CN115155636B - Sodium-boron co-doped carbon nitride photocatalyst, reduced graphene oxide composite film, and preparation method and application thereof - Google Patents
Sodium-boron co-doped carbon nitride photocatalyst, reduced graphene oxide composite film, and preparation method and application thereof Download PDFInfo
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Classifications
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- B01J35/39—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a sodium-boron co-doped carbon nitride photocatalyst, a reduced graphene oxide composite film, a preparation method and application thereof, wherein the preparation method of the photocatalyst comprises the following steps: mixing and grinding melamine and sodium salt, calcining under argon, cooling, washing with water, filtering and collecting, freeze-drying to obtain sodium single doped carbon nitride nano-sheet, mixing and grinding with sodium borohydride, calcining under argon protection, cooling, washing with water, filtering and collecting, and freeze-drying to obtain the final product. According to the preparation method, the sodium-boron co-doped carbon nitride nano sheet is obtained by adopting a two-step calcination method, the graphene oxide is reduced and filtered to obtain the reduced graphene oxide film, and finally the catalyst is crosslinked on the surface of the film to obtain the reduced graphene oxide composite film for synergistic catalytic separation, so that the preparation process is simple, the operation is easy, the energy band structure of the catalyst is optimized by sodium-boron co-doping, the visible light catalytic efficiency is improved, and the composite film realizes the surface confinement through entrapping antibiotics to strengthen the degradation and removal effects of the antibiotics.
Description
Technical Field
The invention belongs to the technical field of preparation of catalytic film materials, and particularly relates to a sodium-boron co-doped carbon nitride photocatalyst, a reduced graphene oxide composite film, a preparation method and application thereof.
Background
In recent years, antibiotics have been attracting attention as a novel micro-contaminant because they induce the generation of resistance genes. Sulfamethoxazole is one of the typical antibiotics that is frequently detected in various water bodies. However, conventional methods for treating antibiotic pollution, including adsorption, fenton, activated sludge, etc., have respective limitations. The membrane separation technology has low energy consumption, high efficiency and the likeThe method has the advantages that the method is widely applied to the removal of micro pollutants, but is simple in physical separation and does not degrade the pollutants. Based on this, a separation membrane having a catalytic function is a hot spot of research in recent years. In the aspect of separation membranes, the graphene oxide membrane has a plurality of advantages of good pollution resistance and the like, but is easy to generate interlayer swelling, and the stability of the membrane can be enhanced after the graphene oxide membrane is reduced. In the aspect of catalysts, the semiconductor photocatalysis technology is used as a high-grade oxidation technology, and has the characteristics of clean energy, low cost, mild reaction and the like, thereby being important to be applied to degrading trace pollutants such as antibiotics. Conventional semiconductor photocatalyst TiO 2 Only ultraviolet light can be absorbed, and the ultraviolet light only accounts for 7% of the full spectrum energy of sunlight.
The carbon nitride is used as a novel semiconductor photocatalyst, so that visible light catalysis can be realized, and the photocatalyst has the advantages of rich raw materials, proper energy band and the like. However, unmodified carbon nitride has problems of low visible light absorptivity, fast photo-generated electron-hole pair recombination, low charge separation efficiency, and the like, which limit practical application. Previous researches show that various modification methods such as morphology regulation, nonmetallic/metallic element doping, nitrogen defect introduction and the like can effectively regulate the energy band structure and the electronic structure of the carbon nitride. However, the modification research on carbon nitride is still insufficient at present, and it is necessary to develop a simple modification method to obtain a catalyst with high efficiency and low cost. Furthermore, the modified photocatalyst is loaded on the membrane, so that the cooperative degradation of pollutants in the interception process can be realized.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a sodium-boron co-doped carbon nitride photocatalyst, a reduced graphene oxide composite film, a preparation method and application. The invention provides a preparation method and application of a visible light catalyst with simple operation and high catalytic activity, wherein the visible light catalyst is loaded on a reduced graphene oxide membrane to obtain a reduced graphene oxide composite membrane with synergistic catalytic separation.
The specific technical scheme adopted by the invention is as follows:
a preparation method of a sodium-boron co-doped carbon nitride photocatalyst comprises the following steps:
1) Mixing sodium salt and melamine according to the mass ratio of 3-6:1, fully grinding in a mortar, then placing in a crucible, calcining in a tube furnace under the protection of argon, heating to 500-600 ℃ from room temperature at the heating rate of 3-5 ℃/min, preserving heat, calcining for 2-4 hours, naturally cooling to room temperature, washing with deionized water under the assistance of ultrasound, filtering, collecting, and freeze-drying to obtain the sodium single doped carbon nitride nano-sheet;
2) Mixing sodium borohydride and the sodium single doped carbon nitride nano sheet obtained in the step 1) according to the mass ratio of 0.1-1:1, fully grinding in a mortar, then placing in a quartz boat, calcining in a tubular furnace under the protection of argon, heating to 400-500 ℃ from room temperature at the heating rate of 8-12 ℃/min, preserving heat, calcining for 0.2-1 h, naturally cooling to room temperature, washing with deionized water for three times under the assistance of ultrasound, filtering, collecting, and freeze-drying to obtain the sodium-boron co-doped carbon nitride nano sheet, namely the preparation is completed.
Preferably, in the step 1), the sodium salt is sodium chloride, and the mass ratio of the sodium salt to the melamine is 4-5:1; the calcination condition in the step 1) is that the material is heated to 500-550 ℃ at a heating rate of 4-5 ℃/min and then is calcined for 2-3 hours in a heat preservation way.
Preferably, the mass ratio of the sodium borohydride to the sodium singly doped carbon nitride nano-sheet in the step 2) is 0.4-0.5:1; the calcination condition in the step 2) is that the material is heated to 450-470 ℃ at a heating rate of 8-10 ℃/min and then is calcined for 0.4-0.5 h in a heat preservation way.
Preferably, the filtration conditions described in step 1) and step 2) are collected by filtration with a 0.45 μm mixed cellulose ester Membrane (MCE) at a pressure of 1 bar.
Further, the freeze-drying temperature in the step 1) and the step 2) is below-80 ℃ and the drying time is above 20 hours.
The sodium-boron co-doped carbon nitride photocatalyst prepared by the invention can be well applied to the degradation of antibiotics in wastewater by visible light catalysis, and the application method comprises the following steps: adjusting the pH value of the antibiotic wastewater to be neutral, and then adding the sodium-boron co-doped carbon nitride photocatalyst, wherein the concentration of the antibiotic in the wastewaterThe solid-liquid ratio of the photocatalyst to the wastewater is 1 mg:0.5-2 mL, the formed suspension is firstly placed in a darkroom and stirred for 20-40 min to reach adsorption-desorption equilibrium, then the photo-catalytic degradation reaction is carried out under the illumination of a xenon lamp, wherein the illumination wavelength is more than 420nm, and the illumination intensity is 200-300 mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The antibiotic is preferably sulfamethoxazole. .
The preparation method of the reduced graphene oxide composite membrane for synergistic catalytic separation comprises the following steps:
s1: carrying out ultraviolet reduction on the graphene oxide solution, taking a support film as a substrate, carrying out suction filtration to form a film, and drying to form a reduced graphene oxide film on the surface of the support film;
s2: dispersing the sodium-boron co-doped carbon nitride photocatalyst in water to form suspension, then carrying out suction filtration on the sodium-boron co-doped carbon nitride photocatalyst to the surface of the reduced graphene oxide film, carrying out crosslinking fixation through a crosslinking agent, and drying to obtain the reduced graphene oxide film with synergistic catalytic separation.
Preferably, in step S1, the support membrane is a PVDF or PES commercial membrane, the membrane having an average pore size of 0.05 to 0.2. Mu.m, preferably 0.1. Mu.m; the concentration of the graphene oxide solution is 0.005-0.02 g/L, preferably 0.01g/L, and the ultraviolet reduction condition is that the graphene oxide solution is reduced for 4-6 hours under 365nm wavelength.
Preferably, the load of the reduced graphene oxide on the support film is 0.005-0.015mg/cm 2 Preferably 0.01mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The loading of the sodium-boron co-doped carbon nitride photocatalyst on the membrane is 0.4-0.6mg/cm 2 Preferably 0.5mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The cross-linking agent is prepared by mixing a polyvinyl alcohol solution with the mass concentration of 0.05-0.2% and a glutaraldehyde solution with the mass concentration of 8-12% according to the volume ratio of 1:1.
The reduced graphene oxide composite membrane for synergistic catalytic separation can be well applied to the degradation of antibiotics in wastewater by visible light catalysis, and the application method comprises the following steps: under illumination, adopting a dead-end filtration mode to intercept and degrade antibiotics in the wastewater, and enabling the wastewater to pass through the reduced graphene oxide composite membrane under the pressure of 1.5-3 bar; the antibiotic is preferably sulfamethoxazole.
Compared with the prior art, the invention has the following advantages:
1) The sodium-boron co-doped carbon nitride nanosheet material has the advantages of wide raw material sources, low cost, easy obtainment and simple process, and is suitable for large-scale industrial production;
2) The sodium-boron co-doped carbon nitride nano sheet material prepared by the method constructs carbon nitride nano sheets with different sodium-boron doping ratios by changing the adding amount of sodium borohydride;
3) Compared with unmodified carbon nitride nano sheet material, the sodium-boron co-doped carbon nitride nano sheet material prepared by the method has more suitable energy band, lower photo-generated electron-hole pair recombination rate and higher charge separation efficiency.
4) When the sodium-boron co-doped carbon nitride nano sheet material prepared by the method is used for degrading sulfamethoxazole, the early reaction rate of the sodium-boron co-doped carbon nitride nano sheet material is obviously higher than that of unmodified carbon nitride under the condition of the same catalyst addition. Within 120min, the removal rate of the sodium-boron co-doped carbon nitride nano sheet material with the mixing ratio of 0.4 to sulfamethoxazole reaches more than 99 percent, and the removal rate of the sulfamethoxazole is only 48.6 percent after being unmodified.
5) The sodium-boron co-doped carbon nitride nano sheet material prepared by the method can realize the efficient degradation of sulfamethoxazole under the condition that the pH value is neutral.
6) The reduced graphene oxide composite membrane prepared by the method can realize effective interception and catalytic degradation of sulfamethoxazole.
Drawings
FIG. 1 shows an unmodified carbon nitride BCN (FIG. a), a sodium-single doped carbon nitride nanosheet DCD-Na (FIG. b), and a sodium-boron co-doped carbon nitride nanosheet DCD-NaB with a mixing ratio of 0.1 in example 1 of the present invention 0.1 (Panel c), sodium boron co-doped carbon nitride nanoplatelets DCD-NaB with a mixing ratio of 0.4 0.4 (Panel d), sodium boron co-doped carbon nitride nanoplatelets DCD-NaB with mixing ratio of 1 1 Scanning electron microscope image, sodium boron co-doped carbon nitride nanoplatelet DCD-NaB with mixing ratio of 0.4 of (image e) 0.4 (figure f) Transmission Electron microscopy;
FIG. 2 shows the results of BCN, DCD-Na, DCD-NaB in example 1 0.1 、DCD-NaB 0.4 And DCD-NaB 1 An XRD pattern of (b);
FIG. 3 shows BCN, DCD-Na, DCD-NaB in example 1 0.1 、DCD-NaB 0.4 And DCD-NaB 1 Is a infrared spectrogram of (2);
FIG. 4 shows BCN, DCD-Na, DCD-NaB in example 1 0.1 、DCD-NaB 0.4 And DCD-NaB 1 XPS graph of (2);
FIG. 5 shows BCN, DCD-Na, DCD-NaB in example 2 0.1 、DCD-NaB 0.4 And DCD-NaB 1 An efficiency map of visible light degradation of sulfamethoxazole;
FIG. 6 shows BCN, DCD-Na, DCD-NaB in example 2 0.1 、DCD-NaB 0.4 And DCD-NaB 1 Is a graph of the reaction kinetic constants of (2).
Fig. 7 shows the sulfamethoxazole rejection and water flux of the reduced graphene oxide membranes at different loadings in example 3.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
The invention discloses a preparation method of a reduced graphene oxide composite membrane for synergistic catalytic separation, which comprises the following steps:
1) Mixing sodium salt and melamine according to the mass ratio of 3-6:1, fully grinding in a mortar, then placing in a crucible, calcining in a tube furnace under the protection of argon, heating to 500-600 ℃ from room temperature at the heating rate of 3-5 ℃/min, preserving heat, calcining for 2-4 hours, naturally cooling to room temperature, washing with deionized water under the assistance of ultrasound, filtering, collecting, and freeze-drying to obtain the sodium single doped carbon nitride nano-sheet;
2) Mixing sodium borohydride and the sodium single doped carbon nitride nano sheet obtained in the step 1) according to the mass ratio of 0.1-1:1, fully grinding in a mortar, then placing in a quartz boat, calcining in a tubular furnace under the protection of argon, heating to 400-500 ℃ from room temperature at the heating rate of 8-12 ℃/min, preserving heat, calcining for 0.2-1 h, naturally cooling to room temperature, washing with deionized water for three times under the assistance of ultrasound, filtering, collecting, and freeze-drying to obtain the sodium-boron co-doped carbon nitride nano sheet, namely the preparation is completed.
(3) And carrying out ultraviolet reduction on the graphene oxide solution, carrying out suction filtration on the graphene oxide solution by taking a support film PVDF/PES as a substrate to form a film, and drying the film to form a reduced graphene oxide film on the surface of the support film. Dispersing the sodium-boron co-doped carbon nitride photocatalyst in water to form a suspension, then carrying out suction filtration on the sodium-boron co-doped carbon nitride photocatalyst to the surface of the reduced graphene oxide film, carrying out crosslinking fixation through a crosslinking agent, and drying to obtain the reduced graphene oxide film with synergistic catalytic separation.
Example 1
In this embodiment, the preparation method of the sodium-boron co-doped carbon nitride nanosheet material comprises the following steps:
1) Firstly, 15g of sodium chloride and 3g of melamine were weighed, sufficiently ground in an agate mortar, and then placed in an alumina crucible. Subsequently, the mixture was calcined in a tube furnace under Ar atmosphere, heated from room temperature to 550℃at a heating rate of 5℃per minute, and then calcined at a temperature of 2 hours. After cooling to room temperature, the calcined product was placed in 500mL of deionized water and sonicated for 20min, and then the product was collected through a 0.45 μm mixed cellulose ester Membrane (MCE), and the salt was removed 3 times by washing with water. And freeze-drying the collected carbon nitride nano-sheets for more than 20 hours at the temperature of minus 80 ℃ and preserving at room temperature. The obtained sodium single doped carbon nitride nano-sheet is named as DCN-Na.
2) Uniformly mixing 200mg of sodium single doped carbon nitride nano-sheet (namely DCN-Na) with 20, 80 or 200mg of sodium borohydride, calcining in a tubular furnace under Ar atmosphere, heating to 450 ℃ from room temperature at a heating rate of 10 ℃/min, and preserving heat and calcining for 0.5h. After cooling to room temperature, the calcined product was placed in 100mL of deionized water and sonicated for 20min, and then the product was collected through a 0.45 μm mixed cellulose ester Membrane (MCE), and washed 3 times with water to remove unreacted sodium borohydride. Drying the collected materials at-80deg.C for more than 20 hr, and preserving at room temperature. Obtaining the sodium-boron co-doped carbon nitride nano-sheet which is marked as DCN-NaB y Y is the mixing mass ratio of sodium borohydride and DCN-Na, and the values of y are 0.1, 0.4 and 1 respectively according to the feeding amount of sodium borohydride of 20, 80 or 200 mg.Meanwhile, in this example, an experimental group control, i.e., unmodified carbon nitride, was also set and designated as BCN.
The preparation method of the unmodified carbon nitride (namely BCN) comprises the steps of weighing 10g of melamine, putting the melamine into a 50mL ceramic crucible with a cover, then putting the melamine into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for 4 hours, cooling to room temperature, grinding, sieving with a 300-mesh sieve, and preserving at room temperature to obtain the finished product.
After the preparation, the five materials (namely BCN, DCD-Na, DCD-NaB 0.1 、DCD-NaB 0.4 And DCD-NaB 1 ) Characterization of morphology and the like is carried out, five materials are respectively observed by adopting a Zeiss G300 type field emission scanning electron microscope, and DCN-NaB is observed by adopting a JEM-1400flash type transmission electron microscope 0.4 The crystal structure of the five materials was measured by using a Bruker D8 advanced XRD instrument containing Cu ka radiation, the functional groups contained in the five materials were measured by using a Scientific Nicolet 6700 fourier transform infrared spectrometer, the element types contained in the five materials were measured by using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer, and the results of the test analysis obtained by the above characterization means are shown in fig. 1 to 4, and the following description is made:
in FIG. 1, (a) is an SEM image of BCN, (b) is an SEM image of DCD-Na, and (c) is DCD-NaB 0.1 (d) is DCD-NaB 0.4 (e) is DCD-NaB 1 (f) is DCD-NaB 0.4 Is a TEM image of (1).
As can be seen from fig. 1, in the SEM image, the BCN profile presents irregular blocks, and the interior presents a layered stack structure; DCN-Na presents a flake structure, and the surface is smoother and free of defects. The reason is that the ground sodium chloride crystal has higher surface energy, a large amount of melamine molecules are adsorbed on the surface of the crystal, naCl remains in the original state under a high-temperature environment (550 ℃) because of higher melting point (801 ℃), and the melamine molecules undergo thermal polymerization reaction in a two-dimensional crystal face until carbon nitride is formed. DCD-NaB 0.1 、DCD-NaB 0.4 And DCD-NaB 1 Also has a flake structure, smooth surface and no change of nano-size after secondary calcination with sodium borohydrideMorphology of rice flakes. In TEM image, DCD-NaB 0.4 The nano-sheet is thinner, has obvious folds inside, but has no obvious defects.
FIG. 2 is BCN, DCD-Na, DCD-NaB 0.1 、DCD-NaB 0.4 And DCD-NaB 1 XRD patterns of the five materials. As can be seen from fig. 2, BCN has two characteristic diffraction peaks at 2θ=13.1° and 27.4 °, representing (100) and (002) planes of BCN, respectively, where the (100) plane is in-plane stacking of carbon nitride and the (002) plane is interlayer stacking. DCN-Na and DCN-NaB compared to BCN y The intensity of the diffraction peak at 13.1 deg. is significantly reduced and almost vanishes, indicating that the in-plane order of the material is destroyed. The half-width of the diffraction peak at 27.4 degrees becomes larger, which also shows that the interlayer structure is damaged to a certain extent, and the diffraction peak moves to higher 2 theta with the increase of the dosage of sodium borohydride, so that the interlayer stacking distance of the nano-sheets becomes smaller gradually.
FIG. 3 is BCN, DCD-Na, DCD-NaB 0.1 、DCD-NaB 0.4 And DCD-NaB 1 Infrared spectrograms of the five materials. As can be seen from FIG. 3, DCN-Na and DCN-NaB y At 2180cm -1 A new peak appears at this point due to asymmetric stretching vibrations of-C.ident.N, at 810cm -1 、1000-1800cm -1 3000-3500cm -1 The peak intensity was significantly reduced compared to BCN, which means that the carbon nitride had nitrogen defects introduced after modification.
FIG. 4 is BCN, DCD-Na, DCD-NaB 0.1 、DCD-NaB 0.4 And DCD-NaB 1 XPS graphs of five materials. As can be seen from FIG. 4, in DCN-Na and DCN-NaB y Characteristic peaks of Na appear in the DCN-NaB y Characteristic peaks of B appear, which indicates that the Na, B elements were successfully doped into the corresponding samples.
Example 2
Five materials prepared in example 1 were used to degrade sulfamethoxazole in water as follows:
the sulfamethoxazole solid is dissolved by 0.1M NaOH to prepare mother solution with the concentration of 100ppm, and then the mother solution is diluted to 5ppm by deionized water, and the pH value is adjusted to 7 for standby. 20mL of 5ppm sulfamethoxazole solution was added to a 100mL beaker followed by the addition ofAdding 20mg of catalyst, and uniformly dispersing by ultrasonic treatment for 2 min. The beaker was placed on a magnetic stirrer with a rotation speed of 400rpm, using a xenon lamp (lambda) with a power of 300W>420 nm) as a light source, the light power was 250mW/cm 2 . Before illumination, the suspension is placed in a darkroom and stirred for 30min to reach adsorption-desorption equilibrium, then 0.5mL of liquid is taken every 20min and is analyzed after passing through a water system film of 0.22 mu m, and the temperature of a reaction system is controlled to be maintained at room temperature by adopting air cooling in the reaction process.
The concentration of the sulfamethoxazole aqueous solution is measured by a Agilent Technologies 1200Series high performance liquid chromatograph, the running condition of the high performance liquid chromatograph is set to 30 percent acetonitrile and 70 percent 0.1 percent formic acid in the mobile phase, the flow rate is 1.0mL/min, the detection wavelength is set to 270nm, the sample injection amount is 10 mu L, the total running time is 6min, and the detection limit of the sulfamethoxazole is about 0.1 mu g/L.
According to the operation mode, the experimental results of the efficiency of the different catalytic materials in degrading the sulfamethoxazole by the visible light at different times are shown in fig. 5. As can be seen from FIG. 5, in BCN, DCD-Na, DCD-NaB 0.1 、DCD-NaB 0.4 And DCD-NaB 1 Of the five materials, sodium-boron co-doped carbon nitride nano sheet material DCD-NaB with the mixing ratio of 0.4 0.4 The degradation rate of the sulfamethoxazole is highest, and reaches more than 99 percent in 120min, while the unmodified carbon nitride can only degrade 48.6 percent in the same time. In addition, the sodium-boron co-doped carbon nitride nanosheet material has been found to show a tendency of a rising and falling degradation rate of sulfamethoxazole with the increase of the mixing ratio.
The experimental results in fig. 5 were fitted to a quasi-first order kinetic equation, and the fitting results are shown in fig. 6. As can be seen from FIG. 6, the sodium-boron co-doped carbon nitride nanosheet material DCD-NaB with a mixing ratio of 0.4 0.4 The degradation rate constant for sulfamethoxazole is 7.5 times that of unmodified carbon nitride.
The sodium-boron co-doped carbon nitride nano-sheet prepared by the invention improves the visible light catalytic activity of carbon nitride by means of morphology regulation, sodium-boron element doping, nitrogen defect introduction and other modification means, and realizes the efficient degradation of sulfamethoxazole.
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the invention.
Example 3
The preparation method of the reduced graphene oxide composite membrane adopts a dead-end filtration system for intercepting sulfamethoxazole in water, and comprises the following steps:
500mL of the 0.01g/L graphene oxide solution was reduced under 365nm ultraviolet light for 4h. Then, a mixed solution containing xmg reduced graphene oxide is taken, a PVDF commercial membrane (the average pore diameter of the membrane is about 0.1 μm) is taken as a supporting membrane, and is subjected to suction filtration at 1bar to form a membrane, wherein the suction filtration area of the PVDF commercial membrane is 20cm 2 And x is 0.05, 0.1, 0.15, 0.2 and 0.25, and then drying at 60 ℃ overnight to obtain the reduced graphene oxide film.
The water flux and the p-sulfamethoxazole rejection rate of the reduced graphene oxide membrane are verified, and the experimental steps are as follows: the membrane was first pressed at 29psi (2 bar), the pure water flux was measured over 30min and the final stable value was recorded as the membrane water flux. For the same membrane, after the water flux was measured, pure water in the system was changed to an aqueous sulfamethoxazole solution, and a sulfamethoxazole aqueous solution trapping experiment was performed at a pressure of 29psi for 40min at room temperature, wherein the concentration of the sulfamethoxazole aqueous solution was 5mg/L. The rejection rate of the sulfamethoxazole is calculated by measuring the concentration of the sulfamethoxazole in the percolate collected at the filtering time of 40min and the concentration of the sulfamethoxazole in the water inflow. The concentration of the sulfamethoxazole aqueous solution is measured by a Agilent Technologies 1200Series high performance liquid chromatograph, the running condition of the high performance liquid chromatograph is set to 30 percent acetonitrile and 70 percent 0.1 percent formic acid in the mobile phase, the flow rate is 1.0mL/min, the detection wavelength is set to 270nm, the sample injection amount is 10 mu L, the total running time is 6min, and the detection limit of the sulfamethoxazole is about 0.1 mu g/L. The water flux and the p-sulfamethoxazole rejection of the reduced graphene oxide membrane are shown in figure 7, according to the above operation mode.
Dispersing the prepared sodium-boron co-doped carbon nitride photocatalyst in water to form a suspension (the preparation concentration is 0.1 g/L), then taking the suspension containing 10mg of the catalyst, further taking the prepared reduced graphene oxide film (x takes the value of 0.2) as a support film, carrying out suction filtration on the sodium-boron co-doped carbon nitride photocatalyst to the surface of the reduced graphene oxide film, carrying out cross-linking fixation by using 10mL of polyvinyl alcohol solution with the mass concentration of 0.1% and 10mL of glutaraldehyde solution with the mass concentration of 10%, and drying to obtain the reduced graphene oxide film with synergistic catalytic separation.
Then, under illumination (illumination conditions are the same as in example 2), a dead-end filtration mode is adopted for interception and degradation of the sulfamethoxazole in water, and a sulfamethoxazole aqueous solution (5 mg/L) is subjected to synergistic catalytic separation of the reduced graphene oxide membrane under the pressure of 2 bar. In the process, the sulfamethoxazole can be trapped on the surface by the reduced graphene oxide membrane, and the photocatalyst is also loaded on the surface of the membrane, so that the contact between the sulfamethoxazole and the photocatalyst can be increased by a surface limiting strategy, and the percolate with the filtering time of 40min is measured, and the percolate basically does not contain the sulfamethoxazole, which shows that the degradation rate and the degradation rate of the sulfamethoxazole are further improved, so that the sulfamethoxazole removing effect is better than that of the example 2.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (10)
1. The preparation method of the reduced graphene oxide composite membrane for the synergistic catalytic separation of the antibiotics in the catalytic degradation wastewater under the visible light is characterized by comprising the following steps of:
s1: carrying out ultraviolet reduction on the graphene oxide solution, taking a support film as a substrate, carrying out suction filtration to form a film, and drying to form a reduced graphene oxide film on the surface of the support film;
s2: dispersing the sodium-boron co-doped carbon nitride photocatalyst in water to form a suspension, then carrying out suction filtration on the sodium-boron co-doped carbon nitride photocatalyst to the surface of a reduced graphene oxide film, carrying out crosslinking fixation through a crosslinking agent, and drying to obtain the reduced graphene oxide film with synergistic catalytic separation;
the cross-linking agent is prepared by mixing a polyvinyl alcohol solution with the mass concentration of 0.05-0.2% and a glutaraldehyde solution with the mass concentration of 8-12% according to the volume ratio of 1:1;
the preparation method of the sodium-boron co-doped carbon nitride photocatalyst comprises the following steps:
1) Mixing sodium salt and melamine according to a mass ratio of 3-6:1, fully grinding in a mortar, placing in a crucible, calcining in a tube furnace under the protection of argon, heating to 500-600 ℃ from room temperature at a heating rate of 3-5 ℃/min, preserving heat, calcining for 2-4 hours, naturally cooling to room temperature, washing with deionized water under the assistance of ultrasound, filtering, collecting, and freeze-drying to obtain a sodium single doped carbon nitride nano sheet;
2) Mixing sodium borohydride and the sodium single doped carbon nitride nano sheet obtained in the step 1) according to the mass ratio of 0.1-1:1, fully grinding in a mortar, then placing in a quartz boat, calcining in a tubular furnace under the protection of argon, heating to 400-500 ℃ from room temperature at the heating rate of 8-12 ℃/min, preserving heat, calcining for 0.2-1 h, naturally cooling to room temperature, washing with deionized water for three times under the assistance of ultrasound, filtering, collecting, and freeze-drying to obtain the sodium-boron co-doped carbon nitride nano sheet, namely the preparation is completed.
2. The reduced graphene oxide composite membrane for collaborative catalytic separation for catalytic degradation of antibiotics in wastewater under visible light as claimed in claim 1, wherein sodium salt in step 1) is sodium chloride, and the mass ratio of sodium salt to melamine is 4-5:1; and the calcination condition in the step 1) is that the material is heated to 500-550 ℃ at a heating rate of 4-5 ℃/min, and then is subjected to heat preservation and calcination for 2-3 hours.
3. The reduced graphene oxide composite membrane for synergistic catalytic separation of antibiotics in catalytic degradation wastewater under visible light as claimed in claim 1, wherein the mass ratio of sodium borohydride to sodium single doped carbon nitride nano-sheet in step 2) is 0.4-0.5:1; and 2) heating to 450-470 ℃ at a heating rate of 8-10 ℃/min under the calcining condition in the step 2), and then preserving heat and calcining for 0.4-0.5 h.
4. The reduced graphene oxide composite membrane for synergistic catalytic separation of antibiotics in wastewater for catalytic degradation under visible light as claimed in claim 1, wherein the freeze-drying temperature in step 1) and step 2) is below-80 ℃ and the drying time is above 20 h.
5. The reduced graphene oxide composite membrane for collaborative catalytic separation for catalytic degradation of antibiotics in wastewater under visible light according to claim 1, wherein in step S1, the support membrane is a PVDF or PES commercial membrane, and the average pore diameter of the membrane is 0.05-0.2 μm; the concentration of the graphene oxide solution is 0.005-0.02 g/L, and the ultraviolet reduction condition is that the graphene oxide solution is reduced for 4-6 hours under 365-nm wavelength.
6. The reduced graphene oxide composite membrane for synergistic catalytic separation of antibiotics in wastewater catalyzed degradation under visible light as claimed in claim 5, wherein the concentration of the graphene oxide solution is 0.01 g/L.
7. The reduced graphene oxide composite membrane for synergistic catalytic separation of antibiotics in wastewater catalyzed degradation under visible light as claimed in claim 1, wherein the load of reduced graphene oxide on the support membrane is 0.005-0.015mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The loading of the sodium-boron co-doped carbon nitride photocatalyst on the membrane is 0.4-0.6mg/cm 2 。
8. The reduced graphene oxide composite membrane for synergistic catalytic separation of antibiotics in wastewater catalyzed degradation under visible light as claimed in claim 7, wherein the loading amount of reduced graphene oxide on the support membrane is 0.01mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The loading of the sodium-boron co-doped carbon nitride photocatalyst on the membrane is 0.5mg/cm 2 。
9. The application of the reduced graphene oxide composite membrane subjected to synergistic catalytic separation in photocatalytic degradation of antibiotics in wastewater, which is characterized in that the application method comprises the following steps: under illumination, the method of dead-end filtration is used for interception and degradation of antibiotics in the wastewater, so that the wastewater passes through the reduced graphene oxide composite membrane under the pressure of 1.5-3 bar.
10. The use of a co-catalytically separated reduced graphene oxide composite membrane according to claim 1 for photocatalytic degradation of an antibiotic in wastewater, wherein the antibiotic is sulfamethoxazole.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104174437A (en) * | 2014-09-10 | 2014-12-03 | 天津工业大学 | Graphene/C60/g-C3N4 heterojunction composite film and preparation method thereof |
CN109395763A (en) * | 2018-12-14 | 2019-03-01 | 山东大学 | A kind of sulfur doping g-C3N4Porous composite photo-catalyst of/C-dot and the preparation method and application thereof |
CN110292868A (en) * | 2019-06-19 | 2019-10-01 | 广东工业大学 | A kind of amination graphene oxide and the composite modified membrane material of graphite phase carbon nitride and its preparation method and application |
CN110479350A (en) * | 2019-09-12 | 2019-11-22 | 哈尔滨工业大学 | A kind of preparation method of thin layer nitride porous carbon photochemical catalyst |
CN111215118A (en) * | 2020-02-18 | 2020-06-02 | 盐城工学院 | Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof |
CN111962083A (en) * | 2020-08-15 | 2020-11-20 | 青岛农业大学 | Graphite-phase carbon nitride @ graphene composite film photoanode for photoproduction cathodic protection |
-
2022
- 2022-06-28 CN CN202210739648.5A patent/CN115155636B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104174437A (en) * | 2014-09-10 | 2014-12-03 | 天津工业大学 | Graphene/C60/g-C3N4 heterojunction composite film and preparation method thereof |
CN109395763A (en) * | 2018-12-14 | 2019-03-01 | 山东大学 | A kind of sulfur doping g-C3N4Porous composite photo-catalyst of/C-dot and the preparation method and application thereof |
CN110292868A (en) * | 2019-06-19 | 2019-10-01 | 广东工业大学 | A kind of amination graphene oxide and the composite modified membrane material of graphite phase carbon nitride and its preparation method and application |
CN110479350A (en) * | 2019-09-12 | 2019-11-22 | 哈尔滨工业大学 | A kind of preparation method of thin layer nitride porous carbon photochemical catalyst |
CN111215118A (en) * | 2020-02-18 | 2020-06-02 | 盐城工学院 | Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof |
CN111962083A (en) * | 2020-08-15 | 2020-11-20 | 青岛农业大学 | Graphite-phase carbon nitride @ graphene composite film photoanode for photoproduction cathodic protection |
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