CN109499594B - CdIn2S4 nano octahedron modified Ta3N5Preparation method of core-shell composite photocatalyst - Google Patents
CdIn2S4 nano octahedron modified Ta3N5Preparation method of core-shell composite photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 45
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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 claims abstract description 12
- 229940012189 methyl orange Drugs 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
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- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
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- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 17
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
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- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of preparation of inorganic nano composite materials and environmental management, and particularly discloses CdIn with visible light activity2S4Nano octahedron modified Ta3N5A preparation method of a core-shell composite photocatalyst. Preparation of CdIn in different proportions by in situ hydrothermal method2S4Nano octahedron modified Ta3N5A core-shell composite photocatalyst. The advantages of the two materials and the matched energy band structure are combined, so that efficient transfer of photo-generated electrons between different energy levels is realized, the separation efficiency of photo-generated carriers is improved, and further, efficient degradation of the dye methyl orange under visible light is realized. The invention has the advantages of environment-friendly preparation raw materials, simple method, mild hybridization reaction conditions, short period, low cost and the like. The invention reports the core-shell composite photocatalyst, CdIn for the first time2S4Nano octahedron modified Ta3N5The core-shell structure shows excellent photocatalytic degradation activity and has important application prospect in the aspect of treating dye wastewater.
Description
Technical Field
The invention belongs to the field of inorganic nano materials, and relates to CdIn2S4Nano octahedron modified Ta3N5A preparation method of the core-shell composite photocatalyst and application thereof in the field of environmental management.
Background
Since the 21 st century, with the rapid development of industrialization and the continuous increase of the world population, the problem of water pollution becomes one of the key factors restricting the development of modern industry and human survival; the photocatalytic oxidation degradation technology based on the semiconductor material is considered to be one of ideal ways for solving the pollution problem of various water organic compounds due to the advantages of high efficiency, green, no secondary pollution and the like. However, at present, most of semiconductor photocatalysts have wide forbidden bands and can only be excited by ultraviolet light, so that the utilization of sunlight is limited; meanwhile, the higher photon-generated carrier recombination rate leads to lower overall photon quantum efficiency of the material; therefore, the development of highly efficient visible light-responsive photocatalysts is an inevitable need for the development of photocatalytic technology.
In recent years, with the development of functional materials, ternary metal sulfides have received great attention as a novel photocatalyst with unique photoelectric properties and catalytic performance, and CdIn2S4One of the most representative types is a cubic spinel type semiconductor belonging to the Fd3m space group. Bulk CdIn2S4The forbidden band width of the material is 2.1-2.6eV, and the material has extremely strong visible light absorption performance; meanwhile, the photocatalyst has good physical and chemical stability, and is considered to be a novel photocatalytic material with great development potential. However, the higher efficiency of photogenerated electron-hole recombination has inhibited its rapid development in the field of photocatalysis. The research shows that the hybrid heterojunction is well-solved by compositely constructing the hybrid heterojunction with other main semiconductors.
Ta due to Ta-N bonds contained in the structure and conductivity similar to noble metals3N5The catalyst has excellent thermal stability, mechanical strength, conductivity and catalytic performance; meanwhile, the photocatalyst has narrow forbidden band width (2.1eV), good chemical stability and strong absorption capacity in a visible light region, and is considered as an ideal visible light photocatalyst. Therefore, by combining the advantages of the two materials and the matched energy band structure, on one hand, the CdIn can be widened2S4The light absorption range of the material improves the quantum yield; on the other hand, the hybrid heterojunction is constructed by virtue of the matched band gap, so that the high-efficiency transfer of photo-generated electrons between different energy levels is realized, the separation efficiency of photo-generated carriers is improved, and the photocatalytic activity of the material is greatly improved. Thus the invention provides a CdIn2S4Nano octahedron modified Ta3N5The preparation method of the core-shell composite photocatalyst is used for researching the catalytic efficiency of the core-shell composite photocatalyst under visible light. The inspection shows that there is no reference to CdIn2S4Nano octahedron and Ta3N5The reports of hybrid, therefore, CdIn2S4Nano octahedron modified Ta3N5The core-shell compound is a novel photocatalyst.
Disclosure of Invention
In order to widen the spectral absorption range and improve the photocatalytic quantum efficiency, the invention aims to provide CdIn2S4Nano octahedron modified Ta3N5A preparation method of the core-shell composite photocatalyst; the method prepares the CdIn by an in-situ method2S4Nano octahedron modified Ta3N5The core-shell composite photocatalyst can be used for degrading dye methyl orange under visible light, and comprises the following specific steps:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to a certain molar ratio, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into a certain volume of ethanol aqueous solution, and stirring for 20min to form a colorless transparent solution;
(2) weighing a certain mass of Ta3N5Adding the nano particles into the transparent solution obtained in the step (1), continuously stirring for 10-30min, and ultrasonically dispersing the uniformly mixed suspension for 10-40min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles into a reaction kettle for reaction for a period of time, after the reaction is finished, cooling to room temperature, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the CdIn2S4Nano octahedron modified Ta3N5A core-shell composite photocatalyst.
In the step (1), the millimole ratio of the tetrahydrate cadmium nitrate, the hydrated indium nitrate and the thioacetamide is (0.1-4) to (0.2-8) to (0.8-32); the dosage ratio of the cadmium nitrate tetrahydrate to the ethanol aqueous solution is 0.1-4mmol:10-60 mL; in the ethanol water solution, the volume ratio of the absolute ethanol to the deionized water is 1: 0.5-1.
In step (2), Ta3N5The particle size of the nanoparticles is in the range of 300-600 nm.
In the step (3), the reaction temperature is controlled at 160-220 ℃, and the reaction time is 8-36 h.
The CdIn of the invention2S4Nano octahedron modified Ta3N5In the core-shell composite photocatalyst, CdIn2S4The mass fraction of the nano octahedron is 50-95%, and the CdIn2S4The side length of the nano octahedron is 50-80 nm.
The invention relates to CdIn2S4Nano octahedron modified Ta3N5The application of the core-shell composite photocatalyst can be used for catalytic oxidation degradation of dye methyl orange under visible light.
The CdIn prepared by the invention2S4Nano octahedron modified Ta3N5The core-shell composite photocatalyst and the technical effect brought by the catalytic degradation of the dye methyl orange under visible light are as follows:
(1) the invention prepares CdIn for the first time2S4Nano octahedron modified Ta3N5The core-shell composite photocatalyst has the advantages of safe and pollution-free raw materials, simple preparation method, mild reaction conditions, few reaction steps, simple and convenient operation, short preparation period and low cost, and is beneficial to industrial production;
(2) CdIn prepared by the invention2S4Nano octahedron modified Ta3N5The core-shell composite photocatalyst has excellent visible light response performance, good light stability and excellent quantum yield; meanwhile, due to the hybrid heterojunction constructed by the two matched band gaps, the separation efficiency of a photon-generated carrier is effectively improved, and the recombination of photon-generated electrons and holes is inhibited, so that the great leap of the photocatalytic quantum efficiency is realized.
(3) Relatively single CdIn2S4CdIn for nano-octahedral catalytic effect2S4Nano octahedron modified Ta3N5Composite photocatalyst exhibitionThe photocatalyst has excellent photocatalytic activity, realizes the high-efficiency degradation of methyl orange by the compound under visible light, and has excellent application prospect.
Drawings
FIG. 1: CdIn prepared as in example 22S4Nano octahedron modified Ta3N5SEM picture of the compound photocatalyst of nucleocapsid;
FIG. 2: CdIn prepared as in example 62S4Nano octahedron modified Ta3N5A TEM image of the core-shell composite photocatalyst;
FIG. 3: CdIn prepared as in example 52S4Nano octahedron modified Ta3N5A solid ultraviolet-visible spectrum diagram of the core-shell composite photocatalyst;
FIG. 4: CdIn prepared as in example 42S4Nano octahedron modified Ta3N5PL diagram of the core-shell composite photocatalyst.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
The degradation experiment is carried out in a DW-03 type photochemical reactor, a xenon lamp of 250W is used as a simulated solar light source, ultraviolet light is filtered by a filter, and CdIn under visible light is evaluated2S4Nano octahedron modified Ta3N5The degradation efficiency of the core-shell composite photocatalyst to pollutants. The method comprises the following specific steps: 70mL (10mg/L) of methyl orange solution (MO) is added into the reactor and the initial value is measured, then 20mg of composite photocatalyst is added, the lamp is turned on for illumination for 210min, samples are taken every 30min in the period, after centrifugal separation, supernatant liquid is taken, and the absorbance of the supernatant liquid is measured at the maximum absorption wavelength of pollutants by using an ultraviolet-visible spectrophotometer. The degradation rate eta of the methyl orange solution is calculated according to the absorbance before and after the illumination (C)0-Ct)/C0X 100%, wherein C0Absorbance of the sample at the very beginning of the light irradiation, CtThe absorbance of the sample after 3.5h of light irradiation.
Example 1:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to the millimolar ratio of 0.1:0.2:0.8, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into 10mL of ethanol water solution, wherein the volume ratio of absolute ethanol to deionized water is 1:0.5, and stirring for 20min to form colorless transparent solution;
(2) 47mg of Ta are weighed out3N5Adding the nano particles into the transparent solution obtained in the step (1), continuously stirring for 10min, and ultrasonically dispersing the uniformly mixed suspension for 10min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles into a 100ml polytetrafluoroethylene reaction kettle, reacting for 8h at 160 ℃, cooling to room temperature after the reaction is finished, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the CdIn2S4Nano octahedron modified Ta3N5Core-shell composite photocatalyst, in which CdIn2S4The mass fraction of the nano octahedron is 50%.
(4) The sample is irradiated for 210min under visible light, and the degradation efficiency of the sample on methyl orange reaches 52.6 percent.
Example 2:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to the millimolar ratio of 0.5:1:4, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into 20mL of ethanol water solution, wherein the volume ratio of absolute ethanol to deionized water is 1:0.6, and stirring for 20min to form colorless transparent solution;
(2) 156.7mg of Ta are weighed out3N5Adding the nano particles into the transparent solution obtained in the step (1), continuously stirring for 15min, and ultrasonically dispersing the uniformly mixed suspension for 20min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles into a 100ml polytetrafluoroethylene reaction kettle, reacting for 12h at 170 ℃, cooling to room temperature after the reaction is finished, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the CdIn2S4Nano octahedron modified Ta3N5Core-shell composite photocatalyst, in which CdIn2S4The mass fraction of the nano octahedron is 60 percent.
(4) The sample is irradiated for 210min under visible light, and the degradation efficiency of the sample on methyl orange reaches 68.3 percent.
The SEM image of the composite photocatalyst sample 2 prepared according to example 2 in the attached figure 1 of the invention is clear that CdIn is2S4Exhibit a nano-octahedral structure, Ta3N5Is of a nano-bulk structure, CdIn2S4Nano octahedron synthesized Ta3N5Wrapped therein, the composite core-shell structure was demonstrated to have been successfully prepared.
Example 3:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to the molar ratio of 1:2:8, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into 30mL of ethanol aqueous solution, wherein the volume ratio of absolute ethanol to deionized water is 1:0.7, and stirring for 20min to form colorless transparent solution;
(2) 201.45mg of Ta are weighed out3N5Adding the nano particles into the transparent solution obtained in the step (1), then continuing stirring for 20min, and then ultrasonically dispersing the uniformly mixed suspension for 25min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles into a 100ml polytetrafluoroethylene reaction kettle, reacting for 16h at 180 ℃, cooling to room temperature after the reaction is finished, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the CdIn2S4Nano octahedron modified Ta3N5Core-shell composite photocatalyst, in which CdIn2S4The mass fraction of the nano octahedron is 70 percent.
(4) The sample is irradiated for 210min under visible light, and the degradation efficiency of the sample on methyl orange reaches 78.62 percent.
Example 4:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to the molar ratio of 2:4:16, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into 40mL of ethanol aqueous solution, wherein the volume ratio of absolute ethanol to deionized water is 1:0.8, and stirring for 20min to form colorless transparent solution;
(2) 235.2mg of Ta are weighed out3N5Adding the nano particles into the transparent solution obtained in the step (1), continuously stirring for 25min, and ultrasonically dispersing the uniformly mixed suspension for 30min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles into a 100ml polytetrafluoroethylene reaction kettle, reacting for 22h at 190 ℃, cooling to room temperature after the reaction is finished, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the CdIn2S4Nano octahedron modified Ta3N5Core-shell composite photocatalyst, in which CdIn2S4The mass fraction of the nano octahedron is 80 percent.
(4) The sample is irradiated for 210min under visible light, and the degradation efficiency of the sample on methyl orange reaches 92%.
PL drawing of composite photocatalyst sample 4 prepared in accordance with example 4 of FIG. 4 of the present invention, from which it is clear that the monomer CdIn2S4The nano octahedron shows high PL intensity, which means that the recombination rate of internal electron carriers is high, and Ta is introduced3N5And then, the PL intensity of the composite material is greatly attenuated, and the result clearly shows that the construction of the composite structure greatly improves the integral quantum efficiency and is beneficial to greatly improving the integral photocatalytic activity.
Example 5:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to the molar ratio of 3:6:24, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into 50mL of ethanol aqueous solution, wherein the volume ratio of absolute ethanol to deionized water is 1:0.9, and stirring for 20min to form colorless transparent solution;
(2) 156.68mg of Ta are weighed out3N5Adding the nanoparticles into the transparent solution obtained in the step (1), continuously stirring for 30min, and mixingUltrasonically dispersing the uniform suspension for 35min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles into a 100ml polytetrafluoroethylene reaction kettle, reacting for 28h at 200 ℃, cooling to room temperature after the reaction is finished, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the CdIn2S4Nano octahedron modified Ta3N5Core-shell composite photocatalyst, in which CdIn2S4The mass fraction of the nano octahedron is 90 percent.
(4) The sample is irradiated for 210min under visible light, and the degradation efficiency of the sample on methyl orange reaches 96.4 percent.
In figure 3 of the drawings, the solid ultraviolet-visible absorption spectrum of the composite photocatalyst sample 5 prepared according to example 5 of the present invention is shown, compared with the monomer CdIn2S4For nanomaterials, Ta is introduced3N5And then, the absorption edge of the composite material generates great red shift, which proves that the composite catalyst is a visible light response type catalyst and has strong visible light capture capability.
Example 6:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to the molar ratio of 4:8:32, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into 60mL of ethanol aqueous solution, wherein the volume ratio of absolute ethanol to deionized water is 1:1, and stirring for 20min to form colorless transparent solution;
(2) weighing 98.96mg of Ta3N5Adding the nano particles into the transparent solution obtained in the step (1), continuously stirring for 30min, and ultrasonically dispersing the uniformly mixed suspension for 40min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles into a 100ml polytetrafluoroethylene reaction kettle, reacting for 36h at 220 ℃, cooling to room temperature after the reaction is finished, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuumTo obtain CdIn2S4Nano octahedron modified Ta3N5Core-shell composite photocatalyst, in which CdIn2S4The mass fraction of the nano octahedron is 89.3%.
(4) The sample is irradiated for 210min under visible light, and the degradation efficiency of the sample on methyl orange reaches 82.4 percent.
TEM image of composite photocatalyst sample 6 of the present invention prepared in accordance with example 6 in FIG. 2 shows CdIn2S4The nano octahedron is closely adhered to Ta3N5The core-shell structure is formed on the nano block, and further proves that the composite material is successfully prepared.
Claims (4)
1. CdIn2S4Nano octahedron modified Ta3N5The preparation method of the core-shell composite photocatalyst is characterized by comprising the following steps:
(1) sequentially weighing cadmium nitrate tetrahydrate, indium nitrate hydrate and thioacetamide according to a certain molar ratio, adding the cadmium nitrate tetrahydrate, the indium nitrate hydrate and the thioacetamide into a certain volume of ethanol aqueous solution, and stirring to form a colorless transparent solution; wherein, the millimole ratio of the tetrahydrate cadmium nitrate, the hydrate indium nitrate and the thioacetamide is (0.1-4) to (0.2-8) to (0.8-32); wherein the dosage ratio of the cadmium nitrate tetrahydrate to the ethanol aqueous solution is 0.1-4mmol:10-60 mL;
(2) weighing a certain mass of Ta3N5Adding the nano particles into the transparent solution obtained in the step (1), then continuing stirring for 10-30min, and then ultrasonically dispersing the uniformly mixed suspension for 10-40min to obtain uniformly dispersed Ta3N5Mixing the nano particle liquid; said Ta3N5The particle size range of the nano particles is 300-600 nm;
(3) uniformly dispersing Ta prepared in the step (2)3N5Transferring the mixed solution of the nano particles to a reaction kettle for reaction at the temperature of 160-220 ℃ for 8-36h, cooling to room temperature after the reaction is finished, washing the obtained product for a plurality of times by using secondary deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the CdIn2S4Nano octahedron modified Ta3N5A core-shell composite photocatalyst.
2. The CdIn of claim 12S4Nano octahedron modified Ta3N5The preparation method of the core-shell composite photocatalyst is characterized in that in the step (1), the volume ratio of absolute ethyl alcohol to deionized water in the ethanol aqueous solution is 1: 0.5-1; the stirring time is 20 min.
3. CdIn prepared by the preparation method according to any one of claims 1-22S4Nano octahedron modified Ta3N5The core-shell composite photocatalyst is characterized in that CdIn in the composite photocatalyst2S4The mass fraction of the nano octahedron is 50-95%, and the CdIn2S4The side length of the nano octahedron is 50-80 nm.
4. The CdIn of claim 32S4Nano octahedron modified Ta3N5The application of the core-shell composite photocatalyst is characterized in that the CdIn is prepared by mixing2S4Nano octahedron modified Ta3N5The core-shell composite photocatalyst is used for catalytic oxidation degradation of dye methyl orange under visible light.
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