CN115970751B - Mesoporous TS-1 photocatalyst and preparation method and application thereof - Google Patents
Mesoporous TS-1 photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 39
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 229960003276 erythromycin Drugs 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 7
- 239000003242 anti bacterial agent Substances 0.000 claims description 6
- 229940088710 antibiotic agent Drugs 0.000 claims description 6
- 230000003115 biocidal effect Effects 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000002808 molecular sieve Substances 0.000 abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
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- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 239000013078 crystal Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 aluminosilicate anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
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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 discloses a mesoporous TS-1 photocatalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving a mesoporous template agent and tetrapropylammonium hydroxide in water to obtain a solution A; mixing TEOS with TBOT to obtain solution B; wherein, the molar ratio of mesoporous template agent, TPAOH, TEOS, TBOT and water is 0-5:24:100:4:2400 a; dropwise adding the solution B into the solution A under the stirring condition to obtain a uniform mixed solution; irradiating the mixed solution under an ultraviolet lamp, transferring the mixed solution into a hydrothermal kettle after the lamp is finished, and crystallizing; after crystallization, centrifuging, washing, drying and roasting the product to obtain the mesoporous TS-1 photocatalyst. The mesoporous molecular sieve is synthesized by the photocatalysis technology, so that the consumption of a template agent can be reduced, the cost is reduced, the synthesis time is greatly shortened, the generation of free radicals is efficient and controllable, and the synthesized mesoporous TS-1 photocatalyst has good degradation effect on erythromycin in water under ultraviolet light.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a mesoporous TS-1 photocatalyst, and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Zeolite molecular sieve is a kind of microporous aluminosilicate crystal with regular pore canal, has excellent catalysis, adsorption separation and ion exchange performance, and has been widely used in important fields related to energy and environment, such as petroleum refining, petrochemical industry, fine chemical industry, daily chemical industry, etc. Because of its excellent adsorption performance, unique MFI topology, selective catalytic function, special surface active environment and different electron-hole separation mechanisms, it has received extensive attention in the catalytic field, and has been known as one of the representatives of novel catalytic materials in the green chemistry field. Currently, molecular sieves have been partially studied for photocatalytic degradation of trace antibiotics in wastewater. Because of the deep knowledge of zeolite molecular sieves and the increasing demand for molecular sieves in industry, molecular sieve synthesis has been provided with a number of well-established synthetic methods, including hydrothermal synthesis, solvothermal synthesis, dry gel conversion, solventless synthesis, and the like. The hydrothermal synthesis method is the most common and most classical method in the current molecular sieve synthesis, and refers to a synthesis method which is carried out by utilizing reactants in aqueous solution to carry out specific chemical reactions under the conditions of a certain temperature (100-1000 ℃) and a certain pressure (1-100 MPa). However, these methods have problems of severe synthesis conditions (high temperature and high pressure), long synthesis period, expensive template agent, and the like.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a mesoporous TS-1 photocatalyst, and a preparation method and application thereof. The mesoporous TS-1 photocatalyst synthesized by the light-assisted method has a crystal structure and a specific surface area superior to those of TS-1 synthesized by the traditional hydrothermal method, has a remarkable effect on degrading erythromycin in water, is simple in synthesis method, saves cost, provides possibility for realizing efficient, energy-saving and green synthesis of the light-responsive molecular sieve material, and provides a new method for determining other photocatalysts and catalytic reaction technical conditions.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a method for preparing a mesoporous TS-1 photocatalyst, comprising the following steps:
Dissolving mesoporous template agent and tetrapropylammonium hydroxide (TPAOH) in water to obtain solution A;
Mixing TEOS with TBOT to obtain solution B;
wherein, the molar ratio of mesoporous template agent, TPAOH, TEOS, TBOT and water is 0-5:24:100:4:2400 a;
Dropwise adding the solution B into the solution A under the stirring condition to obtain a uniform mixed solution;
irradiating the mixed solution under an ultraviolet lamp, transferring the mixed solution into a hydrothermal kettle after the lamp is finished, and crystallizing;
after crystallization, centrifuging, washing, drying and roasting the product to obtain the mesoporous TS-1 photocatalyst.
Ultraviolet irradiation can introduce hydroxyl free radicals into the reaction system, the hydroxyl free radicals catalyze the depolymerization of aluminosilicate gel by destroying Si, al-O-Si and Al bonds, and catalyze the polymerization of aluminosilicate anions around hydrated cations by reforming Si, al-O-Si and Al bonds, so that the crystallization of TS-1 is promoted.
In some embodiments, the mesoporous templating agent is F-127, CTAB, or P-123.
Preferably, the mesoporous template agent is F-127.
In some embodiments, the mixed solution is irradiated under an ultraviolet lamp for a period of 1-3 hours.
In some embodiments, the crystallization temperature is 150-200deg.C and the crystallization time is 40-50h. The crystallization temperature is low, the product can not be synthesized, and the energy consumption is high when the crystallization temperature is too high.
In some embodiments, the centrifugation is performed at a rotational speed of 7000-8000r/min and for a centrifugation time of 3-5min.
In some embodiments, the temperature of drying is 50-120 ℃ and the drying time is 2-12 hours.
In some embodiments, the calcination temperature is 500-600 ℃ and the calcination time is 5-7 hours. The temperature is too low to remove the templating agent.
In a second aspect, the invention provides a mesoporous TS-1 photocatalyst prepared by the preparation method.
In a third aspect, the invention provides application of the mesoporous TS-1 photocatalyst in photocatalytic degradation of antibiotics in wastewater.
Preferably, the antibiotic is erythromycin.
Preferably, the method for degrading erythromycin in wastewater by adopting the mesoporous TS-1 photocatalyst comprises the following steps: adding the mesoporous TS-1 photocatalyst into the wastewater containing antibiotics, stirring and mixing under dark condition, and then irradiating with ultraviolet light with the power of an ultraviolet lamp of 300-500W.
It is further preferred that the stirring time is at least 30 minutes under dark conditions to ensure that adsorption-desorption equilibrium is achieved between the catalyst and the antibiotic, and the time of uv irradiation is at least 1 hour.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
The invention utilizes the photocatalysis technology to assist in synthesizing the mesoporous molecular sieve, can reduce the dosage of the template agent, reduce the cost, greatly shorten the synthesis time, and has high efficiency and controllable generation of free radicals, and the synthesized mesoporous TS-1 photocatalyst has good degradation effect on erythromycin in water under ultraviolet light.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an X-ray diffraction (XRD) pattern of the prepared mesoporous TS-1 photocatalyst in different proportions;
FIG. 2 shows the degradation rate of erythromycin by various photocatalysts;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the prepared mesoporous TS-1 photocatalyst in different proportions;
FIG. 4 shows the degradation rate of TS-1.7F-127 photocatalyst when it is recycled.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
Dissolving a certain amount of F-127 in deionized water, and adding a proper amount of TPAOH aqueous solution to obtain solution A; mixing TEOS with TBOT to obtain solution B; dropwise adding the solution B into the solution A under high-speed stirring to form a mixed solution; irradiating the mixed solution for 2 hours under ultraviolet; after the lamp is finished, transferring the solution into a hydrothermal kettle, and crystallizing at 170 ℃ for 48 hours; after crystallization, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; after the end, the collected solids were ground into a powder. The molar ratio between the substances is 100TEOS:24TPAOH:4TBOT:2400H 2 O: xF-127.
In this example, the molar ratio x of mesoporous template agent F-127 was 0, and the resulting mesoporous TS-1 photocatalyst was designated TS-1 0F-127.
Example 2
Dissolving a certain amount of F-127 in deionized water, and adding a proper amount of TPAOH aqueous solution to obtain solution A; mixing TEOS with TBOT to obtain solution B; dropwise adding the solution B into the solution A under high-speed stirring to form a mixed solution; irradiating the mixed solution for 2 hours under ultraviolet; after the lamp is finished, transferring the solution into a hydrothermal kettle, and standing and crystallizing for 48 hours at 170 ℃; after crystallization, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; after the end, the collected solids were ground into a powder. The molar ratio between the substances is 100TEOS:24TPAOH:4TBOT:2400H 2 O: xF-127.
In this example, the molar ratio x of mesoporous template agent F-127 was 0.3, and the resulting mesoporous TS-1 photocatalyst was designated TS-1.3F-127.
Example 3
Dissolving a certain amount of F-127 in deionized water, and adding a proper amount of TPAOH aqueous solution to obtain solution A; mixing TEOS with TBOT to obtain solution B; dropwise adding the solution B into the solution A under high-speed stirring to form a mixed solution; irradiating the mixed solution for 2 hours under ultraviolet; after the lamp is finished, transferring the solution into a hydrothermal kettle, and standing and crystallizing for 48 hours at 170 ℃; after crystallization, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; after the end, the collected solids were ground into a powder. The molar ratio between the substances is 100TEOS:24TPAOH:4TBOT:2400H 2 O: xF-127.
In this example, the molar ratio x of mesoporous template agent F-127 was 0.7, and the resulting mesoporous TS-1 photocatalyst was designated TS-1.7F-127.
Comparative example 1
TS-1 is synthesized by a traditional hydrothermal method: under the protection of nitrogen, a certain amount of TEOS is slowly dripped into the TPAOH water solution, and stirring is continued until the solution is colorless and transparent; measuring a certain amount of TBOT and anhydrous isopropanol, uniformly mixing, slowly adding the mixed solution into the solution through a syringe, and continuously stirring at a high speed for 2 hours under the protection of nitrogen; placing the mixed solution in a constant-temperature water bath at 80 ℃, adding a certain amount of distilled water, continuously preserving heat at 80 ℃ under the protection of nitrogen, removing isopropanol added in the solution and alcohol generated during the hydrolysis of a silicon source and a titanium source, and finally obtaining a light yellow transparent solution; transferring the obtained solution into a hydrothermal kettle, standing and crystallizing for 72h at 170 ℃; after crystallization, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; after the end, the collected solids were ground into a powder.
In this comparative example, the resulting TS-1 photocatalyst was designated as hydrothermal TS-1.
Comparative example 2
Dissolving a certain amount of F-127 in deionized water, and adding a proper amount of TPAOH aqueous solution to obtain solution A; mixing TEOS with TBOT to obtain solution B; dropwise adding the solution B into the solution A under high-speed stirring to form a mixed solution; stirring the mixed solution for 2 hours; after the completion, transferring the solution into a hydrothermal kettle, standing and crystallizing for 48 hours at 170 ℃; after crystallization, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; after the end, the collected solids were ground into a powder. The molar ratio between the substances is 100TEOS:24TPAOH:4TBOT:2400H 2 O: xF-127.
In this comparative example, the molar ratio x of mesoporous template F-127 was 0.7, and the resulting mesoporous TS-1 photocatalyst was recorded as TS-1.7F-127 free of UV.
Antibiotic degradation experiments:
The photocatalytic activity of mesoporous TS-1 was evaluated by degradation of erythromycin by ultraviolet light. The above-mentioned different samples (i.e., samples obtained in examples 1-3, comparative examples 1-2) were weighed and placed in a 20mL quartz bottle, and 10mg of the photocatalyst was dispersed in 15mL of an aqueous erythromycin solution, before irradiation, the suspension was stirred in the dark for 30 minutes to ensure that adsorption-desorption equilibrium was achieved between the catalyst and erythromycin molecules, the quartz bottle was irradiated with a 500W mercury lamp, condensed with cooling water at 10℃and after the end of irradiation, the suspension was sucked by a syringe, the liquid was separated by an organic nylon filter membrane of 0.22 μm, and the corresponding absorption of erythromycin at the 242nm characteristic band was monitored by an ultraviolet-ultraviolet spectrophotometer, and the adsorption rate and degradation rate of erythromycin were calculated using the formula (1).
Degradation rate = (1-C t/C0) ×100% (1)
Formula (1): c 0 —initial concentration of antibiotic; c t - -concentration of antibiotic at a certain point in time.
Materials were evaluated for reusability and stability by cyclic degradation experiments. And (3) recycling the catalyst after degrading the antibiotics after high-speed centrifugation, washing and centrifuging the obtained solid with absolute ethyl alcohol for three times, removing impurities remained on the surface of the catalyst, and putting the catalyst into a drying oven for drying at 120 ℃ for 12 hours. Repeating the steps for 5 times of cyclic use, and calculating the corresponding degradation rate.
In conclusion, the mesoporous TS-1 is successfully synthesized by a photo-assisted-hydrothermal method, as shown in fig. 1, diffraction peaks (7.8 degrees, 8.8 degrees, 23.2 degrees, 23.8 degrees and 24.5 degrees) of the prepared mesoporous TS-1 photocatalyst are orthogonal symmetry, and corresponding crystal faces are (101), (200), (501), (150) and (313) respectively, and belong to an MFI (two-dimensional ten-membered ring system) zeolite structure, so that the successful synthesis of the mesoporous TS-1 is shown. As the F-127 content increases, the intensity of the TS-1 characteristic peak gradually increases.
Under the condition of ultraviolet irradiation, the performance of the catalyst for degrading erythromycin by photocatalysis is studied. As shown in fig. 2, the composite materials obtained in example 1, example 2 and example 3 have better degradation effect, wherein the example 3 has the best effect, and the degradation rate is 85.91% in 1h, which indicates that the photocatalytic performance of synthesizing mesoporous TS-1 by a photo-assisted-hydrothermal method is superior to that of synthesizing TS-1 by a traditional hydrothermal method and that of synthesizing TS-1 without adding light. As shown in FIG. 3, the morphology of the mesoporous TS-1 photocatalyst of the present invention is particle aggregate.
As shown in FIG. 4, the degradation rate of TS-10.7F-127 prepared in example 4 is still more than 65% after 4 times of circulation, and the stability is good.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The application of the mesoporous TS-1 photocatalyst in photocatalytic degradation of antibiotics in wastewater is characterized in that: the antibiotic is erythromycin; the preparation method of the mesoporous TS-1 photocatalyst comprises the following steps:
Dissolving a mesoporous template agent and tetrapropylammonium hydroxide in water to obtain a solution A;
Mixing TEOS with TBOT to obtain solution B;
Wherein, the molar ratio of the mesoporous template agent to TPAOH, TEOS, TBOT to water is 0.3-5:24:100:4:2400 a;
Dropwise adding the solution B into the solution A under the stirring condition to obtain a uniform mixed solution;
irradiating the mixed solution under an ultraviolet lamp, transferring the mixed solution into a hydrothermal kettle after the lamp is finished, and crystallizing;
After crystallization, centrifuging, washing, drying and roasting the product to obtain the mesoporous TS-1 photocatalyst;
the mesoporous template agent is F-127, CTAB or P-123;
the mixed solution is irradiated under an ultraviolet lamp for 1-3 hours.
2. The use according to claim 1, characterized in that: the crystallization temperature is 150-200 ℃ and the crystallization time is 40-50h.
3. The use according to claim 1, characterized in that: the roasting temperature is 500-600 ℃, and the roasting time is 5-7h.
4. The use according to claim 1, characterized in that: the method for degrading erythromycin in wastewater by adopting the mesoporous TS-1 photocatalyst comprises the following steps: adding the mesoporous TS-1 photocatalyst into the wastewater containing antibiotics, stirring and mixing under dark condition, and then irradiating with ultraviolet light with the power of an ultraviolet lamp of 300-500W.
5. The use according to claim 4, characterized in that: stirring under dark condition for at least 30min, and ultraviolet irradiation for at least 1 hr.
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| CN111468176A (en) * | 2020-05-15 | 2020-07-31 | 山东师范大学 | Composite catalyst and preparation method and application thereof |
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| CN110194465A (en) * | 2019-05-31 | 2019-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nanometer hierarchical pore TS-1 molecular sieve and products thereof and application |
| CN111468176A (en) * | 2020-05-15 | 2020-07-31 | 山东师范大学 | Composite catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| Reversing Titanium Oligomer Formation towards High-Efficiency and Green Synthesis of Titanium-Containing Molecular Sieves;Dong Lin et al.;《Angew. Chem. Int. Ed.》;20201221;第60卷;第3446页右栏第2段， Supporting Information中第S4页制备部分 * |
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