CN113457713A - Preparation method of carbon nitride based single-atom catalyst, product and application thereof - Google Patents
Preparation method of carbon nitride based single-atom catalyst, product and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 28
- 239000011574 phosphorus Substances 0.000 claims description 28
- 239000000919 ceramic Substances 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- -1 compound cobalt chloride hexahydrate Chemical class 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229960003339 sodium phosphate Drugs 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000004098 Tetracycline Substances 0.000 abstract description 14
- 229960002180 tetracycline Drugs 0.000 abstract description 14
- 229930101283 tetracycline Natural products 0.000 abstract description 14
- 235000019364 tetracycline Nutrition 0.000 abstract description 14
- 150000003522 tetracyclines Chemical class 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 description 22
- 230000000593 degrading effect Effects 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 210000000078 claw Anatomy 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003911 water pollution 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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- 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
-
- 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
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
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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
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a preparation method of a carbon nitride-based single-atom catalyst, a product and application thereof. Adding phosphorus-doped carbon nitride and a metal soluble compound into deionized water, stirring, evaporating to dry, grinding and uniformly mixing, then carrying out heat treatment under the protection of protective gas, and naturally cooling to obtain the carbon nitride-based single-atom catalyst. The carbon nitride based single-atom catalyst prepared by the method can be used for various reactions such as photocatalytic degradation of dyes, photocatalytic decomposition of water for hydrogen production, photocatalytic nitrogen fixation and the like, and the photocatalytic degradation of tetracycline is excellent in performance, simple in preparation process and suitable for large-scale popularization.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a preparation method of a carbon nitride-based single-atom catalyst, and a product and application thereof.
Background
With the development and progress of human society, a large number of unreasonable applications of colored dyes and antibiotics, etc., have resulted in serious water pollution. Secondly, the rapid development of modern society requires a large amount of energy, and the greenhouse effect caused by the transitional use of fossil energy has already made a tangible impact on the global environment. Among a plurality of novel energy sources, hydrogen becomes the first choice of clean energy in the future due to the characteristics of high energy density, only water as a byproduct and the like. In the production of hydrogen, the best mode is currently considered to be the photocatalytic or electrocatalytic production of hydrogen from water. The use of the catalyst cannot be avoided no matter the environmental pollution problem is solved, or the energy crisis is solved.
Carbon nitride is a yellow nanocrystal, the crystal structure of which is similar to that of graphite, so that it is easy to form a graphene-like two-dimensional structure by means of exfoliation, which results in a very large specific surface area. In addition, the carbon nitride also has excellent photocatalytic performance. And the energy band has moderate structure, rich sources and low cost. These advantages make it an ideal catalyst support. However, in order to improve the catalytic performance, it is usually necessary to support metal atoms as active sites on the surface.
The monatomic catalyst is used as a novel catalyst, and attracts the attention of the majority of scientific researchers. This is because for the nano metal particles, it is often metal atoms on the surface, which causes a problem of low metal utilization rate. When the size of the metal nano-particles is continuously reduced until the metal nano-particles are dispersed into single atoms, the metal utilization efficiency can reach 100 percent. And the surface energy is extremely large, and the chemical reactivity with adsorbates is also greatly enhanced. However, the existing single atom preparation method has complicated steps and high preparation difficulty, which causes great obstruction to the application of the single atom preparation method in multiple fields.
According to the invention, by introducing phosphorus atoms into a carbon nitride molecular structure, the high electron donating capability of the phosphorus atoms and the characteristic of the phosphorus atoms of being rich in uncoordinated lone-pair electrons are utilized, so that the carbon nitride molecular structure can be used as a claw to firmly anchor metal atoms and prevent the metal atoms from being agglomerated into nano particles; furthermore, the subsequent heat treatment may also be carried out in such a way that it is further dispersed into monoatomic atoms. The carbon nitride based single atom catalyst prepared by the method provided by the invention has the advantages of high efficiency of photocatalytic degradation of dye and tetracycline, simple operation, low preparation difficulty and suitability for large-scale production.
Disclosure of Invention
Aiming at the defects of complicated steps and high preparation difficulty of the existing carbon nitride-based metal monoatomic catalyst, the invention aims to provide a preparation method of the carbon nitride-based monoatomic catalyst.
Yet another object of the present invention is to: provides a carbon nitride based single atom catalyst product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of a carbon nitride based single atom catalyst comprises the following steps:
1) weighing a carbon nitride precursor and a phosphorus source, wherein the mass ratio of the carbon nitride precursor to the phosphorus source is (0.01-100); putting the mixture into a beaker, adding a solvent to fully dissolve the mixture, and stirring the mixture at a temperature of between 60 and 100 ℃ until the solvent is evaporated to dryness; then placing the mixture into a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible into a muffle furnace, heating to 400-650 ℃, keeping the temperature and roasting for 0.1-15 h at the rate of 1-20 ℃/min, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding the ground phosphorus-doped carbon nitride into deionized water, and adding a metal soluble compound into a beaker, wherein the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound is 1: 0.001-100; keeping the temperature at 60-100 ℃, stirring until deionized water is evaporated to dryness, putting the mixture into a porcelain boat, heating the tube furnace to 400-800 ℃ under the protection of protective gas, keeping the temperature for 0.1-10 h, and naturally cooling to obtain the carbon nitride based monatomic catalyst.
According to the invention, by introducing a phosphorus atom into a carbon nitride molecular structure, the carbon nitride molecular structure is used as a claw to firmly anchor metal atoms by utilizing the characteristics of rich uncoordinated lone-pair electrons and strong electron donating capability, so that the metal atoms are prevented from being aggregated to form nano particles, and the difficulty in forming a single-atom catalyst is reduced. And the subsequent post-heat treatment can further enhance the dispersion.
In the step 1), the carbon nitride precursor is one or a mixture of melamine, cyanuric acid, dicyandiamide, cyanamide, urea and melamine cyanuric acid; the phosphorus source is one or a mixture of hydroxyethylidene diphosphonic acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hexametaphosphate, sodium phosphate and sodium pyrophosphate; the solvent is one or mixture of water, ethanol, ethylene glycol, glycerol and acetone; the mass ratio of the carbon nitride precursor to the solvent is 1: 1-10000.
In the step 2), the metal soluble compound is one or a mixture of cobalt chloride hexahydrate, nickel chloride hexahydrate, cobalt acetate, cobalt nitrate and copper nitrate; the mass ratio of the phosphorus-doped carbon nitride to the deionized water is 1: 1-10000; the protective gas is one or a mixture of nitrogen, argon, helium and hydrogen-argon.
The invention also provides a carbon nitride based single atom catalyst prepared by any one of the methods.
The invention also provides an application of the carbon nitride based single-atom catalyst as a catalyst in photocatalytic degradation.
The invention has the advantages that: the carbon nitride based single-atom catalyst prepared by the method can be used for various reactions such as photocatalytic degradation of dyes, photocatalytic water decomposition hydrogen production, photocatalytic nitrogen fixation and the like, and the photocatalytic degradation of tetracycline is excellent in performance, simple in preparation process and suitable for large-scale popularization.
Drawings
FIG. 1 shows that the carbon nitride based single atom catalyst prepared by the method of the present invention and the commercial P25 catalyst have the performance of degrading tetracycline under visible light.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
A carbon nitride based single atom catalyst is prepared by the following steps:
1) weighing carbon nitride precursor melamine and phosphorus source hydroxyethylidene diphosphonic acid, wherein the mass ratio of the carbon nitride precursor to the phosphorus source is 1: 0.1; putting the carbon nitride precursor into a beaker, adding the mixture into a solvent, wherein the mass ratio of the carbon nitride precursor to the solvent is 1:1000 by taking a mixed solution of water and ethylene glycol as the solvent, fully dissolving the carbon nitride precursor and the solvent, and stirring the mixture at 80 ℃ until the solvent is evaporated to dryness to obtain a uniform mixture of the carbon nitride precursor and a phosphorus source; then placing the mixture into a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation roasting for 4h, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding the crushed phosphorus-doped carbon nitride into deionized water to enable the mass ratio of the phosphorus-doped carbon nitride to the deionized water to be 1:1000, and adding a metal soluble compound cobalt chloride hexahydrate to enable the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound to be 1:0.01 in a beaker; keeping the temperature at 90 ℃, stirring until the deionized water is evaporated to dryness, putting the mixture into a porcelain boat, heating the tube furnace to 500 ℃ under the protection of the protective gas hydrogen-argon mixed gas, keeping the temperature for 5 hours, and naturally cooling to obtain the carbon nitride based monatomic catalyst.
The performance of the prepared carbon nitride based single atom catalyst for degrading tetracycline under visible light is shown in figure 1.
Example 2
A carbon nitride based single atom catalyst, which is prepared by the following steps similar to the steps of the example 1:
1) accurately weighing a carbon nitride precursor dicyanodiamide and a phosphorus source disodium hydrogen phosphate to ensure that the mass ratio of the carbon nitride precursor to the phosphorus source is 1: 0.2; firstly, putting the carbon nitride precursor into a beaker, adding a solvent, wherein water is used as the solvent in the embodiment, the mass ratio of the carbon nitride precursor to the solvent is 1:2000, so that the carbon nitride precursor and the solvent are fully dissolved, and then stirring at 85 ℃ until the solvent is evaporated to dryness, so as to obtain a uniform mixture of the carbon nitride precursor and a phosphorus source; putting the mixture into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation roasting for 5h, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding deionized water, wherein the mass ratio of the phosphorus-doped carbon nitride to the deionized water is 1:2000, adding a metal soluble compound nickel chloride hexahydrate into a beaker, keeping the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound at 1:0.01, stirring at 90 ℃ until the deionized water is evaporated to dryness, putting the deionized water into a porcelain boat, heating a tubular furnace to 700 ℃ under the protection of protective gas nitrogen, keeping the temperature for 2 hours, and naturally cooling to obtain the carbon nitride based monatomic catalyst.
The performance of the prepared carbon nitride based single atom catalyst for degrading tetracycline under visible light is shown in figure 1.
Example 3
A carbon nitride based single atom catalyst, which is prepared by the following steps similar to the steps of the example 1:
1) accurately weighing carbon nitride precursor cyanamide and phosphorus source sodium pyrophosphate to ensure that the mass ratio of the carbon nitride precursor to the phosphorus source is 1:0.5, firstly putting the carbon nitride precursor to the phosphorus source into a beaker, adding a solvent ethylene glycol, wherein the mass ratio of the carbon nitride precursor to the solvent is 1:500, fully dissolving the carbon nitride precursor to the phosphorus source, and then stirring at 90 ℃ until the solvent is evaporated to dryness to obtain a uniform mixture of the carbon nitride precursor and the phosphorus source; putting the mixture into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 600 ℃ at the heating rate of 10 ℃/min, keeping the temperature and roasting for 2h, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding deionized water, wherein the mass ratio of the phosphorus-doped carbon nitride to the deionized water is 1:1500, adding a metal soluble compound copper nitrate into a beaker, the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound is 1:0.015, stirring the mixture until the deionized water is evaporated to dryness, putting the mixture into a ceramic boat, heating the tube furnace to 600 ℃ under the protection of protective gas argon for 3 hours, and naturally cooling the mixture to obtain the carbon nitride based monatomic catalyst.
FIG. 1 shows that the carbon nitride based single atom catalyst prepared by the method of the present invention and the commercial P25 catalyst have the performance of degrading tetracycline under visible light.
The method for measuring the degradation efficiency of the tetracycline comprises the following steps: first, an aqueous tetracycline solution having a concentration of 20 mg/L was prepared. 100 ml of the tetracycline aqueous solution was added to a quartz tube, and 20 mg of a carbon nitride photocatalyst was added thereto, followed by sonication for 10 minutes and stirring in the dark for 30 minutes to reach adsorption equilibrium. Then, a 300 watt xenon lamp with a filter was turned on, and 5 ml of an aqueous tetracycline solution was taken after 30 minutes of irradiation. After the carbon nitride photocatalyst is removed by centrifugation, the light intensity is read at 358 nm by using an ultraviolet-visible spectrophotometer, and the tetracycline degradation efficiency is obtained by dividing the light intensity by the light intensity of the initial tetracycline aqueous solution.
Compared with the commercial catalyst, the carbon nitride based single atom catalyst prepared by the method has excellent performance of degrading tetracycline by photocatalysis.
Claims (8)
1. A preparation method of a carbon nitride based single atom catalyst is characterized by comprising the following steps:
1) weighing a carbon nitride precursor and a phosphorus source, wherein the mass ratio of the carbon nitride precursor to the phosphorus source is (0.01-100); putting the mixture into a beaker, adding a solvent to fully dissolve the mixture, and stirring the mixture at a temperature of between 60 and 100 ℃ until the solvent is evaporated to dryness; then placing the mixture into a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible into a muffle furnace, heating to 400-650 ℃, keeping the temperature and roasting for 0.1-15 h at the rate of 1-20 ℃/min, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding the ground phosphorus-doped carbon nitride into deionized water, and adding a metal soluble compound into a beaker, wherein the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound is 1: 0.001-100; keeping the temperature at 60-100 ℃, stirring until deionized water is evaporated to dryness, putting the mixture into a porcelain boat, heating the tube furnace to 400-800 ℃ under the protection of protective gas, keeping the temperature for 0.1-10 h, and naturally cooling to obtain the carbon nitride based monatomic catalyst.
2. The method for preparing the carbon nitride based monatomic catalyst according to claim 1, wherein in the step 1), the carbon nitride precursor is one of melamine, cyanuric acid, dicyandiamide, cyanamide, urea, melamine cyanuric acid, or any combination thereof; the phosphorus source is one or any combination of hydroxyethylidene diphosphonic acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hexametaphosphate, sodium phosphate and sodium pyrophosphate; the solvent is one or any combination of water, ethanol, glycol, glycerol and acetone; the mass ratio of the carbon nitride precursor to the solvent is 1: 1-10000.
3. The method for preparing the carbon nitride based single-atom catalyst according to claim 1, wherein the metal soluble compound in the step 2) is one of cobalt chloride hexahydrate, nickel chloride hexahydrate, cobalt acetate, cobalt nitrate and copper nitrate or any mixture thereof; the mass ratio of the phosphorus-doped carbon nitride to the deionized water is 1: 1-10000; the protective gas is one or a mixture of nitrogen, argon, helium and hydrogen-argon.
4. A method for preparing a carbon nitride based monatomic catalyst according to any one of claims 1 to 3, characterized by comprising the steps of:
1) weighing carbon nitride precursor melamine and phosphorus source hydroxyethylidene diphosphonic acid, wherein the mass ratio of the carbon nitride precursor to the phosphorus source is 1: 0.1; putting the carbon nitride precursor into a beaker, adding the mixture into a solvent, wherein the mass ratio of the carbon nitride precursor to the solvent is 1:1000 by taking a mixed solution of water and ethylene glycol as the solvent, fully dissolving the carbon nitride precursor and the solvent, and stirring the mixture at 80 ℃ until the solvent is evaporated to dryness to obtain a uniform mixture of the carbon nitride precursor and a phosphorus source; then placing the mixture into a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation roasting for 4h, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding the crushed phosphorus-doped carbon nitride into deionized water to enable the mass ratio of the phosphorus-doped carbon nitride to the deionized water to be 1:1000, and adding a metal soluble compound cobalt chloride hexahydrate to enable the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound to be 1:0.01 in a beaker; keeping the temperature at 90 ℃, stirring until the deionized water is evaporated to dryness, putting the mixture into a porcelain boat, heating the tube furnace to 500 ℃ under the protection of the protective gas hydrogen-argon mixed gas, keeping the temperature for 5 hours, and naturally cooling to obtain the carbon nitride based monatomic catalyst.
5. A method for preparing a carbon nitride based monatomic catalyst according to any one of claims 1 to 3, characterized by comprising the steps of:
1) accurately weighing a carbon nitride precursor dicyanodiamide and a phosphorus source disodium hydrogen phosphate to ensure that the mass ratio of the carbon nitride precursor to the phosphorus source is 1: 0.2; firstly, putting the carbon nitride precursor into a beaker, adding a solvent, wherein water is used as the solvent in the embodiment, the mass ratio of the carbon nitride precursor to the solvent is 1:2000, so that the carbon nitride precursor and the solvent are fully dissolved, and then stirring at 85 ℃ until the solvent is evaporated to dryness, so as to obtain a uniform mixture of the carbon nitride precursor and a phosphorus source; putting the mixture into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation roasting for 5h, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding deionized water, wherein the mass ratio of the phosphorus-doped carbon nitride to the deionized water is 1:2000, adding a metal soluble compound nickel chloride hexahydrate into a beaker, keeping the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound at 1:0.01, stirring at 90 ℃ until the deionized water is evaporated to dryness, putting the deionized water into a porcelain boat, heating a tubular furnace to 700 ℃ under the protection of protective gas nitrogen, keeping the temperature for 2 hours, and naturally cooling to obtain the carbon nitride based monatomic catalyst.
6. A method for preparing a carbon nitride based monatomic catalyst according to any one of claims 1 to 3, characterized by comprising the steps of:
1) accurately weighing carbon nitride precursor cyanamide and phosphorus source sodium pyrophosphate to ensure that the mass ratio of the carbon nitride precursor to the phosphorus source is 1:0.5, firstly putting the carbon nitride precursor to the phosphorus source into a beaker, adding a solvent ethylene glycol, wherein the mass ratio of the carbon nitride precursor to the solvent is 1:500, fully dissolving the carbon nitride precursor to the phosphorus source, and then stirring at 90 ℃ until the solvent is evaporated to dryness to obtain a uniform mixture of the carbon nitride precursor and the phosphorus source; putting the mixture into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 600 ℃ at the heating rate of 10 ℃/min, keeping the temperature and roasting for 2h, and naturally cooling to obtain phosphorus-doped carbon nitride;
2) grinding and crushing the obtained phosphorus-doped carbon nitride, adding deionized water, wherein the mass ratio of the phosphorus-doped carbon nitride to the deionized water is 1:1500, adding a metal soluble compound copper nitrate into a beaker, the mass ratio of the phosphorus-doped carbon nitride to the metal soluble compound is 1:0.015, stirring the mixture until the deionized water is evaporated to dryness, putting the mixture into a ceramic boat, heating the tube furnace to 600 ℃ under the protection of protective gas argon for 3 hours, and naturally cooling the mixture to obtain the carbon nitride based monatomic catalyst.
7. A carbon nitride based single atom catalyst, characterized in that it is prepared according to the process of any one of claims 1 to 7.
8. Use of a carbon nitride based monatomic catalyst according to claim 7 as a catalyst in photocatalytic degradation.
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