CN115970751A - 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 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960003276 erythromycin Drugs 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 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
- 230000001678 irradiating effect Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 7
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- 230000003115 biocidal effect Effects 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 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 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 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
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
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- 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
- 230000000274 adsorptive effect Effects 0.000 description 1
- -1 aluminosilicate anions Chemical class 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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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 solution A; mixing TEOS and TBOT to obtain solution B; wherein the mol ratio of the mesoporous template agent to the TPAOH to the TEOS to the TBOT to the water is 0-5:24:100:4:2400; dripping the B liquid into the A liquid 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 lighted, and crystallizing; and after crystallization is finished, centrifuging, washing, drying and roasting the product to obtain the mesoporous TS-1 photocatalyst. The mesoporous molecular sieve synthesized by the photocatalysis technology can reduce the dosage of the template agent, reduce the cost, greatly shorten the synthesis time, efficiently and controllably generate free radicals, and the synthesized mesoporous TS-1 photocatalyst has good degradation effect on erythromycin in a water body under ultraviolet light.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a mesoporous TS-1 photocatalyst as well as 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.
The zeolite molecular sieve is a microporous aluminosilicate crystal with regular pore channels, has excellent catalytic, adsorptive separation and ion exchange properties, and is widely applied to important fields closely related to energy and environment, such as petroleum refining, petrochemical industry, fine chemical industry, daily chemical industry and the like. Due to excellent adsorption property, unique MFI topological structure, selective catalytic function, special surface active environment and different electron-hole separation mechanisms, the material is widely concerned in the catalytic field and is praised as one of representatives of novel catalytic materials in the green chemical field. At present, molecular sieves have been partially studied for photocatalytic degradation of trace antibiotics in wastewater. Due to the intensive knowledge of zeolite molecular sieves and the increasing demand of molecular sieves in industry, molecular sieve synthesis has been provided with some mature synthetic methods, including hydrothermal synthesis, solvent thermal synthesis, dry gel conversion, solvent-free synthesis, etc. The hydrothermal synthesis method is the most common and classical method in the synthesis of molecular sieves at present, and is a synthesis method which is carried out by utilizing reactants in aqueous solution to carry out specific chemical reaction under the conditions of certain temperature (100-1000 ℃) and 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 photo-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 of degrading erythromycin in a water body, is simple in synthesis method, saves cost, provides possibility for realizing efficient, energy-saving and green synthesis of a photoresponse molecular sieve material, and provides a new method for determining other photocatalysts and catalytic reaction technical conditions.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a mesoporous TS-1 photocatalyst, which comprises the following steps:
dissolving a mesoporous template agent and tetrapropylammonium hydroxide (TPAOH) in water to obtain solution A;
mixing TEOS and TBOT to obtain solution B;
wherein the mol ratio of the mesoporous template agent to the TPAOH to the TEOS to the TBOT to the water is 0-5:24:100:4:2400;
dripping the B liquid into the A liquid 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 lighted, and crystallizing;
and after crystallization is finished, centrifuging, washing, drying and roasting the product to obtain the mesoporous TS-1 photocatalyst.
Ultraviolet irradiation can introduce hydroxyl free radicals into a reaction system, the hydroxyl free radicals can catalyze depolymerization of aluminosilicate gel by destroying Si, al-O-Si and Al bonds, and can catalyze polymerization of aluminosilicate anions around hydrated cations by reforming Si, al-O-Si and Al bonds, so that crystallization of TS-1 is promoted.
In some embodiments, the mesoporous templating agent is F-127, CTAB, or P-123.
Preferably, the mesoporous template 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 150-200 ℃ and the crystallization time is 40-50h. The product can not be synthesized at low crystallization temperature, and the energy consumption is large when the crystallization temperature is too high.
In some embodiments, the centrifugation is performed at a speed of 7000 to 8000r/min for a period of 3 to 5min.
In some embodiments, the drying temperature is 50-120 ℃ and the drying time is 2-12h.
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 template agent completely.
In a second aspect, the invention provides a mesoporous TS-1 photocatalyst prepared by the preparation method.
In a third aspect, the invention provides an application of the mesoporous TS-1 photocatalyst in photocatalytic degradation of antibiotics in wastewater.
Preferably, the antibiotic is erythromycin.
Preferably, the method for degrading the erythromycin in the wastewater by using the mesoporous TS-1 photocatalyst comprises the following steps: adding the mesoporous TS-1 photocatalyst into wastewater containing antibiotics, stirring and mixing under a dark condition, and then irradiating by adopting ultraviolet light with the power of 300-500W.
It is further preferred that the stirring time in the dark is at least 30min to ensure that the adsorption-desorption equilibrium between the catalyst and the antibiotic is achieved, and the ultraviolet irradiation time is at least 1h.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
the invention utilizes the photocatalysis technology to assist in synthesizing the mesoporous molecular sieve, so that the dosage of the 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 a water body under ultraviolet light.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is an X-ray diffraction (XRD) pattern of mesoporous TS-1 photocatalyst prepared in different proportions;
FIG. 2 shows the degradation rate of erythromycin by different photocatalysts;
FIG. 3 is a Scanning Electron Microscope (SEM) image of mesoporous TS-1 photocatalysts prepared in different proportions;
FIG. 4 shows the degradation rate of TS-1.7F-127 photocatalyst when it is recycled.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 present invention will be further described with reference to the following 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 and TBOT to obtain solution B; dripping the B liquid into the A liquid under high-speed stirring to form a mixed solution; irradiating the mixed solution for 2 hours under ultraviolet; after the illumination is finished, transferring the solution into a hydrothermal kettle, and crystallizing for 48 hours at 170 ℃; after crystallization is finished, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; at the end, the collected solid was ground to 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 the mesoporous templating agent F-127 was 0, and the obtained mesoporous TS-1 photocatalyst was denoted as 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 and TBOT to obtain solution B; dripping the B liquid into the A liquid under high-speed stirring to form a mixed solution; irradiating the mixed solution for 2 hours under ultraviolet; after the illumination is finished, transferring the solution into a hydrothermal kettle, and standing and crystallizing for 48 hours at 170 ℃; after crystallization is finished, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; at the end, the collected solid was ground to a powder. The molar ratio between the substances is 100TEOS:24TPAOH:4TBOT:2400H 2 O：xF-127。
In the embodiment, the molar ratio x of the mesoporous template agent F-127 is 0.3, and the obtained mesoporous TS-1 photocatalyst is marked as 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 and TBOT to obtain solution B; dripping the B liquid into the A liquid under high-speed stirring to form a mixed solution; irradiating the mixed solution for 2 hours under ultraviolet; after the illumination is finished, transferring the solution into a hydrothermal kettle, and standing and crystallizing at 170 ℃ for 48 hours; after crystallization is finished, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; at the end, the collected solid was ground to a powder. The molar ratio between each substance is 100TEOS:24TPAOH:4TBOT:2400H 2 O：xF-127。
In this example, the molar ratio x of the mesoporous template F-127 was 0.7, and the obtained mesoporous TS-1 photocatalyst was denoted as TS-1.7F-127.
Comparative example 1
Synthesizing TS-1 by using a traditional hydrothermal method: under the protection of nitrogen, a certain amount of TEOS is slowly dripped into TPAOH aqueous solution, and the solution is continuously stirred until the solution is colorless and transparent after the addition; measuring a certain amount of TBOT, uniformly mixing with anhydrous isopropanol, slowly adding the mixed solution into the solution through an injector, 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, keeping the temperature of 80 ℃ under the protection of nitrogen, and removing isopropanol added in the solution and alcohol generated in hydrolysis of a silicon source and a titanium source to obtain a light yellow transparent solution; transferring the obtained solution into a hydrothermal kettle, standing and crystallizing at 170 ℃ for 72 hours; after crystallization is finished, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; at the end, the collected solid was ground to a powder.
In this comparative example, the resulting TS-1 photocatalyst was noted as hydrothermal TS-1.
Comparative example 2
Dissolving a certain amount of F-127 in deionized water, adding a proper amount of TPAOH for dissolvingObtaining solution A; mixing TEOS and TBOT to obtain solution B; dripping the B liquid into the A liquid under high-speed stirring to form a mixed solution; stirring the mixed solution for 2 hours; after the reaction is finished, transferring the solution into a hydrothermal kettle, and standing and crystallizing for 48 hours at 170 ℃; after crystallization is finished, washing and drying to obtain white precipitate, and calcining the dried solid in a muffle furnace at 550 ℃ for 6 hours; at the end, the collected solid was ground to a powder. The molar ratio between the substances is 100TEOS:24TPAOH:4TBOT:2400H 2 O：xF-127。
In the comparative example, the molar ratio x of the mesoporous template F-127 is 0.7, and the obtained mesoporous TS-1 photocatalyst is marked as TS-1.7F-127 without UV.
Antibiotic degradation experiments:
the photocatalytic activity of the mesoporous TS-1 is evaluated by degrading erythromycin under ultraviolet light. The above different samples (i.e., the samples obtained in examples 1-3 and comparative examples 1-2) were weighed into 20mL quartz bottles, 10mg of the photocatalyst was dispersed in 15mL of an erythromycin aqueous solution, the suspension was stirred in the dark for 30min before light irradiation to ensure that the adsorption-desorption equilibrium between the catalyst and the erythromycin molecule was achieved, the quartz bottles were irradiated with a 500W mercury lamp and condensed with cooling water at 10 ℃, after the irradiation was completed, the suspension was sucked up with a syringe, the liquid was separated through a 0.22 μm organic nylon filter, the corresponding absorption of erythromycin at a 242nm characteristic band was monitored with an ultraviolet spectrophotometer, and the adsorption and degradation rates of erythromycin were calculated using the formula (1).
Degradation rate = (1-C) t /C 0 )×100％(1)
Formula (1): c 0 -initial concentration of antibiotic; c t -the concentration of the antibiotic at a certain time.
The reusability and stability of the materials were evaluated by cyclic degradation experiments. And (3) recovering the catalyst after degrading the antibiotics through high-speed centrifugation, washing and centrifuging the obtained solid for three times by using absolute ethyl alcohol, removing impurities remained on the surface of the catalyst, and drying the catalyst in a drying oven at 120 ℃ for 12 hours. And repeating the steps on the dried photocatalytic material, recycling for 5 times, and calculating the corresponding degradation rate.
In conclusion, the mesoporous TS-1 is successfully synthesized by the photo-assisted-hydrothermal method, as shown in FIG. 1, diffraction peaks (7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.5 °) of the prepared mesoporous TS-1 photocatalyst are in orthogonal symmetry, corresponding crystal planes are (101), (200), (501), (150) and (313), and the mesoporous TS-1 is successfully synthesized. As the content of F-127 is increased, the intensity of the TS-1 characteristic peak is gradually increased.
Under the condition of ultraviolet illumination, the performance of the catalyst for degrading the erythromycin by photocatalysis is researched. As shown in FIG. 2, the composite materials obtained in examples 1, 2 and 3 have better degradation effect, wherein the effect of example 3 is the best, and the degradation rate is 85.91% within 1h, which indicates that the photocatalytic performance of the mesoporous TS-1 synthesized by the photo-assisted-hydrothermal method is better than that of the TS-1 synthesized by the traditional hydrothermal method and that of the TS-1 synthesized without adding light. As shown in FIG. 3, the mesoporous TS-1 photocatalyst of the invention has a particle aggregate morphology.
As shown in FIG. 4, the TS-10.7F-127 prepared in example 4 has a degradation rate of more than 65% after being circulated for 4 times, and has good stability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a mesoporous TS-1 photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
dissolving a mesoporous template and tetrapropylammonium hydroxide in water to obtain a solution A;
mixing TEOS and TBOT to obtain solution B;
wherein the mol ratio of the mesoporous template agent to the TPAOH to the TEOS to the TBOT to the water is 0-5:24:100:4:2400;
dripping the B liquid into the A liquid 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 lighted, and crystallizing;
and after crystallization is finished, centrifuging, washing, drying and roasting the product to obtain the mesoporous TS-1 photocatalyst.
2. The method for preparing the mesoporous TS-1 photocatalyst according to claim 1, wherein the method comprises the following steps: the mesoporous template is F-127, CTAB or P-123.
3. The method for preparing the mesoporous TS-1 photocatalyst according to claim 1, wherein the method comprises the following steps: irradiating the mixed solution under an ultraviolet lamp for 1-3h.
4. The method for preparing the mesoporous TS-1 photocatalyst according to claim 1, wherein the method comprises the following steps: the crystallization temperature is 150-200 ℃, and the crystallization time is 40-50h.
5. The method for preparing the mesoporous TS-1 photocatalyst according to claim 1, wherein the method comprises the following steps: the roasting temperature is 500-600 ℃, and the roasting time is 5-7h.
6. A mesoporous TS-1 photocatalyst is characterized in that: prepared by the preparation method of any one of claims 1 to 5.
7. The use of the mesoporous TS-1 photocatalyst of claim 6 in photocatalytic degradation of antibiotics in wastewater.
8. Use according to claim 7, characterized in that: the antibiotic is erythromycin.
9. Use according to claim 7, characterized in that: the method for degrading the erythromycin in the wastewater by adopting the mesoporous TS-1 photocatalyst comprises the following steps: and adding the mesoporous TS-1 photocatalyst into wastewater containing antibiotics, stirring and mixing under a dark condition, and irradiating by adopting ultraviolet light with the power of 300-500W.
10. Use according to claim 9, characterized in that: stirring in dark for at least 30min, and irradiating with ultraviolet light for at least 1h.
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Patent Citations (4)
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| CN107398299A (en) * | 2017-05-09 | 2017-11-28 | 浙江师范大学 | A kind of preparation method and application of the catalyst of modified TS 1 |
| CN108246362A (en) * | 2018-01-16 | 2018-07-06 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications of bulky grain TS-1 Titanium Sieve Molecular Sieve |
| 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 |
|---|
| DONG LIN ET AL.: "Reversing Titanium Oligomer Formation towards High-Efficiency and Green Synthesis of Titanium-Containing Molecular Sieves", 《ANGEW. CHEM. INT. ED.》, vol. 60, 21 December 2020 (2020-12-21), pages 3446 * |
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