CN111097477B - Preparation and application of ultrathin two-dimensional layered composite photocatalytic material - Google Patents
Preparation and application of ultrathin two-dimensional layered composite photocatalytic material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 33
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 38
- 239000004202 carbamide Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 30
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 abstract description 24
- 229960004989 tetracycline hydrochloride Drugs 0.000 abstract description 24
- 238000006731 degradation reaction Methods 0.000 abstract description 11
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- 230000004298 light response Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000004098 Tetracycline Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a preparation method and application of an ultrathin two-dimensional layered composite photocatalytic material3N4Nanosheets; g to C3N4Dispersing the nanosheets into deionized water, adding a graphene oxide solution, ultrasonically stirring, cooling, refluxing, stirring, cooling, and centrifugally washing to obtain g-C3N4a/rGO complex; in (NO)3)3·5H2Adding O, hexadecyl trimethyl ammonium bromide and thioacetamide into deionized water, ultrasonically stirring, and adding g-C3N4Performing ultrasonic stirring, cooling reflux, stirring, cooling, centrifuging, washing and vacuum drying on the/rGO compound to obtain the ultrathin two-dimensional layered composite photocatalytic material. The preparation method is simple in process, and the prepared photocatalytic material has a wide visible light response range and has an efficient tetracycline hydrochloride degradation effect under visible light irradiation.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to preparation and application of a photocatalytic material. The photocatalyst has high-efficiency tetracycline hydrochloride degradation performance under the irradiation of visible light, and has wide prospect in the application of treating tetracycline antibiotic drugs remained in wastewater.
Background
With the widespread use of tetracycline antibiotics, the solution of such drugs remaining in aqueous solutions has become a significant problem that must be faced by today's society. Tetracycline antibiotics are widely used for preventing infections caused by bacteria and the like, but also cause serious damage to the development of the liver, kidney and tooth bones of a human body, and are generally prohibited from being used by children. Tetracycline antibiotics administered to humans or animals are only partially absorbed and mostly excreted via urine and feces, and the residues of such drugs are currently detected in various bodies of water. It is difficult to dispose of the residual tetracycline antibiotics in the conventional wastewater treatment process. The discovery of the photocatalysis technology provides possibility for solving the major problem, the photocatalysis technology not only can degrade antibiotic drugs remained in the wastewater, but also is green and environment-friendly, cannot pollute the environment again, and mainly only needs solar energy to drive the process, so that the photocatalysis technology is convenient to use.
In order to obtain an efficient treatment of waste water with tetracycline antibiotics, a number of correlations have been made in recent years, such as the patent application "A Ag/g-C3N4A composite photocatalyst and its preparing process (application No. 201710247024.0) disclose an Ag/g-C photocatalyst3N4The composite photocatalyst consists of Ag particle and g-C3N4Formed by compounding nano sheets, Ag particles are uniformly dispersed in g-C3N4When the nano-sheet surface is used for simulating and degrading tetracycline (20 mg/L) in wastewater, the degradation rate only reaches 85.6% within 120 min. The patent application 'preparation method of composite material for efficient adsorption-photocatalytic degradation of antibiotics' (application number 201810647240.9) discloses a preparation method of composite material for efficient adsorption-photocatalytic degradation of antibiotics, and the photocatalyst makes full use of synergistic effect of adsorption and photocatalysis to improve the removal effect of environmental pollutants. The patent application, nitrogen-doped carbon quantum dot with photocatalytic performance and preparation method thereof and tetracycline hydrochloride degradation method (application number 201910397425.3), discloses a nitrogen-doped carbon quantum dot with photocatalytic performance and preparation method thereof and tetracycline hydrochloride degradation method, wherein the nitrogen-doped carbon quantum dot has excellent dispersibility and catalytic efficiency and can further catalyze saltDegrading acid tetracycline; meanwhile, the preparation method has the advantages of controllable product appearance, low cost and good reproducibility.
However, the above-disclosed preparation methods all have the disadvantage of complicated preparation process.
Disclosure of Invention
The invention aims to provide g-C of ultrathin two-dimensional layered composite (2D/2D/2D composite) with simple and feasible preparation process3N4/rGO/In2S3A preparation method of a photocatalytic material.
The invention also aims to provide an application method of the photocatalytic material prepared by the preparation method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: ultrathin two-dimensional layered composite g-C3N4/rGO/In2S3The preparation method of the photocatalytic material specifically comprises the following steps:
1) preparation of g-C3N4Nanosheet: weighing 5-20 g of urea, filling the urea into a 25-100 mL crucible, heating the urea to 520-550 ℃ at a heating rate of 2-5 ℃/min in a muffle furnace, preserving heat for 2-4 h, naturally cooling the urea to 20-30 ℃, then heating to 520-550 ℃ at a heating rate of 2-5 ℃/min, preserving heat for 2-4 h, naturally cooling to 20-30 ℃, grinding the urea into powder, and obtaining g-C3N4Nanosheets;
2) composite g-C3N4Nanoplatelets and reduced graphene (rGO): 0.2 to 1g of g-C3N4Dispersing the nanosheets into a three-neck flask filled with 40-200 mL of deionized water, adding 1-5 mL of graphene oxide solution with the mass volume concentration of 2mg/mL, and ultrasonically stirring for 20-30 min to enable the g-C3N4Uniformly mixing the nanosheets and graphene oxide, cooling and refluxing at the temperature of 90-95 ℃, stirring for 4-6 h, cooling, and centrifugally washing to obtain g-C3N4a/rGO complex;
3) 0.0457 to 0.3205g of In (NO)3)3·5H2O, 0.3645-1.4580 g Cetyl Trimethyl Ammonium Bromide (CTAB) and 0.027-0.189 g Thioacetamide (TAA) are added into a container containing 100-200 mL of the mixtureUltrasonically stirring the mixture in a three-neck flask with water being separated for 10 to 20min, and then adding 0.1 to 0.2g of g-C3N4Ultrasonically stirring a/rGO compound for 20-30 min to uniformly mix the solution, cooling and refluxing the solution at the temperature of 90-95 ℃, stirring the solution for 4-6 h, cooling the solution, centrifugally washing the solution, and drying the solution in vacuum for 12h to obtain the ultrathin two-dimensional layered composite photocatalytic material (g-C)3N4/rGO/In2S3）。
The other technical scheme adopted by the invention is as follows: an application of the photocatalytic material prepared by the preparation method in treating tetracycline antibiotic drugs remained in wastewater.
The preparation method firstly leads two-dimensional (2D) g-C to be treated by a reflux device3N4rGO of 2D to form g-C3N4(ii)/rGO; passing through the reflux device again to remove 2D In2S3In situ growth to g-C3N4On the surface of/rGO, the whole preparation process is simple; the prepared photocatalyst has larger specific surface area, more active sites and fast electron transfer rate due to the compounding of the ultrathin 2D nano material, and a compounded sample has better adsorbability on tetracycline hydrochloride, so that the whole material shows more excellent photocatalytic activity in the degradation process of the tetracycline hydrochloride.
The invention adopts a simple sintering method to prepare g-C3N4Nanosheets, and enabling the g-C to be subjected to two-step reflux3N4Nanosheet, rGO nanosheet and In2S3The nano sheets are successfully compounded together, so that the ternary compounding of a two-dimensional material, the two-dimensional material and the two-dimensional material is realized, the response range of visible light is widened, the rapid conduction of electrons is realized, more active sites are exposed, the tetracycline hydrochloride has good adsorbability, and the g-C is ensured3N4/rGO/In2S3The photocatalytic material has an efficient tetracycline hydrochloride degradation effect under the irradiation of visible light, and has a wide application prospect in the aspect of treating tetracycline antibiotic drugs remaining in wastewater. The photocatalytic material prepared by the preparation method widens the response range of visible lightIncrease of g-C by providing more active sites and accelerating electron conduction3N4/rGO/In2S3The performance of the composite material for degrading tetracycline hydrochloride by photocatalysis.
Drawings
FIG. 1 is an X-ray diffraction pattern of the photocatalytic material obtained in example 1.
FIG. 2 is a scanning electron microscope photograph of the photocatalytic material obtained in example 1.
FIG. 3 is a transmission electron microscope photograph of the photocatalytic material obtained in example 1.
FIG. 4 is a mapping chart of the photocatalytic material obtained in example 1.
FIG. 5 is a UV-VIS diffuse reflectance spectrum of the photocatalytic material obtained in example 1.
FIG. 6 is a graph showing the change of the concentration of tetracycline hydrochloride in a solution with the time of irradiation in an experiment in which tetracycline hydrochloride degradation was performed under visible light irradiation to simulate the treatment of antibiotic drugs remaining in wastewater in example 1, comparative example 2, comparative example 3, and comparative example 4.
FIG. 7 is a graph showing the change of the concentration of tetracycline hydrochloride in the solution at various times in the case of tetracycline hydrochloride degradation of example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Weighing 5g of urea, filling the urea into a 25mL crucible, heating the urea to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, preserving heat for 4h, naturally cooling the urea to 20 ℃, heating the urea to 520 ℃ at the heating rate of 2 ℃/min, preserving heat for 2h, naturally cooling the urea to 25 ℃, grinding the urea into powder to obtain g-C3N4Nanosheets; 0.2g of g-C3N4Dispersing the nano sheets into a three-neck flask filled with 100mL of deionized water, adding 1mL of graphene oxide solution with the mass volume concentration of 2mg/mL, and ultrasonically stirring for 20min to enable the g-C concentration to be within the range of3N4Uniformly mixing the nano-sheets and graphene oxide, cooling and refluxing at the temperature of 95 ℃, stirring for 6 hours, centrifugally washing after the solution is cooled,to obtain g-C3N4a/rGO complex; adding 0.2289g of In (NO)3)3·5H2O, 0.3645g of cetyltrimethylammonium bromide and 0.135g of thioacetamide were put into a three-necked flask containing 100mL of deionized water, stirred ultrasonically for 20min, and then 0.2g of g-C was added3N4Ultrasonically stirring the/rGO compound for 20min to uniformly mix the solution, cooling and refluxing at 95 ℃, stirring for 4h, cooling the solution, and centrifugally washing to obtain the ultrathin two-dimensional layered compound g-C3N4/rGO/In2S3A photocatalytic material.
The X-ray diffraction spectrum of the photocatalytic material prepared in example 1 is shown in FIG. 1, and the X-ray diffraction peak of the photocatalytic material is shown in FIG. 1 to be from g to C3N4And In2S3The common components are formed, no other impurity peak appears, the peak of rGO is very weak and can not be obviously seen on XRD, which indicates that the prepared photocatalytic material is g-C3N4/rGO/In2S3And (c) a complex. The scanning electron micrograph of the composite, as shown in FIG. 2, shows that the composite prepared was entirely in the form of a sheet. Fig. 3 is a transmission electron micrograph of the composite, and it can be seen that the composite prepared is a nanosheet. FIG. 4 is a mapping chart of the complex, which shows the distribution of four elements, C, N, In and S, at the same position In the complex, indicating that the resulting complex is g-C3N4/rGO/In2S3The complex of (1). Fig. 5 is a graph of the uv-vis diffuse reflectance spectrum of the composite, which can be seen to have good uv and visible absorption.
Comparative example 1
Weighing 5g of urea, filling the urea into a 25mL crucible, heating the urea to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, preserving heat for 4h, naturally cooling the urea, heating the urea to 520 ℃ at the heating rate of 2 ℃/min, preserving heat for 2h, grinding the urea into powder after the urea is naturally cooled to obtain g-C3N4Nanosheets.
Comparative example 2
Weighing 5g of urea, putting the urea into a 25mL crucible, heating the urea to 550 ℃ in a muffle furnace at the heating rate of 5 ℃/min, preserving the heat for 4h,naturally cooling, heating to 520 deg.C at a heating rate of 2 deg.C/min, maintaining for 2 hr, naturally cooling, and grinding into powder to obtain g-C3N4Nanosheets; 0.2g of g-C3N4Dispersing the nano sheets into a three-neck flask filled with 100mL of deionized water, adding 1mL of graphene oxide solution with the mass volume concentration of 2mg/mL, and ultrasonically stirring for 20min to enable the g-C concentration to be within the range of3N4Uniformly mixing the nanosheets and graphene oxide, cooling and refluxing at the temperature of 95 ℃, stirring for 6 hours, cooling the solution, and centrifuging and washing to obtain g-C3N4the/rGO composite samples.
Comparative example 3
Adding 0.2289g of In (NO)3)3·5H2Adding O, 0.3645g hexadecyl trimethyl ammonium bromide and 0.135g thioacetamide into a three-neck flask containing 100mL of deionized water, ultrasonically stirring for 20min, cooling and refluxing at 95 ℃, stirring for 4h, cooling the solution, centrifugally washing, and vacuum drying for 12h to obtain In2S3And (3) sampling.
Comparative example 4
Weighing 5g of urea, filling the urea into a 25mL crucible, heating the urea to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, preserving heat for 4h, naturally cooling the urea, heating the urea to 520 ℃ at the heating rate of 2 ℃/min, preserving heat for 2h, naturally cooling the urea, grinding the urea into powder, and obtaining g-C3N4A nanosheet of (a); adding 0.2289g of In (NO)3)3·5H2O, 0.3645g of cetyltrimethylammonium bromide and 0.135g of thioacetamide were put into a three-necked flask containing 100mL of deionized water, stirred ultrasonically for 20min, and then 0.2g of g-C was added3N4Ultrasonic stirring for 20min to mix the solution uniformly, cooling and refluxing at 95 deg.C, stirring for 4 hr, cooling, centrifuging, washing, and vacuum drying for 12 hr to obtain g-C3N4 /In2S3The composite sample of (1).
Example 2
Weighing 20g of urea, placing into a 100mL crucible, heating to 535 deg.C at a heating rate of 3.5 deg.C/min in a muffle furnace, maintaining for 3h, naturally cooling to 25 deg.C, and heating to 5 deg.C at a heating rate of 5 deg.C/minKeeping the temperature at 50 ℃ for 4h, naturally cooling the mixture, then grinding the cooled mixture into powder at 30 ℃ to obtain g-C3N4Nanosheets; 1g of g-C3N4Dispersing the nano sheets into a three-neck flask containing 200mL of deionized water, adding 5mL of graphene oxide solution with the mass volume concentration of 2mg/mL, and ultrasonically stirring for 30min to enable the g-C3N4Uniformly mixing the nanosheets and graphene oxide, cooling and refluxing at 90 ℃, stirring for 4 hours, cooling the solution, and centrifugally washing to obtain g-C3N4a/rGO complex; 0.0457g of In (NO)3)3·5H2O, 0.9113g of cetyltrimethylammonium bromide and 0.189g of thioacetamide were put into a three-necked flask containing 200mL of deionized water, stirred ultrasonically for 15min, and then 0.1g of g-C was added3N4Ultrasonically stirring the/rGO compound for 30min to uniformly mix the solution, cooling and refluxing the solution at the temperature of 92 ℃, stirring the solution for 6h, cooling the solution, and centrifugally washing the solution to obtain the ultrathin two-dimensional layered compound g-C3N4/rGO/In2S3A photocatalytic material.
Example 3
Weighing 12.5g of urea, filling the urea into a 65mL crucible, heating the urea to 520 ℃ at the heating rate of 2 ℃/min in a muffle furnace, preserving heat for 2h, naturally cooling the urea to 30 ℃, heating the urea to 535 ℃ at the heating rate of 3.5 ℃/min, preserving heat for 3h, naturally cooling the urea to 20 ℃, and grinding the urea into powder to obtain g-C3N4Nanosheets; 0.6g of g-C3N4Dispersing the nano sheets into a three-neck flask filled with 40mL of deionized water, adding 3mL of graphene oxide solution with the mass volume concentration of 2mg/mL, and ultrasonically stirring for 25min to enable the g-C3N4Uniformly mixing the nanosheets and graphene oxide, cooling and refluxing at the temperature of 92.5 ℃, stirring for 5 hours, cooling the solution, and centrifuging and washing to obtain g-C3N4a/rGO complex; 0.3205g of In (NO)3)3·5H2O, 1.4580g of cetyltrimethylammonium bromide and 0.027g of thioacetamide were added to a three-necked flask containing 150mL of deionized water, stirred ultrasonically for 10min, and then 0.15g of g-C was added3N4Ultrasonic stirring for 25min to mix the solution, and cooling at 90 deg.CRefluxing, stirring for 5h, cooling the solution, and centrifuging and washing to obtain ultrathin two-dimensional layered composite g-C3N4/rGO/In2S3A photocatalytic material.
Characterization of sample photocatalytic effect (taking photocatalytic degradation of tetracycline hydrochloride solution as an example): preparing a tetracycline hydrochloride solution with the mass volume concentration of 20 mg/L; taking five vessels, and injecting 40mL of the tetracycline hydrochloride solution into each vessel; respectively weighing 25mg of the photocatalyst prepared in the embodiment 1, the sample prepared in the comparative example 2, the sample prepared in the comparative example 3 and the sample prepared in the comparative example 4, adding one sample into each vessel, immersing the samples into tetracycline hydrochloride solution, standing for a period of time in a dark environment, then completely placing the vessels under visible light for irradiation, respectively testing the absorbance of the tetracycline hydrochloride solution in five vessels at a fixed time, then calculating the concentration of the rhodamine-B solution at the testing time according to the Lambert beer law, and representing the photocatalytic performance through the concentration change of the tetracycline hydrochloride solution. The concentration change curve of the tetracycline hydrochloride solution is shown in fig. 6, and it can be seen from fig. 6 that the photocatalyst prepared in example 1 has rapid degradation performance on tetracycline hydrochloride under the irradiation of visible light. As shown in FIG. 7, it can be seen that the absorbance of the tetracycline hydrochloride solution is substantially close to 0 at 30min, which indicates that the tetracycline hydrochloride solution is substantially completely degraded after being irradiated by visible light for 30min, and thus the photocatalytic material prepared by the preparation method of the present invention has a strong degradation capability of tetracycline hydrochloride.
Claims (4)
1. The preparation method of the ultrathin two-dimensional layered composite photocatalytic material is characterized by comprising the following steps of:
1) heating 5-20 g of urea in a muffle furnace to 520-550 ℃, preserving heat for 2-4 h, naturally cooling to 20-30 ℃, then heating to 520-550 ℃, preserving heat for 2-4 h, naturally cooling to 20-30 ℃, and grinding to obtain g-C3N4Nanosheets;
2) 0.2 to 1g of g-C3N4Nano meterDispersing the sheet into deionized water, adding 1-5 mL of graphene oxide solution, and ultrasonically stirring to obtain g-C3N4Uniformly mixing the nanosheets and graphene oxide, cooling and refluxing at the temperature of 90-95 ℃, stirring, cooling, and centrifugally washing to obtain g-C3N4a/rGO complex;
3) 0.0457 to 0.3205g of In (NO)3)3·5H2Adding O, 0.3645-1.4580 g of hexadecyl trimethyl ammonium bromide and 0.027-0.189 g of thioacetamide into deionized water, ultrasonically stirring, and then adding 0.1-0.2 g of g-C3N4And ultrasonically stirring the/rGO compound to uniformly mix the solution, cooling and refluxing the solution at the temperature of 90-95 ℃, stirring the solution, cooling the solution, centrifugally washing the cooled solution, and drying the cooled solution in vacuum to obtain the ultrathin two-dimensional layered composite photocatalytic material.
2. The method for preparing the ultrathin two-dimensional layered composite photocatalytic material as claimed in claim 1, wherein the mass-volume concentration of the graphene oxide solution in the step 2) is 2 mg/mL.
3. The application of the ultrathin two-dimensional layered composite photocatalytic material prepared by the preparation method of claim 1 in wastewater treatment.
4. The application of the ultrathin two-dimensional layered composite photocatalytic material as claimed in claim 3, wherein the composite photocatalytic material is applied to treatment of tetracycline antibiotic drugs remaining in wastewater.
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| CN112371162A (en) * | 2020-12-28 | 2021-02-19 | 兰州大学 | Preparation and application of graphite-phase carbon nitride/titanium tin solid solution heterojunction photocatalytic degradation material |
| CN113385195A (en) * | 2021-07-23 | 2021-09-14 | 兰州大学 | Preparation and application of tungsten disulfide/indium sulfide heterojunction photocatalytic material |
| CN114768844A (en) * | 2022-03-23 | 2022-07-22 | 桂林电子科技大学 | Ultrathin porous flaky g-C3N4Preparation method and application of photocatalyst |
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