CN111420690A - Preparation of ZnO-g-C3N4 photocatalyst and application thereof in water ibuprofen degradation drugs - Google Patents
Preparation of ZnO-g-C3N4 photocatalyst and application thereof in water ibuprofen degradation drugs Download PDFInfo
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- CN111420690A CN111420690A CN201910024022.4A CN201910024022A CN111420690A CN 111420690 A CN111420690 A CN 111420690A CN 201910024022 A CN201910024022 A CN 201910024022A CN 111420690 A CN111420690 A CN 111420690A
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/34—Organic compounds containing oxygen
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- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention provides ZnO-g-C3N4The preparation of the photocatalyst and the application thereof in the drug for degrading ibuprofen in water body by synthesizing g-C3N4And ZnO are reacted to prepare the photocatalyst ZnO-g-C3N4The photocatalytic degradation rate of the photocatalyst on the drug wastewater, particularly the photocatalytic degradation rate of ibuprofen drugs in a water body is evaluated, and the degradation rate can reach 93.7%; the ZnO-g-C provided by the invention3N4The photocatalyst has the advantages of simple preparation method, low cost and environmental protection.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to ZnO-g-C3N4The preparation of the photocatalyst and the application of the photocatalyst in the degradation of ibuprofen in water.
Background
The photocatalytic oxidation technology is one of the technologies with application prospects in an advanced oxidation method, and has the outstanding advantages of high efficiency, stability, no secondary pollution, suitability for degradation of various organic pollutants and the like.
g-C3N4The photocatalytic material is a novel photocatalytic material due to the outstanding advantages of high photocatalytic activity, good stability, low price of raw materials and no metal, however, the single-phase catalyst usually has unsatisfactory photocatalytic performance due to low quantum efficiency. Due to g-C3N4The material has high photoproduction electron-hole recombination rate, so that the catalytic efficiency is low, and the application of the material in photocatalysis is limited. To increase g-C3N4In recent years, many modification methods have been studied. For g-C3N4The nonmetallic elements to be modified include S, N, C, B, F, P, etc., which are believed to substitute C, N, H elements in the 3-s-triazine structural unit to form g-C3N4The lattice defect enables the photoproduction electron-hole pair to be effectively separated, and the photocatalysis performance of the photoproduction electron-hole pair is effectively improved.
Wang et al used dicyandiamide and FeCl3As raw material, Fe is synthesized by thermal polycondensation3+Doped g-C3N4。Fe3+Doping can reduce g-C3N4And enlarging the g-C3N4The photocatalyst is used for visible light activation of H in the absorption range of visible light2O2The catalytic effect of the mineralized rhodamine B is remarkable.
Modified g-C3N4Researches on catalytic degradation of wastewater containing dye are many, but researches on photocatalytic degradation of wastewater containing drugs are still few, especially on photocatalytic degradation of ibuprofen drugs in waterDegradation studies are very rare.
Ibuprofen (Ibuprofen, IBU), also known as Ibuprofen, is a typical representative of the phenylpropanoid nonsteroidal anti-inflammatory drugs, white or slightly white crystalline powder, tasteless.
Ibuprofen enters the environment through various ways during production and use and becomes a ubiquitous pollutant in the environment (soil, surface water, underground water, seawater). Discharge of the effluent from a sewage treatment plant is one of the major routes leading to ibuprofen into the water environment. In recent years, ibuprofen medicaments are often detected in a water body environment, although the concentration of the detected medicaments is generally low, ibuprofen has bioaccumulation property, can cause harm to human health and the safety and balance of an ecological system, and researches show that the long-term intake of trace IBU can cause biological malformation, microbial drug resistance and the like. Therefore, it is an urgent task to seek for efficient removal of drugs in sewage, especially IBU.
Currently, degradation researches on ibuprofen include microbial degradation, Fenton oxidation degradation and the like, but the researches still have the conditions of high cost, insufficient environmental protection, low degradation efficiency and the like.
Therefore, it is highly desirable to provide a green and environment-friendly modified g-C with high degradation efficiency3N4The photocatalyst is used for degrading ibuprofen in water.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: ZnO-g-C3N4The preparation of the photocatalyst and the application thereof in the drug for degrading ibuprofen in water body by synthesizing g-C3N4And ZnO are reacted to prepare the photocatalyst ZnO-g-C3N4The photocatalytic degradation rate of the photocatalyst on the drug wastewater is explored, particularly the photocatalytic degradation rate on the ibuprofen drug in the water body is explored, and the degradation rate can reach 93.7%; the ZnO-g-C provided by the invention3N4The preparation method of the photocatalyst is simple and environment-friendly, and the obtained ZnO-g-C3N4The photocatalyst activity was high, and the present invention was completed.
The object of the present invention is to provide the following:
in a first aspect, the invention provides a photocatalyst ZnO-g-C3N4The method for preparing (1), the method comprising the steps of:
Wherein, step 1 includes the following steps:
step 1-1, adding a ZnO precursor into a solvent I for dispersion;
step 1-2, heating for reaction;
and 1-3, carrying out post-treatment on the I to obtain ZnO.
Wherein, step 2 includes the following steps:
step 2-1, putting a carbon-nitrogen source into a crucible, crushing and then calcining;
step 2-2, post-treatment of II to give g-C3N4；
Preferably, the carbon-nitrogen source is selected from small molecular weight nitrogen-containing organic matters with a carbon-nitrogen ratio of 1:2, preferably selected from cyanamide, dicyandiamide, melamine and urea, and more preferably selected from melamine;
the calcination temperature is 450-650 ℃;
the post-treatment II comprises cooling to room temperature and grinding.
Wherein, step 3 comprises the following steps:
step 3-1, adding the ZnO prepared in the step 1 into a dispersing agent to be uniformly dispersed;
step 3-2, adding the prepared g-C into the system3N4Mixing uniformly, and heating for reaction;
step 3-3, post-treating III to obtain the photocatalyst ZnO-g-C3N4。
In a second aspect, the invention also provides a photocatalyst ZnO-g-C prepared by the method in the first aspect3N4The application of the compound in photocatalytic degradation of drug wastewaterThe method is preferably used for degrading sewage containing ibuprofen medicaments, and the degradation rate can reach 93.7 percent.
Drawings
FIG. 1 shows the products of examples 1 to 5 and g-C3N4XRD spectrogram of ZnO sample;
FIG. 2 shows the products of examples 1 to 5 and g-C3N4Ultraviolet-visible diffuse reflection spectrogram of the ZnO sample;
FIG. 3 shows the products of examples 1 to 5 and g-C3N4And a degradation curve graph of the ZnO sample to ibuprofen;
FIG. 4 shows different initial concentrations of ibuprofen versus 20% ZnO-g-C3N4The effect of photocatalytic performance;
FIG. 5 shows 20% ZnO-g-C3N4The influence of the dosage of the ibuprofen on the removal of ibuprofen pollutants;
FIGS. 6 to 12 show g-C, respectively3N4Particle size analysis charts of the products of examples 1 to 5 and ZnO samples.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
As described in the background of the invention, g-C is modified3N4The catalyst is very little used for research of ibuprofen medicaments for degrading water bodies. Through a great deal of research and experiments, the inventor discovers that ZnO-g-C prepared by the method provided by the invention3N4The photocatalyst shows excellent performance in the drug for degrading ibuprofen in water, which is very surprising for the inventor. To date, no report has been found about the present invention.
According to a first aspect of the present invention, there is provided a photocatalyst ZnO-g-C3N4The method for preparing (1), the method comprising the steps of:
Wherein,
the step 1 comprises the following steps:
step 1-1, adding a ZnO precursor into a solvent I for dispersion;
in one embodiment, the precursor is selected from zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, preferably zinc nitrate; in the present invention, zinc nitrate hexahydrate is more preferably used.
In one embodiment, the solvent I is water, preferably distilled water, deionized water, purified water, more preferably distilled water;
in a preferred embodiment, the solvent I is used in an amount that the mass ratio of the zinc nitrate hexahydrate to the volume of the solvent I is 1g (5-20) m L, such as 1g:10m L.
In the step 1-1, strong ammonia water is also added, the concentration of the strong ammonia water is 20 percent, and the strong ammonia water mainly provides hydroxide ions. Moreover, the performance of the obtained final product is better by using stronger ammonia water.
In a preferred embodiment, the amount of the concentrated ammonia water is such that the volume ratio of the mass of the zinc nitrate hexahydrate to the volume of the concentrated ammonia water is 2g (1.5-3.5) m L, such as 2 g: 2.5m L.
In a preferred embodiment, the precursor is added into the solvent I, stirred, and after all the precursor is dissolved, concentrated ammonia water is added, and then the stirring is continued until the precursor is uniformly mixed.
Step 1-2, heating for reaction;
in one embodiment, the temperature of the reaction is 140 to 180 ℃; preferably 150 to 170 ℃, such as 160 ℃; the reaction time is 8-16 h, preferably 10-14 h, such as 12 h.
And 1-3, carrying out post-treatment on the I to obtain ZnO.
The post-treatment I comprises cooling to room temperature, centrifuging, washing the solid and drying.
The purpose of the centrifugation is solid-liquid separation, and the centrifugation equipment is not particularly limited, and can be common centrifugation equipment; after centrifugation a solid was obtained.
In a preferred embodiment, the washing solvent II is distilled water.
In a preferred embodiment, the drying temperature is 80 ℃.
In the present invention, the ZnO particles obtained have a diameter mainly distributed between 0.500 and 200.000. mu.m, and an average particle diameter of about 22.16. mu.m.
In the invention, the step 2 comprises the following steps:
step 2-1, putting a carbon-nitrogen source into a crucible, crushing and then calcining;
step 2-2, post-treatment of II to give g-C3N4；
Preferably, the carbon-nitrogen source is selected from small molecular weight nitrogen-containing organic matters with a carbon-nitrogen ratio of 1:2, preferably selected from cyanamide, dicyandiamide, melamine and urea, and more preferably selected from melamine;
the calcination temperature is 450-650 ℃, such as 550 ℃;
the post-treatment II comprises cooling to room temperature and grinding.
g-C provided by the invention3N4Mainly distributed between 45.000 and 800.000 μm in diameter, and the average particle diameter is about 51.11 μm.
In the invention, the step 3 comprises the following steps:
step 3-1, adding the ZnO prepared in the step 1 into a dispersing agent to be uniformly dispersed;
in one embodiment, the dispersant is an alcohol, preferably selected from methanol, ethanol, isopropanol, more preferably methanol;
the step 3-1 also comprises dispersing ZnO in the dispersing agent by ultrasonic oscillation, and the inventor finds that the obtained photocatalyst ZnO-g-C is dispersed for 30min by ultrasonic oscillation3N4The photocatalytic activity of (A) is higher.
In one embodiment, the ratio of the mass of ZnO to the volume of the dispersant is 1g (30-90) m L, such as 1g:60m L.
Step 3-2, adding the prepared g-C into the system3N4Mixing uniformly, and heating for reaction;
the reaction temperature is 130-170 ℃, preferably 140-160 ℃, such as 150 ℃;
the inventors found that the reaction temperature for the heating reaction cannot be too high or too low, preferably 150 ℃, and the obtained photocatalyst ZnO-g-C3N4The activity of the ibuprofen photocatalytic degradation is higher.
In one embodiment, the ZnO has a mass that is equal to the mass of the ZnO and the mass of the ZnO is equal to the mass of the ZnO and the mass of the g-C3N4The ratio of the sum of the masses of (5-85): 100, preferably (10-80): 100, such as 15:100, 20:100, 30:100, 50:100, 75: 100.
Step 3-3, post-treating III to obtain the photocatalyst ZnO-g-C3N4。
The post-treatment III comprises centrifugation, washing and drying.
In one embodiment, the washing solvent III is absolute ethyl alcohol, and the inventor finds that the photocatalyst ZnO-g-C obtained by washing and then drying is3N4The activity of the ibuprofen on photocatalytic degradation is higher.
In one embodiment, the drying temperature is 110 ℃.
The photocatalyst provided by the invention is 75% ZnO-g-C3N4The particle diameter of (A) is mainly distributed between 0.200 and 100.000 mu m, and the average particle diameter is about 5.767 mu m; 20% ZnO-g-C3N4Mainly distributed between 0.100 and 75.000 μm in diameter, and the average particle diameter is about 4.221 μm.
The ZnO-g-C provided by the invention3N4In the ultraviolet-visible diffuse reflection spectrum of the photocatalyst, a strong absorption peak exists in a visible light region of 400-600 nm. And g-C3N4Compared with ZnO catalyst, ZnO-g-C3N4The absorption capacity of the composite photocatalyst in a 400-nm visible light region is enhanced, which shows that ZnO and g-C3N4Interaction occurs between them.
According to a second aspect of the present invention, there is provided a photocatalyst ZnO-g-C prepared by the preparation method of the first aspect3N4Use of (A) for the photocatalytic degradation of pharmaceutical effluents, preferably for the degradation of ibuprofen-containing effluentsThe degradation rate of the sewage of the medicine can reach 93.7 percent.
The inventor finds that 20 percent ZnO-g-C after 4 hours of photocatalytic reaction when the initial concentration of ibuprofen pollutant is 0.01 mmol/L, the adding amount of the photocatalyst is 1.00 g/L3N4The removal rate of the ibuprofen medicament reaches 92.8 percent;
when the initial concentration of ibuprofen is 0.02 mmol/L and the dosage of the catalyst is 2.00 g/L, the ibuprofen is irradiated by visible light for 4 hours, and 20 percent ZnO-g-C3N4The removal rate of the ibuprofen photocatalytic degradation reaches 93.7 percent.
The inventors believe that this may be due to the appropriate amounts of ZnO and g-C3N4The composition improves the separation efficiency of photon-generated carriers, reduces the particle diameter, increases the specific surface area and is more favorable for the photocatalytic degradation of ibuprofen (ibuprofen).
The ZnO-g-C provided by the invention3N4The preparation of the photocatalyst and the application thereof in the water ibuprofen degradation drug have the following beneficial effects:
(1) the preparation method of the photocatalyst provided by the invention is simple and easy to implement;
(2) the photocatalyst ZnO-g-C prepared by the preparation method of the photocatalyst provided by the invention3N4The cost is low, and the environment is protected;
(3) the photocatalyst provided by the invention has high degradation efficiency of ibuprofen medicament in medicament wastewater, especially water, which can reach 93.7%, and has popularization and application prospects.
Examples
Preparation of ZnO samples
Weighing 2g Zn (NO)3)2·6H2Adding O into a beaker filled with 20m of L distilled water, continuously stirring for 20 minutes, then adding 2.5m of L concentrated ammonia water into the zinc nitrate solution, and continuing stirring until the mixture is completely mixed;
transferring the solution into a reaction kettle, and reacting for 12 hours at 160 ℃;
and finally, taking out the reaction kettle, cooling to room temperature, transferring the sediment into a centrifugal tube, centrifuging, washing with distilled water, and drying at 80 ℃ to obtain the ZnO sample.
3 4Preparation of g-CN samples
Weighing 10g of melamine, putting the melamine into a crucible, and calcining the melamine for 2 hours at 550 ℃ in a muffle furnace;
cooling to room temperature, taking out the product, placing into a mortar, and grinding to obtain g-C3N4And (3) sampling.
Example 1
Adding 0.5g of ZnO into a beaker, adding 30m of L methanol, and performing ultrasonic treatment for 30 minutes to uniformly disperse the ZnO;
2.83g of g-C were added to the above system3N4The ZnO accounts for 15 percent of the proportion of the composite product, and the ZnO is stirred and mixed evenly;
transferring the mixed solution into a reaction kettle, and reacting for 4 hours at 150 ℃;
washing with anhydrous ethanol, and drying at 110 deg.C to obtain photocatalyst ZnO-g-C3N4Product, marked 15% ZnO-g-C3N4。
Example 2
This example is the same as that used in example 1, except that g-C is used3N42.0g of g-C were added in this example3N4(ii) a Obtaining the photocatalyst ZnO-g-C3N4Product, marked as 20% ZnO-g-C3N4。
Example 3
This example is the same as that used in example 1, except that g-C is used3N4In this example, 1.17g of g-C was added3N4(ii) a Obtaining the photocatalyst ZnO-g-C3N4Product, marked 30% ZnO-g-C3N4。
Example 4
This example is the same as that used in example 1, except that g-C is used3N4In this example, 0.5g of g-C was added3N4(ii) a Obtaining the photocatalyst ZnO-g-C3N4Product, marked as 50% ZnO-g-C3N4。
Example 5
This example is the same as that used in example 1, except that g-C is used3N4In this example, 0.17g of g-C was added3N4(ii) a Obtaining the photocatalyst ZnO-g-C3N4Product, marked as 75% ZnO-g-C3N4。
Comparative example
Comparative example 1
According to "Suhaiying et al" g-C3N4/TiO2Mechanism of degradation of ibuprofen by composite photocatalyst, chinese environmental science, 2017, 37 (1): 195-202' shows that the degradation rate of ibuprofen in water is only 81.3%.
Examples of the experiments
XRD analysis of sample of Experimental example 1
Measurement of the photocatalyst obtained in example 1 to 5 and g-C3N4The XRD spectrum of the ZnO sample shows that the result is shown in figure 1.
Wherein, in figure 1,
(a)g-C3N4,(b)15％ZnO-g-C3N4,(c)20％ZnO-g-C3N4,(d) 30％ZnO-g-C3N4,(e)50％ZnO-g-C3N4,(f)75％ZnO-g-C3N4,(g) ZnO；
as can be seen from FIG. 1, pure g-C3N4A characteristic diffraction peak appears at 12.3 degrees, corresponding to g-C3N4The (100) crystal face of (A) shows a characteristic diffraction peak at 27.6 degrees, corresponding to g-C3N4(002) crystal face of (a); the pure ZnO sample has 9 characteristic diffraction peaks which respectively correspond to (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal faces in sequence, and the positions of the (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal faces are not shifted along with the increasing of ZnO content, which shows that ZnO and g-C3N4During the compounding process, no interaction occursThe crystal lattice changes significantly. After recombination, no new crystalline phase was found, indicating that ZnO and g-C are the only ones3N4No other impurities are present.
Experimental example 2 ultraviolet-visible diffuse reflectance Spectroscopy analysis of sample
The photocatalysts prepared in examples 1 to 5 and g-C3N4The ZnO sample was subjected to UV-visible diffuse reflectance spectroscopy, and the results are shown in FIG. 2.
Wherein (a) g-C3N4,(b)15％ZnO-g-C3N4,(c)20％ZnO-g-C3N4, (d)30％ZnO-g-C3N4,(e)50％ZnO-g-C3N4,(f)75％ZnO-g-C3N4, (g)ZnO；
As can be seen from FIG. 2, and g-C3N4Compared with ZnO catalyst, ZnO-g-C3N4The absorption capacity of the composite catalyst in a 400-one 600nm visible light region is enhanced, which shows that ZnO and g-C are3N4Interaction occurs between them.
Experimental example 3 photocatalytic activity analysis of sample I
A defined amount of each catalyst powder (products of examples 1 to 5, and g-C)3N4ZnO sample) and a target solution (ibuprofen solution) with a certain concentration of 50m L are respectively mixed in a quartz tube and stirred to ensure that the target solution is fully contacted with catalyst powder, in a photocatalytic degradation experiment, a xenon lamp with the power of 500W is used as a light source and is carried out in an XPA-7 type photoreactor, in the photocatalytic degradation reaction process, the quartz tube in the reactor is always connected in a constant-temperature circulating water system to keep the reaction temperature constant at room temperature in the reaction process.
Reacting under dark condition for 30min under stirring, sampling, centrifuging, and measuring absorbance A0(ii) a Turning on a 500W xenon lamp visible light source, performing light treatment for a certain time, sampling, centrifuging twice, centrifuging for 20 minutes each time, and measuring the absorbance At(ii) a The degradation rate was calculated as W (%) - (A)0－At)/A0× 100 calculation of the degradation rate at 100%, and plotting the degradation rateThe results are shown in FIG. 3. and, when tested, the initial concentration of ibuprofen was set at 0.01 mmol/L and the amount of photocatalyst added was 1.00 g/L.
Wherein, in FIG. 3, (a) blank, (b) ZnO, (C) 15% ZnO-g-C3N4,(d) 20％ZnO-g-C3N4,(e)30％ZnO-g-C3N4,(f)50％ZnO-g-C3N4,(g) 75％ZnO-g-C3N4,(h)g-C3N4。
As can be seen from FIG. 3, as the ZnO content increases, ZnO-g-C3N4The removal rate of ibuprofen increased and then decreased gradually. When the mass percentage of ZnO is 20 percent, 20 percent of ZnO-g-C3N4The photocatalytic performance of the ibuprofen inhibitor reaches the maximum value, and after 4 hours of photocatalytic reaction, the ibuprofen inhibitor can remove 92.8 percent of ibuprofen.
Experimental example 4 photocatalytic activity analysis of sample II
Different initial concentrations of ibuprofen were tested against 20% ZnO-g-C3N4The influence rule of the photocatalytic performance is that in the experiment of the influence of different ibuprofen initial concentrations on the removal, the initial concentrations of ibuprofen are respectively set to be 0.01, 0.02, 0.05 and 0.10 mmol/L, and 20 percent ZnO-g-C3N4The amount of the surfactant added was 1.00 g/L. the test method was the same as in example 3. the test results are shown in FIG. 4.
In FIG. 4, (a) is 0.01 mmol/L, (b) is 0.02 mmol/L, (c) is 0.05 mmol/L, and (d) is 0.10 mmol/L.
As can be seen from FIG. 4, the final removal rate of ibuprofen gradually decreased as the initial concentration of ibuprofen increased, at an initial concentration of 0.01 mmol/L, ibuprofen was removed in only 4 hours, at an initial concentration of 0.10 mmol/L, the removal rate of ibuprofen was only 50.6% after 4 hours, indicating that the initial concentration of ibuprofen had a greater effect on its final removal rate.
Experimental example 5 photocatalytic activity analysis of sample III
The influence of different adding amounts of the photocatalyst on the removal of ibuprofen is tested, and 20 percent of ZnO-g-C is added in the experiment3N4The adding amount of the photocatalyst is respectively setAt 0.10, 0.50, 1.00 and 2.00 g/L, the initial concentration of ibuprofen was set at 0.02 mmol/L. the test procedure is the same as in experimental example 3. the results are shown in FIG. 5.
In FIG. 5, (a) is 0.10 g/L, (b) is 0.50 g/L, (c) is 1.00 g/L, and (d) is 2.00 g/L.
As can be seen from FIG. 5, the final removal rate of ibuprofen gradually increased with the increase of the added amount of the photocatalyst, when the added amount of the photocatalyst was 0.10 g/L, the removal rate of ibuprofen was only 47.8% within 4h, when the added amount of the photocatalyst was increased to 1.00 g/L, the removal rate of ibuprofen was 78.2% within 4h, and when the added amount of the photocatalyst was increased to 2.00 g/L, the removal rate of ibuprofen was 93.7%.
Experimental example 6 particle size analysis of sample
The photocatalysts prepared in examples 1 to 5 and g-C3N4The results of analyzing the particle size of the ZnO sample are shown in table 1 and fig. 6 to 12.
TABLE 1 particle size and specific surface area of different samples
| Sample (I) | ① | ② | ③ | ④ | ⑤ | ⑥ | ⑦ |
| Average particle diameter/. mu.m | 51.11 | 35.79 | 4.221 | 8.033 | 7.665 | 5.767 | 22.16 |
| Specific surface area cm2/g | 3175 | 5567 | 17989 | 15091 | 14834 | 15785 | 7547 |
Note ① g-C3N4,②15％ZnO-g-C3N4,③20％ZnO-g-C3N4,④30％ZnO-g-C3N4,⑤50％ZnO-g-C3N4,⑥75％ZnO-g-C3N4,⑦ZnO
Wherein, fig. 6 and fig. 12 are g-C respectively3N4And a particle size diagram of ZnO. FIG. 7, FIG. 8, FIG. 9, FIG. 10 and FIG. 11 show ZnO-g-C prepared in examples 1 to 5, respectively3N4Particle size plot of photocatalyst samples.
As can be seen from FIG. 7, 15% ZnO-g-C3N4Mainly distributed between 2.000 and 400.000 μm in diameter, and the average particle diameter is about 35.79 μm;
as can be seen from FIG. 8, 20% ZnO-g-C3N4Mainly distributed between 0.100 and 75.000 μm in diameter and having an average particle size of about 4.221 μm;
as can be seen from FIG. 9, 30% ZnO-g-C3N4The particle diameter of (A) is mainly distributed between 0.200 and 100.000 mu m, and the average particle diameter is about 8.033 mu m;
as can be seen from FIG. 10, 50% ZnO-g-C3N4The particle diameter of (A) is mainly distributed between 0.200 and 100.000 mu m, and the average particle diameter is about 7.665 mu m;
as can be seen from FIG. 11, 75% ZnO-g-C3N4The particle diameter of (A) is mainly distributed between 0.200 and 100.000 mu m, and the average particle diameter is about 5.767 mu m;
as can be seen from FIG. 6, g-C3N4The particle diameter of (A) is mainly distributed between 45.000 and 800.000 mu m, and the average particle diameter is about 51.11 mu m;
as can be seen from FIG. 12, the particle diameters of ZnO are mainly distributed between 0.500 and 200.000. mu.m, and the average particle diameter is about 22.16 μm;
in conclusion, the particle size of the composite products with different mass fractions approximately tends to decrease along with the increase of the mass fraction of ZnO, and the particle size of the composite sample is larger than that of g-C3N4And ZnO is small. The present inventors have found that the smaller the particle diameter of the photocatalyst, the larger the specific surface area, the stronger the light absorbing ability, and the higher the photocatalytic activity.
As can be seen from Table 1, 20% ZnO-g-C3N4Has the smallest particle diameter and the largest specific surface area, thereby having the best photocatalytic activity; ZnO-g-C3N4Compared with single sample ZnO and g-C, the composite sample3N4Has a large specific surface area, so that the catalytic activity of the composite sample is higher than that of the single sample.
In conclusion, when the photocatalyst provided by the invention is 20% ZnO-g-C3N4The dosage of the ibuprofen is 1.00 g/L, the initial concentration of ibuprofen pollutant is 0.01 mmol/L, and 20 percent of ZnO-g-C is obtained after 4 hours of photocatalytic reaction3N4The removal rate of the ibuprofen medicament by the photocatalyst reaches 92.8 percent;
when the photocatalyst provided by the invention is 20 percent of ZnO-g-C3N4When the dosage is 2.00 g/L, the initial concentration of ibuprofen is 0.02 mmol/L, the solution is irradiated by visible light for 4h, and 20% ZnO-g-C3N4The removal rate of the photocatalyst to ibuprofen reaches 93.7%.
Compared with the comparative example 1, the photocatalyst provided by the invention has excellent photocatalytic degradation performance on ibuprofen medicaments in water.
In the invention, the removal rate of the ibuprofen is the degradation rate of the ibuprofen.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. Photocatalyst ZnO-g-C3N4The method for preparing (c), wherein the method comprises the steps of:
step 1, preparing ZnO;
step 2, preparation of g-C3N4；
Step 3, preparing photocatalyst ZnO-g-C3N4。
2. The method of claim 1, wherein step 1 comprises the steps of:
step 1-1, adding a ZnO precursor into a solvent I for dispersion;
step 1-2, heating for reaction;
and 1-3, carrying out post-treatment on the I to obtain ZnO.
3. The method according to claim 2, wherein in step 1-1, the precursor is selected from the group consisting of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, preferably zinc nitrate;
the solvent I is water, preferably distilled water, deionized water and purified water, and more preferably distilled water;
in the step 1-1, strong ammonia water is also added.
4. The production method according to claim 2, wherein, in the step 1-2,
the reaction temperature is 140-180 ℃; the reaction time is 8-16 h, preferably 10-14 h.
5. The method of claim 2, wherein the post-treating step I in steps 1-3 comprises cooling to room temperature, centrifuging, washing the solid, and drying.
6. The method of claim 1, wherein step 2 comprises the steps of:
step 2-1, putting a carbon-nitrogen source into a crucible, crushing and then calcining;
step 2-2, post-treatment of II to give g-C3N4；
Preferably, the carbon-nitrogen source is selected from small molecular weight nitrogen-containing organic matters with a carbon-nitrogen ratio of 1:2, preferably selected from cyanamide, dicyandiamide, melamine and urea, and more preferably selected from melamine;
the calcination temperature is 450-650 ℃;
the post-treatment II comprises cooling to room temperature and grinding.
7. The method of claim 1, wherein step 3 comprises the steps of:
step 3-1, adding the ZnO prepared in the step 1 into a dispersing agent to be uniformly dispersed;
step 3-2, adding the prepared g-C into the system3N4Mixing uniformly, and heating for reaction;
step 3-3, post-treating III to obtain the photocatalyst ZnO-g-C3N4。
8. The method according to claim 7, wherein in step 3-1, the dispersant is an alcohol, preferably selected from methanol, ethanol, isopropanol, more preferably methanol;
the step 3-1 also comprises ultrasonic oscillation dispersion.
9. The method of claim 7, wherein in step 3-2, the reaction temperature is 130-170 ℃, preferably 140-160 ℃, such as 150 ℃;
in step 3-3, the post-treatment III comprises centrifugation, washing and drying.
10. Photocatalyst ZnO-g-C prepared by the preparation method according to one of claims 1 to 93N4The method is characterized in that the method is used for photocatalytic degradation of drug sewage, preferably sewage containing ibuprofen drugs, and the degradation rate of the sewage can reach 93.7%.
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