CN113578369A - Modified g-C3N4Material, method for the production thereof and use thereof - Google Patents
Modified g-C3N4Material, method for the production thereof and use thereof Download PDFInfo
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- CN113578369A CN113578369A CN202111039937.6A CN202111039937A CN113578369A CN 113578369 A CN113578369 A CN 113578369A CN 202111039937 A CN202111039937 A CN 202111039937A CN 113578369 A CN113578369 A CN 113578369A
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- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 33
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 33
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 33
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- -1 polyethylene Polymers 0.000 claims abstract description 18
- 239000004698 Polyethylene Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229920000573 polyethylene Polymers 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004743 Polypropylene Substances 0.000 claims abstract description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 16
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052573 porcelain Inorganic materials 0.000 description 31
- 238000005303 weighing Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a modified g-C3N4A material and a preparation method and application thereof belong to the technical field of catalyst preparation, and the preparation method comprises the following steps: taking polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer as a mesoporous template agent, triethanolamine as a microporous template agent, adding ammonia water, and taking tetraethoxysilane as a silicon source to prepare mesoporous-microporous SiO2And is ready for use; combining nitrogen-containing organic substances with dopantsAdding the product into deionized water, heating until the product is dissolved to obtain a solution, then adding mesoporous/microporous silicon dioxide into the solution, stirring until the solution is uniform, and drying to obtain a mixture; calcining the mixture, cooling and grinding to obtain the doped SiO2/g‑C3N4Materials, i.e. modified g-C3N4A material; wherein the compound for doping is one or two of a rare earth element compound or a non-metal element compound. The preparation method is simple, and the prepared catalyst can effectively reduce organic matters in the papermaking wastewater.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to modified g-C3N4Material and method for the production thereofAnd uses thereof.
Background
Desertification is one of the most serious environmental problems facing the world today with local and global effects. As the herdsmen are over grazing, the grassland becomes barren slowly, many natural pastures have become deserts and gobi, and in addition, the large amount of mining of mineral products also causes the environment to be further deteriorated, the greening area is gradually reduced, the environment is deteriorated, and the sand storm occurs. Environmental problems become an increasingly important topic, along with the rapid development of society, the importance of energy problems is increasingly highlighted, and non-renewable energy sources such as coal and the like are gradually reduced, so that great opportunity is brought to the development of novel clean energy sources. In continuous research, solar energy is a renewable, environment-friendly and pollution-free green clean energy, becomes an ideal novel energy, attracts the attention of a large number of researchers, and increasingly occupies an important position.
Photocatalysis is the conversion of light energy into chemical energy. The earlier teaching of rattan island showa of 1967, which was known to the world, was in the background of the energy crisis and was attracting the attention of a large number of researchers. The photocatalyst is a substance that does not change itself under irradiation of light but can promote a chemical reaction. Since the photocatalyst only provides a place where a reaction occurs, the time for which it acts is relatively long and stable, and waste of resources and generation of reaction pollutants can be reduced.
The carbon nitride has excellent photocatalytic performance under visible light, and is graphite phase carbon nitride (g-C)3N4) Is a carbon-nitrogen compound material with a lamellar structure. At present for g-C3N4The hottest research is that the material has visible light response performance, and has the advantages of capability of absorbing visible light, proper chemical potential, environmental friendliness, no pollution and the like. It was found that g-C3N4The photocatalysis capability of the material is not separated from the structural property of the material, and the N ═ C-N bond in the material is SP of nitrogen atom2Orbital hybridization forms, which is a special bonding system that provides g-C3N4Complete electronic structure, and easy formation of photo-generated electron-holeAnd (4) carrying out acupoint pairs. It was also found that g-C3N4The material has a forbidden band width of 2.7eV, can absorb visible light with a wavelength of 475nm, and is a potential photocatalyst capable of being applied to various productions. However, g-C3N4Still has certain disadvantages, g-C3N4Because of the lamellar space structure, the visible light utilization efficiency is low, the photocatalytic performance and photocatalytic efficiency are greatly limited and cannot be generally applied, and therefore, the g-C is required to be applied3N4Modified to improve its photocatalytic performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a modified g-C3N4 material, a preparation method and application thereof.
It is a first object of the present invention to provide a modified g-C3N4The preparation method of the material comprises the following steps:
step 1, taking a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer as a mesoporous template agent, taking triethanolamine as a microporous template agent, adding ammonia water, and taking tetraethoxysilane as a silicon source to prepare mesoporous-microporous SiO2And is ready for use;
step 2, adding nitrogen-containing organic matters and doping compounds into deionized water, heating at 60-80 ℃ until the nitrogen-containing organic matters and the doping compounds are dissolved to obtain a solution, then adding the mesoporous/microporous silicon dioxide obtained in the step 1 into the solution, stirring the solution uniformly, and drying the solution to obtain a mixture; calcining the mixture, cooling and grinding to obtain the doped SiO2/g-C3N4Materials, i.e. modified g-C3N4A material; wherein the compound for doping is one or two of a rare earth element compound or a non-metal element compound.
Preferably, in the step 1, the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and triethanolamine are dissolved in deionized water, stirred to be uniformly mixed, ammonia water is added, after stirring for 30-40min, ethyl orthosilicate is added, stirring is carried out for 20min, standing reaction is carried out for 36-48h at 70-80 ℃, precipitates are collected, and drying is carried out to obtain the catalystTo meso-microporous SiO2；
Wherein the ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the triethanolamine to the deionized water to the ammonia water to the ethyl orthosilicate is 0.5g to 4-7.5 g: 30 ml: 4 g: 2.5 g.
Preferably, in step 1, the rotation speed of the stirring is 300-500rpm
Preferably, in step 1, the drying condition is 60 ℃ for 6 h.
Preferably, the nitrogen-containing organic compound, the doping compound and the meso-microporous SiO2The mass ratio of (A) to (B) is 5: 0.263-0.328: 0.0625.
preferably, the nitrogen-containing organic compound in step 2 is one of thiourea, dicyandiamide and melamine.
Preferably, the compound of the rare earth element in the step 2 is lanthanum nitrate, and the non-metal element is boron trioxide.
Preferably, the calcination condition in step 2 is to heat up to 500-550 ℃, and the temperature is kept for 4-5h, with the heating rate of 2-3 ℃/min.
A second object of the present invention is to prepare a modified g-C according to the above process3N4A material.
It is a third object of the present invention to provide the above-mentioned modified g-C3N4The material is applied to degrading organic matters in papermaking wastewater.
Compared with the prior art, the invention has the following beneficial effects:
(1) the mesoporous-microporous silicon dioxide is prepared by taking the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer as a mesoporous template and taking triethanolamine as a microporous template, and the unique pore channel structure of the mesoporous-microporous silicon dioxide can improve the diffusion coefficient of substances and effectively improve the catalytic performance;
(2) the modified g-C is prepared by adopting a thermal polymerization method to prepare modified g-C by taking nitrogen-containing organic matters as raw materials and adding mesoporous-microporous silicon dioxide3N4The method has simple operation and mild reaction condition, and the prepared modified g-C3N4The material can be used for degrading organic matters in papermaking wastewater.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following experimental methods and detection methods were all conventional methods unless otherwise specified, and the following reagents and raw materials were all commercially available reagents and raw materials unless otherwise specified, and the aqueous ammonia used in the present invention was 25% concentrated aqueous ammonia.
Example 1
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 4g of triethanolamine, dissolving in 30ml of deionized water, after dissolving and uniformly mixing, dropwise adding 4g of ammonia water under the stirring state, then stirring at the rotating speed of 300rpm for 30min, then adding 2.5g of ethyl orthosilicate, stirring at the rotating speed of 500rpm for 20min, standing at 80 ℃ for 48h, collecting precipitate, then drying at 60 ℃ for 6h, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of dicyandiamide and 0.263g of lanthanum nitrate, adding the mixture into 50ml of deionized water, heating the mixture at the temperature of 60 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring to uniform, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7h to obtain a mixture, pouring the mixture into a porcelain boat, placing in a muffle furnace, heating to 500 deg.C at 2.8 deg.C/min, keeping the temperature for 4h, after the reaction is finished, naturally cooling to room temperature, taking out the porcelain boat, grinding into powder with agate mortar to obtain La-doped SiO2/g-C3N4A material.
Example 2
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 4g of triethanolamine, dissolving in 30ml of deionized water, dropwise adding 4g of ammonia water under the stirring state after dissolving and uniformly mixing, and then stirring at the rotating speed of 300rpm for 30min, then adding 2.5g of tetraethoxysilane, stirring for 20min at the rotating speed of 500rpm, standing for 48h at the temperature of 80 ℃, collecting precipitates, drying for 6h at the temperature of 60 ℃, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of dicyandiamide and 0.263g of boron trioxide, adding the mixture into 50ml of deionized water, heating the mixture at the temperature of 60 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring to uniform, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7h to obtain a mixture, pouring the mixture into a porcelain boat, placing in a muffle furnace, heating to 500 deg.C at 2.8 deg.C/min, keeping the temperature for 4h, after the reaction is finished, naturally cooling to room temperature, taking out the porcelain boat, grinding into powder with agate mortar to obtain B-doped SiO2/g-C3N4A material.
Example 3
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 4g of triethanolamine, dissolving in 30ml of deionized water, after dissolving and uniformly mixing, dropwise adding 4g of ammonia water under the stirring state, then stirring at the rotating speed of 300rpm for 30min, then adding 2.5g of ethyl orthosilicate, stirring at the rotating speed of 500rpm for 20min, standing at 80 ℃ for 48h, collecting precipitate, then drying at 60 ℃ for 6h, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of dicyandiamide, 0.1315g of boron trioxide and 0.1315g of lanthanum nitrate, adding the mixture into 50ml of deionized water, heating the mixture at the temperature of 60 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring to uniform, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7h to obtain a mixture, pouring the mixture into a porcelain boat, placing in a muffle furnace, heating to 500 deg.C at 2.8 deg.C/min, keeping the temperature for 4h, after the reaction is finished, naturally cooling to room temperature, taking out the porcelain boat, grinding into powder with agate mortar to obtain La-B doped SiO2/g-C3N4A material.
Example 4
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxideDissolving triblock copolymer and 4g triethanolamine in 30ml deionized water, after dissolving and uniformly mixing, dropwise adding 4g ammonia water under the stirring state, then stirring at the rotating speed of 300rpm for 30min, then adding 2.5g tetraethoxysilane, stirring at the rotating speed of 500rpm for 20min, standing at 80 ℃ for 48h, collecting precipitate, drying at 60 ℃ for 6h, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of thiourea, 0.1315g of boron trioxide and 0.1315g of lanthanum nitrate, adding the mixture into 50ml of deionized water, heating the mixture at the temperature of 60 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring to uniform, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7h to obtain a mixture, pouring the mixture into a porcelain boat, placing in a muffle furnace, heating to 500 deg.C at 2.8 deg.C/min, keeping the temperature for 4h, after the reaction is finished, naturally cooling to room temperature, taking out the porcelain boat, grinding into powder with agate mortar to obtain La-B doped SiO2/g-C3N4A material.
Example 5
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 4g of triethanolamine, dissolving in 30ml of deionized water, after dissolving and uniformly mixing, dropwise adding 4g of ammonia water under the stirring state, then stirring at the rotating speed of 300rpm for 30min, then adding 2.5g of ethyl orthosilicate, stirring at the rotating speed of 500rpm for 20min, standing at 80 ℃ for 48h, collecting precipitate, then drying at 60 ℃ for 6h, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of melamine, 0.1315g of boron trioxide and 0.1315g of lanthanum nitrate, adding the melamine, the 0.1315g of boron trioxide and the 0.1315g of lanthanum nitrate into 50ml of deionized water, heating the mixture at the temperature of 60 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring to uniform, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7h to obtain a mixture, pouring the mixture into a porcelain boat, placing in a muffle furnace, heating to 500 deg.C at 2.8 deg.C/min, keeping the temperature for 4h, after the reaction is finished, naturally cooling to room temperature, taking out the porcelain boat, grinding into powder with agate mortar to obtain La-B doped powderSiO2/g-C3N4A material.
Example 6
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 7.5g of triethanolamine, dissolving in 30ml of deionized water, after dissolving and uniformly mixing, dropwise adding 4g of ammonia water under the stirring state, then stirring at the rotating speed of 400rpm for 40min, then adding 2.5g of ethyl orthosilicate, stirring at the rotating speed of 500rpm for 20min, standing at 70 ℃ for 40h, collecting precipitate, then drying at 60 ℃ for 6h, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of dicyandiamide, 0.164g of boron trioxide and 0.164g of lanthanum nitrate, adding the mixture into 50ml of deionized water, heating the mixture at 80 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring to uniform, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7h to obtain a mixture, pouring the mixture into a porcelain boat, placing in a muffle furnace, heating to 500 deg.C at 2.8 deg.C/min, keeping the temperature for 4h, after the reaction is finished, naturally cooling to room temperature, taking out the porcelain boat, grinding into powder with agate mortar to obtain La-B doped SiO2/g-C3N4A material.
Example 7
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 6g of triethanolamine, dissolving in 30ml of deionized water, after dissolving and uniformly mixing, dropwise adding 4g of ammonia water under the stirring state, then stirring for 35min at the rotating speed of 500rpm, then adding 2.5g of ethyl orthosilicate, stirring for 20min at the rotating speed of 500rpm, standing for 48h at 75 ℃, collecting precipitates, then drying for 6h at 60 ℃, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of dicyandiamide, 0.1315g of boron trioxide and 0.1315g of lanthanum nitrate, adding the mixture into 50ml of deionized water, heating the mixture at 70 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7 hr to obtain a mixture, and mixingPouring the mixture into a porcelain boat, placing the porcelain boat in a muffle furnace, heating to 550 ℃ at the speed of 2.8 ℃/min, preserving heat for 4.5 hours, naturally cooling to room temperature after the reaction is finished, taking out the porcelain boat, grinding the porcelain boat into powder by using an agate mortar to obtain La-B doped SiO2/g-C3N4A material.
Example 8
Step 1, weighing 0.5g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 4g of triethanolamine, dissolving in 30ml of deionized water, after dissolving and uniformly mixing, dropwise adding 4g of ammonia water under the stirring state, then stirring at the rotating speed of 300rpm for 30min, then adding 2.5g of ethyl orthosilicate, stirring at the rotating speed of 500rpm for 20min, standing at 80 ℃ for 36h, collecting precipitate, then drying at 60 ℃ for 6h, and drying to obtain mesoporous-microporous SiO2。
Step 2, weighing 5g of dicyandiamide and 0.295g of lanthanum nitrate, adding the mixture into 50ml of deionized water, heating the mixture at the temperature of 60 ℃ until the mixture is dissolved to obtain a solution, and then weighing 0.0625g of mesoporous-microporous SiO2Adding into the above solution, stirring to uniform, transferring to a culture dish, placing in an oven, drying at 60 deg.C for 7h to obtain a mixture, pouring the mixture into a porcelain boat, placing in a muffle furnace, heating to 520 deg.C at 2.8 deg.C/min, keeping the temperature for 5h, after the reaction is finished, naturally cooling to room temperature, taking out the porcelain boat, grinding into powder with agate mortar to obtain La-doped SiO2/g-C3N4A material.
Comparative example 1
Weighing 5g of melamine, pouring the melamine into a porcelain boat, placing the porcelain boat in a muffle furnace, heating to 500 ℃ at the speed of 2.8 ℃/min, keeping the temperature for 4h, naturally cooling to room temperature after the reaction is finished, taking out the porcelain boat, grinding the porcelain boat into powder by using an agate mortar, and obtaining g-C3N4A material.
Comparative example 2
Weighing 5g of dicyandiamide, pouring the dicyandiamide into a porcelain boat, placing the porcelain boat in a muffle furnace, heating to 500 ℃ at the speed of 2.8 ℃/min, keeping the temperature for 4h, naturally cooling the porcelain boat to room temperature after the reaction is finished, taking out the porcelain boat, grinding the porcelain boat into powder by using an agate mortar to obtain g-C3N4A material.
Comparative example 3
Weighing 5g of thiourea, pouring the thiourea into a porcelain boat, placing the porcelain boat in a muffle furnace, heating to 500 ℃ at the speed of 2.8 ℃/min, preserving heat for 4h, naturally cooling to room temperature after the reaction is finished, taking out the porcelain boat, grinding the porcelain boat into powder by using an agate mortar, and obtaining g-C3N4A material.
In order to obtain the particle sizes of the different materials, the materials were subjected to particle size measurements using a Zeta potential and particle size analyzer model Zeta Plus, manufactured by brueck hein instruments, usa. And mixing a small amount of sample with water, putting the mixture into an ultrasonic machine cleaning instrument for ultrasonic treatment until the sample is uniformly dispersed, transferring the mixture into a cuvette special for measurement, and then measuring, wherein the result is as follows.
TABLE 1 mean particle size of the different materials
| Raw materials | Doping element | Average particle diameter/. mu.m | |
| Example 1 | Dicyandiamide | La | 0.514 |
| Example 2 | Dicyandiamide | B | 0.767 |
| Example 3 | Dicyandiamide | La、B | 0.544 |
| Example 4 | Thiourea | La、B | 0.661 |
| Example 5 | Melamine | La、B | 0.526 |
| Example 6 | Dicyandiamide | La、B | 0.549 |
| Example 7 | Dicyandiamide | La、B | 0.553 |
| Example 8 | Dicyandiamide | La | 0.521 |
| Comparative example 1 | Melamine | / | 0.809 |
| Comparative example 2 | Dicyandiamide | / | 0.958 |
| Comparative example 3 | Thiourea | / | 0.965 |
As can be seen from Table 1, g-C prepared using melamine, dicyandiamide, thiourea as precursors3N4The grain size is different, after the elements are doped, the g-C is adjusted3N4The particle diameter of (A) is reduced because the element is incorporated so that g-C is3N4Grain growth is inhibited.
In order to further verify the catalytic effect of the catalyst prepared in this example, a catalytic effect experiment was performed, and the specific experiment was as follows:
the nondegradable organic wastewater sample is paper-making wastewater from a certain paper mill, and the COD (chemical oxygen demand) in the wastewater is 1340 mg/L.
The test method comprises the following steps: a certain amount of wastewater is taken, an 18w underwater ultraviolet lamp is inserted, potassium persulfate with the total water content of 0.5 percent is added, and aeration is carried out from the bottom, so that the catalyst is in a fluidized state. The reactants of examples 1-8 and comparative examples 1-3 were added to the wastewater, respectively, the amount of each reactant was 3% of the mass of the wastewater, and the reaction was carried out for 1 hour at room temperature, followed by sampling and detection, and the results are shown in table 2 below.
TABLE 2 catalytic Effect of different materials
| Raw materials | COD concentration (mg/L) of effluent | COD removal Rate (%) | |
| Example 1 | Dicyandiamide | 545 | 59.3 |
| Example 2 | Dicyandiamide | 597 | 55.4 |
| Example 3 | Dicyandiamide | 573 | 57.2 |
| Example 4 | Thiourea | 594 | 55.7 |
| Example 5 | Melamine | 550 | 59.0 |
| Example 6 | Dicyandiamide | 589 | 56.0 |
| Example 7 | Dicyandiamide | 593 | 55.7 |
| Example 8 | Dicyandiamide | 549 | 59.0 |
| Comparative example 1 | Melamine | 735 | 45.1 |
| Comparative example 2 | Dicyandiamide | 750 | 44.0 |
| Comparative example 3 | Thiourea | 783 | 41.6 |
As can be seen from table 2, after doping with the element, the particle size of the materials prepared in examples 1 to 8 is significantly reduced, but the catalytic performance thereof is improved, because the reduction of the particle size is beneficial to the distribution of the active component, reduces the problem of agglomeration of the active component, increases the amount of the active center, and improves the catalytic performance. It can be seen from examples 1 to 3 that the catalytic effect after doping with La is better than that after doping with B, B and La. Examples 3-5 show that the catalyst prepared by using melamine as a precursor has better catalytic effect.
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. Modified g-C3N4The preparation method of the material is characterized by comprising the following steps of:
step 1, taking a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer as a mesoporous template agent, taking triethanolamine as a microporous template agent, adding ammonia water, and taking tetraethoxysilane as a silicon source to prepare mesoporous-microporous SiO2And is ready for use;
step 2, adding nitrogen-containing organic matters and doping compounds into deionized water, heating at 60-80 ℃ until the nitrogen-containing organic matters and the doping compounds are dissolved to obtain a solution, then adding the mesoporous/microporous silicon dioxide obtained in the step 1 into the solution, stirring the solution uniformly, and drying the solution to obtain a mixture; calcining the mixture, cooling and grinding to obtain the doped SiO2/g-C3N4Materials, i.e. modified g-C3N4A material; wherein the compound for doping is one or two of a rare earth element compound or a non-metal element compound.
2. A modified g-C according to claim 13N4The preparation method of the material is characterized in that in the step 1, the triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide and triethanolamine are dissolved in deionized water, stirred to be uniformly mixed, and addedAmmonia water, stirring for 30-40min, adding ethyl orthosilicate, stirring for 20min, standing at 70-80 deg.C for 36-48h, collecting precipitate, and drying to obtain mesoporous-microporous SiO2；
Wherein the ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the triethanolamine to the deionized water to the ammonia water to the ethyl orthosilicate is 0.5g to 4-7.5 g: 30 ml: 4 g: 2.5 g.
3. A modified g-C according to claim 23N4The preparation method of the material is characterized in that in the step 1, the stirring speed is 300-500 rpm.
4. A modified g-C according to claim 33N4The preparation method of the material is characterized in that in the step 1, the drying condition is drying for 6 hours at 60 ℃.
5. A modified g-C according to claim 13N4The preparation method of the material is characterized in that the material comprises nitrogen-containing organic matter, a compound for doping and mesoporous-microporous SiO2The mass ratio of (A) to (B) is 5: 0.263-0.328: 0.0625.
6. a modified g-C according to claim 53N4The preparation method of the material is characterized in that the nitrogen-containing organic matter in the step 2 is one of thiourea, dicyandiamide and melamine.
7. A modified g-C according to claim 63N4The preparation method of the material is characterized in that the rare earth element compound in the step 2 is lanthanum nitrate, and the non-metal element is boron trioxide.
8. A modified g-C according to claim 73N4The preparation method of the material is characterized in that the calcination condition in the step 2 is to heat up to 500-550 ℃, the temperature is kept for 4-5h, and the heating rate is 2-3 ℃/min.
9. A modified g-C prepared by the method of any one of claims 1-83N4A material.
10. A modified g-C as claimed in claim 93N4The material is applied to degrading organic matters in papermaking wastewater.
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