CN113751025B - MnNb 3 S 6 Preparation method and application of piezoelectric catalytic material - Google Patents
MnNb 3 S 6 Preparation method and application of piezoelectric catalytic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000010453 quartz Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002917 insecticide Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 27
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 9
- 239000005875 Acetamiprid Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000003708 ampul Substances 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005297 material degradation process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
MnNb 3 S 6 The preparation method and application of the piezoelectric catalyst comprise the following specific steps: step 1, mixing and grinding manganese powder, niobium pentachloride and thiourea to obtain precursor powder with uniform dispersion; step 2, placing the precursor powder obtained in the step 1 into a quartz boat, and placing the quartz boat into a tube furnace; step 3, calcining at high temperature in nitrogen atmosphere, and cooling to room temperature after the reaction is finished; grinding the product obtained in the step 3 to obtain MnNb 3 S 6 A catalytic material; the invention realizes MnNb 3 S 6 The quick and simple synthesis of the material discovers MnNb 3 S 6 Piezocatalysis performance of the material, prepared MnNb 3 S 6 The material has the advantages of high purity, good crystallinity, strong catalytic activity and the like, and can be used for piezoelectric catalytic removal of the neonicotinoid insecticides.
Description
Technical Field
The invention belongs to the field of environmental catalysis, and relates to a method for preparing a MnNb alloy 3 S 6 A preparation method and application of piezoelectric catalytic material.
Background
With the rapid development of industry and agriculture in China, water environment pollution is increasingly aggravated. Neonicotinoid insecticides have been used to control sucking pests by replacing organic phosphorus and other conventional insecticides, because of their strong killing effect on pests, and are one of the commercial insecticides widely used at present. Due to the high water solubility of acetamiprid (solubility in water 4.2 g.L -1 ) And excessive use can cause environmental pollution and affect human health. Thus, there is a need for a rapid and efficient method of removal from waterResidual acetamiprid.
Piezoelectric catalysis is a catalysis technology which starts to be studied in the last ten years, utilizes the non-central symmetry of semiconductor material crystal lattice, generates deformation polarization under the action of mechanical stress (ultrasonic wave or water flow, etc.), and generates built-in electric field to provide driving force for charge carriers in the crystal, thereby effectively improving e - -h + Thereby producing a large amount of OH and O 2 - And the like active groups are used for degrading organic pollutants. The piezoelectric catalysis technology has simple operation, high efficiency and low cost, and is an ideal choice for environmental remediation, so that the development of a new piezoelectric catalysis material for removing pesticides is significant.
MnNb 3 S 6 Belonging to hexagonal system, researchers have been able to obtain a product with the formula I as early as 1970 2 Is synthesized by a gas phase transmission method 3 S 6 A material. The research adopts manganese powder, niobium powder and sulfur powder as raw materials, firstly, reacting at 850 ℃ for 80 h, then placing the obtained powder in a quartz ampoule bottle, adding sublimated iodine into the ampoule bottle, sealing the ampoule bottle in a sealing manner, placing the sealed quartz ampoule bottle in the middle of a furnace, keeping the middle temperature of the furnace at 800 ℃ and the temperatures at the two ends of the furnace at 950 ℃, and reacting for a period of time to obtain MnNb 3 S 6 A material. Researchers in 2020 have used the same method to produce high purity Mn powder, nb powder and S powder>99.9%) is sealed in a quartz tube, heated to 800 ℃ in a high temperature sintering furnace, and the two ends of the tube are respectively kept at 800 ℃ and 950 ℃ for reacting for several days to obtain MnNb 3 S 6 . As is clear from the above study, mnNb has been reported 3 S 6 The material synthesis method has long experimental period, higher requirements on equipment and complex operation, so that the MnNb needs to be rapidly and simply synthesized by research 3 S 6 A method of material. The method is that the initial reactant is weighed according to the stoichiometric ratio, then the reaction mixture is ground into powder and placed in a crucible, the required atmosphere is introduced, and the reaction is carried out for a period of time at a certain temperature, thus obtaining the product. The method has low equipment requirement, simple operation, and short experimental periodShort, the compounds can be prepared in large quantities. In the established MnNb 3 S 6 In the preparation method, a tubular furnace one-step high-temperature calcination method is not yet adopted for preparing MnNb 3 S 6 Is reported in (3).
Thus, suitable preparation conditions are found to establish MnNb 3 S 6 The one-step high-temperature calcination method of the material and the application of the material in the removal of pesticide residues in the environment are significant.
Disclosure of Invention
To overcome the defects in the prior art, the invention aims to provide a method for preparing MnNb 3 S 6 Method for preparing MnNb by directly calcining at high temperature by adopting tubular furnace for the first time and application of catalytic material 3 S 6 A catalyst. Compared with the prior art, the preparation of MnNb by the traditional method is avoided 3 S 6 When the method is used, the raw materials are firstly filled in a quartz ampoule, then the quartz ampoule is sealed in a melting way, and then the quartz ampoule is placed in a tube furnace for calcination. The method has the advantages of low cost and easy acquisition of the initial raw materials, simple operation process and MnNb synthesized by the method 3 S 6 The material has high purity and strong catalytic activity. The invention discovers MnNb for the first time 3 S 6 The piezoelectric catalysis performance of the material provides a new piezoelectric catalyst, and opens up a new way for removing the neonicotinoid insecticides such as acetamiprid and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme: mnNb 3 S 6 The preparation method of the piezoelectric catalytic material comprises the following steps:
step 1, preparing reaction precursor powder;
step 2, placing the reaction precursor powder obtained in the step 1 into a 20mL quartz boat, placing the quartz boat into a tube furnace, and reacting at 1050-1150 ℃ in a nitrogen atmosphere;
step 3, after the reaction is completed, taking out the quartz boat after the tube furnace is naturally cooled to room temperature;
step 4, grinding the product obtained in the step 3 to obtain MnNb 3 S 6 Piezoelectric catalytic materials.
The reaction precursor powder in the step 1 is prepared by the following steps:
a. 1.8mmol of manganese powder, 3.0mmol of niobium pentachloride and 12.0mmol of thiourea are weighed;
b. and d, placing the manganese powder, niobium pentachloride and thiourea weighed in the step a into an agate mortar, and grinding for 5min to prepare reaction precursor powder.
In the step 2, the heating rate is 3-7 ℃/min.
In the step 2, the heat preservation time is 2.5-3.5 h.
The MnNb 3 S 6 The piezoelectric catalytic material is applied as a piezoelectric catalytic material.
50 mg MnNb is weighed 3 S 6 Placing a piezoelectric catalytic material in a glass jar filled with a 50 mL acetamiprid solution with the concentration of 10 mg/L, placing the glass jar in a dark place for 30 min, placing the glass jar in a piezoelectric catalytic device for a degradation experiment, sampling at the moment 0 as a blank control, sampling every 3 min during degradation, filtering the obtained solution by a microporous filter membrane, placing the filtered solution in a centrifuge tube, testing the absorbance of the solution by an ultraviolet spectrophotometer, and calculating the degradation rate of acetamiprid according to the change of the absorbance in the reaction process.
The method has the beneficial effects that:
compared with the prior art, the method synthesizes MnNb by adopting a simpler method 3 S 6 The piezoelectric catalytic material has the following specific advantages:
1) The experimental operation steps are simple, the experimental period is short, the implementation is easy, and the application range is wide.
2) MnNb produced by the present invention 3 S 6 The catalytic material has high purity and high reaction activity.
3) For the first time find MnNb 3 S 6 The material has piezoelectric catalysis performance, and can be applied to piezoelectric catalysis for removing the neonicotinoid insecticide acetamiprid, and has short removal time and high removal efficiency.
4) The invention widens the MnNb 3 S 6 The new way of material synthesis is beneficial to further developing other similar catalysts.
Drawings
FIG. 1 shows a method according to the inventionPreparing MnNb 3 S 6 X-ray diffraction pattern of the piezocatalytic material.
FIG. 2a shows MnNb in example 1 of the method of the present invention 3 S 6 Scanning electron microscope image of piezocatalysis material.
FIG. 2b shows MnNb in example 2 of the method of the present invention 3 S 6 Scanning electron microscope image of piezocatalysis material.
FIG. 2c shows MnNb in example 3 of the method of the present invention 3 S 6 Scanning electron microscope image of piezocatalysis material.
FIG. 3 shows MnNb produced by the method of the present invention 3 S 6 Degradation profile of piezo-electric catalytic material.
Detailed Description
The invention will be further illustrated by reference to specific examples.
Example 1
Step 1, preparing reaction precursor powder, which specifically comprises the following steps:
a. 1.8mmol of manganese powder, 3.0mmol of niobium pentachloride and 12.0mmol of thiourea were weighed, namely 0.0987g of manganese powder, 0.8103g of niobium pentachloride and 0.9132g of thiourea;
b. and d, placing the manganese powder, niobium pentachloride and thiourea weighed in the step a into an agate mortar, and grinding for 5min to prepare reaction precursor powder.
Step 2, placing the reaction precursor powder obtained in the step 1 into a 20mL quartz boat, placing the quartz boat into a tube furnace, and preserving heat for 2.5 hours under the condition of 1050 ℃ at a heating rate of 3 ℃/min under the nitrogen atmosphere;
step 3, after the reaction is completed, taking out the quartz boat after the tube furnace is naturally cooled to room temperature;
step 4, grinding the product obtained in the step 3 to obtain MnNb 3 S 6 Piezoelectric catalytic materials.
As shown in FIG. 1, line 1 is the MnNb produced in this example 3 S 6 X-ray diffraction pattern of the piezocatalytic material. Line 1 has high peak intensity, sharp peak, no impurity peak, and high purity with MnNb 3 S 6 Standard powder diffraction file (JCPDS 89-4821) was consistent, indicating the resultant product knotsGood crystal and high purity.
Example 2
Step 1, preparing reaction precursor powder, which specifically comprises the following steps:
a. 1.8mmol of manganese powder, 3.0mmol of niobium pentachloride and 12.0mmol of thiourea are weighed, namely 0.0989g of manganese powder, 0.8105g of niobium pentachloride and 0.9134g of thiourea are weighed;
b. and d, placing the manganese powder, niobium pentachloride and thiourea weighed in the step a into an agate mortar, and grinding for 5min to prepare reaction precursor powder.
Step 2, placing the reaction precursor powder obtained in the step 1 into a 20mL quartz boat, placing the quartz boat into a tube furnace, and preserving heat for 3.0h under the condition of 1100 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere;
step 3, after the reaction is completed, taking out the quartz boat after the tube furnace is naturally cooled to room temperature;
step 4, grinding the product obtained in the step 3 to obtain MnNb 3 S 6 Piezoelectric catalytic materials.
As shown in FIG. 1, line 2 is the MnNb produced in this example 3 S 6 X-ray diffraction pattern of the piezocatalytic material. Line 2 has high peak intensity, sharp peak, no impurity peak, and no MnNb 3 S 6 The standard powder diffraction file (JCPCDS 89-4821) is consistent, which shows that the obtained product has good crystallization and high purity.
Example 3
Step 1, preparing reaction precursor powder, which specifically comprises the following steps:
a. 1.8mmol of manganese powder, 3.0mmol of niobium pentachloride and 12.0mmol of thiourea are weighed, namely 0.0991g of manganese powder, 0.8107g of niobium pentachloride and 0.9136g of thiourea are weighed;
b. placing the manganese powder, niobium pentachloride and thiourea weighed in the step a into an agate mortar, and grinding for 5min to prepare reaction precursor powder;
step 2, placing the reaction precursor powder obtained in the step 1 into a 20mL quartz boat, placing the quartz boat into a tube furnace, and preserving heat at the temperature of 1150 ℃ and at the heating rate of 7 ℃/min under the nitrogen atmosphere and 3.5h;
step 3, after the reaction is completed, taking out the quartz boat after the tube furnace is naturally cooled to room temperature;
step 4, grinding the product obtained in the step 3 to obtain MnNb 3 S 6 Piezoelectric catalytic materials.
As shown in FIG. 1, line 3 is the MnNb produced in this example 3 S 6 X-ray diffraction pattern of the piezocatalytic material. Line 3 has high peak intensity, sharp peak, no impurity peak, and no MnNb 3 S 6 The standard powder diffraction file (JCPCDS 89-4821) is consistent, which shows that the obtained product has good crystallization and high purity.
As shown in FIG. 2a, mnNb produced in example 1 3 S 6 Scanning electron microscope image of piezocatalysis material. As can be seen from the figure, mnNb prepared in this example 3 S 6 The piezoelectric catalytic material has lamellar morphology, a small amount of agglomeration phenomenon occurs due to high-temperature sintering, and the lamellar is broken. As shown in FIG. 2b, mnNb produced in example 2 3 S 6 Scanning electron microscope image of piezocatalysis material. As can be seen from the figure, mnNb prepared in this example 3 S 6 The piezoelectric catalytic material also has an irregular lamellar morphology. As shown in FIG. 2c, mnNb produced in example 3 3 S 6 Scanning electron microscope image of piezocatalysis material. As can be seen from the figure, mnNb prepared in this example 3 S 6 The piezoelectric catalytic material also has an irregular lamellar morphology.
MnNb prepared by the method of the invention 3 S 6 The catalytic material is subjected to a piezoelectricity catalytic degradation experiment. Acetamiprid was used as a degradation model for testing piezoelectric activity. The concentration is 10 mg L -1 Acetamiprid solution and 0.05g MnNb 3 S 6 Piezoelectric catalytic material is added into the glass cylinder together, and the piezoelectric power is set to 520W. Before each reaction starts, the glass jar is placed in a dark environment for 30 min to reach adsorption-desorption equilibrium, and then a sample of 0 min is extracted as reference of the data. Starting a piezoelectric catalytic device, starting piezoelectric catalytic degradation, introducing cooling water in the experimental process, sampling once every 3 min, filtering the solution by a microporous filter membrane, placing the solution into a centrifuge tube, and testing the absorbance by an ultraviolet spectrophotometer. Root of Chinese characterThe degradation rate was calculated from the relationship between absorbance and concentration, and the experimental results are shown in fig. 3.
In FIG. 3, the degradation time is on the abscissa, the degradation rate is on the ordinate, and line 1 is MnNb prepared in example 1 3 S 6 Piezoelectric catalytic material degradation curve, line 2 is MnNb prepared in example 2 3 S 6 Piezoelectric catalytic material degradation curve, line 3 is MnNb prepared in example 3 3 S 6 Piezoelectric catalytic material degradation curve. As can be seen from FIG. 3, the MnNb prepared by the method of the present invention 3 S 6 The piezoelectric catalytic material has higher degradation rate to acetamiprid solution, short degradation time and good removal effect.
Claims (2)
1. MnNb 3 S 6 The preparation method of the piezoelectric catalytic material is characterized by comprising the following steps:
step 1, preparing reaction precursor powder;
the reaction precursor powder in the step 1 is prepared by the following steps:
a. 1.8mmol of manganese powder, 3.0mmol of niobium pentachloride and 12.0mmol of thiourea are weighed;
b. placing the manganese powder, niobium pentachloride and thiourea weighed in the step a into an agate mortar, and grinding for 5min to prepare reaction precursor powder;
step 2, placing the reaction precursor powder obtained in the step 1 into a 20mL quartz boat, placing the quartz boat into a tube furnace, and reacting at 1050-1150 ℃ in a nitrogen atmosphere;
in the step 2, the heating rate is 3-7 ℃/min; in the step 2, the heat preservation time is 2.5-3.5 h;
step 3, after the reaction is completed, taking out the quartz boat after the tube furnace is naturally cooled to room temperature;
step 4, grinding the product obtained in the step 3 to obtain MnNb 3 S 6 Piezoelectric catalytic materials.
2. A MnNb as claimed in claim 1 3 S 6 The piezoelectric catalytic material is applied as a piezoelectric catalytic material.
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