CN116726969A - Modified graphite phase carbon nitride photocatalyst and preparation method and application thereof - Google Patents
Modified graphite phase carbon nitride photocatalyst and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 141
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- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims description 3
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
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Abstract
The preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps: (1) Respectively placing melamine and cyanuric acid powder into deionized water for mixing, stirring and drying to obtain a white mixed solid; (2) Calcining the white mixed solid in a muffle furnace, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder; (3) Adding the pale yellow product powder, cobalt salt and gadolinium salt into deionized water, oscillating and drying to obtain a mixed solid; (4) Grinding the mixed solid, placing the ground mixed solid into a tube furnace for high-temperature polymerization, and cooling to room temperature after the reaction is finished to obtain powder; (5) And (3) alternately washing the powder with absolute ethyl alcohol and deionized water to remove impurities, and finally drying to obtain the modified graphite-phase carbon nitride photocatalyst. The modified graphite phase carbon nitride photocatalyst can efficiently degrade antibiotics, has good photocatalytic effect on antibiotics, can realize efficient removal effect under a low-power light source, has simple preparation process and low cost, and can be produced in a large scale.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a modified graphite phase carbon nitride photocatalyst, and a preparation method and application thereof.
Background
Graphite carbonitride (g-C) 3 N 4 ) The metal-free semiconductor photocatalyst has the band gap of 2.7eV, excellent chemical stability and thermal stability, no harm to human body, easy modification and the like, and is considered as an ideal candidate material in the field of photocatalysis. However, it also has disadvantages such as low production yields, smaller surface area, fewer active sites, and a narrower visible response range (l<450 nm) and limited light absorption, the photo-generated electron-hole pairs are easy to be rapidly compounded, and the research on the modified graphite phase carbon nitride photocatalyst material is not yet reported, so how to provide a modified graphite phase carbon nitride photocatalyst material which is simple to prepare, large in surface area, stable and efficient is a technical problem to be solved by the technicians in the field.
Antibiotics have been widely used as clinical therapeutics for the treatment of infections in humans and animals. Excessive use of antimicrobial agents leads to increased antibiotic residues in wastewater and natural water environments, which present serious health risks and environmental problems. Typically, untreated wastewater from hospitals, pharmaceutical industry, aquaculture and animal husbandry contains a large amount of antibiotic residues. Migration and transformation of these antibiotics and their metabolites inevitably leads to serious ecosystem risks. The risk of the ecosystem caused by antibiotic contamination can be divided into the direct risk of toxic effects on organisms, or the potential risk of induction of Antibiotic Resistance Genes (ARGs) and alteration of microbial community structure. The toxic effects of antibiotics can lead to a disturbed microbial community, disturbing ecological balance. Even at low concentrations, antibiotics and their metabolites exhibit biological toxicity and may produce synergistic toxic effects with other co-existing contaminants such as microplastic and heavy metals. Antibiotic residues in particular in soil and aquatic environments reach the bodies of animals and humans through food (e.g. vegetables, fish) and drinking water. Therefore, studies on the removal of antibiotics in water environments are not slow, and studies on the removal of antibiotics in environments are necessary.
Different physicochemical methods are currently used by researchers to purify wastewater containing antibiotics. Membrane filtration, adsorption, chemical oxidation, electrocatalytic oxidation, coagulation flocculation, microwave-assisted catalysis, photocatalysis, etc. are all used as the main means for treating antibiotics. Compared with other traditional water treatment technologies, the photocatalysis technology has the advantages of high efficiency, no subsequent process, environmental protection and the like under the drive of illumination (such as sunlight and artificial light sources), however, the high-power light source with 300w,500w and even 1000w is usually adopted as the light source with photocatalysis function at present, the temperature generated under the illumination of the high-power light source can reach 100-200 ℃, the requirements on photocatalysis equipment are higher, the energy consumption is higher, and the application of the photocatalysis technology is hindered. Therefore, it is necessary to explore a photocatalysis effect under a low-power light source, and provide a new idea for photocatalysis application, energy conservation and environmental protection.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified graphite phase carbon nitride photocatalyst, a preparation method and application thereof, and aims to obtain the modified graphite phase carbon nitride photocatalyst which is simple to prepare, rich in pore structure and high in photocatalytic efficiency by utilizing rare earth modified graphite phase carbon nitride.
In order to achieve the above object, the present invention is specifically as follows:
the preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively placing melamine and cyanuric acid powder into deionized water for mixing, stirring and drying to obtain a white mixed solid;
(2) Calcining the white mixed solid in a muffle furnace, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder;
(3) Adding the pale yellow product powder obtained in the step (2) and cobalt salt and gadolinium salt into deionized water for dissolution, oscillating and drying to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), placing the ground mixed solid in a tube furnace for high-temperature pyrolysis reaction, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder obtained in the step (4) with absolute ethyl alcohol and deionized water to remove impurities, and finally drying to obtain the modified graphite-phase carbon nitride photocatalyst.
Further, the mass ratio of the melamine to the cyanuric acid powder to the deionized water in the step (1) is 1:1:5, stirring by magnetic force for 8-12 h; the temperature of the drying is 70-100 ℃ and the drying time is 10-12 h.
Further, the calcination temperature of the muffle furnace in the step (2) is 350-550 ℃, and the calcination time is 2-4 h.
Further, the cobalt salt in the step (3) is cobalt nitrate hexahydrate, the gadolinium salt is gadolinium nitrate hexahydrate, the oscillation time is 30-60min, the drying temperature is 70-100 ℃, and the drying time is 10-12 h.
Further, the mass ratio of the light yellow product powder in the step (4) to cobalt salt and gadolinium salt is 1:0.01 to 0.09: 0.04-0.20, the heating rate of the tube furnace is 10+/-1 ℃/min, the high-temperature pyrolysis temperature in the tube furnace is 300-500 ℃, and the high-temperature pyrolysis time in the tube furnace is 1-4 h.
Further, the content of the absolute ethyl alcohol in the step (5) is more than or equal to 99.7%, the times of alternate washing are 3-7, the drying temperature is 70-100 ℃, and the drying time is 10-12 h.
The modified graphite phase carbon nitride photocatalyst is obtained by the preparation method of the modified graphite phase carbon nitride photocatalyst.
Further, the modified graphite phase carbon nitride photocatalyst is applied to catalytic degradation of antibiotics.
Further, the antibiotic is any one or the combination of more than two of ciprofloxacin hydrochloride, enrofloxacin, levofloxacin, norfloxacin, tetracycline and aureomycin.
Further, the method comprises the following steps: the modified graphite phase carbon nitride is prepared according to the following proportion of 10 to 80:1 into antibiotic wastewater with the concentration of 10-200 mg/L for stirring for 30-60min, carrying out catalytic degradation under the irradiation of an LED lamp with the power of 30w and the wavelength of 450-470nm, and filtering the liquid obtained after the reaction for 20-200 min by using a filter membrane with the aperture of 0.22-0.45 mu m to obtain the water sample after photocatalysis.
THE ADVANTAGES OF THE PRESENT INVENTION
1. The invention utilizes metal cobalt and rare earth metal gadolinium to modify to obtain the modified graphite phase carbon nitride photocatalyst with large specific surface area, more active sites and good photocatalytic performance, further expands the specific surface area or changes the chemical composition of the surface of the modified graphite phase carbon nitride photocatalyst, thereby improving the photocatalytic capability of the modified graphite phase carbon nitride photocatalyst, realizing higher removal effect under a low-power light source, widening the application range of rare earth elements in the field of photocatalytic materials, simultaneously being beneficial to reducing the use of electric energy, providing a more energy-saving and environment-friendly method for treating antibiotic wastewater, and having the characteristics of simple preparation process flow, low preparation cost and huge mass production.
2. The modified graphite phase carbon nitride photocatalyst prepared by the invention has the advantages of increased specific surface area, increased active sites, acceleration of separation of electron and hole pairs, high photocatalytic activity and good recycling performance, and the photocatalytic efficiency of the modified graphite phase carbon nitride photocatalyst is about 4 times that of the original graphite phase carbon nitride.
3. The modified graphite phase carbon nitride prepared by the invention is applied to the catalytic degradation of antibiotics in water, can efficiently degrade the antibiotics under the LED lamp with the power of 30w and the wavelength range of 450-470nm, has good photocatalytic effect on the antibiotics, and is a more environment-friendly mode compared with the currently commonly used 500w high-power light source, the use of a 30w low-power light source can reduce the influence of temperature on the photocatalytic process on one hand; on the other hand, the use of low-power light source for photocatalysis can reduce the use of electric energy, and a more energy-saving way is provided for photocatalytic degradation of antibiotic wastewater. In addition, the modified graphite phase carbon nitride can also be used for degrading various compounds in water by photocatalysis, so that the way of controlling the antibiotic pollution in the water body is widened, a novel method is provided for treating the antibiotic wastewater, and the way of treating the antibiotic wastewater is widened.
Drawings
Fig. 1 is an SEM image of the raw graphite phase carbon nitride powder and the modified graphite phase carbon nitride powder prepared in example 1.
Fig. 2 is an XRD pattern of the modified graphite phase carbon nitride prepared in example 1.
FIG. 3 is a UV-Vis diagram of modified graphite phase carbon nitride prepared in example 1.
Fig. 4 shows the degradation efficiency of the modified graphite-phase carbon nitride prepared in example 1 on ciprofloxacin hydrochloride under an LED lamp.
Fig. 5 shows the recycling effect of the modified graphite-phase carbon nitride prepared in example 2 in photocatalytic degradation of ciprofloxacin hydrochloride under an LED lamp.
Fig. 6 is a graph showing the detection of ciprofloxacin hydrochloride degradation efficiency under an LED lamp for the modified graphite-phase carbon nitride prepared in example 1, example 4, and example 5 in example 6.
Fig. 7 is a graph showing the detection of ciprofloxacin hydrochloride degradation efficiency under an LED lamp for the modified graphite-phase carbon nitrides prepared in example 1, example 7 and example 8 in example 9.
FIG. 8 is the effect of different preparation temperatures on the photocatalytic performance of the modified graphite phase carbon nitride catalyst of example 1.
FIG. 9 is a graph showing the effect of different calcination times on the photocatalytic performance of the modified graphite phase carbon nitride catalyst of example 1.
Fig. 10 is an effect of initial concentration on photocatalytic performance of the modified graphite phase carbon nitride catalyst of example 1.
FIG. 11 is an effect of pH of the initial solution on photocatalytic performance of the modified graphite phase carbon nitride catalyst of example 1.
Fig. 12 is an effect of photocatalytic light source power on photocatalytic performance of the modified graphite phase carbon nitride catalyst of example 1.
Fig. 13 is a graph showing the main radical groups generated in the low power photocatalytic reaction of the modified graphite phase carbon nitride catalyst of example 1.
Detailed Description
The invention is further illustrated in the following drawings and detailed description, which are not intended to limit the scope of the invention.
Example 1
The preparation method of the modified graphite phase carbon nitride photocatalyst provided in the embodiment 1 comprises the following steps:
(1) Respectively putting 2g of melamine and 2g of cyanuric acid powder into 100ml of deionized water, mixing, magnetically stirring for 12 hours, uniformly mixing, and drying at 80 ℃ for 12 hours to obtain a white mixed solid;
(2) And (3) placing the white mixed solid in a muffle furnace with the calcination temperature of 550 ℃ for calcination for 4 hours, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder, wherein the pale yellow product powder is original graphite phase carbon nitride powder.
(3) Adding 1g of the original graphite phase carbon nitride powder obtained in the step (2), 0.12g of gadolinium nitrate hexahydrate and 0.05g of cobalt nitrate hexahydrate into 50ml of deionized water for dissolution, oscillating for 30min, and drying at 80 ℃ for 12h to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), then placing the ground mixed solid in a tube furnace, heating to 450 ℃ at a heating rate of 10+/-1 ℃/min, keeping a pyrolysis reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder in the step (4) with absolute ethyl alcohol and deionized water for 3-7 times to remove impurities, wherein the content of the absolute ethyl alcohol is more than or equal to 99.7%, and finally drying the powder at the temperature of 70-100 ℃ for 10-12 hours to obtain the modified graphite phase carbon nitride photocatalyst.
The application of the modified graphite phase carbon nitride photocatalyst obtained by the preparation method in the catalytic degradation of antibiotics is any one or the combination of more than two of ciprofloxacin hydrochloride, enrofloxacin, levofloxacin, norfloxacin, tetracycline and aureomycin, and the application of the modified graphite phase carbon nitride photocatalyst in the catalytic degradation of antibiotics comprises the following steps: the modified graphite phase carbon nitride is prepared according to the following proportion of 10 to 80:1 into antibiotic wastewater with the concentration of 10-200 mg/L for stirring for 30-60min, carrying out catalytic degradation under the irradiation of an LED lamp with the power of 30w and the wavelength of 450-470nm, and filtering the liquid obtained after the reaction for 20-200 min by using a filter membrane with the aperture of 0.22-0.45 mu m to obtain the water sample after photocatalysis.
SEM characterization of the original graphite phase carbon nitride powder obtained in the step (2) and the modified graphite phase carbon nitride photocatalyst obtained in the step (5) is shown in figure 1, wherein (a) and (b) are scanning electron microscope images of the original graphite phase carbon nitride powder; (c) And (d) scanning electron microscope image of modified graphite phase carbon nitride photocatalyst.
From the portions (a) and (b) in fig. 1, it can be seen that the original graphite phase carbon nitride powder exhibits a rod-like morphology and has a large specific surface area and a loosely crosslinked three-dimensional structure. From the portions (c) and (d) of fig. 2, it can be seen that the morphology of the modified graphite-phase carbon nitride photocatalyst prepared in step (5) does not change greatly as compared with the original graphite-phase carbon nitride powder prepared in step (1), but it shows more pores and a larger specific surface area, and the surface is smoother and has no obvious ravines. The porous three-dimensional structure is provided, and more active sites can be generated due to the large specific surface area, so that the pollutant is subjected to photocatalytic degradation in the porous three-dimensional structure of the modified graphite phase carbon nitride, and the photocatalytic degradation capacity of the pollutant is improved.
XRD characterization is carried out on the original graphite phase carbon nitride powder prepared in the step (2) and the modified graphite phase carbon nitride photocatalyst prepared in the step (5), and the test result is shown in figure 2:
it can be seen that the (002) crystal face characteristic peak of the original graphite phase carbon nitride material is obvious, and the modified graphite phase carbon nitride photocatalyst has no obvious characteristic peak of cobalt and gadolinium, because of low content, amorphous form, small particle size (less than or equal to 10 nm) and high dispersibility.
3. The original graphite phase carbon nitride material prepared in the step (2) and the modified graphite phase carbon nitride photocatalyst prepared in the step (5) are respectively subjected to UV-Vis characterization, and the test results are shown in figure 3:
it can be seen that the modified graphite phase carbon nitride photocatalyst obtained in the step (5) has obvious red shift in the absorption wavelength region with the original graphite phase carbon nitride material prepared in the step (2), because the photocatalytic performance of the original graphite phase carbon nitride material loaded with cobalt and gadolinium is obviously improved.
Example 2
The original graphite phase carbon nitride material prepared in the step (2) in the example 1 and the modified graphite phase carbon nitride photocatalyst prepared in the step (5) are subjected to photocatalysis performance research, and specifically comprise the following steps:
80mg of the original graphite phase carbon nitride material and 80mg of the modified graphite phase carbon nitride photocatalyst are respectively added into two bottles, and the concentration of 100mL is 20 mg.L -1 In the dark, for 30 minutes to reach the adsorption-desorption equilibrium. Then, the target solution was irradiated with simulated light from a 30w power LED lamp, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was measured with an ultraviolet-visible spectrophotometer at 271nm wavelength.
As shown in fig. 4, it can be seen that the photocatalytic degradation efficiency of ciprofloxacin hydrochloride by the modified graphite-phase carbon nitride photocatalyst irradiated under the LED lamp with the power of 30w for 150 minutes reaches about 85%, and compared with the original graphite-phase carbon nitride material prepared in step (2) of example 1, the photocatalytic efficiency of the modified graphite-phase carbon nitride photocatalyst prepared in step (5) is remarkably improved.
Example 3
The modified graphite phase carbon nitride photocatalyst prepared in the step (5) of the example 1 is subjected to the study of the cycle performance, and comprises the following steps:
the modified graphite phase carbon nitride photocatalyst reacted in the example 2 is recovered, the modified graphite phase carbon nitride photocatalyst is alternately washed with deionized water and ethanol for 3 to 7 times, and is dried for 12 hours at the temperature of 80 ℃ for standby, and the above-mentioned process is repeated for the recovered modified graphite phase carbon nitride photocatalyst, and the recycling effect is shown in figure 5. After the cycle is carried out for 5 times, the photocatalytic degradation efficiency of the modified graphite phase carbon nitride photocatalyst to ciprofloxacin hydrochloride still reaches more than 80%, which proves that the prepared modified graphite phase carbon nitride photocatalyst has excellent stability.
Example 4
The preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively putting 2g of melamine and 2g of cyanuric acid powder into 100ml of deionized water, mixing, magnetically stirring for 12 hours, uniformly mixing, and drying at 80 ℃ for 12 hours to obtain a white mixed solid;
(2) And (3) placing the white mixed solid in a muffle furnace with the calcination temperature of 550 ℃ for calcination for 4 hours, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder, wherein the pale yellow product powder is original graphite phase carbon nitride powder.
(3) Adding 1g of the original graphite phase carbon nitride powder obtained in the step (2), 0.04g of gadolinium nitrate hexahydrate and 0.05g of cobalt nitrate hexahydrate into 50ml of deionized water for dissolution, oscillating for 30min, and drying at 80 ℃ for 12h to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), then placing the ground mixed solid in a tube furnace, heating to 450 ℃ at a heating rate of 10+/-1 ℃/min, keeping a pyrolysis reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder in the step (4) with absolute ethyl alcohol and deionized water for 3-7 times to remove impurities, wherein the content of the absolute ethyl alcohol is more than or equal to 99.7%, and finally drying the powder at the temperature of 70-100 ℃ for 10-12 hours to obtain the modified graphite phase carbon nitride photocatalyst.
Example 5
The preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively putting 2g of melamine and 2g of cyanuric acid powder into 100ml of deionized water, mixing, magnetically stirring for 12 hours, uniformly mixing, and drying at 80 ℃ for 12 hours to obtain a white mixed solid;
(2) And (3) placing the white mixed solid in a muffle furnace with the calcination temperature of 550 ℃ for calcination for 4 hours, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder, wherein the pale yellow product powder is original graphite phase carbon nitride powder.
(3) Adding 1g of the original graphite phase carbon nitride powder obtained in the step (2), 0.20g of gadolinium nitrate hexahydrate and 0.05g of cobalt nitrate hexahydrate into 50ml of deionized water for dissolution, oscillating for 30min, and drying at 80 ℃ for 12h to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), then placing the ground mixed solid in a tube furnace, heating to 450 ℃ at a heating rate of 10+/-1 ℃/min, keeping a pyrolysis reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder in the step (4) with absolute ethyl alcohol and deionized water for 3-7 times to remove impurities, wherein the content of the absolute ethyl alcohol is more than or equal to 99.7%, and finally drying the powder at the temperature of 70-100 ℃ for 10-12 hours to obtain the modified graphite phase carbon nitride photocatalyst.
Example 6
The modified graphite phase carbon nitride photocatalyst prepared in the step (5) of the example 1 is recorded as 0.12Gd-0.05Co-CN; the modified graphite-phase carbon nitride photocatalyst prepared in the step (5) of example 4 is denoted as 0.04Gd-0.05Co-CN; the modified graphite phase carbon nitride photocatalyst prepared in the step (5) of example 5 is recorded as 0.20Gd-0.05Co-CN for photocatalysis performance research, and specifically comprises the following steps:
80mg0.04 Gd-0.05Co-CN, 80mg0.12Gd-0.05Co-CN and 80mg0.20 Gd-0.05Co-CN are added to the same three bottles respectively, and the concentration of 100mL is 20mg.L -1 In the dark, for 30 minutes to reach the adsorption-desorption equilibrium. Then using a 30w power LED lamp to simulate illumination, irradiating the target solution, collecting samples every 30 minutes, filtering through a 0.45 mu m microporous membrane, and then using an ultraviolet-visible spectrophotometer to test ciprofloxacin hydrochloride in the solution at 271nm wavelengthConcentration.
As shown in fig. 6, it can be seen that after the LED lamp with power of 30w is irradiated for 150 minutes, the photocatalytic degradation efficiencies of 0.04Gd-0.05Co-CN, 0.12Gd-0.05Co-CN and 0.20Gd-0.05Co-CN on ciprofloxacin hydrochloride are 80.62%, 84.98% and 72.36%, respectively, which indicates that the 0.12Gd-0.05Co-CN has good photocatalytic degradation performance. The reason is that only a small amount of gadolinium exists in the 0.04Gd-0.05Co-CN, and less gadolinium is loaded on the surface of graphite phase carbon nitride, so that active sites are fewer, and the photocatalytic efficiency is reduced. The aggregation of excessive gadolinium loading on the graphite phase carbon nitride inhibits light absorption and photocatalytic activity and even shields the active sites of the graphite phase carbon nitride.
Example 7
The preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively putting 2g of melamine and 2g of cyanuric acid powder into 100ml of deionized water, mixing, magnetically stirring for 12 hours, uniformly mixing, and drying at 80 ℃ for 12 hours to obtain a white mixed solid;
(2) And (3) placing the white mixed solid in a muffle furnace with the calcination temperature of 550 ℃ for calcination for 4 hours, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder, wherein the pale yellow product powder is original graphite phase carbon nitride powder.
(3) Adding 1g of the original graphite phase carbon nitride powder obtained in the step (2), 0.12g of gadolinium nitrate hexahydrate and 0.01g of cobalt nitrate hexahydrate into 50ml of deionized water for dissolution, oscillating for 30min, and drying at 80 ℃ for 12h to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), then placing the ground mixed solid in a tube furnace, heating to 450 ℃ at a heating rate of 10+/-1 ℃/min, keeping a pyrolysis reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder in the step (4) with absolute ethyl alcohol and deionized water for 3-7 times to remove impurities, wherein the content of the absolute ethyl alcohol is more than or equal to 99.7%, and finally drying the powder at the temperature of 70-100 ℃ for 10-12 hours to obtain the modified graphite phase carbon nitride photocatalyst.
Example 8
The preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively putting 2g of melamine and 2g of cyanuric acid powder into 100ml of deionized water, mixing, magnetically stirring for 12 hours, uniformly mixing, and drying at 80 ℃ for 12 hours to obtain a white mixed solid;
(2) And (3) placing the white mixed solid in a muffle furnace with the calcination temperature of 550 ℃ for calcination for 4 hours, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder, wherein the pale yellow product powder is original graphite phase carbon nitride powder.
(3) Adding 1g of the original graphite phase carbon nitride powder obtained in the step (2), 0.12g of gadolinium nitrate hexahydrate and 0.09g of cobalt nitrate hexahydrate into 50ml of deionized water for dissolution, oscillating for 30min, and drying at 80 ℃ for 12h to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), then placing the ground mixed solid in a tube furnace, heating to 450 ℃ at a heating rate of 10+/-1 ℃/min, keeping a pyrolysis reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder in the step (4) with absolute ethyl alcohol and deionized water for 3-7 times to remove impurities, wherein the content of the absolute ethyl alcohol is more than or equal to 99.7%, and finally drying the powder at the temperature of 70-100 ℃ for 10-12 hours to obtain the modified graphite phase carbon nitride photocatalyst.
Example 9
The modified graphite phase carbon nitride photocatalyst prepared in the step (5) of the example 1 is recorded as 0.12Gd-0.05Co-CN; the modified graphite-phase carbon nitride photocatalyst prepared in the step (5) of example 7 is denoted as 0.12Gd-0.01Co-CN; the modified graphite phase carbon nitride photocatalyst prepared in the step (5) of example 8 is recorded as 0.12Gd-0.09Co-CN for photocatalysis performance research, and specifically comprises the following steps:
80mg0.12Gd-0.01Co-CN, 80mg0.12Gd-0.05Co-CN, 80mg0.12Gd-0.09Co-CN were added to the same 100mL of three bottles at a concentration of 20mg.L -1 Stirring in the dark in ciprofloxacin hydrochloride aqueous solutionStirred for 30 minutes to reach adsorption-desorption equilibrium. Then, the target solution was irradiated with simulated light from a 30w power LED lamp, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was measured with an ultraviolet-visible spectrophotometer at 271nm wavelength.
As shown in fig. 7, it can be seen that after the LED lamp with power of 30w is irradiated for 150 minutes, the photocatalytic degradation efficiencies of 0.12Gd-0.01Co-CN, 0.12Gd-0.05Co-CN and 0.12Gd-0.09Co-CN on ciprofloxacin hydrochloride are 73.43%, 84.98% and 84.94%, respectively, which indicates that the 0.12Gd-0.05Co-CN has good photocatalytic degradation performance. The reason is that less cobalt loading on the graphite phase carbon nitride surface results in fewer active sites, which reduces photocatalytic efficiency. Excessive cobalt loading on the graphite phase carbon nitride aggregates to inhibit light absorption and photocatalytic activity and even to block the active sites of the graphite phase carbon nitride.
Example 10
The preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively putting 2g of melamine and 2g of cyanuric acid powder into 100ml of deionized water, mixing, magnetically stirring for 12 hours, uniformly mixing, and drying at 80 ℃ for 12 hours to obtain a white mixed solid;
(2) And (3) placing the white mixed solid in a muffle furnace with the calcination temperature of 550 ℃ for calcination for 4 hours, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder, wherein the pale yellow product powder is original graphite phase carbon nitride powder.
(3) Adding 1g of the original graphite phase carbon nitride powder obtained in the step (2), 0.12g of gadolinium nitrate hexahydrate and 0.05g of cobalt nitrate hexahydrate into 50ml of deionized water for dissolution, oscillating for 30min, and drying at 80 ℃ for 12h to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), then placing the ground mixed solid in a tube furnace, respectively heating to 300 ℃, 350 ℃, 400 ℃, 450 ℃ and 500 ℃ at a heating rate of 10+/-1 ℃/min, and keeping the pyrolysis reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder in the step (4) with absolute ethyl alcohol and deionized water for 3-7 times to remove impurities, wherein the content of the absolute ethyl alcohol is more than or equal to 99.7%, and finally drying at the temperature of 70-100 ℃ for 10-12 hours to obtain the modified graphite-phase carbon nitride photocatalyst under different preparation temperature conditions.
The modified graphite phase carbon nitride photocatalyst under different preparation temperature conditions is respectively added into five bottles of the same 100mL with the concentration of 20 mg.L -1 In the dark, for 30 minutes to reach the adsorption-desorption equilibrium. Then, the target solution was irradiated with simulated light from a 30w power LED lamp, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was measured with an ultraviolet-visible spectrophotometer at 271nm wavelength.
The test results are shown in fig. 8, and it can be seen that the photocatalytic degradation efficiency of the modified graphite phase carbon nitride photocatalyst on ciprofloxacin hydrochloride is also improved from 76.45% to 87.73% as the preparation temperature is increased from 300 ℃ to 500 ℃. This is because the temperature is another decisive factor for the elemental composition of the prepared Gd-Co-CN, the higher the temperature, the more stable the prepared Gd-Co-CN. But with further increases in the preparation temperature, it causes reduced yields of Gd-Co-CN product and collapse of the structure.
Example 11
The preparation method of the modified graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively putting 2g of melamine and 2g of cyanuric acid powder into 100ml of deionized water, mixing, magnetically stirring for 12 hours, uniformly mixing, and drying at 80 ℃ for 12 hours to obtain a white mixed solid;
(2) And (3) placing the white mixed solid in a muffle furnace with the calcination temperature of 550 ℃ for calcination for 4 hours, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder, wherein the pale yellow product powder is original graphite phase carbon nitride powder.
(3) Adding 1g of the original graphite phase carbon nitride powder obtained in the step (2), 0.12g of gadolinium nitrate hexahydrate and 0.05g of cobalt nitrate hexahydrate into 50ml of deionized water for dissolution, oscillating for 30min, and drying at 80 ℃ for 12h to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), then placing the ground mixed solid in a tube furnace, heating to 450 ℃ at a heating rate of 10+/-1 ℃/min, respectively maintaining the pyrolysis reaction for 1h, 2h, 3h and 4h, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder in the step (4) with absolute ethyl alcohol and deionized water for 3-7 times to remove impurities, wherein the content of the absolute ethyl alcohol is more than or equal to 99.7%, and finally drying at the temperature of 70-100 ℃ for 10-12 hours to obtain the modified graphite-phase carbon nitride photocatalyst under different calcination time.
The modified graphite phase carbon nitride photocatalyst under different calcination time is added into four bottles with the same 100mL concentration of 20 mg.L -1 In the dark, for 30 minutes to reach the adsorption-desorption equilibrium. Then, the target solution was irradiated with simulated light from a 30w power LED lamp, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was measured with an ultraviolet-visible spectrophotometer at 271nm wavelength.
As shown in fig. 9, it can be seen that, as the calcination time increases, the photocatalytic degradation efficiency of the modified graphite-phase carbon nitride photocatalyst on ciprofloxacin hydrochloride gradually increases, but too long calcination time causes collapse of Gd-Co-CN structure, thereby reducing the photocatalytic degradation efficiency.
Example 12
The modified graphite phase carbon nitride catalyst prepared in the embodiment 1 is degraded into ciprofloxacin hydrochloride solutions with different initial concentrations under the condition of a light-emitting diode (LED) lamp with the power of 30w, and the method comprises the following steps:
100mL of ciprofloxacin hydrochloride wastewater having initial concentrations of 10mg/L, 20mg/L and 30mg/L, respectively, was added to 3 250mL Erlenmeyer flasks, and then 80mg of the modified graphite-phase carbon nitride catalyst of example 1 was added to each of the three Erlenmeyer flasks, followed by stirring in the dark for 30 minutes, to achieve adsorption-desorption equilibrium. The target solution was illuminated with a 30w power LED lamp simulated illumination, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was then tested with an ultraviolet-visible spectrophotometer at 271nm wavelength.
The test results are shown in fig. 9, and the photocatalytic degradation efficiency of the modified graphite-phase carbon nitride catalyst prepared in example 1 on ciprofloxacin hydrochloride is reduced along with the increase of the concentration of ciprofloxacin hydrochloride, but the degradation efficiency in a 30mg/L ciprofloxacin hydrochloride solution is still better.
Example 13
The modified graphite phase carbon nitride catalyst prepared in the example 1 is degraded into ciprofloxacin hydrochloride solutions with different initial pH values under a 30w power LED lamp, and the method comprises the following steps:
100mL ciprofloxacin hydrochloride wastewater with initial pH of 3, 7 and 11, respectively, was added to 3 conical flasks with mass concentration of 20mg/L, and then 80mg of the modified graphite-phase carbon nitride catalyst of example 1 was added to the three conical flasks, respectively, and stirred in the dark for 30 minutes to reach adsorption-desorption equilibrium. The target solution was irradiated with 30w of LED lamp simulated light, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was then tested with an ultraviolet-visible spectrophotometer at 271nm wavelength.
As shown in fig. 10, the above test results show that the modified graphite-phase carbon nitride catalyst has the best degradation effect on ciprofloxacin hydrochloride when the pH is neutral 7, and the peracid or the over-alkali can reduce the adsorption effect of the dark reaction on ciprofloxacin hydrochloride, thereby affecting the photocatalytic efficiency of the modified graphite-phase carbon nitride on ciprofloxacin hydrochloride.
Example 14
The modified graphite phase carbon nitride catalyst prepared in the example 1 is used for degrading ciprofloxacin hydrochloride under the light sources with different powers, and the method comprises the following steps:
100mL ciprofloxacin hydrochloride wastewater, the mass concentration of which is 20mg/L, was added to 3 250mL Erlenmeyer flasks, and 80mg of the modified graphite-phase carbon nitride catalyst of example 1 was added to each of the three Erlenmeyer flasks, followed by stirring in the dark for 30 minutes, to achieve adsorption-desorption equilibrium. The target solution was irradiated with simulated light using 30w, 150w and 300w LED lamps, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was then measured at 271nm wavelength using an ultraviolet-visible spectrophotometer.
The test results are shown in fig. 11, and the photocatalytic effect of the modified graphite-phase carbon nitride catalyst on ciprofloxacin hydrochloride is improved along with the increase of the power of the light source, which shows that the high-power light source can improve the photocatalytic effect to a certain extent, but the high-power light source can still realize better photocatalytic effect and reduce the requirements on photocatalytic equipment.
Example 15
The modified graphite phase carbon nitride catalyst prepared in example 1 was used for radical detection, and comprises the following steps:
100mL ciprofloxacin hydrochloride wastewater, the mass concentration of which is 20mg/L, was added to 3 250mL Erlenmeyer flasks, and 80mg of the modified graphite-phase carbon nitride catalyst of example 1 was added to each of the three Erlenmeyer flasks, followed by stirring in the dark for 30 minutes, to achieve adsorption-desorption equilibrium. Then adding methanol, disodium ethylenediamine tetraacetate (EDTA-2 Na) and p-benzoquinone (p-BQ) as hydroxyl radical (OH), hole pair (h) into three conical flasks respectively + ) And superoxide radical (. O) 2- ) Is a quencher of (a). The target solution was irradiated with 30w of LED lamp simulated light, samples were collected every 30 minutes, filtered through a 0.45 μm microporous membrane, and the ciprofloxacin hydrochloride concentration in the solution was then tested with an ultraviolet-visible spectrophotometer at 271nm wavelength.
The test results are shown in fig. 12, and the addition of methanol has little influence on the degradation of ciprofloxacin hydrochloride by the modified graphite-phase carbon nitride catalyst, and the removal rate is 81.89%. The addition of EDTA-2Na and p-BQ has obvious inhibition effect on the degradation of ciprofloxacin hydrochloride, and the removal rate is respectively reduced to 36.82 percent and 25.08 percent. Indicating that active groups can be generated in the low-power photocatalytic reaction process, and the generated main active groups, namely O, are utilized 2- And h + Can realize high-efficiency degradation of ciprofloxacin hydrochloride.
Claims (10)
1. The preparation method of the modified graphite phase carbon nitride photocatalyst is characterized by comprising the following steps of:
(1) Respectively placing melamine and cyanuric acid powder into deionized water for mixing, stirring and drying to obtain a white mixed solid;
(2) Calcining the white mixed solid in a muffle furnace, cooling to room temperature after the reaction is finished to obtain a pale yellow product, and grinding the pale yellow product into powder to obtain pale yellow product powder;
(3) Adding the pale yellow product powder obtained in the step (2) and cobalt salt and gadolinium salt into deionized water for dissolution, oscillating and drying to obtain a mixed solid;
(4) Grinding the mixed solid in the step (3), placing the ground mixed solid in a tube furnace for high-temperature pyrolysis reaction, and cooling to room temperature after the reaction is finished to obtain powder;
(5) And (3) alternately washing the powder obtained in the step (4) with absolute ethyl alcohol and deionized water to remove impurities, and finally drying to obtain the modified graphite-phase carbon nitride photocatalyst.
2. The method for preparing a modified graphite phase carbon nitride photocatalyst according to claim 1, wherein the mass ratio of melamine powder, cyanuric acid powder and deionized water in the step (1) is 1:1:50, wherein the stirring is magnetic stirring, and the stirring time is 8-12 h; the temperature of the drying is 70-100 ℃ and the drying time is 10-12 h.
3. The method for preparing a modified graphite phase carbon nitride photocatalyst according to claim 1, wherein the calcination temperature of the muffle furnace in the step (2) is 350-550 ℃ and the calcination time is 2-4 h.
4. The method for preparing the modified graphite phase carbon nitride photocatalyst according to claim 1, wherein the cobalt salt in the step (3) is cobalt nitrate hexahydrate, the gadolinium salt is gadolinium nitrate hexahydrate, the oscillation time is 30-60min, the drying temperature is 70-100 ℃, and the drying time is 10-12 h.
5. The method for preparing the modified graphite phase carbon nitride photocatalyst according to claim 1, wherein the mass ratio of the light yellow product powder in the step (3) to cobalt salt and gadolinium salt is 1: 0.01-0.09:0.04-0.20, the heating rate of the tube furnace is 10+/-1 ℃/min, the pyrolysis temperature in the tube furnace is 300-500 ℃, and the pyrolysis time in the tube furnace is 1-4 h.
6. The method for preparing modified graphite phase carbon nitride photocatalyst according to claim 1, wherein the content of absolute ethyl alcohol in step (5) is not less than 99.7%, the number of times of alternate washing is 3-7, the drying temperature is 70-100 ℃, and the drying time is 10-12 h.
7. A modified graphite-phase carbon nitride photocatalyst obtained by the method for producing a modified graphite-phase carbon nitride photocatalyst according to any one of claims 1 to 6.
8. The use of a modified graphite phase carbon nitride photocatalyst according to claim 7 in the catalytic degradation of antibiotics.
9. The use of the modified graphite phase carbon nitride photocatalyst according to claim 8 in the catalytic degradation of antibiotics, wherein the antibiotics are any one or a combination of more than two of ciprofloxacin hydrochloride, enrofloxacin, levofloxacin, norfloxacin, tetracycline and aureomycin.
10. The use of a modified graphite phase carbon nitride photocatalyst according to claim 8 for the catalytic degradation of antibiotics, comprising the steps of: the modified graphite phase carbon nitride is prepared according to the following proportion of 10 to 80:1 into antibiotic wastewater with the concentration of 10-200 mg/L for stirring for 30-60min, carrying out catalytic degradation under the irradiation of an LED lamp with the power of 30w and the wavelength of 450-470nm, and filtering the liquid obtained after the reaction for 20-200 min by using a filter membrane with the aperture of 0.22-0.45 mu m to obtain the water sample after photocatalysis.
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