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
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- 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
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- 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
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- 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
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- 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
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- 230000003197 catalytic effect Effects 0.000 claims description 3
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- 229910052736 halogen Inorganic materials 0.000 claims 1
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- 229940073609 bismuth oxychloride Drugs 0.000 description 58
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- 230000000694 effects Effects 0.000 description 9
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 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
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 229930002875 chlorophyll Natural products 0.000 description 1
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- 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
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
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- 238000006303 photolysis reaction Methods 0.000 description 1
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- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
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- B01J35/39—Photocatalytic properties
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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.
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