CN111229313B - Preparation method and application of flower-ball-shaped BiOCl/TCPP composite photocatalyst - Google Patents
Preparation method and application of flower-ball-shaped BiOCl/TCPP composite photocatalyst Download PDFInfo
- Publication number
- CN111229313B CN111229313B CN202010112292.3A CN202010112292A CN111229313B CN 111229313 B CN111229313 B CN 111229313B CN 202010112292 A CN202010112292 A CN 202010112292A CN 111229313 B CN111229313 B CN 111229313B
- Authority
- CN
- China
- Prior art keywords
- tcpp
- flower
- ball
- composite photocatalyst
- biocl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 title claims abstract 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 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 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- -1 1-hexadecyl-3-methylimidazole halogen salt Chemical class 0.000 claims description 7
- WLOADVWGNGAZCW-UHFFFAOYSA-N 3-phenyl-23H-porphyrin-2,18,20,21-tetracarboxylic acid Chemical compound OC(=O)C=1C(N2C(O)=O)=C(C(O)=O)C(=N3)C(C(=O)O)=CC3=CC(N3)=CC=C3C=C(N=3)C=CC=3C=C2C=1C1=CC=CC=C1 WLOADVWGNGAZCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- 230000000593 degrading effect Effects 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 58
- 238000010586 diagram Methods 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- 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
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of preparation of a photocatalytic nano composite material and environmental management, and relates to a preparation method and application of a flower-ball-shaped BiOCl/TCPP composite photocatalyst; the method comprises the following steps: dissolving TCPP in ethylene glycol, and obtaining TCPP dispersion liquid after ultrasonic stirring; then adding Bi (NO)3)3·5H2O, PVP and [ C16Mim]Cl to obtain suspension, stirring, transferring the suspension to a high-pressure reaction kettle for reaction, cooling to room temperature after reaction, filtering, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain a flower-ball-shaped BiOCl/TCPP composite photocatalyst; the method is simple and easy to implement, short in flow, green and recyclable in used solvent, and environment-friendly; the prepared composite photocatalyst has more excellent performance of degrading organic pollutants in water by visible light catalysis, and has higher application potential in the aspect of water pollution treatment.
Description
Technical Field
The invention belongs to the field of preparation of photocatalytic nano composite materials and environmental management, and particularly relates to a preparation method and application of a flower-ball-shaped BiOCl/TCPP composite photocatalyst.
Background
With the acceleration of the industrialization process and the rapid improvement of the living standard of people, the two main problems facing human beings are the exhaustion of energy and the environmental pollution caused by a large amount of industrial wastewater and domestic wastewater, and the green sustainable development of ecological economy is seriously hindered. Semiconductor photocatalytic technology is considered as an effective means to solve energy crisis and to deal with environmental pollution problems. The water photolysis technology for converting solar energy into clean hydrogen energy thoroughly solves the crisis caused by fossil energy exhaustion, and photocatalytic degradation of toxic organic pollutants becomes an economic, feasible and effective way for solving the problem of water pollution. However, most photocatalysts used in semiconductor photocatalysis technology have the defects of wide energy band gap, low light quantum efficiency and the like, and can show good photocatalytic activity only under the condition of ultraviolet light, which obviously greatly limits the practical application of the photocatalysts, and therefore, the development of the high-activity photocatalyst is one of the main works in the field of photocatalytic research.
In the development of a novel photocatalyst, bismuth oxychloride (BiOCl) nano material as a novel bismuth-based semiconductor material has attracted extensive attention due to its unique photoelectric properties and photocatalytic properties. However, the defects of low separation-transmission efficiency of photocarrier ions, narrow photoresponse range and the like cause the low photocatalytic activity of the BiOCl material, and the large-scale practical application of the material is hindered. Researchers have used a number of methods to improve the photocatalytic efficiency of BiOCl, such as morphology design, element doping, and semiconductor recombination. The photocatalyst with different microcosmic morphologies has different specific surface areas, has important relations on the adsorption contact of the catalyst and a target degradation product and the separation and recombination of a photon-generated carrier, and influences the photocatalytic activity of the photocatalyst. In addition, the BiOCl material is compounded with other semiconductors, so that the method is an effective method for widening the photoresponse range of the photocatalyst and improving the photocatalytic activity.
Porphyrins are the main components of chlorophyll and play an important role in the photosynthesis of green plants. Inspired by the nature, porphyrin compounds (such as tetracarboxyphenyl porphyrin (TCPP) and the like) are widely used as effective electron donors in the processes of photocatalytic hydrogen production and pollutant degradation, and the charge transfer in the photocatalytic process is promoted. Porphyrin compounds have been reported to photocatalytically degrade pollutants. Such as: the nano-flaky CuTCPP/Bi prepared by the Zhijie Zhang et al2WO6The composite photocatalyst shows better photocatalytic activity on RhB under visible light conditions, but CuTCPP/Bi2WO6Composite photocatalysisThe preparation can be completed in two steps, and the process is complicated. The following steps are repeated: jung Zhang et al prepared MTPP/g-C by reflux method3N4The composite photocatalyst is prepared by taking tetrahydrofuran as a reaction solvent, and the prepared composite photocatalyst can be used for degrading RhB. However, tetrahydrofuran used in the preparation process is a toxic reagent and is not environmentally friendly. So far, no literature report exists at home and abroad on the research of degrading antibiotic organic pollutants by a composite photocatalyst prepared by compounding a porphyrin compound and a BiOCl material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve one of the problems and provides a preparation method of a flower-ball-shaped BiOCl/TCPP composite photocatalyst, which can be used for efficiently catalyzing and degrading antibiotic organic pollutants in a water body under visible light.
In order to achieve the above purpose, the specific steps of the invention are as follows:
dissolving Tetracarboxylphenylporphyrin (TCPP) in ethylene glycol, and stirring under ultrasonic conditions to obtain tetracarboxylphenylporphyrin dispersion; then sequentially adding Bi (NO)3)3·5H2O, polyvinylpyrrolidone (PVP) and 1-hexadecyl-3-methylimidazolium halide ionic liquid ([ C)16Mim]Cl) is added into the tetracarboxyphenyl porphyrin dispersion liquid to obtain a suspension, the suspension is transferred into a high-pressure reaction kettle after being stirred for a period of time, the reaction is carried out under a certain temperature condition, the suspension is cooled to room temperature after the reaction is finished, and the flower-ball-shaped BiOCl/TCPP composite photocatalyst is obtained after filtration, washing by deionized water and absolute ethyl alcohol respectively and vacuum drying.
Preferably, the dosage ratio of the tetracarboxyphenylporphyrin to the glycol in the step is 0.001-0.01 g: 15-25 mL.
Preferably, the stirring time in the above step is 60-120 min.
Preferably, said Bi (NO) in the above step3)3·5H2O，PVP，[C16Mim]The dosage ratio of Cl to tetracarboxyphenylporphyrin is 0.5-1.0 mmoL: 0.2-0.4 g: 0.5-1.0 mmoL: 0.001-0.01 g.
Preferably, the suspension is stirred for 1-3 hours in the above steps.
Preferably, the certain temperature condition in the above step is 120-160 ℃, and the reaction time is 12-26 h.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the preparation method adopts a one-step in-situ hydrothermal method to prepare the flower-ball-shaped BiOCl/TCPP composite photocatalyst, has simple and easy preparation process, shorter flow and mild reaction conditions, and is suitable for mass production.
(2) In the preparation process of the flower-ball-shaped BiOCl/TCPP composite photocatalyst, PVP is used as a solvent, and the PVP has low toxicity, excellent solubility and environmental friendliness.
(3) The invention uses ionic liquid ([ C ] in the preparation process of the flower-ball-shaped BiOCl/TCPP composite photocatalyst16Mim]Cl) is a chlorine source and a cosolvent at the same time, the ionic liquid is a 'green solvent' which is difficult to volatilize, stable in property and free of pollution, and can be recycled, so that the utilization rate of the solvent is improved.
(4) The hydrothermal reaction temperature for preparing the spherical-flower BiOCl/TCPP composite photocatalyst is 120-160 ℃, the reaction temperature can better control the spherical-flower shape of the BiOCl/TCPP composite photocatalyst, the flower-shaped structure has higher specific surface area and stable micro-shape, and the photocatalytic activity of the catalyst is improved to a certain extent.
(5) In the invention, BiOCl and tetracarboxylphenylporphyrin TCPP are technically compounded to prepare the flower-ball-shaped BiOCl/TCPP composite photocatalyst. TCPP has a macrocyclic conjugated structure, has good absorption in a visible light region, has the capability of capturing and converting electrons, effectively promotes the separation and transmission of photon-generated carriers, and can greatly enhance the photocatalytic activity of the catalyst. Compared with a BiOCl material, the activity of the catalyst for catalytic degradation of organic pollutants in water under visible light is improved by over 64%, the degradation effect is obvious, and a new idea is provided for the design of a novel composite photocatalyst and the treatment of water pollution.
Drawings
FIG. 1 is an EDS diagram of a flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3 of the invention.
In FIG. 2, a is an SEM image of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3; b is a TEM image of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3.
In FIG. 3, a is a DRS diagram of the BiOCl material prepared in example 3; b is a DRS diagram of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3.
In fig. 4 a is the BET plot of the BiOCl material prepared in example 3; b is a BET diagram of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3.
In FIG. 5, a is an activity diagram of BiOCl material prepared in example 3 for catalyzing and degrading tetracycline hydrochloride; b is an activity diagram of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3 for catalyzing and degrading tetracycline hydrochloride.
Detailed Description
The invention is further illustrated by the following examples and the accompanying drawings, and the scope of the invention is not limited to the following examples.
Example 1:
0.001g of TCPP was dissolved in 15mL of ethylene glycol and stirred under ultrasonic conditions for 60min to obtain a TCPP dispersion. 0.5mmol of Bi (NO) are added in turn3)3·5H2O, 0.2g of PVP and 0.5mmol of [ C16Mim ]]And adding Cl into 0.001g of TCPP dispersion liquid to obtain suspension, stirring for 60min, transferring the suspension into a high-pressure reaction kettle, reacting for 26h at 120 ℃, cooling to room temperature after the reaction is finished, filtering, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the flower-ball-shaped BiOCl/TCPP composite photocatalyst.
Example 2:
0.0028g of TCPP was dissolved in 18mL of ethylene glycol and stirred under ultrasonic conditions for 70min to give a TCPP dispersion. 0.6mmol of Bi (NO) are added in turn3)3·5H2O, 0.23g of PVP and 0.6mmol of [ C16Mim ]]Adding Cl into 0.003g of TCPP dispersion to obtain suspension, stirring for 70min, transferring the suspension into a high-pressure reaction kettle, reacting at 130 ℃ for 18h, cooling to room temperature after the reaction is finished, filtering, and removing ionsAnd respectively washing water and absolute ethyl alcohol, and drying in vacuum to obtain the flower-ball-shaped BiOCl/TCPP composite photocatalyst.
Example 3:
0.0035g of TCPP was dissolved in 20mL of ethylene glycol and stirred under ultrasonic conditions for 90min to obtain a TCPP dispersion. Sequentially adding 1.0mmol of Bi (NO)3)3·5H2O, 0.25g of PVP and 1.0mmol of [ C16Mim ]]And adding Cl into 0.006g of TCPP dispersion liquid to obtain suspension, stirring for 90min, transferring the suspension into a high-pressure reaction kettle, reacting at 140 ℃ for 24h, cooling to room temperature after the reaction is finished, filtering, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the flower-ball-shaped BiOCl/TCPP composite photocatalyst.
Example 4:
0.007g of TCPP was dissolved in 22mL of ethylene glycol and stirred under ultrasonic conditions for 100min to obtain a TCPP dispersion. 0.7mmol of Bi (NO) are added in turn3)3·5H2O, 0.28g of PVP and 0.7mmol of [ C16Mim ]]And adding Cl into 0.008g of TCPP dispersion liquid to obtain suspension, stirring for 100min, transferring the suspension into a high-pressure reaction kettle, reacting at 150 ℃ for 20h, cooling to room temperature after the reaction is finished, filtering, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the flower-ball-shaped BiOCl/TCPP composite photocatalyst.
Example 5:
0.01g of TCPP was dissolved in 25mL of ethylene glycol and stirred under ultrasonic conditions for 120min to obtain a TCPP dispersion. Sequentially adding 1.0mmol of Bi (NO)3)3·5H2O, 0.4g of PVP and 1.0mmol of [ C16Mim ]]And adding Cl into 0.01g of TCPP dispersion liquid to obtain suspension, stirring for 180min, transferring the suspension into a high-pressure reaction kettle, reacting for 26h at 120 ℃, cooling to room temperature after the reaction is finished, filtering, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the flower-ball-shaped BiOCl/TCPP composite photocatalyst.
Application example:
and (3) carrying out photocatalytic activity evaluation on the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in the example 3. The activity evaluation experiment is carried out in a DW-03 type photochemical reactor, a light source of solar energy is simulated by an Xe lamp, ultraviolet light is filtered by a filter, and the degradation efficiency of the flower-ball-shaped BiOCl/TCPP composite photocatalyst to tetracycline hydrochloride under the visible light of solar energy is measured. The specific operation steps are as follows:
100mL of tetracycline hydrochloride solution (20mg/L) was added to the reactor and its initial absorbance value was measured. Weighing 40mg of each of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 1, example 2, example 3, example 4 and example 5, adding the weighed flower-ball-shaped BiOCl/TCPP composite photocatalyst into the tetracycline hydrochloride solution, stirring in a dark place for 30min, turning on a Xe lamp light source after desorption reaches equilibrium, sampling every 30min, performing centrifugal separation, and measuring the absorbance of a supernatant at the maximum absorption wavelength (357nm) of the tetracycline hydrochloride to obtain the degradation efficiency of the flower-ball-shaped BiOCl/TCPP composite photocatalyst on the tetracycline hydrochloride within 2 h.
FIG. 1 is an EDS diagram of a flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3 of the invention; as can be seen from the figure, the prepared flower-ball-shaped BiOCl/TCPP composite photocatalyst contains C, N, Bi, O and Cl elements, and the flower-ball-shaped BiOCl/TCPP composite photocatalyst is successfully prepared.
In FIG. 2, a is an SEM picture of the flower-spherical BiOCl/TCPP composite photocatalyst prepared in example 3, and b is a TEM picture of the flower-spherical BiOCl/TCPP composite photocatalyst prepared in example 3; as can be seen from the figure, the BiOCl/TCPP composite photocatalyst is in a flower ball shape, and the flower ball is formed by stacking sheet layers and has the size of 0.2-0.4 mu m.
In FIG. 3, a is a DRS diagram of the BiOCl material prepared in example 3, and b is a DRS diagram of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3; as can be seen from the figure, compared with BiOCl, the light absorption of the BiOCl/TCPP composite photocatalyst is subjected to red shift and moves to a visible light region, which shows that the BiOCl/TCPP composite photocatalyst has higher response to visible light.
In FIG. 4, a is a BET diagram of the BiOCl material prepared in example 3, and b is a BET diagram of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3; from the adsorption-desorption isotherms in the figure, the specific surface area of BiOCl was 34.3170m2The specific surface area of the BiOCl/TCPP composite photocatalyst is 40.5049m2Higher specific surface area is favorable for the catalystMore adsorption contact with the target degradation product is beneficial to the improvement of the catalytic activity.
In FIG. 5, a is an activity diagram of the BiOCl material prepared in example 3 for catalytically degrading tetracycline hydrochloride, and b is an activity diagram of the flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared in example 3 for catalytically degrading tetracycline hydrochloride; as can be seen from the figure, the flower-ball-shaped BiOCl/TCPP composite photocatalyst has higher degradation activity than BiOCl within 2 h. The calculation shows that the degradation rate of BiOCl to tetracycline hydrochloride is 49.22%; the degradation rate of the flower-ball-shaped BiOCl/TCPP composite photocatalyst to tetracycline hydrochloride is 76.29%.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (7)
1. A preparation method of a flower-ball-shaped BiOCl/TCPP composite photocatalyst is characterized by comprising the following steps:
dissolving tetracarboxyphenyl porphyrin TCPP in ethylene glycol, and stirring under an ultrasonic condition to obtain a TCPP dispersion liquid; sequentially adding Bi (NO)3)3•5H2Adding O, polyvinylpyrrolidone and 1-hexadecyl-3-methylimidazole halogen salt ionic liquid into the TCPP dispersion liquid to obtain a suspension, stirring for a period of time, transferring the suspension into a high-pressure reaction kettle, reacting at a certain temperature, cooling to room temperature after the reaction is finished, filtering, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the flower-ball-shaped BiOCl/TCPP composite photocatalyst.
2. The preparation method of the flower-ball-shaped BiOCl/TCPP composite photocatalyst, as claimed in claim 1, wherein the dosage ratio of the tetracarboxyphenylporphyrin TCPP to the ethylene glycol is 0.001-0.01 g: 15-25 mL.
3. The preparation method of the flower-ball-shaped BiOCl/TCPP composite photocatalyst, as claimed in claim 1, wherein the stirring time under the ultrasonic condition is 60-120 min.
4. The method for preparing the flower-ball-shaped BiOCl/TCPP composite photocatalyst as claimed in claim 1, wherein the Bi (NO) is3)3•5H2The dosage ratio of O, polyvinylpyrrolidone, 1-hexadecyl-3-methylimidazolium halide ionic liquid to tetracarboxyphenylporphyrin TCPP is 0.5-1.0 mmoL, 0.2-0.4 g, 0.5-1.0 mmoL and 0.001-0.01 g.
5. The preparation method of the flower-ball-shaped BiOCl/TCPP composite photocatalyst, as claimed in claim 1, wherein the suspension is stirred for a period of time of 1-3 hours.
6. The preparation method of the flower-ball-shaped BiOCl/TCPP composite photocatalyst, as claimed in claim 1, wherein the certain temperature condition is 120-160 ℃ and the reaction time is 12-26 h.
7. The flower-ball-shaped BiOCl/TCPP composite photocatalyst prepared by the method according to any one of claims 1-6 is applied to catalytic degradation of tetracycline hydrochloride in a water body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010112292.3A CN111229313B (en) | 2020-02-24 | 2020-02-24 | Preparation method and application of flower-ball-shaped BiOCl/TCPP composite photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010112292.3A CN111229313B (en) | 2020-02-24 | 2020-02-24 | Preparation method and application of flower-ball-shaped BiOCl/TCPP composite photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111229313A CN111229313A (en) | 2020-06-05 |
| CN111229313B true CN111229313B (en) | 2022-05-20 |
Family
ID=70878344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010112292.3A Active CN111229313B (en) | 2020-02-24 | 2020-02-24 | Preparation method and application of flower-ball-shaped BiOCl/TCPP composite photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111229313B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112774727A (en) * | 2021-01-27 | 2021-05-11 | 江苏大学 | Flake TPP/Bi2WO6Preparation method of composite photocatalyst |
| CN113181974A (en) * | 2021-04-08 | 2021-07-30 | 华南理工大学 | Bismuth oxide-carbon nitride-porphyrin composite photocatalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391766A (en) * | 2011-07-29 | 2012-03-28 | 北京立高防水工程有限公司 | Flame-retardant spray polyurea elastomer coating and preparation method thereof |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN110639610A (en) * | 2019-09-18 | 2020-01-03 | 江苏大学 | Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst |
-
2020
- 2020-02-24 CN CN202010112292.3A patent/CN111229313B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391766A (en) * | 2011-07-29 | 2012-03-28 | 北京立高防水工程有限公司 | Flame-retardant spray polyurea elastomer coating and preparation method thereof |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN110639610A (en) * | 2019-09-18 | 2020-01-03 | 江苏大学 | Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| Biomimetic Platinum Nanozyme Immobilized on 2D Metal−Organic Frameworks for Mitochondrion-Targeting and Oxygen Self-Supply Photodynamic Therapy;Zhiguo Gao等;《ACS Appl. Mater. Interfaces》;20191224;第12卷;全文 * |
| 类石墨相氮化碳复合材料光催化性能的研究;李文奇;《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑》;20190515(第05期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111229313A (en) | 2020-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112844484B (en) | Boron nitride quantum dot/porous metal organic framework composite photocatalytic material and preparation method and application thereof | |
| CN111229313B (en) | Preparation method and application of flower-ball-shaped BiOCl/TCPP composite photocatalyst | |
| CN110639610B (en) | Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst | |
| CN112619659B (en) | Nickel oxide nanosheet and bismuth molybdate nanofiber heterojunction photocatalytic material as well as preparation method and application thereof | |
| CN111715300B (en) | Zinc ferrite/Bi-MOF/tannic acid composite visible light catalyst | |
| CN111203234A (en) | CdIn2S4Nanoblock/SnIn4S8Preparation method of difunctional composite photocatalyst with sheet stacking structure | |
| CN113244962A (en) | Preparation method and application of singlet oxygen generating zirconium porphyrin-based MOF-graphene composite photocatalyst | |
| CN111992255B (en) | Flaky g-C for removing bisphenol A in water3N4ZIF-8/AgBr composite material and preparation method thereof | |
| CN109999917B (en) | Covalent organic framework-based composite photocatalyst for degrading organic pollutants in water and preparation method thereof | |
| CN110624574B (en) | Double Bi4O5I2Preparation method of photocatalytic material and application of photocatalytic material in degrading MC-LR | |
| CN107117683B (en) | Method for catalytically degrading low-concentration antibiotics In water body by using MOFs containing In-Co under visible light | |
| CN111468100B (en) | Preparation method of in-situ grown polyacid niobium/graphene photocatalyst and application of in-situ grown polyacid niobium/graphene photocatalyst in tetracycline degradation | |
| CN113231101A (en) | Preparation and application of Cu-NM-101(Fe) photocatalyst | |
| CN109865528B (en) | Semiconductor photocatalyst material and processing technology thereof | |
| CN110201722B (en) | Silver phosphate composite photocatalyst for treating rose bengal B in high-salinity wastewater and preparation method and application thereof | |
| CN114990614B (en) | Embedded SrTiO 3 /ZnIn 2 S 4 Preparation method and application of nanocomposite structure material | |
| CN113559856B (en) | Preparation method of barium titanate/silver iodate heterojunction photocatalyst | |
| CN102407104B (en) | Preparation method of mesoporous nano molybdenum-loaded tungsten trioxide highly effective photocatalyst | |
| CN117258844A (en) | Preparation method of Co (II) visible light catalyst containing mixed ligand | |
| CN114160129A (en) | Preparation method of titanium dioxide/porous carbon supported composite photocatalyst | |
| CN115301265A (en) | Supermolecule self-assembly synthesized C-g-C 3 N 4 /Bi 4 O 5 Br 2 Preparation method of composite photocatalytic material | |
| CN112973743A (en) | BC/Bi4O5Br2Preparation method of composite photocatalytic material | |
| CN113337900A (en) | Photocatalytic fabric and preparation method and application thereof | |
| CN113117700A (en) | Bi4O5Br2Preparation method of photocatalytic material | |
| CN112774727A (en) | Flake TPP/Bi2WO6Preparation method of composite photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |