CN108793312B - Method for removing antibiotics by using carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst - Google Patents
Method for removing antibiotics by using carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst Download PDFInfo
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Classifications
-
- 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
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
Abstract
The invention discloses a method for removing antibiotics by using a carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst, which adopts the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst to treat the antibiotics, wherein the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst takes graphite-phase carbon nitride as a carrier, and the surface of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is modified with nitrogen-doped hollow mesoporous carbon and bismuth trioxide. According to the method, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is used for photocatalytic degradation of antibiotics, so that different types of antibiotics can be effectively removed, the method has the advantages of high removal rate, high removal speed, easiness in implementation, high safety, low cost, no secondary pollution and the like, particularly, the antibiotics in the water can be efficiently removed, and the method has a good practical application prospect.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, relates to a method for removing antibiotics by using a carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst, and particularly relates to a method for removing antibiotics in a water body by using a carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst.
Background
Antibiotics are secondary metabolites with anti-pathogen or other activities generated by microorganisms (including bacteria, fungi and actinomycetes) or higher animals and plants in the life process, and can interfere with the development function and play a role of other living cells. In recent decades, because antibiotics are widely used in medicine, livestock raising, aquaculture and the like, the antibiotics are often detected in natural water, sewage, soil and other environmental media due to excessive and incomplete metabolism, and the unmetabolized antibiotics are likely to influence the development of biological cells, the circulation of an ecosystem and promote the propagation of drug-resistant pathogenic bacteria, thereby having adverse effects on the ecological environment and human health. In past research, many methods have been used to remove antibiotic contaminants, including filtration, adsorption, advanced oxidation, biodegradation, photocatalytic degradation, etc., where filtration and adsorption simply transfer the contaminants from one phase to the next and do not mineralize them into carbon dioxide and water; although the advanced oxidation method has good removal effect, secondary pollution is caused, and the cost is high; although the biological method is low in cost, the required time is long, and the removal effect is interfered by multiple factors. Of these, photocatalytic degradation can be seen as an effective and environmentally friendly process. However, in the previous studies, the following problems still remain in the photocatalyst used for photocatalytic degradation: low light utilization efficiency, fast photoproduction electron-hole recombination, poor photocatalytic performance, poor stability (easy precipitation) and the like, and the wide application of photocatalytic degradation is greatly limited because the photocatalyst still has a large number of defects. Therefore, how to comprehensively improve the problems and defects in the existing photocatalytic degradation technology and obtain a photocatalytic material with strong light absorption capacity, low photoproduction electron-hole recombination rate and good photocatalytic performance to realize the rapid and efficient treatment of antibiotics is of great significance for expanding the application range of the photocatalytic degradation technology in the treatment of antibiotics.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for removing antibiotics by using a carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst for catalysis, which has the advantages of high removal rate, quick removal, simplicity, effectiveness, easiness in implementation, high safety, low cost and no secondary pollution.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for removing antibiotics by using a carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is disclosed, wherein the method adopts the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst to treat the antibiotics; the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst takes graphite-phase carbon nitride as a carrier, and the surface of the graphite-phase carbon nitride is modified with the nitrogen-doped hollow mesoporous carbon and the bismuth trioxide.
In the method, the mass percentage of the graphite-phase carbon nitride in the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is 85-91%, the mass percentage of the nitrogen-doped hollow mesoporous carbon is 2-5%, and the mass percentage of the bismuth trioxide is 7-11%.
In the above method, a further improvement is that the preparation method of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst comprises the following steps:
s1, ultrasonically dispersing melamine, bismuth nitrate pentahydrate and nitrogen-doped hollow mesoporous carbon in ethanol, and heating to completely volatilize the ethanol to obtain a photocatalyst precursor mixture;
and S2, calcining the photocatalyst precursor mixture obtained in the step S1 to obtain the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst.
In the above method, further improvement is that in step S1, the method for preparing nitrogen-doped hollow mesoporous carbon includes the following steps:
(1) adding propyl orthosilicate into the ethanol/water mixed solution, adding ammonia water, and stirring to obtain a milky mixed solution;
(2) simultaneously adding resorcinol, formaldehyde and melamine into the emulsion mixed solution obtained in the step (1), stirring, centrifuging, cleaning, drying and grinding to obtain a nitrogen-doped hollow mesoporous carbon precursor;
(3) and (3) carbonizing the nitrogen-doped hollow mesoporous carbon precursor obtained in the step (2), desiliconizing, filtering, cleaning and drying to obtain the nitrogen-doped hollow mesoporous carbon.
In the step (1), the volume ratio of the propyl orthosilicate, the ethanol/water mixed solution and the ammonia water is 17.3-34.6: 800: 20-30; the volume ratio of the ethanol to the water in the ethanol/water mixed solution is 3: 1-7: 1; the stirring time is 10 min-20 min.
In the step (2), the ratio of the resorcinol, the formaldehyde and the melamine is 2.2-4.4 g: 2.8-5.6 mL: 1.52-3.04 g; the stirring time is 20-30 h; the centrifugation is carried out at the rotating speed of 6000rpm to 8000 rpm; the cleaning adopts ethanol-water mixed solution; the volume ratio of the ethanol to the water in the ethanol-water mixed solution is 1: 2-1: 3; the drying is carried out at a temperature of 80 ℃ to 100 ℃.
In the above method, further improvement, in the step (3), the carbonization is performed under a nitrogen atmosphere; controlling the flow rate of nitrogen to be 200 mL/min-400 mL/min in the carbonization process; controlling the temperature rise rate to be 5-10 ℃/min in the carbonization process; the carbonization temperature is 600-800 ℃; the carbonization time is 4-5 h; the desiliconization adopts 10 to 20 mass percent hydrofluoric acid solution; the desiliconization is carried out at the temperature of 40-60 ℃; the desiliconization time is 20-24 h; the cleaning step is to clean the solid product obtained by filtering until the pH value is 6.8-7.2; the drying is carried out at a temperature of 80 ℃ to 100 ℃.
In the step S1, the mass ratio of the melamine to the nitrogen-doped hollow mesoporous carbon is 45: 1 to 90: 1; the mass ratio of the melamine to the bismuth nitrate pentahydrate is 9: 1-18: 1; the mass ratio of the bismuth nitrate pentahydrate to the nitrogen-doped hollow mesoporous carbon is 5: 1-10: 1; the time of ultrasonic dispersion is 1-2 h.
In a further improvement of the above method, in step S2, the calcining is performed in a nitrogen atmosphere; controlling the flow rate of nitrogen to be 200 mL/min-400 mL/min in the calcining process; controlling the heating rate to be 2.3 ℃/min-2.5 ℃/min in the calcining process; the calcining temperature is 530-550 ℃; the calcining time is 4-5 h.
In a further improvement of the above method, in step S2, the method further includes grinding the calcined product; the grinding time is 15 min-30 min.
The method is further improved, and the method for removing the antibiotics in the water body by using the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst for catalysis comprises the following steps: mixing the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst with an aqueous solution containing antibiotics, stirring under a dark condition, carrying out a photocatalytic reaction after adsorption balance is achieved, and finishing the treatment of the antibiotics.
In the method, the proportion of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst to the aqueous solution containing the antibiotic is further improved to be 0.5-1 g: 1L.
In the method, the antibiotic in the water solution containing the antibiotic is tetracycline hydrochloride and/or ciprofloxacin hydrochloride; the concentration of the antibiotic in the water solution containing the antibiotic is 10 mg/L-20 mg/L.
In the method, the rotation speed of the stirring is 500-800 rpm; the stirring time is 30-60 min; the photocatalytic reaction is carried out under the irradiation of a xenon lamp; the optical power of the xenon lamp is 45-50W; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 60-120 min.
The innovation points of the invention are as follows:
aiming at the following problems of the existing photocatalyst: the invention creatively dopes nitrogen into hollow mesoporous carbon (N-HMCs) and bismuth trioxide (Bi) and has the advantages of small specific surface area, poor light absorption performance, low photoproduction electron-hole separation rate, easy recombination, weak photocatalysis performance and the like2O3) Modified in graphite phase carbon nitride (g-C)3N4) The surface of the material is modified, thereby constructing a ternary Z-type photocatalyst and remarkably improving g-C3N4Light absorption ability and photocatalytic performance. In one aspect, N-HMCs and Bi2O3The introduction of the N-HMCs can form a Z-type heterojunction structure among the three, wherein the N-HMCs can be in the range of g-C3N4And Bi2O3Plays a good role in electron transfer and is positioned in Bi2O3Electrons in conduction band can be rapidly transferred to g-C through N-HMCs3N4The valence band changes the transmission path of electrons, accelerates the separation efficiency of photoproduction electrons and holes, and reduces the recombination of the photoproduction electrons and the holes. On the other hand, the increase of the efficiency of separating the photo-generated electrons from the holes enables the accumulation of Bi2O3The holes in the valence band are more and more, so the reducibility of the holes is stronger and more, and the holes are accumulated in g-C3N4The conduction band has more and more electrons, so that the oxidability of the material is stronger and stronger, and the photocatalytic performance of the photocatalytic material is obviously improved. In addition, the N-HMCs are multifunctional carbon nano materials and serve as conductive mediators of the Z-type photocatalyst, and the light absorption performance of the photocatalyst can be remarkably improved by doping the N-HMCs in the Z-type photocatalyst, so that the transfer of photo-generated electrons is promoted, the recombination of the photo-generated electrons and holes is reduced, the service life of photo-generated electron current is prolonged, and the photocatalytic performance of the catalyst is improved. Moreover, because the N-HMCs are black, the doping of the N-HMCs can promote the absorption of light, and because the N-HMCs have hollow structures, the reflection of light in the N-HMCs can be increased, and the absorption of light is further enhanced; simultaneously, the bismuth trioxide has better response to ultraviolet light and visible lightThereby increasing the absorption of light by the composite material, and thereby reducing the g-C3N4N-HMCs and Bi2O3The combination of the three materials can enlarge the absorption of the photocatalytic material to light, thereby further improving the utilization rate of light. Furthermore, g-C3N4And Bi2O3The doped N-HMCs have huge specific surface area and pore volume, and the porous characteristic and the excellent specific surface area can provide a large amount of active sites for removing pollutants, so that reactants are favorably adsorbed on the surface of the material, the reactants are closer to a reaction active center, the redox reaction is accelerated, the photocatalytic degradation of the pollutants is accelerated, and the photocatalytic performance of the material is further improved. Therefore, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst has the advantages of strong light absorption capacity, low photo-generated electron-hole recombination rate, good photocatalytic performance and the like, can be widely used for removing pollutants (such as antibiotics) in the environment through photocatalysis, and has good application prospect.
In the invention, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is used for photocatalytic degradation of antibiotics, and the Z-shaped degradation mechanism is met, and the method specifically comprises the following steps: generated from Bi under the condition of illumination2O3Electron transfer of valence band to Bi2O3Conduction band, thereby generating holes. To be in Bi2O3The conduction band electrons are rapidly transmitted to g-C through N-HMCs3N4The valence band of (2) is generated from g-C3N4Electrons of the valence band of (2) are transferred together to g-C3N4So that g-C3N4The conduction band of (a) accumulates a large number of electrons. Accumulated in Bi2O3The holes in the valence band are more and more, so the reducibility of the holes is stronger and more, and the holes are accumulated in g-C3N4The conduction band has more and more electrons, so that the oxidation property of the conduction band is stronger and the strong oxidation reduction property can convert oxygen into superoxide radical (O) with strong oxidation property2 −) To make waterConverted into a strongly oxidizing hydroxyl radical (. OH). The final antibiotic is in the form of O with strong oxidizing property2 −And OH, and a reducing cavity is degraded into carbon dioxide and water. Therefore, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst can quickly and efficiently degrade various types of antibiotics in water.
Compared with the prior art, the invention has the advantages that:
(1) the method for removing the antibiotics in the water body by using the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst for catalysis, disclosed by the invention, can effectively remove different types of antibiotics by using the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst for photocatalytic degradation, has the advantages of high removal rate, high removal speed, easiness in implementation, high safety, low cost, no secondary pollution and the like, particularly can realize the efficient removal of the antibiotics in the water body, and has a good practical application prospect.
(2) In the invention, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst has the advantages of strong light absorption capability, low photoproduction electron-hole recombination rate, good photocatalytic performance, good stability and the like, and is a novel photocatalytic material.
(3) In the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst, the graphite-phase carbon nitride is optimized to be 85-91% in mass percentage, the nitrogen-doped hollow mesoporous carbon is optimized to be 2-5% in mass percentage, and the bismuth trioxide is optimized to be 7-11% in mass percentage, so that the ternary Z-shaped photocatalyst has better photocatalytic performance because the nitrogen-doped hollow mesoporous carbon and the bismuth trioxide have important influence on the performance of the graphite-phase carbon nitride. For example, when the mass percentage of the nitrogen-doped hollow mesoporous carbon is higher than 5%, the doping amount of the nitrogen-doped hollow mesoporous carbon is too large, and since the nitrogen-doped hollow mesoporous carbon has excellent adsorption performance, pollutants (such as antibiotics) can be completely adsorbed, and the photocatalytic performance of graphite-phase carbon nitride can be reduced, at this time, the obtained material can be regarded as an adsorbent, but not a photocatalyst, only the pollutants are transferred from one phase to another phase, the photocatalytic performance of the photocatalyst is difficult to completely remove the pollutants, and the value of the photocatalyst cannot be embodied; when the mass percentage of the nitrogen-doped hollow mesoporous carbon is lower than 2%, the absorption of the catalyst to light can be reduced due to too small doping amount of the nitrogen-doped hollow mesoporous carbon, so that the transfer of photo-generated electron current is reduced, active sites required by reaction can be reduced, and the photocatalytic performance is reduced. For another example, when the mass percentage of the bismuth trioxide is higher than 11%, too much doping amount of the bismuth trioxide can hinder absorption of light by graphite-phase carbon nitride, so that generation of photo-generated electrons-holes of the catalyst is influenced, and the composite catalyst cannot show good photocatalytic performance due to weak photocatalytic performance of the bismuth trioxide; when the mass percentage of the bismuth trioxide is less than 7%, the doping amount of the bismuth trioxide is too small, which may have adverse effects on the transmission of photo-generated electrons and holes, thereby also reducing the photocatalytic performance of the composite catalyst. Therefore, the optimum photocatalytic performance can be exerted only when the contents of the nitrogen-doped hollow mesoporous carbon and the bismuth trioxide are proper, and particularly, the mass percentage of the graphite-phase carbon nitride is 85-91%, the mass percentage of the nitrogen-doped hollow mesoporous carbon is 2-5%, and the mass percentage of the bismuth trioxide is 7-11%, so that the synergistic effect of the three materials can be further promoted, the ternary Z-type photocatalyst can obtain better photocatalytic performance, and antibiotics can be removed more thoroughly.
(4) The preparation method of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst has the advantages of simple process, easily controlled conditions, low cost and the like, and is suitable for large-scale industrial production.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is SEM images of nitrogen-doped hollow mesoporous carbon (N-HMCs), carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite phase Carbon Nitride (CN) and bismuth trioxide (BO) prepared in example 1 of the present invention, wherein (a) is CN, (b) is BO, (c) is N-HMCs, and (d) is CHB.
FIG. 2 is a TEM image of N-doped hollow mesoporous carbon (N-HMCs), carbon nitride/N-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite phase Carbon Nitride (CN), and bismuth trioxide (BO) prepared in example 1 of the present invention, wherein (a) is CN, (b) is BO, (c) is N-HMCs, and (d) is CHB.
Fig. 3 is an XRD chart of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) prepared in example 1 of the present invention.
Fig. 4 is a uv-vis diffuse reflectance spectrum of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) prepared in example 1 of the present invention.
Fig. 5 is a photoluminescence curve of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) prepared in example 1 of the present invention.
Fig. 6 is a graph showing the degradation effect of carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) on tetracycline hydrochloride in example 1 of the present invention.
Fig. 7 is a graph showing the degradation effect of carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) on ciprofloxacin hydrochloride in example 2 of the present invention.
Fig. 8 is a graph of the degradation effect corresponding to when the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is used for repeatedly treating tetracycline hydrochloride solution and ciprofloxacin hydrochloride solution in example 3 of the present invention.
Fig. 9 is a graph showing the degradation effect of tetracycline hydrochloride after addition of a capture agent when a carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is used for catalytically degrading tetracycline hydrochloride in a water body in example 4 of the present invention.
Fig. 10 is a degradation mechanism diagram of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst in embodiment 4 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the adopted process is a conventional process, the adopted equipment is conventional equipment, and the obtained data are average values of three or more repeated experiments.
Example 1
A method for removing antibiotics by using a carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst, in particular to a method for removing tetracycline hydrochloride in a water body by catalysis, which comprises the following steps:
adding 100mg of carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst into 100mL of 10 mg/L tetracycline hydrochloride (TCH) solution, uniformly mixing, adsorbing tetracycline hydrochloride under the conditions of 30 ℃ and 600rpm in the dark, and reaching adsorption balance after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420 nm), and carrying out photocatalytic reaction for 60 min under the conditions of 30 ℃ and 600rpm to finish the TCH treatment.
The tetracycline hydrochloride (TCH) solution is treated under the same conditions by taking graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) and carbon nitride/nitrogen-doped hollow mesoporous carbon/silver phosphate photocatalyst (CHA) as references.
Tetracycline hydrochloride (TCH) solution without any catalyst addition was used as a blank.
In this embodiment, the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is prepared by using graphite-phase carbon nitride as a carrier, and modifying the surface of the graphite-phase carbon nitride with nitrogen-doped hollow mesoporous carbon and bismuth trioxide.
In this example, in the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst, the mass percentage of graphite-phase carbon nitride was 88%, the mass percentage of nitrogen-doped hollow mesoporous carbon was 3.5%, and the mass percentage of bismuth trioxide was 8.5%.
In this embodiment, the preparation method of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst includes the following steps:
(1) 34.6 mL of propyl orthosilicate was added to 800mL of an ethanol/water mixture (the volume ratio of ethanol to water in the ethanol/water mixture was 7: 1), and 30 mL of aqueous ammonia (NH) was added3·H2O, 25 wt%), and stirred at room temperature for 10 min to obtain a uniform milky mixture.
(2) Simultaneously adding 4.4 g of resorcinol, 5.6mL of formaldehyde and 3.04 g of melamine into the milky mixed liquid obtained in the step (1), and continuously stirring for 20 hours at room temperature to obtain an earthy yellow substance; centrifuging the obtained earthy yellow substance at the rotating speed of 6000rpm, rinsing the solid substance obtained by centrifuging with ethanol-water mixed solution (the volume ratio of ethanol to water in the ethanol-water mixed solution is 1: 2), drying in an oven at 80 ℃, and grinding the dried substance into powder to obtain the nitrogen-doped hollow mesoporous carbon precursor.
(3) Placing the nitrogen-doped hollow mesoporous carbon precursor obtained in the step (2) in a zone with N2The tube furnace is carbonized, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2Heating the nitrogen-doped hollow mesoporous carbon precursor to 700 ℃ at the heating rate of 5 ℃/min and calcining for 4h at the flow rate of 200mL/min to obtain black carbide; putting the black carbide into a polytetrafluoroethylene beaker, adding sufficient hydrofluoric acid solution with the mass fraction of 20% into the polytetrafluoroethylene beaker, and desiliconizing the black carbide in a water bath at 60 ℃ for 24 hours; and filtering the desiliconized substance, washing the solid substance obtained by filtering with ultrapure water until the pH is =7.0, and drying in an oven at 80 ℃ to obtain the nitrogen-doped hollow mesoporous carbon which is recorded as N-HMCs.
(4) And (3) simultaneously adding 0.1 g of N-HMCs obtained in the step (3), 4.5 g of melamine and 0.5g of bismuth nitrate pentahydrate into 50 mL of absolute ethyl alcohol, carrying out ultrasonic treatment in a water bath for 1h, placing the mixture into a magnetic stirring water bath kettle at the temperature of 80 ℃, and continuously stirring until the ethyl alcohol is completely volatilized to obtain a uniform photocatalyst precursor mixture.
(5) Loading the photocatalyst precursor mixture obtained in the step (4) into a crucible with a cover, and placing the crucible with a cover in a crucible with an N2The tube furnace of (1) is used for calcining, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2Heating the photocatalyst precursor mixture to 550 ℃ according to the heating rate of 2.3 ℃/min at the flow rate of 200mL/min, calcining for 4h, naturally cooling to room temperature, grinding the obtained calcined product in an agate mortar for 15 min, and uniformly grinding to obtain the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (g-C)3N4/N-HMCs/Bi2O3) And is denoted as CHB.
In this embodiment, the method for preparing graphite-phase carbon nitride includes the following steps: 5g of melamine were placed in a crucible, covered with a lid and placed with N2The tube furnace of (1) is used for calcining, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2The flow rate is 200mL/min, the melamine is heated to 550 ℃ according to the heating rate of 2.3 ℃/min and calcined for 4h, and the mixture is naturally cooledCooling to room temperature, grinding the calcined product in an agate mortar for 15 min, and grinding uniformly to obtain graphite-phase carbon nitride (g-C)3N4) And is denoted as CN.
In this embodiment, the preparation method of bismuth trioxide includes the following steps: placing 5g of bismuth nitrate pentahydrate in a crucible, covering the crucible with a cover, and placing the crucible with N2The tube furnace of (1) is used for calcining, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2Heating bismuth nitrate pentahydrate to 550 ℃ at the heating rate of 2.3 ℃/min at the flow rate of 200mL/min, calcining for 4h, naturally cooling to room temperature, grinding the calcined product in an agate mortar for 15 min, and uniformly grinding to obtain bismuth trioxide (Bi)2O3) Denoted as BO.
In this embodiment, the preparation method of the graphite-phase carbon nitride/bismuth trioxide includes the following steps: adding 4.5 g of melamine and 0.5g of bismuth nitrate pentahydrate into 50 mL of absolute ethyl alcohol, placing the mixture in a water bath for ultrasonic treatment for 1h, continuously stirring the mixture in a magnetic stirring water bath kettle at the temperature of 80 ℃, and obtaining a uniform mixture after the ethyl alcohol is completely volatilized. Transferring the mixture to a crucible, covering it, placing it with N2The tube furnace of (1) is used for calcining, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2Heating the mixture to 550 ℃ at a heating rate of 2.3 ℃/min at a flow rate of 200mL/min, calcining for 4h, naturally cooling to room temperature, grinding the obtained calcined product in an agate mortar for 15 min, and uniformly grinding to obtain graphite-phase carbon nitride/bismuth trioxide (g-C)3N4/Bi2O3) And is denoted as CB.
In this embodiment, the preparation method of the graphite-phase carbon nitride/nitrogen-doped hollow mesoporous carbon includes the following steps: adding 4.5 g of melamine and 0.1 g of the prepared N-HMCs into 50 mL of absolute ethyl alcohol, placing the mixture in a water bath for 1h of ultrasonic treatment, continuously stirring the mixture in a magnetic stirring water bath kettle at the temperature of 80 ℃, and obtaining a uniform mixture after the ethyl alcohol is completely volatilized. Transferring the mixture to a crucible, covering it, placing it with N2The tube furnace of (1) is used for calcining, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2The flow rate was 200mL/min, and the mixture was heatedHeating to 550 ℃ at the speed of 2.3 ℃/min, calcining for 4h, naturally cooling to room temperature, grinding the calcined product in an agate mortar for 15 min, and uniformly grinding to obtain graphite-phase carbon nitride/nitrogen-doped hollow mesoporous carbon (g-C)3N4/N-HMCs) as CH.
In this embodiment, the preparation method of the bismuth trioxide/nitrogen-doped hollow mesoporous carbon comprises the following steps: adding 0.5g of bismuth nitrate pentahydrate and 0.1 g of the prepared N-HMCs into 50 mL of absolute ethyl alcohol, placing the mixture in a water bath for ultrasonic treatment for 1h, continuously stirring the mixture in a magnetic stirring water bath kettle at the temperature of 80 ℃, and obtaining a uniform mixture after the ethyl alcohol is completely volatilized. Transferring the mixture to a crucible, covering it, placing it with N2The tube furnace of (1) is used for calcining, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2The flow rate is 200mL/min, the mixture is heated to 550 ℃ according to the heating rate of 2.3 ℃/min and calcined for 4h, the mixture is naturally cooled to room temperature, the obtained calcined product is placed in an agate mortar to be ground for 15 min and is uniformly ground, and the bismuth trioxide/nitrogen doped hollow mesoporous carbon (Bi) is obtained2O3/N-HMCs), as BH.
In this embodiment, the method for preparing carbon nitride/nitrogen-doped hollow mesoporous carbon/silver phosphate includes the following steps: 80mL of ultrapure water and 10mL of 0.5M Na were added2HPO4Adding into a beaker, stirring in the dark at 25 deg.C for 5min, adding 10mL of 0.5M AgNO prepared in situ3Stirring the solution in dark for 20min, centrifuging the stirred product at 10000rpm for 5min, drying the centrifuged solid at 60 deg.C, and grinding to obtain silver phosphate (Ag)3PO4). 0.1 g of the N-HMCs prepared above, 4.5 g of melamine and 0.5g of silver phosphate are simultaneously added into 50 mL of absolute ethyl alcohol, subjected to ultrasonic treatment in a water bath for 1h, placed in a magnetic stirring water bath kettle at 80 ℃ and continuously stirred until the ethyl alcohol is completely volatilized, and a uniform mixture is obtained. Loading the mixture into crucible with cover, and placing in crucible with N2The tube furnace of (1) is used for calcining, and specifically comprises the following steps: under nitrogen atmosphere and controlling N2The flow rate is 200mL/min, the mixture is heated to 550 ℃ according to the heating rate of 2.3 ℃/min and calcined for 4h, the mixture is naturally cooled to the room temperature, and the obtained calcined product is placed in a containerGrinding in agate mortar for 15 min, and grinding uniformly to obtain the carbon nitride/nitrogen doped hollow mesoporous carbon/silver phosphate photocatalyst (g-C)3N4/N-HMCs/Ag3PO4) And is denoted as CHA.
FIG. 1 is SEM images of nitrogen-doped hollow mesoporous carbon (N-HMCs), carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite phase Carbon Nitride (CN) and bismuth trioxide (BO) prepared in example 1 of the present invention, wherein (a) is CN, (b) is BO, (c) is N-HMCs, and (d) is CHB. As shown in FIG. 1, the N-HMCs are regular and uniform spheres and have a plurality of pores distributed on the surface; g-C3N4Is a layered structure of castellations and has a smooth surface; bi2O3The product is in a solid block shape, and has sharp edges and smooth surface; in the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst, the three materials of the carbon nitride, the nitrogen-doped hollow mesoporous carbon and the bismuth trioxide are firmly connected together, and the N-HMCs and the Bi are2O3Randomly distributed in g-C3N4Above.
FIG. 2 is a TEM image of N-doped hollow mesoporous carbon (N-HMCs), carbon nitride/N-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite phase Carbon Nitride (CN), and bismuth trioxide (BO) prepared in example 1 of the present invention, wherein (a) is CN, (b) is BO, (c) is N-HMCs, and (d) is CHB. As can be seen from fig. 2, the N-HMCs have a hollow inner cavity-porous shell structure, wherein the pore passage of the N-HMCs penetrates through the shell portion and reaches the hollow cavity, the external dimension of the N-HMCs is about 300 nm, and the shell thickness is about 50 nm; CN is a laminated structure; BO is in the form of nanoparticles; the transmission electron micrograph of CHB shows that the three materials are tightly bound together and that the N-HMCs and BO are randomly distributed on the CN surface.
Fig. 3 is an XRD chart of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) prepared in example 1 of the present invention. As can be seen from FIG. 3, CN has two typical crystal planes, namely (100) and (002); BO exhibits multiple crystallographic planes, namely (120), (200), (222), (-014) and (-241) crystallographic planes; the peaks of CH and BH are similar to but slightly different from those of their corresponding monomers, which is caused by the introduction of N-HMCs. Peaks of CB and CHB contain both CN crystal planes and BO crystal planes, which indicates that the CHB of the invention is successfully synthesized.
Fig. 4 is a uv-vis diffuse reflectance spectrum of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) prepared in example 1 of the present invention. As can be seen from FIG. 4, CHB has very good absorption for both UV and visible light, while other monomeric or binary materials have significantly lower absorption than CHB, indicating that the N-HMCs and Bi of the present invention are2O3Modification of g-C3N4The formed z-type heterojunction can remarkably improve the absorption performance of the material to light, thereby improving the utilization rate of the light.
Fig. 5 is a photoluminescence curve of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) prepared in example 1 of the present invention. As can be seen from FIG. 5, the fluorescence intensity of both the monomeric and binary materials is relatively high, indicating that these materials have fast photogenerated electron-hole recombination. The CHB fluorescence intensity is obviously reduced, which shows that the N-HMCs and Bi of the invention2O3Modification of g-C3N4The formed Z-shaped heterojunction improves the separation efficiency of the photo-generated electrons and the photo-generated holes and reduces the recombination of the photo-generated electrons and the photo-generated holes.
From the results shown in fig. 1-5, the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst formed by compounding the nitrogen-doped hollow mesoporous carbon, the bismuth trioxide and the graphite-phase carbon nitride has the advantages of strong light absorption capability, low photo-generated electron-hole recombination rate, good photocatalytic performance and the like.
Fig. 6 is a graph showing the degradation effect of carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) on tetracycline hydrochloride in example 1 of the present invention. As can be seen from fig. 6, compared with other single or binary photocatalysts, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst of the present invention has the best removal effect on TCH, and the removal rate reaches 90.06%. The maximum removal rate of TCH by the carbon nitride/nitrogen-doped hollow mesoporous carbon/silver phosphate photocatalyst (CHA) is 83.61%, which is lower than the removal rate of TCH by the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB) of the invention, probably because of g-C3N4N-HMCs and Ag3PO4Only a general heterojunction structure is formed among the three, and a Z-type heterojunction structure is not formed, so that the electron-hole separation rate is difficult to improve, and simultaneously Ag3PO4Is poor in stability and is easily corroded by light under the illumination condition, thereby also affecting the performance of the material. Therefore, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst has better photocatalytic performance, can more thoroughly remove antibiotics in water, and other monomers, binary photocatalysts or ternary photocatalysts cannot achieve the degradation effect.
In addition, as tested: in the embodiment, when the mass percentage of the N-HMCs is higher than 5%, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst can remove the TCH by 99.15% under a dark reaction, but the TCH is only transferred from one phase to another phase, and the TCH cannot be completely eliminated; when the mass percentage of N-HMCs is lower than 2%, the removal rate of TCH by the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is lower than 78.34%; when Bi is present2O3When the mass percentage content is higher than 11 percent, the carbon nitride/nitrogen doping of the inventionThe removal rate of TCH by the hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is lower than 73.89%; when Bi is present2O3When the mass percentage of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is less than 7%, the removal rate of TCH by the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is less than 84.53%. Therefore, in the invention, when the mass percentage of the graphite-phase carbon nitride is 85-91%, the mass percentage of the nitrogen-doped hollow mesoporous carbon is 2-5%, the mass percentage of the bismuth trioxide is 7-11%, and the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst has a better degradation effect on antibiotics.
Example 2
A method for removing antibiotics by using a carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst, in particular to a method for removing ciprofloxacin hydrochloride in a water body by catalysis, which comprises the following steps:
adding 100mg of carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst into 100mL of 10 mg/L ciprofloxacin hydrochloride (CFH) solution, uniformly mixing, adsorbing ciprofloxacin hydrochloride at 30 ℃ and 600rpm in the dark, and achieving adsorption balance after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420 nm), and carrying out photocatalytic reaction for 60 min under the conditions of 30 ℃ and 600rpm to finish the treatment of the ciprofloxacin hydrochloride.
The ciprofloxacin hydrochloride solution is treated under the same conditions by taking graphite phase Carbon Nitride (CN), bismuth trioxide (BO), graphite phase carbon nitride/bismuth trioxide (CB), graphite phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH) and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) as references.
Ciprofloxacin hydrochloride solution without any catalyst added was used as a blank.
Fig. 7 is a graph showing the degradation effect of carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst (CHB), graphite-phase Carbon Nitride (CN), bismuth trioxide (BO), graphite-phase carbon nitride/bismuth trioxide (CB), graphite-phase carbon nitride/nitrogen-doped hollow mesoporous Carbon (CH), and bismuth trioxide/nitrogen-doped hollow mesoporous carbon (BH) on ciprofloxacin hydrochloride in example 2 of the present invention. As can be seen from fig. 7, compared with other single or binary photocatalysts, the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst of the present invention has the best removal effect on CFH, and the removal rate reaches 78%.
Example 3
Investigating the stability of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst for removing antibiotics in water body
A first group: the method for investigating the stability of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst in removing tetracycline hydrochloride in the water body comprises the following steps:
(1) adding 100mg of carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst into 100mL of 10 mg/L tetracycline hydrochloride (TCH) solution, uniformly mixing, adsorbing tetracycline hydrochloride under the conditions of 30 ℃ and 600rpm in the dark, and reaching adsorption balance after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420 nm), and carrying out photocatalytic reaction for 60 min under the conditions of 30 ℃ and 600rpm to finish the TCH treatment.
(2) And (3) after the treatment in the step (1) is finished, centrifugally separating the mixed solution obtained after the degradation is finished at 6000rpm, removing the supernatant obtained by centrifugation, adding 100mL of 10 mg/L tetracycline hydrochloride (TCH) solution, and repeatedly treating the tetracycline hydrochloride solution under the same condition as that in the step (1) for 6 times. The degradation efficiency of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst on tetracycline hydrochloride was determined after each treatment, and the results are shown in FIG. 8.
Second group: the method for investigating the stability of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst in removing ciprofloxacin hydrochloride in the water body comprises the following steps:
(1) adding 100mg of carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst into 100mL of 10 mg/L ciprofloxacin hydrochloride (CFH) solution, uniformly mixing, adsorbing ciprofloxacin hydrochloride under the conditions of 30 ℃ and 600rpm in the dark, and achieving adsorption balance after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420 nm), and carrying out photocatalytic reaction for 60 min under the conditions of 30 ℃ and 600rpm to finish the treatment of the ciprofloxacin hydrochloride.
(2) After the treatment in the step (1), the mixed solution obtained after the degradation is centrifugally separated at 6000rpm, the supernatant obtained by centrifugation is removed, 100mL of ciprofloxacin hydrochloride solution with the concentration of 10 mg/L is added, and the ciprofloxacin hydrochloride solution is repeatedly treated under the same conditions as the step (1) for 6 times. After each treatment, the degradation efficiency of the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst on ciprofloxacin hydrochloride was determined, and the result is shown in fig. 8.
Fig. 8 is a graph of the degradation effect corresponding to when the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is used for repeatedly treating tetracycline hydrochloride solution and ciprofloxacin hydrochloride solution in example 3 of the present invention. As can be seen from fig. 8, after 6 cycles of experiments, the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst of the present invention still exhibits a good degradation effect on the degradation of antibiotics, wherein the degradation rate on tetracycline hydrochloride after 6 cycles is still 81.03%, and the degradation rate on ciprofloxacin hydrochloride is 69.39%, which indicates that the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst of the present invention has excellent stability.
Example 4
The method for investigating the generation condition of free radicals in the process of catalytically degrading TCH in water by using the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst comprises the following steps:
(1) 3 parts of carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst are taken, each 100mg of the three-component Z-type photocatalyst is added into 100mL of tetracycline hydrochloride (TCH) solution with the concentration of 10 mg/L respectively, the three-component Z-type photocatalyst is uniformly mixed, tetracycline hydrochloride is adsorbed under the conditions of 30 ℃ and 600rpm in the dark, and the adsorption balance is reached after 30 min.
(2) Adding 3 parts of the mixed solution obtained in the step (1) after the adsorption balance is achieved1 mM of triethanolamine (TEA, for capture h) was added separately+) 1 mM p-benzoquinone (BQ, for trapping. O)2 −) And 1 mM isopropanol (IPA, for capture. OH).
(3) And (3) placing each mixed solution obtained in the step (2) under a xenon lamp (lambda is more than 420 nm), and carrying out photocatalytic reaction for 60 min under the conditions of 30 ℃ and 600rpm to finish the TCH treatment.
Control group: no trapping agent is added, and the method specifically comprises the following steps: adding 100mg of carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst into 100mL of 10 mg/L tetracycline hydrochloride (TCH) solution, uniformly mixing, adsorbing tetracycline hydrochloride under the conditions of 30 ℃ and 600rpm, and reaching adsorption balance after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420 nm), and carrying out photocatalytic reaction for 60 min under the conditions of 30 ℃ and 600rpm to finish the TCH treatment.
Fig. 9 is a graph showing the degradation effect of tetracycline hydrochloride after addition of a capture agent when a carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst is used for catalytically degrading tetracycline hydrochloride in a water body in example 4 of the present invention. As can be seen from FIG. 9, compared to the case where no radical scavenger is added, the degradation rate of tetracycline hydrochloride is significantly reduced, wherein the degradation rates of tetracycline hydrochloride after the addition of triethanolamine, benzoquinone, and isopropanol are 41.06%, 31.32%, and 72.63%, respectively, and are reduced by 49%, 58.74%, and 17.43%, respectively, indicating that three radicals (h) are present (i.e., three radicals are present)+，·O2 −OH) plays an important role in the photodegradation of TCH, where O2 −Has the greatest effect on TCH degradation, and then h+Then OH.
Fig. 10 is a degradation mechanism diagram of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst in embodiment 4 of the present invention. As can be seen from FIG. 10, the photocatalytic degradation of antibiotics by the three-element Z-type photocatalyst of carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide of the present invention follows the Z-type degradation mechanism, i.e., the generation of Bi under the illumination condition2O3Electron transfer of valence band to Bi2O3Conducting the belt fromAnd holes are generated. To be in Bi2O3The conduction band electrons are rapidly transmitted to g-C through N-HMCs3N4The valence band of (2) is generated from g-C3N4Electrons of the valence band of (2) are transferred together to g-C3N4So that g-C3N4The conduction band of (a) accumulates a large number of electrons. Accumulated in Bi2O3The holes in the valence band are more and more, so the reducibility of the holes is stronger and more, and the holes are accumulated in g-C3N4The conduction band has more and more electrons, so that the oxidation property of the conduction band is stronger and the strong oxidation reduction property can convert oxygen into superoxide radical (O) with strong oxidation property2 −) So that the water is converted into a strongly oxidizing hydroxyl radical (. OH). The final antibiotic is in the form of O with strong oxidizing property2 −And OH, and a reducing cavity is degraded into carbon dioxide and water.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (9)
1. A method for removing antibiotics by using a carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is characterized in that the method adopts the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst to treat the antibiotics; the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst takes graphite-phase carbon nitride as a carrier, and the surface of the graphite-phase carbon nitride is modified with nitrogen-doped hollow mesoporous carbon and bismuth trioxide; the mass percentage content of graphite phase carbon nitride in the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst is 85-91%, the mass percentage content of nitrogen-doped hollow mesoporous carbon is 2-5%, and the mass percentage content of bismuth trioxide is 7-11%.
2. The method of claim 1, wherein the preparation method of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst comprises the following steps:
s1, ultrasonically dispersing melamine, bismuth nitrate pentahydrate and nitrogen-doped hollow mesoporous carbon in ethanol, and heating to completely volatilize the ethanol to obtain a photocatalyst precursor mixture;
and S2, calcining the photocatalyst precursor mixture obtained in the step S1 to obtain the carbon nitride/nitrogen-doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst.
3. The method according to claim 2, wherein in the step S1, the method for preparing the nitrogen-doped hollow mesoporous carbon comprises the following steps:
(1) adding propyl orthosilicate into the ethanol/water mixed solution, adding ammonia water, and stirring to obtain a milky mixed solution;
(2) simultaneously adding resorcinol, formaldehyde and melamine into the emulsion mixed solution obtained in the step (1), stirring, centrifuging, cleaning, drying and grinding to obtain a nitrogen-doped hollow mesoporous carbon precursor;
(3) and (3) carbonizing the nitrogen-doped hollow mesoporous carbon precursor obtained in the step (2), desiliconizing, filtering, cleaning and drying to obtain the nitrogen-doped hollow mesoporous carbon.
4. The method according to claim 3, wherein in the step (1), the volume ratio of the propyl orthosilicate, the ethanol/water mixed solution and the ammonia water is 17.3-34.6: 800: 20-30; the volume ratio of the ethanol to the water in the ethanol/water mixed solution is 3: 1-7: 1; the stirring time is 10 min-20 min;
in the step (2), the ratio of the resorcinol, the formaldehyde and the melamine is 2.2-4.4 g to 2.8-5.6 mL to 1.52-3.04 g; the stirring time is 20-30 h; the centrifugation is carried out at the rotating speed of 6000rpm to 8000 rpm; the cleaning adopts ethanol-water mixed solution; the volume ratio of the ethanol to the water in the ethanol-water mixed solution is 1: 2-1: 3; the drying is carried out at the temperature of 80-100 ℃;
in the step (3), the carbonization is performed in a nitrogen atmosphere; controlling the flow rate of nitrogen to be 200 mL/min-400 mL/min in the carbonization process; controlling the temperature rise rate to be 5-10 ℃/min in the carbonization process; the carbonization temperature is 600-800 ℃; the carbonization time is 4-5 h; the desiliconization adopts 10 to 20 mass percent hydrofluoric acid solution; the desiliconization is carried out at the temperature of 40-60 ℃; the desiliconization time is 20-24 h; the cleaning step is to clean the solid product obtained by filtering until the pH value is 6.8-7.2; the drying is carried out at a temperature of 80 ℃ to 100 ℃.
5. The method as claimed in claim 2, wherein in the step S1, the mass ratio of melamine to nitrogen-doped hollow mesoporous carbon is 45: 1-90: 1; the mass ratio of the melamine to the bismuth nitrate pentahydrate is 9: 1-18: 1; the mass ratio of the bismuth nitrate pentahydrate to the nitrogen-doped hollow mesoporous carbon is 5: 1-10: 1; the ultrasonic dispersion time is 1-2 h;
in the step S2, the calcination is performed under a nitrogen atmosphere; controlling the flow rate of nitrogen to be 200 mL/min-400 mL/min in the calcining process; controlling the heating rate to be 2.3 ℃/min-2.5 ℃/min in the calcining process; the calcining temperature is 530-550 ℃; the calcining time is 4-5 h;
in step S2, grinding the calcined product; the grinding time is 15 min-30 min.
6. The method according to any one of claims 1 to 5, wherein the step of removing antibiotics in the water body by using the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst comprises the following steps: mixing the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst with an aqueous solution containing antibiotics, stirring under a dark condition, carrying out a photocatalytic reaction after adsorption balance is achieved, and finishing the treatment of the antibiotics.
7. The method of claim 6, wherein the ratio of the carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-type photocatalyst to the antibiotic-containing aqueous solution is 0.5-1 g: 1L.
8. The method according to claim 7, wherein the antibiotic in the antibiotic-containing aqueous solution is tetracycline hydrochloride and/or ciprofloxacin hydrochloride; the concentration of the antibiotic in the water solution containing the antibiotic is 10 mg/L-20 mg/L.
9. The method according to claim 7 or 8, wherein the rotation speed of the stirring is 500 rpm to 800 rpm; the stirring time is 30-60 min; the photocatalytic reaction is carried out under the irradiation of a xenon lamp; the optical power of the xenon lamp is 45-50W; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 60-120 min.
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