CN116689041B - Dye sensitization type TiO 2 Photocatalyst of @ HOFs, preparation method and application - Google Patents
Dye sensitization type TiO 2 Photocatalyst of @ HOFs, preparation method and application Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 107
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 206010070834 Sensitisation Diseases 0.000 title claims abstract description 15
- 230000008313 sensitization Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000013384 organic framework Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002135 nanosheet Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- RTSZQXSYCGBHMO-UHFFFAOYSA-N 1,2,4-trichloro-3-prop-1-ynoxybenzene Chemical compound CC#COC1=C(Cl)C=CC(Cl)=C1Cl RTSZQXSYCGBHMO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 208000017983 photosensitivity disease Diseases 0.000 abstract description 2
- 231100000434 photosensitization Toxicity 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 89
- 239000004408 titanium dioxide Substances 0.000 description 44
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 16
- 239000000975 dye Substances 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 6
- 238000000527 sonication Methods 0.000 description 5
- 238000003260 vortexing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001878 scanning electron micrograph 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
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
Abstract
The invention discloses dye sensitization type TiO 2 An HOFs photocatalyst, a preparation method and application thereof, which belong to the technical fields of material science, environmental science and synthesis. The invention combines hydrogen bond organic framework material and TiO 2 Dispersing in deionized water, performing ultrasonic treatment, and then performing rotational speed vortex vibration to obtain a milky suspension; centrifuging the milky suspension, and drying the obtained solid sample to obtain dye sensitized TiO 2 @ HOFs photocatalysts. The invention combines HOF-TCPB-373 with TiO 2 Combining to prepare the RhB sensitized TiO 2 The @ HOF photocatalyst can effectively solve the problems of RhB-TiO 2 The method has the advantages of low sensitization efficiency in the system, high photosensitization and catalytic activity, and wide application prospect in the field of photocatalysis.
Description
Technical Field
The invention belongs to the technical fields of material science, environmental science and synthesis, and in particular relates to dye sensitization type TiO 2 An HOFs photocatalyst, a preparation method and application thereof.
Background
Titanium dioxide (TiO) 2 ) Is a catalyst widely applied in the field of photocatalysis, and has the advantages of high photocatalytic activity, strong oxidizing property, no corrosiveness, chemical stability, low cost and the like. But TiO 2 There are also problems of large band gap, low visible light absorption efficiency, poor water dispersibility, etc., which will result in a decrease in quantum yield thereof, a decrease in separation efficiency of photogenerated electron-hole pairs, and thus limit photocatalytic activity thereof. Therefore, to improve TiO 2 Various TiO-based materials have been synthesized based on the photocatalytic properties of (C) 2 The structure and composition of the composite material are modified, and dye sensitization is one of effective methods.
Organic dyes are widely used in daily life and industrial processes and are a common source of water pollution due to their toxicity and limited biodegradability. Most dyes are colored and have excellent light absorbing ability. Therefore, the dye can be used as a sensitizer of the photocatalyst in the photodegradation process. Rhodamine B (rhodoamineb, rhB) is a common organic dye that has the ability to absorb visible light and is excited to generate photoelectrons. However, rhb sensitized TiO 2 And does not exhibit significant improvement in photocatalytic activity. TiO (titanium dioxide) 2 And the material with a proper energy band structure is used for adjusting the band gap, promoting the separation and transfer of charges between RhB and the catalyst and improving the sensitization efficiency.
The hydrogen bond organic frameworks (HOFs) are crystalline porous materials formed by connecting organic structural elements through intermolecular hydrogen bonds, and are also called Supermolecule Organic Frameworks (SOFs) and the like, and the unique physical and chemical properties of the porous materials make the porous materials have important progress in the fields of gas storage and separation, proton conduction, biomedical treatment, molecular recognition, heterogeneous catalysis and the like. However, flexible and reversible hydrogen bonding results in poor stability of HOFs materials, limiting their application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a dye sensitization type TiO 2 An HOFs photocatalyst, a preparation method and application thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
dye sensitization type TiO 2 Photo-catalyst of HOFs, HOFs material and TiO 2 Compounding according to the mass ratio of 10-90:90-10. I.e. TiO, in 100% by mass of the total 2 The ratio of the material is 10-90%, and the balance is HOFs material. Further, the HOFs material is HOF-TCPB-373 nanometer sheet, and the preparation method comprises the following steps:
1) Will H 4 Dissolving TCPB in an organic solvent, putting the dissolved sample into deionized water, and performing heating treatment under a sealing condition to obtain colorless flaky crystals;
2) Pulverizing and grinding the colorless flaky crystals, dispersing the colorless flaky crystals in an organic solvent, soaking the obtained mixture in an ice water bath, and standing to obtain a suspension;
3) Centrifuging the suspension at 8000-12000rpm for 10-30min to obtain HOF-TCPB-373 nanometer sheet.
Further, the heat treatment in step 1) means maintaining at 373K for 2 to 10 days.
Further, the H in step 1) 4 The dosage ratio of TCPB to organic solvent is (10-80) mg to (1-10) mL; the organic solvent is DMF.
Further, in step 2), the organic solvent is ethanol.
The invention also provides the dye sensitization type TiO 2 The preparation method of the @ HOFs photocatalyst comprises the following steps:
HOFs and TiO 2 Dispersing in deionized water, performing ultrasonic treatment, and then performing vortex vibration at a rotating speed of 2500rpm to obtain milky suspension; centrifuging the milky suspension at 8000-12000rpm, and drying the solid sample to obtain dye sensitized TiO 2 @ HOFs photocatalysts.
Further, the TiO 2 The mass percentage in the system is 10-90%. Preferably 20%, 40%, 60%, 80%.
The invention also provides the dye sensitization type TiO 2 Application of @ HOFs photo-catalyst in degrading rhodamine B in wastewater.
Compared with the prior art, the invention has the following advantages and technical effects:
HOF-TCPB-373 is a highly stable HOF material, which shows excellent thermal, hydrolytic and acid-base stability due to its double hydrogen bond and 2-fold interpenetrating structure. The invention combines HOF-TCPB-373 with TiO 2 Combining to prepare the RhB sensitized TiO 2 The @ HOF composite catalyst can effectively solve the problem of RhB-TiO 2 The problem of low sensitization efficiency in the system, high-efficiency photosensitization and catalytic activity, and wide application prospect in the field of photocatalysis, and the method is specific: (1) HOF-TCPB-373 has ultra-thin nano-sheet morphology, and is beneficial to granular TiO 2 Surface adhesion to form composite materialsA heterojunction structure; (2) HOF-TCPB-373 has photochemical activity, possibly with TiO 2 Generating synergistic photocatalysis; (3) The HOF-TCPB-373 contains rich carboxyl groups to enhance TiO 2 And provides an electronegative surface to promote adsorption of cationic RhB on the catalyst, promote contact and charge transfer of the catalyst with RhB in aqueous solution.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 shows dye-sensitized TiO according to an embodiment of the present invention 2 Schematic diagram of preparation flow of @ HOFs photocatalyst;
FIG. 2 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And an X-ray diffraction pattern of HOF-TCPB-73;
FIG. 3 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And FTIR spectra of HOF-TCPB-73;
FIG. 4 40% TiO prepared in example 1 2 SEM image and EDS element distribution map of @ HOFs photocatalyst;
FIG. 5 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And XPS spectrum of HOF-TCPB-73;
FIG. 6 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And nitrogen adsorption and desorption isotherms of HOF-TCPB-73;
FIG. 7 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And HOF-TCPB-73;
FIG. 8 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And a Zeta potential map of HOF-TCPB-73;
FIG. 9 shows 40% TiO as prepared in examples 1-4 2 @HOFs、20％TiO 2 @HOFs、60％TiO 2 @HOFs、80％TiO 2 The @ HOFs photocatalyst is used for treating R in aqueous solutionComparison of the kinetics of elimination of hB;
FIG. 10 shows 40% TiO as prepared in examples 1-4 2 @HOFs、20％TiO 2 @HOFs、60％TiO 2 @HOFs、80％TiO 2 The adsorption and photodegradation capacities of the @ HOFs photocatalyst on RhB in the aqueous solution are compared;
FIG. 11 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And UV-vis diffuse reflectance spectra of HOF-TCPB-73.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the following examples of the present invention are all commercially available.
The invention provides dye sensitization type TiO 2 The preparation method of the @ HOFs photocatalyst comprises the following steps:
1) Will be 10-80mgH 4 TCPB is dissolved in 1-10mLDMF and placed in a cover-less glass bottle, which is then placed in a large beaker containing 5-50mL deionized water. The beaker was sealed and kept at 373K for 2-10 days to give colorless platelet crystals. These bulk crystals were milled for 30-60 minutes and then dispersed in 20-200mL ethanol (analytically pure) to give a mixture. Soaking the mixture in ice water bath for 10-120 min, standing for 12-24 hr, and centrifuging the obtained suspension at 8000-12000rpm for 10-30min to obtain HOF-TCPB-373 nanometer sheet;
2) HOF-TCPB-373 nano-sheet and TiO 2 Mixing and dispersing in deionized water according to the mass ratio of 10-90:90-10, wherein the adding amount of the deionized water is TiO in the system 2 Is 10-90% by mass (in the system, tiO 2 10-90% by mass, which means that the mass percentage of HOF-TCPB-373 nanosheets is 10-90% by mass, as in the following examples of the invention. Ultrasonic treatment for 10-60 min, and vortex vibration at 2500rpm for 10-60 min to obtain milky suspension. Centrifuging the milky suspension at 8000-12000rpm for 10-30min, separating solid sample, and drying at 80-150deg.C for 12-48 hr to obtain x% TiO 2 HOF (x is TiO) 2 Is contained in the formula (I).
Dye sensitization type TiO prepared by the invention 2 The performance test method of the @ HOFs photocatalyst is as follows:
in a quartz reaction kettle, the photocatalytic activity of the catalyst was evaluated under the conditions of circulating water cooling and magnetic stirring. 5-50mgTiO 2 @HThe OF photocatalyst is dispersed in 10-500mL OF RhB aqueous solution with initial concentration OF 5-50 mg/L. First, the system is kept in the dark for 30-120 minutes to reach adsorption-desorption equilibrium. Subsequently, a 300W xenon lamp was used as a light source to initiate photocatalytic degradation, and visible light was provided by selecting the wavelength of the filter. The wavelength ranges are 420-800nm,500-800nm or single 520nm. The concentration of RhB was determined by UV-visible spectroscopy.
The following examples serve as further illustration of the technical scheme of the present invention, and FIG. 1 is a schematic flow chart of the preparation of the photocatalyst according to the following examples of the present invention.
Example 1
1) Will be 20mgH 4 TCPB was dissolved in 1mLDMF and placed in a cover-less glass bottle, which was then placed in a large beaker containing 10mL of deionized water. The beaker was sealed and kept at 373K for 2 days, and colorless flaky crystals were precipitated. The pellet was taken out and dried, and after 30 minutes of grinding, it was dispersed in 50mL of ethanol to obtain a mixture. Soaking the mixture in ice water bath for 30 minutes, standing for 12 hours, and centrifuging the obtained suspension at 12000rpm for 10 minutes to obtain HOF-TCPB-373 nano-sheets;
2) HOF-TCPB-373 nano-sheet and TiO 2 Mixing and dispersing in deionized water, wherein the adding amount of the deionized water is TiO in the system 2 40% by mass (60% by mass of HOF-TCPB-373 nanosheets). Sonication for 10 minutes followed by vortexing at 2500rpm for 30 minutes gave a milky suspension. The milky suspension was centrifuged at 10000rpm for 10 minutes, the solid sample was separated and subsequently dried at 100℃for 12 hours, the product obtained being designated 40% TiO 2 @HOF。
Example 2
As in example 1, the difference is that TiO is in the system 2 20% by mass of (HOF-TCPB-373 nanosheets 80% by mass) and the obtained product was designated as 20% TiO 2 @HOF。
Example 3
As in example 1, the difference is that TiO is in the system 2 Is 60 percent (HOF-TCPB-373 nanometer sheet is 4 percent by mass)0%) of the product was recorded as 60% TiO 2 @HOF。
Example 4
As in example 1, the difference is that TiO is in the system 2 80% by mass (HOF-TCPB-373 nanosheets 20% by mass), the product obtained was noted as 80% TiO 2 @HOF。
Example 5
1) Will be 50mgH 4 TCPB was dissolved in 5mLDMF and placed in a cover-less glass bottle, which was then placed in a large beaker containing 20mL of deionized water. The beaker was sealed and kept at 373K for 3 days to precipitate colorless platelet crystals. The flaky crystals were ground for 30 minutes and then dispersed in 100mL of ethanol to obtain a mixture. Soaking the mixture in ice water bath for 30 minutes, standing for 12 hours, and centrifuging the obtained suspension at 12000rpm for 10 minutes to obtain HOF-TCPB-373 nano-sheets;
2) HOF-TCPB-373 nano-sheet and TiO 2 Mixing and dispersing in deionized water, wherein the adding amount of the deionized water is TiO in the system 2 40% by mass (60% by mass of HOF-TCPB-373 nanosheets). Sonication for 10 minutes followed by vortexing at 2500rpm for 30 minutes gave a milky suspension. The milky suspension was centrifuged at 10000rpm for 10 minutes, the solid sample was separated and subsequently dried at 100℃for 12 hours, the product obtained being designated 40% TiO 2 @HOF。
Example 6
1) Will be 50mgH 4 TCPB was dissolved in 5mLDMF and placed in a cover-less glass bottle, which was then placed in a large beaker containing 20mL of deionized water. The beaker was sealed and kept at 373K for 3 days to give colorless platelet crystals. The flaky crystals were ground for 30 minutes and then dispersed in 150mL of ethanol to obtain a mixture. Soaking the mixture in ice water bath for 30 minutes, standing for 12 hours, and centrifuging the obtained suspension at 12000rpm for 10 minutes to obtain HOF-TCPB-373 nano-sheets;
2) HOF-TCPB-373 nano-sheet and TiO 2 Mixing and dispersing in deionized water, wherein the adding amount of the deionized water is TiO in the system 2 The mass percentage of (2) is as follows40% (HOF-TCPB-373 nano-sheet mass percentage 60%). Sonication for 10 minutes followed by vortexing at 2500rpm for 30 minutes gave a milky suspension. The milky suspension was centrifuged at 12000rpm for 10 minutes, the solid sample was separated and subsequently dried at 120℃for 12 hours, the product obtained being designated 40% TiO 2 @HOF。
Example 7
1) Will be 20mgH 4 TCPB was dissolved in 5mLDMF and placed in a cover-less glass bottle, which was then placed in a large beaker containing 10mL of deionized water. The beaker was sealed and kept at 373K for 2 days to give colorless platelet crystals. The flaky crystals were ground for 30 minutes and then dispersed in 50mL of ethanol to obtain a mixture. Soaking the mixture in ice water bath for 30 minutes, standing for 12 hours, and centrifuging the obtained suspension at 12000rpm for 10 minutes to obtain HOF-TCPB-373 nano-sheets;
2) HOF-TCPB-373 nano-sheet and TiO 2 Mixing and dispersing in deionized water, wherein the adding amount of the deionized water is TiO in the system 2 Is 60 percent (the mass percentage of HOF-TCPB-373 nanometer sheet is 40 percent). Sonication for 10 minutes followed by vortexing at 2500rpm for 30 minutes gave a milky suspension. The milky suspension was centrifuged at 8000rpm for 20 minutes, the solid sample was separated and subsequently dried at 100℃for 12 hours, the resulting product was designated 60% TiO 2 @HOF。
Example 8
1) Will be 20mgH 4 TCPB was dissolved in 1mLDMF and placed in a cover-less glass bottle, which was then placed in a large beaker containing 10mL of deionized water. The beaker was sealed and kept at 373K for 2 days to give colorless platelet crystals. The flaky crystals were ground for 30 minutes and then dispersed in 100mL of ethanol to obtain a mixture. Soaking the mixture in ice water bath for 30 minutes, standing for 12 hours, and centrifuging the obtained suspension at 12000rpm for 10 minutes to obtain HOF-TCPB-373 nano-sheets;
2) HOF-TCPB-373 nano-sheet and TiO 2 Mixing and dispersing in deionized water, wherein the adding amount of the deionized water is TiO in the system 2 40% by mass (HO)The mass percentage of the F-TCPB-373 nano-sheet is 60 percent). Sonication for 20 minutes followed by vortexing at 2500rpm for 30 minutes gave a milky suspension. The milky suspension was centrifuged at 12000rpm for 10 minutes, the solid sample was separated and subsequently dried at 150℃for 12 hours, the resulting product was designated 40% TiO 2 @HOF。
FIG. 2 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And the X-ray diffraction pattern of HOF-TCPB-73. As can be seen from the figure, 40% TiO 2 The spectrogram of the @ HOFs photocatalyst comprises anatase type TiO 2 Meanwhile, the weak diffraction peaks at 2θ=24.8, 22.3 and 19.7 are similar to the partial diffraction peak positions of HOF-TCPB-373, indicating that TiO 2 And HOF-TCPB-373 at TiO 2 It is possible that all of the @ HOFs retain their original crystalline structure.
FIG. 3 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And HOF-TCPB-73, from which it can be seen that 40% TiO 2 HOF at 4000-800cm -1 The peak position is similar to HOF-TCPB-373; while at 800cm -1 To 500cm -1 Absorption peak of (2) and TiO 2 The consistency is caused by the stretching vibration of Ti-O-Ti; 1720-1620cm -1 The nearby weak absorption peaks can be attributed to-COOH and TiO in HOF-TCPB-373 2 Ti-O in (a) in (b).
FIG. 4 is a 40% TiO prepared in example 1 2 SEM image and EDS elemental distribution plot of @ HOFs photocatalyst. From the SEM photograph, 40% TiO can be observed 2 Spherical @ HOF; and shown in EDS element distribution diagram, 40% TiO 2 The @ HOF photocatalyst has a large number of Ti, O and C elements, which indicates that the photocatalyst is doped successfully.
FIG. 5 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And HOF-TCPB-73, from which it can be seen that 40% TiO 2 Ti in the @ HOF composite 4+ Is present.
FIG. 6 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And nitrogen adsorption and desorption isotherms for HOF-TCPB-73. From the figureAs can be seen in (c) 40% tio 2 @ HOF and TiO 2 All showed type II isotherms with type I hysteresis, indicating 40% TiO 2 The @ HOF has a molecular structure with TiO 2 A similar macroporous structure. 40% TiO 2 @HOF、TiO 2 BET specific surface areas of HOF-TCPB-373 were 26.68m, respectively 2 /g、51.44m 2 /g、5.87m 2 And/g. It can be seen that 40% TiO 2 The contact area of the HOF-TCPB-373 in the process of photocatalytic degradation of the RhB is effectively increased by the HOF photocatalyst.
FIG. 7 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And HOF-TCPB-73. As can be seen from fig. 7, tiO 2 HOF-TCPB-373 and 40% TiO 2 The water contact angles of @ HOF were 105 °, 39, 51 °, respectively. This is illustrated with TiO 2 In comparison, 40% TiO 2 The @ HOF photocatalyst has higher hydrophilicity and can promote the dissolution of the catalyst and O in water 2 Contact, in turn, facilitates the formation of oxygen reactive species.
FIG. 8 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And the Zeta potential map of HOF-TCPB-73. As can be seen from the figure, with TiO 2 (-3.37 mV) compared to HOF-TCPB-373 (-4.50 mV), 40% TiO 2 The zeta potential of the @ HOF photocatalyst was more negative and was-23.78 mV, indicating that the photocatalyst could form a more stable colloid in water.
Test example 1
In a quartz reaction kettle, the photocatalytic activity of the catalyst was evaluated under the conditions of circulating water cooling and magnetic stirring.
15mg of the 40% TiO prepared in examples 1-4 were reacted with 2 @HOF，20％TiO 2 @HOF，60％TiO 2 @HOF，80％TiO 2 @HOF, HOF-TCPB-373 and TiO 2 Respectively, in 30mL of RhB aqueous solution with initial concentration of 10 mg/L. First, the established system was kept in the dark for 30 minutes to reach adsorption-desorption equilibrium, and then photocatalytic degradation was started using a 300W xenon lamp as a light source, and visible light was provided by selecting the wavelength of the filter. The wavelength was 520nm. Determination of RhB by UV-visible spectrometryConcentration.
FIG. 9 shows 40% TiO as prepared in examples 1-4 2 @HOFs、20％TiO 2 @HOFs、60％TiO 2 @HOFs、80％TiO 2 Comparison of removal kinetics of RhB in aqueous solution by @ HOFs photocatalyst; it can be seen that the efficiency of removal of RhB by HOF-TCPB-373 was 18.8% under dark conditions, indicating that it has adsorption capacity attributable to the presence of a large number of conjugated aromatic rings. In contrast, tiO 2 Hardly adsorbing any RhB. 40% TiO as prepared in examples 1-4 compared to HOF-TCPB-373 2 @HOF、20％TiO 2 @HOF、60％TiO 2 @HOF、80％TiO 2 The @ HOFs all show more excellent RhB adsorption; the greater the mass ratio of HOF-TCPB-373, the higher the adsorption efficiency. When the mass percentage of HOF-TCPB-373 is 80 percent (20 percent TiO) 2 @ HOF), the adsorption efficiency was the highest, 38.1%. This indicates that HOF-TCPB-373 is present in TiO 2 The adsorption of RhB in the @ HOF photocatalyst plays a key role, and compared with the original HOF-TCPB-373, tiO 2 The adsorption capacity of @ HOF is improved.
After 30min, adsorption and desorption reach equilibrium, and photosensitive degradation of RhB is started. HOF-TCPB-373 and TiO 2 All of which exhibit photocatalytic activity, FIG. 10 is a graph of 40% TiO prepared in examples 1-4 2 @HOFs、20％TiO 2 @HOFs、60％TiO 2 @HOFs、80％TiO 2 The adsorption and photodegradation capacities of the @ HOFs photocatalyst on RhB in aqueous solution were compared. The photodegradation efficiency for RhB was 44.2% and 46.8%, respectively, and the total removal rate reached 63.0% and 46.8%, respectively. TiO when in a photocatalyst 2 At 40%, 60% and 80% by mass of TiO 2 The photodegradation efficiency of RhB by @ HOF is not greatly changed and is 64.3-66.2%. In addition, 40% TiO 2 The total removal of RhB by @ HOF was 95.5%, combining photodegradation (64.3%) and adsorption (31.2%).
FIG. 11 is a 40% TiO prepared in example 1 2 Photocatalyst @ HOFs and TiO 2 And HOF-TCPB-73, from which it can be seen that HOF-TCPB-373, tiO 2 And 40% TiO 2 The @ HOFs all exhibit absorption bands in the uv region. With TiO 2 In comparison, at 40% TiO 2 Slight red shifts were observed at the edges of the @ HOF. This can be attributed to the fact that the conjugated aromatic ring present in HOF-TCPB-373 enhances electron delocalization.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (7)
1. Dye sensitization type TiO 2 Application of @ HOFs photo-catalyst in degrading rhodamine B in wastewater is characterized in that the dye sensitized TiO 2 The @ HOFs photocatalyst is prepared by mixing a hydrogen bond organic framework material with TiO 2 Is compounded according to a proportion, wherein the TiO is 2 The mass ratio is 10-90%; the hydrogen bond organic framework material is HOF-TCPB-373 nano-sheets;
the preparation method of the HOF-TCPB-373 nanometer sheet comprises the following steps:
1) Will H 4 Dissolving TCPB in an organic solvent, putting the dissolved sample into deionized water, and performing heating treatment under a sealing condition to obtain colorless flaky crystals;
2) Pulverizing and grinding the colorless flaky crystals, dispersing the colorless flaky crystals in an organic solvent, soaking the obtained mixture in an ice water bath, and standing to obtain a suspension;
3) Centrifuging the suspension at 8000-12000rpm for 10-30min to obtain HOF-TCPB-373 nanometer sheet;
the H is 4 The structural formula of TCPB is:
。
2. the use according to claim 1, wherein the heat treatment in step 1) is maintained at 373K for 2-10 days.
3. The use according to claim 1, wherein in step 1) the H 4 The dosage ratio of TCPB to organic solvent is (10-80) mg to (1-10) mL; the organic solvent is DMF.
4. The use according to claim 1, wherein in step 2) the organic solvent is ethanol.
5. The use according to claim 1, characterized in that the dye-sensitized TiO 2 The preparation method of the @ HOFs photocatalyst comprises the following steps:
hydrogen bond organic framework material and TiO 2 Dispersing in deionized water, mixing, and shaking by vortex to prepare milky suspension;
centrifuging to separate the milky suspension to obtain solid sample, and drying to obtain dye sensitized TiO 2 @ HOFs photocatalysts.
6. The use of claim 5, wherein the vortex shaking is at a speed of 2500rpm.
7. The use according to claim 5, characterized in that the centrifugation is carried out in particular at 8000-12000rpm for 10-30 minutes.
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