CN110639610A - Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst - Google Patents
Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 230000007547 defect Effects 0.000 title claims abstract description 81
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 title claims abstract 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000011780 sodium chloride Substances 0.000 claims abstract description 21
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 12
- 229930195725 Mannitol Natural products 0.000 claims abstract description 12
- 239000000594 mannitol Substances 0.000 claims abstract description 12
- 235000010355 mannitol Nutrition 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 51
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 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 15
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
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- B01J35/39—
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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
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
-
- 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
-
- 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
Abstract
The invention belongs to the field of functional composite materials, and relates to a preparation method of a defect-rich BiOCl/TPP composite photocatalyst, which comprises the following steps: adding Bi (NO)3)3·5H2Dissolving O in mannitol, adding PVP and NaCl solution, stirring, transferring to a high-pressure reaction kettle, and carrying out solvothermal reaction to obtain ultrathin BiOCl; dispersing in ethylene glycol, transferring to a high-pressure reaction kettle for solvothermal reaction to obtain defect-rich BiOCl; dispersing in ethanol, adding into mixed solution of TPP and ethanol, performing solvent thermal reaction, filtering, washing, and drying to obtain the product rich in defectsBiOCl/TPP composite photocatalyst; the method has the advantages of low reaction temperature, mild conditions, easily controlled reaction process, no pollutant discharge and green synthesis; the prepared composite photocatalyst has more excellent performance of degrading organic pollutants in water body by visible light catalysis, and has good application prospect in the aspect of treating organic wastewater.
Description
Technical Field
The invention belongs to the field of functional composite materials, and particularly relates to a preparation method and application of a defect-rich BiOCl/TPP composite photocatalyst.
Background
With the rapid development of economy, environmental pollution, especially water resource pollution, is becoming more and more serious. Organic pollutants (such as antibiotics and the like) threaten the survival of microorganisms and organisms in the water body, destroy the self-cleaning capacity of the water body and seriously affect the health of human beings. The application of the photocatalytic technology to degrade organic pollutants in water is considered to be the most promising effective way for treating water pollution at present. The semiconductor photocatalyst is widely applied to the research of photocatalytic degradation of organic pollutants in water bodies due to the fact that the semiconductor photocatalyst has a special electronic structure.
The BiOCl material is a novel layered semiconductor photocatalyst, has excellent visible light responsiveness and catalytic activity, and is widely concerned by researchers in the field of photocatalysis. However, only a few of photogenerated electrons and holes generated by the BiOCl material under illumination can migrate to the surface of the material and participate in catalytic reaction, so that the catalytic efficiency is low, and the further application of the BiOCl material in the field of photocatalytic degradation of organic pollutants is limited. Thus, thinning BiOCl to form a few-layer or single-layer ultrathin nanosheet structure is considered. Meanwhile, pits are dug on the basal plane of the BiOCl ultrathin nanosheet to form rich defects, and the rich defects can shorten the migration distance of carriers, so that the photon-generated carriers can rapidly migrate from the inside of the material to the surface to participate in the catalytic degradation reaction of organic pollutants.
In order to further solve the problems of narrow light absorption range and low sunlight utilization rate of the BiOCl material, the method for compounding the BiOCl material to obtain the composite photocatalyst is one of the methods for solving the problems in the research field at present. Porphyrins (such as Tetraphenylporphyrin (TPP) and the like) are heterocyclic compounds with large conjugated systems and have excellent energy-electron transfer performance. At present, porphyrins have been reported to be applied in the field of photocatalytic degradation; for example, AijianWang et al successfully prepare TPP/Bi by using a reflux stirring method2O2CO3Composite photocatalystHowever, a toxic reagent tetrahydrofuran is used in the preparation process, and the composite photocatalyst only has a degradation effect on RhB with a simple structure; in addition, Jung Zhang et al prepared MTPP/g-C by reflux method3N4The tetrahydrofuran is also used as a solvent in the preparation process of the composite photocatalyst, and the prepared photocatalyst acts on the degradation of RhB. The composite photocatalyst uses a toxic reagent tetrahydrofuran in the preparation process, breaks away from the concept of green environmental protection, is not beneficial to actual production, and only has a photocatalytic degradation effect on RhB with a simple structure. Although the porphyrin compound is used as a photocatalyst, the research on the application of the porphyrin compound and the BiOCl material as a photocatalytic degradation antibiotic organic substance has not been reported at home and abroad.
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 defect-rich BiOCl/TPP composite photocatalyst, which can be used for efficiently catalyzing and degrading 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:
(1) adding Bi (NO)3)3·5H2Dissolving O in mannitol solution, adding polyvinylpyrrolidone (PVP) and NaCl solution under stirring, and stirring for a while to obtain mixed solution; transferring the mixed solution into a high-pressure reaction kettle, reacting at a certain temperature, cooling to room temperature after reaction, filtering, washing, and vacuum drying to obtain ultrathin BiOCl;
(2) dispersing the ultrathin BiOCl obtained in the step (1) in ethylene glycol, stirring under an ultrasonic condition to obtain a mixed solution, transferring the mixed solution to a high-pressure reaction kettle, reacting under a certain temperature condition, cooling to room temperature after reaction, filtering, washing and drying in vacuum to obtain defect-rich BiOCl;
(3) dispersing the defect-rich BiOCl obtained in the step (2) in ethanol a to obtain a mixed solution A; then dispersing Tetraphenylporphyrin (TPP) in ethanol B to obtain a mixed solution B; and dropwise adding the mixed solution B into the mixed solution A to obtain a mixed solution C, stirring for a period of time, transferring the mixed solution C into a high-pressure reaction kettle, reacting at a certain temperature, cooling to room temperature after reaction, filtering, washing and vacuum drying to obtain the defect-rich BiOCl/TPP composite photocatalyst.
Preferably, said Bi (NO) in step (1)3)3·5H2The dosage ratio of the O, mannitol solution and PVP is 0.5-1 mmoL: 15-35 mL: 0.2-0.4 g; the concentration of the mannitol solution is 0.1 mol/L.
Preferably, said Bi (NO) in step (1)3)3·5H2The molar ratio of O to NaCl in the NaCl solution was 1: 1.
Preferably, the stirring in the step (1) is carried out for a period of time of 30-60 min; the certain temperature condition is 140-180 ℃, and the reaction time is 3-6 h.
Preferably, the dosage ratio of the ultrathin BiOCl to the ethylene glycol in the step (2) is 0.1-0.3 g: 15-25 mL.
Preferably, the stirring time in the step (2) is 1-3 h; the certain temperature condition is 120-160 ℃, and the reaction time is 8-16 h.
Preferably, the dosage ratio of the defect-rich BiOCl to the ethanol a in the step (3) is 0.1-0.3 g: 15-25 mL; the dosage ratio of TPP to ethanol b is 0.002-0.015 g to 5-10 mL.
Preferably, the volume ratio of the mixed solution A to the mixed solution B in the step (3) is 1-2: 1.
Preferably, the stirring in the step (3) is carried out for a period of time of 30-60 min; the certain temperature condition is
The reaction time is 8-14 h at 120-160 ℃.
Preferably, the vacuum drying in the steps (1) - (3) is carried out at the temperature of 40-80 ℃ for a period of time
6～12h。
Wherein, the ethanol a and the ethanol b in the step (3) are both conventional ethanol reagents, and letters a and b are added for distinguishing.
Compared with the prior art, the invention has the following remarkable advantages:
(1) in the preparation process of the ultrathin BiOCl, synthetic water-soluble high polymer PVP is used as a solvent, the PVP has low toxicity and excellent solubility and biocompatibility, and the preparation process is free of pollutant discharge and is green and environment-friendly.
(2) The reaction temperature for preparing the defect-rich BiOCl/TPP composite photocatalyst is 120-160 ℃, the appearance of the defect-rich BiOCl ultrathin nanosheet can be better controlled in the temperature range, and the photo-generated carriers can be rapidly transferred to the surface to effectively participate in the photocatalytic degradation reaction of organic pollutants.
(3) The defect-rich BiOCl/TPP composite photocatalyst with an ultrathin nanosheet structure is technically compounded by adopting a defect-rich BiOCl material and a porphyrin compound TPP, the utilization rate of the photocatalyst to sunlight is improved by utilizing the synergistic effect of the defect-rich BiOCl material and the porphyrin compound TPP, the effective separation efficiency of a photon-generated carrier is promoted, the degradation efficiency is improved by more than 45% compared with that of the BiOCl material in the activity of catalyzing and degrading organic pollutants in a water body under visible light, the effect is obvious, and a new thought 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 defect-rich BiOCl/TPP composite photocatalyst prepared in example 1 of the invention.
In FIG. 2, a is a TEM image of the ultrathin BiOCl prepared in example 1, b is a TEM image of the defect-rich BiOCl prepared in example 1, and c is a TEM image of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1.
In fig. 3, a is a transient photoelectricity diagram of the ultrathin BiOCl prepared in example 1, b is a transient photoelectricity diagram of the defect-rich BiOCl prepared in example 1, and c is a transient photoelectricity diagram of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1.
In FIG. 4, a is a graph of the ultra-thin BiOCl prepared in example 1 for catalyzing and degrading tetracycline hydrochloride; b is a graph of the defect-rich BiOCl prepared in example 1 for catalyzing and degrading tetracycline hydrochloride; c is a graph of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1 for catalyzing and degrading tetracycline hydrochloride.
In FIG. 5, a is a DRS map of the ultrathin BiOCl prepared in example 1; b is a DRS map of the defect-rich BiOCl prepared in example 1; c is a DRS map of TPP prepared in example 1; d is a DRS diagram of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1.
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:
(1) adding 1mmol of Bi (NO)3)3·5H2Dissolving O in 35mL of mannitol solution with the concentration of 0.1mol/L, adding 0.4g of PVP under stirring, adding NaCl solution, wherein the amount of NaCl in the NaCl solution is 1mmol, continuously stirring for 60min to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and reacting at 180 ℃ for 3 h; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 40 ℃ for 12h to obtain ultrathin BiOCl;
(2) dispersing 0.2g of the ultrathin BiOCl obtained in the step (1) in 20mL of ethylene glycol, performing ultrasonic treatment and stirring for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 15 hours at 140 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 40 ℃ for 12h to obtain defect-rich BiOCl;
(3) dispersing 0.1g of the defect-rich BiOCl obtained in the step (2) in 15mL of ethanol a to obtain a mixed solution A; then 0.002g of TPP is dispersed in 5mL of ethanol B to obtain a mixed solution B; and dripping 10mL of the solution B into 10mL of the solution A to obtain a mixed solution C, stirring for 60min, transferring the mixed solution C into a high-pressure reaction kettle, reacting for 12h at 140 ℃, cooling, filtering, collecting precipitate, washing, and vacuum drying for 12h at 40 ℃ to obtain the defect-rich BiOCl/TPP composite photocatalyst.
Example 2:
(1) 0.5mmol of Bi (NO)3)3·5H2Dissolving O in 15mL of 0.1mol/L mannitol solution, adding 0.2g of PVP under stirring, adding NaCl solution with NaCl content of 0.5mmol, stirring for 30min to obtain mixed solution, transferring the mixed solution to a high-pressure reaction kettle,reacting for 6 hours at 140 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 80 ℃ for 6 hours to obtain ultrathin BiOCl;
(2) dispersing 0.1g of the ultrathin BiOCl obtained in the step (1) in 15mL of ethylene glycol, performing ultrasonic treatment and stirring for 1h, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 16h at 120 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 80 ℃ for 6 hours to obtain defect-rich BiOCl;
(3) dispersing 0.1g of the defect-rich BiOCl obtained in the step (2) in 15mL of ethanol a to obtain a mixed solution A; then 0.005g of TPP is dispersed in 5mL of ethanol B to obtain a mixed solution B; and dropwise adding 5mL of the solution B into 10mL of the solution A to obtain a mixed solution C, stirring for 30min, transferring the mixed solution C into a high-pressure reaction kettle, reacting for 14h at 120 ℃, cooling, filtering, collecting precipitate, washing, and vacuum drying for 6h at 80 ℃ to obtain the defect-rich BiOCl/TPP composite photocatalyst.
Example 3:
(1) 0.8mmol of Bi (NO)3)3·5H2Dissolving O in 25mL of mannitol solution with the concentration of 0.1mol/L, adding 0.32g of PVP under stirring, adding NaCl solution, wherein the amount of NaCl in the NaCl solution is 0.8mmol, continuously stirring for 30min to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 4h at 160 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 60 ℃ for 8 hours to obtain ultrathin BiOCl;
(2) dispersing 0.3g of the ultrathin BiOCl obtained in the step (1) in 25mL of ethylene glycol, performing ultrasonic treatment and stirring for 3 hours, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 12 hours at 150 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 60 ℃ for 8h to obtain defect-rich BiOCl;
(3) dispersing 0.3g of the defect-rich BiOCl obtained in the step (2) in 25mL of ethanol a to obtain a mixed solution A; then 0.015g of TPP is dispersed in 10mL of ethanol B to obtain a mixed solution B; and dripping 10mL of the solution B into 15mL of the solution A to obtain a mixed solution C, stirring for 60min, transferring the mixed solution C into a high-pressure reaction kettle, reacting for 8h at 160 ℃, cooling, filtering, collecting precipitate, washing, and vacuum drying for 6h at 80 ℃ to obtain the defect-rich BiOCl/TPP composite photocatalyst.
Example 4:
(1) 0.6mmol of Bi (NO)3)3·5H2Dissolving O in 20mL of mannitol solution with the concentration of 0.1mol/L, adding 0.24g of PVP under stirring, adding NaCl solution, wherein the amount of NaCl in the NaCl solution is 0.6mmol, continuously stirring for 50min to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 4h at 150 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 50 ℃ for 8 hours to obtain ultrathin BiOCl;
(2) dispersing 0.15g of the ultrathin BiOCl obtained in the step (1) in 20mL of ethylene glycol, performing ultrasonic treatment and stirring for 2 hours, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 8 hours at 160 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 50 ℃ for 8h to obtain defect-rich BiOCl;
(3) dispersing 0.15g of the defect-rich BiOCl obtained in the step (2) in 20mL of ethanol a to obtain a mixed solution A; then 0.01g of TPP is dispersed in 8mL of ethanol B to obtain a mixed solution B; and dropwise adding 8mL of the solution B into 8mL of the solution A to obtain a mixed solution C, stirring for 50min, transferring the mixed solution C into a high-pressure reaction kettle, reacting for 10h at 150 ℃, cooling, filtering, collecting precipitate, washing, and vacuum drying for 10h at 50 ℃ to obtain the defect-rich BiOCl/TPP composite photocatalyst.
Example 5:
(1) 0.7mmol of Bi (NO)3)3·5H2Dissolving O in 22mL of mannitol solution with the concentration of 0.1mol/L, adding 0.28g of PVP under stirring, adding NaCl solution, wherein the amount of NaCl in the NaCl solution is 0.7mmol, continuously stirring for 45min to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 5h at 170 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 60 ℃ for 8 hours to obtain ultrathin BiOCl;
(2) dispersing 0.2g of the ultrathin BiOCl obtained in the step (1) in 20mL of ethylene glycol, performing ultrasonic treatment and stirring for 3 hours, transferring the mixed solution into a high-pressure reaction kettle, and reacting for 12 hours at 130 ℃; after cooling, filtering, collecting precipitate, washing, and vacuum drying at 60 ℃ for 8h to obtain defect-rich BiOCl;
(3) dispersing 0.2g of the defect-rich BiOCl obtained in the step (2) in 20mL of ethanol a to obtain a mixed solution A; then 0.06g of TPP is dispersed in 8mL of ethanol B to obtain a mixed solution B; and dripping 10mL of the solution B into 12mL of the solution A to obtain a mixed solution C, stirring for 50min, transferring the mixed solution C into a high-pressure reaction kettle, reacting for 10h at 130 ℃, cooling, filtering, collecting precipitate, washing, and vacuum drying for 10h at 60 ℃ to obtain the defect-rich BiOCl/TPP composite photocatalyst.
Application example:
and (3) evaluating the photocatalytic activity of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1. 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 light filter, and the degradation efficiency of the defect-rich BiOCl/TPP 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 defect-rich BiOCl/TPP composite photocatalyst prepared in example 1, example 2, example 3, example 4 and example 5, adding the defect-rich BiOCl/TPP composite photocatalyst into the tetracycline hydrochloride solution, stirring for 20min in a dark place, turning on a Xe lamp light source after desorption is balanced, sampling every 30min, after centrifugal separation, measuring the absorbance of a supernatant at the maximum absorption wavelength (357nm) of the tetracycline hydrochloride, and obtaining the degradation efficiency of the defect-rich BiOCl/TPP composite photocatalyst on the tetracycline hydrochloride within 2 h.
FIG. 1 is an EDS diagram of a defect-rich BiOCl/TPP composite photocatalyst prepared in example 1 of the invention; as can be seen from the figure, the prepared defect-rich BiOCl/TPP composite photocatalyst contains C, N, Bi, O and Cl elements, and the defect-rich BiOCl/TPP composite photocatalyst is successfully prepared.
In FIG. 2, a is a TEM image of the ultrathin BiOCl prepared in example 1, b is a TEM image of the defect-rich BiOCl prepared in example 1, and c is a TEM image of the defect-rich BiOCl/TPP composite photocatalyst (c) prepared in example 1; the structure of the ultrathin flake layer can be observed from the figure, which shows that the prepared ultrathin BiOCl, defect-rich BiOCl and defect-rich BiOCl/TPP composite photocatalyst are all in flake layered structures, and the size of the composite photocatalyst is 30-50 nm.
In fig. 3, a is a transient photoelectricity diagram of the ultrathin BiOCl prepared in example 1, b is a transient photoelectricity diagram of the defect-rich BiOCl prepared in example 1, and c is a transient photoelectricity diagram of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1; as can be seen from the figure, the defect-rich BiOCl/TPP composite photocatalyst shows a higher current value than that of a pure BiOCl monomer, which indicates that the defect-rich BiOCl/TPP composite photocatalyst has higher photogenerated carrier separation efficiency than that of ultrathin BiOCl and defect-rich BiOCl.
In FIG. 4, a is a graph comparing the activity of the ultrathin BiOCl prepared in example 1 for catalyzing and degrading tetracycline hydrochloride; b is a comparison graph of the activity of the defect-rich BiOCl prepared in example 1 for catalyzing and degrading tetracycline hydrochloride; c is an activity comparison graph of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1 for catalyzing and degrading tetracycline hydrochloride; as can be seen from the figure, the defect-rich BiOCl/TPP composite photocatalyst has higher degradation activity than that of the ultrathin BiOCl and the defect-rich BiOCl within 2 h; by calculation, it can be known that: the degradation rate of the ultrathin BiOCl to tetracycline hydrochloride is 18.4%; the degradation rate of the defect-rich BiOCl to tetracycline hydrochloride is 43.8%; the degradation rate of the defect-rich BiOCl/TPP to tetracycline hydrochloride is 64.6%.
In FIG. 5, a is a DRS map of the ultrathin BiOCl prepared in example 1; b is a DRS map of the defect-rich BiOCl prepared in example 1; c is a DRS map of TPP prepared in example 1; d is a DRS diagram of the defect-rich BiOCl/TPP composite photocatalyst prepared in example 1; as can be seen from the figure, compared with a BiOCl monomer, the light absorption of the BiOCl/TPP composite photocatalyst is shifted to a visible light region, which shows that the composite photocatalyst has higher response to visible light and improves the utilization rate of the visible light.
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 (10)
1. A preparation method of a defect-rich BiOCl/TPP composite photocatalyst is characterized by comprising the following steps:
(1) adding Bi (NO)3)3·5H2Dissolving O in mannitol solution, adding polyvinylpyrrolidone and NaCl solution under stirring, and continuously stirring for a period of time to obtain a mixed solution; transferring the mixed solution into a high-pressure reaction kettle, reacting at a certain temperature, cooling to room temperature after reaction, filtering, washing, and vacuum drying to obtain ultrathin BiOCl;
(2) dispersing the ultrathin BiOCl obtained in the step (1) in ethylene glycol, stirring under an ultrasonic condition to obtain a mixed solution, transferring the mixed solution to a high-pressure reaction kettle, reacting under a certain temperature condition, cooling to room temperature after reaction, filtering, washing and drying in vacuum to obtain defect-rich BiOCl;
(3) dispersing the defect-rich BiOCl obtained in the step (2) in ethanol a to obtain a mixed solution A; then dispersing tetraphenylporphyrin in ethanol B to obtain a mixed solution B; and dropwise adding the mixed solution B into the mixed solution A to obtain a mixed solution C, stirring for a period of time, transferring the mixed solution C into a high-pressure reaction kettle, reacting at a certain temperature, cooling to room temperature after reaction, filtering, washing and vacuum drying to obtain the defect-rich BiOCl/TPP composite photocatalyst.
2. The method for preparing the defect-rich BiOCl/TPP composite photocatalyst as claimed in claim 1, wherein the Bi (NO) in the step (1)3)3·5H2The dosage ratio of the O to the mannitol solution to the polyvinylpyrrolidone is 0.5-1 mmoL: 15-35 mL: 0.2-0.4 g; the concentration of the mannitol solution is 0.1 mol/L.
3. The defect-rich BiO of claim 1The preparation method of the Cl/TPP composite photocatalyst is characterized in that the Bi (NO) in the step (1)3)3·5H2The molar ratio of O to NaCl in the NaCl solution was 1: 1.
4. The preparation method of the defect-rich BiOCl/TPP composite photocatalyst as claimed in claim 1, wherein the stirring period in the step (1) is 30-60 min; the certain temperature condition is 140-180 ℃, and the reaction time is 3-6 h.
5. The preparation method of the defect-rich BiOCl/TPP composite photocatalyst, as claimed in claim 1, wherein the dosage ratio of the ultrathin BiOCl to ethylene glycol in step (2) is 0.1-0.3 g: 15-25 mL.
6. The preparation method of the defect-rich BiOCl/TPP composite photocatalyst as claimed in claim 1, wherein the stirring time in the step (2) is 1-3 hours; the certain temperature condition is 120-160 ℃, and the reaction time is 8-16 h.
7. The preparation method of the defect-rich BiOCl/TPP composite photocatalyst, as claimed in claim 1, wherein the dosage ratio of the defect-rich BiOCl to ethanol a in step (3) is 0.1-0.3 g: 15-25 mL; the dosage ratio of the tetraphenylporphyrin to the ethanol b is 0.002-0.015 g to 5-10 mL.
8. The preparation method of the defect-rich BiOCl/TPP composite photocatalyst as claimed in claim 1, wherein, preferably, the volume ratio of the mixed solution A to the mixed solution B in the step (3) is 1-2: 1; stirring for a period of 30-60 min; the certain temperature condition is 120-160 ℃, and the reaction time is 8-14 h.
9. The preparation method of the defect-rich BiOCl/TPP composite photocatalyst, as claimed in claim 1, is characterized in that the vacuum drying in steps (1) - (3) is carried out at 40-80 ℃ for 6-12 hours.
10. The defect-rich BiOCl/TPP composite photocatalyst prepared by the method according to any one of claims 1 to 9 is applied to catalytic degradation of tetracycline hydrochloride in a water body.
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