CN110560139A - Preparation method of three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance - Google Patents
Preparation method of three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 14
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000583 acetic acid Drugs 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 229910020350 Na2WO4 Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000032900 absorption of visible light Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 1
- 239000004098 Tetracycline Substances 0.000 description 11
- 229960002180 tetracycline Drugs 0.000 description 11
- 229930101283 tetracycline Natural products 0.000 description 11
- 235000019364 tetracycline Nutrition 0.000 description 11
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000007281 self degradation Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance, which comprises the following steps: step 1), dissolving urea in a mixed solution of water and ethanol, stirring, adding melamine, and stirring for 1 h. And 2) transferring the mixture into a hydrothermal reaction kettle for constant-temperature reaction for 24 hours, cooling, washing, centrifugally collecting a solid product, and drying for 10 hours. Step 3), transferring the solid dried in the step 2) into a muffle furnace for twice calcination, and cooling to room temperature to obtain single 3D-C3N4. Step 4), weighing Na2WO4Dissolving 2H2O in water, and weighing Bi (NO)3)3·5H2Dissolving O in glacial acetic acid, mixing the two solutions, and adding 3D-C3N4, stirring for 1 h. And 5) transferring the solution to a hydrothermal reaction kettle for constant-temperature reaction for 6 hours. Cooling, washing, centrifuging and collecting solid productAnd drying to obtain the finished product. The invention prepares the 3D-C with a three-dimensional structure3N4The specific surface area of the material is increased, and the absorption of visible light and the adsorption of pollutants are facilitated.
Description
Technical Field
The invention relates to the technical field of nano material synthesis, in particular to a preparation method of a three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance.
Background
In recent years, visible light driven catalysts have been regarded as the most promising green method for reducing environmental pollution, and in the past decades, semiconductor materials have been widely used for environmental pollution abatement due to their unique carrier transport mechanisms. Wherein the graphitic carbonitride (g-C) has a narrow band gap3N4) The photocatalyst is considered to be a promising metal-free polymer photocatalyst due to the characteristics of stability, non-toxic harmless physical and chemical properties, large surface abundance and the like.
However, due to C3N4The higher electron-hole recombination efficiency and lower visible light response limit further applications. To this end, many methods have been used to increase C3N4Wherein the construction of heterostructures has proven to be one of the most efficient approaches. In subsequent studies, Bi was found2WO6The material is proved to be a suitable choice for constructing a semiconductor heterostructure due to the characteristics of no toxicity, no harm, stable physicochemical property, good visible light response, easiness in preparation and the like.
Furthermore, based on some studies we found that C3N4The layered structure of (2) faces the problem of stacking between layers and easy agglomeration. These problems lead to a reduction in the specific surface area of the material, further suppression of absorption of visible light, and an excessive number of stacked layers adversely affect the transport of photogenerated carriers.
The 3D material has the advantages of large specific surface area, high adsorption capacity and the like, which is beneficial to the rapid and high-efficiency contact of pollutants and a catalyst, provides an attachment platform for more reaction active sites, and accelerates the degradation rate of the pollutants
disclosure of Invention
The invention aims to solve the problems that: provides a preparation method of a three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance by changing C3N4in a three-dimensional structure, 3D-C of a three-dimensional structure is prepared3N4The specific surface area of the material is increased, which is beneficial to the absorption of visible light and pollutionAnd (4) adsorbing the substance. And preparing 3D-C3N4/Bi2WO6Composite material, by 3D-C3N4And Bi2WO6The synergistic effect between the two components achieves the purpose of improving C3N4The purpose of the photocatalytic performance. .
The technical scheme provided by the invention for solving the problems is as follows: the preparation method of the three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance comprises the following steps:
A preparation method of a three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance comprises the following steps:
Step 1), dissolving a certain amount of urea in a mixed solution of water and ethanol, fully stirring for 30min, adding a certain amount of melamine, and continuously and violently stirring for 1 h;
Step 2), transferring the mixture into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at a constant temperature of 180 ℃ for 24 hours, cooling to room temperature, washing with water and ethanol, centrifuging, collecting a solid product, and drying at 60 ℃ for 10 hours;
Step 3), transferring the solid dried in the step 2) into a muffle furnace, calcining for 2 hours at 520 ℃, cooling to room temperature, and calcining again under the same conditions as the primary conditions; cooling to room temperature to obtain single 3D-C3N4；
step 4), weighing a certain amount of Na2WO4·2H2Dissolving O in water, weighing a certain amount of Bi (NO)3)3·5H2Dissolving O in glacial acetic acid, mixing the two solutions, and adding a certain amount of 3D-C obtained in step 3)3N4Stirring vigorously for 1 h;
Step 5), transferring the solution into a 50mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, and reacting for 6h at the constant temperature of 160 ℃; after cooling to room temperature, the solid product was collected by centrifugation, washed with water and ethanol, respectively, and dried at 60 ℃ overnight to give the final composite.
Preferably, the molar ratio of the added urea to the added melamine in step 1) is 5: 1.
preferably, the volume ratio of the water to the ethanol in the step 1) is 5: 2.
Preferably, the temperature rise rate of the calcination in the step 3) is 3 ℃/min.
Preferably, Na in said step 4)2WO4·2H2O、Bi(NO3)3·5H2O and 3D-C3N4In a molar ratio of 1:2: 3.
Preferably, Na in said step 4)2WO4·2H2the molar ratio of O to water is 1: 555; bi (NO)3)3·5H2The molar ratio of O to glacial acetic acid is 1: 22.
Compared with the prior art, the invention has the advantages that:
(1) 3D-C prepared by the preparation method3N4The composite material is prepared by adopting a soft template method, does not adopt a traditional hard template and acid corrosion, and is more environment-friendly.
(2) 3D-C prepared by the preparation method3N4The calcination temperature is optimized, two-step calcination is adopted, and the crystallinity of the material is better.
(3) The 3D-C is prepared by the preparation method3N4/Bi2WO6In the process of the composite material, an in-situ growth method is adopted, so that the process is simpler.
(4) 3D-C prepared by the preparation method3N4/Bi2WO6The composite material has larger specific surface area and can adsorb more free O2And contaminants, by 3D-C3N4And Bi2WO6The synergistic effect between the two components enhances the separation efficiency of electron holes and improves the photocatalytic performance of the composite material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a drawing ofX% 3D-CC of the invention3N4/Bi2WO6(X-10, 20,30) and pure 3D-C3N4Pure Bi2WO6XRD pattern of (a);
FIG. 2 is X% 3D-C3N4/Bi2WO6(X-10, 20,30) and pure 3D-C3N4Pure Bi2WO6FTIR spectra of (1).
In FIG. 3, a is 20% 3D-C3N4/Bi2WO6Pure 3D-C3N4Pure Bi2WO6XPS survey of (a); b is 20% 3D-C3N4/Bi2WO6Pure Bi2WO6Bi4f diagram; c is 20% 3D-C3N4/Bi2WO6Pure Bi2WO6FIG. W4 f;
D is 20% 3D-C3N4/Bi2WO6Pure Bi2WO6O1s diagram; e is 20% 3D-C3N4/Bi2WO6Pure 3D-C3N4C1s diagram; f is 20% of 3D-C3N4/Bi2WO6Pure 3D-C3N4Diagram N1 s.
In FIG. 4, a is pure 3D-C3N4SEM picture of (1); b is 20% 3D-C3N4/Bi2WO6SEM picture of (1); c is 20% 3D-C3N4/Bi2WO6A TEM image of (B); d is 20% 3D-C3N4/Bi2WO6HRTEM of (g).
FIG. 5 shows composite materials and pure 3D-C in different proportions3N4And pure Bi2WO6A curve of the degradation efficiency of the Tetracycline (TC) under visible light and a Tetracycline (TC) self-degradation curve graph.
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to implement the embodiments of the present invention by using technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Example 1
a preparation method of a three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance comprises the following steps:
Step 1), dissolving a certain amount of urea in a mixed solution of water and ethanol, fully stirring for 30min, adding a certain amount of melamine, and continuously and violently stirring for 1 h;
Step 2), transferring the mixture into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at a constant temperature of 180 ℃ for 24 hours, cooling to room temperature, washing with water and ethanol, centrifuging, collecting a solid product, and drying at 60 ℃ for 10 hours;
Step 3), transferring the solid dried in the step 2) into a muffle furnace, calcining for 2 hours at 520 ℃, cooling to room temperature, and calcining again under the same conditions as the primary conditions; cooling to room temperature to obtain single 3D-C3N4；
Step 4), weighing a certain amount of Na2WO4·2H2Dissolving O in water, weighing a certain amount of Bi (NO)3)3·5H2Dissolving O in glacial acetic acid, mixing the two solutions, and adding a certain amount of 3D-C obtained in step 3)3N4Stirring vigorously for 1 h;
step 5), transferring the solution into a 50mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, and reacting for 6h at the constant temperature of 160 ℃; after cooling to room temperature, the solid product was collected by centrifugation, washed with water and ethanol, respectively, and dried at 60 ℃ overnight to give the final composite.
The molar ratio of the added urea to the added melamine in the step 1) is 5: 1.
the volume ratio of water to ethanol in the step 1) is 5: 2.
The heating rate of the calcination in the step 3) is 3 ℃/min.
Na in the step 4)2WO4·2H2O、Bi(NO3)3·5H2O and 3D-C3N4In a molar ratio of 1:2: 3.
Preferably, Na in said step 4)2WO4·2H2The molar ratio of O to water is 1: 555; bi (NO)3)3·5H2The molar ratio of O to glacial acetic acid is 1: 22.
FIG. 1 is X% 3D-C3N4/Bi2WO6(X-10, 20,30) and pure 3D-C3N4Pure Bi2WO6XRD pattern of (a).
Pure g-C3N4In the XRD pattern of (a), two characteristic peaks are observed at 2 θ of 13.1 ° and 27.2 °, which are an in-plane structural stacking pattern of a typical aromatic system and an interlayer stacking pattern of a conjugated aromatic system, and belong to typical g-C3N4diffraction peaks. For pure Bi2WO6Diffraction peaks at 2 θ of 28.5 °,33.1 °,47.3 °,56.0 °,58.3 °,76.2 ° and 78.3 ° are consistent with those shown by PDF cards (JCPDS PDF No.26-1044), and are respectively assigned to the 103,200,220,303,107,109,307 crystal plane, and are well shown to be identical to pure Bi in the composite materials of various proportions2WO6Similar characteristic peaks indicate that Bi is not changed in the composite material generation process2WO6The crystal structure of (1). In the composite, no C was clearly observed3N4May be due to C3N4Is less doped, and has a diffraction peak of 27.2 DEG and Bi2WO6Due to coincidence of peaks. And with C3N4The increase of the doping amount gradually strengthens the diffraction peak of 28.5 degrees in the composite material, which is probably benefited by C3N4And Bi2WO6Good coexistence of the above.
The successful preparation of the composite photocatalyst is determined by utilizing FT-IR, XPS (X-ray photoelectron spectroscopy), a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM) and a high-resolution transmission electron microscope (HRTEM):
In FIG. 2, pure Bi2WO6The absorption peaks at 1380cm-1 and 440cm-1, 570cm-1 are due to typical bridging mode stretching of W-O-W bonds and Bi-O stretching vibrations, respectively, pure 3D-C3N4In the case of the compound having a structure in which the peak at 812cm-1 is assigned to the s-triazine ring mode, and the absorption peaks at 1247cm-1 and 1572cm-1 are C-The absorption peak at 1632cm-1 due to the N-heterocycle is C-N stretching vibration, the absorption peak at 1335cm-1 belongs to C-N absorption peak, the peak at 731cm-1 is due to W-O stretching vibration, and the absorption band at 3000-3500cm-1 is attributed to amino and surface hydroxyl. In the composite material, the carbon nano-particles are shown to be mixed with pure C3N4And pure Bi2WO6Similar characteristic peaks, consistent with the XRD results, indicate C in the composite3N4And Bi2WO6Good coexistence
In FIG. 3, a is 20% 3D-C3N4/Bi2WO6Pure 3D-C3N4Pure Bi2WO6The XPS survey shows peaks at binding energies of about 288.3eV, 398.1eV, 529.8eV, 159.4eV and 35.7eV, respectively, corresponding to C1s, N1s, O1s and Bi, respectively4f. W4f, which shows Bi2WO6And C3N4Indeed in the composite, which is consistent with the previous results; in b, the peaks with the binding energies of 164.7eV and 159.4eV are respectively assigned to Bi4f5[ 2 ] and Bi4f7/2 of Bi2WO6Medium typical Bi3 +; the peaks with the binding energy of 37.8eV and 35.7eV in c are respectively assigned to W4f5w4f7/2 and Bi2WO6W6 +; in d, the O1s peak of the composite material can be fitted into three peaks at 529.8eV, 530.6eV and 531.9eV, respectively attributed to Bi-O, W-O and surface adsorbed-OH, H2O or O2With simple Bi2WO6In contrast, the composite moved to a low binding energy of 529.6eV at 529.8 eV; in e, peaks with binding energies of 288.1eV, 286.1eV and 284.7eV are respectively assigned to SP2 hybridized N-C-N, mixed carbon C-N and C-C; in f, the peak of the composite material N1s can be fitted into three peaks of 398.1eV, 399.2eV and 400.4eV, which are respectively assigned to SP2The hybridized C-N-C, N- (C)3 and surface uncondensed amino groups (C-N-H), while the peak at 403.9ev binding energy is probably due to pi excitation. Furthermore, the peaks at 399.2eV, 400.4eV, and 403.9eV all shift to higher binding energies, and the shift in O1s from N1s is attributable to C13N4And Bi2WO6The close interaction between them, which indicates that in the composite material, C3N4And Bi2WO6Not just simple physical mixing, but the creation of heterostructures.
In FIG. 4, a is 3D-C3N4Can find the 3D-C prepared by us3N4Presenting a porous spatial corrugation structure; b clearly shows flower-like Bi2WO6attached to corrugated 3D-C3N4A substrate; the Transmission Electron Micrograph (TEM) of the composite material in c also shows Bi2WO6And 3D-C3N4The adhesion state of (a) was consistent with the result of Scanning Electron Microscopy (SEM) of fig. b; d clearly visible 3D-C3N4and Bi2WO6And form a tight interface due to C3N4In XRD pattern, (100) plane diffraction is not clear, C3N4Has poor two-dimensional order, so that C is hardly observed3N4the lattice fringes of (2). Thus, the sharp lattice fringes in HRTEM are attributed to Bi2WO6Calculated lattice width of 0.312nm, corresponding to Bi in an orthorhombic structure2WO6Consistent with the above XRD, XPS, etc., results, indicating successful formation of the composite.
FIG. 5 shows composite materials and pure 3D-C in different proportions3N4And pure Bi2WO6A curve of the degradation efficiency of the Tetracycline (TC) under visible light and a Tetracycline (TC) self-degradation curve graph. It can be seen from the figure that the self-degradation of TC is almost negligible without any catalyst addition. After the catalyst is added, the composite material is obviously better than pure C in the aspect of photocatalytic degradation of TC3N4And pure Bi2WO6Wherein 20% of 3D-C3N4/Bi2WO6the best degradation was shown and TC was almost completely degraded within 120 minutes. And plate C3N4/Bi2WO6comparison of composite materialsCorrugated 3D-C3N4/Bi2WO6the composite material has obviously better degradation efficiency of TC. This shows that Bi2WO6And 3D-C3N4Generation of three-dimensional structure is all to C3N4The photocatalytic activity is improved.
The invention has the beneficial effects that:
(1) 3D-C prepared by the preparation method3N4The composite material is prepared by adopting a soft template method, does not adopt a traditional hard template and acid corrosion, and is more environment-friendly.
(2) 3D-C prepared by the preparation method3N4The calcination temperature is optimized, two-step calcination is adopted, and the crystallinity of the material is better.
(3) The 3D-C is prepared by the preparation method3N4/Bi2WO6In the process of the composite material, an in-situ growth method is adopted, so that the process is simpler.
(4) 3D-C prepared by the preparation method3N4/Bi2WO6The composite material has larger specific surface area and can adsorb more free O2And contaminants, by 3D-C3N4And Bi2WO6The synergistic effect between the two components enhances the separation efficiency of electron holes and improves the photocatalytic performance of the composite material.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (6)
1. A preparation method of a three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance is characterized by comprising the following steps: the method comprises the following steps:
Step 1), dissolving a certain amount of urea in a mixed solution of water and ethanol, fully stirring for 30min, adding a certain amount of melamine, and continuously and violently stirring for 1 h;
Step 2), transferring the mixture into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at a constant temperature of 180 ℃ for 24 hours, cooling to room temperature, washing with water and ethanol, centrifuging, collecting a solid product, and drying at 60 ℃ for 10 hours;
Step 3), transferring the solid dried in the step 2) into a muffle furnace, calcining for 2 hours at 520 ℃, cooling to room temperature, and calcining again under the same conditions as the primary conditions; cooling to room temperature to obtain single 3D-C3N4；
Step 4), weighing a certain amount of Na2WO4·2H2Dissolving O in water, weighing a certain amount of Bi (NO)3)3·5H2Dissolving O in glacial acetic acid, mixing the two solutions, and adding a certain amount of 3D-C obtained in step 3)3N4Stirring vigorously for 1 h;
Step 5), transferring the solution into a 50mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, and reacting for 6h at the constant temperature of 160 ℃; after cooling to room temperature, the solid product was collected by centrifugation, washed with water and ethanol, respectively, and dried at 60 ℃ overnight to give the final composite.
2. The preparation method of the three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance as claimed in claim 1, wherein the preparation method comprises the following steps: the molar ratio of the added urea to the added melamine in the step 1) is 5: 1.
3. The preparation method of the three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance as claimed in claim 1, wherein the preparation method comprises the following steps: the volume ratio of water to ethanol in the step 1) is 5: 2.
4. The preparation method of the three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance as claimed in claim 1, wherein the preparation method comprises the following steps: the heating rate of the calcination in the step 3) is 3 ℃/min.
5. The preparation method of the three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance as claimed in claim 1, wherein the preparation method comprises the following steps: na in the step 4)2WO4·2H2O、Bi(NO3)3·5H2O and 3D-C3N4In a molar ratio of 1:2: 3.
6. The preparation method of the three-dimensional carbon nitride and bismuth tungstate composite material with excellent photocatalytic performance as claimed in claim 1, wherein the preparation method comprises the following steps: na in the step 4)2WO4·2H2The molar ratio of O to water is 1: 555; bi (NO)3)3·5H2The molar ratio of O to glacial acetic acid is 1: 22.
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