CN111266126B - Preparation method and application of sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst - Google Patents
Preparation method and application of sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst Download PDFInfo
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- CN111266126B CN111266126B CN202010115591.2A CN202010115591A CN111266126B CN 111266126 B CN111266126 B CN 111266126B CN 202010115591 A CN202010115591 A CN 202010115591A CN 111266126 B CN111266126 B CN 111266126B
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Abstract
A sulfur-doped graphite-like phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst takes a sulfur-doped graphite-like phase carbon nitride nanosheet as a carrier, and graphene and ferroferric oxide particles are modified on the sulfur-doped graphite-like phase carbon nitride nanosheet. The preparation method comprises the steps of preparing the sulfur-doped graphite-phase carbon nitride nanosheet by high-temperature pyrolysis of thiourea, preparing the sulfur-doped graphite-phase carbon nitride-loaded graphene composite material by an impregnation method, and preparing the sulfur-doped graphite-phase carbon nitride-loaded graphene and ferroferric oxide composite photocatalyst material by an alkaline-thermal coprecipitation method. The composite magnetic photocatalyst has the advantages of high photocatalytic activity, good stability, easy recovery of magnetic force, simple preparation process, low cost and good safety. The composite magnetic photocatalyst can be used for treating wastewater containing various antibiotic drugs, and has the advantages of good stability and practicability, high efficiency, simple and convenient operation, low cost and high recycling value.
Description
Technical Field
The invention belongs to the technical field of functional composite photocatalysts and application thereof, and relates to a graphite-like phase carbon nitride nanosheet composite photocatalyst as well as a preparation method and application thereof, in particular to a preparation method and application of a sulfur-doped graphite-like phase carbon nitride nanosheet loaded graphene and ferroferric oxide composite magnetic photocatalyst.
Background
In recent years, the problems of environmental water pollution and energy shortage are increasingly highlighted, and the traditional environmental remediation technology can not meet the requirements of people gradually, so that the search for a novel efficient and energy-saving environmental remediation technology becomes one of the current popular researches. In recent years, researches on photocatalytic advanced oxidation technology based on semiconductor catalysts have attracted attention from researchers all over the world by virtue of the characteristics of good effect, low cost, easy operation and the like, and nanotechnology using nano semiconductor catalyst materials has been rapidly developed. With the updating and development of the efficient visible light catalyst, the method also has good application prospect in removing the organic matters which are difficult to degrade in the water body by using the visible light as a light source.
Currently, graphite-like phase carbon nitride (g-C) 3 N 4 ) Due to its unique semiconductor band structure and excellent chemical stability and no metal component, simple preparation process and low price, it is introduced into the field of photocatalysis as a visible light catalyst, which can be prepared by simple steps from some cheap precursors such as urea, thiourea, melamine, etc. While g-C 3 N 4 Has high thermal stability, acid and alkali resistance, strong conductivity and proper conduction band and valence band, and has good photocatalytic performance, such as g-C 3 N 4 Has wide application prospect in the field of photocatalysis. However, the conventional methods for preparing graphite-like carbon nitride have the problems of large bulk particles, small specific surface area, low crystallinity, incomplete polymerization and the like, so that the application prospect of the carbon nitride material is limited, and the preparation method can be further improved. Meanwhile, in terms of use properties, the conventional graphite-like carbon nitride also has the problems of high recombination rate of photo-generated electron holes, difficulty in recovering a catalyst used in the field of water treatment and the like. Therefore, the research on the composite modification catalytic effect of the graphite-phase carbon nitride which is cheap and environment-friendly is more in line with the purpose of degrading environmental water pollutants by the photocatalysis technology.
Because of the high saturation magnetization and superparamagnetic property, the ferroferric oxide nano material is widely applied to a plurality of fields of information storage, sensor design, medical targeted drug delivery, sewage treatment and the like at present, and some researchers form a plurality of semiconductor photocatalysts such as titanium dioxide/ferroferric oxide, zinc oxide/ferroferric oxide and the like by taking the ferroferric oxide as a magnetic carrier. The research on the properties of the composite catalyst shows that the successfully compounded composite catalyst material not only has magnetism, but also has stronger photocatalytic performance in the degradation aspect of organic pollutants in water. The phenomenon occurs because the ferroferric oxide material has high conductivity and a proper energy band structure, so that the separation and transmission of photo-generated electron hole pairs can be improved, and the recombination rate of the photo-generated electron hole is reduced. Graphene is widely applied to the application aspects of capacitors and semiconductor composite materials by virtue of a special two-dimensional honeycomb structure and excellent mechanical heat, light and electron conduction capabilities. Meanwhile, the photocatalyst has high specific area and lower manufacturing cost, so that the photocatalyst has good prospect in the aspect of compounding with a semiconductor photocatalyst as an intermediate.
Therefore, the purpose of the work is to combine the graphite-like phase carbon nitride, the graphene and the ferroferric oxide into a composite photocatalyst material, so that the photocatalysis performance and the recycling durability of the semiconductor photocatalyst are improved, and the work has important research significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst which is high in photocatalytic activity, good in stability and easy to recycle, and an application of the photocatalyst in antibiotic degradation. The visible light semiconductor catalyst material prepared by the technology is a crystalline substance, has a nano-scale particle size, and can be uniformly distributed and stably exist in an aqueous solution. The technology has simple process, wide raw materials and low cost, meets the actual production requirement, and has great industrial application potential in the aspects of semiconductor catalyst materials, solar energy, water treatment and organic matter degradation and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst comprises sulfur-doped graphite-phase carbon nitride nanosheets, graphene and ferroferric oxide particles; the single-layer graphene is attached to the surface of the sulfur-doped graphite-phase carbon nitride nanosheet to form a graphene-loaded sulfur-doped graphite-phase carbon nitride nanosheet composite material; the ferroferric oxide particles are attached to the surface of the graphene-loaded sulfur-doped graphite-phase carbon nitride nanosheet composite material to form the ferroferric oxide and graphene-loaded sulfur-doped graphite-phase carbon nitride nanosheet composite material.
In the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst, preferably, the single-layer graphene is attached to the surface of the sulfur-doped graphite-phase carbon nitride nanosheet through a dipping dispersion method, and the mass ratio of the single-layer graphene to the sulfur-doped graphite-phase carbon nitride nanosheet is 1 (500-1000); the ferroferric oxide particles are attached between layers and on the surface of the sulfur-doped graphite-phase carbon nitride nanosheets by an alkali-thermal coprecipitation method, and the mass ratio of the ferroferric oxide particles to the sulfur-doped graphite-phase carbon nitride nanosheets is 1 (5-20).
As a general technical concept, the invention provides a preparation method of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst, which comprises the following steps:
s1, thiourea is used as a precursor, the mixture is heated for a certain time in a special device and high-temperature environment, and sulfur-doped carbon nitride nanosheets are obtained after screening, grinding and sieving treatment.
And S2, mixing the graphene oxide solution with the sulfur-doped carbon nitride nanosheets obtained in the step S1, and performing ultrasonic dispersion to obtain the sulfur-doped graphite-like phase carbon nitride nanosheet-loaded graphene composite photocatalyst.
S3, dispersing and mixing ferrous chloride and ferric chloride solution with the sulfur-doped carbon nitride nanosheet-loaded graphene composite photocatalyst obtained in the step S2, heating in a water bath, and adding ammonia water to realize alkali-heat coprecipitation to obtain the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst.
In the above preparation method, preferably, the preparation method of the sulfur-doped graphite-like phase carbon nitride nanosheet includes the following steps:
(1) preparing a precursor: weighing 20-30 g of thiourea, wherein the thiourea does not need to be subjected to any pretreatment;
(2) and (3) calcining: two crucibles, 40 ml and 100 ml, were prepared and the thiourea obtained in step (1) was placed in a small crucible of 40 ml. The 40 ml crucible was then placed in a 100 ml crucible as shown in figure 1. Then, a cover is covered on the 100 ml crucible, the crucible and the cover are wound by using tin foil paper to be fixed, and finally the crucible and the cover are placed into a muffle furnace to be heated and calcined.
(3) Setting a programmed temperature rise step: and (3) setting a heating program at a heating rate of 2-3 ℃ per minute from a room temperature state, heating to 550 ℃, and keeping the temperature for 3-4 hours for calcination, wherein no inert protective gas is needed in the calcination process.
(4) And after the calcination and heat preservation are finished, naturally cooling to room temperature. The crucible is opened, the beige substance which is the target material of the sulfur-doped graphite-like carbon nitride nanosheet is covered on the pot cover of the 100 ml crucible and attached to the inner wall of the pot, and the beige substance is ground and sieved by a 300-mesh sieve.
In the preparation method, preferably, the preparation method of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene composite photocatalyst comprises the following steps:
(1) adding the graphene dispersion into a mixed solution of ethanol and water, and stirring for 0.5 to 1 hour
(2) Adding sulfur-doped graphite-like carbon nitride nanosheets into the obtained dispersion, stirring the mixture solution for 0.5 to 1 hour, and then ultrasonically dispersing for 0.5 to 1 hour to obtain the sulfur-doped carbon nitride nanosheet loaded graphene composite photocatalyst suspension.
(3) And centrifugally collecting, washing and drying to obtain the sample sulfur-doped carbon nitride nanosheet loaded graphene composite photocatalyst.
In the preparation method of the sulfur-doped graphite-like carbon nitride nanosheet-loaded graphene composite photocatalyst, preferably, in the step (1), the volume ratio of ethanol to water in the ethanol-water mixed solution is 1 (1-2);
and/or in the step (2), the mass ratio of the graphene dispersion to the sulfur-doped graphite-phase carbon nitride nanosheets is 1 (500-1000), and the mass-to-volume ratio of the sulfur-doped graphite-phase carbon nitride nanosheets to the solution of ethanol and water is 1 g (50-60) ml;
and/or in the step (3), the drying temperature of the sulfur-doped carbon nitride nanosheet loaded graphene composite photocatalyst is 60-70 ℃, and the time is 7-8 hours.
In the above preparation method, preferably, the preparation method of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst comprises the following steps:
(1) dissolving ferric trichloride and ferric dichloride tetrahydrate in distilled water, and adding the solution into the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene composite photocatalyst suspension.
(2) The mixed solution is heated and stirred for 30 to 40 minutes, then ammonia water is rapidly added into the mixed solution and continuously stirred for 30 to 40 minutes, and then the solution is naturally cooled.
(3) The prepared precipitate is collected by centrifugation, washed with ethanol and water alternately for 2-3 times, and dried in an oven for 10 hours.
In the preparation method of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst, preferably, in the step (1), the mass ratio of ferric trichloride to ferrous chloride tetrahydrate is (1.6-1.8): 1; the mass volume ratio of the ferric trichloride to the distilled water is 1 g (80-650 ml); the mass ratio of the ferric trichloride to the sulfur-doped graphite-phase carbon nitride nanosheets is 1 (2-13); the mass ratio of the generated ferroferric oxide particles to the sulfur-doped graphite-phase carbon nitride nanosheets is 1 (5-20).
And/or, in the step (2): the heating temperature is 80-85 ℃;
and/or, in the step (2): the ammonia water is generally 5-10 ml;
and/or, in the step (3): the temperature of the oven is set to be 60-70 ℃.
As a general technical concept, the invention also provides an application of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst prepared by the preparation method in antibiotic wastewater treatment, which comprises the following steps: mixing the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene, a ferroferric oxide composite magnetic photocatalyst and antibiotic wastewater to perform photocatalytic reaction, and finishing the treatment of the antibiotic wastewater.
In the above application, preferably, the addition amount of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst is 0.2 g to 1.5 g of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst added to each liter of the antibiotic wastewater;
and/or the antibiotics in the antibiotic wastewater are ranitidine and oxytetracycline; the initial concentration of the antibiotics in the antibiotic wastewater is 2-20 mg per liter;
and/or the light source of the photocatalytic reaction is a xenon lamp;
and/or the time of the photocatalytic reaction is 0.8-1 hour.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst, which takes a sulfur-doped graphite-phase carbon nitride nanosheet as a carrier and modifies graphene and ferroferric oxide particles on the sulfur-doped graphite-phase carbon nitride nanosheet. Firstly, the sulfur-doped graphite-like phase carbon nitride nanosheets are adopted, and the doping of the thionine can improve the absorption capacity and the electron conduction capacity of the graphite-like phase carbon nitride in visible light and can further improve the photocatalytic effect of the graphite-like phase carbon nitride material; meanwhile, the graphene-loaded sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene composite catalyst disclosed by the invention has the advantages that the specific surface area is further increased due to the graphene loading, the material can be promoted to provide more active sites, so that the contact between the catalyst material and a reactant is more sufficient, the transfer of photo-generated electrons on the surface of a semiconductor is facilitated, the hole recombination rate of the photo-generated electrons is reduced, and the photocatalytic efficiency is improved. And secondly, the ferroferric oxide particles are loaded on the sulfur-doped graphite-phase carbon nitride nanosheets, and the ferroferric oxide particles and the sulfur-doped graphite-phase carbon nitride nanosheets are tightly combined to form a heterojunction, so that separation of photo-generated electrons and holes is facilitated, and the recombination of the photo-generated electrons and the holes is reduced, thereby improving the photocatalytic performance of the material. Meanwhile, due to the addition of ferroferric oxide, the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst has magnetism, the effective separation and recycling performance of the photocatalyst is improved, and the application of the photocatalyst in the field of water treatment is enhanced.
2. The invention also provides a preparation method of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst, thiourea, graphene dispersion, ferrous chloride tetrahydrate and ferric chloride are used as raw materials, the sulfur-doped graphite-phase carbon nitride nanosheet is prepared through a muffle furnace program type high-temperature method, graphene is attached to the surface of the sulfur-doped graphite-phase carbon nitride nanosheet through an impregnation method, and the sulfur-doped carbon nitride nanosheet-loaded graphene composite photocatalyst is prepared. And loading ferroferric oxide particles on the surface of the sulfur-doped carbon nitride nanosheet-loaded graphene composite photocatalyst by an alkaline-thermal coprecipitation method to prepare the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst. The whole process steps of the invention are simple and easy to implement, the whole process steps are carried out under the normal pressure condition, the requirement on equipment is lower, and a reactor with high pressure operation such as a reaction kettle is not required, so that the risk of an experiment is reduced. Meanwhile, the raw materials used by the method are common cheap chemicals, no dangerous chemicals are used, and the method has the characteristics of safety, low cost and the like. Compared with other methods, the preparation method has the advantages of simple and convenient operation, low cost, high safety coefficient, low energy consumption and the like.
3. According to the preparation method of the sulfur-doped graphite-like carbon nitride nanosheet, thiourea is used as a precursor, and the thiourea is formed by special elements, so that the graphite-like carbon nitride prepared at high temperature contains a small amount of sulfur doping, and the doping of the thionin can improve the absorption capacity and the electron conduction capacity of the graphite-like carbon nitride in visible light, and can further improve the photocatalytic effect of the graphite-like carbon nitride material; meanwhile, ammonia gas can be released from the thiourea substance in the high-temperature pyrolysis process, and the ammonia gas can pass through the surface of the material in the release process, so that the surface of the material is uneven, and the specific surface area of carbon nitride is increased. Meanwhile, the ammonia gas can bring out target materials in the rising process, and the materials can be uniformly dispersed around the pot wall through a special crucible stacking device, so that the high-efficiency sulfur-doped graphite-like carbon nitride nanosheet is obtained through the method.
4. The invention also provides a method for treating the antibiotic wastewater. The prepared sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst is added into wastewater containing antibiotics, photocatalytic reaction is carried out under the irradiation of visible light, and the effect of degrading the antibiotics within a certain time is good under conventional conditions. Meanwhile, the magnetic catalyst has the characteristics of simple use of green ring, low cost, good cyclability, high stability, easy separation and the like.
Drawings
FIG. 1 is a schematic diagram illustrating the position of a crucible during the preparation of a sulfur-doped graphite-like carbon nitride material according to an embodiment of the present invention.
FIG. 2 is a drawing of sulfur-doped graphite-like carbon nitride nanosheets (g-C) in an embodiment of the present invention 3 N 4 ) The sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (x% -Fe) containing ferroferric oxide with different mass fractions 3 O 4 /GE/CN), Graphene (Graphene) and ferroferric oxide particles (Fe) 3 O 4 ) XRD pattern of (a).
Fig. 3 is a scanning electron microscope image of the sulfur-doped graphite-phase carbon nitride nanosheet and the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst in the embodiment of the present invention; the composite magnetic photocatalyst comprises a sulfur-doped graphite-phase carbon nitride nanosheet, a graphene-loaded ferroferric oxide composite magnetic photocatalyst, a sulfur-doped graphite-phase carbon nitride nanosheet, and c and d.
FIG. 4 shows sulfur-doped graphite-like carbon nitride nanosheets (g-C) in an embodiment of the present invention 3 N 4 ) Sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (x% -Fe) containing ferroferric oxide with different mass fractions 3 O 4 FT-IR spectrum of/GE/CN).
Fig. 5 is a Mapping diagram of element distribution of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst in the embodiment of the present invention.
Fig. 6 is an ultraviolet-visible light absorption spectrum (UV-Vis) diagram of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst in the embodiment of the present invention.
Fig. 7 is a hysteresis loop curve diagram of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst in the embodiment of the present invention.
FIG. 8 is a sulfur-doped graphite-like carbon nitride nanosheet (g-C) in an embodiment of the present invention 3 N 4 ) The sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene composite photocatalyst (0.1% wt-GE/CN) and the sulfur-doped graphite-phase carbon nitride nanosheet-loaded ferroferric oxide composite photocatalyst (20% wt-Fe) 3 O 4 /CN), sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (x% -Fe) containing ferroferric oxide with different mass fractions 3 O 4 /GE/CN) in the visible region (wavelength. lambda.)>400 nm) of the sample, the relationship of the concentration of ranitidine along with the change of photocatalytic time in the photocatalytic degradation process is shown schematically.
FIG. 9 shows an embodiment of the invention in which a sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) 3 O 4 /GE/CN) in the visible region (wavelength. lambda.)>400 nm) under different initial concentrations, the relationship diagram of the change of the concentration of ranitidine along with the photocatalytic time in the process of photocatalytic degradation of ranitidine wastewater with different initial concentrations.
FIG. 10 shows that different sulfur-doped graphite-phase carbon nitride nanosheets are used to support a graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) 3 O 4 The concentration of/GE/CN) is in the visible light region (wavelength lambda)>400 nm) of the sample, the relationship of the concentration of ranitidine along with the change of photocatalytic time in the photocatalytic degradation process is shown schematically.
FIG. 11 shows that the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) in the embodiment of the present invention 3 O 4 /GE/CN) in the visible region (wavelength. lambda.)>400 nm) under different pH values, the concentration of ranitidine changes along with the photocatalytic time in the process of photocatalytic degradation of ranitidine wastewater with different pH values.
FIG. 12 shows a sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) in an embodiment of the present invention 3 O 4 /GE/CN) in the visible region (wavelength. lambda.)>400 nm) under the condition of photocatalytic degradation of waste water containing ranitidine and oxytetracycline, and a schematic diagram of the relationship between the concentration of ranitidine and oxytetracycline along with the change of photocatalytic time.
FIG. 13 shows an embodiment of the invention in which a sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) 3 O 4 /GE/CN) in the visible region (wavelength. lambda.)>400 nm), the concentration of ranitidine changes along with the photocatalytic time in the process of photocatalytic degradation of ranitidine wastewater by repeated cyclic utilization for many times.
Detailed Description
The invention is further described with reference to the following figures and examples.
The raw materials and instruments used in the following examples are commercially available, wherein the light source system was a rotary photochemical reactor phchemiii, equipped with a 300 watt xenon lamp, purchased from nigbit, beijing.
Example 1
Specifically, a sulfur-doped graphite-phase carbon nitride nano-material with ferroferric oxide accounting for 20 mass percent is preparedSheet-loaded graphene (mass fraction is 0.2%) and ferroferric oxide composite magnetic photocatalyst (20% -Fe) 3 O 4 /GE/CN) include sulfur-doped graphite-like carbon nitride nanosheets, graphene dispersions (commercially available), ferroferric oxide particles. The catalyst takes sulfur-doped graphite-like phase carbon nitride nanosheets as a carrier, and graphene and ferroferric oxide particles are modified on the sulfur-doped graphite-like phase carbon nitride nanosheets.
In this embodiment, graphene and ferroferric oxide particles are uniformly attached to the surface of the sulfur-doped graphite-phase carbon nitride nanosheet.
In the embodiment, a sulfur-doped graphite-phase carbon nitride-loaded graphene photocatalyst composite material is formed by loading and modifying a graphene dispersion on a sulfur-doped graphite-phase carbon nitride nanosheet in a dipping manner, wherein the mass ratio of graphene to the sulfur-doped graphite-phase carbon nitride nanosheet is 1: 500;
in the embodiment, ferroferric oxide particles are loaded and modified on a sulfur-doped graphite-phase carbon nitride-loaded graphene photocatalyst composite material in an alkaline-thermal coprecipitation mode to form the sulfur-doped graphite-phase carbon nitride-loaded graphene and ferroferric oxide photocatalyst composite material, wherein the mass ratio of ferroferric oxide to sulfur-doped graphite-phase carbon nitride nanosheets is 1: 5;
the preparation method of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst composite material of the embodiment comprises the following steps:
(1) preparing a precursor: weighing 20 g of thiourea, wherein the thiourea does not need to be subjected to any pretreatment;
(2) and (3) calcining: two crucibles of 40 ml and 100 ml are prepared, and the thiourea obtained in step (1) is placed in a small crucible of 40 ml. The 40 ml crucible was then placed in a 100 ml crucible as shown in figure 1. Then, a cover is covered on the 100 ml crucible, the crucible and the cover are wound by using tin foil paper to be fixed, and finally the crucible and the cover are placed into a muffle furnace to be heated and calcined.
(3) Setting a programmed temperature rise step: and (3) setting a temperature rise program at the temperature rise rate of 2 ℃ per minute from the room temperature state, raising the temperature to 550 ℃ and preserving the temperature for 4 hours for calcination, wherein no inert protective gas is needed in the calcination process.
(4) And after the calcination heat preservation is finished, naturally cooling to room temperature. Opening the crucible, covering the crucible with 100 ml of crucible and attaching beige substances on the inner wall of the crucible, namely the sulfur-doped graphite-like carbon nitride nanosheets serving as the target materials, and grinding and sieving the nanosheets by a 300-mesh sieve to obtain the sulfur-doped graphite-like carbon nitride nanosheets.
(5) 0.1 ml (i.e. 0.4 mg) of the graphene dispersion (4 mg per ml, commercially available) was added to 100 ml of absolute ethanol/water (V) 1 /V 2 1: 1) in the mixed solution, stirring was carried out at 600 rpm for 0.5 hour
(6) And (4) adding 0.2 g of sulfur-doped graphite-like carbon nitride nanosheets prepared in the step (4) into the dispersion obtained in the step (5), stirring the mixture solution at 600 rpm for 0.5 hour, and then ultrasonically dispersing for 0.5 hour to prepare the sulfur-doped graphite-like carbon nitride-loaded graphene composite photocatalyst suspension.
(7) 0.07 g of ferric chloride and 0.042 g of ferrous chloride tetrahydrate were dissolved in 10 ml of deionized water and added to the suspension of step (6). The mixed solution was stirred at 80 ℃ for 30 minutes at 600 rpm, then 10 ml of ammonia water was quickly added to the mixed solution and stirring was continued for 30 minutes at 600 rpm, and finally the solution was allowed to cool naturally. (step (7) supplement, namely preparing sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst containing different ferroferric oxide mass fractions (5-30%), and only adding ferric chloride and ferrous chloride tetrahydrate with different masses to complete the preparation, wherein the specific required masses are shown in the following table.)
TABLE 1 different mass fractions Fe 3 O 4 Permeability meter for preparing material by/GE/CN
(8) And (3) collecting the prepared precipitate by centrifugation, alternately washing the precipitate by deionized water and absolute ethyl alcohol for 3 times respectively, drying the precipitate in air at 60 ℃ for 10 hours, grinding and sieving the dried precipitate by a 300-mesh screen, and finally preparing the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst.
Material characterization 1X-ray diffraction Spectroscopy (XRD)
Graphene and ferroferric oxide composite magnetic photocatalyst (Fe) supported on sulfur-doped graphite-phase carbon nitride nanosheets prepared in example 1 3 O 4 /GE/CN), sulfur-doped graphite-like carbon nitride nanosheets (g-C) 3 N 4 ) And Graphene (Graphene) and ferroferric oxide particles (Fe) 3 O 4 ) The results of XRD analysis by an X-ray spectrometer are shown in FIG. 2. As can be seen from FIG. 2, the sulfur-doped graphite-like phase carbon nitride nanosheets (g-C) prepared in example 1 3 N 4 ) Shows typical carbon nitride diffraction peak, Graphene (Graphene) is amorphous and amorphous, has no fixed standard characteristic peak, and ferroferric oxide particles (Fe) 3 O 4 ) Shows a typical ferroferric oxide diffraction peak, and contains sulfur-doped graphite-phase carbon nitride nanosheets with different ferroferric oxide mass fractions and loaded graphene and ferroferric oxide composite magnetic photocatalyst (Fe) 3 O 4 /GE/CN) shows diffraction peaks similar to those of graphite-phase carbon nitride nanosheets, and also contains characteristic peaks of ferroferric oxide. The crystal structure of the graphite phase carbon nitride nanosheet is not changed by the load of the graphene and the ferroferric oxide with different mass fractions, which has very important significance for maintaining the excellent photocatalytic performance of the composite material.
Scanning electron microscope SEM analysis was performed on the sulfur-doped graphite-phase carbon nitride nanosheets and the sulfur-doped graphite-phase carbon nitride nanosheets-supported graphene and ferroferric oxide composite magnetic photocatalyst in example 1, and the results are shown in fig. 3, where (a) (b) is the sulfur-doped graphite-phase carbon nitride nanosheets, and (c) (d) is the sulfur-doped graphite-phase carbon nitride nanosheets-supported graphene and ferroferric oxide composite magnetic photocatalyst. As can be seen from fig. 3, (a) (b) pure sulfur-doped graphite-like phase carbon nitride nanosheets exhibit a typical platelet structure and a smooth surface; in contrast, (c) (d) the sulfur-doped graphite-phase carbon nitride nanosheets load graphene and ferroferric oxide composite magnetic photocatalyst, more ferroferric oxide particles are distributed on the surface of the photocatalyst, and are well dispersed on the surface and the periphery of the sulfur-doped graphite-phase carbon nitride nanosheets, so that the material is magnetic, the surface of the material is rough and uneven, the specific surface area of the material is increased, the large specific surface area can provide more active sites and adsorb more pollutants, and the photocatalytic reaction is promoted to be carried out.
Material characterization 3 Fourier Infrared transform Spectroscopy characterization (FT-IR)
The sulfur-doped graphite-phase carbon nitride nanosheets and the sulfur-doped graphite-phase carbon nitride nanosheets loaded graphene and ferroferric oxide composite magnetic photocatalyst in example 1 were subjected to infrared absorption spectrum FT-IR analysis, respectively. The results are shown in fig. 4, and the positions of the characteristic peaks of the several materials are not obviously different, which indicates that the materials have the same molecular structure. At 812cm -1 The characteristic peak in position is due to the stretching vibration of the triazine ring unit; at 1250- -1 The several characteristic peaks are mainly due to C in the graphite-like phase carbon nitride nanosheet structural unit 6 N 7 Stretching and contracting vibration of the ring; the result shows that the crystal structure of the graphite phase carbon nitride nanosheet is not changed by the loading of the graphene and the ferroferric oxide with different mass fractions, which has very important significance for maintaining the excellent photocatalytic performance of the composite material.
EDX elemental analysis and Mapping elemental distribution analysis were performed on the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and the ferroferric oxide composite magnetic photocatalyst in example 1, respectively, and the results are shown in the graph. According to the EDX line scanning result of the element energy spectrum, the composite material detects five elements of carbon, nitrogen, oxygen, sulfur and iron, and the contents are shown in the following table 2:
table 2 EDX elemental analysis table
| Element(s) | Weight (%) | Atom (%) |
| Carbon (C) | 42.57 | 49.14 |
| Nitrogen | 45.15 | 44.68 |
| Oxygen gas | 5.06 | 4.38 |
| Sulfur | 0.04 | 0.02 |
| Iron | 7.18 | 1.78 |
| Total amount of | 100.00 | 100.00 |
Compared with a pure graphite-like phase carbon nitride nanosheet, detection of the elements shows that the material successfully combines ferroferric oxide and graphene as carriers. And as shown in the element distribution Mapping chart of fig. 5, through compounding, three composite elements of oxygen, sulfur and iron are uniformly distributed among the layers or on the surface of the carbon nitride nanosheets, which has very important significance for maintaining the excellent photocatalytic performance of the composite material.
The catalytic activity of the photocatalyst is closely related to the light absorption capacity. Therefore, the light absorption properties of the sample studied by the ultraviolet-visible absorption spectrum are shown in fig. 6. The absorption edge of the sulfur-doped graphite-like carbon nitride nanosheet sample is 450nm, indicating that the photocatalyst activity is provided under the irradiation of visible light. While adding Fe to the sample 3 O 4 Further increasing the visible light absorption and enhancing the absorption intensity. The higher light absorption of the composite material can be attributed to Fe 3 O 4 The intercalation effect of the nanoparticles, which results in multiple absorptions of reflected light by the internal spaces between the layers and thus an increase in absorbance. Higher light absorption can absorb more photons and promote the photocatalytic reaction.
Material characterization 6 composite catalyst magnetic verification (VSM hysteresis curve)
The hysteresis loop curve VSM analysis was performed on the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst in example 1, and the result is shown in fig. 7. 5% -Fe 3 O 4 (ii) GE/CN with 20% -Fe 3 O 4 The hysteresis loops of both samples,/GE/CN, show that they are superparamagnetic and do not have significant remanence. Simultaneous magnetization of the composite material with Fe 3 Proportional to the ratio of O4, Fe 3 O 4 The smaller the proportion, the smaller the magnetization intensity, and the composite photocatalyst was uniformly distributed in the aqueous solution in the experiment according to FIG. 7 (a), and the material could be separated from the water within 2 minutes under the action of the external magnet, as shown in FIG. 7 (b). The good magnetism enhances the recycling performance of the material, reduces the cost on the basis of high efficiency, and strengthens the application of the material in the fields of water treatment and the like.
Example 2
An application of a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst in treatment of ranitidine antibiotic wastewater comprises the following steps:
(1) 50 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 was weighed 3 O 4 /GE/CN), adding the mixture into 50 ml of ranitidine wastewater with the initial concentration of 5 mg per liter, and then placing the ranitidine wastewater into a photocatalytic reaction device to stir for 30 minutes at the speed of 500 revolutions per minute in dark and dark light-proof environments.
(2) The 300 watt xenon lamp is used as a light source, and a cut-off filter with the wavelength of less than 400 nanometers is used for ensuring that the ranitidine and the composite photocatalyst are in a visible light region (the wavelength is lambda)>400 nm) for 60 minutes, and finishing the treatment of the ranitidine in the wastewater. And (3) determining the sampling time for judging the photocatalytic reaction progress degree as 0, 2, 5, 10, 15, 20, 30, 40, 50 and 60 minutes in the reaction progress, measuring the peak area absorbance value of the ranitidine in the solution at the moment by using a liquid chromatograph, and combining a standard curve to obtain the corresponding concentration C of the ranitidine at different illumination times. With time t as ordinate, C/C 0 As ordinate (where C 0 Initial ranitidine concentration at time 0), the results are shown in fig. 8.
(3) A group of ranitidine wastewater of 5 milligrams per liter without any catalyst is set as a blank control, and in addition, 50 milligrams of sulfur-doped graphite-phase carbon nitride nanosheets (g-C) are respectively weighed 3 N 4 ) The composite photocatalyst comprises a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene composite photocatalyst (0.1% -GE/CN) and a ferroferric oxide particle-loaded graphene composite material (0.1% -GE/Fe) 3 O 4 ) And a sulfur-doped graphite-phase carbon nitride nanosheet-supported ferroferric oxide composite photocatalyst (20% -Fe) 3 O 4 /CN), and other ferroferric oxide-loaded sulfur-doped graphite-phase carbon nitride nanosheets with different mass fractions to load graphene and ferroferric oxide composite magnetic photocatalyst (X% -Fe) 3 O 4 /GE/CN), the above-mentioned photocatalytic degradation step of ranitidine wastewater was repeated, and the results are shown in FIG. 8.
(4) As is clear from FIG. 8, the sulfur-doped graphite-based phase of the invention of example 1The removal rate of the carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst to ranitidine within 60 minutes can reach 80.23%, which is higher than that of a blank group (2.83%) and sulfur-doped graphite-phase carbon nitride nanosheets (g-C) 3 N 4 ) The group (31.78%) is high, and the photocatalytic degradation efficiency is obviously improved. Therefore, compared with a control group, the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst has higher photocatalytic activity than a pure sulfur-doped graphite-phase carbon nitride nanosheet, namely the composite photocatalyst has higher catalytic efficiency and better removal effect on the antibiotic ranitidine.
Example 3
An application of a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst in treatment of ranitidine antibiotic wastewater comprises the following steps:
(1) weighing 50 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 3 O 4 /GE/CN), adding the mixture into 50 ml of ranitidine wastewater with the initial concentration of 5 mg per liter, and then placing the ranitidine wastewater into a photocatalytic reaction device to stir for 30 minutes at the speed of 500 revolutions per minute in dark and dark light-proof environments.
(2) The 300 watt xenon lamp is used as a light source, and a cut-off filter with the wavelength of less than 400 nanometers is used for ensuring that the ranitidine and the composite photocatalyst are in a visible light region (the wavelength is lambda)>400 nm) for 60 minutes, and finishing the treatment of the ranitidine in the wastewater. And (3) determining the sampling time for judging the photocatalytic reaction progress degree as 0, 2, 5, 10, 15, 20, 30, 40, 50 and 60 minutes in the reaction progress, measuring the peak area absorbance value of the ranitidine in the solution at the moment by using a liquid chromatograph, and combining a standard curve to obtain the corresponding concentration C of the ranitidine at different illumination times. With time t as ordinate, C/C 0 As ordinate (where C 0 Initial ranitidine concentration at time 0) results are shown in fig. 9.
(3) In addition, ranitidine wastewater with initial concentrations of 2, 10 and 15 milligrams per liter is respectively prepared, and the above-mentioned steps of the photocatalytic degradation of ranitidine wastewater are repeated, and the result is shown in fig. 9.
(4) As can be seen from fig. 9, for ranitidine wastewater with an initial concentration of 2 mg per liter, the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst disclosed in this embodiment 1 can be completely removed for ranitidine within 60 minutes, and as the initial concentration of ranitidine increases, the reaction time required for degradation increases, and the final removal rate decreases. This is mainly due to the fact that the amount of catalyst is fixed, the number of reactive sites provided is fixed, and the higher the concentration of contaminants, the longer the time required for complete removal.
Example 4
An application of a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst in treatment of ranitidine antibiotic wastewater comprises the following steps:
(1) weighing 50 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 3 O 4 /GE/CN), adding the mixture into 50 ml of ranitidine wastewater with the initial concentration of 5 mg per liter, and then placing the ranitidine wastewater into a photocatalytic reaction device to stir for 30 minutes at the speed of 500 revolutions per minute in dark and dark light-proof environments.
(2) The 300 watt xenon lamp is used as a light source, and a cut-off filter with the wavelength of less than 400 nanometers is used for ensuring that the ranitidine and the composite photocatalyst are in a visible light region (the wavelength is lambda)>400 nm) for 60 minutes, and finishing the treatment of the ranitidine in the wastewater. And (3) determining the sampling time for judging the photocatalytic reaction progress degree as 0, 2, 5, 10, 15, 20, 30, 40, 50 and 60 minutes in the reaction progress, measuring the peak area absorbance value of the ranitidine in the solution at the moment by using a liquid chromatograph, and combining a standard curve to obtain the corresponding concentration C of the ranitidine at different illumination times. With time t as ordinate, C/C 0 As the ordinate (wherein C) 0 Initial ranitidine concentration at time 0), the results are shown in fig. 10.
(3) In additionIn addition, 10 mg, 25 mg and 75 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 are respectively weighed 3 O 4 /GE/CN), was added to 50 ml of ranitidine wastewater with an initial concentration of 5 mg per liter, and the above-mentioned photocatalytic degradation step of ranitidine wastewater was repeated, with the results shown in fig. 10.
(4) As can be seen from fig. 10, the reaction time required for degradation and the final removal rate vary with the concentration of the composite photocatalyst added. Within the scope of this example, the rate and efficiency of the degradation reaction increases with increasing catalyst concentration, primarily because the contaminant concentration is constant, the number of reactive sites provided increases with increasing catalyst, and the rate and efficiency of degradation increases with increasing catalyst concentration.
Example 5
An application of a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst in treatment of ranitidine antibiotic wastewater comprises the following steps:
(1) weighing 50 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 3 O 4 /GE/CN), was added to 50 ml of ranitidine wastewater with an initial concentration of 5 mg per liter having a pH of 3 (pH adjusted using 0.1 mol per liter of hydrochloric acid and sodium hydroxide), and then placed in a photocatalytic reaction apparatus to be stirred at 500 rpm for 30 minutes in dark and light-tight environment.
(2) The 300 watt xenon lamp is used as a light source, and a cut-off filter with the wavelength of less than 400 nanometers is used for ensuring that the ranitidine and the composite photocatalyst are in a visible light region (the wavelength is lambda)>400 nm) for 60 minutes, and finishing the treatment of the ranitidine in the wastewater. The sampling time for judging the photocatalytic reaction progress is determined as 0, 2, 5, 10, 15, 20, 30, 40, 50 and 60 minutes in the reaction progress, the absorbance value of the peak area of ranitidine in the solution at the moment is measured by using a liquid chromatograph, and the standard curve is combined to obtain the light intensity of the ranitidine at different illumination timesThe concentration C of ranitidine accordingly. With time t as ordinate, C/C 0 As ordinate (where C 0 Initial ranitidine concentration at time 0), the results are shown in fig. 11.
(3) In addition, the pH of 50 ml of ranitidine wastewater with initial concentration of 5 mg/l was adjusted to 5, 7, 9, 11, respectively, and the above-mentioned steps of photocatalytic degradation of ranitidine wastewater were repeated, and the results are shown in fig. 11.
(4) As can be seen from fig. 11, the degradation rate and the final removal rate were different depending on the ph of the ranitidine wastewater. Within the range of this example, when the pH of the ranitidine wastewater is 3 and 11 is in a more acidic or more alkaline environment, the catalyst prepared in example 1 has a lower efficiency of degrading ranitidine. When the ranitidine wastewater is in a neutral environment with the pH value of 5, 7, 9 and the like, the catalyst prepared in the embodiment 1 has better degradation efficiency on ranitidine, and the environment is more in line with the actual utilization scene.
Example 6
An application of a sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst in treatment of ranitidine and oxytetracycline antibiotic wastewater comprises the following steps:
(1) weighing 50 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 3 O 4 /GE/CN), adding the mixture into 50 ml of ranitidine wastewater with the initial concentration of 5 mg per liter, and then placing the ranitidine wastewater into a photocatalytic reaction device to stir for 30 minutes at the speed of 500 revolutions per minute in dark and dark light-proof environments.
(2) The 300 watt xenon lamp is used as a light source, and a cut-off filter with the wavelength of less than 400 nanometers is used for ensuring that the ranitidine and the composite photocatalyst are in a visible light region (the wavelength is lambda)>400 nm) for 60 minutes, and finishing the treatment of the ranitidine in the wastewater. The sampling time for judging the photocatalytic reaction progress is determined as 0, 2, 5, 10, 15, 20, 30, 40, 50 and 60 minutes in the reaction progress, a liquid chromatograph is used for measuring the peak area absorbance value of the ranitidine in the solution at the moment, and the standard curve is combined to obtain the corresponding time of different illumination timesC, of ranitidine. With time t as ordinate, C/C 0 As ordinate (where C 0 Initial ranitidine concentration at time 0) results are shown in fig. 12.
(3) Weighing 50 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 3 O 4 /GE/CN), adding the mixture into 50 ml of oxytetracycline waste water with the initial concentration of 5 mg/L (0.1 mol/L hydrochloric acid and sodium hydroxide are used for adjusting the pH value of an oxytetracycline solution to be 7), and then placing the mixture into a photocatalytic reaction device to stir for 30 minutes at the speed of 500 revolutions per minute in dark and dark environments.
(4) The 300W xenon lamp is used as a light source, and a cut-off filter with the wavelength of less than 400 nanometers is used for ensuring that the ranitidine and the composite photocatalyst are in a visible light region (the wavelength is lambda)>400 nm) for 60 minutes, and finishing the treatment of the oxytetracycline in the wastewater. And (3) determining the sampling time for judging the progress degree of the photocatalytic reaction as 0, 2, 5, 10, 15, 20, 30, 40, 50 and 60 minutes in the reaction, measuring the peak area absorbance value of the oxytetracycline in the solution at the moment by using a liquid chromatograph, and combining a standard curve to obtain the corresponding concentration C of the oxytetracycline at different illumination times. With time t as ordinate, C/C 0 As ordinate (where C 0 The initial oxytetracycline concentration at time 0) and the results are shown in fig. 11.
(4) As can be seen from fig. 12, the removal rate of ranitidine in 60 minutes by the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst disclosed in this embodiment 1 can reach 80.23%, and 5 mg/l of oxytetracycline solution can be completely removed in 60 minutes, which shows that the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst disclosed in the present invention has a good removal effect on various different types of antibiotics.
Example 7
The recycling stability of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst in the treatment of ranitidine antibiotic wastewater comprises the following steps:
(1) 50 mg of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst (20% -Fe) prepared in example 1 was weighed 3 O 4 /GE/CN), adding the mixture into 50 ml of ranitidine wastewater with the initial concentration of 5 mg per liter, and then placing the ranitidine wastewater in a photocatalytic reaction device to stir for 30 minutes at the speed of 500 revolutions per minute in dark and dark light-proof environment.
(2) The 300 watt xenon lamp is used as a light source, and a cut-off filter with the wavelength of less than 400 nanometers is used for ensuring that the ranitidine and the composite photocatalyst are in a visible light region (the wavelength is lambda)>400 nm) for 60 minutes, and finishing the treatment of the ranitidine in the wastewater. And (3) determining the sampling time for judging the photocatalytic reaction progress degree as 0, 2, 5, 10, 15, 20, 30, 40, 50 and 60 minutes in the reaction progress, measuring the peak area absorbance value of the ranitidine in the solution at the moment by using a liquid chromatograph, and combining a standard curve to obtain the corresponding concentration C of the ranitidine at different illumination times. With time t as ordinate, C/C 0 As the ordinate (wherein C) 0 Initial ranitidine concentration at time 0), the results are shown in fig. 12.
(3) After the degradation was completed for 60 minutes each time, the catalyst material prepared in example 1 was absorbed and separated in the wastewater using a magnet, and washed three times with 40 ml of ultrapure water and absolute ethanol alternately, and finally the separated material was baked in an oven at 60 ℃ for 8 hours. And (5) drying and then degrading for the next time.
(4) As can be seen from fig. 13, after four times of recycling, the degradation efficiency of the composite photocatalyst material prepared in example 1 to ranitidine is not significantly reduced, which indicates that the composite photocatalyst prepared in the present invention has good photocatalytic stability and recycling performance.
The foregoing description and description of the embodiments are provided to facilitate the understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications can be made to these teachings and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above description and the description of the embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst is characterized in that: the preparation method comprises the following steps of taking sulfur-doped graphite-phase carbon nitride nanosheets as carriers, wherein the sulfur-doped graphite-phase carbon nitride nanosheets are modified with graphene and ferroferric oxide particles;
the graphene is attached to the surface of the sulfur-doped graphite-phase carbon nitride nanosheet through an impregnation method, and the ferroferric oxide is attached to the interlayer or the surface of the sulfur-doped graphite-phase carbon nitride nanosheet through an alkaline-thermal coprecipitation method;
the mass ratio of the graphene to the sulfur-doped graphite-phase carbon nitride nanosheet is 1: 500-1000;
the mass ratio of the ferroferric oxide particles to the sulfur-doped graphite-phase carbon nitride nanosheets is 1: 5-20; the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst is prepared through the following steps:
s1, precursor preparation: weighing a precursor thiourea in a ceramic crucible, wherein the thiourea does not need to be subjected to any pretreatment; putting the mixture into a muffle furnace for heating and calcining; a temperature rise step setting: setting a temperature rise program at a temperature rise rate of 2-3 ℃ per minute from a room temperature state, raising the temperature to 540-550 ℃, and keeping the temperature for 3-4 hours for calcination, wherein no inert shielding gas is needed in the calcination process; after the calcination and heat preservation are finished, naturally cooling to room temperature; screening, grinding and sieving to obtain the sulfur-doped graphite-phase carbon nitride nanosheets;
s2, adding the graphene dispersoid into a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water in the mixed solution of the ethanol and the water is 1: 1-2, and stirring for 0.5-1 hour to prepare a graphene suspension; adding the sulfur-doped graphite-phase carbon nitride nanosheets into the obtained graphene suspension, stirring for 0.5 to 1 hour, and then ultrasonically dispersing for 0.5 to 1 hour to obtain a sulfur-doped carbon nitride nanosheet loaded graphene composite photocatalyst suspension;
s3, dissolving ferric chloride and ferric dichloride tetrahydrate in distilled water, adding the solution into the sulfur-doped carbon nitride nanosheet loaded graphene composite photocatalyst suspension, stirring for 30-40 minutes at 80-85 ℃, then quickly adding ammonia water, continuously stirring for 30-40 minutes, and then naturally cooling the solution; and (3) centrifugally collecting the prepared precipitate, alternately washing the precipitate with ethanol and water for 2-3 times, and drying the precipitate in an oven for 7-10 hours to obtain the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst.
2. The sulfur-doped graphite-like carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst as claimed in claim 1, wherein the ammonia water is 5-10 ml; and/or the drying temperature in the oven is 60-70 ℃.
3. The application of the sulfur-doped graphite-phase carbon nitride nanosheet-supported graphene and ferroferric oxide composite magnetic photocatalyst as defined in any one of claims 1 to 2 in antibiotic wastewater treatment, is characterized in that: mixing the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene, a ferroferric oxide composite magnetic photocatalyst and antibiotic wastewater to perform photocatalytic reaction, and finishing the treatment of the antibiotic wastewater.
4. The application of claim 3, wherein the addition amount of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst is 0.2-1.5 g of the sulfur-doped graphite-phase carbon nitride nanosheet-loaded graphene and ferroferric oxide composite magnetic photocatalyst added to each liter of antibiotic wastewater.
5. The use according to claim 4, wherein the antibiotic in the antibiotic wastewater is ranitidine and/or oxytetracycline.
6. The use according to claim 5, wherein the concentration of ranitidine and/or oxytetracycline in the antibiotic wastewater is 5-15 mg per liter.
7. Use according to claim 6, wherein the light source is a xenon lamp light source.
8. The use according to claim 7, wherein the photocatalytic reaction time is 0.8 to 1 hour.
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