CN112871194A - Bismuth vanadate composite photocatalytic material and preparation method thereof - Google Patents
Bismuth vanadate composite photocatalytic material and preparation method thereof Download PDFInfo
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- bismuth vanadate
- nitrogen carbide
- bismuth
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 98
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 92
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 92
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 146
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- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 150000001621 bismuth Chemical class 0.000 claims abstract description 12
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- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 239000000843 powder Substances 0.000 description 10
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 7
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 7
- 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 7
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 3
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- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 239000010842 industrial wastewater Substances 0.000 description 1
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B01J35/39—
-
- B01J35/50—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to the technical field of photocatalysis, and particularly relates to a bismuth vanadate composite photocatalytic material and a preparation method thereof. The preparation method of the bismuth vanadate composite photocatalytic material comprises the following steps: performing first calcination treatment on melamine to obtain melem; mixing the melem with pyromellitic dianhydride, and then carrying out second calcination treatment to obtain a nitrogen carbide material connected with an aromatic diimine structure; and adding the nitrogen carbide material connected with the aromatic diimine structure into a mixed solution containing bismuth salt and vanadate, and growing bismuth vanadate particles on the surface of the nitrogen carbide material to obtain the bismuth vanadate composite photocatalytic material. The preparation method can improve the visible light absorption of the optical composite material and inhibit the recombination of electron-hole pairs, thereby improving the efficiency of degrading pollutants by photocatalysis.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a bismuth vanadate composite photocatalytic material and a preparation method thereof.
Background
In recent years, with the increasing strength of national environmental protection measures, the problem of treating industrial wastewater, domestic sewage and rivers becomes a research hotspot of people. The emission standard of high-pollution emission enterprises in the printing industry is gradually improved, the traditional treatment method has high cost and low treatment efficiency, and particularly, organic pollutants are difficult to remove. In the last 70 th century, the phenomenon that titanium dioxide realizes conversion of solar energy into chemical energy under the condition of solar illumination is discovered, and solar energy is used as a new photocatalytic technology at the development place of renewable clean energy. Therefore, the application of the photocatalytic technology in sewage treatment has the outstanding advantages of high efficiency, stability, no secondary pollution, catalyst reutilization, suitability for degradation of various organic pollutants and the like, and becomes a favored technology. However, the ultraviolet light in sunlight only accounts for about 5%, which is a key factor for limiting the wide application of the photocatalytic technology in the field of environmental protection. Therefore, whether the photocatalyst can respond under visible light or not, and the main design purpose of the photocatalyst is to perform stable, controllable and efficient photocatalytic reaction by utilizing sunlight with maximum efficiency.
Bismuth vanadate is used as a semiconductor photocatalytic material containing heavy metal elements harmful to human bodies. Meanwhile, the forbidden band width of the titanium dioxide photocatalyst is about 2.4eV, and compared with titanium dioxide, the titanium dioxide photocatalyst has the advantage of visible light catalytic activity. Bismuth vanadate has the advantages of good visible light absorption capacity, high photochemical stability, strong oxidation-reduction capacity, no toxicity and the like in the field of photocatalysis, is an excellent semiconductor material, and has good application prospect. However, the bismuth vanadate has the problems of poor conductivity and high electron-hole pair recombination rate, and the application of the bismuth vanadate in the field of photocatalysis is also limited.
Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to provide a bismuth vanadate composite photocatalytic material and a preparation method thereof, and aims to solve the technical problems that the existing bismuth vanadate composite nitrogen carbide has poor conductivity and a photon-generated carrier is easy to compound.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a bismuth vanadate composite photocatalytic material on one hand, which comprises the following steps:
performing first calcination treatment on melamine to obtain melem;
mixing the melem with pyromellitic dianhydride, and then carrying out second calcination treatment to obtain a nitrogen carbide material connected with an aromatic diimine structure;
and adding the nitrogen carbide material connected with the aromatic diimine structure into a mixed solution containing bismuth salt and vanadate, and growing bismuth vanadate particles on the surface of the nitrogen carbide material to obtain the bismuth vanadate composite photocatalytic material.
The invention provides a bismuth vanadate composite photocatalytic material, which comprises a lamellar nitrogen carbide material and bismuth vanadate particles combined on the surface of the lamellar nitrogen carbide material, wherein the nitrogen carbide in the lamellar nitrogen carbide material is connected with an aromatic diimine structure.
According to the preparation method of the bismuth vanadate composite photocatalytic material, the aromatic diimine structure is spliced in the grid structure of the nitrogen carbide to adjust the position of a valence band conduction band of the nitrogen carbide, and then the bismuth vanadate is loaded on the modified surface of the nitrogen carbide to form the composite photocatalytic material, so that the visible light absorption of the photocatalytic material can be improved, the recombination of electron-hole pairs can be inhibited, and the efficiency of photocatalytic degradation of pollutants can be improved. The preparation method has the advantages of simple operation, mass production, low cost and low cycle production, and compared with the prior art, the obtained product has higher pollutant removal capacity and higher reutilization rate, thereby having wide application.
The bismuth vanadate composite photocatalytic material provided by the invention comprises a lamellar nitrogen carbide material and bismuth vanadate particles combined on the surface of the lamellar nitrogen carbide material, wherein the nitrogen carbide in the lamellar nitrogen carbide material is connected with an aromatic diimine structure. The aromatic diimine structure can adjust the valence band conduction band position of the nitrogen carbide, is introduced into the skeleton of the nitrogen carbide to reduce the conduction band position of the nitrogen carbide, simultaneously improves the transmission capability of electrons, reduces the recombination of photon-generated carriers, thereby improving the light absorption performance, improving the photocatalytic activity, and finally improving the efficiency of degrading pollutants by photocatalysis, thereby having wide application.
Drawings
Fig. 1 is a schematic diagram of a spliced aromatic diimine structure in a nitrogen carbide structure in a bismuth vanadate composite photocatalyst provided by an embodiment of the present invention;
fig. 2 is a scanning electron microscope picture of the bismuth vanadate composite photocatalyst provided by the embodiment of the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On one hand, the embodiment of the invention provides a preparation method of a bismuth vanadate composite photocatalytic material, which comprises the following steps:
s01: performing first calcination treatment on melamine to obtain melem;
s02: mixing the melem with pyromellitic dianhydride, and then carrying out second calcination treatment to obtain a nitrogen carbide material connected with an aromatic diimine structure;
s03: and adding the nitrogen carbide material connected with the aromatic diimine structure into a mixed solution containing bismuth salt and vanadate, and growing bismuth vanadate particles on the surface of the nitrogen carbide material to obtain the bismuth vanadate composite photocatalytic material.
According to the preparation method of the bismuth vanadate composite photocatalytic material provided by the embodiment of the invention, the aromatic diimine structure is spliced in the grid structure of the nitrogen carbide to adjust the position of a valence band conduction band of the nitrogen carbide, and then the bismuth vanadate is loaded on the modified surface of the nitrogen carbide to form the composite photocatalytic material, so that the visible light absorption of the photocatalytic material can be improved, the recombination of electron-hole pairs can be inhibited, and the efficiency of photocatalytic degradation of pollutants can be improved. The preparation method has the advantages of simple operation, mass production, low cost and low cycle production, and compared with the prior art, the obtained product has higher pollutant removal capacity and higher reutilization rate, thereby having wide application.
The embodiment of the invention provides a bismuth vanadate composite photocatalytic material with visible light response and recycling characteristics, which improves the light absorption capacity of bismuth vanadate, effectively separates electron-hole pairs and enhances the photocatalytic capacity. The forbidden bandwidth of bismuth vanadate is about 2.4eV, which determines the function of photocatalytic reaction under visible light, and the nitrogen carbide has a very suitable semiconductor band edge position, and can improve the light absorption performance of bismuth vanadate by compounding with the bismuth vanadate, thereby improving the photocatalytic performance. However, the bismuth vanadate is compounded with pure nitrogen carbide, and then the defects of poor conductivity and easy recombination of photon-generated carriers still exist, but in the method, electron-deficient aromatic diimine is introduced into a nitrogen carbide framework, as shown in fig. 1, so that the position of a modified nitrogen carbide conduction band can be reduced, the electron transmission capability is improved, the rapid recombination of photon-generated carriers is reduced, the bismuth vanadate and the modified nitrogen carbide are compounded, the effect of reducing the recombination of photon-generated carriers can be achieved, the light absorption performance is improved, and the photocatalytic activity is improved.
In one embodiment, the first calcination process comprises: heating to 400-450 ℃ at the heating rate of 10-20 ℃/min, and then preserving the heat for 4-6 h. Melamine is calcined at the temperature of 400-450 ℃ to form melem which is an intermediate of the carbon nitride (the sintering temperature is generally higher than 550 ℃ for preparing the carbon nitride by sintering the melamine), so the melem calcined at the temperature can be subsequently subjected to dehydration condensation with pyromellitic dianhydride to form the carbon nitride material connected with the aromatic diimine structure.
In one embodiment, the second calcination process comprises: heating to 350 ℃ at the heating rate of 10-20 ℃/min, and then preserving the heat for 4-6 h. Sintering under the temperature condition can dehydrate and condense melem and pyromellitic dianhydride to obtain the carbon nitride connected with an aromatic diimine structure, but not form the carbon nitride without modification through thermal condensation between melem.
In one embodiment, the mixed solution further contains sodium dodecyl benzene sulfonate which plays a role of a surfactant in a hydrothermal reaction, so that the shape and size of the formed bismuth vanadate are more uniform, and the agglomeration phenomenon of the bismuth vanadate is not easy to occur; further, the molar ratio of the bismuth salt to the vanadate in the mixed solution is 1: 1.
In one embodiment, the step of adding the nitrogen carbide material with the aromatic diimine structure connected to the nitrogen carbide material into a mixed solution containing bismuth salt and vanadate, and growing bismuth vanadate particles on the surface of the nitrogen carbide material comprises the following steps:
s031, preparing bismuth salt solution and vanadate solution;
s032, mixing the bismuth salt solution and the vanadate solution, and adding sodium dodecyl benzene sulfonate to obtain a mixed solution;
and S033, adding the nitrogen carbide material into the mixed solution, performing magnetic stirring, and performing a hydrothermal reaction.
In the preparation process, bismuth vanadate particles can grow on the surface of the nitrogen carbide material. Furthermore, the nitrogen carbide material is a lamellar nitrogen carbide material, the thickness of the lamellar nitrogen carbide material is 100-500nm, and the planar size of the lamellar is 5-10 μm. The bismuth vanadate particles growing on the surface are rod-shaped particles with the particle size of 500nm-2 mu m. In the size range, more rod-shaped particles of bismuth vanadate can grow on the nitrogen carbide material connected with the aromatic diimine structure, so that the bismuth vanadate composite photocatalytic material has larger specific surface area, and larger photocatalytic reaction active sites are increased.
Further, the magnetic stirring time is 1-2h, and the nitrogen carbide material connected with the aromatic diimine structure can be better dispersed in the mixed solution under the condition. Further, the temperature of the hydrothermal reaction is 180-220 ℃, the time is 1-2h, and rod-shaped bismuth vanadate particles can be better grown on the nitrogen carbide material connected with the aromatic diimine structure under the condition.
Further, after the hydrothermal reaction, the steps of filtering, washing, drying and grinding are also included in sequence.
On the other hand, the embodiment of the invention also provides a bismuth vanadate composite photocatalytic material, which comprises a lamellar nitrogen carbide material and bismuth vanadate particles combined on the surface of the lamellar nitrogen carbide material, wherein the nitrogen carbide in the lamellar nitrogen carbide material is connected with an aromatic diimine structure.
The bismuth vanadate composite photocatalytic material provided by the embodiment of the invention comprises a lamellar nitrogen carbide material and bismuth vanadate particles combined on the surface of the lamellar nitrogen carbide material, wherein the nitrogen carbide in the lamellar nitrogen carbide material is connected with an aromatic diimine structure. The aromatic diimine structure can adjust the valence band conduction band position of the nitrogen carbide, is introduced into the skeleton of the nitrogen carbide to reduce the conduction band position of the nitrogen carbide, simultaneously improves the transmission capability of electrons, reduces the recombination of photon-generated carriers, thereby improving the light absorption performance, improving the photocatalytic activity, and finally improving the efficiency of degrading pollutants by photocatalysis, thereby having wide application.
Specifically, the valence band conduction band of the modified nitrogen carbide (with the aromatic diimine structure) can be adjusted in position and compounded with bismuth vanadate, so that the degradation for removing various organic pollutants such as methylene blue, rhodamine B, methyl orange and the like which are difficult to degrade is improved. The photocatalyst has excellent photocatalytic performance under sunlight and can be stably recycled; compared with the traditional methods of physical adsorption, biodegradation, chemical decomposition and the like, the method for removing pollutants by using the bismuth vanadate composite photocatalytic material has higher removal rate and reutilization rate, and experiments prove that the bismuth vanadate loaded on the surface of the modified nitrogen carbide photocatalytic material can be widely applied in practice.
Further, the bismuth vanadate composite photocatalytic material is composed of the lamellar nitrogen carbide material connected with the aromatic diimine structure and bismuth vanadate particles combined on the surface of the lamellar nitrogen carbide material.
Further, the thickness of the lamellar carbonized nitrogen material is 100-500nm, and the planar size of the lamellar is 5-10 μm; the bismuth vanadate particles are rod-shaped particles with the particle size of 500nm-2 mu m. The mass ratio of the lamellar nitrogen carbide material to the bismuth vanadate particles is (1: 3) - (7: 13). The weight percentage of bismuth vanadate is 65-75%, and the weight percentage of aromatic diimine structure modified nitrogen carbide is 25-35%, based on 100% of the total weight of the bismuth vanadate composite photocatalytic material.
Further, the bismuth vanadate composite photocatalytic material is prepared by the preparation method of the bismuth vanadate composite photocatalytic material.
In one embodiment, a preparation method of a bismuth vanadate composite photocatalyst comprises the following steps:
(1) adding 5-10g of melamine into a crucible, placing the crucible in a muffle furnace, heating to 400-450 ℃ at the heating rate of 10-20 ℃/min, and calcining for 4-6h to obtain melem powder;
(2) uniformly mixing 2-5g of melem and pyromellitic dianhydride in equal mass, adding the mixture into a crucible, putting the crucible into a muffle furnace, heating the mixture to 350 ℃ at the heating rate of 10-20 ℃/min, and keeping the temperature for 4-6h to perform secondary calcination to obtain modified carbon nitride powder;
(3) adding 1-5mmol of bismuth nitrate pentahydrate into a beaker filled with 10mL of deionized water, adding 10mL of 4mol/L nitric acid solution, and stirring in a magnetic stirrer until the solution is completely dissolved;
(4) adding the ammonium metavanadate with the equal molar weight in the step (3) into a beaker filled with 10mL of deionized water, and fully stirring in a magnetic stirrer; pouring the solution obtained in the step (3) into the solution, continuously and fully stirring the solution for 1 to 2 hours, finally adding 0.1 to 0.25g of sodium dodecyl benzene sulfonate, and continuously stirring the solution for 0.5 to 1 hour until the solution is completely dissolved;
(5) adding the modified carbonized nitrogen powder obtained in the step (2) into the suspension obtained in the step (4), fully stirring the mixture in a magnetic stirrer for 1 to 2 hours to obtain a suspension, transferring the suspension into a 50mL hydrothermal reaction kettle, and placing the hydrothermal reaction kettle in an air drying oven for heat preservation for 1.5 hours at 200 ℃;
(6) and (5) carrying out suction filtration, washing, drying and grinding on the suspension obtained in the step (5) to obtain a final product.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Comparative example 1
The preparation method of the bismuth vanadate photocatalyst comprises the following steps:
step S01: weighing 5mmol of bismuth nitrate pentahydrate and bismuth nitrate pentahydrate, adding the weighed materials into a beaker filled with 10mL of deionized water, adding 10mL of 4mol/L nitric acid solution, and stirring the mixture in a magnetic stirrer until the mixture is completely dissolved;
step S02: weighing 5mmol of ammonium metavanadate, adding the ammonium metavanadate into a beaker filled with 10mL of deionized water, and fully stirring the mixture in a magnetic stirrer; and pouring the solution obtained in the step S01 into the solution, continuously and fully stirring the solution for 1 to 2 hours, finally adding 0.25g of sodium dodecyl benzene sulfonate, and continuously stirring the solution for 0.5 to 1 hour till the solution is completely dissolved.
Step S03: transferring the uniform precursor solution obtained in the step S02 to a 50mL reaction kettle, placing the reaction kettle in a drying oven, heating to 200 ℃, and preserving heat for 1.5 h;
step S04: performing suction filtration and washing on the precursor solution reacted in the step S03 for 3-4 times by using deionized water until the PH value is 7;
step S05: and finally, putting the sample into a drying oven, setting the temperature to be 70 ℃, drying for 12-24h, transferring and grinding the sample, and finally obtaining the bismuth vanadate powder sample.
Comparative example 2
The preparation method of the bismuth vanadate composite nitrogen carbide photocatalyst comprises the following steps:
step S01: weighing 5mmol of bismuth nitrate pentahydrate and bismuth nitrate pentahydrate, adding the weighed materials into a beaker filled with 10mL of deionized water, adding 10mL of 4mol/L nitric acid solution, and stirring the mixture in a magnetic stirrer until the mixture is completely dissolved;
step S02: weighing 5mmol of ammonium metavanadate, adding the ammonium metavanadate into a beaker filled with 10mL of deionized water, and fully stirring the mixture in a magnetic stirrer; and pouring the solution obtained in the step S01 into the solution, continuously and fully stirring the solution for 1 to 2 hours, finally adding 0.25g of sodium dodecyl benzene sulfonate, and continuously stirring the solution for 0.5 to 1 hour till the solution is completely dissolved.
Step S03: weighing 0.405-0.567g of the carbonized nitrogen powder, adding into the beaker of the step S02, and continuously stirring for 1-2h in a halving way;
step S04: transferring the uniform precursor solution obtained in the step S03 to a 50mL reaction kettle, placing the reaction kettle in a drying oven, heating to 200 ℃, and preserving heat for 1.5 h;
step S05: performing suction filtration and washing on the precursor solution reacted in the step S04 for 3-4 times by using deionized water until the PH value is 7;
step S06: and finally, putting the sample into a drying oven, setting the temperature to be 70 ℃, drying for 12-24h, transferring and grinding the sample, and finally obtaining the bismuth vanadate composite nitrogen carbide powder sample.
Example 1
A preparation method of a bismuth vanadate composite modified composite photocatalytic material for nitrogen carbide comprises the following steps:
step S01: weighing 10g of melamine, adding the melamine into a crucible, putting the crucible into a muffle furnace, heating the crucible to 400-450 ℃ at the heating rate of 10-20 ℃/min, and calcining the crucible for 4-6h to obtain melem powder;
step S02: uniformly mixing 2g of melem and 2g of pyromellitic dianhydride, adding the mixture into a crucible, putting the crucible into a muffle furnace, heating the mixture to 300-350 ℃ at the heating rate of 10-20 ℃/min, and carrying out secondary calcination for 4-6h to obtain modified carbon nitride powder;
step S03: weighing 5mmol of bismuth nitrate pentahydrate and bismuth nitrate pentahydrate, adding the weighed materials into a beaker filled with 10mL of deionized water, adding 10mL of 4mol/L nitric acid solution, and stirring the mixture in a magnetic stirrer until the mixture is completely dissolved;
step S04: weighing 5mmol of ammonium metavanadate, adding the ammonium metavanadate into a beaker filled with 10mL of deionized water, and fully stirring the mixture in a magnetic stirrer; and pouring the solution obtained in the step S03 into the solution, continuously and fully stirring the solution for 1 to 2 hours, finally adding 0.25g of sodium dodecyl benzene sulfonate, and continuously stirring the solution for 0.5 to 1 hour till the solution is completely dissolved.
Step S05: weighing 0.405-0.567g of modified nitrogen carbide powder, adding into the beaker of the step S04, and continuously stirring for 1-2h in a halving manner;
step S06: transferring the uniform precursor solution obtained in the step S05 to a 50mL reaction kettle, placing the reaction kettle in a drying oven, heating to 200 ℃, and preserving heat for 1.5 h;
step S07: performing suction filtration and washing on the precursor solution reacted in the step S06 for 3-4 times by using deionized water until the PH value is 7;
step S08: and finally, putting the sample into a drying oven, setting the temperature to be 70 ℃, drying for 12-24h, transferring and grinding the sample to finally obtain a bismuth vanadate composite modified nitrogen carbide powder sample, wherein a scanning electron microscope picture of the sample is shown in figure 2, and bismuth vanadate particles grow on the surface of the lamellar modified nitrogen carbide (connected with an aromatic diimine structure) material.
Performance detection
The photocatalytic degradation effect experiment is carried out on the products prepared in the example 1 and the comparative examples 1-2, and the specific steps are as follows:
20mg of photocatalyst products of examples and comparative examples are respectively tested in a degradation experiment that the photocatalyst products are dispersed in 80mL of methylene blue solution with the concentration of 20mg/L and rhodamine B, and the photocatalyst surface and dye adsorption equilibrium is achieved by stirring in a dark reaction for 30 min. Then a 300W xenon lamp (lambda is more than or equal to 420nm) is turned on to simulate sunlight to carry out photocatalytic reaction, the photocatalytic reaction is carried out at normal temperature and normal pressure, a 300W xenon lamp (lambda is more than or equal to 420nm) is selected as a light source, and sampling analysis is carried out every 20 min. The absorbance of the methylene blue solution and rhodamine B was measured using an ultraviolet-visible spectrophotometer at wavelengths of 664nm and 550 nm. The degradation rate of the photocatalyst was calculated according to the formula [1- (initial concentration-end concentration)/initial concentration ] x 100%, and the 130min degradation results are shown in table 1 below.
TABLE 1
Sample (I) | Comparative example 1 | Comparative example2 | Example 1 |
Degradation rate of methylene blue | 49.3% | 74.6% | 90.1% |
Degradation rate of rhodamine B | 52.7% | 75.3% | 93.5% |
As can be seen from table 1 above, compared with comparative example 1 and comparative example 2, the degradation rate of the bismuth vanadate composite modified nitrogen carbide photocatalyst prepared in example 1 of the present invention to methylene blue and rhodamine B in a methylene blue solution is significantly improved. Therefore, the photo-degradation capability of the bismuth vanadate composite modified nitrogen carbide photocatalyst prepared by the method provided by the embodiment of the invention is remarkably improved.
The nitrogen carbide photocatalytic material obtained by the bismuth vanadate composite modification obtained in example 1 was subjected to a repeated experiment on the photocatalytic degradation effects of a methylene blue solution and rhodamine B, and the photocatalyst obtained in each example was tested three times in accordance with the test method described in the performance test, and the methylene blue test results were: 90.1%, 88.8% and 88.3%, and the test results of rhodamine B are respectively as follows: 93.5%, 93.0% and 92.2%. The results show that: the photocatalytic effect of the composite photocatalyst prepared in example 1 is not obviously reduced after three times of repeated tests. Therefore, the bismuth vanadate composite photocatalyst prepared by the method provided by the embodiment of the invention can effectively degrade two different organic pollutants, and the method provided by the invention can effectively separate electron-hole pairs generated in the bismuth vanadate photocatalytic process, so that the bismuth vanadate composite photocatalyst can show the maximum photocatalytic performance. The invention can stably prepare a large amount of bismuth vanadate composite photocatalyst, and the high-efficiency and stable catalytic performance can be widely applied to actual sewage treatment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a bismuth vanadate composite photocatalytic material is characterized by comprising the following steps:
performing first calcination treatment on melamine to obtain melem;
mixing the melem with pyromellitic dianhydride, and then carrying out second calcination treatment to obtain a nitrogen carbide material connected with an aromatic diimine structure;
and adding the nitrogen carbide material connected with the aromatic diimine structure into a mixed solution containing bismuth salt and vanadate, and growing bismuth vanadate particles on the surface of the nitrogen carbide material to obtain the bismuth vanadate composite photocatalytic material.
2. The method for preparing the bismuth vanadate composite photocatalytic material according to claim 1, wherein the first calcining treatment process comprises the following steps: heating to 400-450 ℃ at the heating rate of 10-20 ℃/min, and then preserving the heat for 4-6 h.
3. The method for preparing the bismuth vanadate composite photocatalytic material according to claim 1, wherein the second calcining treatment process comprises the following steps: heating to 350 ℃ at the heating rate of 10-20 ℃/min, and then preserving the heat for 4-6 h.
4. The method for preparing the bismuth vanadate composite photocatalytic material according to claim 1, wherein the mixed solution further contains sodium dodecyl benzene sulfonate; and/or the presence of a gas in the gas,
the molar ratio of the bismuth salt to the vanadate in the mixed solution is 1: 1.
5. The method for preparing a bismuth vanadate composite photocatalytic material according to any one of claims 1 to 4, wherein the step of adding the nitrogen carbide material connected with the aromatic diimine structure into a mixed solution containing bismuth salt and vanadate, and growing bismuth vanadate particles on the surface of the nitrogen carbide material comprises the following steps:
preparing a bismuth salt solution and a vanadate solution;
mixing the bismuth salt solution and the vanadate solution, and adding sodium dodecyl benzene sulfonate to obtain a mixed solution;
and adding the nitrogen carbide material into the mixed solution, performing magnetic stirring, and performing hydrothermal reaction.
6. The method for preparing a bismuth vanadate composite photocatalytic material according to claim 5,
the temperature of the hydrothermal reaction is 180-200 ℃, and the time is 1-2 h; and/or the presence of a gas in the gas,
the magnetic stirring time is 1-2 h.
7. The method for preparing the bismuth vanadate composite photocatalytic material as claimed in claim 5, wherein the steps of filtering, washing, drying and grinding are sequentially carried out after the hydrothermal reaction.
8. The bismuth vanadate composite photocatalytic material is characterized by comprising a lamellar nitrogen carbide material and bismuth vanadate particles combined on the surface of the lamellar nitrogen carbide material, wherein the nitrogen carbide in the lamellar nitrogen carbide material is connected with an aromatic diimine structure.
9. The bismuth vanadate composite photocatalytic material as defined in claim 8, wherein the thickness of the lamellar nitrogen carbide material is 100-500nm, and the planar size of the lamellar is 5-10 μm; and/or the presence of a gas in the gas,
the bismuth vanadate particles are rod-shaped particles with the particle size of 500nm-2 mu m; and/or the presence of a gas in the gas,
the mass ratio of the lamellar nitrogen carbide material to the bismuth vanadate particles is (1: 3) - (7: 13).
10. The bismuth vanadate composite photocatalytic material according to claim 8, wherein the bismuth vanadate composite photocatalytic material is prepared by the preparation method of the bismuth vanadate composite photocatalytic material according to any one of claims 1 to 7.
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