CN114130414B - Preparation method, active catalyst and application of graphite type carbon nitride material - Google Patents
Preparation method, active catalyst and application of graphite type carbon nitride material Download PDFInfo
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- CN114130414B CN114130414B CN202111476129.6A CN202111476129A CN114130414B CN 114130414 B CN114130414 B CN 114130414B CN 202111476129 A CN202111476129 A CN 202111476129A CN 114130414 B CN114130414 B CN 114130414B
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 52
- 239000010439 graphite Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 35
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims abstract description 7
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims description 17
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 13
- 239000000356 contaminant Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 8
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- METKIMKYRPQLGS-GFCCVEGCSA-N (R)-atenolol Chemical compound CC(C)NC[C@@H](O)COC1=CC=C(CC(N)=O)C=C1 METKIMKYRPQLGS-GFCCVEGCSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960002274 atenolol Drugs 0.000 claims description 4
- 229960005489 paracetamol Drugs 0.000 claims description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 13
- 238000002386 leaching Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 32
- 238000006731 degradation reaction Methods 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- 239000004570 mortar (masonry) Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003344 environmental pollutant Substances 0.000 description 11
- 231100000719 pollutant Toxicity 0.000 description 11
- 239000010865 sewage Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
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- 239000003814 drug Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- -1 carbon nitrides Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the field of environmental protection, and particularly relates to a preparation method, an active catalyst and application of a graphite type carbon nitride material. The preparation method of the graphite type carbon nitride material comprises the following steps: preparing a carbon nitride precursor, a triaminophenyl ligand and iron phthalocyanine as raw materials according to the mass ratio of (0.4-1) to (0.1-1); calcining the three raw materials at the calcining temperature of 500-700 ℃ for 1-5h, and obtaining a massive solid calcining product. Wherein the carbon nitride precursor comprises cyanamide, thiourea, dicyandiamide, melamine or urea. The triaminophenyl ligand includes 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, or tris (4-aminophenyl) amine. The graphite-type carbon nitride product can be used as a catalyst with non-photocatalytic activity. The invention solves the problem that the existing graphite type carbon nitride material does not have non-photocatalytic activity; high metal usage in the material. Avoiding secondary pollution caused by leaching a large amount of metal and improving the reusability of the catalyst.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a preparation method of a graphite type carbon nitride material, an active catalyst with non-photocatalytic activity, application of the graphite type carbon nitride material and a sewage treatment method.
Background
The advanced oxidation technology of persulfate activation is a water treatment technology for rapidly and effectively removing refractory organic pollutants. The water treatment process has the advantages of low cost, high reaction stability, wide water quality adaptability, high degradation rate and the like. The persulfate needs to be added with a special catalyst to activate the organic pollutant when treating the organic pollutant; the graphite type carbon nitride material is widely used in the field of photocatalysis due to the characteristics of simple preparation, high chemical stability, visible light response and the like, and meanwhile, the application in the field of water pollution control comprises degradation of organic pollutants and activation of persulfate. Notably, the inherent defects of graphite-type carbon nitride such as high photo-generated electron-hole recombination rate, narrow visible light absorption range, etc. severely limit the photocatalytic activity. In addition, graphite-type carbon nitrides have poor electron transport ability, and therefore, the materials generally do not have catalytic activity in the absence of light.
In order to expand the practical application prospect of graphite-type carbon nitride, the scholars try a plurality of modification methods to endow the graphite-type carbon nitride with non-photocatalytic activity. The conventional method is to mix transition metal elements such as iron, cobalt, cerium, manganese, etc. into graphite type carbon nitride. However, the amount of the transition metal compound modifier is currently too high, for example, in the publication (J.Hazard. Mater. 2018,354, 63-71) by those skilled in the art, such as Yong Feng, changzhong Liao, lingjun Kong et al, in Journalof Hazardous Materials, the amount of iron doping is increased to 3.3wt% in order to improve the catalytic activity of graphite-type carbon nitride. In addition, in the article of J. Environmental Science & Technology (environ. Sci. Technology.2018, 52, 4, 2197-2205), the iron doping amount was further increased to 3.46wt% for improving the graphite type carbon nitride catalytic activity, which was published by those skilled in hongchao li, chao bean, bingcai Pan, et al. However, the stability of graphite-type carbon nitride to metal chelation is not enough for long-term application, and the graphite-type carbon nitride has a common metal leaching phenomenon when coping with complex water conditions, and is easy to cause secondary pollution in water environment. For example, in the article (environ. Sci. Technology. 2018, 52, 4, 2197-2205), the optimum catalyst had an iron leaching of 0.25mg/L under acidic conditions. Along with the leaching of iron, the reusability of the catalyst is greatly affected, and the catalytic efficiency is reduced to 68% after five cycles.
Therefore, how to improve the non-photocatalytic performance of the graphite type carbon nitride and reduce the dosage of the metal modifier has important significance for improving the practical value of the graphite type carbon nitride in the field of sewage treatment, but the prior art still has no good technical scheme which can be popularized and applied.
Disclosure of Invention
The method aims to solve the problems that the existing graphite type carbon nitride material does not have non-photocatalytic activity in the sewage treatment process and the metal consumption is high in the existing metal modified graphite type carbon nitride non-photocatalyst. The invention provides a graphite type carbon nitride material, application thereof and a sewage treatment method.
The invention is realized by adopting the following technical scheme:
the preparation process of graphite type carbon nitride material includes the following steps:
preparing a carbon nitride precursor, a triaminophenyl ligand and iron phthalocyanine as raw materials according to the mass ratio of (0.4-1) to (0.1-1); after the three raw materials are fully and uniformly mixed, the mixture is calcined for 1 to 5 hours at the calcining temperature of 500 to 700 ℃ to obtain a solid calcining product which is the required graphite type carbon nitride material.
As a further improvement of the invention, the carbon nitride precursor is used as a micromolecule for providing rich carbon and nitrogen elements, and the regular heptazine structure is generated through thermal condensation polymerization under the high temperature condition. The carbon nitride precursor may be selected to include one or more of mono-cyanamide, thiourea, dicyandiamide, melamine, and urea. The preparation method of the carbon nitride precursor material is simple, the cost is low, the property is stable, and the raw materials are simple and easy to obtain. The specific use can be selected according to the needs, and in fact, other small molecular materials which can give stable heptazine structures generated by high-temperature thermal polycondensation reaction besides the carbon nitride precursor materials listed above can also be used as the carbon nitride precursor raw materials required in the invention.
The triaminophenyl ligand in the present invention includes one or more of 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, and tris (4-aminophenyl) amine. In the invention, the tri-aminophenyl ligand raw material is mainly used for improving the conductivity of the material by regulating and controlling the delocalization of pi electrons in the reaction process, thereby being more beneficial to the electron transmission of the product and improving the catalytic activity of the product.
The self structure of the iron phthalocyanine in the raw material is porphyrin ring chelated Shan Yuanzi iron, which is more favorable for the dispersion of iron atoms in the calcination process. Wherein, after iron phthalocyanine is used as a doping raw material of transition metal and matched with a triaminophenyl ligand for use, the iron phthalocyanine and the triaminophenyl ligand can exert better synergistic effect; and the catalyst can exert more efficient catalytic activity under the condition of extremely low doping amount. The graphite type carbon nitride material prepared by the invention obviously reduces the doping amount of the metal element to below 0.025wt% while improving the catalytic activity, so that the dissolution of the metal element is obviously reduced when the material is dispersed in water environment.
As a further improvement of the invention, in the calcination process, the raw materials after being uniformly mixed are firstly sent into a muffle furnace, and then the muffle furnace is heated at a constant speed, and the heating rate is controlled to be 2.5-10 ℃/min; and after the furnace temperature reaches the calcination temperature, preserving heat and calcining for 2-4h, and after the calcination is finished, taking out the product from the muffle furnace and naturally cooling to room temperature.
The invention also comprises an active catalyst with non-photocatalytic activity, and the active catalyst is a product prepared by the preparation method of the graphite type carbon nitride material.
The invention also comprises the application of the graphite type carbon nitride material, and the graphite type carbon nitride material is used as an active catalyst for degrading organic pollutants in wastewater by utilizing persulfate; the graphite type carbon nitride material is a product prepared by the preparation method of the graphite type carbon nitride material.
As a further improvement of the present invention, persulfates include potassium persulfate and sodium persulfate.
As a further improvement of the present invention, the organic contaminants include atenolol, rhodamine, acetaminophen, phenol and 2, 4-dichlorophenol.
The invention also comprises a sewage treatment method, and the treatment process is specifically as follows: adding the best amount of persulfate and active catalyst into the sewage according to the expert experience values of the addition amounts of different medicines when treating different pollutants in the sewage containing target pollutants, and uniformly mixing and stirring the sewage; until the concentration of the target pollutant is reduced below the allowable value of the target pollutant in the sewage.
Among the target contaminants include atenolol, rhodamine, acetaminophen, phenol, and 2, 4-dichlorophenol. Persulfates are used to degrade target contaminants, including potassium persulfate and sodium persulfate. The active catalyst catalytically activates persulfate to degrade organic pollutants; thereby improving the degradation rate and the removal rate of the organic pollutants. The active catalyst is the product prepared by the preparation method of the graphite type carbon nitride material.
After the sewage treatment method provided by the invention is used for adding medicines, the degradation process of the organic pollutants can be completed under the conditions of illumination and shading.
The technical scheme provided by the invention has the following beneficial effects:
the preparation method can obtain an improved graphite type carbon nitride material, and the electron transmission capacity and the photocatalytic activity of the material are enhanced through the improvement of the formula; more importantly, the product has obvious non-photocatalytic activity. Therefore, when the product provided by the invention is used as an active catalyst for degrading organic pollutants by persulfate, the product is not limited by illumination intensity, and the stable degradation efficiency of the organic pollutants can be maintained.
The performance improvement of the material is realized by the synergistic effect of the triaminophenyl ligand and the iron phthalocyanine. In the high-temperature polymerization process of the carbon nitride product, the electron transmission performance of the material is improved, and the catalytic activity of the final product is effectively exerted. The dispersion of metal elements on the surface of the graphite type carbon nitride material can be improved, so that the product catalytic activity is ensured, and meanwhile, the doping amount of the metal elements in the graphite type carbon nitride material is reduced. The doping amount of the metal element in the graphite type carbon nitride material provided by the invention can be as low as below 0.025wt%, and secondary pollution caused by massive leaching of the metal element in water environment can be effectively avoided. Meanwhile, the recycling rate of the product in water pollution purification can be improved.
Drawings
Fig. 1 is a process flow diagram of a preparation method of a graphite type carbon nitride material according to an embodiment of the present invention.
FIG. 2 is a product image of a graphite type carbon nitride material prepared according to various embodiments of the present invention.
Fig. 3 is an XRD spectrum of the graphite type carbon nitride material prepared in the present invention and comparative example.
Fig. 4 is an EIS spectrum of the graphite type carbon nitride material prepared in the present invention and comparative example.
FIG. 5 is a graph showing the change of catalytic activity with the increase of the number of cycles when the graphite type carbon nitride material prepared according to the present invention is repeatedly used.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The preparation method of the graphite type carbon nitride material in this embodiment, as shown in fig. 1, comprises the following steps:
according to the mass ratio of 2000 (0.4-1) to 0.1-1, preparing a carbon nitride precursor, a triaminophenyl ligand and iron phthalocyanine as raw materials. The carbon nitride precursor may be selected to include one or more of mono-cyanamide, thiourea, dicyandiamide, melamine, and urea. The trisaminophenyl ligand comprises one or more of 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and tris (4-aminophenyl) amine.
After the three raw materials are fully and uniformly mixed, the raw materials are firstly sent into a muffle furnace, and then the muffle furnace is heated at a constant speed, and the heating rate is controlled to be 2.5-10 ℃/min; calcining at 500-700 deg.c for 1-5 hr, taking out the product from the muffle furnace and cooling naturally to room temperature; the obtained solid calcined product is the required graphite type carbon nitride material.
The products produced by the preparation methods provided and their properties are further described below by way of specific production examples.
Example 1
20g of urea, 1mg of iron phthalocyanine, 4mg of 1,3, 5-tris (4-aminophenyl) benzene are weighed out; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 2.5 ℃ per minute, preserving heat for 1 hour, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN1.
Example 2
20g of an equal mass ratio mixture of dicyandiamide and dicyandiamide, 5mg of iron phthalocyanine, 4mg of 1,3, 5-tris (4-aminophenyl) benzene are weighed; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 600 ℃ at a heating rate of 2.5 ℃ per minute, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN2.
Example 3
20g of urea, 10mg of iron phthalocyanine, 4mg of 1,3, 5-tris (4-aminophenyl) benzene are weighed out; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 600 ℃ at a heating rate of 5 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN3.
Example 4
20g dicyandiamide, 3mg iron phthalocyanine, 6mg 1,3, 5-tris (4-aminophenyl) benzene are weighed out; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 650 ℃ at a heating rate of 5 ℃ per min, preserving heat for 3 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN4.
Example 5
Weighing 20g of an equal mass ratio mixture of thiourea and cyanamide, 7mg of iron phthalocyanine, 8mg of 1,3, 5-tris (4-aminophenyl) benzene and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 2.5 ℃ per minute, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN5.
Example 6
Weighing 20g of an equal mass ratio mixture of melamine, mono-cyanamide and dicyandiamide, 3mg of iron phthalocyanine, 10mg of an equal mass ratio mixture of 1,3, 5-tris (4-aminophenyl) benzene and tris (4-aminophenyl) amine; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 650 ℃ at a heating rate of 10 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN6.
Example 7
20g of urea, 1mg of iron phthalocyanine, 6mg of 1,3, 5-tris (4-aminophenyl) benzene are weighed out; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 5 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN7. CN7,400 mg was collected, and therefore, the iron content was 0.025% by weight.
Example 8
20g of cyanamide, 1mg of iron phthalocyanine, 6mg of tris (4-aminophenyl) amine are weighed out; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 10 ℃ per min, preserving heat for 3 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN8.
Example 9
20g dicyandiamide, 1mg iron phthalocyanine, 6mg 1,3, 5-tris (4-aminophenyl) benzene are weighed; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 700 ℃ at a heating rate of 10 ℃ per minute, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN9.
Example 10
20g of an equal mass ratio mixture of thiourea and melamine, 6mg of iron phthalocyanine, 8mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine are weighed; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 500 ℃ at a heating rate of 5 ℃ per min, preserving heat for 5 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN10.
Example 11
Weighing a mixture of 20g of melamine, 1mg of iron phthalocyanine, 6mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and tris (4-aminophenyl) amine according to the equal mass ratio, uniformly mixing, putting the mixture into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 650 ℃ at a heating rate of 5 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN11.
Example 12
20g dicyandiamide, 1mg iron phthalocyanine, 6mg tris (4-aminophenyl) amine are weighed out; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 700 ℃ at a heating rate of 5 ℃ per min, preserving heat for 5 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN12.
Example 13
20g of urea, 1mg of iron phthalocyanine, 6mg of tris (4-aminophenyl) amine are weighed out; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 700 ℃ at a heating rate of 5 ℃ per min, preserving heat for 3 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN13.
Example 14
20g of an equal mass ratio mixture of melamine and urea, 1mg of iron phthalocyanine, 6mg of 1,3, 5-tris (4-aminophenyl) benzene are weighed; mixing uniformly, placing into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 650 ℃ at a heating rate of 5 ℃ per min, preserving heat for 4 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN14.
In order to determine the relationship between the physicochemical properties of each raw material and the final product in the graphite type carbon nitride material provided by the present application, the present application also uses example 7 as a control group, adopts the principle of controlling variables to prepare four groups of products, and uses the four groups of samples as a comparative example. Specifically, the preparation method of the comparative example is as follows:
comparative example 1
Weighing 20g of urea and 1mg of iron phthalocyanine, uniformly mixing, putting into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 5 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN15.
Comparative example 2
Weighing 20g of urea and 6mg of 1,3, 5-tris (4-aminophenyl) benzene, uniformly mixing, putting into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 5 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN16.
Comparative example 3
Weighing 20g of urea, loading the urea into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 5 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN17.
Comparative example 4
Weighing 20g of urea and 50mg of iron phthalocyanine, uniformly mixing, putting into a ceramic crucible with a cover, and placing the crucible into a muffle furnace; heating the muffle furnace from room temperature to 550 ℃ at a heating rate of 5 ℃ per min, preserving heat for 2 hours, and naturally cooling to room temperature after calcining; the resulting solid was collected and ground into a powder in an agate mortar, designated CN18.
The physical properties of the products are observed, and the products of the scheme and the comparative example are uniform powdery products. Among them, fig. 2 shows a comparative view of the appearance between the product of the present case (CN 7) and the product of the comparative example (CN 17). The product is dark brown, and the proportion of the types of the raw materials in different embodiments is different in the shades of different colors; whereas the product of the comparative example was lighter in colour and milky yellow.
Then, the products of CN 1-18 prepared by the following test tests are designed to detect and determine the physicochemical properties of each group of samples. Specific test trials include:
test 1:
the CN17 product is prepared by adopting the production raw materials of the graphite type carbon nitride materials which are conventional in the market and according to the production process provided by the scheme. CN7 is prepared according to the raw materials and the preparation process provided by the scheme. The test uses the products of CN7 and CN17 as samples, and uses the X-ray diffraction technique to analyze; XRD spectra of the CN7 and CN17 samples shown in FIG. 3 were plotted according to the analysis results.
Analysis of the data in the XDR spectrum revealed that: CN17 has characteristic diffraction peaks of typical carbon nitride (100) and (002) planes. While the CN17 and CN7 spectra are similar, indicating that the modification of iron phthalocyanine and the triaminophenyl ligand maintains a periodic stack structure of the catalyst similar to that in comparative example 3.
Test run 2
Next, the electrochemical workstation was used to perform electrochemical impedance spectroscopy test data on the products of CN7 and CN17 as samples, and an electrochemical impedance spectroscopy (Electrochemical Impedance Spectroscopy, abbreviated as EIS) chart of the samples of CN7 and CN17 as shown in fig. 4 was drawn according to the test data.
Analysis of the data in the EIS spectrum can reveal: compared with CN17, the arc radius of the CN7 spectrogram is obviously reduced, which shows that after the conventional carbon nitride material is modified by the iron phthalocyanine and the triaminophenyl ligand, the resistivity of the material is reduced, and the electron transmission is more facilitated. Namely: the modification method provided by the implementation can effectively improve the conductivity of the graphite type carbon nitride material, thereby being beneficial to improving the catalytic efficiency of the material.
Test 3
Graphite type carbon nitride material in CN1-17 prepared in the previous example is weighed as an active catalyst, and potassium hydrogen persulfate or sodium hydrogen persulfate is randomly selected as a pollutant degradation medicine. Both were added to 10 mL aqueous organic contaminant solutions and a contaminant degradation test was performed.
The organic pollutants selected in the pollutant degradation test are respectively as follows:
contaminant 1:2, 4-dichlorophenol.
Contaminant 2: atenolol.
Contaminant 3: rhodamine.
Contaminant 4: acetaminophen.
Contaminant 5: and (3) phenol.
In the solution system of the pollutant degradation test, the concentration of the added active catalyst is 0.1 g/L, the concentration of potassium hydrogen persulfate or sodium hydrogen persulfate is 1 mmol/L, and the concentration of the organic pollutant is 10 mg/L.
The solution system was magnetically stirred under light shielding. The solution after the reaction was then sampled at regular intervals. Separating solid in the sample with a filter membrane, measuring the concentration of residual 2, 4-dichlorophenol in the sampled solution with high performance liquid chromatography, and further calculating apparent rate constants (min -1 ). The test results of each test group were counted to obtain test data of the following table.
Table 1: degradation rate detection results of each group of active catalysts in pollutant degradation test
The analysis table shows that when the graphite type carbon nitride materials (CN 1-14) generated by the preparation method provided by the embodiment are used as active catalysts, the catalytic degradation rate of pollutants is improved by 87-264 times compared with the conventional graphite type carbon nitride product (CN 17) under the shading condition. This demonstrates that the material provided in this example has significantly enhanced catalytic activity and has significant non-photocatalytic activity.
Furthermore, by comparing CN7, CN15 and CN18, it can be found that: under the condition that the iron phthalocyanine dosage is the same (CN 7 and CN 15), the graphite type carbon nitride material obtained without adding the triaminophenyl ligand has no non-photocatalytic activity.
For the carbon nitride material produced according to the conventional preparation method, after the consumption of iron phthalocyanine is increased by 50 times (CN 18), the obtained product only has the non-photocatalytic activity equivalent to that of CN7 prepared by the method. This shows that in the technical scheme provided in this embodiment, the addition of the triaminophenyl ligand can greatly reduce the doping amount of the metal, so as to reduce the risk of secondary pollution caused by metal leaching.
Test run 4
In order to verify how the degradation efficiency changes with the increase of the cycle number after repeated use when the graphite type carbon nitride material provided by the application degrades organic pollutants, the following test is specially made. In this test, the product CN7 of example 7 was used as a test sample, and the contaminant removal rate of the sample was measured in five cycles. The pollutant degradation test procedure is as in test 3, and the organic pollutant in the degradation test is 2, 4-dichlorophenol. The reuse effect graph as shown in fig. 5 is drawn according to the change curve of the pollutant removal rate. In the figure, the abscissa indicates the number of times of use of the catalyst, and the ordinate indicates the removal rate of the organic pollutant 2, 4-dichlorophenol.
The test data in the analysis chart show that the graphite-type carbon nitride material provided by the embodiment can be recycled for five times, and the active catalytic degradation efficiency of the 2, 4-dichlorophenol is gradually reduced, but the final degradation efficiency still can reach about 90%. Furthermore, in the continuing test, it was found that the degradation efficiency rapidly decreased after the number of cycles exceeded 8. It can thus be roughly judged that: the optimal cycle number of the material in the catalytic degradation process of the organic pollutants is 5 times, and the limit cycle number is 8 times.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The preparation method of the graphite type carbon nitride material is characterized by comprising the following steps:
preparing a carbon nitride precursor, a triaminophenyl ligand and iron phthalocyanine as raw materials according to the mass ratio of (0.4-1) to (0.1-1); after the three raw materials are fully and uniformly mixed, the mixture is calcined for 1 to 5 hours at the calcining temperature of 500 to 700 ℃ to obtain a solid calcining product which is the required graphite type carbon nitride material.
2. The method for preparing a graphite type carbon nitride material according to claim 1, wherein: the carbon nitride precursor comprises one or more of cyanamide, thiourea, dicyandiamide, melamine and urea.
3. The method for preparing a graphite type carbon nitride material according to claim 1, wherein: the trisaminophenyl ligand comprises one or more of 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and tris (4-aminophenyl) amine.
4. The method for preparing a graphite type carbon nitride material according to claim 1, wherein: in the calcination process, the raw materials after being uniformly mixed are firstly sent into a muffle furnace, and then the muffle furnace is heated at a constant speed, and the heating rate is controlled to be 2.5-10 ℃/min; and after the furnace temperature reaches the calcination temperature, preserving heat and calcining for 2-4h, and after the calcination is finished, taking out the product from the muffle furnace and naturally cooling to room temperature.
5. An active catalyst having non-photocatalytic activity, characterized by: the active catalyst is a product prepared by the preparation method of the graphite type carbon nitride material according to any one of claims 1 to 4.
6. An application of a graphite type carbon nitride material is characterized in that: graphite type carbon nitride material is used as an active catalyst for degrading organic pollutants in wastewater by utilizing persulfate; the graphite type carbon nitride material is a product prepared by the preparation method of the graphite type carbon nitride material in any one of claims 1 to 4.
7. The use of a graphitic carbon nitride material according to claim 6, wherein: the persulfate includes potassium persulfate and sodium persulfate.
8. The use of a graphitic carbon nitride material according to claim 6, wherein: the organic contaminants include atenolol, rhodamine, acetaminophen, phenol, and 2, 4-dichlorophenol.
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| WO2021139023A1 (en) * | 2020-01-06 | 2021-07-15 | 东南大学 | Graphite-like carbon nitride doped modified microsphere catalyst, and preparation method therefor and application thereof |
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