CN114570406A - Carbon nitride composite photocatalytic material for organic sewage remediation and preparation method thereof - Google Patents
Carbon nitride composite photocatalytic material for organic sewage remediation and preparation method thereof Download PDFInfo
- Publication number
- CN114570406A CN114570406A CN202210273837.8A CN202210273837A CN114570406A CN 114570406 A CN114570406 A CN 114570406A CN 202210273837 A CN202210273837 A CN 202210273837A CN 114570406 A CN114570406 A CN 114570406A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- sewage
- nitride composite
- photocatalytic material
- composite photocatalytic
- 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
- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000010865 sewage Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005067 remediation Methods 0.000 title description 4
- 239000004098 Tetracycline Substances 0.000 claims abstract description 18
- 229960002180 tetracycline Drugs 0.000 claims abstract description 18
- 229930101283 tetracycline Natural products 0.000 claims abstract description 18
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 18
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 18
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 claims description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000002060 nanoflake Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 abstract description 2
- 238000009395 breeding Methods 0.000 abstract 1
- 230000001488 breeding effect Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 10
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 229940088710 antibiotic agent Drugs 0.000 description 7
- 239000000975 dye Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B01J35/61—
-
- 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
-
- 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
- B01J37/12—Oxidising
-
- 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
- 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
- C02F2101/308—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
-
- 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
- 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
- C02F2305/10—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 relates to a carbon nitride composite photocatalytic material for repairing organic sewage and a preparation method thereof, wherein the composite material is nano-flaky g-C3N5Is a matrix, and Ag is tightly adhered to the surface of the matrix by an in-situ deposition method2CO3The specific preparation steps of the nano-particles are firstly to prepare nano-flaky g-C by a secondary calcination method3N5Then the Ag is titrated2CO3Compounding of nanoparticles to g-C3N5Preparing the carbon nitride composite photocatalytic material on the surface. The carbon nitride composite photocatalytic material prepared by the invention has the advantages of environmental protection, no toxicity, simple preparation process, low cost, large specific surface area, high pollutant removal efficiency and the like, and can effectively remove methylene blue and tetracycline in sewage. The invention can be used for sewage treatment in printing and dyeing, medical treatment, breeding and other industries, and provides effective reference for efficient repair of organic sewage.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and water treatment, and particularly relates to a carbon nitride composite photocatalytic material for organic sewage remediation and a preparation method thereof.
Background
Water pollution is a serious environmental problem facing the world, in which dye-containing sewage has a great influence on the environment and human health. It is reported that about 70 million tons of different kinds of synthetic dyes are discharged from various industries to an aqueous environment without any pretreatment every year, while methylene blue is one of the most common industrial azo dyes, and these dye sewage and its intermediate products have a complicated and stable aromatic structure, thus being difficult to be degraded and having carcinogenic effects, resulting in various dysfunctions of human bodies. In addition, the dye can block the irradiation of sunlight to influence the photosynthesis process of aquatic plants. Antibiotics have a great role in helping humans and animals to fight diseases, so that the antibiotics are widely applied to human and veterinary medicine, agricultural fields and the like, and tens of thousands of kinds of antibiotics such as tetracycline, ciprofloxacin and the like are consumed every year all over the world. However, due to the nature of antibiotics, they are only partially metabolically degraded in humans and animals, leaving large quantities of unmetabolized antibiotic residues to be discharged into the aquatic environment. Because most antibiotics have high chemical stability and strong bactericidal capacity, the traditional sewage treatment method can not effectively remove the antibiotics from the sewage, and the antibiotics also can accumulate in the environment and mutate bacteria and pathogens generating drug resistance, thereby causing serious threats to human bodies and ecological systems.
The conventional sewage treatment methods comprise physical flocculation precipitation, adsorption, ion exchange, biological treatment and the like, and the traditional treatment technologies have weak pollutant removal capacity and long treatment period and cannot completely and harmlessly treat pollutants. In the process of treating pollutants, the photocatalyst absorbs sunlight to generate electrons and holes, and active oxygen species are generated through a series of oxidation-reduction reactions to contact and react with organic pollutants, so that the pollutants are mineralized into CO2And H2And (O). Compared with the traditional treatment technology, the photocatalysis has the advantages of simple operation, rapid and thorough reaction, no secondary pollution and the like.
The Carbon Nitride (CN) material is a low cost, metal-free photocatalyst with visible light activity, and g-C3N5(2.2eV) as a novel carbon nitride materialg-C as widely reported before3N4(2.7eV), which has a lower band gap and a unique electronic band structure, thus exhibiting more excellent photocatalytic activity. In addition, researches show that different semiconductor materials are compounded, so that advantages of the different materials are complementary, the separation rate of electron-hole is improved, and the photocatalytic performance of the material is greatly improved.
The invention prepares the nano flaky g-C with excellent adsorption and photocatalytic performances by a thermal oxidation stripping method for the first time3N5Then with a narrow bandgap semiconductor Ag2CO3Compounding to prepare the carbon nitride composite photocatalyst for repairing organic sewage. The catalyst can effectively remove the methylene blue in the dye wastewater and the tetracycline in the antibiotic wastewater, and can provide an effective reference for the restoration of the organic wastewater.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a carbon nitride composite photocatalytic material for repairing organic sewage and a preparation method thereof.
The invention provides a nano flaky g-C3N5Is a matrix with Ag tightly adhered on its surface2CO3The method for preparing the carbon nitride composite photocatalytic material by the nano particles is characterized in that g-C is calcined twice3N5The nano-sheet structure with larger specific surface area is provided, so that Ag is obtained2CO3The nanoparticles are better loaded on the semiconductor material, so that more contact sites exist between the catalyst and pollutants, and the specific operation steps are as follows:
(1) weighing 5-30 g of 3-amino-1, 2, 4-triazole in a crucible with a cover, fully grinding the medicine by using a mortar rod, putting the crucible with the cover into a muffle furnace to keep the crucible in a semi-closed state, heating to 500-550 ℃ at a speed of 3-10 ℃/min, keeping the temperature for 3-4 hours, naturally cooling to room temperature in the muffle furnace, fully grinding to obtain brown powder in a block shape g-C3N5；
(2) Weighing the block g-C prepared in the step (1)3N50.5-5 g of powder is uniformly dispersed in a crucibleFully contacting the powder with air in a crucible, putting the crucible into a muffle furnace, keeping the crucible open, heating to 500-520 ℃ at a speed of 3-10 ℃/min, keeping the temperature for 3-4 hours, then heating to 520-550 ℃ at the same speed, keeping the temperature for 2-3 hours, and naturally cooling to room temperature in the muffle furnace to obtain light yellow powder which is nano-flaky g-C3N5；
(3) Weighing the nano flaky g-C prepared in the step (2)3N50.1-2 g of powder is placed in 20-200 mL of ultrapure water, stirred for 1-2 hours and subjected to ultrasonic treatment for 3-4 hours to obtain a suspension;
(4) weighing 0.0123-0.246 g of silver nitrate, dissolving in 5-40 mL of ultrapure water, adding into the suspension in the step (3), and stirring for 1-2 hours under a dark condition;
(5) weighing 0.006-0.1217 g of sodium bicarbonate, dissolving the sodium bicarbonate in 20-30 mL of ultrapure water, transferring the prepared sodium bicarbonate solution into a burette, controlling the titration speed to be 10-15 mL/h, dripping the sodium bicarbonate solution into the turbid liquid obtained in the step (4) under a dark condition, continuously stirring for 8-12 hours after the titration is finished, standing for 1-2 hours after the stirring is finished, and then washing and centrifuging for 3-5 times by using the ultrapure water and absolute ethyl alcohol;
(6) putting the material obtained in the step (5) into a vacuum drying oven, drying for 8-12 hours at 50-60 ℃, fully grinding the obtained yellow solid which is the carbon nitride composite photocatalytic material for use, and controlling the nano flaky g-C3N5The carbon nitride composite photocatalytic materials with different mass ratios can be prepared by using the silver nitrate and the sodium bicarbonate according to the steps.
The invention also provides a method for applying the novel carbon nitride composite photocatalytic material to repair organic sewage, which comprises the following steps:
adding the prepared material into methylene blue with the volume of 100-200 mL and the mass concentration of 40-60 mg/L and tetracycline solution with the mass concentration of 40-80 mg/L respectively, adding 0.5-1 g of the material into each liter of sewage, adding a magnetic rotor, performing dark treatment on a magnetic stirrer with the rotating speed of 800-1000 rpm for 30-40 minutes, reacting under the irradiation of visible light for 90-120 minutes, taking 2-4 mL of pollutant solution every 15-20 minutes, filtering the pollutant solution by a filter membrane, and then putting the pollutant solution into a colorimetric tube, and measuring the residual amounts of the methylene blue and the tetracycline in the sewage by an ultraviolet-visible spectrophotometry method.
Compared with the prior art, the invention has the advantages that:
1. the invention prepares the nano flaky g-C by a thermal oxidation stripping method for the first time3N5Its larger surface area is beneficial to Ag2CO3The nano particles are distributed on the surface, the contact area of the material and pollutants can be effectively increased, and the removal efficiency of the material to the pollutants is greatly improved.
2. The carbon nitride composite photocatalytic material is environment-friendly and nontoxic, has a simple preparation process, is convenient to operate, uses low raw materials, and is easy to realize industrial production.
3. The carbon nitride composite photocatalytic material has high photocatalytic efficiency on methylene blue and tetracycline in sewage, and provides a new way for efficient remediation of organic sewage.
Drawings
FIG. 1 is a digital photograph of a carbon nitride composite photocatalytic material according to example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the carbon nitride composite photocatalytic material according to example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1:
(1) weighing 5g of 3-amino-1, 2, 4-triazole in a crucible with a cover, fully grinding the medicine by using a mortar rod, putting the crucible with the cover into a muffle furnace to keep the crucible in a semi-closed state,heating to 500 deg.C at a rate of 3 deg.C/min, keeping the temperature for 3 hr, naturally cooling to room temperature in a muffle furnace, and grinding to obtain brown powder in the form of block g-C3N5；
(2) Weighing the block g-C prepared in (1)3N5Uniformly dispersing 0.8g of powder in a crucible to ensure that the powder is fully contacted with air, putting the crucible into a muffle furnace, keeping the crucible open, heating to 500 ℃ at the speed of 3 ℃/min, keeping the temperature for 3 hours, then heating to 520 ℃ at the same speed, keeping the temperature for 2 hours, naturally cooling to room temperature in the muffle furnace to obtain light yellow powder which is nano-flaky g-C3N5；
(3) Weighing the nano flaky g-C prepared in the step (2)3N50.3g of powder is put in 60mL of ultrapure water, stirred for 1 hour and ultrasonically treated for 4 hours to obtain suspension;
(4) weighing 0.0369g of silver nitrate, dissolving in 10mL of ultrapure water, adding into the suspension in the step (3), and stirring for 1 hour under the dark condition;
(5) weighing 0.01826g of sodium bicarbonate, dissolving the sodium bicarbonate in 25mL of ultrapure water, transferring the prepared sodium bicarbonate solution into a burette, controlling the titration speed to be 10mL/h, dripping the sodium bicarbonate solution into the suspension in the step (4) under the dark condition, continuing stirring for 12 hours after the titration is finished, standing for 1 hour after the stirring is finished, and then washing and centrifuging for 3 times by using the ultrapure water and absolute ethyl alcohol;
(6) drying the material obtained in the step (5) in a vacuum drying oven at 60 ℃ for 12 hours to obtain a yellow solid which is a carbon nitride composite photocatalytic material, fully grinding the yellow solid for use, and controlling the nano flaky g-C3N5The carbon nitride composite photocatalytic materials with different mass ratios can be prepared by using the silver nitrate and the sodium bicarbonate according to the steps;
the prepared carbon nitride composite photocatalytic material is shown in figure 1, and is yellow and powdery in appearance; the Ag-Ag alloy is placed under a scanning electron microscope, and the structure of the Ag-Ag alloy is shown in figure 22CO3The nanoparticles are well distributed in g-C3N5A surface.
Example 2:
the carbon nitride composite photocatalytic material is used for treating methylene blue in printing and dyeing wastewater, and comprises the following steps:
100mL of methylene blue solution with the concentration of 60mg/L is taken, the carbon nitride composite photocatalytic material prepared in the example 1 is added into a wastewater sample, the addition amount of each liter of wastewater is 1g, the reactor is placed on a magnetic stirrer with the rotation speed of 800rpm for reaction, the dark treatment is carried out for 30 minutes, samples are taken every 15 minutes, then a 300W xenon lamp (provided with a filter with the lambda of less than 400 nm) is used as a visible light source for photocatalytic reaction, the illumination lasts for 90 minutes totally, and the samples are taken every 15 minutes. The residual concentration of methylene blue in the sample was determined using ultraviolet spectrophotometry at a wavelength of 664nm and the calculated removal results are shown in table 1.
Table 1: removal rate of carbon nitride composite photocatalytic material to methylene blue in different time
| Time (minutes) | 15 | 30 | 45 | 60 | 75 | 90 | 105 | 120 |
| Removal Rate (%) | 37.7 | 41.4 | 55.4 | 69.1 | 78.8 | 86.7 | 92.1 | 97.0 |
As can be seen from Table 1, with the increase of the treatment time of the carbon nitride composite photocatalytic material on the methylene blue wastewater, the removal rate of the methylene blue is gradually increased, and the removal rate reaches 97% after the visible light is irradiated for 90 minutes, which indicates that the material can effectively remove the methylene blue in the wastewater.
Example 3:
the carbon nitride composite photocatalytic material is used for treating tetracycline in sewage, and comprises the following steps:
taking 100mL of tetracycline solution with the concentration of 40mg/L, adding the carbon nitride composite photocatalytic material prepared in example 1 into a wastewater sample, wherein the addition amount of the tetracycline solution in each liter of wastewater is 0.5g, placing a reactor on a magnetic stirrer with the rotation speed of 800rpm for reaction, performing dark treatment for 30 minutes, sampling once every 15 minutes, then performing photocatalytic reaction by taking a 300W xenon lamp (provided with an optical filter with lambda <400 nm) as a visible light source, and performing light irradiation for 100 minutes totally, and sampling once every 20 minutes. The residual concentration of tetracycline in the sample was determined by uv spectrophotometry at 356nm and the calculated removal results are shown in table 2.
Table 2: removal rate of carbon nitride composite photocatalytic material to tetracycline in different time
| Time (minutes) | 15 | 30 | 50 | 70 | 90 | 110 | 130 |
| Removal Rate (%) | 2.9 | 4.6 | 82.6 | 89.6 | 95.4 | 96.3 | 98.1 |
As can be seen from the table 2, the removal rate of tetracycline is gradually increased along with the increase of the treatment time of the carbon nitride composite photocatalytic material on the tetracycline sewage, and the removal rate reaches 98.1% after the visible light irradiation for 100 minutes, which indicates that the material can effectively remove the tetracycline in the sewage.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and various process schemes having no substantial difference from the concept of the present invention are within the protection scope of the present invention.
Claims (2)
1. A carbon nitride composite photocatalytic material for repairing organic sewage, which is characterized in that,the carbon nitride composite photocatalytic material is in a nano-sheet shape of g-C3N5Is a substrate loaded with Ag2CO3The preparation method of the nano-particles and the carbon nitride composite photocatalytic material comprises the following steps:
(1) weighing 5-30 g of 3-amino-1, 2, 4-triazole in a crucible with a cover, fully grinding the medicine by using a mortar rod, putting the crucible with the cover into a muffle furnace to keep the crucible in a semi-closed state, heating to 500-550 ℃ at a speed of 3-10 ℃/min, keeping the temperature for 3-4 hours, naturally cooling to room temperature in the muffle furnace, fully grinding to obtain brown powder in a block shape g-C3N5；
(2) Weighing the block g-C prepared in the step (1)3N5Uniformly dispersing 0.5-5 g of powder in a crucible to enable the powder to be fully contacted with air, putting the crucible into a muffle furnace, keeping the crucible in an open state, heating to 500-520 ℃ at a speed of 3-10 ℃/min, keeping the temperature for 3-4 hours, then heating to 520-550 ℃ at the same speed, keeping the temperature for 2-3 hours, and naturally cooling to room temperature in the muffle furnace to obtain light yellow powder which is nano-flaky g-C3N5；
(3) Weighing the nano flaky g-C prepared in the step (2)3N50.1-2 g of powder is placed in 20-200 mL of ultrapure water, stirred for 1-2 hours and subjected to ultrasonic treatment for 3-4 hours to obtain a suspension;
(4) weighing 0.0123-0.246 g of silver nitrate, dissolving in 5-40 mL of ultrapure water, adding into the suspension in the step (3), and stirring for 1-2 hours under a dark condition;
(5) weighing 0.006-0.1217 g of sodium bicarbonate, dissolving the sodium bicarbonate in 20-30 mL of ultrapure water, transferring the prepared sodium bicarbonate solution into a burette, controlling the titration speed to be 10-15 mL/h, dripping the sodium bicarbonate solution into the turbid liquid obtained in the step (4) under a dark condition, continuously stirring for 8-12 hours after the titration is finished, standing for 1-2 hours after the stirring is finished, and then washing and centrifuging for 3-5 times by using the ultrapure water and absolute ethyl alcohol;
(6) putting the material obtained in the step (5) into a vacuum drying oven, drying for 8-12 hours at 50-60 ℃, fully grinding the obtained yellow solid which is the carbon nitride composite photocatalytic material for use, and controlling the nanoFlake g-C3N5The carbon nitride composite photocatalytic material with different mass ratios can be prepared according to the steps by using the silver nitrate and the sodium bicarbonate.
2. The method for removing methylene blue and tetracycline from sewage by using the carbon nitride composite photocatalytic material as described in claim 1, wherein the method comprises the following steps: respectively taking a certain amount of methylene blue sewage and tetracycline sewage, wherein the mass concentration of the methylene blue sewage is 0.04-0.06 g/L, and the mass concentration of the tetracycline sewage is 0.04-0.08 g/L; adding a certain amount of carbon nitride composite photocatalytic material into sewage, wherein the addition amount of the carbon nitride composite photocatalytic material in each liter of sewage is 0.5-1 g by weight, reacting for 2-3 hours on a magnetic stirrer with the rotating speed of 800-1000 rpm, performing dark treatment for 30-40 minutes, then adding light for reaction, sampling once at intervals, filtering by a filter membrane, then putting into a colorimetric tube, and measuring the residual amounts of methylene blue and tetracycline in the sewage by an ultraviolet-visible spectrophotometry method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210273837.8A CN114570406A (en) | 2022-03-19 | 2022-03-19 | Carbon nitride composite photocatalytic material for organic sewage remediation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210273837.8A CN114570406A (en) | 2022-03-19 | 2022-03-19 | Carbon nitride composite photocatalytic material for organic sewage remediation and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114570406A true CN114570406A (en) | 2022-06-03 |
Family
ID=81777382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210273837.8A Pending CN114570406A (en) | 2022-03-19 | 2022-03-19 | Carbon nitride composite photocatalytic material for organic sewage remediation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114570406A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155589A (en) * | 2022-08-22 | 2022-10-11 | 成都工业学院 | Photocatalyst capable of activating sulfite to degrade tetracycline and preparation method and application thereof |
| CN115501893A (en) * | 2022-09-29 | 2022-12-23 | 塔里木大学 | Novel g-C 3 N 5 Preparation method of-BiOCl heterojunction photocatalyst |
-
2022
- 2022-03-19 CN CN202210273837.8A patent/CN114570406A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155589A (en) * | 2022-08-22 | 2022-10-11 | 成都工业学院 | Photocatalyst capable of activating sulfite to degrade tetracycline and preparation method and application thereof |
| CN115155589B (en) * | 2022-08-22 | 2023-07-21 | 成都工业学院 | Photocatalyst capable of activating sulfite to degrade tetracycline, and preparation method and application thereof |
| CN115501893A (en) * | 2022-09-29 | 2022-12-23 | 塔里木大学 | Novel g-C 3 N 5 Preparation method of-BiOCl heterojunction photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hasanpour et al. | Photocatalytic performance of aerogels for organic dyes removal from wastewaters: Review study | |
| Wong et al. | Wet chemically synthesized ZnO structures for photodegradation of pre-treated palm oil mill effluent and antibacterial activity | |
| CN114570406A (en) | Carbon nitride composite photocatalytic material for organic sewage remediation and preparation method thereof | |
| Qayum et al. | Efficient decontamination of multi-component wastewater by hydrophilic electrospun PAN/AgBr/Ag fibrous membrane | |
| CN110538672A (en) | Composite visible light response photocatalyst material and preparation method and application thereof | |
| CN109603882B (en) | Method for treating organic pollutants and carrying out photocatalytic sterilization by using modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst | |
| CN109317183B (en) | Boron nitride quantum dot/ultrathin porous carbon nitride composite photocatalytic material and preparation method and application thereof | |
| CN110124655B (en) | Zinc oxide/carbon quantum dot composite photocatalyst and preparation method and application thereof | |
| CN109289884A (en) | A kind of silver-silver orthophosphate-tungstic acid tri compound nano-photocatalyst material and its preparation method and application | |
| CN112337459A (en) | Preparation method of bismuth tungstate composite photocatalyst | |
| CN108479772B (en) | Gold-doped nano zinc oxide composite material, preparation method thereof and application thereof in photocatalytic degradation of tetracycline | |
| CN104841463A (en) | BiOCl/P25 composite photocatalyst, and preparation method and applications thereof | |
| CN108325516A (en) | A kind of BiVO4/InVO4Hetero-junctions catalyst and its preparation method and application | |
| CN110182888B (en) | Photocatalytic reaction device and process for treating rose bengal B high-salinity wastewater | |
| Das et al. | ZrO2@ chitosan composite for simultaneous photodegradation of three emerging contaminants and antibacterial application | |
| CN115138369A (en) | Molybdenum trioxide composite material and preparation method and application thereof | |
| CN108514889A (en) | A kind of fluorescence doped carbon nanometer N, B-CDs catalyst and its preparation method and application | |
| CN113231059B (en) | Composite catalyst for electron beam sewage treatment and preparation method and application thereof | |
| Wang et al. | Synthesis of CuO@ TiO2 nanocomposite and its photocatalytic and electrochemical properties. Application for treatment of azo dyes in industrial wastewater | |
| Rajapandi et al. | Ziziphus mauritiana-derived nitrogen-doped biogenic carbon dots: Eco-friendly catalysts for dye degradation and antibacterial applications | |
| CN115159627B (en) | Flowing water driven molybdenum disulfide/carbon felt flexible piezoelectric material, preparation method thereof and application of material to degradation of antibiotics | |
| CN106582500B (en) | Adsorbable degradation Cr (VI) diatomite composite material of one kind and preparation method thereof | |
| CN109569681A (en) | Silver nanoparticles loaded and the sodium tantalate composite photo-catalyst of graphite phase carbon nitride nanometer sheet and its preparation method and application | |
| CN114797814A (en) | Preparation method of modified natural wood material and application of modified natural wood material in sewage treatment | |
| CN109420497A (en) | A kind of InVO4-AgVO3 hetero-junctions catalyst and its preparation method and application |
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 |