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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B01J37/12—Oxidising
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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.
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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 |
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Publication number | Priority date | Publication date | Assignee | Title |
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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 |
CN115501893B (en) * | 2022-09-29 | 2024-07-16 | 塔里木大学 | g-C3N5Preparation method of BiOCl heterojunction photocatalyst |
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