3N4/Ag-TiO2A catalyst.
(4) Preparing a composite photocatalyst: 1g of covalent organic framework nanomaterial (COF) and 10g of g-C prepared in step (3) above3N4/Ag-TiO2Adding the catalyst into ethanol, mixing by ultrasonic for 30min, heating to 50 deg.C, reacting for 4h, centrifuging, collecting solid, and drying to obtain COF modified g-C3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF。
(5) Preparation of polyacrylonitrile nanofiber membrane loaded with composite photocatalyst
S1: adding 70g of polyacrylonitrile with the average molecular weight of 20000 into 1000g of DMF, and mechanically stirring for 2 hours at 50 ℃ to obtain a spinning solution A;
s2: 14g of composite photocatalyst g-C3N4/Ag-TiO2Adding @ COF into the spinning solution A obtained in the step S1, and performing ultrasonic dispersion for 1h at room temperature to obtain a spinning solution B;
s3: and (4) injecting the spinning solution B obtained in the step (S2) into a syringe, carrying out electrospinning on the spinning solution B at an applied voltage of 12k V and a feeding speed of 0.8ml/h, wrapping a roller collector by using aluminum foil as a receiving medium, wherein the distance between the collector and the needle of the syringe is 10cm, and the rotating speed of the roller collector is 70 rpm. And drying the fiber membrane collected by the collector in a blast oven at 40 ℃ for 8h to finally obtain the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst.
FIG. 2 shows g-C prepared in example 13N4/Ag-TiO2Transmission Electron Microscope (TEM) pictures of the catalyst; from the figure, Ag can be seenThe nano particles are uniformly distributed in g-C3N4Surface of (2), prepared g-C3N4/Ag-TiO2The catalyst exhibits a two-dimensional sheet structure. FIG. 3 is g-C prepared in example 13N4/Ag-TiO2High-power transmission electron microscope (HRTEM) picture of the catalyst, and TiO with better crystal form can be seen from figure 32The nanoparticles and Ag nanoparticles are distributed in g-C3N4Of (2) is provided. Fig. 4 is a HETEM photograph of the COF used in example 1, from which it can be observed that the internal microstructure of the COF prepared in the present invention is a layered structure. FIG. 5 is g-C modified by covalent organic framework nanomaterial (COF) prepared in example 13N4/Ag-TiO2TEM photograph of composite photocatalyst, from which g-C was observed3N4/Ag-TiO2The nanoparticles are supported on the COF sheets.
Example 2
(1) Ag doped TiO2Preparing nano particles: 0.1mol of Ti (SO)4)2Adding into 400ml 1.0M sulfuric acid solution, stirring to dissolve, and adding 0.01mol AgNO3Transferring to a reaction kettle, sealing, keeping the temperature at 280 ℃ for 10h, collecting the precipitate, washing with distilled water for 5 times, and drying to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2。
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): adding 10g melamine into 60ml hydrochloric acid, stirring to form a paste mixture, freeze-drying at-60 deg.C for 18h, calcining at 600 deg.C for 4h, and naturally cooling to room temperature to obtain g-C3N4。
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: 4g of g-C prepared in the above step (2)3N4With 1g of Ag-TiO prepared in step (1) above2The nano particles are ball-milled and mixed evenly and react for 3 hours in a high-pressure kettle at the temperature of 400 ℃ to obtain g-C3N4/Ag-TiO2A catalyst.
(4) Preparing a composite photocatalyst: 3g of covalent organic skeleton nanomaterial (COF)And 10g of g-C prepared in the above step (3)3N4/Ag-TiO2Adding the catalyst into ethanol, mixing by ultrasonic wave for 40min, heating to 60 deg.C, reacting for 5h, centrifuging, collecting solid, and drying to obtain COF modified g-C3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF。
(5) Preparation of polyacrylonitrile nanofiber membrane loaded with composite photocatalyst
S1: adding 80g of polyacrylonitrile with the average molecular weight of 30000 into 1000g of DMF, and mechanically stirring for 3 hours at the temperature of 60 ℃ to obtain a spinning solution A;
s2: 24g of composite photocatalyst g-C3N4/Ag-TiO2Adding @ COF into the spinning solution A obtained in the step S1, and performing ultrasonic dispersion for 2 hours at room temperature to obtain a spinning solution B;
s3: and (4) injecting the spinning solution B obtained in the step (S2) into an injector, electro-spinning the spinning solution B at an applied voltage of 18k V and a feeding speed of 1.0ml/h, wrapping a roller collector by using aluminum foil as a receiving medium, wherein the distance between the collector and the needle of the injector is 12cm, and the rotating speed of the roller collector is 100 rpm. And drying the fiber membrane collected by the collector in a blast oven at 40 ℃ for 8h to finally obtain the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst.
FIG. 6 shows Ag-TiO compound prepared in example 22、g-C3N4、g-C3N4/Ag-TiO2And a composite photocatalyst g-C3N4/Ag-TiO2X-ray diffraction analysis plot of @ COF. Peaks at 25.3 °,37.8 °,47.9 °,53.9 °,55.0 °,62.7 °,68.8 ° and 70.3 ° of 2 θ are assigned to anatase TiO2The (101), (004), (200), (105), (211), (204), (116) and (220) crystal planes of (a) also show that the introduction of Ag does not change the structure of titanium dioxide. g-C3N4In the graph of (2), diffraction peaks of 21.5 ° and 27.3 ° ascribed to the (002) crystal face were observed, while diffraction peaks appearing in the vicinity of 13.1 ° showed that g-C of the layered structure was prepared in this example3N4. From g to C3N4/Ag-TiO2In the curve of @ COFThe composite photocatalyst can be observed to combine the characteristic diffraction peaks of the three, and the diffraction peaks near 12.7 degrees and 29.5 degrees belong to COF, thereby confirming the synthesis of the composite photocatalyst.
FIG. 7 shows Ag-TiO in this example2、g-C3N4/Ag-TiO2And g-C3N4/Ag-TiO2UV-visible diffuse reflectance spectrum of @ COF (UV-Vis DRS). As can be seen, with g-C3N4And after a heterostructure is formed by adding the COF, the visible light absorption of the prepared composite photocatalyst can be obviously enhanced, which shows that the COF and the g-C are3N4/Ag-TiO2The pi-pi conjugation between them enhances the transport of charge carriers and photoexcited electrons.
Fig. 8 is a transmission electron micrograph of the polyacrylonitrile nanofiber membrane supporting the composite photocatalyst in example 2. As can be seen from the figure, the composite photocatalyst is embedded into the surface of the fiber, indicating that the existence of COF improves g-C3N4/Ag-TiO2Interfacial forces with polyacrylonitrile.
Example 3
(1) Ag doped TiO2Preparing nano particles: 0.1mol of Ti (SO)4)2Adding into 600ml 1.5M sulfuric acid solution, stirring to dissolve, and adding 0.02mol AgNO3Transferring to a reaction kettle, sealing, keeping the temperature at 300 ℃ for 8h, collecting the precipitate, washing with distilled water for 5 times, and drying to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2。
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): adding 10g melamine into 60ml hydrochloric acid, stirring to form a paste mixture, freeze-drying at-60 deg.C for 18h, calcining at 650 deg.C for 5h, and naturally cooling to room temperature to obtain g-C3N4。
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: 5g of g-C prepared in the above step (2)3N4With 1g of Ag-TiO prepared in step (1) above2The nano particles are uniformly mixed by ball millingUniformly reacting in an autoclave at 450 ℃ for 3h to obtain g-C3N4/Ag-TiO2A catalyst.
(4) Preparing a composite photocatalyst: 4g of covalent organic framework nanomaterial (COF) and 10g of g-C prepared in step (3) above3N4/Ag-TiO2Adding a catalyst into ethanol, mixing by ultrasonic wave for 50min, heating to 60 ℃, reacting for 7h, centrifuging, collecting solid, and drying to obtain COF modified g-C3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF。
(5) Preparation of polyacrylonitrile nanofiber membrane loaded with composite photocatalyst
S1: adding 80g of polyacrylonitrile with the average molecular weight of 30000 into 1000g of DMF, and mechanically stirring for 3 hours at 60 ℃ to obtain a spinning solution A;
s2: 28g of composite photocatalyst g-C3N4/Ag-TiO2Adding @ COF into the spinning solution A obtained in the step S1, and performing ultrasonic dispersion for 2 hours at room temperature to obtain a spinning solution B;
s3: and (4) injecting the spinning solution B obtained in the step (S2) into a syringe, carrying out electrospinning on the spinning solution B at an applied voltage of 20k V and a feeding speed of 1.2ml/h, wrapping a roller collector by using aluminum foil as a receiving medium, wherein the distance between the collector and the needle of the syringe is 16cm, and the rotating speed of the roller collector is 120 rpm. And drying the fiber membrane collected by the collector in a forced air oven at 50 ℃ for 10h to finally obtain the polyacrylonitrile nano-fiber membrane loaded with the composite photocatalyst.
Example 4
(1) Ag doped TiO2Preparing nanoparticles: 0.1mol of Ti (SO)4)2Adding into 600ml of 2.0M sulfuric acid solution, stirring for dissolving, and adding 0.02mol of AgNO3Transferring to a reaction kettle, sealing, keeping the temperature at 350 ℃ for 8h, collecting the precipitate, washing with distilled water for 5 times, and drying to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2。
(2) Graphitic carbon nitride (g-C)3N4) Is/are as followsPreparation: adding 10g melamine into 60ml hydrochloric acid, stirring to form a paste mixture, freeze-drying at-60 deg.C for 18h, calcining at 700 deg.C for 6h, and naturally cooling to room temperature to obtain g-C3N4。
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: 6g of g-C prepared in the above step (2)3N4With 1g of Ag-TiO prepared in step (1) above2The nano particles are ball-milled and mixed evenly and react for 5 hours in a high-pressure kettle at the temperature of 500 ℃ to obtain g-C3N4/Ag-TiO2A catalyst.
(4) Preparing a composite photocatalyst: 5g of covalent organic framework nanomaterial (COF) and 10g of g-C prepared in step (3) above3N4/Ag-TiO2Adding the catalyst into ethanol, mixing by ultrasonic wave for 50min, heating to 70 deg.C, reacting for 8h, centrifuging, collecting solid, and drying to obtain COF-modified g-C3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF。
(5) Preparation of polyacrylonitrile nanofiber membrane loaded with composite photocatalyst
S1: adding 80g of polyacrylonitrile with the average molecular weight of 40000 into 1000g of DMF, and mechanically stirring for 4 hours at 80 ℃ to obtain a spinning solution A;
s2: 32g of composite photocatalyst g-C3N4/Ag-TiO2Adding @ COF into the spinning solution A obtained in the step S1, and performing ultrasonic dispersion for 3 hours at room temperature to obtain a spinning solution B;
s3: and (3) injecting the spinning solution B of the step S2 into a syringe, carrying out electrospinning on the spinning solution B at an applied voltage of 25k V and a feeding speed of 1.5ml/h, wrapping a roller collector by using aluminum foil as a receiving medium, wherein the distance between the collector and the needle of the syringe is 16cm, and the rotating speed of the roller collector is 120 rpm. And drying the fiber membrane collected by the collector in a forced air oven at 50 ℃ for 10 hours to finally obtain the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst.
Comparative example 1
(1) Ag doped TiO2Preparing nano particles: 0.1mol of Ti (SO)4)2Adding into 400ml 1.0M sulfuric acid solution, stirring to dissolve, and adding 0.01mol AgNO3Transferring to a reaction kettle, sealing, keeping the temperature at 240 ℃ for 8h, collecting precipitate, washing with distilled water for 5 times, and drying to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2。
(2) Preparation of polyacrylonitrile nanofiber membrane
S1: adding 80g of polyacrylonitrile with the average molecular weight of 30000 into 1000g of DMF, and mechanically stirring for 3 hours at 60 ℃ to obtain a spinning solution A;
s2: 24g of Ag-TiO2Adding the nano particles into the spinning solution A obtained in the step S1, and performing ultrasonic dispersion for 2 hours at room temperature to obtain a spinning solution B;
s3: and (3) injecting the spinning solution B of the step S2 into an injector, carrying out electrospinning on the spinning solution B at an applied voltage of 18k V and a feeding speed of 1.0ml/h, wrapping a roller collector by using aluminum foil as a receiving medium, wherein the distance between the collector and the needle of the injector is 12cm, and the rotating speed of the roller collector is 100 rpm. And drying the fiber membrane collected by the collector in a forced air oven at 40 ℃ for 8h to finally obtain the polyacrylonitrile nanofiber membrane.
Comparative example 2
(1) Ag doped TiO2Preparing nano particles: 0.1mol of Ti (SO)4)2Adding into 400ml 1.0M sulfuric acid solution, stirring to dissolve, and adding 0.01mol AgNO3Transferring to a reaction kettle, sealing, keeping the temperature at 240 ℃ for 8h, collecting the precipitate, washing with distilled water for 5 times, and drying to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2。
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): adding 10g melamine into 60ml hydrochloric acid, stirring to form a paste mixture, freeze-drying at-60 deg.C for 18h, calcining at 600 deg.C for 4h, and naturally cooling to room temperature to obtain g-C3N4；
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: 4g of g-C prepared in the above step (2)3N4With 1g of Ag-TiO prepared in step (1) above2The nano particles are ball-milled and mixed evenly and react for 3 hours in a high-pressure kettle at 400 ℃ to obtain g-C3N4/Ag-TiO2A catalyst;
(4) preparation of polyacrylonitrile nanofiber membrane
S1: adding 80g of polyacrylonitrile with the average molecular weight of 30000 into 1000g of DMF, and mechanically stirring for 3 hours at the temperature of 60 ℃ to obtain a spinning solution A;
s2: 24g of g-C3N4/Ag-TiO2Adding the mixture into the spinning solution A obtained in the step S1, and performing ultrasonic dispersion for 2 hours at room temperature to obtain a spinning solution B;
s3: and (3) injecting the spinning solution B of the step S2 into an injector, carrying out electrospinning on the spinning solution B at an applied voltage of 18k V and a feeding speed of 1.0ml/h, wrapping a roller collector by using aluminum foil as a receiving medium, wherein the distance between the collector and the needle of the injector is 12cm, and the rotating speed of the roller collector is 100 rpm. And drying the fiber membrane collected by the collector in a forced air oven at 40 ℃ for 8h to finally obtain the polyacrylonitrile nanofiber membrane.
Performance testing
The invention tests the photocatalytic performance of the polyacrylonitrile membrane by photocatalytic degradation of methylene blue under visible light. The evaluation of the photocatalytic performance of the test was carried out in a photocatalytic reactor as follows: 0.03g of the polyacrylonitrile fiber membrane prepared in example 1, example 2, example 3, example 4, and comparative example 1 and comparative example 2 was added to a 30mL quartz tube of a 0.2mol/L methylene blue solution, the quartz tube was placed in a photochemical reactor after ultrasonic oscillation for 15min, after stirring for 30min in the dark to reach equilibrium, 3mL of the solution was centrifuged every 30min, and the absorbance was measured at 664nm using an ultraviolet-visible spectrophotometer (U-3010, Hitachi) to calculate the degradation rate of methylene blue.
The experimental results show that the degradation efficiency of the methylene blue of the polyacrylonitrile nano-fiber films prepared in the embodiments 1, 2, 3 and 4 is respectively 90.2%, 91.7%, 90.8% and 89.7% after the polyacrylonitrile nano-fiber films are irradiated for 120min by visible light; the degradation efficiency of methylene blue of the polyacrylonitrile nano-fiber membrane prepared in the comparative example 1 of the invention after being irradiated for 120min by visible light is 49.6%, the degradation efficiency of methylene blue of the polyacrylonitrile nano-fiber membrane prepared in the comparative example 2 of the invention after being irradiated for 120min by visible light is 76.5%, and fig. 9 is a graph showing the change of the concentration of methylene blue with time when the materials prepared in the examples 2, 1 and 2 degrade methylene blue solution. The good catalytic effect shows that the ternary heterostructure is effectively dispersed in the polyacrylonitrile fiber membrane, thereby being beneficial to the photocatalytic reaction.
The above description of the specific embodiments of the present invention is not intended to limit the present invention, and those skilled in the art may make various changes and modifications according to the present invention without departing from the spirit of the present invention, which is defined by the scope of the appended claims.
Claims (10)
1. A polyacrylonitrile nanometer fiber membrane loaded with a composite photocatalyst is characterized in that the polyacrylonitrile nanometer fiber membrane comprises polyacrylonitrile and the composite photocatalyst;
wherein the composite photocatalyst consists of organic covalent skeleton nano material (COF) and graphite carbon nitride (g-C)3N4) And silver-doped nano titanium dioxide.
2. The composite photocatalyst-supported polyacrylonitrile nanofiber membrane according to claim 1, wherein the composite photocatalyst is prepared by a method comprising the following steps:
(1) ag doped TiO2Preparing nano particles: mixing Ti (SO)4)2Adding into 0.8-2.0M sulfuric acid solution, stirring to dissolve, and adding AgNO3Transferring the mixture to a reaction kettle, sealing the reaction kettle, preserving the heat for 8 to 15 hours at the temperature of 240-350 ℃, collecting the precipitate, washing the precipitate with distilled water, and drying the precipitate to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2；
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): mixing melamineAdding into hydrochloric acid, stirring to form a pasty mixture, freeze-drying at-80 to-50 ℃ for 12 to 24 hours, calcining the pasty at 550 to 700 ℃ for 2 to 6 hours, and naturally cooling to room temperature to obtain g-C3N4；
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: g-C prepared in the step (2)3N4And the Ag-TiO prepared in the step (1)2The nano particles are ball-milled and mixed evenly and react for 1-5 h in an autoclave with the temperature of 300-3N4/Ag-TiO2A catalyst;
(4) preparing a composite photocatalyst: covalent organic framework nano material (COF) and g-C prepared in the step (3)3N4/Ag-TiO2Adding into ethanol, mixing with ultrasound for 30-60min, heating to 50-70 deg.C, reacting for 4-8h, centrifuging, collecting solid, and drying to obtain covalent organic framework nanometer material (COF) modified g-C3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF。
3. The composite photocatalyst-loaded polyacrylonitrile nanofiber membrane according to claim 2, wherein in step (1), the AgNO is3With Ti (SO)4)2Is 0.05 to 0.2:1, more preferably 0.1: 1;
preferably, in step (1), the sulfuric acid solution is mixed with Ti (SO)4)2The ratio of (B) is 300-700ml:0.1 mol; further preferably 400ml:0.1 mol;
preferably, in step (1), the sulfuric acid solution is a 0.8-1M sulfuric acid solution;
preferably, in the step (1), after sealing, the temperature is kept at 260-280 ℃ for 8-10 h;
preferably, in step (1), the distilled water washing is performed 5 to 8 times.
4. The composite photocatalyst-supported polyacrylonitrile nanofiber membrane according to claim 2, wherein in step (2), the amount ratio of melamine to hydrochloric acid is 10g:50ml-80ml, more preferably 10g:60 ml;
preferably, in the step (2), the freeze-drying is carried out at-80 to-60 ℃ for 12 to 18 hours;
preferably, in step (2), the calcination is carried out at 550-600 ℃ for 2-4 hours;
preferably, in step (3), said g-C3N4With Ag-TiO2The mass ratio of the nano particles is 2-6: 1, and more preferably 4: 1;
preferably, in the step (3), the reaction is carried out in an autoclave at 400 ℃ and 300 ℃ for 1 to 3 hours;
preferably, in step (4), the COF is reacted with g-C3N4/Ag-TiO2Is 1-5:10, further preferably 3: 10;
preferably, in step (4), the reaction is carried out by heating to 50-60 ℃ for 4-5 h.
5. A preparation method of a polyacrylonitrile nanofiber membrane loaded with a composite photocatalyst is characterized by comprising the following steps:
s1: adding polyacrylonitrile into N, N-Dimethylformamide (DMF), and mechanically stirring at 50-80 deg.C for 2-4h to obtain spinning solution A;
s2: mixing the composite photocatalyst g-C3N4/Ag-TiO2Adding @ COF into the spinning solution A prepared in the step S1, and ultrasonically dispersing for 1-3h at room temperature to obtain a spinning solution B;
s3: and (4) injecting the spinning solution B prepared in the step (S2) into an injector, adjusting electrostatic spinning parameters to perform electrospinning, and drying the collected fiber membrane in a blast oven at 40-60 ℃ for 8-12h to finally obtain the polyacrylonitrile nano-fiber membrane loaded with the composite photocatalyst.
6. The preparation method according to claim 5, characterized in that, in step S1, the polyacrylonitrile has an average molecular weight of 20000-;
preferably, in step S1, the mass ratio of polyacrylonitrile to DMF is 7-15:100, and further preferably 7-8: 100.
7. The method according to claim 5, wherein the g-C is added in step S23N4/Ag-TiO2The amount of addition of @ COF is 20 to 40%, further preferably 30%, of the mass of polyacrylonitrile used in step S1.
8. The method according to claim 5, wherein the electrospinning parameters in the step S3 are: the voltage is 12-25kV, the distance between the needle head of the injector for spinning and the receiving device is 10-20cm, the rotating speed of the roller collector is 70-150rpm, and the feeding speed is 0.8-1.5 ml/h; further preferably, the electrospinning parameters are: the voltage was 18kV, the distance between the syringe needle and the receiving device was 12cm, the rotational speed of the drum collector was 100rpm, and the feed rate was 1.0 ml/h.
9. The production method according to claim 5, wherein in step S2, the composite photocatalyst g-C3N4/Ag-TiO2@ COF is prepared by a process comprising the steps of:
(1) ag doped TiO2Preparing nano particles: mixing Ti (SO)4)2Adding into 0.8-2.0M sulfuric acid solution, stirring to dissolve, and adding AgNO3Transferring the mixture to a reaction kettle, sealing the reaction kettle, preserving the heat for 8 to 15 hours at the temperature of 240-350 ℃, collecting the precipitate, washing the precipitate with distilled water, and drying the precipitate to obtain Ag-doped TiO2Nanoparticles, labelled Ag-TiO2；
(2) Graphitic carbon nitride (g-C)3N4) The preparation of (1): adding melamine into hydrochloric acid, stirring to form a pasty mixture, freeze-drying at-80 to-50 ℃ for 12-24h, calcining the pasty mixture at 550-700 ℃ for 2-6 h, and naturally cooling to room temperature to obtain g-C3N4；
(3)g-C3N4/Ag-TiO2Preparation of the catalyst: g-C prepared in the step (2)3N4And the Ag-TiO prepared in the step (1)2The nano particles are ball-milled and mixed evenly and react for 1-5 h in an autoclave with the temperature of 300-3N4/Ag-TiO2A catalyst;
(4) preparing a composite photocatalyst: covalent organic framework nano material (COF) and g-C prepared in the step (3)3N4/Ag-TiO2Adding into ethanol, mixing with ultrasound for 30-60min, heating to 50-70 deg.C, reacting for 4-8h, centrifuging, collecting solid, and drying to obtain covalent organic framework nanometer material (COF) modified g-C3N4/Ag-TiO2I.e. composite photocatalysts, marked g-C3N4/Ag-TiO2@COF；
Preferably, in step (1), the AgNO is3With Ti (SO)4)2Is 0.05 to 0.2:1, more preferably 0.1: 1;
preferably, in step (1), the sulfuric acid solution is mixed with Ti (SO)4)2The ratio of (B) is 300-700ml:0.1 mol; further preferably 400ml:0.1 mol;
preferably, in step (1), the sulfuric acid solution is a 0.8-1.0M sulfuric acid solution;
preferably, in the step (1), after sealing, the temperature is kept at 260-280 ℃ for 8-10 h;
preferably, in the step (1), the distilled water washing is performed 5 to 8 times;
preferably, in step (2), the melamine and hydrochloric acid are used in a ratio of 10g:50ml to 80ml, more preferably 10g to 60 mml;
preferably, in the step (2), the freeze-drying is carried out at-80 to-60 ℃ for 12 to 18 hours;
preferably, in step (2), the calcination is carried out at 550-600 ℃ for 2-4 hours;
preferably, in step (3), said g-C3N4With Ag-TiO2The mass ratio of the nano particles is 2-6: 1, and more preferably 4: 1;
preferably, in the step (3), the reaction is carried out in an autoclave at 400 ℃ and 300 ℃ for 1 to 3 hours;
preferablyIn step (4), the COF is reacted with g-C3N4/Ag-TiO2Is 1-5:10, further preferably 3: 10;
preferably, in the step (4), heating to 50-60 ℃ for reaction for 4-5 h;
preferably, in step (4), the covalent organic framework nanomaterial (COF) is prepared by a method comprising:
under the protection of nitrogen, cyanuric chloride, anhydrous piperazine and potassium carbonate in a molar ratio of 1:1.5:3 are added into 1, 4-dioxane, wherein the use amount of the 1, 4-dioxane is 4 times of the molar amount of the anhydrous piperazine, the temperature is increased to 110 ℃ under the condition of stirring for reaction for 48 hours, after the reaction is finished, solid is collected by filtration, the obtained solid product is washed by dichloromethane, ethanol and water in sequence until the filtrate is colorless, then the solid is collected, and the solid is dried in vacuum at 50 ℃ for 8 hours, so that the covalent organic framework nano material (COF) is obtained.
10. An application of the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst in any one of claims 1 to 4 or the polyacrylonitrile nanofiber membrane loaded with the composite photocatalyst, which is prepared by the preparation method in any one of claims 5 to 9, as a photocatalytic material in sewage treatment.
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