CN113600215B - Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation method and application of QDs composite photocatalyst - Google Patents
Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation method and application of QDs composite photocatalyst Download PDFInfo
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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
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention belongs to the technical field of photocatalysis, and relates to a porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation method and application of QDs composite photocatalyst, and preparation method comprises the steps of mixing g-C 3 N 4 QDs and Ni 5 P 4 Respectively dispersing in ethanol, and performing ultrasonic treatment to obtain g-C 3 N 4 Ethanol solution of QDs and Ni 5 P 4 g-C 3 N 4 QDs occupies Ni 5 P 4 1 to 8 percent of the mass of Ni 5 P 4 The solution was added dropwise to g-C 3 N 4 Continuously ultrasonic treating the QDs solution until it is uniform, adding acetone, stirring for 18-28 hr, precipitating for 3-5 hr, pouring out supernatant, and drying to obtain porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs 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 great popularization value.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and in particular relates to a porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation method and application of QDs composite photocatalyst.
Background
In recent years, a large amount of organic pollutants containing antibiotics, dyes, agrochemicals and the like flow into water bodies to cause harm to plants and aquatic organisms, and meanwhile, the organic pollutants possibly threaten human health, so that effective technical means are necessary to solve the pollution problem. Solar energy is used as one of the main energy sources for sustainable development, and can be converted by means of photovoltaic auxiliary electrolysis, photoelectrochemical cells, photocatalysis and the like. Among them, the photocatalytic technology has received a great deal of attention as a method for efficiently degrading organic pollutants. A number of photocatalysts have been developed subsequently, principally 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 drawbacks such as being expensive, toxic, harmful to the environment, etc.
Graphite phase carbon nitride (g-C) 3 N 4 ) As a nonmetallic semiconductor, it has been shown to be particularly advantageous in the field of photocatalytic materials. For example, the composite material mainly comprises C, N elements with rich contents, so that the composite cost is low; the energy level between bands can be adjusted, the chemical stability is high, the edge is rich in N sources, and the method is nontoxic and harmless. However, the original g-C 3 N 4 The photocatalytic activity of the catalyst is not high, the specific surface area is relatively low, and the catalyst is unfavorable for light absorption; second raw g-C 3 N 4 The photo-generated electron-hole pair is easy to be combined, is unfavorable for the occurrence of photoreaction and severely limits g-C 3 N 4 Is a practical application of the above.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to overcome the problems, the invention provides a porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 A preparation method of QDs composite photocatalyst.
The technical scheme adopted for solving the technical problems is as follows: porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 The preparation method of the QDs composite photocatalyst comprises the following steps:
(1)g-C 3 N 4 preparation of QDs: calcining melamine to obtain blocky g-C 3 N 4 Grinding uniformly, adding nitric acid, acidifying and refluxing at 100-130deg.C for 15-28 hr, washing with distilled water to neutrality, transferring the mixture into stainless steel autoclave of polytetrafluoroethylene, maintaining at 130-180deg.C for 10-15 hr, cooling to room temperature, centrifuging, and collecting g-C 3 N 4 QDs；
(2) Porous flower ball Ni 5 P 4 Is prepared from the following steps: ni (NO) 3 ) 2 ·6H 2 O, urea and NH 4 F dispersing in distilled water, stirring to dissolve and disperse thoroughly, transferring to stainless steel autoclave of polytetrafluoroethylene, maintaining at 100-140deg.C for 8-12 hr, cooling to room temperature, centrifuging, and collecting precursor Ni (OH) 2 Subsequently NaH is added 2 PO 2 ·H 2 Mixing O, placing the mixture in a tube furnace, heating to 320-380deg.C at a heating rate of 3-5deg.C/min under argon atmosphere, and maintaining for 2-5 hr to obtain porous flower ball Ni 5 P 4 Wherein Ni (NO) 3 ) 2 ·6H 2 O, urea and NH 4 F has a mass ratio of 1-2:2-3:5-7;
(3) Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation of QDs composite photocatalyst: will g-C 3 N 4 QDs and Ni 5 P 4 Respectively dispersing in ethanol, and performing ultrasonic treatment to obtain g-C 3 N 4 Ethanol solution of QDs and Ni 5 P 4 g-C 3 N 4 QDs occupies Ni 5 P 4 1 to 8 percent of the mass of Ni 5 P 4 The solution was added dropwise to g-C 3 N 4 Continuing to carry out ultrasonic treatment on the QDs solution until the QDs solution is uniform, adding acetone, stirring for 18-28h, and precipitating 3-After 5 hours, the supernatant is poured out and dried (preferably at 60 ℃) to obtain the porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalysts.
Further, in the step (1), the calcining method is as follows: heating to 500-550deg.C at 2-5deg.C/min, and maintaining for 3-5h.
In step (2), ni (NO) 3 ) 2 ·6H 2 O, urea and NH 4 F amount is determined to obtain the porous flower ball Ni 5 P 4 Preferably, ni (NO) 3 ) 2 ·6H 2 O, urea and NH 4 F has a mass ratio of 1:3:6, and pure porous flower ball Ni can be obtained under the ratio 5 P 4 And 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 a heating rate of 3 ℃/min.
Porous flower ball Ni prepared by the method 5 P 4 Capture of g-C 3 N 4 The QDs composite photocatalyst is used as a catalyst in the reaction of photocatalytic degradation of antibiotics.
The invention synthesizes g-C 3 N 4 Then acidizing to obtain graphite phase carbon nitride quantum dot (g-C 3 N 4 QDs)，g-C 3 N 4 QDs are smaller in size, thus possessing a large number of active sites, a larger specific surface area and good edge effects.
The invention obtains the blocky g-C by calcining melamine 3 N 4 Then acidizing and preparing the g-C by a hydrothermal method 3 N 4 QDs, ni of porous flower ball morphology 5 P 4 Is prepared by a simple low-temperature phosphating method; g-C by ultrasonic impregnation 3 N 4 QDs are uniformly loaded on the porous flower ball Ni 5 P 4 Obtaining the porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 The QDs composite photocatalyst 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-C 3 N 4 the raw materials used in the preparation process of the QDs are fewer, the assistance of a template agent is not needed, and the QDs are more environment-friendly; the adopted hydrothermal synthesis method can obtain g-C with uniform particle size 3 N 4 QDs。
(2) Porous flower ball Ni prepared by low-temperature phosphating method 5 P 4 The preparation method is simple to operate, low in preparation cost, larger in specific surface area and capable of effectively improving photocatalytic degradation efficiency.
(3) The ultrasonic impregnation method adopted in the preparation of the composite photocatalyst is simple, convenient and feasible, 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 produced in various examples of the invention 3 N 4 QDs、Ni 5 P 4 Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalyst g-C 3 N 4 QDs/x％Ni 5 P 4 X-ray diffraction pattern of (2);
FIG. 2 is g-C 3 N 4 TEM images of QDs;
FIG. 3 is a porous flower ball Ni 5 P 4 SEM images of (a);
FIG. 4 is a graph of g-C in various embodiments of the invention 3 N 4 QDs、Ni 5 P 4 Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalyst g-C 3 N 4 QDs/x％Ni 5 P 4 The degradation effect of (a hatched portion of 0 to 20min in the figure represents a dark reaction);
FIG. 5 is a graph of g-C in various embodiments of the invention 3 N 4 QDs、Ni 5 P 4 Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalyst g-C 3 N 4 QDs/x％Ni 5 P 4 Is a photocatalytic experimental cycle chart.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
example 1
(1)g-C 3 N 4 Preparation of QDs: placing melamine in a tubular furnace, heating to 500-550deg.C at 2-5deg.C/min, maintaining for 3-5 hr, grinding uniformly, adding nitric acid, acidifying and refluxing at 100-130deg.C for 15-28 hr, washing with distilled water to neutrality, transferring the mixture into stainless steel autoclave of polytetrafluoroethylene, maintaining at 130-180deg.C for 10-15 hr, cooling to room temperature, centrifuging, and collecting g-C 3 N 4 QDs；
(2) Porous flower ball Ni 5 P 4 Is prepared from the following steps: 1.0g of Ni (NO) 3 ) 2 ·6H 2 O, 3.0g urea and 6.0g NH 4 F is dispersed in 100ml distilled water, stirred until the F is fully dissolved and dispersed, transferred into a stainless steel autoclave of polytetrafluoroethylene, kept for 8 to 12 hours at 100 to 140 ℃, cooled to room temperature, and centrifugally collected into a precursor Ni (OH) 2 Subsequently NaH is added 2 PO 2 ·H 2 Mixing O, placing the mixture in a tube furnace, heating to 320-380deg.C at a heating rate of 3-5deg.C/min under argon atmosphere, and maintaining for 2-5 hr to obtain porous flower ball Ni 5 P 4 ；
(3) Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation of QDs composite photocatalyst: will be 0.1g-C 3 N 4 QDs and Ni 5 P 4 Respectively dispersing in ethanol, and performing ultrasonic treatment until the mixture is fully dispersed to obtain g-C 3 N 4 QDs solution and Ni 5 P 4 Solution of Ni 5 P 4 The solution was added dropwise to g-C 3 N 4 Continuing to carry out ultrasonic treatment in the QDs solution until the QDs solution is uniformAdding acetone, stirring for 18-28 hr, precipitating for 3-5 hr, pouring out supernatant, and drying at 60deg.C to obtain porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalyst, called g-C for short 3 N 4 QDs/1％Ni 5 P 4 。
Example 2
(1)g-C 3 N 4 Preparation of QDs: placing melamine in a tubular furnace, heating to 500-550deg.C at 2-5deg.C/min, maintaining for 3-5 hr, grinding uniformly, adding nitric acid, acidifying and refluxing at 100-130deg.C for 15-28 hr, washing with distilled water to neutrality, transferring the mixture into stainless steel autoclave of polytetrafluoroethylene, maintaining at 130-180deg.C for 10-15 hr, cooling to room temperature, centrifuging, and collecting g-C 3 N 4 QDs；
(2) Porous flower ball Ni 5 P 4 Is prepared from the following steps: 1.0g of Ni (NO) 3 ) 2 ·6H 2 O, 3.0g urea and 6.0g NH 4 F is dispersed in 100ml distilled water, stirred until the F is fully dissolved and dispersed, transferred into a stainless steel autoclave of polytetrafluoroethylene, kept for 8 to 12 hours at 100 to 140 ℃, cooled to room temperature, and centrifugally collected into a precursor Ni (OH) 2 Subsequently NaH is added 2 PO 2 ·H 2 Mixing O, placing the mixture in a tube furnace, heating to 320-380deg.C at a heating rate of 3-5deg.C/min under argon atmosphere, and maintaining for 2-5 hr to obtain porous flower ball Ni 5 P 4 ；
(3) Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation of QDs composite photocatalyst: will be 0.1g-C 3 N 4 QDs and Ni 5 P 4 Respectively dispersing in ethanol, and performing ultrasonic treatment until the mixture is fully dispersed to obtain g-C 3 N 4 QDs solution and Ni 5 P 4 Solution of Ni 5 P 4 The solution was added dropwise to g-C 3 N 4 Continuously ultrasonic treating the QDs solution until it is uniform, adding acetone, stirring for 18-28 hr, precipitating for 3-5 hr, pouring out supernatant, and drying at 60deg.C to obtain porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalyst, called g-C for short 3 N 4 QDs/5％Ni 5 P 4 。
Example 3
(1)g-C 3 N 4 Preparation of QDs: placing melamine in a tubular furnace, heating to 500-550deg.C at 2-5deg.C/min, maintaining for 3-5 hr, grinding uniformly, adding nitric acid, acidifying and refluxing at 100-130deg.C for 15-28 hr, washing with distilled water to neutrality, transferring the mixture into stainless steel autoclave of polytetrafluoroethylene, maintaining at 130-180deg.C for 10-15 hr, cooling to room temperature, centrifuging, and collecting g-C 3 N 4 QDs；
(2) Porous flower ball Ni 5 P 4 Is prepared from the following steps: 1.0g of Ni (NO) 3 ) 2 ·6H 2 O, 3.0g urea and 6.0g NH 4 F is dispersed in 100ml distilled water, stirred until the F is fully dissolved and dispersed, transferred into a stainless steel autoclave of polytetrafluoroethylene, kept for 8 to 12 hours at 100 to 140 ℃, cooled to room temperature, and centrifugally collected into a precursor Ni (OH) 2 Subsequently NaH is added 2 PO 2 ·H 2 Mixing O, placing the mixture in a tube furnace, heating to 320-380deg.C at a heating rate of 3-5deg.C/min under argon atmosphere, and maintaining for 2-5 hr to obtain porous flower ball Ni 5 P 4 ；
(3) Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation of QDs composite photocatalyst: will be 0.1g-C 3 N 4 QDs and Ni 5 P 4 Respectively dispersing in ethanol, and performing ultrasonic treatment until the mixture is fully dispersed to obtain g-C 3 N 4 QDs solution and Ni 5 P 4 Solution of Ni 5 P 4 The solution was added dropwise to g-C 3 N 4 Continuously ultrasonic treating the QDs solution until it is uniform, adding acetone, stirring for 18-28 hr, precipitating for 3-5 hr, pouring out supernatant, and drying at 60deg.C to obtain porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalyst, called g-C for short 3 N 4 QDs/8％Ni 5 P 4 。
Example 4
Porous flower ball Ni 5 P 4 Is prepared from the following steps: 1.5g Ni (NO) was weighed out 3 ) 2 ·6H 2 O, 3.0g Urea and 0.8g NH 4 F is added into 70mL of distilled water, stirred uniformly, transferred into a stainless steel autoclave made of polytetrafluoroethylene material and heated at 110 ℃ for 10h. 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 . The obtained Ni (OH) 2 With 1.0g NaH 2 PO 2 ·H 2 Placing O in a porcelain boat, heating to 350 ℃ at a heating rate of 3 ℃/min under argon atmosphere, maintaining for 2.5h, and cooling to room temperature to obtain porous flower ball Ni 5 P 4 。
Example 5
Porous flower ball Ni 5 P 4 Is prepared from the following steps: 1.5g Ni (NO) was weighed out 3 ) 2 ·6H 2 O, 3.0g Urea and 0.8g NH 4 F is added into 70mL of distilled water, stirred uniformly, transferred into a stainless steel autoclave made of polytetrafluoroethylene material and heated at 110 ℃ for 10h. 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 . The obtained Ni (OH) 2 With 1.0g NaH 2 PO 2 ·H 2 Placing O in a porcelain boat, heating to 350 ℃ at a heating rate of 3 ℃/min under argon atmosphere, keeping for 4.5h, and cooling to room temperature to obtain porous flower ball Ni 5 P 4 . Porous flower ball Ni prepared in examples 1 to 3 5 P 4 Capture of g-C 3 N 4 The crystal structure of QDs composite photocatalyst was analyzed by Japanese science D/max2500PC autorotation X-ray diffractometer, wherein X-ray is Cu target K alpha
The voltage is 40kV, the current is 100mA, the step size is 0.02 DEG, and the scanning range is 10 DEG-80 deg. The X-ray diffraction pattern is shown in figure 1, g-C 3 N 4 QDs exhibit two typical (100) and (002) diffraction peaks centered at 13.1 ° and 27.8 °, respectively; ni (Ni) 5 P 4 The peak position accords with the standard card; g-C 3 N 4 QDs/Ni 5 P 4 The peak position of the (C) is consistent with that of a pure sample, and the successful synthesis of the two-phase mixture is fully shown.
The g-C prepared in examples 1 to 3 3 N 4 The morphology and structure of QDs were analyzed by Japanese electron JEOL JEM-2100 transmission electron microscope, and as can be seen from FIG. 2, g-C was prepared by a simple thermal polymerization method 3 N 4 The QDs have uniform particle size and are mainly distributed at 5-6nm.
Ni prepared in examples 1 to 5 5 P 4 The morphological structure of (a) was analyzed by JSM-6360A scanning electron microscope in Japan, and as can be seen from FIG. 3, ni was calcined for 3.5 hours 5 P 4 Obviously has a flower-ball shape, and simultaneously presents a porous structure on the flower piece, (b) is calcined for 2.5h, ni 5 P 4 Only has a porous structure and does not have a flower ball shape; (c) For calcination for 4.5h, ni 5 P 4 The porous flower ball structure is completely absent and sharp needle-like shapes are present, so that control of the calcination time is necessary.
Porous flower ball Ni prepared in examples 1 to 3 5 P 4 Capture of g-C 3 N 4 The QDs composite photocatalyst is used as a photocatalyst for degrading norfloxacin. 30mg of photocatalyst is added into 30mg/L of norfloxacin aqueous 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 illumination using a 3mL pipette, and repeated 5 times, and then the suspension was analyzed on an ultraviolet visible absorption spectrometer. As can be seen from FIG. 4, g-C was measured within 120 minutes 3 N 4 QDs/8％Ni 5 P 4 The degradation rate of the compound photocatalyst for degrading norfloxacin can reach 92%, and the prepared g-C can be seen 3 N 4 QDs/8％Ni 5 P 4 The composite photocatalyst has higher photocatalytic activity.
To verify the porous flower ball Ni prepared by the invention 5 P 4 Capture of g-C 3 N 4 Stability of QDs composite photocatalyst porous flower ball Ni prepared in example 3 5 P 4 Capture of g-C 3 N 4 The QDs composite photocatalyst was subjected to a photocatalytic cycle test. As shown in FIG. 5, the degradation rate of the para-ofloxacin after four cycles can still be achieved85% or more, representing porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 The QDs composite photocatalyst has good stability.
The foregoing description, given above with reference to the preferred embodiments of the present invention. The related workers can completely make various changes and modifications within the scope not departing from the technical idea of the invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (5)
1. Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 The preparation method of the QDs composite photocatalyst is used for photocatalytic degradation of norfloxacin, and is characterized by comprising the following steps of: the method comprises the following steps of:
（1）g-C 3 N 4 preparation of QDs: calcining melamine to obtain blocky g-C 3 N 4 Grinding uniformly, adding nitric acid, acidifying and refluxing at 100-130deg.C for 15-28h, washing with distilled water to neutrality, transferring the mixture into stainless steel autoclave of polytetrafluoroethylene, maintaining at 130-180deg.C for 10-15h, cooling to room temperature, centrifuging, and collecting g-C 3 N 4 QDs；
(2) Porous flower ball Ni 5 P 4 Is prepared from the following steps: ni (NO) 3 ) 2 •6H 2 O, urea and NH 4 F dispersing in distilled water, stirring to dissolve and disperse thoroughly, transferring to stainless steel autoclave of polytetrafluoroethylene, maintaining at 100-140deg.C for 8-12h, cooling to room temperature, centrifuging, and collecting precursor Ni (OH) 2 Subsequently NaH is added 2 PO 2 ·H 2 Mixing O, placing the mixture in a tube furnace, heating to 350deg.C at a heating rate of 3-5deg.C/min under argon atmosphere, and maintaining for 3.5 hr to obtain porous flower ball Ni 5 P 4 Wherein Ni (NO) 3 ) 2 •6H 2 O, urea and NH 4 The mass ratio of F is 1-2:2-3:5-7;
(3) Porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 Preparation of QDs composite photocatalyst: will g-C 3 N 4 QDs and Ni 5 P 4 Respectively dispersing in ethanol, and performing ultrasonic treatment to obtain g-C 3 N 4 Ethanol solution of QDs and Ni 5 P 4 g-C 3 N 4 QDs occupies Ni 5 P 4 8% by mass of Ni 5 P 4 The solution was added dropwise to g-C 3 N 4 Continuously ultrasonic treating the QDs solution until it is uniform, adding acetone, stirring for 18-28h, precipitating for 3-5 hr, pouring out supernatant, and drying to obtain porous flower ball Ni 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalysts.
2. Porous flower ball Ni according to claim 1 5 P 4 Capture of g-C 3 N 4 The preparation method of the QDs composite photocatalyst is characterized by comprising the following steps of: in the step (1), the calcining method comprises the following steps: raising the temperature to 500-550 ℃ at 2-5 ℃/min, and keeping the temperature at 3-5h.
3. Porous flower ball Ni according to claim 1 5 P 4 Capture of g-C 3 N 4 The preparation method of the QDs composite photocatalyst is characterized by comprising the following steps of: ni (NO) in step (2) 3 ) 2 •6H 2 O, urea and NH 4 The mass ratio of F is 1:3:6.
4. Porous flower ball Ni according to claim 1 5 P 4 Capture of g-C 3 N 4 The preparation method of the QDs composite photocatalyst is characterized by comprising the following steps of: in the step (2), the mixture is heated to 350 ℃ under argon atmosphere at a heating rate of 3 ℃/min and kept at 3h.
5. Porous flower ball Ni as claimed in any of claims 1 to 4 5 P 4 Capture of g-C 3 N 4 Porous flower ball Ni prepared by preparation method of QDs composite photocatalyst 5 P 4 Capture of g-C 3 N 4 QDs composite photocatalysts.
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