CN108176407B - Ce-In composite material photocatalyst and preparation method and application thereof - Google Patents
Ce-In composite material photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 101100202428 Neopyropia yezoensis atps gene Proteins 0.000 claims abstract description 96
- 239000002243 precursor Substances 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 30
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 41
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 38
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 claims description 36
- 229960000892 attapulgite Drugs 0.000 claims description 21
- 229910052625 palygorskite Inorganic materials 0.000 claims description 21
- 229960003405 ciprofloxacin Drugs 0.000 claims description 19
- 239000004201 L-cysteine Substances 0.000 claims description 18
- 235000013878 L-cysteine Nutrition 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 16
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- 238000005406 washing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 11
- 235000018417 cysteine Nutrition 0.000 description 11
- 239000003242 anti bacterial agent Substances 0.000 description 10
- 229940088710 antibiotic agent Drugs 0.000 description 10
- 238000002604 ultrasonography Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to CeO2‑In2S3An ATPs composite material photocatalyst, a preparation method and application thereof, belonging to the technical field of environmental protection material preparation. Adding Ce (NO)3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding deionized water, and magnetically stirring uniformly; then In is added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, placing in a muffle furnace, heating and calcining, naturally cooling to room temperature, taking out, and grinding to obtain solid powder CeO2‑In2S3/ATPs composite photocatalyst. The invention realizes the use of CeO2‑In2S3The ATPs nano composite material is used as a photocatalyst for degrading antibiotic wastewater.
Description
Technical Field
The invention relates to CeO2-In2S3An ATPs composite material photocatalyst, a preparation method and application thereof, belonging to the technical field of environmental protection material preparation.
Background
Antibiotics, as a class of Pharmaceuticals and Personal Care Products (PPCPs), are a class of natural, semi-synthetic or synthetic compounds that possess antimicrobial activity and that selectively inhibit or affect biological functions at low concentrations, both antibacterial and interfering with other cellular developmental functions. Along with rapid progress of medical technology and biological science, the types of antibiotics are rapidly amplified, the generation of antibiotic resistance genes and the risk of forming drug-resistant strains are induced and accelerated by the massive use of the antibiotics, more than 90 percent of parts which cannot be completely absorbed by animals and human bodies are subjected to metabolic reactions such as hydroxylation, cracking and the like, and finally the parts are directly discharged into the environment in the form of original drugs. The long-term presence of low concentrations of antibiotics can have an impact on the microbial community in the water body and affect higher organisms through the transfer of the food chain, disrupting ecosystem balance, and thus leaving antibiotics in the environment is potentially harmful. The quinonone antibiotics such as ciprofloxacin are one of the most widely applied broad-spectrum antibiotics in the world at present, and a large amount of residues of the quinonone antibiotics in environmental media such as water, soil and the like have great threat and hidden danger to human health. Therefore, the elimination of the problem of the remaining quininone antibiotics in the environment is imminent.
The photocatalytic oxidation technology is an environment-friendly water pollution control and elimination technology, and becomes a hot point of research of people in recent years. Researchers are constantly exploring new high-efficiency semiconductor photocatalysts. In2S3Metalloid sulfide and CeO2The rare earth metal oxide is a visible light response semiconductor with excellent performance, and the photocatalytic activity of the rare earth metal oxide can be greatly improved by compounding two excellent semiconductor materials to construct a composite material heterojunction. The Attapulgite (ATPs) is used as a natural high-quality mineral carrier, and is an excellent photocatalyst carrier by virtue of the advantages of unique rod-shaped structure, large specific surface area, no toxicity, no harm, low cost and the like. By preparing CeO2-In2S3The heterojunction is loaded on ATPs composite photocatalyst to degrade and remove organic pollutants of the quinolones antibiotics in the water body, and the method becomes a hotspot of current research.
Disclosure of Invention
The invention adopts a high-temperature calcination method and a hydrothermal method as technical means to prepare CeO2-In2S3/ATPs composite photocatalyst.
The invention is carried out according to the following steps:
(1)In2S3preparation of ATPs precursors:
adding InCl3·4H2Putting O (indium chloride tetrahydrate) and L-cysteine into a glass beaker, adding deionized water to completely dissolve the O (indium chloride tetrahydrate) and the L-cysteine, performing magnetic stirring, adding attapulgite, stirring and ultrasonically mixing the mixture uniformly, transferring the mixture into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven to calcine, and filtering, washing and collecting the obtained solid, namely In2S3/ATPs precursors.
The calcination conditions are as follows: calcining at 160 ℃ for 12 h.
(2)CeO2-In2S3Preparation of ATPs composite photocatalyst:
adding Ce (NO)3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding deionized water, and magnetically stirring uniformly; then the In prepared In the step (1)2S3Adding ATPs precursor into the mixed solution, magnetically stirring, placing in a muffle furnace, heating and calcining, naturally cooling to room temperature, taking out, and grinding to obtain solid powder CeO2-In2S3/ATPs composite photocatalyst.
The heating and calcining conditions are as follows: heating and calcining at 400 ℃ for 3 h.
Wherein the optimal mass ratio of the indium chloride tetrahydrate, the L-cysteine and the attapulgite in the step (1) is 1: 1.6: 2.
wherein, the cerous nitrate hexahydrate and In step (2)2S3Mass ratio of ATPs precursor is 5.2: 1.
in the technical scheme, the dosage of the deionized water can completely dissolve the soluble solid.
CeO prepared according to the above procedure2-In2S3/ATPs composite photocatalyst, wherein CeO is contained in the composite photocatalyst2The mass percentage of the catalyst is 67 percent.
CeO obtained according to the preparation method described above2-In2S3The ATPs composite photocatalyst is applied to degrading ciprofloxacin in antibiotic wastewater.
Indium chloride tetrahydrate (InCl) for use in the present invention3·4H2O), L-cysteine (C)3H7NO2S), cerium nitrate hexahydrate (Ce (NO)3)3·6H2O) are all analytically pure and purchased from national pharmaceutical chemical reagent company Limited; attapulgite is purchased from Xuyi Xin Yuan technology Co., Ltd;
ciprofloxacin antibiotic was a standard and purchased from shanghai shunbo bioengineering limited.
The invention has the beneficial effects that:
the invention realizes the use of CeO2-In2S3The ATPs nano composite material is used as a photocatalyst for degrading antibiotic wastewater. The semiconductor material is used as a photocatalyst, is excited under visible light, realizes special catalysis or conversion through an interface interaction effect with pollutant molecules, and enables surrounding oxygen and water molecules to be excited into substances with strong oxidizing property such as oxygen free radicals and hydroxyl free radicals with strong oxidizing property, thereby achieving the purpose of degrading harmful organic substances in the environment.
Drawings
FIG. 1 shows CeO2-In2S3UV-vis diagram of ATPs composite photocatalyst.
FIG. 2 shows CeO2-In2S3PL diagram of ATPs composite photocatalyst.
FIG. 3 shows CeO2-In2S3SEM image of/ATPs composite photocatalyst.
Detailed Description
The invention is further illustrated by the following examples.
The difference of the implementation conditions of the examples can lead to the composite photocatalytic material having different material structures and interface contact effects, thereby leading to the difference of degradation rates. The method is researched, and the optimal process parameters in the implementation process of the method are respectively as follows: InCl3·4H20.45g of O, 0.72g of L-cysteine, 0.9g of attapulgite and In2S3The optimal calcination condition of the ATPs precursor is calcination for 12 hours at 160 ℃; ce (NO)3)3·6H2O5.20 g, CeO2-In2S3The optimal calcination condition of the ATPs composite photocatalyst is that the composite photocatalyst is calcined at 400 ℃ for 3 hours, and the optimal degradation effect can reach 89.38%.
Photocatalytic activity evaluation of the photocatalyst prepared in the present invention: in DW-01 type photochemical reactionIrradiating with visible light lamp, adding 100mL ciprofloxacin simulated wastewater into a reactor, measuring initial value, adding the prepared photocatalyst, magnetically stirring, starting an aeration device, introducing air to keep the catalyst in a suspended or floating state, sampling and analyzing at an interval of 10min during the irradiation process, centrifuging, collecting supernatant, and purifying with lambda-gamma fluorescent powdermaxAbsorbance was measured with a spectrophotometer at 278nm and by the formula: dr ═ 1-Ai/A0]The degradation rate is calculated by multiplying 100%. Wherein A is0To reach the absorbance of ciprofloxacin solution at adsorption equilibrium, AiThe absorbance of the ciprofloxacin solution was determined for the timed samples.
Example 1:
(1)In2S3preparation of ATPs precursors:
0.15g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.24g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O (indium chloride tetrahydrate) and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 63.13% within 60 min.
Example 2:
(1)In2S3preparation of ATPs precursors:
0.30g of InCl was weighed out3·4H2O (indium chloride tetrahydrate) and 0.48g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O (indium chloride tetrahydrate) and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 68.92% within 60 min.
Example 3:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.72g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3/ATpreparing a Ps composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 89.38% within 60 min.
Example 4:
(1)In2S3preparation of ATPs precursors:
0.60g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.96g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O (indium chloride tetrahydrate) and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 69.58% within 60 min.
Example 5:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.72g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O and the cysteine, the mixture is stirred by magnetic force, then 0.45g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 76.87% within 60 min.
Example 6:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.72g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O and the cysteine, the mixture is stirred by magnetic force, 1.35g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 82.44% within 60 min.
Example 7:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.72g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 6 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 59.12% within 60 min.
Example 8:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.72g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 24 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 73.51% within 60 min.
Example 9:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2Placing O (indium chloride tetrahydrate) and 0.72g L-cysteine into a glass beaker, adding deionized water to completely dissolve the O and the cysteine, magnetically stirring, adding 0.9g of attapulgite, stirring and ultrasonically mixing the mixture uniformly, transferring the mixture into a 100mL hydrothermal reaction kettle, calcining the mixture in an oven at 160 ℃ for 12h, filtering, washing and collecting the mixture to obtain the indium chloride tetrahydrateThe obtained solid is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
2.60g of Ce (NO) are weighed out3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 77.04% within 60 min.
Example 10:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.72g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
weighing 7.80g Ce (NO)3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 400 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs compositeA photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 71.35% within 60 min.
Example 11:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2O (indium chloride tetrahydrate) and 0.72g L-cysteine are put into a glass beaker, deionized water is added to completely dissolve the O and the cysteine, the mixture is stirred by magnetic force, then 0.9g of attapulgite is added, the mixture is stirred and mixed evenly by ultrasound, then the mixture is transferred into a 100mL hydrothermal reaction kettle and is put into a baking oven to be calcined for 12 hours at 160 ℃, and the solid obtained by filtering, washing and collecting is In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, placing in a muffle furnace, heating and calcining at 350 deg.C for 3 hr, naturally cooling to room temperature, taking out, and grinding to obtain solid powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 76.00% within 60 min.
Example 12:
(1)In2S3preparation of ATPs precursors:
0.45g of InCl was weighed3·4H2Placing O (indium chloride tetrahydrate) and 0.72g L-cysteine into a glass beaker, adding deionized water to completely dissolve, magnetically stirring, adding 0.9g of attapulgite, stirring and ultrasonically mixing uniformly, and transferring the mixture to 100mL of hydrothermal waterPutting the mixture into a reaction kettle, calcining the mixture for 12 hours at 160 ℃, filtering, washing and collecting the obtained solid, namely In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
5.20g of Ce (NO) are weighed3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding 30mL of deionized water, and magnetically stirring uniformly; then, 1.0g of In prepared In step (1) was added2S3Adding ATPs precursor into the mixed solution, magnetically stirring, calcining in a muffle furnace at 500 deg.C for 3 hr, cooling to room temperature, grinding to obtain solid CeO powder2-In2S3/ATPs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the ciprofloxacin antibiotic reaches 70.66% within 60 min.
FIG. 1 shows CeO2-In2S3UV-vis diagram of/ATPs composite photocatalyst, wherein CeO is shown in diagram2-In2S3Compared with the light response capability of the composite photocatalyst without CeO in ATPs (atomic emission complexes)2Coupled In2S3the/ATPs precursors have partial reinforcement.
FIG. 2 shows CeO2-In2S3PL diagram of/ATPs composite photocatalyst, in which CeO is shown2-In2S3the/ATPs composite photocatalyst has minimum fluorescence intensity, which indicates that the recombination probability of photogenerated electrons and holes is lowest.
FIG. 3 shows CeO2-In2S3SEM image of/ATPs composite photocatalyst, from which CeO can be seen2-In2S3The shape of the/ATPs is a composite material of nano flower balls, amorphous blocks and short-rod attapulgite.
Claims (4)
1. A Ce-In composite photocatalyst is used for degrading ciprofloxacin In antibiotic wastewater, and is characterized by being prepared by the following method:
(1)In2S3preparation of ATPs precursors:
adding InCl3·4H2Putting O (indium chloride tetrahydrate) and L-cysteine into a glass beaker, adding deionized water to completely dissolve the O (indium chloride tetrahydrate) and the L-cysteine, performing magnetic stirring, adding attapulgite, stirring and ultrasonically mixing the mixture uniformly, transferring the mixture into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven to calcine, and filtering, washing and collecting the obtained solid, namely In2S3/ATPs precursors;
(2)CeO2-In2S3preparation of ATPs composite photocatalyst:
adding Ce (NO)3)3·6H2Placing O (cerous nitrate hexahydrate) in a crucible, adding deionized water, and magnetically stirring uniformly; then the In prepared In the step (1)2S3Adding ATPs precursor into the solution, magnetically stirring, placing in a muffle furnace, heating, calcining, naturally cooling to room temperature, taking out, and grinding to obtain solid powder (CeO)2-In2S3/ATPs composite photocatalyst;
controlling the mass ratio and the calcining condition of the indium chloride tetrahydrate, the L-cysteine and the attapulgite in the step (1); cerium nitrate hexahydrate and In step (2)2S3The Ce-In composite photocatalyst with optimal degradation efficiency is obtained by the mass ratio of ATPs precursors and the heating and calcining conditions.
2. The Ce-In composite photocatalyst as claimed In claim 1, wherein In the step (1), the calcination conditions are as follows: calcining for 12h at 160 ℃; the mass ratio of the indium chloride tetrahydrate, the L-cysteine and the attapulgite is 1: 1.6: 2.
3. the Ce-In composite photocatalyst as claimed In claim 1, wherein In the step (2), the heating and calcining conditions are as follows: heating and calcining for 3h at the temperature of 400 ℃; the cerium nitrate hexahydrate and In2S3Mass ratio of ATPs precursor is 5.2: 1.
4. the Ce-In composite photocatalyst of claim 1, wherein the prepared CeO2-In2S3/ATPs composite photocatalyst, wherein CeO is contained in the composite photocatalyst2The mass percentage of the catalyst is 67 percent.
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