CN110327914B - Tungsten trioxide/cadmium tungstate nanofiber photocatalytic material and preparation method and application thereof - Google Patents
Tungsten trioxide/cadmium tungstate nanofiber photocatalytic material and preparation method and application thereof Download PDFInfo
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 35
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 229930101283 tetracycline Natural products 0.000 claims abstract description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 33
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
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- 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 12
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
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- 229940040944 tetracyclines Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- -1 tungsten trioxide-cadmium Chemical compound 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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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
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/58—
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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 relates to a tungsten trioxide/cadmium tungstate nanofiber photocatalytic material as well as a preparation method and application thereof. Dissolving ammonium metatungstate and cadmium acetate in a mixed solvent consisting of absolute ethyl alcohol and N, N-dimethylformamide, and adding polyvinylpyrrolidone to obtain a spinnable precursor sol; preparing precursor fiber by controlling rheological property and spinning technological parameters of spinnable precursor sol, then calcining the precursor fiber at high temperature at different temperatures to obtain the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material, and preparing the nanofiber photocatalytic material with a tube-in-tube structure by the preferable experimental scheme of the invention. The tungsten trioxide/cadmium tungstate nanofiber photocatalytic material prepared by the invention realizes high-efficiency photocatalytic degradation of tetracycline under visible light, the degradation rate can reach 93.1% within 120min, the preparation method is simple in steps, low in cost and capable of being recycled, and the application cost is greatly reduced.
Description
Technical Field
The invention relates to a tungsten trioxide/cadmium tungstate nanofiber photocatalytic material as well as a preparation method and application thereof, belonging to the technical field of photocatalytic materials.
Background
With the continuous development of the current social industrial production, pollutants such as sewage, antibiotics and the like generated in the industrial production process have serious influence on the life and the physical health of people. Therefore, the treatment of environment purification is an urgent problem to be solved. In the current environmental problem remediation, semiconductor photocatalytic technology has the unique property of directly utilizing solar energy as a light source to drive redox reaction, and thus, a new approach to solving environmental problems is provided.
Cadmium tungstate (CdWO)4) Has better chemical, optical and structural properties and excellent thermal stability in all the tungstates. And, cadmium tungstate (CdWO)4) Is rich in terrestrial resources and low in costThe material has good catalytic performance and electrochemical stability. However, CdWO4Has a wide band gap (3.8eV), limits the response range to the solar spectrum, and the rapid recombination of photogenerated carriers also limits the practical application of the photogenerated carriers. Thus, a series of semiconductors are used in combination with CdWO4The heterojunction is compositely constructed, so that the photocatalytic performance of the heterojunction is improved. For example, Colloids and Surfaces A. physical and Engineering assays 522(2017):346-354, CdWO prepared by hydrothermal method in combination with water bath method is reported4a/BiOI photocatalyst; chinese patent document CN105642316A (application No. 201510975834.9) discloses a method for preparing BiOI/CdWO4A method for preparing a heterojunction photocatalyst is characterized in that bismuth nitrate, sodium tungstate, potassium iodide and cadmium acetate are used as raw materials, and a two-step hydrothermal method is adopted to prepare the BiOI/CdWO4A heterojunction photocatalyst, the catalyst is CdWO in a nano rod shape4Loading irregular nano-particles BiOI on the surface; CdWO prepared by the prior art4Compared with a single photocatalyst, the photocatalyst with the/BiOI heterostructure has a certain improvement on the photocatalytic effect; but the prepared material has poor dispersibility and serious agglomeration, the morphology is not beneficial to the transmission and separation of photon-generated carriers, and the prepared photocatalyst is difficult to recycle.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a tungsten trioxide/cadmium tungstate nanofiber photocatalytic material as well as a preparation method and application thereof, which realize the efficient photocatalytic degradation of tetracycline under visible light, and the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material can be recycled, thereby greatly reducing the production cost, and the tube-in-tube nano structure with special appearance is prepared by a preferable experimental scheme.
Description of terms:
room temperature: the room temperature according to the invention has the meaning known in the art and is generally 20-25 ℃.
The technical scheme of the invention is as follows:
a tungsten trioxide/cadmium tungstate nanofiber photocatalytic material is characterized in that the photocatalytic material is a composite nanofiber material composed of tungsten trioxide and cadmium tungstate.
According to the invention, the composite nano fiber is a one-dimensional linear structure, the diameter is 100-600nm, and the length is 3-15 μm.
According to the invention, the composite nanofiber is a tube-in-tube structure comprising a nanotube core and a hollow nanometer outer tube, the length is 10-15 μm, and the diameters of the nanotube core and the hollow nanometer outer tube are respectively 100-200nm and 400-500 nm.
According to the invention, the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material is preferably prepared by preparing a spinnable precursor sol from ammonium metatungstate, cadmium acetate and polyvinylpyrrolidone as reaction raw materials, and performing electrostatic spinning and calcination.
Further preferably, the mol ratio of Cd to W in the spinnable precursor sol is 1 (1-3).
A preparation method of a tungsten trioxide/cadmium tungstate nanofiber photocatalytic material comprises the following steps:
(1) preparation of spinnable precursor sol
Dissolving ammonium metatungstate and cadmium acetate in a mixed solvent composed of absolute ethyl alcohol and N, N-dimethylformamide, adding polyvinylpyrrolidone (PVP) until the viscosity is 0.1-1.0 Pa.S, and uniformly stirring to obtain a spinnable precursor sol;
(2) preparation of tungsten trioxide/cadmium tungstate precursor fiber
Performing electrostatic spinning on the spinnable precursor sol obtained in the step (1) under the conditions that the temperature is 15-35 ℃, the voltage is 10-30kV, and the ejection rate is 0.1-1.5mL/h to obtain precursor fiber;
(3) preparation of tungsten trioxide/cadmium tungstate nanofiber photocatalytic material
And (3) drying the precursor fiber prepared in the step (2) at the temperature of 40-100 ℃ for 12-36h, heating to 400-600 ℃ at the speed of 1-5 ℃/min, and preserving the heat for 60-180min to obtain the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material.
Preferably, according to the present invention, the spinnable precursor sol in step (1) has a Cd to W molar ratio of 1: (1-3); further preferably, the mol ratio of Cd to W in the spinnable precursor sol is 1: (1.25-2).
According to the present invention, it is preferable that the volume ratio of the absolute ethyl alcohol and the N, N-dimethylformamide in the mixed solvent in the step (1) is 1: (0.5-2); further preferably, the volume ratio of the absolute ethyl alcohol to the N, N-dimethylformamide in the mixed solvent is 1: (1-2).
According to the present invention, the molar volume ratio of the cadmium acetate to the mixed solvent in the step (1) is preferably 1: (8-15) with the unit of mol/L.
Preferably according to the present invention, the weight average molecular weight of the polyvinylpyrrolidone in step (1) is 4 to 300 ten thousand; more preferably, the weight average molecular weight of the polyvinylpyrrolidone is 100 to 150 ten thousand; most preferably, the polyvinylpyrrolidone has a weight average molecular weight of 130 ten thousand, and an optimal nanofiber photocatalytic material can be obtained.
Preferably according to the invention, the receiving distance of the electrostatic spinning in the step (2) is 20-35 cm; the spraying rate is 1.5mL/h, the voltage is 20-30kV, and the temperature is 20-25 ℃.
According to the invention, the drying condition in the step (3) is preferably 40-60 ℃ for 12-24 h.
Preferably, in step (3), the temperature is raised to 500-600 ℃ at a rate of 1-3 ℃/min, and the temperature is maintained for 60-120 min.
Further preferably, in the step (3), the temperature is raised to 500 ℃ at the rate of 3 ℃/min, and the temperature is maintained for 120 min. The tungsten trioxide-cadmium tungstate nanofiber photocatalytic material prepared under the temperature rising condition is of a tube-in-tube structure comprising a nanotube core and a hollow nanometer outer tube, the length of the tube-in-tube structure is 10-15 mu m, and the diameters of the nanotube core and the hollow nanometer outer tube are respectively 100-200nm and 400-500 nm.
Dissolving ammonium metatungstate and cadmium acetate in a mixed solvent consisting of absolute ethyl alcohol and N, N-dimethylformamide, and adding polyvinylpyrrolidone to obtain a spinnable precursor sol; preparing precursor fiber by controlling rheological property and spinning technological parameters of spinnable precursor sol, then calcining the precursor fiber at high temperature at different temperatures to obtain the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material, and preparing the nanofiber photocatalytic material with a tube-in-tube structure by the preferable experimental scheme of the invention. The tungsten trioxide/cadmium tungstate nanofiber photocatalytic material prepared by the invention realizes efficient photocatalytic degradation of tetracycline under visible light, can be recycled, and further reduces the cost.
The tungsten trioxide/cadmium tungstate nanofiber photocatalytic material is applied to photocatalytic oxidation degradation of tetracycline.
The invention has the following beneficial effects:
1. for photocatalytic materials, the micro-morphology is one of the key factors affecting their photocatalytic performance. The tungsten trioxide/cadmium tungstate nanofiber photocatalytic material with the one-dimensional linear structure, in particular to the preferable nanofiber photocatalytic material with the pipe-in-pipe structure, is beneficial to the transmission and transfer of electrons and the transmission and separation of photo-generated carriers, so that more photo-generated electrons and holes are ensured to participate in an oxidation-reduction reaction, the photocatalytic efficiency is greatly improved, and the degradation rate can reach 93.1% within 120min when tetracycline is oxidized by photocatalysis under the irradiation of visible light.
2. The tungsten trioxide/cadmium tungstate nano-fiber photocatalytic material prepared by the method has relatively uniform diameter and size, and overcomes the defect of easy agglomeration of a hydrothermal method; WO3With CdWO4After the composite material is compounded, the material can absorb more visible light, and the photocatalytic efficiency is improved.
3. The preparation method has simple steps, easy operation and low cost; and the material with the one-dimensional linear morphology is convenient to recover by a sedimentation method, can be recycled, and further reduces the cost.
Drawings
FIG. 1 shows WO obtained in example 13/CdWO4An X-ray diffraction (XRD) spectrum of the nanofiber photocatalytic material;
FIG. 2 shows WO obtained in example 13/CdWO4SEM images of nanofiber photocatalytic materials; in the figure, a is WO3/CdWO4The SEM image of the nanofiber photocatalytic material with low magnification, and b is the SEM image with high magnification;
FIG. 3 shows WO obtained in example 13/CdWO4TEM images of nanofiber photocatalytic materials; in the figure, a is WO3/CdWO4A TEM image with low magnification of the nanofiber photocatalytic material, and b is a TEM image with high magnification;
FIG. 4 shows WO obtained in example 23/CdWO4TEM images of nanofiber photocatalytic materials; in the figure, a is WO3/CdWO4A TEM image with low magnification of the nanofiber photocatalytic material, and b is a TEM image with high magnification;
FIG. 5 shows WO obtained in example 33/CdWO4TEM images of nanofiber photocatalytic materials; in the figure, a is WO3/CdWO4A TEM image with low magnification of the nanofiber photocatalytic material, and b is a TEM image with high magnification;
FIG. 6 shows WO obtained in comparative example 23/CdWO4SEM image of the composite photocatalytic material; in the figure, a is WO3/CdWO4The composite photocatalytic material is an SEM image with low magnification, and b is an SEM image with high magnification;
FIG. 7 shows WO obtained in example 13/CdWO4The nano-fiber photocatalytic material is used for photocatalytic degradation of an absorbance curve of tetracycline under the irradiation of a simulated sunlight source; the curve in the graph sequentially corresponds to the 0-120min in the graph from top to bottom;
FIG. 8 shows WO obtained in example 23/CdWO4The nano-fiber photocatalytic material is used for photocatalytic degradation of an absorbance curve of tetracycline under the irradiation of a simulated sunlight source; the curve in the graph sequentially corresponds to the 0-120min in the graph from top to bottom;
FIG. 9 shows WO obtained in comparative example 13/CdWO4The composite photocatalytic material photocatalytically degrades the absorbance curve of tetracycline under the irradiation of a simulated sunlight light source; the curve in the graph sequentially corresponds to the 0-120min in the graph from top to bottom;
FIG. 10 shows WO obtained in comparative example 23/CdWO4The composite photocatalytic material photocatalytically degrades the absorbance curve of tetracycline under the irradiation of a simulated sunlight light source; the curves in the figure correspond from top to bottom in sequenceThe time is 0-120 min;
FIG. 11 shows WO obtained in example 13/CdWO4C/C of tetracycline solution after catalytic reaction of nanofiber photocatalytic material0A graph of change with illumination time; in the figure, a is C/C of 60min dark reaction0Variation curve diagram, b is C/C under illumination condition0A variation graph;
FIG. 12 shows WO obtained in example 23/CdWO4C/C of tetracycline solution after catalytic reaction of nanofiber photocatalytic material0A graph of change with illumination time; in the figure, a is C/C of 60min dark reaction0Variation curve diagram, b is C/C under illumination condition0A variation graph;
FIG. 13 shows WO obtained in comparative example 13/CdWO4C/C of tetracycline solution after catalytic reaction of composite photocatalytic material0A graph of change with illumination time; in the figure, a is C/C of 60min dark reaction0Variation curve diagram, b is C/C under illumination condition0A variation graph;
FIG. 14 shows WO obtained in comparative example 23/CdWO4C/C of tetracycline solution after catalytic reaction of composite photocatalytic material0A graph of change with illumination time; in the figure, a is C/C of 60min dark reaction0Variation curve diagram, b is C/C under illumination condition0A variation graph;
FIG. 15 shows WO obtained in example 13/CdWO4The degradation efficiency histogram of the nanofiber photocatalytic material on tetracycline is repeatedly recycled for four times under the irradiation of a simulated sunlight source;
FIG. 16 shows WO obtained in comparative example 13/CdWO4The composite photocatalytic material is used for repeatedly and circularly utilizing the tetracycline degradation efficiency histogram for four times under the irradiation of a simulated sunlight light source.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto. Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are commercially available; the equipment used is conventional equipment. Wherein: the polyvinylpyrrolidone is polyvinylpyrrolidone K90, and has a weight average molecular weight of 130 ten thousand.
Example 1
Tungsten trioxide/cadmium tungstate (WO)3/CdWO4) The preparation method of the nanofiber photocatalytic material comprises the following steps:
(1) preparation of spinnable precursor sol: 0.3079g (W: 1.25mmol) of ammonium metatungstate and 0.2665g (Cd: 1mmol) of cadmium acetate are dissolved in a mixed solvent consisting of 5mL of absolute ethyl alcohol and 5mL of N, N-dimethylformamide, stirred until the cadmium acetate is completely dissolved, 1g of polyvinylpyrrolidone (PVP) is added, and stirred uniformly to obtain a spinnable precursor sol with the viscosity of 0.5 Pa.S;
(2)WO3/CdWO4preparing precursor fiber: spraying the spinnable precursor sol into a receiving plate by using a plastic injector with a stainless steel needle, wherein the receiving distance between the stainless steel needle of the injector and the receiving plate is 20cm, the spraying speed of the spinnable precursor sol is 1.5mL/h, the voltage is 20kV, the electrostatic spinning temperature is controlled at 25 ℃, and precursor fiber is obtained;
(3)WO3/CdWO4preparing a nanofiber photocatalytic material: drying the precursor fiber prepared in the step (2) in a drying oven at 60 ℃ for 12h, then placing the dried precursor fiber in a high-temperature furnace, heating to 500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 120min to obtain WO3/CdWO4A nanofiber photocatalytic material.
FIG. 1 shows the WO prepared in this example3/CdWO4An X-ray diffraction (XRD) spectrum of the nanofiber photocatalytic material;
FIG. 2 shows the WO prepared in this example3/CdWO4SEM images of nanofiber photocatalytic materials; FIG. 3 shows the WO prepared in this example3/CdWO4TEM images of nanofiber photocatalytic materials; as can be seen from FIG. 1, after sintering at 500 ℃ WO3/CdWO4Diffraction peak and monoclinic CdWO of nanofiber photocatalytic material4(JCPDS No.14-0676) and monoclinic WO3(JCPDS No.71-2141) can correspond well to(ii) a As can be seen from FIG. 2, the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material prepared in this example is a tube-in-tube structure including a nanotube core and a hollow nanometer outer tube, and has relatively uniform diameter, a length of 10-15 μm, and diameters of the nanotube core and the hollow nanometer outer tube are respectively 100-200nm and 400-500 nm; fig. 3 further demonstrates the morphology of the prepared WO3/CdWO4 nanofiber photocatalytic material as a tube-in-tube structure comprising a nanotube core and a hollow nanotube outer tube.
Example 2
Tungsten trioxide/cadmium tungstate (WO)3/CdWO4) The preparation method of the nanofiber photocatalytic material comprises the following steps:
(1) preparation of spinnable precursor sol: 0.3695g (W: 1.5mmol) of ammonium metatungstate and 0.2665g (Cd: 1mmol) of cadmium acetate are dissolved in a mixed solvent consisting of 5mL of absolute ethyl alcohol and 7mL of N, N-dimethylformamide, stirred until the cadmium acetate is completely dissolved, 1g of polyvinylpyrrolidone (PVP) is added, and stirred uniformly to obtain a spinnable precursor sol with the viscosity of 0.5 Pa.S;
(2)WO3/CdWO4preparing precursor fiber: spraying the spinnable precursor sol into a receiving plate by using a plastic injector with a stainless steel needle, wherein the receiving distance between the stainless steel needle of the injector and the receiving plate is 25cm, the spraying speed of the spinnable precursor sol is 1.5mL/h, the voltage is 20kV, the electrostatic spinning temperature is controlled at 25 ℃, and precursor fiber is obtained;
(3)WO3/CdWO4preparing a nanofiber photocatalytic material: drying the precursor fiber prepared in the step (2) in a drying oven at 60 ℃ for 12h, then placing the dried precursor fiber in a high-temperature furnace, heating to 550 ℃ at the heating rate of 1 ℃/min, and preserving heat for 120min to obtain WO3/CdWO4A nanofiber photocatalytic material.
FIG. 4 shows the WO obtained in this example3/CdWO4TEM images of nanofiber photocatalytic materials. As can be seen from FIG. 4, WO prepared in this example3/CdWO4The diameter of the nanofiber photocatalytic material is 400-500nm, the diameter is relatively uniform, the length is 10-15 mu m, and the nanofiber photocatalytic material is in a one-dimensional linear shape.
Example 3
Tungsten trioxide/cadmium tungstate (WO)3/CdWO4) The preparation method of the nanofiber photocatalytic material comprises the following steps:
(1) preparation of spinnable precursor sol: 0.4927g (W: 2mmol) of ammonium metatungstate and 0.2665g (Cd: 1mmol) of cadmium acetate are dissolved in a mixed solvent consisting of 5mL of absolute ethyl alcohol and 9mL of N, N-dimethylformamide, stirred until the cadmium acetate is completely dissolved, 1.2g of polyvinylpyrrolidone (PVP) is added, and stirred uniformly to obtain a spinnable precursor sol with the viscosity of 0.7 Pa.S;
(2)WO3/CdWO4preparing precursor fiber: spraying the spinnable precursor sol into a receiving plate by using a plastic injector with a stainless steel needle, wherein the receiving distance between the stainless steel needle of the injector and the receiving plate is 25cm, the spraying speed of the spinnable precursor sol is 1.5mL/h, the voltage is 25kV, the electrostatic spinning temperature is controlled at 25 ℃, and precursor fiber is obtained;
(3)WO3/CdWO4preparing a nanofiber photocatalytic material: drying the precursor fiber prepared in the step (2) in a drying oven at 40 ℃ for 24h, then placing the precursor fiber in a high-temperature furnace, heating to 550 ℃ at the heating rate of 1 ℃/min, and preserving heat for 120min to obtain WO3/CdWO4A nanofiber photocatalytic material.
FIG. 5 shows the WO obtained in this example3/CdWO4TEM images of nanofiber photocatalytic materials. As can be seen from FIG. 5, WO prepared in this example3/CdWO4The diameter of the nano-fiber photocatalytic material is 300-500nm, the length is 3-8 μm, the nano-fiber photocatalytic material is in a one-dimensional linear shape, and large particles are arranged on the fiber.
Example 4
Tungsten trioxide/cadmium tungstate (WO)3/CdWO4) The preparation method of the nanofiber photocatalytic material comprises the following steps:
(1) preparation of spinnable precursor sol: 0.6159g (W: 2.5mmol) of ammonium metatungstate and 0.2665g (Cd: 1mmol) of cadmium acetate are dissolved in a mixed solvent consisting of 5mL of absolute ethyl alcohol and 10mL of N, N-dimethylformamide, stirred until the cadmium acetate is completely dissolved, 1.2g of polyvinylpyrrolidone (PVP) is added, and stirred uniformly to obtain a spinnable precursor sol with the viscosity of 0.8 Pa.S;
(2)WO3/CdWO4preparing precursor fiber: spraying the spinnable precursor sol into a receiving plate by using a plastic injector with a stainless steel needle, wherein the receiving distance between the stainless steel needle of the injector and the receiving plate is 20cm, the spraying speed of the spinnable precursor sol is 1.5mL/h, the voltage is 25kV, the electrostatic spinning temperature is controlled at 25 ℃, and precursor fiber is obtained;
(3)WO3/CdWO4preparing a nanofiber photocatalytic material: drying the precursor fiber prepared in the step (2) in a drying oven at 40 ℃ for 24h, then placing the precursor fiber in a high-temperature furnace, heating to 600 ℃ at the heating rate of 2 ℃/min, and preserving heat for 60min to obtain WO3/CdWO4A nanofiber photocatalytic material.
Example 5
Tungsten trioxide/cadmium tungstate (WO)3/CdWO4) The preparation method of the nanofiber photocatalytic material comprises the following steps:
(1) preparation of spinnable precursor sol: 0.7390g (W: 3mmol) of ammonium metatungstate and 0.2665g (Cd: 1mmol) of cadmium acetate are dissolved in a mixed solvent consisting of 5mL of absolute ethyl alcohol and 10mL of N, N-dimethylformamide, stirred until the cadmium acetate is completely dissolved, 1g of polyvinylpyrrolidone (PVP) is added, and the mixture is uniformly stirred to obtain a spinnable precursor sol with the viscosity of 1Pa & S;
(2)WO3/CdWO4preparing precursor fiber: spraying the spinnable precursor sol into a receiving plate by using a plastic injector with a stainless steel needle, wherein the receiving distance between the stainless steel needle of the injector and the receiving plate is 30cm, the spraying speed of the spinnable precursor sol is 1.5mL/h, the voltage is 30kV, the electrostatic spinning temperature is controlled at 20 ℃, and precursor fiber is obtained;
(3)WO3/CdWO4preparing a nanofiber photocatalytic material: drying the precursor fiber prepared in the step (2) in a drying oven at 60 ℃ for 12h, then placing the dried precursor fiber in a high-temperature furnace, heating to 600 ℃ at the heating rate of 2 ℃/min, and preserving heat for 120min to obtain WO3/CdWO4Nanofiber photocatalysisAnd (4) melting the material.
Comparative example 1
Tungsten trioxide/cadmium tungstate (WO)3/CdWO4) The preparation method of the composite photocatalytic material is a conventional hydrothermal method and comprises the following steps:
(1)CdWO4preparation of nanorods
Adding 5mmol of Na2WO4·2H2O and 5mmol Cd (NO)3)2·4H2Dissolving O in 15mL of deionized water, stirring for 30min, and dropwise adding ammonia water until the pH value of the solution is 9.30 in the stirring process; putting the obtained transparent white solution into a stainless steel autoclave, and heating at the high temperature of 180 ℃ for 24 hours; washing with anhydrous ethanol and deionized water for multiple times to obtain white powder;
(2) adopts a CVD method to synthesize WO3Sheet structure
Placing 0.5g of tungsten powder into an alumina crucible and a muffle furnace, heating to 600 ℃ at a heating rate of 10 ℃/min, and calcining for 3h at 600 ℃; then cooling at room temperature, and collecting yellow powder;
(3)WO3/CdWO4preparation of composite photocatalytic material
Respectively placing the white powder prepared in the step (1) and the yellow powder prepared in the step (2) into a glass beaker containing 10mL of absolute ethyl alcohol according to the mass ratio of 1:1, and ultrasonically dispersing for 1 h; mixing the dispersed dispersion liquid, magnetically stirring for 1h, and heating at 80 ℃ for 12 h; calcining the obtained powder at the high temperature of 550 ℃ for 2 hours to obtain WO3/CdWO4A composite photocatalytic material.
Comparative example 2
Tungsten trioxide/cadmium tungstate (WO)3/CdWO4) The preparation method of the composite photocatalytic material comprises the following steps:
(1) preparation of spinnable precursor sol: 0.9854g (W: 4mmol) of ammonium metatungstate and 0.2665g (Cd: 1mmol) of cadmium acetate are dissolved in a mixed solvent consisting of 5mL of absolute ethyl alcohol and 5mL of N, N-dimethylformamide, stirred until the cadmium acetate is completely dissolved, 1.5g of polyvinylpyrrolidone (PVP) is added, and stirred uniformly to obtain a spinnable precursor sol with the viscosity of 0.7 Pa.S;
(2)WO3/CdWO4preparing precursor fiber: spraying the spinnable precursor sol into a receiving plate by using a plastic injector with a stainless steel needle, wherein the receiving distance between the stainless steel needle of the injector and the receiving plate is 25cm, the spraying speed of the spinnable precursor sol is 1.5mL/h, the voltage is 25kV, the electrostatic spinning temperature is controlled at 25 ℃, and precursor fiber is obtained;
(3)WO3/CdWO4preparing a nanofiber photocatalytic material: drying the precursor fiber prepared in the step (2) in a drying oven at 40 ℃ for 24h, then placing the precursor fiber in a high-temperature furnace, heating to 500 ℃ at the heating rate of 1 ℃/min, and preserving heat for 60min to obtain WO3/CdWO4A composite photocatalytic material.
FIG. 6 shows WO obtained by the present comparative example3/CdWO4SEM image of composite photocatalytic material, and WO prepared in the comparative example can be seen from FIG. 63/CdWO4The composite photocatalytic material is a broken tubular photocatalytic material with large particles, and compared with the nanofiber photocatalytic materials prepared in examples 1 and 2, the sample prepared in the comparative example is uneven in appearance and serious in tubular breakage.
Application example 1
Photocatalytic degradation of tetracyclines
WO obtained in example 1 and example 23/CdWO4Nanofiber photocatalytic material and WO prepared in comparative examples 1 and 23/CdWO4The composite photocatalytic material is applied to photocatalytic degradation of Tetracycline (TC), a 500W xenon lamp is used as a light source, a sunlight source is simulated, the concentration of a Tetracycline (TC) solution is 50mg/L, and the method comprises the following specific steps:
firstly, adding 0.06g of photocatalytic material into 50mL of Tetracycline (TC) solution at room temperature, then placing the solution in a dark box, magnetically stirring the solution for 60min to achieve adsorption-desorption balance, and taking out 4mL of solution every 10 min; then, turning on a simulated light source, and taking 4mL of solution every 20 min; centrifuging the solution taken out each time, taking supernatant, and testing the absorbance of the supernatant at the highest peak (370nm) by using a UV-2550 spectrophotometer respectively; and recovering the photocatalytic material.
FIG. 7 is an absorbance curve of the WO3/CdWO4 nano-fiber photocatalytic material with a tube-in-tube structure prepared in example 1 for photocatalytic degradation of Tetracycline (TC) under the irradiation of a simulated light source, and FIG. 8 is a WO 8 with a one-dimensional linear structure prepared in example 23/CdWO4The absorbance curve of the nano-fiber photocatalytic material for photocatalytic degradation of Tetracycline (TC) under the irradiation of a simulated light source is shown in FIG. 9, which is WO prepared in comparative example 13/CdWO4The absorbance curve of the composite photocatalytic material for photocatalytic degradation of Tetracycline (TC) under the irradiation of a simulated light source is shown in FIG. 10, which is WO prepared in comparative example 23/CdWO4The composite photocatalytic material photocatalytically degrades an absorbance curve of Tetracycline (TC) under the irradiation of a simulated light source, and the detection wavelength is 300-500 nm. As can be seen from the figure, the peak absorbance of the tetracycline solution is at 370nm, WO of examples 1 and 23/CdWO4After the catalytic reaction of the nanofiber photocatalytic material is carried out for 120min under a simulated light source, the absorbance values of tetracycline solutions at 370nm are lower than those of the composite photocatalytic materials of comparative example 1 and comparative example 2, which shows that the WO of the one-dimensional linear structure, especially the pipe-in-pipe structure, prepared by the invention3/CdWO4The photocatalysis efficiency of the nano-fiber photocatalysis material is obviously improved, and the WO of the pipe-in-pipe structure3/CdWO4The nanofiber photocatalytic material has a better degradation effect on Tetracycline (TC).
The absorbance curve of the WO3/CdWO4 nanofiber photocatalytic material with a tube-in-tube structure prepared in example 1 in the dark reaction 60min is shown in fig. 11a, the absorbance curve of the WO3/CdWO4 nanofiber photocatalytic material with a one-dimensional linear structure prepared in example 2 in the dark reaction 60min is shown in fig. 12a, the absorbance curve of the WO3/CdWO4 composite photocatalytic material prepared in comparative example 1 in the dark reaction 60min is shown in fig. 13a, the absorbance curve of the WO3/CdWO4 composite photocatalytic material prepared in comparative example 2 in the dark reaction 60min is shown in fig. 14a, the purpose of the dark reaction is to eliminate the influence of the adsorption of the photocatalytic material, and the results show that the dark reaction stage, the WO 891 and the WO 2 prepared in example 2 have the absorption curve3/CdWO4Nano-fiber photocatalytic material and WO prepared in comparative example 1 and comparative example 23/CdWO4Composite photocatalytic material in darkAfter the reaction is carried out for 10 minutes, the absorbance of the tetracycline solution is basically unchanged, which indicates that the tetracycline is not catalytically degraded by the photocatalytic material under the dark reaction condition;
the absorbance change curves of the reaction solutions of the WO3/CdWO4 nanofiber photocatalytic material with the tube-in-tube structure prepared in example 1 under different illumination times are shown in fig. 11b, the absorbance change curves of the WO3/CdWO4 nanofiber photocatalytic material with the one-dimensional linear structure prepared in example 2 under different illumination times are shown in fig. 12b, the absorbance change curves of the WO3/CdWO4 composite photocatalytic material prepared in comparative example 1 under different illumination times are shown in fig. 13b, the absorbance change curves of the WO3/CdWO4 composite photocatalytic material prepared in comparative example 2 under different illumination times are shown in fig. 14b, and the WO3/CdWO4 nanofiber photocatalytic material with the tube-in-tube structure prepared in comparative example 1 is shown in fig. 11b3/CdWO4Nanofiber photocatalytic material and WO one-dimensional linear structure prepared in example 23/CdWO4Nanofiber photocatalytic material and WO prepared in comparative examples 1 and 23/CdWO4Composite photocatalytic material, WO of one-dimensional linear structure, in particular tube-in-tube structure, prepared by the invention3/CdWO4The nano-fiber photocatalytic material has obviously higher photocatalytic efficiency, and the WO of a pipe-in-pipe structure3/CdWO4The nanofiber photocatalytic material has a better degradation effect on Tetracycline (TC).
And (3) calculating the photocatalytic oxidation degradation efficiency of the photocatalytic material to the Tetracycline (TC) according to the formula (I).
Formula (I):
η＝[(C0-Ct)/C0]×100％，
in the formula (I), C0Absorbance, C, measured for the first time of the solutiontAbsorbance measured as time t.
The degradation efficiency of the WO3/CdWO4 nanofiber photocatalytic material with the tube-in-tube structure, prepared in example 1, on Tetracycline (TC) by repeated recycling four times under the irradiation of a simulated light source is shown in FIG. 15, and the WO3/CdWO4 composite photocatalytic material, prepared in comparative example 1, is repeatedly recycled four times under the irradiation of the simulated light source on Tetracycline (TC) degradation efficiencyThe decomposition efficiency is shown in fig. 16, and it can be seen from the graph that after four times of recycling, the photocatalytic effect of the WO3/CdWO4 nanofiber photocatalytic material with a tube-in-tube structure prepared in example 1 is still very high, which is as high as 91.3%, while after four times of recycling, the degradation efficiency of the sample is reduced by about 18%, which is only 46.3%, after the WO3/CdWO4 composite photocatalytic material prepared in comparative example 1 is recycled, which indicates that the sample prepared in the invention has poor recycling performance and stability compared with the sample prepared in example 1, and thus, the WO3/CdWO4 nanofiber photocatalytic material prepared in a tube-in-tube structure is demonstrated to have high photocatalytic effect, which is still high in efficiency, and has poor recycling performance and stability3/CdWO4The nanofiber photocatalytic material has good stability, can be recycled, and greatly reduces the production cost.
Claims (8)
1. The application of the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material in the photocatalytic oxidative degradation of tetracycline; the photocatalytic material is a composite nanofiber material consisting of tungsten trioxide and cadmium tungstate, and is prepared by preparing a spinnable precursor sol by taking ammonium metatungstate, cadmium acetate and polyvinylpyrrolidone as reaction raw materials, and performing electrostatic spinning and calcination, wherein the preparation method comprises the following steps:
(1) preparation of spinnable precursor sol
Dissolving ammonium metatungstate and cadmium acetate in a mixed solvent composed of absolute ethyl alcohol and N, N-dimethylformamide, adding polyvinylpyrrolidone (PVP) until the viscosity is 0.1-1.0 Pa.S, and uniformly stirring to obtain a spinnable precursor sol;
(2) preparation of tungsten trioxide/cadmium tungstate precursor fiber
Performing electrostatic spinning on the spinnable precursor sol obtained in the step (1) under the conditions that the temperature is 15-35 ℃, the voltage is 10-30kV, and the ejection rate is 0.1-1.5mL/h to obtain precursor fiber;
(3) preparation of tungsten trioxide/cadmium tungstate nanofiber photocatalytic material
And (3) drying the precursor fiber prepared in the step (2) at the temperature of 40-100 ℃ for 12-36h, heating to 400-600 ℃ at the speed of 1-5 ℃/min, and preserving the heat for 60-180min to obtain the tungsten trioxide/cadmium tungstate nanofiber photocatalytic material.
2. The use according to claim 1, wherein the composite nanofiber has a one-dimensional linear structure with a diameter of 100-600nm and a length of 3-15 μm.
3. The use of claim 1, wherein the composite nanofiber is a tube-in-tube structure comprising a nanotube core and a hollow nanotube outer tube, the length of the composite nanofiber is 10-15 μm, and the diameters of the nanotube core and the hollow nanotube outer tube are 100-200nm and 400-500nm, respectively.
4. The use according to claim 1, wherein the spinnable precursor sol in step (1) has a molar ratio of Cd to W of 1: (1-3).
5. The use according to claim 1, wherein the volume ratio of the absolute ethanol to the N, N-dimethylformamide in the mixed solvent in the step (1) is 1: (0.5-2).
6. The use of claim 1, wherein the molar volume ratio of the cadmium acetate to the mixed solvent in step (1) is 1: (8-15) with the unit of mol/L.
7. The use according to claim 1, wherein the polyvinylpyrrolidone of step (1) has a weight average molecular weight of 4 to 300 ten thousand.
8. The use according to claim 1, wherein the electrospinning in step (2) is received at a distance of 20-35 cm; the spraying rate is 1.5mL/h, the voltage is 20-30kV, and the temperature is 20-25 ℃.
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