CN112844437A - Preparation method of high-crystalline carbon nitride photo-Fenton catalyst and application of high-crystalline carbon nitride photo-Fenton catalyst in degradation of emerging pollutants - Google Patents
Preparation method of high-crystalline carbon nitride photo-Fenton catalyst and application of high-crystalline carbon nitride photo-Fenton catalyst in degradation of emerging pollutants Download PDFInfo
- Publication number
- CN112844437A CN112844437A CN202110149303.XA CN202110149303A CN112844437A CN 112844437 A CN112844437 A CN 112844437A CN 202110149303 A CN202110149303 A CN 202110149303A CN 112844437 A CN112844437 A CN 112844437A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- photo
- fenton catalyst
- crystalline carbon
- fenton
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 24
- 230000015556 catabolic process Effects 0.000 title claims abstract description 23
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 21
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- -1 halogen salt Chemical class 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000356 contaminant Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 229960001193 diclofenac sodium Drugs 0.000 description 15
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 13
- 229960001259 diclofenac Drugs 0.000 description 9
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 9
- CGIGDMFJXJATDK-UHFFFAOYSA-N indomethacin Chemical compound CC1=C(CC(O)=O)C2=CC(OC)=CC=C2N1C(=O)C1=CC=C(Cl)C=C1 CGIGDMFJXJATDK-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 239000008247 solid mixture Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 5
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 description 4
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 4
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 4
- 229960000623 carbamazepine Drugs 0.000 description 4
- 229960000740 enrofloxacin Drugs 0.000 description 4
- 229960000905 indomethacin Drugs 0.000 description 4
- 229960002009 naproxen Drugs 0.000 description 4
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 4
- 229960005404 sulfamethoxazole Drugs 0.000 description 4
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 4
- 229960003500 triclosan Drugs 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical class Cl* 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006552 photochemical reaction Methods 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002876 beta blocker Substances 0.000 description 1
- 229940097320 beta blocking agent Drugs 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Images
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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- 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
Landscapes
- 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)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention belongs to the technical field of treatment of emerging pollutants, and particularly relates to a preparation method of a high-crystalline carbon nitride photo-Fenton catalyst and application thereof in degradation of emerging pollutants, wherein dicyanodiamine is calcined to obtain carbon nitride, then the carbon nitride is mixed with halogen salt, and the mixture is calcined again in an inert gas atmosphere; and finally, preparing the high-crystallization carbon nitride photo-Fenton catalyst after suction filtration, washing and drying. The method has simple synthesis process and good repeatability, can be used for large-scale production, and the prepared carbon nitride photo-Fenton catalyst has obviously improved crystallinity and improved electron transfer rate. Under the condition of existence of a strong oxidant, the catalytic degradation performance of the composite material is greatly enhanced, the composite material has a strong degradation effect on PPCPs, can be applied to degrading emerging pollutants, has a synergistic effect when being applied to treating the wastewater of the emerging pollutants, and can prevent secondary pollution.
Description
Technical Field
The invention belongs to the technical field of emerging pollutant treatment, and particularly relates to a preparation method of a high-crystalline carbon nitride photo-Fenton catalyst and application of the high-crystalline carbon nitride photo-Fenton catalyst in degrading emerging pollutants.
Background
The emerging Pollutants may be chemicals that may affect human health or the ecosystem, but are not currently (or only recently) regulated, such as Pharmaceuticals and Personal Care Products (PPCPs), Persistent Organic Pollutants (POPs), Disinfection By-Products (DBPs), mercury, and the like, and their degradation Products. Among them, the most common PPCPs include human and veterinary drugs such as anti-inflammatory agents, analgesics, antibiotics, beta-blockers, antidepressants, lipid regulators, and disinfectants or fragrances in personal care products. Although the concentration of PPCPs in the environment is generally between ng/L and mug/L, the PPCPs have certain polarity and are difficult to volatilize, and the PPCPs are continuously accumulated in the water environment, so that the physiological activities of algae and aquatic organisms are influenced, and the balance of an ecological system is seriously damaged.
Different scholars have carried out a great deal of research aiming at the PPCPs removal method, mainly comprising biodegradation, physical-chemical method, advanced oxidation and combination technology thereof, and the difference of the removal rate of the PPCPs by the methods is large. Although various methods for processing PPCPs at the present stage in China have certain effects, the methods also have some limitations. The biological treatment method has good degradation effect on partial PPCPs, but is not ideal for removing the PPCPs with poor biodegradability. In the degradation process, the toxicity of some intermediate products is higher than that of the parent products, which poses serious threat to the water environment safety in China. Therefore, it is very important to find a high-efficiency, green and economic degradation technology.
Graphitized carbon nitride, commonly known as g-C3N4The graphene is a polymer layered material, and the structure of the graphene is similar to that of graphene. It has the advantages of high stability, low toxicity, easy preparation, etc. and is excellent photocatalytic material. However, due to g-C3N4Severe recombination probability of photogenerated carriers, limited inversionDue to the defects of active sites and the like, the photocatalytic activity of the photocatalyst is low, and the degradation of PPCPs and other new pollutants in a water body is limited. Therefore, it is necessary to control g-C3N4The catalyst is modified to improve the catalytic performance of the catalyst, so that the catalyst has better application value.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a high-crystallization carbon nitride photo-Fenton catalyst, the preparation method is simple, the cost and the energy consumption are low, the prepared catalyst has high catalytic degradation efficiency and excellent stability, has a strong degradation effect on PPCPs, and can be applied to degrading new pollutants.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a high-crystallization carbon nitride photo-Fenton catalyst, which comprises the following steps:
s1, calcining dicyanodiamine at high temperature to obtain carbon nitride;
s2, mixing carbon nitride with halogen salt, grinding, and heating and calcining in an inert gas atmosphere to obtain a yellow-green solid;
and S3, adding water into the yellow-green solid, heating and stirring, and then carrying out suction filtration, washing and drying to obtain the high-crystalline carbon nitride photo-Fenton catalyst.
According to the invention, the carbon nitride is modified by calcining the carbon nitride and the halogen salt, so that the carbon nitride photo-Fenton catalyst with obviously improved crystallinity is prepared, the preparation cost is low, the preparation process is simple, the requirement on preparation conditions is low, the catalyst can be repeatedly used for many times, and a complex regeneration process is not needed. Meanwhile, the method can also improve the electron transfer rate of the carbon nitride material, reduce the electron hole recombination rate and improve the catalytic performance, when the method is applied to treating wastewater containing PPCPs, the wastewater can efficiently degrade the PPCPs in the water due to the photo-Fenton reaction, on one hand, the reaction conditions are mild, and persulfate can be activated to generate active substances such as hydroxyl radicals, sulfate radicals, superoxide radicals and the like; on the other hand, has synergistic effect and can continuously generate substances (H) with strong oxidizing property+、O2 -、SO4 -And OH) to efficiently remove antibiotic substances in water and mineralize the antibiotic substances into H2O and CO2And the like, so as to prevent secondary pollution; in addition, the carbon nitride photo-Fenton catalyst is used for carrying out the photo-Fenton reaction of wastewater, so that the problems that the pH value of a reaction system is too strict by the traditional Fenton oxidation method, the treated water has colors, a large amount of sludge is generated and the like can be solved.
Preferably, the calcining temperature in step S2 is 350-600 ℃, the time is 3-5 h, and the temperature rise rate is 4-5 ℃ per min. Further, the temperature of the calcination is 350 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃. Specifically, the temperature of the calcination is 550 ℃ or 600 ℃.
Preferably, the halogen salt in step S2 is a mixture of a plurality of halogen salts. Further, the halogen salt in step S2 is a mixture of two halogen salts of the same halogen. Further, in step S2, the mass ratio of the two halogen salts is 1: 1-1.6: 1. Specifically, the mass ratio of the two halogen salts in step S2 is 1.0: 1. 1.2: 1. 1.4: 1. 1.6: 1.
specifically, the halogen salt mixture is lithium chloride, a potassium chloride mixture or a potassium bromide and lithium bromide mixture. More specifically, the mass ratio of lithium chloride to potassium chloride or potassium bromide to lithium bromide is 1.0: 1. 1.2: 1. 1.4: 1. 1.6: 1.
preferably, the calcining temperature in step S1 is 450-550 ℃, the time is 2-4 h, and the temperature rise rate is 2-4 ℃ per min. Further, the calcination temperature in step S1 is 550 ℃, the time is 3h, and the temperature rise rate is 3 ℃/min.
Preferably, the inert gas of step S2 includes, but is not limited to, nitrogen.
Preferably, in the step S3, the heating and stirring are performed at 80-90 ℃ for not less than 0.5 h. Further, the heating and stirring are carried out at 85 ℃ for 0.5 h.
Preferably, the washing in step S3 is washing with water and ethanol several times.
The invention also provides the high-crystalline carbon nitride photo-Fenton catalyst prepared by the preparation method.
The invention also provides application of the high-crystalline carbon nitride photo-Fenton catalyst in degrading emerging pollutants.
The invention also provides application of the high-crystalline carbon nitride photo-Fenton catalyst in treatment of wastewater containing emerging pollutants.
Preferably, the emerging contaminants are PPCPs. Further, the PPCPs include, but are not limited to, Naproxen (NPX), Indomethacin (IDM), Carbamazepine (CBZ), Triclosan (TCS), Sulfamethoxazole (SMZ), Enrofloxacin (ENR), and Diclofenac (DCF) or diclofenac sodium.
The invention also provides a treatment method of wastewater containing PPCPs, which comprises the following steps:
s1, adding the high-crystalline carbon nitride photo-Fenton catalyst into wastewater containing PPCPs pollutants, and stirring in the absence of light to achieve adsorption-desorption balance;
and S2, adding persulfate, then turning on a light source and continuously stirring to enable the wastewater containing the PPCPs to generate a photo-Fenton reaction.
Preferably, the amount of the highly crystalline carbon nitride photo-Fenton catalyst to be added is (0.1 to 0.9) g/L. Further, the amount of the highly crystalline carbon nitride photo-fenton catalyst to be charged was 0.5 g/L.
Preferably, the addition amount of the persulfate is (0.2-2) mmol/L. Further, the persulfate includes, but is not limited to, potassium persulfate.
Preferably, the concentration of the PPCPs in the wastewater is not more than 40 mg/L.
Preferably, the stirring time in the step S1 is 0.5-1 h.
Preferably, the time of the photo-fenton reaction in step S2 is 0.5 to 2 hours. Further, the time of the photo-fenton reaction was 1 hour.
Preferably, the light source used in the photo-fenton reaction in step S2 is a 500W xenon lamp, and a 420nm filter is used to filter out the uv light.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a high-crystallization carbon nitride photo-Fenton catalyst, which comprises the steps of firstly calcining dicyanodiamine to obtain carbon nitride, then mixing the carbon nitride with halogen salt, and calcining again in an inert gas atmosphere; and finally, preparing the high-crystallization carbon nitride photo-Fenton catalyst after suction filtration, washing and drying. The method has simple synthesis process and good repeatability, can be used for large-scale production, and the prepared carbon nitride photo-Fenton catalyst has obviously improved crystallinity and improved electron transfer rate. Under the condition of existence of a strong oxidant, the catalytic degradation performance of the catalyst is greatly enhanced, the catalyst has a strong degradation effect on PPCPs, and the catalyst can be applied to degrading new pollutants. The composite material has a synergistic effect when being applied to treating emerging pollutant wastewater, can continuously generate strong oxidizing substances under visible light to efficiently remove emerging pollutants in water, mineralizes the emerging pollutants into harmless micromolecular substances, and prevents secondary pollution.
Drawings
FIG. 1 is a TEM test result chart (A is CCN-550; B is carbon nitride BCN);
FIG. 2 shows the photo-Fenton degradation efficiency of CCN-T on diclofenac sodium;
FIG. 3 shows the efficiency of CCN-550 in degrading different PPCPs contaminants;
FIG. 4 shows the degradation efficiency of CCN-550 on diclofenac under different concentrations of potassium persulfate.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 highly crystalline carbon nitride photo-fenton catalyst prepared from different calcination temperatures
The preparation method comprises the following steps:
(1) weighing 4g of dicyanodiamine, placing the dicyanodiamine in an alumina crucible, transferring the alumina crucible to a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, calcining, and keeping the temperature for 3 hours to obtain light yellow solid BCN (BCN is carbon nitride which is not calcined by molten salt);
(2) mixing 0.4g of BCN, 2.2g of potassium chloride and 1.8g of lithium chloride, fully grinding the obtained solid mixture (7000 meshes), transferring the solid mixture to a tubular furnace, heating to 350-600 ℃ at a heating rate of 4.5 ℃/min in a nitrogen atmosphere, calcining, and keeping for 4 hours to obtain a yellow-green solid.
(3) Adding 500mL of ultrapure water into the calcined yellow-green solid, and heating and stirring at 85 ℃ for 0.5 h; and then carrying out suction filtration, washing the obtained product for 3 times by using ultrapure water after the suction filtration, then washing the obtained product for 2 times by using absolute ethyl alcohol, drying the obtained product for 24 hours in an oven at 50 ℃, and grinding and sieving the obtained product (7000 meshes) after the obtained product is cooled to room temperature to obtain the CCN-T photo-Fenton catalyst (powder). Wherein T is the corresponding calcining temperature in the step (2), and T is 350, 450, 500, 550 and 600.
The CCN-550 photo-fenton catalyst prepared above was subjected to Transmission Electron Microscopy (TEM) test, and the test results are shown in fig. 1. As can be seen from FIG. 1, CCN-550 is more crystalline and has a distinct lattice structure (compare to carbon nitride BCN).
In addition, the TEM test results of CCN-350, CCN-450, CCN-500, and CCN-600 are similar to that of CCN-550.
Example 2 preparation of highly crystalline carbon nitride photo-Fenton catalyst from Bromide salt
The preparation method comprises the following steps:
(1) weighing 4g of dicyanodiamine, placing the dicyanodiamine in an alumina crucible, transferring the alumina crucible to a muffle furnace, raising the temperature to 550 ℃ at a heating rate of 3 ℃/min, calcining, and keeping the temperature for 3 hours to obtain light yellow solid BCN;
(2) mixing 0.4g of BCN, 2.2g of potassium bromide and 1.8g of lithium bromide, fully grinding the obtained solid mixture (7000 meshes), transferring the solid mixture to a tubular furnace, raising the temperature to 550 ℃ at the heating rate of 4.5 ℃/min under the nitrogen atmosphere, calcining, and keeping for 4 hours to obtain a yellow-green solid;
(3) adding 500mL of ultrapure water into the calcined yellow-green solid, and heating and stirring at 85 ℃ for 0.5 h; and then carrying out suction filtration, washing the obtained product for 3 times by using ultrapure water after the suction filtration, then washing the obtained product for 2 times by using absolute ethyl alcohol, drying the obtained product for 24 hours in a drying oven at 50 ℃, and grinding and sieving the obtained product (7000 meshes) after the obtained product is cooled to room temperature to obtain the CCN-Br photo-Fenton catalyst (powder).
The TEM test results of CCN-Br were similar to that of CCN-550.
Example 3 high crystalline carbon nitride photo-Fenton catalysts prepared from different halide salt ratios
The preparation method comprises the following steps:
(1) weighing 4g of dicyanodiamine, placing the dicyanodiamine in an alumina crucible, transferring the alumina crucible to a muffle furnace, raising the temperature to 550 ℃ at a heating rate of 3 ℃/min, calcining, and keeping the temperature for 3 hours to obtain light yellow solid BCN;
(2) adding 0.4g of BCN into a certain proportion of mixed chlorine salt (potassium chloride and lithium chloride in a mass ratio of 1: 1-1.6: 1), fully grinding the obtained solid mixture (7000 meshes), transferring the solid mixture into a tubular furnace, heating to 550 ℃ at a heating rate of 4.5 ℃/min in the nitrogen atmosphere, calcining, and keeping for 4 hours to obtain a yellow-green solid;
(3) adding 500mL of ultrapure water into the calcined yellow-green solid, and heating and stirring at 85 ℃ for 0.5 h; and then carrying out suction filtration, washing the obtained product for 3 times by using ultrapure water after the suction filtration, then washing the obtained product for 2 times by using absolute ethyl alcohol, drying the obtained product for 24 hours in a drying oven at 50 ℃, and grinding and sieving the obtained product (7000 meshes) after the obtained product is cooled to room temperature to obtain the CCN-R photo-Fenton catalyst (powder). R is the mass ratio of potassium chloride to lithium chloride, and R is 1.0: 1,1.2: 1,1.4: 1,1.6: 1.
the TEM test results of CCN-R are similar to that of CCN-550.
Experimental example 1 application of high-crystalline carbon nitride photo-Fenton catalyst in diclofenac sodium wastewater treatment
(1) 25mg of the BCN, CCN-T, CCN-Br and CCN-R catalysts prepared in examples 1-3 were weighed into a quartz photolysis tube, 50mL of a diclofenac sodium solution with a concentration of 20mg/L was added, and the solution was placed in a photochemical reaction chamber (Zhongzhijin source, model: CEL-LB 70-3).
(2) After adsorbing for 30min, 1mmol/L potassium persulfate was added, a 500W xenon lamp (using a 420nm filter to filter out the UV portion) was turned on and the photo-Fenton reaction was carried out with continuous stirring for 1 h. The concentration C of diclofenac sodium remaining in the solution was determined using liquid chromatography. According to the formula N ═ C0-C)/C0X 100%, and calculating the removal rate N of diclofenac sodium, wherein C0Is the initial concentration of diclofenac sodium. Finally obtaining the removal rate of the diclofenac sodium by the photo-Fenton catalyst.
As shown in Table 1, compared with catalysts calcined by bromine salt and chlorine salt, the material calcined by mixed chlorine salt has better catalytic performance; compared with a catalyst calcined under the condition of different proportions of potassium chloride and lithium chloride, the material calcined under the condition that the mass ratio of the potassium chloride to the lithium chloride is 1.2:1 has better catalytic performance.
The effect of CCN-T in application example 1 on diclofenac sodium removal is shown in Table 1 and FIG. 2. For materials calcined at different temperatures, the degradation effect is CCN-550 > CCN-600 > CCN-500 > CCN-450 > CCN-350, which may be related to the crystallinity of the material.
TABLE 1 photo-Fenton degradation rate of CCN-T on diclofenac sodium
| Catalyst and process for preparing same | Removal Rate (%) |
| BCN | 19.02 |
| CCN-350 | 25.28 |
| CCN-450 | 26.53 |
| CCN-500 | 46.26 |
| CCN-550 | 98.54 |
| CCN-600 | 80.94 |
| CCN-Br | 56.67 |
| CCN-1.0：1 | 63.54 |
| CCN-1.2：1 | 98.54 |
| CCN-1.4：1 | 67.21 |
| CCN-1.6：1 | 50.93 |
Experimental example 2 application of high-crystalline carbon nitride photo-Fenton catalyst in PPCPs wastewater treatment
(1) 25mg of the CCN-550 catalyst prepared in example 1 was weighed into a quartz photolysis tube, 50mL of a 20mg/L Naproxen (NPX) solution, an Indomethacin (IDM) solution, a Carbamazepine (CBZ) solution, a Triclosan (TCS) solution, a Sulfamethoxazole (SMZ) solution, an Enrofloxacin (ENR) solution and a Diclofenac (DCF) solution were added, and the mixture was placed in a photochemical reaction chamber.
(2) After adsorbing for 30min, 1mmol/L potassium persulfate was added, a 500W xenon lamp (using a 420nm filter to filter out the UV portion) was turned on and the photo-Fenton reaction was carried out with continuous stirring for 1 h. Determination of solutions using liquid chromatographyC concentration of remaining contaminants. According to the formula N ═ C0-C)/C0X 100%, and calculating the removal rate N of the contaminants, wherein C0Is the initial concentration of the contaminant. Finally obtaining the degradation efficiency of CCN-550 on different PPCPs pollutants.
Table 2 and fig. 3 show the photo-fenton degradation effect of CCN-550 in application example 1 on different PPCPs contaminants. As can be seen from Table 2 and FIG. 3, CCN-550 has strong degradation effect on different PPCPs pollutants.
TABLE 2 CCN-550 degradation efficiency for different PPCPs contaminants
Experimental example 3 treatment effect of highly crystalline carbon nitride photo-Fenton catalyst on diclofenac wastewater under the condition of different concentrations of potassium persulfate
(1) 25mg of the CCN-550 catalyst prepared in example 1 was weighed into a quartz photolysis tube, 50mL of a diclofenac sodium solution with a concentration of 20mg/L was added, and the mixture was placed in a photochemical reaction chamber.
(2) After adsorbing for 30min, adding 0.2-2 mmol/L potassium persulfate, starting a 500W xenon lamp (filtering out ultraviolet part by using a 420nm filter) and continuously stirring for carrying out the photo-Fenton reaction for 1 h. The concentration C of diclofenac sodium remaining in the solution was determined using liquid chromatography. According to the formula N ═ C0-C)/C0X 100%, and calculating the removal rate N of diclofenac sodium, wherein C0Is the initial concentration of diclofenac sodium. Finally obtaining the removal rate of the diclofenac sodium of the photo-Fenton catalyst under the condition of different addition amounts of potassium persulfate.
As can be seen from Table 3 and FIG. 4, when the concentration of potassium persulfate is 0.2 mM-1.0 mM, the efficiency of degrading diclofenac by CCN-550 increases with the increase of the concentration of potassium persulfate; when the concentration of the potassium persulfate is more than 1.0mM, the degradation efficiency of the diclofenac by the CCN-550 is not obviously improved. Therefore, 1.0mM was the optimum concentration for potassium persulfate.
TABLE 3 degradation efficiency of diclofenac by CCN-550 under different concentrations of potassium persulfate
| Concentration of potassium persulfate | Removal Rate (%) |
| 0.2mM | 90.94 |
| 0.5mM | 94.33 |
| 1.0mM | 98.47 |
| 1.5mM | 99.62 |
| 2.0mM | 99.79 |
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A preparation method of a high-crystallization carbon nitride photo-Fenton catalyst is characterized by comprising the following steps:
s1, calcining dicyanodiamine at high temperature to obtain carbon nitride;
s2, mixing carbon nitride with halogen salt, grinding, and heating and calcining in an inert gas atmosphere to obtain a yellow-green solid;
and S3, adding water into the yellow-green solid, heating and stirring, and then carrying out suction filtration, washing and drying to obtain the high-crystalline carbon nitride photo-Fenton catalyst.
2. The method for preparing a highly crystalline carbon nitride photo-fenton catalyst according to claim 1, wherein the calcination temperature in step S2 is (350-600) c, the calcination time is (3-5) h, and the temperature rise rate is (4-5) c/min.
3. The method of claim 1, wherein the halogen salt in step S2 is a mixture of a plurality of halogen salts.
4. The method of claim 3, wherein the halogen salt in step S2 is a mixture of two halogen salts with halogen.
5. The method for preparing a highly crystalline carbon nitride photo-fenton catalyst according to claim 4, wherein the mass ratio of the two halogen salts is 1: 1-1.6: 1.
6. The highly crystalline carbon nitride photo-Fenton catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the highly crystalline carbon nitride photo-fenton catalyst of claim 6 for the degradation of emerging contaminants.
8. A method for treating wastewater containing PPCPs is characterized by comprising the following steps:
s1, adding the high-crystalline carbon nitride photo-Fenton catalyst in the claim 7 into wastewater containing PPCPs pollutants, and stirring the wastewater under the condition of no light to reach the adsorption-desorption balance;
and S2, adding persulfate, then turning on a light source and continuously stirring to enable the PPCPs wastewater to have a photo-Fenton reaction.
9. The method for treating wastewater containing PPCPs according to claim 8, wherein the amount of the highly crystalline carbon nitride photo-Fenton catalyst added is (0.1-0.9) g/L.
10. The method for treating wastewater containing PPCPs according to claim 8, wherein the persulfate is added in an amount of (0.2-2) mmol/L.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210834905.3A CN115254164A (en) | 2021-02-03 | 2021-02-03 | High-crystalline carbon nitride photo-Fenton catalyst, preparation method thereof and application thereof in degradation of emerging pollutants |
| CN202110149303.XA CN112844437A (en) | 2021-02-03 | 2021-02-03 | Preparation method of high-crystalline carbon nitride photo-Fenton catalyst and application of high-crystalline carbon nitride photo-Fenton catalyst in degradation of emerging pollutants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110149303.XA CN112844437A (en) | 2021-02-03 | 2021-02-03 | Preparation method of high-crystalline carbon nitride photo-Fenton catalyst and application of high-crystalline carbon nitride photo-Fenton catalyst in degradation of emerging pollutants |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210834905.3A Division CN115254164A (en) | 2021-02-03 | 2021-02-03 | High-crystalline carbon nitride photo-Fenton catalyst, preparation method thereof and application thereof in degradation of emerging pollutants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112844437A true CN112844437A (en) | 2021-05-28 |
Family
ID=75987671
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210834905.3A Pending CN115254164A (en) | 2021-02-03 | 2021-02-03 | High-crystalline carbon nitride photo-Fenton catalyst, preparation method thereof and application thereof in degradation of emerging pollutants |
| CN202110149303.XA Pending CN112844437A (en) | 2021-02-03 | 2021-02-03 | Preparation method of high-crystalline carbon nitride photo-Fenton catalyst and application of high-crystalline carbon nitride photo-Fenton catalyst in degradation of emerging pollutants |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210834905.3A Pending CN115254164A (en) | 2021-02-03 | 2021-02-03 | High-crystalline carbon nitride photo-Fenton catalyst, preparation method thereof and application thereof in degradation of emerging pollutants |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN115254164A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115445646A (en) * | 2022-08-10 | 2022-12-09 | 湖南农业大学 | Carbon nitride composite photocatalyst and preparation method and application thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428762B1 (en) * | 1999-07-27 | 2002-08-06 | William Marsh Rice University | Powder synthesis and characterization of amorphous carbon nitride, a-C3N4 |
| CN104492470A (en) * | 2015-01-09 | 2015-04-08 | 江苏大学 | Preparation method of graphite type carbon nitride photocatalytic material |
| CN106268909A (en) * | 2016-08-27 | 2017-01-04 | 天津大学 | Solid gas interface Fenton's reaction coupled mode carbonitride catalysis material and preparation thereof and application |
| CN108380235A (en) * | 2018-04-17 | 2018-08-10 | 同济大学 | A kind of preparation method and applications of the heterogeneous class fenton catalyst of graphite phase carbon nitride base |
| CN108584892A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method and applications of crystalline phase azotized carbon nano particle |
| CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
| CN109364978A (en) * | 2018-12-06 | 2019-02-22 | 滨州学院 | Class fenton catalyst preparation method and its application in treatment of Organic Wastewater |
| CN109590006A (en) * | 2018-12-17 | 2019-04-09 | 江苏大学 | A kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts |
| CN109603875A (en) * | 2018-12-14 | 2019-04-12 | 深圳大学 | Carbon nitride material and its preparation method and application |
| CN109603876A (en) * | 2018-12-14 | 2019-04-12 | 深圳大学 | Carbon nitride material and its preparation method and application |
| CN109647485A (en) * | 2019-01-21 | 2019-04-19 | 西安理工大学 | A kind of preparation method of threadiness carbonitride |
| CN110124719A (en) * | 2019-05-21 | 2019-08-16 | 电子科技大学 | A kind of preparation method and application of highly crystalline carbonitride catalysis material |
| CN111013629A (en) * | 2019-12-23 | 2020-04-17 | 华北电力大学 | Catalyst for degrading antibiotics by Fenton-like light and preparation and application thereof |
| CN111250140A (en) * | 2020-03-03 | 2020-06-09 | 武汉大学 | Carbon nitride nanorod array photocatalyst for photocatalytic nitrogen fixation and preparation method thereof |
| CN111715266A (en) * | 2020-07-20 | 2020-09-29 | 广州大学 | LiCl-CN nanotube with visible light catalytic activity and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654665A (en) * | 2018-03-30 | 2018-10-16 | 广东工业大学 | A kind of ultra-thin carbon nitride photocatalyst and its preparation method and application |
-
2021
- 2021-02-03 CN CN202210834905.3A patent/CN115254164A/en active Pending
- 2021-02-03 CN CN202110149303.XA patent/CN112844437A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428762B1 (en) * | 1999-07-27 | 2002-08-06 | William Marsh Rice University | Powder synthesis and characterization of amorphous carbon nitride, a-C3N4 |
| CN104492470A (en) * | 2015-01-09 | 2015-04-08 | 江苏大学 | Preparation method of graphite type carbon nitride photocatalytic material |
| CN106268909A (en) * | 2016-08-27 | 2017-01-04 | 天津大学 | Solid gas interface Fenton's reaction coupled mode carbonitride catalysis material and preparation thereof and application |
| CN108380235A (en) * | 2018-04-17 | 2018-08-10 | 同济大学 | A kind of preparation method and applications of the heterogeneous class fenton catalyst of graphite phase carbon nitride base |
| CN108584892A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method and applications of crystalline phase azotized carbon nano particle |
| CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
| CN109364978A (en) * | 2018-12-06 | 2019-02-22 | 滨州学院 | Class fenton catalyst preparation method and its application in treatment of Organic Wastewater |
| CN109603875A (en) * | 2018-12-14 | 2019-04-12 | 深圳大学 | Carbon nitride material and its preparation method and application |
| CN109603876A (en) * | 2018-12-14 | 2019-04-12 | 深圳大学 | Carbon nitride material and its preparation method and application |
| CN109590006A (en) * | 2018-12-17 | 2019-04-09 | 江苏大学 | A kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts |
| CN109647485A (en) * | 2019-01-21 | 2019-04-19 | 西安理工大学 | A kind of preparation method of threadiness carbonitride |
| CN110124719A (en) * | 2019-05-21 | 2019-08-16 | 电子科技大学 | A kind of preparation method and application of highly crystalline carbonitride catalysis material |
| CN111013629A (en) * | 2019-12-23 | 2020-04-17 | 华北电力大学 | Catalyst for degrading antibiotics by Fenton-like light and preparation and application thereof |
| CN111250140A (en) * | 2020-03-03 | 2020-06-09 | 武汉大学 | Carbon nitride nanorod array photocatalyst for photocatalytic nitrogen fixation and preparation method thereof |
| CN111715266A (en) * | 2020-07-20 | 2020-09-29 | 广州大学 | LiCl-CN nanotube with visible light catalytic activity and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| MICHAEL J. BOJDYS ET AL.: "Ionothermal Synthesis of Crystalline, Condensed, Graphitic Carbon Nitride", 《CHRMISTRY A EUROPEAN JOURNAL》 * |
| 崔玉民: "《氮化碳光催化材料合成及应用》", 31 March 2018, 北京：中国书籍出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115445646A (en) * | 2022-08-10 | 2022-12-09 | 湖南农业大学 | Carbon nitride composite photocatalyst and preparation method and application thereof |
| CN115445646B (en) * | 2022-08-10 | 2024-09-06 | 湖南农业大学 | Carbon nitride composite photocatalyst, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115254164A (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sonawane et al. | Nanocomposites and its applications | |
| US10662095B2 (en) | Ozone-photocatalysis reactor and water treatment method | |
| WO2021232600A1 (en) | Method for efficiently removing organic pollutants from wastewater by means of combined visible light catalysis-clo2 oxidation | |
| CN112194236A (en) | Method for treating salt-containing degradation-resistant wastewater by activating peroxymonosulfate through biochar-copper oxide composite material | |
| WO2022016768A1 (en) | Method for bio-enhanced treatment of refractory organic pollutants based on photoexcitation holes as electron acceptors | |
| CN102225793A (en) | Method for removing ammonia nitrogen, nitrogen nitrate and nitrogen nitrite in water synchronously | |
| CN109621974B (en) | CuMn2O4Method for treating polluted water by ozone catalytic oxidation and removal of pollutants through rGO composite material | |
| CN108264127A (en) | A kind of method of nanoscale gallium vacuum ultraviolet photocatalytic degradation perfluoro caprylic acid | |
| CN108686692A (en) | A kind of photochemical catalyst and its preparation method and application of oxygen doping carbonitride | |
| CN111298821A (en) | Method for preparing novel iron-nitrogen-carbon catalyst by utilizing printing and dyeing wastewater flocculated sludge | |
| CN113351237A (en) | Floating type photocatalytic material, preparation method and treatment device for degrading antibiotic wastewater by using floating type photocatalytic material | |
| CN204079539U (en) | Photocatalytic disinfection reactor for disinfection of reclaimed water and rainwater | |
| CN112844437A (en) | Preparation method of high-crystalline carbon nitride photo-Fenton catalyst and application of high-crystalline carbon nitride photo-Fenton catalyst in degradation of emerging pollutants | |
| Bukhari et al. | Effects of Different Parameters on Photocatalytic Oxidation of Slaughterhouse Wastewater Using TiO | |
| CN106946312B (en) | Method for degrading drinking water disinfection by-product trichloroacetamide by utilizing photocatalytic cement-based material | |
| CN113426436A (en) | Preparation method of composite material and application of composite material in photocatalytic disinfection in water | |
| CN114950494B (en) | Photocatalytic material for catalytic degradation of tetracycline and preparation method thereof | |
| US20220194817A1 (en) | Device and method for degrading chlorinated hydrocarbons in polluted groundwater | |
| CN110642420B (en) | Ce/NaCo2O4/H2O2Method for purifying antibiotic wastewater by near-normal-temperature thermal catalysis | |
| CN110586139B (en) | Fe (III) cluster/bismuth oxyiodate composite photocatalytic material and preparation method and application thereof | |
| CN114180702A (en) | Advanced oxidation sterilization method for transition metal loaded biochar activated peroxymonosulfate | |
| CN111715261A (en) | G-C3N4Application of catalyst in degradation of organic dye in high-salt wastewater | |
| CN110642448A (en) | Purification method for recycling aquaculture wastewater | |
| CN116216665B (en) | Method for degrading trimethoprim by using advanced oxidation technology | |
| CN115028316B (en) | Deep denitrification and decarbonization process for landfill leachate based on porous microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210528 |