CN115555052A - UiO-66@ titanium dioxide composite photocatalyst, and preparation method and application thereof - Google Patents
UiO-66@ titanium dioxide composite photocatalyst, and preparation method and application thereof Download PDFInfo
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- CN115555052A CN115555052A CN202211472034.1A CN202211472034A CN115555052A CN 115555052 A CN115555052 A CN 115555052A CN 202211472034 A CN202211472034 A CN 202211472034A CN 115555052 A CN115555052 A CN 115555052A
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- titanium dioxide
- dioxide composite
- composite photocatalyst
- tetrabutyl titanate
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000013207 UiO-66 Substances 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000004098 Tetracycline Substances 0.000 claims description 20
- 229960002180 tetracycline Drugs 0.000 claims description 20
- 229930101283 tetracycline Natural products 0.000 claims description 20
- 235000019364 tetracycline Nutrition 0.000 claims description 20
- 150000003522 tetracyclines Chemical class 0.000 claims description 17
- 230000001699 photocatalysis Effects 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 229910010413 TiO 2 Inorganic materials 0.000 description 17
- 238000001132 ultrasonic dispersion Methods 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000003068 static effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 3
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention belongs to the technical field of photocatalytic degradation, and relates to a UiO-66@ titanium dioxide composite photocatalyst, and a preparation method and application thereof. Under the inert atmosphere, heating up the UiO-66 to 200 to 400 ℃ by a program for heat treatment; adding the thermally treated UiO-66 and tetrabutyl titanate into an organic solvent, uniformly mixing, adding water, and then treating at 120-220 ℃ by adopting a solvothermal method to obtain the material; wherein the addition ratio of the UO-66 and tetrabutyl titanate after heat treatment is 5-100, and the addition ratio is (mg): and (mL). In the invention, uiO-66 and TiO are mixed 2 Combined construction of heterogeneous composite materials, can inhibitThe photo-generated electron-hole recombination rate promotes charge separation, improves the energy band structure of the material, and is beneficial to enhancing the light absorption capacity and light stability of the material to visible light, thereby improving the photocatalytic degradation capacity of the material.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation, and relates to a UiO-66@ titanium dioxide composite photocatalyst, and a preparation method and application thereof.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The UiO-66 has the advantages of large specific surface area, excellent structure adjustability, rich pore channel structures and the like, and is widely used for photoelectrocatalysis, photodegradation, adsorption and separation. However, pure UiO-66 (Zr) has low separation efficiency of photo-generated electrons and holes, high recombination rate and poor photocatalytic performance.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a UiO-66@ titanium dioxide composite photocatalyst, and a preparation method and application thereof, wherein the UiO-66 and TiO are mixed 2 The heterogeneous composite material is combined to construct, so that the photogenerated electron-hole recombination rate can be inhibited, the charge separation is promoted, the energy band structure of the material is improved, the light absorption capability and the light stability of the material to visible light are enhanced, and the photocatalytic degradation capability of the material is improved.
In order to realize the purpose, the technical scheme of the invention is as follows:
on one hand, the preparation method of the UiO-66@ titanium dioxide composite photocatalyst comprises the following steps:
under the inert atmosphere, heating up the UiO-66 to 200 to 400 ℃ by a program for heat treatment;
adding the thermally treated UiO-66 and tetrabutyl titanate into an organic solvent, uniformly mixing, adding water, and then treating at 120-220 ℃ by adopting a solvent heating method to obtain the product;
wherein the addition ratio of the UiO-66 after heat treatment to the tetrabutyl titanate is (5) - (100): and (mL).
On the other hand, the UiO-66@ titanium dioxide composite photocatalyst is obtained by the preparation method.
In order to improve the photocatalytic activity of UiO-66, tiO is adopted in the invention 2 And compounding the components. The UiO-66 is a metal organic framework structure material, can be compounded by adopting a direct mixing mode, and can also adopt TiO in-situ growth on the surface of the UiO-66 2 The method (2) is combined. However, the research shows that the performance of photocatalytic degradation of tetracycline is not obviously improved after the method is compounded with UiO-66. The invention is further researched and unexpectedly found that when the UiO-66 is heated to 200-400 ℃ by a program for heat treatment, tiO is grown in situ on the surface of the UiO-66 2 The method is compounded, and the performance of the obtained photocatalyst for degrading tetracycline through photocatalysis is obviously improved.
In a third aspect, the UiO-66@ titanium dioxide composite photocatalyst is applied to photocatalytic degradation of tetracycline.
In a fourth aspect, a method for treating tetracycline in water or wastewater by photocatalysis is to add the UiO-66@ titanium dioxide composite photocatalyst into the water or wastewater containing tetracycline to be treated for illumination treatment.
The beneficial effects of the invention are as follows:
1. the invention realizes the preparation of TiO on the surface of the UiO-66 by firstly carrying out heat treatment on the UiO-66 2 A heterojunction composite structure is constructed, the energy band structure of the UiO-66 is improved, and the charge separation efficiency is enhanced, so that the UiO-66-250@ TiO 2 Photocatalyst toolHas high photocatalytic degradation performance.
2. Experiments show that compared with UiO-66, the degradation rate of the photocatalytic degradation tetracycline of the UiO-66@ titanium dioxide composite photocatalyst prepared by the invention can be increased from 47.3% to 99.8%, and the photocatalytic degradation rate is remarkably increased.
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 a XRD result pattern of a material prepared in example 15 of the present invention;
FIG. 2 is a XRD result pattern of the material prepared in example 2 of the present invention;
FIG. 3 is a SEM result chart of the material prepared in example 15 of the present invention;
FIG. 4 is a SEM result chart of the material prepared in example 2 of the present invention;
FIG. 5 is a graph showing the results of photocatalytic degradation of Tetracycline (TC) in materials prepared in examples 2 and 9 to 12 of the present invention;
wherein 2, 9, 10, 11, 12 represent the samples produced in examples 2, 9, 10, 11, 12, respectively.
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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the poor ability of the existing UiO-66 to degrade tetracycline through photocatalysis, the invention provides the UiO-66@ titanium dioxide composite photocatalyst, and a preparation method and application thereof.
The invention provides a preparation method of a UiO-66@ titanium dioxide composite photocatalyst, which comprises the following steps:
under the inert atmosphere, heating up the UiO-66 to 200 to 400 ℃ by a program for heat treatment;
adding the thermally treated UiO-66 and tetrabutyl titanate into an organic solvent, uniformly mixing, adding water, and then treating at 120-220 ℃ by adopting a solvothermal method to obtain the material;
wherein the addition ratio of the UO-66 and tetrabutyl titanate after heat treatment is 5-100, and the addition ratio is (mg): and (mL).
The inert atmosphere may be nitrogen or an inert gas such as helium, neon, or argon.
In some embodiments, the temperature ramp rate of the temperature program is 2 to 20 ℃/min. Preferably 5 to 15 ℃/min.
In some embodiments, the heat treatment time is 1 to 8 hours. The heat treatment temperature is preferably 240 to 260 ℃.
In some embodiments, the heat-treated UiO-66 and tetrabutyl titanate are added to an organic solvent, and the organic solvent is ethanol, and the mixture is uniformly mixed.
In some embodiments, the volume of the reaction system in the solvothermal treatment is 60 to 70% of the volume of the reaction kettle.
In some embodiments, the solvent thermal method is adopted for the treatment time of 5 to 30 hours.
In some embodiments, the amount of water added is 2 to 3 times the volume of tetrabutyl titanate.
In some embodiments, the ratio of the addition of the heat-treated UiO-66 to tetrabutyl titanate is 40: and (mL).
The UiO-66 is a typical material of UiO series MOFs, and is made of Zr 6 O 4 (OH) 4 A nucleus consisting of polyhedral units each of H 2 COOH in BDC are connected to constitute Zr 6 O 4 (OH) 4 (CO 2 ) 12 And (4) clustering. The UiO-66 can be obtained commercially or synthetically. In some embodiments, uiO-66 is via ZrCl 4 And terephthalic acid (BDC) in a molar ratio of 1. More specifically, zrCl 4 Mixing the solution, a terephthalic acid solution and acetic acid, performing ultrasonic dispersion, and reacting for 5 to 30 hours at the temperature of 100 to 200 ℃ to obtain the nano-silver-doped p-phenylene terephthalamide. ZrCl 4 The solvent in the solution and the terephthalic acid solution is DMF (N, N-dimethylformamide).
In another embodiment of the invention, the UiO-66@ titanium dioxide composite photocatalyst is obtained by the preparation method.
The third embodiment of the invention provides an application of the UiO-66@ titanium dioxide composite photocatalyst in photocatalytic degradation of tetracycline.
In a fourth embodiment of the invention, a method for photocatalytic treatment of tetracycline in water or wastewater is provided, wherein the UiO-66@ titanium dioxide composite photocatalyst is added into the water or wastewater containing tetracycline to be treated for light treatment.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1:
this example is the synthesis of UiO-66-250@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1 mL of acetic acid are subjected to uniform ultrasonic dispersion and then to static reaction at 120 ℃ for 24 hours. After centrifugation, the product is washed with methanol several times to obtain UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-250.
3. 40 mg of UiO-66-250 and 0.125 mL of tetrabutyl titanateThe ester was dispersed in 20 mL ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 24 h, cooling to room temperature, washing with ethanol for three times to obtain UiO-66-250@ TiO 2 。
Example 2:
this example was a synthesis of UiO-66-250@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1.37 mL of acetic acid are subjected to uniform ultrasonic dispersion and then subjected to static reaction at 120 ℃ for 24 hours. After centrifugation, the product is washed with methanol several times to obtain UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-250.
3. 40 mg of UiO-66-250 and 0.125 mL of tetrabutyltitanate were dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 24 h, cooling to room temperature, and washing with ethanol for three times to obtain UiO-66-250@TiO 2 。
Example 3:
this example was a synthesis of UiO-66-250@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 After uniform ultrasonic dispersion of 5mL of terephthalic acid (BDC) in DMF (20 mmol/L), and 1.37 mL of acetic acid, the mixture was allowed to react statically at 120 ℃ for 24 hours. After centrifugation, the product is washed with methanol several times to obtain UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 10 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-250.
3. 40 mg of UiO-66-250 and 0.1 mL of tetrabutyltitanate were dispersed in 20 mL of ethanol and stirred at room temperature for 30min. After addition of 0.3 mL of water, the suspension was transferred to30 Heating at 120 deg.C for 24 hr in mL reaction kettle, cooling to room temperature, washing with ethanol for three times to obtain UiO-66-250@ TiO 2 。
Example 4:
this example is the synthesis of UiO-66-250@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 After uniform ultrasonic dispersion of 5mL of terephthalic acid (BDC) in DMF (20 mmol/L), and 1.37 mL of acetic acid, the mixture was allowed to react statically at 120 ℃ for 24 hours. After centrifugation, the product is washed with methanol several times to obtain UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-250.
3. 40 mg of UiO-66-250 and 0.125 mL of tetrabutyltitanate were dispersed in 10 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 24 h, cooling to room temperature, washing with ethanol for three times to obtain UiO-66-250@ TiO 2 。
Example 5:
this example was a synthesis of UiO-66-250@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 After uniform ultrasonic dispersion of 5mL of terephthalic acid (BDC) in DMF (20 mmol/L), and 1.37 mL of acetic acid, the mixture was allowed to react statically at 120 ℃ for 24 hours. After centrifugation, the product was washed with methanol several times to give UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-250.
3. 40 mg of UiO-66-250 and 0.125 mL of tetrabutyltitanate were dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.5 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 24 h, cooling to room temperature, and washing with ethanol for three times to obtain the final productTo UiO-66-250@ TiO 2 。
Example 6:
this example is the synthesis of UiO-66-200 @TiOaccording to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 After uniform ultrasonic dispersion of 5mL of terephthalic acid (BDC) in DMF (20 mmol/L), and 1.37 mL of acetic acid, the mixture was allowed to react statically at 120 ℃ for 24 hours. After centrifugation, the product was washed with methanol several times to give UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 200 ℃ at the speed of 3 ℃/min, and keeping for 2 h to obtain UiO-66-200.
3. 40 mg of UiO-66-200 and 0.125 mL of tetrabutyltitanate were dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 24 h, cooling to room temperature, and washing with ethanol for three times to obtain UiO-66-200@TiO 2 。
Example 7:
this example is the synthesis of UiO-66-200@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1.37 mL of acetic acid are subjected to uniform ultrasonic dispersion and then subjected to static reaction at 120 ℃ for 24 hours. After centrifugation, the product was washed with methanol several times to give UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 200 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-200.
3. 40 mg of UiO-66-200 and 0.125 mL of tetrabutyl titanate were dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 180 ℃ for 24 h, cooling to room temperature, washing with ethanol for three times to obtain UiO-66-200@ TiO 2 。
Example 8:
this example is the synthesis of UiO-66-250@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1.37 mL of acetic acid are subjected to uniform ultrasonic dispersion and then subjected to static reaction at 120 ℃ for 24 hours. After centrifugation, the product was washed with methanol several times to give UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 4 h to obtain UiO-66-250.
3. 40 mg of UiO-66-250 and 0.125 mL of tetrabutyl titanate were dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 15 h, cooling to room temperature, washing with ethanol for three times to obtain UiO-66-250@ TiO 2 。
Example 9:
in this example, the UiO-66-250 photocatalyst was synthesized according to the following steps:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1.37 mL of acetic acid are subjected to uniform ultrasonic dispersion and then subjected to static reaction at 120 ℃ for 24 hours. After centrifugation, the product was washed with methanol several times to give UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-250.
Example 10
This example is the synthesis of UiO-66@ TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1.37 mL of acetic acid are subjected to uniform ultrasonic dispersion and then subjected to static reaction at 120 ℃ for 24 hours. After centrifugation, the product was washed with methanol several times to give UiO-66.
2. 40 mg of UiO-66 and 0.125 mL of tetrabutyltitanate were dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 15 h, cooling to room temperature, and washing with ethanol for three times to obtain UiO-66@ TiO 2 。
Example 11
This example is a synthesis of UiO-66/TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1.37 mL of acetic acid are subjected to uniform ultrasonic dispersion and then subjected to static reaction at 120 ℃ for 24 hours. After centrifugation, the product was washed with methanol several times to give UiO-66.
2. 0.125 mL of tetrabutyl titanate was dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 15 h, cooling to room temperature, and washing with ethanol for three times to obtain TiO 2 (ii) a TiO to be obtained 2 Adding 40 mg of UiO-66 into 20 mL of ethanol, and carrying out ultrasonic treatment for 90 min to obtain UiO-66/TiO 2 。
Example 12
This example is the synthesis of UiO-66-250/TiO according to the following procedure 2 Photocatalyst:
1.5 mLZrCl 4 The solution of terephthalic acid (20 mmol/L) in DMF, 5mL of terephthalic acid (BDC) in DMF, the concentration of which is 20 mmol/L, and 1.37 mL of acetic acid are subjected to uniform ultrasonic dispersion and then subjected to static reaction at 120 ℃ for 24 hours. After centrifugation, the product is washed with methanol several times to obtain UiO-66.
2. 40 mg of UiO-66 was dispersed in a quartz boat, placed in a tube furnace, and subjected to N at a flow rate of 20 mL/min 2 Protecting, raising the temperature to 250 ℃ at the speed of 10 ℃/min, and keeping for 2 h to obtain UiO-66-250.
3. 0.125 mL of tetrabutyltitanate was dispersed in 20 mL of ethanol and stirred at room temperature for 30min. Adding 0.3 mL of water, transferring the suspension into a 30 mL reaction kettle, heating at 120 ℃ for 15 h, cooling to room temperature, and washing with ethanol for three times to obtain TiO 2 (ii) a Will obtainOf TiO 2 2 Adding 40 mg of UiO-66-250 into 20 mL of ethanol, and carrying out ultrasonic treatment for 90 min to obtain UiO-66-250/TiO 2 。
As can be seen from FIG. 1, only the characteristic diffraction peak of the UiO-66 phase appears in the XRD result of the sample prepared in example 15, and the characteristic peak of other substances is not found, which indicates that the main component of the material obtained by the method is UiO-66.
As can be seen from FIG. 2, the XRD results of the samples prepared in example 2 showed the appearance of UiO-66 phase and TiO 2 The characteristic diffraction peak of the phase indicates that the method can successfully prepare the UiO-66-250@ TiO 2 A heterojunction complex.
As can be seen from FIG. 3, the morphology of the sample prepared in example 9 is octahedral, with an average particle size of about 500 nm.
As can be seen from fig. 4, the morphology of the sample prepared in example 2 is still octahedral, and in addition, the roughness of the surface of the material is obviously increased, and a large number of particles exist on the surface.
The photocatalytic degradation performance of the catalyst was measured using a xenon lamp (solar simulated irradiation AM 1.5G) as a light source and tetracycline hydrochloride (TC) as a target pollutant. The prepared sample (10 mg) was dispersed in 100mL of a tetracycline hydrochloride solution at a concentration of 10 mg/L, and the dispersion was kept in a dark environment for 20 minutes. The light source was then turned on and the dispersion (5 ml) was collected every 20 minutes. The residual amount of tetracycline hydrochloride was determined by uv spectrophotometry, and purified water was used as a reference sample. Under the same conditions (2 h, AM 1.5G), the samples prepared in examples 1 to 12 had a degradation rate of photocatalytic degradation of tetracycline of 87.6%, 99.8%, 78.9%, 91.6%, 90.6%, 76.2%, 79.3%, 85.1%, 47.3%, 48.2%, 53.7%, 69.4%, respectively. Wherein, the degradation rate of the photocatalytic degradation tetracycline of the embodiment 2 and the embodiments 9 to 12 is shown in FIG. 5, which shows that only the UiO-66 is subjected to heat treatment and then TiO is prepared on the surface of the film 2 The energy band structure of the material is improved only by the constructed heterojunction composite structure, so that the separation efficiency of photogenerated electrons and holes of the composite photocatalyst is effectively improved, and the performance of the material for photocatalytic degradation of Tetracycline (TC) is improved.
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 UiO-66@ titanium dioxide composite photocatalyst is characterized by comprising the following steps:
under the inert atmosphere, heating up the UiO-66 to 200 to 400 ℃ by a program for heat treatment;
adding the thermally treated UiO-66 and tetrabutyl titanate into an organic solvent, uniformly mixing, adding water, and then treating at 120-220 ℃ by adopting a solvent heating method to obtain the product;
wherein the addition ratio of the UO-66 and tetrabutyl titanate after heat treatment is 5-100, and the addition ratio is (mg): and (mL).
2. The method for preparing the UiO-66@ titanium dioxide composite photocatalyst as claimed in claim 1, wherein the temperature rise rate of programmed temperature rise is 2 to 20 ℃/min.
3. The method for preparing the UiO-66@ titanium dioxide composite photocatalyst as claimed in claim 1, wherein the heat treatment time is 1-8 h.
4. The method for preparing the UiO-66@ titanium dioxide composite photocatalyst as claimed in claim 1, wherein the organic solvent is ethanol in the process of adding the heat-treated UiO-66 and tetrabutyl titanate into the organic solvent for uniform mixing.
5. The method for preparing the UiO-66@ titanium dioxide composite photocatalyst as claimed in claim 1, wherein in the solvothermal treatment, the volume of a reaction system is 60 to 70% of the volume of a reaction kettle.
6. The method for preparing the UiO-66@ titanium dioxide composite photocatalyst as claimed in claim 1, wherein the solvothermal treatment time is 5-30 h.
7. The method for preparing the UiO-66@ titanium dioxide composite photocatalyst as claimed in claim 1, wherein the addition amount of water is 2-3 times of the volume of tetrabutyl titanate.
8. The preparation method of the UiO-66@ titanium dioxide composite photocatalyst as claimed in claim 1, wherein the addition ratio of the heat-treated UiO-66 to tetrabutyl titanate is 40: and (mL).
9. An application of the UiO-66@ titanium dioxide composite photocatalyst prepared by the preparation method of the UiO-66@ titanium dioxide composite photocatalyst as defined in any one of claims 1 to 8 in photocatalytic degradation of tetracycline.
10. A method for treating tetracycline in water or wastewater by photocatalysis is characterized in that the UiO-66@ titanium dioxide composite photocatalyst prepared by the preparation method of the UiO-66@ titanium dioxide composite photocatalyst in any one of claims 1 to 8 is added into the water or wastewater containing tetracycline to be treated for illumination treatment.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722497A (en) * | 2018-05-03 | 2018-11-02 | 华南理工大学 | A kind of TiO2- MOFs photochemical catalysts and the preparation method and application thereof |
| CN110639620A (en) * | 2019-10-12 | 2020-01-03 | 湖南大学 | Composite photocatalyst for degrading tetracycline and preparation method and application thereof |
| CN113058659A (en) * | 2021-03-19 | 2021-07-02 | 东南大学 | Nano TiO (titanium dioxide)2Preparation method and application of/UiO-66 composite material |
| CN113101980A (en) * | 2021-04-15 | 2021-07-13 | 汕头市弘东环境治理有限公司 | TiO with visible light catalytic activity2Preparation method and application of/UiO-66 composite material |
| CN113209941A (en) * | 2021-04-14 | 2021-08-06 | 山东大学 | Hydrophobic dual-ligand metal organic framework material, preparation method and application in VOCs adsorption |
-
2022
- 2022-11-23 CN CN202211472034.1A patent/CN115555052B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722497A (en) * | 2018-05-03 | 2018-11-02 | 华南理工大学 | A kind of TiO2- MOFs photochemical catalysts and the preparation method and application thereof |
| CN110639620A (en) * | 2019-10-12 | 2020-01-03 | 湖南大学 | Composite photocatalyst for degrading tetracycline and preparation method and application thereof |
| WO2021068570A1 (en) * | 2019-10-12 | 2021-04-15 | 湖南大学 | Composite photocatalyst for degrading tetracycline, preparation method therefor and use thereof |
| CN113058659A (en) * | 2021-03-19 | 2021-07-02 | 东南大学 | Nano TiO (titanium dioxide)2Preparation method and application of/UiO-66 composite material |
| CN113209941A (en) * | 2021-04-14 | 2021-08-06 | 山东大学 | Hydrophobic dual-ligand metal organic framework material, preparation method and application in VOCs adsorption |
| CN113101980A (en) * | 2021-04-15 | 2021-07-13 | 汕头市弘东环境治理有限公司 | TiO with visible light catalytic activity2Preparation method and application of/UiO-66 composite material |
Non-Patent Citations (2)
| Title |
|---|
| YANG JIAO ET AL.: "Heat-Treatment of Defective UiO-66 from Modulated Synthesis: Adsorption and Stability Studies", 《THE JOURNAL OF PHYSICAL CHEMISTRY》 * |
| 韩易潼等: "高稳定性金属有机骨架UiO-66的合成与应用", 《应用化学》 * |
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Denomination of invention: UiO-66 @ titanium dioxide composite photocatalyst and its preparation method and application Effective date of registration: 20231020 Granted publication date: 20230512 Pledgee: Branches of Jinan Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG HUANTOU ENVIRONMENT ENGINEERING CO.,LTD. Registration number: Y2023980062074 |
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