CN116371448A - Preparation method of doped mesoporous graphite phase carbon nitride - Google Patents
Preparation method of doped mesoporous graphite phase carbon nitride Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 87
- 239000010439 graphite Substances 0.000 title claims abstract description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 121
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 26
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 26
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000011268 mixed slurry Substances 0.000 claims abstract description 20
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 19
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims abstract description 17
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims abstract description 17
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims abstract description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 17
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 13
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 98
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 17
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 15
- 238000010926 purge Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 33
- 239000004408 titanium dioxide Substances 0.000 abstract description 16
- 229910052719 titanium Inorganic materials 0.000 abstract description 12
- 239000010936 titanium Substances 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 8
- 206010021143 Hypoxia Diseases 0.000 abstract description 4
- 230000007812 deficiency Effects 0.000 abstract description 4
- 230000007954 hypoxia Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- SZHZJPYNAORVRP-UHFFFAOYSA-L dichlorotitanium;ethanol Chemical compound CCO.Cl[Ti]Cl SZHZJPYNAORVRP-UHFFFAOYSA-L 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
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- 238000001179 sorption measurement Methods 0.000 description 6
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical group O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- -1 titanium ions Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/088—Decomposition of a metal salt
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Abstract
The invention discloses a preparation method of doped mesoporous graphite phase carbon nitride, which comprises the following steps: carrying out wet ball milling treatment and pressure boosting and pressure releasing treatment on graphite-phase carbon nitride to obtain graphite-phase carbon nitride fine powder; adding graphite-phase carbon nitride into titanium dichloride ethanol solution, and stirring to obtain coated graphite-phase carbon nitride particles; putting the coated graphite-phase carbon nitride particles into n-butyl titanate diethyl ether liquid, and standing to obtain secondary coated graphite-phase carbon nitride particles; ethyl cellulose and hydroxypropyl cellulose are added into acetone, and ammonium bicarbonate is added to obtain mixed slurry; mixing the mixed slurry with the secondary coated graphite phase carbon nitride particles, and standing at a constant temperature to obtain prefabricated graphite phase carbon nitride; and (3) carrying out ultrasonic treatment on the prefabricated graphite phase carbon nitride, and then sintering to obtain the doped mesoporous graphite phase carbon nitride. The invention uses titanium dichloride as an active origin, improves the connection stability of titanium dioxide and graphite phase carbon nitride, improves the electron flow speed of the titanium dioxide, and shows titanium deficiency and hypoxia.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a preparation method of doped mesoporous graphite phase carbon nitride.
Background
With the continuous deep development of scientific research and continuous industrialization, waste water and waste gas discharged by industry contain a plurality of refractory substances, particularly the refractory organic matter pollution content of various dyes, drug intermediates and the like in the waste water is continuously increased, so that the environment is greatly influenced, and serious threat is brought to human health. The treatment mode of the wastewater is mainly an adsorption method, a membrane separation method and a chemical oxidation method, wherein the adsorption method and the membrane separation method mainly transfer and enrich pollutants, so that local higher pollution concentration is caused, the pollution problem can not be effectively solved, and even secondary pollution can be formed; and the chemical oxidation method utilizes the strong oxidation capability of the chemical oxidation method to quickly remove the nondegradable pollutant. Photocatalysis is an advanced oxidation technology, is a green clean degradation technology taking sunlight as energy power, and has strong potential in the aspect of treating refractory organic matters.
The graphite phase carbon nitride is one of photocatalysts which are developed in recent years after titanium dioxide and zinc oxide, and has the characteristics of visible light response, stable chemical properties and the like, so that the graphite phase carbon nitride becomes a current research hot spot. However, carbon nitride has problems of small specific surface, poor catalytic stability, high hole-electron recombination speed and the like, which results in poor photocatalytic performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of doped mesoporous graphite phase carbon nitride, which solves the defects of the existing graphite phase carbon nitride, utilizes titanium dichloride as an active origin to improve the connection stability of titanium dioxide and the graphite phase carbon nitride, and simultaneously utilizes the residue of divalent titanium ions and a homogeneous structure thereof in the titanium dioxide to improve the electron circulation speed of the titanium dioxide and show titanium deficiency and hypoxia.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of doped mesoporous graphite phase carbon nitride comprises the following steps:
step 1, adding graphite-phase carbon nitride into ethanol, uniformly stirring to form slurry, performing ball milling treatment on the slurry, and performing pressure boosting and pressure relief treatment on the slurry to obtain graphite-phase carbon nitride fine powder, wherein the mass ratio of the graphite-phase carbon nitride to the ethanol is 5:1-3, the stirring speed of uniform stirring is 500-1000r/min, the temperature of ball milling treatment is 10-20 ℃, the ball milling pressure is 0.4-0.6MPa, the pressure boosting and pressure relief treatment is performed in a closed reaction kettle, and the temperature is 80-90 ℃; the pressure release speed of the pressure increasing and releasing treatment is 0.2-0.3MPa/min, the step utilizes the insolubility of graphite phase carbon nitride in ethanol, and the good insolubility and permeability of ethanol are matched, so that a liquid film is formed on the specific surface of the graphite phase carbon nitride, and the liquid film forms good permeation through gaps of the graphite phase carbon nitride, so that ball milling and crushing treatment of graphite phase carbon nitride particles are effectively promoted, expansion of gaps of wet ball milling is improved, and crushing effect of graphite box carbon nitride particles is promoted; in the pressure boosting and pressure releasing treatment, ethanol at the temperature of 80-90 ℃ is converted into ethanol steam, and the ethanol enters fine graphite-phase carbon nitride particle cracks by utilizing the permeability of the steam to achieve the steam permeation effect, and an internal-external pressure difference is formed in the rapid pressure releasing, so that further fragmentation of graphite-phase carbon nitride particles is obtained; in the pressure boosting and pressure releasing treatment, ethanol is converted into steam under the influence of temperature, a pressure state is formed in the system, namely, a high-pressure state is formed in a sealed reaction kettle, the ethanol steam preferentially forms a liquid film on the surfaces of graphite-phase carbon nitride particles, and in the rapid pressure releasing process, the external pressure drops sharply to form a pressure difference between the inside and the outside of the particles, so that gaps are enlarged, and the aim of secondary crushing is fulfilled;
adding titanium dichloride into ethanol, stirring uniformly, adding graphite-phase carbon nitride into the ethanol, stirring at constant temperature for 20-30min, filtering, and then blowing nitrogen to obtain coated graphite-phase carbon nitride particles, wherein the concentration of the titanium dichloride in the ethanol is 20-50g/L, the stirring uniformly stirring speed is 400-600r/min, the concentration of the graphite-phase carbon nitride in the ethanol is 400-600g/L, the stirring speed is 600-1000r/min, the nitrogen blowing adopts nitrogen at 20-30 ℃, the nitrogen does not contain water vapor, the blowing speed is 10-20mL/min, the solubility of the titanium dichloride in the ethanol and the self-adsorption performance of the graphite-phase carbon nitride are utilized, the titanium dichloride is adsorbed to the specific surface of the graphite-phase carbon nitride, the adsorption effect is achieved, the titanium dichloride is preferentially adsorbed by the position with strong activity based on the surface activity characteristic of the graphite-phase carbon nitride, the titanium dichloride forms on the surface of the graphite-phase carbon nitride, and the ethanol is slowly evaporated in the nitrogen blowing process to obtain the adsorption of the titanium dichloride on the surface of the graphite-phase carbon nitride particles; in the deposition process, graphite phase carbon nitride forms adsorptive deposition based on self activity, so as to achieve the effect of surface coating;
step 3, dissolving n-butyl titanate in diethyl ether, uniformly stirring to form a solution, then placing coated graphite-phase carbon nitride particles in the solution, standing for 20-30min, filtering, and drying to obtain secondary coated graphite-phase carbon nitride particles, wherein the concentration of the n-butyl titanate in the diethyl ether is 50-100g/L, the uniformly stirring speed is 600-800r/min, the concentration of the coated graphite-phase carbon nitride particles in the diethyl ether is 300-400g/L, the standing temperature is 20-25 ℃, the drying is performed under a nitrogen atmosphere, and the drying temperature is 40-50 ℃; the method utilizes the solubility of the n-butyl titanate to diethyl ether to form a homogeneous dispersion liquid, and simultaneously reduces the viscosity of the n-butyl titanate and the concentration of the n-butyl titanate; standing coated graphite phase carbon nitride particles in a solution of n-butyl titanate-diethyl ether, forming a liquid film on the surface of the coated graphite phase carbon nitride particles by utilizing the low viscosity of the n-butyl titanate and the permeability of the diethyl ether, filtering to form coated graphite phase carbon nitride particles of a wet film system, drying at a low temperature in a nitrogen environment, removing diethyl ether in the liquid film, and wrapping the surface of the particles with the n-butyl titanate by the formation of the liquid film;
step 4, adding ethyl cellulose and hydroxypropyl cellulose into methanol, uniformly stirring to form a viscous slurry, and heating at constant temperature to form a mixed solid; finally, adding acetone into the mixed solid, uniformly stirring, adding ammonium bicarbonate, and rapidly stirring to obtain mixed slurry; the mass ratio of the ethyl cellulose to the methyl cellulose is 6-10:1, the concentration of the ethyl cellulose in the methanol is 100-400g/L, and the stirring speed is 400-600r/min; the constant temperature heating temperature is 65-70 ℃; the mass ratio of the acetone to the mixed solid is 2-3:7, the stirring speed of uniform stirring is 200-400r/min, the addition amount of the ammonium bicarbonate is 2-5% of the mass of the mixed solid, the stirring speed of rapid stirring is 1000-1500r/min, and the temperature is 5-10 ℃; this step utilizes the solubility of ethylcellulose and hydroxypropyl cellulose in methanol to form a homogeneous dispersion while ensuring that ethylcellulose is able to disperse hydroxypropyl cellulose; in the constant temperature heating process, methanol in the dispersing structure is evaporated, so that mixed solid is obtained, ethyl cellulose is used as a main material of the mixed solid, hydroxypropyl cellulose is used as a doping agent, and when the acetone and the mixed solid are stirred, the mixed solid forms viscous slurry by utilizing the solubility of the acetone;
step 5, uniformly stirring the mixed slurry and the secondary coated graphite phase carbon nitride particles, drying at a constant temperature to obtain a mixed solid, and standing the mixed solid at a constant temperature for 30-50min to obtain prefabricated graphite phase carbon nitride, wherein the mass ratio of the mixed slurry to the secondary coated graphite phase carbon nitride particles is 5-6:3, the uniform stirring speed is 100-200r/min, and the constant temperature drying temperature is 20-30 ℃; the constant-temperature standing temperature is 80-90 ℃; the fluidity of the mixed slurry is utilized to realize the wrapping of the mixed slurry on the secondary coated graphite phase carbon nitride particles, namely, the mixed slurry has higher quality than the secondary coated graphite phase carbon nitride, and can wrap the surface of the secondary coated graphite phase carbon nitride, and the surface ink of the secondary coated graphite phase carbon nitride at the moment is n-butyl titanate and has insolubility with acetone, so that the thin layer characteristic of the liquid film is always attached to the surface of the graphite phase carbon nitride; in the constant temperature drying process, acetone is quickly volatilized based on the volatility of the acetone, ethyl cellulose and hydroxypropyl cellulose are separated out, and secondary coated graphite phase carbon nitride particles and ammonium bicarbonate are mixed and wrapped to form regional dispersion; when the constant temperature standing process is carried out, ammonium bicarbonate forms self decomposition to form carbon dioxide, water vapor and ammonia, and attention needs to be paid to that ethyl cellulose is insoluble in water, but hydroxypropyl cellulose has good water solubility, can absorb water molecules, and is based on the distribution characteristic of the hydroxypropyl cellulose to the water molecules, the transmission of the water molecules in the whole system is brought, so that the in-situ hydrolysis reaction of n-butyl titanate is promoted, a titanic acid structure is formed, the hydrophilia of titanic acid brings about the adsorption of the water molecules, titanium dichloride can react with the water molecules at the moment, a large amount of heat is released when hydrogen is generated, the connection of titanium ions between the titanic acid and graphite phase carbon nitride is promoted, meanwhile, the internal temperature is promoted to rise, the decomposition and release of ammonium bicarbonate are quickened, the water molecules are further released, the circulation treatment effect is formed, the titanium dichloride on the surface of the graphite phase carbon nitride is ensured to show excellent reduction activity at the moment, the active group on the surface of the graphite phase carbon nitride is stably connected, meanwhile, the product of the titanic acid and the water dichloride reaction is titanium oxide, and the titanium oxide structure has good stability and homogeneous property, and the titanium oxide structure of the graphite phase carbon nitride surface is covered with a thin layer, and good stability is met;
step 6, putting the prefabricated graphite phase carbon nitride into an ethanol water solution for ultrasonic treatment for 20-30min, filtering and sintering for 2-4h to obtain doped mesoporous graphite phase carbon nitride, wherein the volume ratio of ethanol to water in the ethanol water solution is 5-8:3, the concentration of the prefabricated graphite phase carbon nitride in the ethanol water solution is 100-200g/L, the ultrasonic treatment adopts interval ultrasonic treatment, the ultrasonic duration is 20-30 s/time, the interval time is 2-5 min/time, the ultrasonic temperature is 20-30 ℃, the ultrasonic frequency is 60-70kHz, and the sintering is performed under the nitrogen atmosphere and the temperature is 250-300 ℃; the method utilizes the solubility of ethanol aqueous solution to ethyl cellulose and hydroxypropyl cellulose to realize the rapid recovery of the ethyl cellulose and the hydroxypropyl cellulose, and simultaneously peels off the ethyl cellulose and the hydroxypropyl cellulose in a spaced ultrasonic treatment mode, and simultaneously can peel off titanic acid with poor fixing effect; in the sintering process, titanic acid is converted into titanium dioxide, so that a mesoporous structure is formed, when titanium dichloride encounters water molecules to form hydrogen, a very small amount of divalent titanium remains in a structural system, and the titanium ion is used as a connecting node to promote the connection stability of the titanium dioxide and graphite-phase carbon nitride, and meanwhile, the titanium ion can promote the oxygen deficiency and titanium deficiency of the surface of the titanium dioxide, so that the electron circulation speed and activity of the titanium dioxide are greatly improved.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the defects of the existing graphite-phase carbon nitride, utilizes titanium dichloride as an active origin, improves the connection stability of titanium dioxide and the graphite-phase carbon nitride, and simultaneously utilizes the residue of divalent titanium ions and the homogeneous structure of divalent titanium ions in the titanium dioxide, improves the electron circulation speed of the titanium dioxide, and shows titanium deficiency and oxygen deficiency.
2. According to the invention, the in-situ hydrolysis reaction system of the titanium material is realized by adopting the wrapping property and the water molecule transmission property of the ethyl cellulose and the hydroxypropyl cellulose, and meanwhile, the ethyl cellulose and the hydroxypropyl cellulose are recycled in an evaporation mode, so that the cost requirement is reduced.
3. The invention adopts wet ball milling and pressure boosting and pressure releasing treatment methods, ensures that the graphite phase carbon nitride achieves grain refinement, and improves the specific surface exposure of the graphite phase carbon nitride.
Detailed Description
The invention is described in detail with reference to examples, but without any limitation to the claims of the invention.
Example 1
A preparation method of doped mesoporous graphite phase carbon nitride comprises the following steps:
step 1, adding graphite-phase carbon nitride into ethanol, uniformly stirring to form slurry, performing ball milling treatment on the slurry, and performing pressure boosting and pressure relief treatment on the slurry to obtain graphite-phase carbon nitride fine powder, wherein the mass ratio of the graphite-phase carbon nitride to the ethanol is 5:1, the stirring speed of uniform stirring is 500r/min, the ball milling treatment temperature is 10 ℃, the ball milling pressure is 0.4MPa, the pressure boosting and pressure relief treatment is performed in a closed reaction kettle, and the temperature is 80 ℃; the pressure release speed of the pressure boosting and releasing treatment is 0.2MPa/min;
adding titanium dichloride into ethanol, stirring uniformly, adding graphite-phase carbon nitride into the ethanol, stirring at constant temperature for 20min, filtering, and then purging with nitrogen to obtain coated graphite-phase carbon nitride particles, wherein the concentration of titanium dichloride in the ethanol is 20g/L, the stirring speed of stirring uniformly is 400r/min, the concentration of graphite-phase carbon nitride in the ethanol is 400g/L, the stirring temperature of constant temperature is 50 ℃, the stirring speed of constant temperature is 600r/min, the nitrogen purging adopts nitrogen at 20 ℃, no water vapor is contained in the nitrogen, and the purging speed is 10mL/min;
step 3, dissolving n-butyl titanate in diethyl ether, uniformly stirring to form a solution, then placing coated graphite-phase carbon nitride particles in the solution, standing for 20min, filtering, and drying to obtain secondary coated graphite-phase carbon nitride particles, wherein the concentration of the n-butyl titanate in the diethyl ether is 50g/L, the stirring speed of the uniform stirring is 600r/min, the concentration of the coated graphite-phase carbon nitride particles in the diethyl ether is 300g/L, the standing temperature is 20 ℃, the drying is carried out under a nitrogen atmosphere, and the drying temperature is 40 ℃;
step 4, adding ethyl cellulose and hydroxypropyl cellulose into methanol, uniformly stirring to form a viscous slurry, and heating at constant temperature to form a mixed solid; finally, adding acetone into the mixed solid, uniformly stirring, adding ammonium bicarbonate, and rapidly stirring to obtain mixed slurry; the mass ratio of the ethyl cellulose to the methyl cellulose is 6:1, the concentration of the ethyl cellulose in the methanol is 100g/L, and the stirring speed is 400r/min; the constant-temperature heating temperature is 65 ℃; the mass ratio of the acetone to the mixed solid is 2:7, the stirring speed of uniform stirring is 200r/min, the addition amount of the ammonium bicarbonate is 2% of the mass of the mixed solid, the stirring speed of rapid stirring is 1000r/min, and the temperature is 5 ℃;
step 5, uniformly stirring the mixed slurry and the secondary coated graphite phase carbon nitride particles, drying at a constant temperature to obtain a mixed solid, and standing the mixed solid at a constant temperature for 30min to obtain prefabricated graphite phase carbon nitride, wherein the mass ratio of the mixed slurry to the secondary coated graphite phase carbon nitride particles is 5:3, the stirring speed of uniform stirring is 100r/min, and the constant temperature drying temperature is 20 ℃; the constant-temperature standing temperature is 80 ℃;
and 6, putting the prefabricated graphite phase carbon nitride into an ethanol water solution for ultrasonic treatment for 20min, filtering and sintering for 2h to obtain the doped mesoporous graphite phase carbon nitride, wherein the volume ratio of ethanol to water in the ethanol water solution is 5:3, the concentration of the prefabricated graphite phase carbon nitride in the ethanol water solution is 100g/L, the ultrasonic treatment adopts interval type ultrasonic treatment, the ultrasonic duration is 20 s/time, the interval time is 2 min/time, the ultrasonic temperature is 20 ℃, the ultrasonic frequency is 60kHz, and the sintering is performed in a nitrogen atmosphere and the temperature is 250 ℃.
Example 2
A preparation method of doped mesoporous graphite phase carbon nitride comprises the following steps:
step 1, adding graphite-phase carbon nitride into ethanol, uniformly stirring to form slurry, performing ball milling treatment on the slurry, and performing pressure boosting and pressure relief treatment on the slurry to obtain graphite-phase carbon nitride fine powder, wherein the mass ratio of the graphite-phase carbon nitride to the ethanol is 5:3, the stirring speed of uniform stirring is 1000r/min, the ball milling treatment temperature is 20 ℃, the ball milling pressure is 0.6MPa, the pressure boosting and pressure relief treatment is performed in a closed reaction kettle, and the temperature is 90 ℃; the pressure release speed of the pressure boosting and releasing treatment is 0.3MPa/min;
adding titanium dichloride into ethanol, stirring uniformly, adding graphite-phase carbon nitride into the ethanol, stirring at constant temperature for 30min, filtering, and then purging with nitrogen to obtain coated graphite-phase carbon nitride particles, wherein the concentration of the titanium dichloride in the ethanol is 50g/L, the stirring speed of stirring uniformly is 600r/min, the concentration of the graphite-phase carbon nitride in the ethanol is 600g/L, the stirring temperature of constant temperature stirring is 60 ℃ and the stirring speed of constant temperature stirring is 1000r/min, nitrogen purging adopts nitrogen at 30 ℃, no water vapor is contained in the nitrogen, and the purging speed is 20mL/min;
step 3, dissolving n-butyl titanate in diethyl ether, uniformly stirring to form a solution, then placing coated graphite-phase carbon nitride particles in the solution, standing for 30min, filtering, and drying to obtain secondary coated graphite-phase carbon nitride particles, wherein the concentration of the n-butyl titanate in the diethyl ether is 100g/L, the stirring speed of the uniform stirring is 800r/min, the concentration of the coated graphite-phase carbon nitride particles in the diethyl ether is 400g/L, the standing temperature is 25 ℃, the drying is carried out under a nitrogen atmosphere, and the drying temperature is 50 ℃;
step 4, adding ethyl cellulose and hydroxypropyl cellulose into methanol, uniformly stirring to form a viscous slurry, and heating at constant temperature to form a mixed solid; finally, adding acetone into the mixed solid, uniformly stirring, adding ammonium bicarbonate, and rapidly stirring to obtain mixed slurry; the mass ratio of the ethyl cellulose to the methyl cellulose is 10:1, the concentration of the ethyl cellulose in the methanol is 100-400g/L, and the stirring speed is 600r/min; the constant-temperature heating temperature is 70 ℃; the mass ratio of the acetone to the mixed solid is 3:7, the stirring speed of uniform stirring is 400r/min, the addition amount of the ammonium bicarbonate is 5% of the mass of the mixed solid, the stirring speed of rapid stirring is 1500r/min, and the temperature is 10 ℃;
step 5, uniformly stirring the mixed slurry and the secondary coated graphite phase carbon nitride particles, drying at a constant temperature to obtain a mixed solid, and standing the mixed solid at a constant temperature for 50min to obtain prefabricated graphite phase carbon nitride, wherein the mass ratio of the mixed slurry to the secondary coated graphite phase carbon nitride particles is 6:3, the stirring speed of uniform stirring is 200r/min, and the constant temperature drying temperature is 30 ℃; the constant-temperature standing temperature is 90 ℃;
and 6, putting the prefabricated graphite phase carbon nitride into an ethanol water solution for ultrasonic treatment for 30min, filtering and sintering for 4h to obtain the doped mesoporous graphite phase carbon nitride, wherein the volume ratio of ethanol to water in the ethanol water solution is 8:3, the concentration of the prefabricated graphite phase carbon nitride in the ethanol water solution is 200g/L, the ultrasonic treatment adopts interval type ultrasonic treatment, the ultrasonic duration is 30 s/time, the interval time is 5 min/time, the ultrasonic temperature is 30 ℃, the ultrasonic frequency is 70kHz, and the sintering is performed in a nitrogen atmosphere and the temperature is 300 ℃.
Example 3
A preparation method of doped mesoporous graphite phase carbon nitride comprises the following steps:
step 1, adding graphite-phase carbon nitride into ethanol, uniformly stirring to form slurry, performing ball milling treatment on the slurry, and performing pressure boosting and pressure relief treatment on the slurry to obtain graphite-phase carbon nitride fine powder, wherein the mass ratio of the graphite-phase carbon nitride to the ethanol is 5:2, the stirring speed of uniform stirring is 800r/min, the ball milling treatment temperature is 15 ℃, the ball milling pressure is 0.5MPa, the pressure boosting and pressure relief treatment is performed in a closed reaction kettle, and the temperature is 85 ℃; the pressure release speed of the pressure boosting and releasing treatment is 0.3MPa/min;
adding titanium dichloride into ethanol, stirring uniformly, adding graphite-phase carbon nitride into the ethanol, stirring at constant temperature for 25min, filtering, and then purging with nitrogen to obtain coated graphite-phase carbon nitride particles, wherein the concentration of titanium dichloride in the ethanol is 40g/L, the stirring speed of stirring uniformly is 500r/min, the concentration of graphite-phase carbon nitride in the ethanol is 500g/L, the stirring temperature at constant temperature is 55 ℃, the stirring speed is 800r/min, the nitrogen purging adopts nitrogen at 25 ℃, no water vapor is contained in the nitrogen, and the purging speed is 15mL/min;
step 3, dissolving n-butyl titanate in diethyl ether, uniformly stirring to form a solution, then placing coated graphite-phase carbon nitride particles in the solution, standing for 25min, filtering, and drying to obtain secondary coated graphite-phase carbon nitride particles, wherein the concentration of the n-butyl titanate in the diethyl ether is 80g/L, the stirring speed of uniform stirring is 700r/min, the concentration of the coated graphite-phase carbon nitride particles in the diethyl ether is 350g/L, the standing temperature is 23 ℃, the drying is carried out under nitrogen atmosphere, and the drying temperature is 45 ℃;
step 4, adding ethyl cellulose and hydroxypropyl cellulose into methanol, uniformly stirring to form a viscous slurry, and heating at constant temperature to form a mixed solid; finally, adding acetone into the mixed solid, uniformly stirring, adding ammonium bicarbonate, and rapidly stirring to obtain mixed slurry; the mass ratio of the ethyl cellulose to the methyl cellulose is 8:1, the concentration of the ethyl cellulose in the methanol is 300g/L, and the stirring speed is 500r/min; the constant-temperature heating temperature is 68 ℃; the mass ratio of the acetone to the mixed solid is 2:7, the stirring speed of uniform stirring is 300r/min, the addition amount of the ammonium bicarbonate is 4% of the mass of the mixed solid, the stirring speed of rapid stirring is 1200r/min, and the temperature is 8 ℃;
step 5, uniformly stirring the mixed slurry and the secondary coated graphite phase carbon nitride particles, drying at a constant temperature to obtain a mixed solid, and standing the mixed solid at a constant temperature for 40min to obtain prefabricated graphite phase carbon nitride, wherein the mass ratio of the mixed slurry to the secondary coated graphite phase carbon nitride particles is 5:3, the stirring speed of uniform stirring is 150r/min, and the constant temperature drying temperature is 25 ℃; the constant-temperature standing temperature is 85 ℃;
and 6, putting the prefabricated graphite phase carbon nitride into an ethanol water solution for ultrasonic treatment for 25min, filtering and sintering for 3h to obtain the doped mesoporous graphite phase carbon nitride, wherein the volume ratio of ethanol to water in the ethanol water solution is 7:3, the concentration of the prefabricated graphite phase carbon nitride in the ethanol water solution is 150g/L, the ultrasonic treatment adopts interval type ultrasonic treatment, the ultrasonic duration is 25 s/time, the interval time is 4 min/time, the ultrasonic temperature is 25 ℃, the ultrasonic frequency is 65kHz, and the sintering is performed in a nitrogen atmosphere and the temperature is 280 ℃.
Comparative example 1
Adding graphite-phase carbon nitride into ethanol, stirring uniformly to form slurry, performing ball milling treatment on the slurry, and performing pressure boosting and pressure relief treatment on the slurry to obtain graphite-phase carbon nitride fine powder, wherein the mass ratio of the graphite-phase carbon nitride to the ethanol is 5:2, the stirring speed of stirring uniformly is 800r/min, the ball milling treatment temperature is 15 ℃, the ball milling pressure is 0.5MPa, the pressure boosting and pressure relief treatment is performed in a closed reaction kettle, and the temperature is 85 ℃; the pressure release speed of the pressure boosting and releasing treatment is 0.3MPa/min.
Comparative example 2
A preparation method of the titanium dioxide-graphite phase carbon nitride composite material comprises the following steps: a1, adding graphite-phase carbon nitride into ethanol, uniformly stirring to form slurry, performing ball milling treatment on the slurry, and performing pressure boosting and pressure relief treatment on the slurry to obtain graphite-phase carbon nitride fine powder, wherein the mass ratio of the graphite-phase carbon nitride to the ethanol is 5:2, the stirring speed of uniform stirring is 800r/min, the temperature of ball milling treatment is 15 ℃, the ball milling pressure is 0.5MPa, the pressure boosting and pressure relief treatment is performed in a closed reaction kettle, and the temperature is 85 ℃; the pressure release speed of the pressure increasing and releasing treatment is 0.3MPa/min, a2, and the titanium dioxide-graphite phase carbon nitride composite material is obtained by blending graphite phase carbon nitride and titanium dioxide particles in ethanol and then filtering.
Performance testing
Performance tests were performed using the products prepared in examples 1-3 and comparative examples 1-2 as test materials.
1. Water treatment test:
the method is carried out according to the national standard GB/T23762-2020 method for testing the purification performance of the photocatalytic material aqueous solution: the method takes methylene blue with the mass concentration of 40mg/L as a photocatalytic degradation object, takes 0.1g of product as a test material, and takes natural sunlight as an irradiation light source, and the test result is as follows:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Degradation rate% | 96.32 | 98.67 | 97.29 | 76.57 | 82.5 |
| Stability% | 98.3 | 98.7 | 98.6 | 95.2 | 75.3 |
The stability test of comparative example 2 shows the phenomenon of powder falling, namely, titanium dioxide is separated from the surface of graphite phase carbon nitride, which indicates that the binding force of the titanium dioxide and the graphite phase carbon nitride is not strong.
2. Antibacterial property test
The antibacterial performance of the photocatalytic antibacterial material and the product according to national standard GB/T23763 is evaluated, the antibacterial rate data of the test result is as follows, wherein the escherichia coli is used as a test strain and natural sunlight is used as an irradiation light source:
| antibacterial rate | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Coli bacterium | 99.92 | 99.97 | 99.95 | 96.15 | 97.58 |
| Staphylococcus spp | 99.90 | 99.94 | 99.91 | 94.84 | 95.23 |
The test data show that the doped mesoporous graphite phase carbon nitride provided by the technical scheme has good visible light photocatalytic performance and good connection stability.
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (10)
1. A preparation method of doped mesoporous graphite phase carbon nitride is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding graphite-phase carbon nitride into ethanol, uniformly stirring to form slurry, performing ball milling treatment on the slurry, and performing pressure boosting and pressure releasing treatment to obtain graphite-phase carbon nitride fine powder;
step 2, adding titanium dichloride into ethanol, uniformly stirring, adding graphite-phase carbon nitride into the mixture, stirring the mixture at constant temperature for 20-30min, filtering the mixture, and purging the mixture with nitrogen to obtain coated graphite-phase carbon nitride particles;
step 3, dissolving n-butyl titanate in diethyl ether, uniformly stirring to form a solution, then placing coated graphite-phase carbon nitride particles, standing for 20-30min, filtering, and drying to obtain secondary coated graphite-phase carbon nitride particles;
step 4, adding ethyl cellulose and hydroxypropyl cellulose into methanol, uniformly stirring to form a viscous slurry, and heating at constant temperature to form a mixed solid; finally, adding acetone into the mixed solid, uniformly stirring, adding ammonium bicarbonate, and rapidly stirring to obtain mixed slurry;
step 5, uniformly stirring the mixed slurry and the secondary coated graphite phase carbon nitride particles, drying at a constant temperature to obtain a mixed solid, and standing the mixed solid at a constant temperature for 30-50min to obtain prefabricated graphite phase carbon nitride;
and 6, putting the prefabricated graphite phase carbon nitride into an ethanol water solution for ultrasonic treatment for 20-30min, filtering, and sintering for 2-4h to obtain the doped mesoporous graphite phase carbon nitride.
2. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the mass ratio of graphite phase carbon nitride to ethanol in the step 1 is 5:1-3, the stirring speed of stirring uniformly is 500-1000r/min, the ball milling treatment temperature is 10-20 ℃, and the ball milling pressure is 0.4-0.6MPa.
3. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the pressure boosting and releasing treatment in the step 1 is carried out in a closed reaction kettle, and the temperature is 80-90 ℃; the pressure release speed of the pressure boosting and releasing treatment is 0.2-0.3MPa/min.
4. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the concentration of titanium dichloride in the step 2 in ethanol is 20-50g/L, the stirring speed of uniform stirring is 400-600r/min, the concentration of graphite-phase carbon nitride in ethanol is 400-600g/L, the constant-temperature stirring temperature is 50-60 ℃ and the stirring speed is 600-1000r/min, nitrogen with the temperature of 20-30 ℃ is adopted for nitrogen purging, no water vapor is contained in the nitrogen, and the purging speed is 10-20mL/min.
5. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the concentration of the n-butyl titanate in the step 3 in diethyl ether is 50-100g/L, the stirring speed of stirring uniformly is 600-800r/min, the concentration of the coated graphite phase carbon nitride particles in diethyl ether is 300-400g/L, the standing temperature is 20-25 ℃, the drying is carried out in a nitrogen atmosphere, and the drying temperature is 40-50 ℃.
6. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the mass ratio of the ethyl cellulose to the methyl cellulose in the step 4 is 6-10:1, the concentration of the ethyl cellulose in the methanol is 100-400g/L, the stirring speed is 400-600r/min, and the constant-temperature heating temperature is 65-70 ℃; the mass ratio of the acetone to the mixed solid is 2-3:7, and the stirring speed of the uniformly stirring is 200-400r/min.
7. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the addition amount of ammonium bicarbonate in the step 4 is 2-5% of the mass of the mixed solid, the stirring speed of rapid stirring is 1000-1500r/min, and the temperature is 5-10 ℃.
8. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the mass ratio of the mixed slurry in the step 5 to the secondary coated graphite phase carbon nitride particles is 5-6:3, the stirring speed of uniform stirring is 100-200r/min, and the constant-temperature drying temperature is 20-30 ℃; the constant temperature standing temperature is 80-90 ℃.
9. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the volume ratio of ethanol to water in the ethanol water solution in the step 6 is 5-8:3, the concentration of the prefabricated graphite phase carbon nitride in the ethanol water solution is 100-200g/L, the ultrasonic treatment adopts interval ultrasonic treatment, the ultrasonic duration time is 20-30 s/time, the interval time is 2-5 min/time, the ultrasonic temperature is 20-30 ℃, and the ultrasonic frequency is 60-70kHz.
10. The method for preparing the doped mesoporous graphite phase carbon nitride according to claim 1, wherein the method comprises the following steps: the sintering in the step 6 is carried out under nitrogen atmosphere, and the temperature is 250-300 ℃.
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