CN110201703B - Preparation method of multi-metal doped carbon nitride composite material - Google Patents
Preparation method of multi-metal doped carbon nitride composite material Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 title abstract description 37
- 239000002184 metal Substances 0.000 title abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- -1 transition metal salts Chemical class 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 16
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- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 5
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 4
- 239000002019 doping agent Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000012984 antibiotic solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the field of inorganic materials, in particular to a preparation method of a multi-metal doped carbon nitride composite material. The preparation method of the composite material comprises the following steps: s1, mixing and dispersing a plurality of metal salts and carbon nitride in water or ethanol, and carrying out ultrasonic treatment for 10-60 min under the condition of 200-1000W, wherein the metal salts are transition metal salts; s2, filtering the suspension obtained after the ultrasonic treatment in the step S1; s3, calcining the filter residue obtained by filtering in the step S2 for 1-3 hours at the temperature of 200-400 ℃. The composite material obtained by using the transition metal salt as the dopant can better realize the separation of carriers, thereby achieving better photocatalysis effect. Furthermore, the photocatalyst containing the carbon nitride composite material prepared by the method has excellent effect on the degradation of macrocyclic resin antibiotics.
Description
Technical Field
The invention relates to the field of inorganic materials, in particular to a preparation method of a multi-metal doped carbon nitride composite material.
Background
Currently, researchers are working on high quality catalysts to solve the problems of energy scarcity and environmental damage. A great deal of effort has been put into designing photocatalytic materials that can effectively apply solar energy. Among them, carbon nitride has become a catalytic material with common application because of its simple preparation method, unique semiconductor electronic band structure and high physical and chemical stability. However, the further application of carbon nitride in the fields of photocatalysis, environmental treatment and the like is seriously influenced by the defects that the specific surface area of the carbon nitride is small, the band gap width is relatively large, generated photon-generated carriers are easy to recombine and the like. Therefore, in recent years, there are many researchers to prove that the photocatalytic activity of carbon nitride in the visible light region is improved by doping carbon nitride with an element so as to shorten the energy gap of carbon nitride and improve the utilization rate of carbon nitride for visible light.
There are two main types of carbon nitride doping, non-metal doping and metal doping. At present, unit metal is mainly adopted for doping, and the problems of easy recombination of photocarriers, low catalytic efficiency and the like exist.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method of a multi-metal doped carbon nitride composite material.
The invention also aims to provide a photocatalyst containing the carbon nitride composite material prepared by the method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a multi-metal doped carbon nitride composite material comprises the following steps:
s1, mixing and dispersing a plurality of transition metal salts and carbon nitride in water or ethanol, and carrying out ultrasonic treatment for 10-60 min under the condition of 200-1000W, wherein the concentration of each metal ion in the transition metal salts is 0.0001-0.02 mol/L; according to the molar ratio, one of the transition metal salts is 1 part, and the other metal salts are 0.1-9 parts; the concentration of the carbon nitride is 0.5-2 g/L;
s2, filtering the suspension obtained after the ultrasonic treatment in the step S1;
s3, calcining the filter residue obtained by filtering in the step S2 for 1-3 hours at the temperature of 200-400 ℃; the transition metal salts include two or more of iron salt, copper salt, nickel salt, cobalt salt or manganese salt.
The above carbon nitride can be obtained by a conventional production method or can be obtained from a commercially available source.
According to the invention, by adopting a transition metal salt ultrasonic dispersion method, metal cations can be more uniformly combined with lone electrons of N element in carbon nitride. The more uniform the distribution of metal ions in the carbon nitride, the more favorable the reduction of the energy band of the composite material, thereby being favorable for electron transition and exerting better photocatalytic effect. The carbon nitride is doped by adopting a plurality of different metals, and because different metals have different conduction effects on photo carriers, the influence degree on the photo carrier recombination is different.
Due to the different degrees of carrier transport effect on carbon nitride by using different metal dopants, for example, carbon nitride materials have a wider fluorescence band around 460nm, which is mainly due to the band-to-band fluorescence phenomenon generated when the optical energy is approximately equal to the band gap energy of carbon nitride. When carbon nitride is doped with the same amount of iron and copper respectively, the fluorescence band of the iron-doped composite material at 460nm is obviously reduced, while the fluorescence band of the copper-doped composite material at 460nm is reduced very weakly. The fluorescence intensity indirectly reflects the degree of carrier separation, and the lower the fluorescence intensity, the faster the carrier separation and the higher the photocatalytic activity.
The above phenomena show that different monatomic doping has different effects on the photocatalytic activity of carbon nitride. When doping carbon nitride with multiple elements, the effect on the photocatalytic activity of carbon nitride is further complicated by the competition of different metal atoms on the surface of carbon nitride. The catalytic performance of the composite material obtained by doping different kinds of metal atoms cannot be predicted. According to the invention, researches show that the relatively good catalytic activity can be obtained by preferably adopting two or more transition metal salts of iron salt, copper salt, nickel salt, cobalt salt or manganese salt.
The transition metal salt comprises 1 part of one metal salt and 0.1-9 parts of other metal salts in molar ratio, for example, the molar ratio of the metal salt used for doping binary transition metal carbon nitride in the nitrogen carbide is (0.1-9): 1, the molar ratio of metal salt used for doping the ternary transition metal carbon nitride is (0.1-9): (0.1-9): 1, the molar ratio of metal salt used for doping quaternary transition metal carbon nitride is (0.1-9): (0.1-9): (0.1-9) 1, wherein the molar ratio of the metal salt used for doping the five-membered transition metal carbon nitride is (0.1-9): (0.1-9): (0.1-9): 1. The above-mentioned molar ratio is a ratio of the amount of the metal salt.
More preferably, the molar ratio of the various metal salts is the same.
More preferably, in the step S3, nitrogen is used as a shielding gas, and the temperature rise rate is 3 to 6 ℃/min. Nitrogen gas is used as a protective gas to prevent the material from being oxidized during the heating process. Heating at a heating rate of 3-6 ℃/min, stopping heating when the temperature rises to 200-400 ℃, and calcining for 1-3 h at the temperature.
Preferably, in step S1, the transition metal salts are dissolved and then mixed with carbon nitride.
Preferably, the carbon nitride is graphite phase carbon nitride.
The photocatalyst comprises the multi-metal doped carbon nitride composite material obtained by the preparation method.
The photocatalyst has a good effect when being applied to degradation of macrocyclic resin antibiotics.
Compared with the prior art, the invention has the following technical effects:
the invention provides a preparation method of a multi-metal doped carbon nitride composite material, and the composite material obtained by preferably selecting a transition metal salt as a dopant can better realize the separation of carriers and achieve a better photocatalysis effect. Further, the photocatalyst containing the carbon nitride composite material prepared by the method has an excellent effect on the degradation of macrocyclic resin antibiotics.
Drawings
FIG. 1 is a diagram of the topography of iron, copper and nickel ternary doped carbon nitride;
FIG. 2 is a light absorption optical diagram of a material (pure carbon nitride on the left, ternary doped carbon nitride on the right);
FIG. 3 is a graph showing the degradation performance of an iron, copper and nickel ternary metal doped carbon nitride (TDCN-1) macrocyclic resin antibiotic;
FIG. 4 is a graph showing the degradation performance of an iron, nickel, manganese, cobalt quaternary metal doped carbon nitride (QDCN-1) macrocyclic resin antibiotic; and;
FIG. 5 is a graph showing the degradation performance of five-element metal-doped carbon nitride (FDCN) macrocyclic resin antibiotics containing iron, copper, nickel, manganese and cobalt.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below with reference to specific examples and comparative examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Unless otherwise specified, the equipment used in the present examples, comparative examples and experimental examples was conventional experimental equipment, and the materials and reagents used were commercially available.
Example 1
Sequentially adding 0.01mmol ferric chloride, 0.01mmol cupric acetate and 0.01mmol nickel nitrate into 100ml absolute ethanol solution, stirring for dissolving for 10min, adding 0.10g carbon nitride powder, and ultrasonically dispersing for 60min to uniformly disperse metal sites in carbon nitride (g-C) 3 N 4 ) On the surface of (a). After the ultrasonic dispersion is finished, performing suction filtration and separation on the product by using a suction filtration device, respectively cleaning the product for three times by using deionized water and absolute ethyl alcohol, and placing the obtained product in a vacuum oven for vacuum drying for 1 day at the temperature of 60 ℃. The dried sample was ground for use.
And calcining the ground sample for 2 hours under the protection of nitrogen and at the conditions of a heating rate of 5 ℃/min and the calcining time of 400 ℃. After calcination, the resulting product is ball milled for use. Namely the product of the iron, copper and nickel ternary metal doped carbon nitride (TDCN-1).
Example 2
Sequentially adding 0.01mmol of ferric nitrate, 0.01mmol of nickel nitrate and 0.01mmol of manganese acetate into 100ml of absolute ethanol solution, stirring and dissolving for 10min, adding 0.10g of carbon nitride powder, and ultrasonically dispersing for 30min to uniformly disperse metal sites in carbon nitride (g-C) 3 N 4 ) On the surface of (a). After the ultrasonic dispersion is finished, performing suction filtration and separation on the product by using a suction filtration device, respectively cleaning the product for three times by using deionized water and absolute ethyl alcohol, and placing the obtained product in a vacuum oven for vacuum drying for 1 day at the temperature of 60 ℃. The dried sample was ground for use.
And calcining the ground sample for 1h under the protection of nitrogen at the temperature rise rate of 4 ℃/min and the calcination time of 300 ℃. After calcination, the resulting product is ball milled for use. Namely the product of the iron, nickel and manganese ternary metal doped carbon nitride (TDCN-2).
Example 3
Sequentially adding 0.01mmol of ferric nitrate, 0.01mmol of nickel nitrate, 0.01mmol of manganese acetate and 0.02mmol of cobalt nitrate into 100ml of absolute ethanol solution, stirring and dissolving for 10min, adding 0.10g of carbon nitride powder, and ultrasonically dispersing for 30min to uniformly disperse metal sites in carbon nitride (g-C) 3 N 4 ) On the surface of (a). After the ultrasonic dispersion is finished, performing suction filtration and separation on the product by using a suction filtration device, respectively cleaning the product for three times by using deionized water and absolute ethyl alcohol, and placing the obtained product in a vacuum oven for vacuum drying for 1 day at the temperature of 60 ℃. The dried sample was ground for use.
And calcining the ground sample for 1h under the protection of nitrogen at the temperature rise rate of 6 ℃/min and the calcining time of 350 ℃. After calcination, the resulting product is ball milled for use. Namely the product of the iron, nickel, manganese and cobalt quaternary metal doped carbon nitride (QDCN-1).
Example 4
Sequentially adding 0.01mmol of ferric nitrate, 0.01mmol of copper acetate, 0.01mmol of nickel nitrate, 0.01mmol of manganese acetate and 0.01mmol of cobalt nitrate into 100ml of absolute ethanol solution, stirring for dissolving for 10min, adding 0.10g of carbon nitride powder, and ultrasonically dispersing for 30min to uniformly disperse metal sites in carbon nitride (g-C) 3 N 4 ) On the surface of (a). After the ultrasonic dispersion is finished, performing suction filtration and separation on the product by using a suction filtration device, respectively cleaning the product for three times by using deionized water and absolute ethyl alcohol, and placing the obtained product in a vacuum oven for vacuum drying for 1 day at the temperature of 60 ℃. The dried sample was ground for use.
And calcining the ground sample for 2 hours under the protection of nitrogen and at the conditions of a heating rate of 5 ℃/min and the calcining time of 400 ℃. After calcination, the resulting product is ball milled for use. Namely iron, copper, nickel, manganese and cobalt five-element metal doped carbon nitride (FDCN) products.
Experimental example 1
And (3) performing surface topography characterization on the metal-doped carbon nitride composite material obtained in the example 1. As shown in fig. 1. Fig. 2 shows the absorption optical diagram of the material. The prepared photocatalyst is taken to carry out a photocatalytic effect experiment, and the specific experimental process is as follows: weighing 100mg of photocatalyst, adding the photocatalyst into 150mL of macrocyclic resin antibiotic solution with the concentration of 10mg/L, stirring the solution in the dark for 30min to achieve adsorption balance, then using a 300W xenon lamp to provide visible light for irradiation to perform photocatalytic reaction, taking about 7mL of solution every 5min, centrifuging and filtering the catalyst, using an ultraviolet visible spectrophotometer to measure the absorbance of the antibiotic solution in the filtrate, and drawing by taking time as an abscissa and taking the concentration ratio of the antibiotic solution in the filtrate to the original concentration as an ordinate during measurement, wherein the experimental result of the catalytic effect is shown in figure 3. The result shows that the synthesized ternary transition metal doped carbon nitride TDCN-1 has better photocatalytic performance than pure carbon nitride, the photodegradation rate can reach 99% within 150min, as shown in figure 4, the photodegradation rate of the synthesized quaternary transition metal doped carbon nitride QDCN-1 can reach 98% within 120min, and as shown in figure 5, the photodegradation rate of the synthesized quinary transition metal doped carbon nitride FCND can reach 99% within 120 min.
Claims (3)
1. The application of the multi-metal-doped carbon nitride composite material in degrading macrocyclic resin antibiotics is characterized in that the multi-metal-doped carbon nitride composite material is prepared by the following steps:
s1, mixing and dispersing a plurality of transition metal salts and carbon nitride in water or ethanol, and carrying out ultrasonic treatment for 10-60 min under the condition of 200-1000W, wherein the concentration of each metal ion in the transition metal salts is 0.0001 mol/L; the molar ratio of each of the plurality of transition metal salts is the same; the concentration of the carbon nitride is 0.5-2 g/L;
s2, filtering the suspension obtained after the ultrasonic treatment in the step S1;
s3, calcining the filter residue obtained by filtering in the step S2 for 1-3 h at 400 ℃ by using nitrogen as a protective gas and at the heating rate of 3-6 ℃/min;
the transition metal salts are ferric chloride, copper acetate, nickel nitrate, cobalt nitrate and manganese acetate.
2. The use of claim 1, wherein the plurality of transition metal salts are dissolved and then mixed with the carbon nitride in step S1.
3. Use according to claim 1, wherein the carbon nitride is graphite phase carbon nitride.
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| CN112138702B (en) * | 2020-10-20 | 2022-06-07 | 苏州大学 | Three-dimensional/two-dimensional Ni-Co bimetallic oxide/g-C3N4Nano composite material and preparation method and application thereof |
| CN112495414A (en) * | 2020-11-19 | 2021-03-16 | 中国科学院山西煤炭化学研究所 | Carbon nitride supported catalyst for preparing low-carbon mixed alcohol from synthesis gas and preparation method and application thereof |
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