CN113600215A - Porous ball of flowers Ni5P4Capture of g-C3N4Preparation method and application of QDs composite photocatalyst - Google Patents
Porous ball of flowers Ni5P4Capture of g-C3N4Preparation method and application of QDs composite photocatalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 32
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
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- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
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- 239000000203 mixture Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
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- 238000001816 cooling Methods 0.000 claims description 11
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
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- 239000003054 catalyst Substances 0.000 claims description 3
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 239000003242 anti bacterial agent Substances 0.000 abstract description 4
- 229940088710 antibiotic agent Drugs 0.000 abstract description 3
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 5
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 4
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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 belongs to the technical field of photocatalysis, and relates to porous ball Ni5P4Capture of g-C3N4The preparation method of the QDs composite photocatalyst and the application thereof, the preparation method comprises the step of mixing g-C3N4QDs and Ni5P4Respectively dispersing in ethanol, and ultrasonic treating to obtain g-C3N4Ethanol solution of QDs and Ni5P4g-C of an ethanol solution of3N4QDs of Ni5P41 to 8 mass percent of Ni5P4The solution was added dropwise to g-C3N4Continuously performing ultrasonic treatment on the solution of QDs until the solution is uniform, adding acetone, stirring for 18-28h, precipitating for 3-5h, pouring out supernatant, and drying to obtain porous ball Ni5P4Capture of g-C3N4QDs composite photocatalysts. The prepared composite photocatalyst provides ideas and means for the fields of photocatalytic degradation of antibiotics, environmental protection and the like, and has a great popularization value.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to porous flower ball Ni5P4Capture of g-C3N4A preparation method and application of a QDs composite photocatalyst.
Background
In recent years, a large amount of organic pollutants containing antibiotics, dyes, agricultural chemicals and the like flow into water, harm is caused to plants and aquatic organisms, and meanwhile, the harm may threaten human health, so that an effective technical means is necessary for solving the pollution problem. Solar energy, as one of the main energy sources for sustainable development, can be converted by means of photovoltaic-assisted electrolysis, photoelectrochemical cells, photocatalysis, and the like. The photocatalytic technology has attracted extensive attention as a method for efficiently degrading organic pollutants. Subsequently, a number of photocatalysts have been developed, mainly metal-based semiconductors, including metal oxides, metal sulfides, metal nitrides, composites thereof, and the like. These inorganic metal semiconductors exhibit certain properties in terms of photocatalysis, but also have some significant disadvantages, such as high price, toxicity, environmental harm, etc.
Graphite phase carbon nitride (g-C)3N4) As a non-metal semiconductor, the photocatalyst has unique advantages in the field of photocatalytic materials. For example, the composition mainly comprises C, N elements with rich content, so the synthesis cost is low; adjustable interband energy level, high chemical stability, rich N source at the edge, no toxicity, no harm and the like. However original g-C3N4The photocatalytic activity is not high, the specific surface area is relatively low, and the absorption of light is not facilitated; second original g-C3N4The photoproduction electron hole pair is easy to recombine, is not beneficial to the occurrence of photoreaction, and seriously limits the g-C3N4The practical application of (1).
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the problems, the invention provides porous ball Ni5P4Capture of g-C3N4A preparation method of QDs composite photocatalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows: porous flower ball Ni5P4Capture of g-C3N4The preparation method of the QDs composite photocatalyst comprises the following steps:
(1)g-C3N4preparation of QDs: calcining melamine to obtain blocky g-C3N4Grinding uniformly, adding nitric acid, acidifying and refluxing at 100-130 deg.C for 15-28h, washing with distilled water to neutrality, transferring the mixture to stainless steel autoclave made of polytetrafluoroethylene, maintaining at 130-180 deg.C for 10-15h, cooling to room temperature, centrifuging, and collecting to obtain g-C3N4 QDs；
(2) Porous ball of flowers Ni5P4The preparation of (1): mixing Ni (NO)3)2·6H2O, Urea and NH4Dispersing F in distilled water, stirring to dissolve and disperse completely, transferring to PTFEKeeping the stainless steel autoclave for ethylene at the temperature of 100-140 ℃ for 8-12h, cooling to room temperature, centrifuging and collecting a precursor Ni (OH)2Followed by addition of NaH2PO2·H2O, then placing the mixture in a tube furnace, heating to 320-380 ℃ at the heating rate of 3-5 ℃/min under the argon atmosphere and keeping for 2-5h to obtain the porous ball Ni5P4In which Ni (NO)3)2·6H2O, urea and NH4The mass ratio of F is 1-2: 2-3: 5-7;
(3) porous ball of flowers Ni5P4Capture of g-C3N4Preparation of QDs composite photocatalyst: g to C3N4QDs and Ni5P4Respectively dispersing in ethanol, and ultrasonic treating to obtain g-C3N4Ethanol solution of QDs and Ni5P4g-C of an ethanol solution of3N4QDs of Ni5P41 to 8 mass percent of Ni5P4The solution was added dropwise to g-C3N4Continuously performing ultrasonic treatment on the QDs solution to be uniform, adding acetone, stirring for 18-28h, precipitating for 3-5h, pouring out supernatant, and drying (preferably at 60 deg.C) to obtain porous ball Ni5P4Capture of g-C3N4QDs composite photocatalysts.
Further, in the step (1), the calcining method comprises the following steps: heating to 500-550 ℃ at the speed of 2-5 ℃/min, and keeping for 3-5 h.
In step (2), Ni (NO)3)2·6H2O, urea and NH4The dosage of F determines the obtained porous ball Ni5P4Preferably, Ni (NO)3)2·6H2O, urea and NH4The mass ratio of F is 1:3:6, and pure porous ball Ni can be obtained under the ratio5P4And the target does not need to be cleaned.
Further, in the step (2), the mixture is heated to 350 ℃ for 3 hours under the argon atmosphere at the heating rate of 3 ℃/min.
Porous ball Ni prepared by the method5P4Capture of g-C3N4QDs recombinationA photocatalyst for use as a catalyst in a photocatalytic degradation reaction of an antibiotic.
The invention is in the synthesis of g-C3N4Then acidizing to obtain the graphite phase carbon nitride quantum dots (g-C)3N4QDs)，g-C3N4QDs are smaller in size and thus possess a large number of active sites, a larger specific surface area and good edge effects.
The invention obtains blocky g-C by calcining melamine3N4Subsequent acidification and hydrothermal preparation to yield g-C3N4QDs, Ni porous ball of flowers morphology5P4Is prepared by a simple low-temperature phosphating method; subjecting g-C to ultrasonic immersion3N4Ni with QDs uniformly loaded on porous flower balls5P4Thus obtaining a porous ball Ni5P4Capture of g-C3N4QDs composite photocatalyst, the catalyst can be applied to the field of photocatalysis. Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
(1)g-C3N4the raw materials used in the QDs preparation process are fewer, and the template agent is not needed for assistance, so that the preparation method is more environment-friendly; the hydrothermal synthesis method can obtain g-C with uniform particle size3N4 QDs。
(2) Porous flower ball Ni prepared by low-temperature phosphating method5P4The method is simple to operate, low in preparation cost and large in specific surface area, and photocatalytic degradation efficiency can be effectively improved.
(3) The ultrasonic impregnation method adopted by the preparation of the composite photocatalyst is simple and easy to implement, has good repeatability, provides ideas and means for the fields of photocatalytic degradation of antibiotics, environmental protection and the like, and has great popularization value.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a graph of g-C prepared in various examples of the present invention3N4 QDs、Ni5P4And porous flower ball Ni5P4Capture of g-C3N4QDs composite photocatalyst g-C3N4 QDs/x％Ni5P4X-ray diffraction patterns of (a);
FIG. 2 is g-C3N4TEM images of QDs;
FIG. 3 is porous ball Ni5P4SEM picture of (1);
FIG. 4 shows g-C in each example of the present invention3N4 QDs、Ni5P4And porous flower ball Ni5P4Capture of g-C3N4QDs composite photocatalyst g-C3N4 QDs/x％Ni5P4Degradation effect graph (the shaded part of 0-20min in the graph represents dark reaction);
FIG. 5 shows g-C in each example of the present invention3N4 QDs、Ni5P4And porous flower ball Ni5P4Capture of g-C3N4QDs composite photocatalyst g-C3N4 QDs/x％Ni5P4Cycle chart of the photocatalytic experiment.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
example 1
(1)g-C3N4Preparation of QDs: placing melamine in a tube furnace, heating to 500-550 ℃ at the speed of 2-5 ℃/min, keeping for 3-5h, grinding uniformly, adding nitric acid, acidifying and refluxing for 15-28h at the temperature of 100-130 ℃, washing to neutrality by using distilled water, transferring the mixture into a stainless steel autoclave of polytetrafluoroethylene, keeping for 10-15h at the temperature of 130-180 ℃, cooling to room temperature, centrifuging and collecting to obtain g-C3N4 QDs；
(2) Porous ball of flowers Ni5P4The preparation of (1): 1.0g of Ni (NO)3)2·6H2O, 3.0g Urea and 6.0g NH4F is dispersed in 100ml of distilled water and stirred until the solution is fully dissolved and dispersed, the solution is transferred to a stainless steel autoclave of polytetrafluoroethylene and kept for 8 to 12 hours at the temperature of 100 ℃ and 140 ℃, after the solution is cooled to the room temperature, the precursor Ni (OH) is centrifugally collected2Followed by addition of NaH2PO2·H2O, then placing the mixture in a tube furnace, heating to 320-380 ℃ at the heating rate of 3-5 ℃/min under the argon atmosphere and keeping for 2-5h to obtain the porous ball Ni5P4；
(3) Porous ball of flowers Ni5P4Capture of g-C3N4Preparation of QDs composite photocatalyst: 0.1g of-C3N4QDs and Ni5P4Respectively dispersing in ethanol, and ultrasonic treating to obtain g-C3N4QDs solution and Ni5P4Solution of Ni5P4The solution was added dropwise to g-C3N4Continuously performing ultrasonic treatment on the QDs solution until the solution is uniform, adding acetone, stirring for 18-28h, precipitating for 3-5h, pouring out supernatant, and drying at 60 ℃ to obtain porous curd Ni5P4Capture of g-C3N4QDs composite photocatalyst, abbreviated as g-C3N4 QDs/1％Ni5P4。
Example 2
(1)g-C3N4Preparation of QDs: placing melamine in a tube furnace, heating to 500-550 ℃ at the speed of 2-5 ℃/min, keeping for 3-5h, grinding uniformly, adding nitric acid, acidifying and refluxing for 15-28h at the temperature of 100-130 ℃, washing to neutrality by using distilled water, transferring the mixture into a stainless steel autoclave of polytetrafluoroethylene, keeping for 10-15h at the temperature of 130-180 ℃, cooling to room temperature, centrifuging and collecting to obtain g-C3N4 QDs；
(2) Porous ball of flowers Ni5P4The preparation of (1): 1.0g of Ni (NO)3)2·6H2O, 3.0g Urea and 6.0g NH4F is dispersed in 100ml of distilled water and stirred until fullDissolving and dispersing, transferring into a stainless steel autoclave of polytetrafluoroethylene, keeping for 8-12h at the temperature of 100-140 ℃, cooling to room temperature, centrifuging and collecting a precursor Ni (OH)2Followed by addition of NaH2PO2·H2O, then placing the mixture in a tube furnace, heating to 320-380 ℃ at the heating rate of 3-5 ℃/min under the argon atmosphere and keeping for 2-5h to obtain the porous ball Ni5P4；
(3) Porous ball of flowers Ni5P4Capture of g-C3N4Preparation of QDs composite photocatalyst: 0.1g of-C3N4QDs and Ni5P4Respectively dispersing in ethanol, and ultrasonic treating to obtain g-C3N4QDs solution and Ni5P4Solution of Ni5P4The solution was added dropwise to g-C3N4Continuously performing ultrasonic treatment on the QDs solution until the solution is uniform, adding acetone, stirring for 18-28h, precipitating for 3-5h, pouring out supernatant, and drying at 60 ℃ to obtain porous curd Ni5P4Capture of g-C3N4QDs composite photocatalyst, abbreviated as g-C3N4 QDs/5％Ni5P4。
Example 3
(1)g-C3N4Preparation of QDs: placing melamine in a tube furnace, heating to 500-550 ℃ at the speed of 2-5 ℃/min, keeping for 3-5h, grinding uniformly, adding nitric acid, acidifying and refluxing for 15-28h at the temperature of 100-130 ℃, washing to neutrality by using distilled water, transferring the mixture into a stainless steel autoclave of polytetrafluoroethylene, keeping for 10-15h at the temperature of 130-180 ℃, cooling to room temperature, centrifuging and collecting to obtain g-C3N4 QDs；
(2) Porous ball of flowers Ni5P4The preparation of (1): 1.0g of Ni (NO)3)2·6H2O, 3.0g Urea and 6.0g NH4F is dispersed in 100ml of distilled water and stirred until the solution is fully dissolved and dispersed, the solution is transferred to a stainless steel autoclave of polytetrafluoroethylene and kept for 8 to 12 hours at the temperature of 100 ℃ and 140 ℃, after the solution is cooled to the room temperature, the precursor Ni (OH) is centrifugally collected2Followed by addition of NaH2PO2·H2O mixtureThen placing the mixture in a tube furnace, heating to 320-380 ℃ at the heating rate of 3-5 ℃/min under the argon atmosphere and keeping for 2-5h to obtain the porous ball Ni5P4；
(3) Porous ball of flowers Ni5P4Capture of g-C3N4Preparation of QDs composite photocatalyst: 0.1g of-C3N4QDs and Ni5P4Respectively dispersing in ethanol, and ultrasonic treating to obtain g-C3N4QDs solution and Ni5P4Solution of Ni5P4The solution was added dropwise to g-C3N4Continuously performing ultrasonic treatment on the QDs solution until the solution is uniform, adding acetone, stirring for 18-28h, precipitating for 3-5h, pouring out supernatant, and drying at 60 ℃ to obtain porous curd Ni5P4Capture of g-C3N4QDs composite photocatalyst, abbreviated as g-C3N4 QDs/8％Ni5P4。
Example 4
Porous ball of flowers Ni5P4The preparation of (1): 1.5g of Ni (NO) are weighed3)2·6H2O, 3.0g Urea and 0.8g NH4F is added into 70mL of distilled water, stirred uniformly, transferred into a stainless steel autoclave made of polytetrafluoroethylene material, and heated at 110 ℃ for 10 hours. After cooling to room temperature, the product was centrifuged and washed three times with distilled water and dried to give the final product Ni (OH)2. Mixing the obtained Ni (OH)2With 1.0g NaH2PO2·H2Placing O in a porcelain boat, heating to 350 ℃ at a heating rate of 3 ℃/min in an argon atmosphere, keeping for 2.5h, cooling to room temperature to obtain porous flower ball Ni5P4。
Example 5
Porous ball of flowers Ni5P4The preparation of (1): 1.5g of Ni (NO) are weighed3)2·6H2O, 3.0g Urea and 0.8g NH4F is added into 70mL of distilled water, stirred uniformly, transferred into a stainless steel autoclave made of polytetrafluoroethylene material, and heated at 110 ℃ for 10 hours. After cooling to room temperature, the product was centrifuged and washed three times with distilled water and dried to give the final productFinal product Ni (OH)2. Mixing the obtained Ni (OH)2With 1.0g NaH2PO2·H2Placing O in a porcelain boat, heating to 350 ℃ at a heating rate of 3 ℃/min in an argon atmosphere, keeping for 4.5h, cooling to room temperature to obtain porous flower ball Ni5P4. Ni porous ball prepared in examples 1 to 35P4Capture of g-C3N4The crystal structure of the QDs composite photocatalyst is analyzed by a Japanese science D/max2500PC autorotation X-ray diffractometer, wherein, the X-ray is Cu target Ka
The voltage is 40kV, the current is 100mA, the step length is 0.02 degrees, and the scanning range is 10-80 degrees. The X-ray diffraction pattern is shown in figure 1, g-C3N4QDs exhibit two typical (100) and (002) diffraction peaks centered at 13.1 ° and 27.8 °, respectively; ni5P4The peak position accords with the standard card; g-C3N4 QDs/Ni5P4The peak position of the compound is consistent with that of the pure sample, and the successful synthesis of the two-phase mixture is fully indicated.
g-C prepared in examples 1-33N4The morphological structure of QDs was analyzed by transmission electron microscope of Japanese Electron JEOL JEM-2100, and it can be seen from FIG. 2 that g-C prepared by a simple thermal polymerization method3N4The QDs have uniform particle size and are mainly distributed at 5-6 nm.
Ni prepared in examples 1 to 55P4The morphological structure of (a) is 3.5h of Ni calcined in a sample analyzed by a scanning electron microscope of JSM-6360A, FIG. 35P4Obviously has the flower-ball shape and simultaneously presents a porous structure on the flower sheet, and (b) is calcined for 2.5h, Ni5P4Only has a porous structure and does not have the appearance of a flower ball; (c) to calcine for 4.5h, Ni5P4It has no porous ball structure and has sharp needle shape, so that it is necessary to control the calcining time.
Ni porous ball prepared in examples 1 to 35P4Captureg-C3N4The QDs composite photocatalyst is used as a photocatalyst to degrade norfloxacin. 30mg of photocatalyst is added into 30mg/L norfloxacin water solution, and a 1000w mercury lamp is used as a light source to carry out photocatalytic degradation reaction. The dark reaction was 20 minutes, 3mL of the suspension was aspirated every 20 minutes after the light illumination using a 3mL pipette gun and repeated 5 times, and the suspension was then analyzed on a uv-vis absorption spectrometer. As can be seen from FIG. 4, g-C occurred within 120 minutes3N4 QDs/8％Ni5P4The degradation rate of the composite photocatalyst for degrading norfloxacin can reach 92 percent, and the g-C prepared can be seen3N4 QDs/8％Ni5P4The composite photocatalyst has higher photocatalytic activity.
In order to verify the porous ball Ni prepared by the invention5P4Capture of g-C3N4Stability of QDs composite photocatalyst, porous ball Ni prepared in example 35P4Capture of g-C3N4The QDs composite photocatalyst was subjected to a photocatalytic cycle test. The experimental result is shown in fig. 5, the degradation rate of norfloxacin after four cycles can still reach more than 85%, and the result shows that the porous microsphere Ni5P4Capture of g-C3N4The QDs composite photocatalyst has good stability.
The foregoing description is provided to illustrate the preferred embodiments of the present invention. Various changes and modifications can be made by workers skilled in the art without departing from the scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (6)
1. Porous flower ball Ni5P4Capture of g-C3N4The preparation method of the QDs composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1)g-C3N4preparation of QDs: calcining melamine to obtain blocky g-C3N4Grinding uniformly and adding nitric acid, acidifying and refluxing at 100-130 deg.C for 15-Washing with distilled water to neutrality for 28h, transferring the mixture to a stainless steel autoclave made of polytetrafluoroethylene, maintaining at 130-180 deg.C for 10-15h, cooling to room temperature, centrifuging, and collecting g-C3N4 QDs；
(2) Porous ball of flowers Ni5P4The preparation of (1): mixing Ni (NO)3)2·6H2O, Urea and NH4F is dispersed in distilled water and stirred until the solution is fully dissolved and dispersed, the solution is transferred to a stainless steel autoclave of polytetrafluoroethylene and kept for 8 to 12 hours at the temperature of 100 ℃ and 140 ℃, after the solution is cooled to the room temperature, the precursor Ni (OH) is centrifugally collected2Followed by addition of NaH2PO2·H2O, then placing the mixture in a tube furnace, heating to 320-380 ℃ at the heating rate of 3-5 ℃/min under the argon atmosphere and keeping for 2-5h to obtain the porous ball Ni5P4In which Ni (NO)3)2·6H2O, urea and NH4The mass ratio of F is 1-2: 2-3: 5-7;
(3) porous ball of flowers Ni5P4Capture of g-C3N4Preparation of QDs composite photocatalyst: g to C3N4QDs and Ni5P4Respectively dispersing in ethanol, and ultrasonic treating to obtain g-C3N4Ethanol solution of QDs and Ni5P4g-C of an ethanol solution of3N4QDs of Ni5P41 to 8 mass percent of Ni5P4The solution was added dropwise to g-C3N4Continuously performing ultrasonic treatment on the solution of QDs until the solution is uniform, adding acetone, stirring for 18-28h, precipitating for 3-5h, pouring out supernatant, and drying to obtain porous ball Ni5P4Capture of g-C3N4QDs composite photocatalysts.
2. Porous curd Ni according to claim 15P4Capture of g-C3N4The preparation method of the QDs composite photocatalyst is characterized by comprising the following steps: in the step (1), the calcining method comprises the following steps: heating to 500-550 ℃ at the speed of 2-5 ℃/min, and keeping for 3-5 h.
3. Porous curd Ni according to claim 15P4Capture of g-C3N4The preparation method of the QDs composite photocatalyst is characterized by comprising the following steps: ni (NO) in step (2)3)2·6H2O, urea and NH4The mass ratio of F is 1:3: 6.
4. Porous curd Ni according to claim 15P4Capture of g-C3N4The preparation method of the QDs composite photocatalyst is characterized by comprising the following steps: in the step (2), the mixture is heated to 350 ℃ at the heating rate of 3 ℃/min for 3h under the argon atmosphere.
5. The porous curd Ni of any one of claims 1 to 45P4Capture of g-C3N4Porous flower ball Ni prepared by preparation method of QDs composite photocatalyst5P4Capture of g-C3N4QDs composite photocatalysts.
6. Porous curd Ni as claimed in claim 55P4Capture of g-C3N4The application of the QDs composite photocatalyst is characterized in that: used as a catalyst in the photocatalytic antibiotic degradation reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261193A (en) * | 2018-11-09 | 2019-01-25 | 辽宁大学 | Ultrasound-solvent structure Bi2O2CO3/g-C3N4The method and its application of flower-shaped composite photo-catalyst |
| CN113117718A (en) * | 2021-03-29 | 2021-07-16 | 安徽建筑大学 | NiCoP-g-C3N4/CdS composite photocatalyst, preparation method and application thereof |
-
2021
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261193A (en) * | 2018-11-09 | 2019-01-25 | 辽宁大学 | Ultrasound-solvent structure Bi2O2CO3/g-C3N4The method and its application of flower-shaped composite photo-catalyst |
| CN113117718A (en) * | 2021-03-29 | 2021-07-16 | 安徽建筑大学 | NiCoP-g-C3N4/CdS composite photocatalyst, preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| CHUNXUE LI ET AL.: ""Facile fabrication of g-C3N4 QDs/BiVO4 Z-scheme heterojunction towards enhancing photodegradation activity under visible light"", 《JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS》 * |
| ZHICHAO SUN ET AL.: ""Phase Effect of NixPy Hybridized with g-C3N4 for Photocatalytic Hydrogen Generation"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 李冬平等: ""Ni5P4/g-C3N4复合光催化剂的制备及光催化性能"", 《高等学校化学学报》 * |
| 林珮瑶: ""金属相镍基磷化物助催化剂的制备、表征及其在光催化分解水产氢领域的研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116273124A (en) * | 2023-03-22 | 2023-06-23 | 陕西科技大学 | Ni-Ni 2 P-Ni 5 P 4 /g-C 3 N 4 Photocatalyst, preparation method and application thereof |
| CN116273124B (en) * | 2023-03-22 | 2024-06-07 | 陕西科技大学 | Ni-Ni2P-Ni5P4/g-C3N4Photocatalyst, preparation method and application thereof |
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