CN111167481B - Preparation method of sulfur-doped titanium dioxide photocatalyst - Google Patents
Preparation method of sulfur-doped titanium dioxide photocatalyst Download PDFInfo
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- CN111167481B CN111167481B CN202010119974.7A CN202010119974A CN111167481B CN 111167481 B CN111167481 B CN 111167481B CN 202010119974 A CN202010119974 A CN 202010119974A CN 111167481 B CN111167481 B CN 111167481B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 37
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 30
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 6
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 47
- 239000010936 titanium Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract 2
- -1 Ti pure metals Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 238000002074 melt spinning Methods 0.000 description 9
- 238000003723 Smelting Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 3
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- 238000006731 degradation reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 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 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 229910004356 Ti Raw Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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Abstract
The application provides a preparation method of a sulfur-doped titanium dioxide photocatalyst, which takes a copper-titanium amorphous alloy as a precursor and comprises the following steps of: A. preparing an amorphous alloy strip from Cu and Ti pure metals according to an atomic ratio, and using the amorphous alloy strip as a precursor for subsequent titanium dioxide preparation; B. ammonium persulfate is prepared into 0.5-2 mol L‑1Adding NaOH (the content is 0.1-1 mol L) into the prepared solution‑1) (ii) a C. Transferring the amorphous strips and the prepared solution to a hydrothermal reaction kettle, reacting at 120-180 ℃ for 10-30 h, washing the obtained product with deionized water, washing with absolute ethyl alcohol, and drying; D. and grinding the dried sample into powder, and carrying out heat treatment under different conditions to obtain the photocatalyst material. The method can effectively prepare the copper-titanium amorphous alloy strip into the sulfur-doped anatase titanium dioxide, and simultaneously realize the doping of sulfur element, so that the forbidden bandwidth of the material is reduced, the light utilization rate is improved, and the photocatalytic performance of the material is improved.
Description
Technical Field
The invention belongs to the field of preparation and synthesis of photocatalytic materials, and particularly relates to a preparation method of a sulfur-doped titanium dioxide photocatalyst.
Background
The water resource occupies an extremely important position in our daily life, and with the continuous promotion of the industrialization process, the problem of water pollution treatment becomes more and more serious. The metal oxide has good performance in the aspect of catalytic degradation treatment of wastewater, such as strong adsorption capacity, high catalytic activity, good chemical stability, low price and the like, so that the metal oxide has obvious advantages in the aspect of sewage treatment. The removal of pollutants by the catalytic technology can not only treat toxic substances which are difficult to degrade by a biological method, but also completely degrade and mineralize organic pollutants into H2O、CO2And inorganic small molecular substances are adopted, so that secondary pollution is avoided, and the method has the characteristics of simplicity, high efficiency, greenness and energy conservation.
When titanium dioxide is used as a photocatalyst, common crystal forms mainly comprise a rutile phase and an anatase phase, wherein the forbidden bandwidth of the rutile phase is 3.0eV, and the forbidden bandwidth of the anatase phase is 3.2 eV. Compared with the prior art, the anatase-phase titanium dioxide with a wider forbidden band has stronger oxidation-reduction capability of electron-hole pairs generated by illumination excitation. However, since anatase phase titanium dioxide has a wide forbidden band width, the efficiency of light utilization is low when a photocatalytic reaction is performed. Therefore, methods such as narrow bandgap semiconductors, noble metal deposition, non-metal element doping and the like are generally loaded into titanium dioxide, so that the photocatalytic performance of the titanium dioxide is improved.
Meanwhile, titanium dioxide particles are refined by a sol-gel method, a direct precipitation method, a micro-emulsion method and other methods, the specific surface area of the material is increased, however, most of the methods need to be calcined at high temperature, and most of the existing preparation methods firstly complete the preparation of the titanium dioxide, and then carry out two-step preparation processes of loading, doping and the like on the prepared titanium dioxide.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a preparation method of a sulfur-doped titanium dioxide photocatalyst, which introduces sulfur element into anatase titanium dioxide with better photocatalytic capability, reduces the forbidden bandwidth of the titanium dioxide and improves the photocatalytic performance of the material. The sulfur element can be introduced into the material while preparing the anatase phase titanium dioxide, so that the preparation of the titanium dioxide and the synchronous preparation of the sulfur element can be realized.
The technical scheme is as follows: the invention provides a preparation method of a sulfur-doped titanium dioxide photocatalyst, which takes a copper-titanium amorphous alloy as a precursor and prepares the sulfur-doped anatase titanium dioxide photocatalyst through selective corrosion reaction, and the preparation method specifically comprises the following steps:
step 1: preparing amorphous Cu from pure copper and pure titaniumxTiyAn alloy strip;
step 2: amorphous state of CuxTiyThe alloy strip is placed in a container with the concentration of 0.5-2 mol L-1Keeping the temperature of a hydrothermal reaction kettle of ammonium persulfate solution at 120-180 ℃ for 10-30 h;
and step 3: cooling, taking out the reaction product, repeatedly soaking and cleaning with deionized water and alcohol, drying, and grinding to obtain amorphous CuxTiyAnd grinding the alloy strip into powder to obtain the sulfur-doped titanium dioxide photocatalyst.
Wherein,
and (3) carrying out heat treatment on the obtained sulfur-doped titanium dioxide photocatalyst obtained in the step (3) at 400-700 ℃ for 1-3 h, and adjusting the morphology, sulfur content, crystal type and the like of the catalyst.
The ammonium persulfate solution contains 0.1-1 mol L of sodium hydroxide-1。
The sulfur-doped titanium dioxide photocatalyst is a microsphere with the average particle size of 2 mu m formed by stacking particles with the particle size of 50-100 nm, and sulfur element in titanium dioxide exists in a doped form.
The amorphous CuxTiyX and y in the alloy strip respectively correspond to the atomic percentages of Cu and Ti elements, wherein x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, and x + y is equal to 100.
In the preparation process, the ratio of the mass of the used amorphous alloy strip to the volume of the ammonium persulfate solution is 5-10 g/L.
Has the advantages that:
(1) the invention is used for preparing the sulfur-doped titanium dioxide photocatalyst, the Cu-Ti amorphous alloy is used as a precursor, the micron spherical anatase phase titanium dioxide photocatalyst constructed by nano-scale and submicron-scale particles is prepared, the particle size of the catalyst is uniform, and sulfur elements are uniformly distributed in the anatase phase titanium dioxide.
(2) Compared with other preparation methods of sulfur-doped titanium dioxide, the method realizes the preparation of anatase-phase titanium dioxide and introduces sulfur doping into the titanium dioxide at the same time, so as to realize the synchronous preparation of the titanium dioxide and the sulfur doping and improve the preparation efficiency of the sulfur-doped titanium dioxide photocatalyst.
(3) The sulfur-doped titanium dioxide prepared by the invention has the advantage that the photocatalytic activity of anatase phase titanium dioxide is improved due to the doping of sulfur element, so that the degradation efficiency of the anatase phase titanium dioxide in the process of photocatalytic degradation of RhB is obviously improved.
Drawings
The accompanying drawings, which form a part of the specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows Cu prepared70Ti30XRD pattern of amorphous alloy strip.
Fig. 2 is an XRD pattern of the prepared sulfur-doped titanium dioxide.
Fig. 3 is an SEM image of a sulfur-doped titanium dioxide material.
Fig. 4 is a TEM spectrum of sulfur doped titanium dioxide.
Fig. 5 shows the elemental surface distribution results of sulfur-doped titanium dioxide.
FIG. 6 shows the UV irradiation of sulfur-doped titanium dioxide to 10mg L-1Photocatalytic degradation curve of rhodamine B solution.
Detailed Description
The preparation method of the sulfur-doped titanium dioxide photocatalyst comprises the following specific steps:
step 1: weighing pure Cu and pure Ti raw materials according to designed atomic ratio, mixing uniformly, and preparing Cu by smelting and rotary quenching methodsxTiyAn amorphous alloy thin strip;
step 2: ammonium persulfate is prepared to be 0.5-2 mol L in concentration-1Adding NaOH into the prepared solution, wherein the content of NaOH is 0.1-1 mol L-1(ii) a And (3) transferring the amorphous strips obtained in the step (1) and the prepared ammonium persulfate solution to a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 10-30 h at the temperature of 120-180 ℃.
And step 3: subjecting the obtained Cu after hydrothermal reactionxTiyTaking out the amorphous alloy thin strip, repeatedly soaking and cleaning the amorphous alloy thin strip by using deionized water and alcohol in sequence, drying the amorphous alloy thin strip, and grinding the amorphous alloy thin strip into powder by grinding, wherein the titanium dioxide photocatalyst is doped with sulfur. Subsequently, the sulfur content and crystallinity of the material can be further adjusted by further heat treatment.
Wherein, the step 1 specifically comprises the following steps:
step 1.1: according to CuxTiyWeighing pure metals of Cu and Ti with the component purity of more than 99.9% in a targeted manner, and uniformly mixing to obtain a smelting raw material, wherein x and y correspond to the atomic percentage of Cu and Ti elements, and x + y is 100;
step 1.2: putting the smelting raw material obtained in the step 1.1 into a vacuum arc smelting furnace, smelting under the argon protective atmosphere, continuously smelting after the raw material is molten, stopping heating to enable the alloy to be cooled to be solidified along with a crucible, turning the alloy over, repeatedly smelting, and cooling to obtain a master alloy ingot with uniform components;
step 1.3: and (3) crushing the master alloy ingot obtained in the step (1.2) into small pieces, putting the small pieces of alloy ingot into a quartz tube with an opening diameter of 1-2 mm, placing the quartz tube into an induction coil of vacuum melt-spinning equipment for fixing, and preparing the amorphous alloy strip precursor for preparing the sulfur-doped titanium dioxide through the vacuum melt-spinning equipment.
The specific preparation method of the ammonium persulfate solution in the step 2 comprises the following steps: weighing solid of ammonium persulfate and sodium hydroxide according to the concentration design, adding the solid into a volumetric flask after dissolving, and fixing the volume to obtain the ammonium persulfate solution for preparing the sulfur-doped titanium dioxide.
In the step 3, the drying is drying in a drying oven at 45 ℃.
The sulfur-doped titanium dioxide obtained in the step 3 is spherical particles with an average particle size of about 2 microns, and the particles with the particle size of 50-100 nm are stacked.
The present invention will be described in detail with reference to examples. The scope of protection of the invention is not limited to the embodiments, and any modification made by those skilled in the art within the scope defined by the claims also falls within the scope of protection of the invention.
Example 1
According to Cu70Ti30Weighing Cu and Ti metal element raw materials with the purity of 99.9 percent as target components, and preparing Cu through vacuum arc melting and vacuum melt spinning70Ti30The amorphous alloy strip and XRD result are shown in figure 1, which shows that the prepared strip is amorphous.
Ammonium persulfate is prepared to be 2mol L in deionized water-1In the preparation process of the solution, sodium hydroxide is added, and the concentration is 0.5mol L-1。
25ml of the prepared ammonium persulfate solution and 200mg of prepared Cu70Ti30Amorphous alloy strip rotorMoving the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20 hours at the temperature of 150 ℃, and cooling the mixture along with the furnace after the reaction is finished.
And taking the cooled strip out of the solution, repeatedly soaking and cleaning the strip by using deionized water and absolute ethyl alcohol in sequence, and drying the strip for 1h in a drying oven at the temperature of 45 ℃ to obtain a dried strip, wherein the XRD result is shown in figure 2.
And grinding the dried strips into powder to prepare the powdery sulfur-doped titanium dioxide photocatalyst. The surface morphology is shown in fig. 3, and the SEM result shows that the prepared titanium dioxide is a particle having an average particle size of about 2 μm. The microparticles are formed by stacking nanoparticles and submicron particles with smaller particle sizes, as shown in fig. 4. The elemental surface distribution results of fig. 5 confirm the loading of elemental sulfur. FIG. 6 shows the photocatalytic performance test result of the material on rhodamine B under ultraviolet light, which shows that the material has excellent photocatalytic performance and can realize approximately complete degradation on 10mg/L rhodamine B solution within 6 minutes. The band gap energy test is carried out by adopting an ultraviolet-visible absorption spectrum (UV-vis) method, and the forbidden bandwidth of the material obtained by a tangent method is 2.9 eV.
Example 2
According to Cu70Ti30Weighing Cu and Ti metal element raw materials with the purity of 99.9 percent as target components, and preparing Cu through vacuum arc melting and vacuum melt spinning70Ti30Amorphous alloy ribbon.
Ammonium persulfate is prepared to be 0.5mol L by deionized water-1In the preparation process of the solution, sodium hydroxide is added, and the concentration is 0.5mol L-1。
25ml of the prepared ammonium persulfate solution and 200mg of prepared Cu70Ti30Transferring the amorphous alloy strip into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at 150 ℃, and cooling along with the furnace after the reaction is finished.
And taking the cooled strip out of the solution, repeatedly soaking and cleaning the strip by using deionized water and absolute ethyl alcohol in sequence, and drying the strip for 1h in a drying oven at the temperature of 45 ℃ to obtain the dried strip.
And grinding the dried strips into powder, and carrying out heat treatment for 1h at 400 ℃ in a heating furnace to obtain the powdered sulfur-doped titanium dioxide photocatalyst.
Example 3
According to Cu70Ti30Weighing Cu and Ti metal element raw materials with the purity of 99.9 percent as target components, and preparing Cu through vacuum arc melting and vacuum melt spinning70Ti30Amorphous alloy ribbon.
Ammonium persulfate is prepared to be 1mol L in deionized water-1In the preparation process of the solution, sodium hydroxide is added, and the concentration is 0.5mol L-1。
25ml of the prepared ammonium persulfate solution and 200mg of prepared Cu70Ti30Transferring the amorphous alloy strip into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at 150 ℃, and cooling along with the furnace after the reaction is finished.
And taking the cooled strip out of the solution, repeatedly soaking and cleaning the strip by using deionized water and absolute ethyl alcohol in sequence, and drying the strip for 1h in a drying oven at the temperature of 45 ℃ to obtain the dried strip.
And grinding the dried strips into powder, and carrying out heat treatment for 1h at 500 ℃ in a heating furnace to obtain the powdered sulfur-doped titanium dioxide photocatalyst.
Example 4
According to Cu70Ti30Weighing Cu and Ti metal element raw materials with the purity of 99.9 percent as target components, and preparing Cu through vacuum arc melting and vacuum melt spinning70Ti30Amorphous alloy ribbon.
Ammonium persulfate is prepared to be 1mol L in deionized water-1In the preparation process of the solution, sodium hydroxide is added, and the concentration is 0.5mol L-1。
25ml of the prepared ammonium persulfate solution and 200mg of prepared Cu70Ti30Transferring the amorphous alloy strip into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at 150 ℃, and cooling along with the furnace after the reaction is finished.
And taking the cooled strip out of the solution, repeatedly soaking and cleaning the strip by using deionized water and absolute ethyl alcohol in sequence, and drying the strip for 1h in a drying oven at the temperature of 45 ℃ to obtain the dried strip.
The dried strips were ground by hand into powder and heat-treated in a heating furnace at 600 ℃ for 1h to obtain a powdered sulfur-doped titanium dioxide photocatalyst.
Example 5
According to Cu70Ti30Weighing Cu and Ti metal element raw materials with the purity of 99.9 percent as target components, and preparing Cu through vacuum arc melting and vacuum melt spinning70Ti30Amorphous alloy ribbon.
Ammonium persulfate is prepared to be 1mol L in deionized water-1In the preparation process of the solution, sodium hydroxide is added, and the concentration is 0.5mol L-1。
25ml of the prepared ammonium persulfate solution and 200mg of prepared Cu70Ti30Transferring the amorphous alloy strip into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at 150 ℃, and cooling along with the furnace after the reaction is finished.
And taking the cooled strip out of the solution, repeatedly soaking and cleaning the strip by using deionized water and absolute ethyl alcohol in sequence, and drying the strip for 1h in a drying oven at the temperature of 45 ℃ to obtain the dried strip.
And grinding the dried strips into powder, and carrying out heat treatment for 1h at 600 ℃ in a heating furnace to obtain the powdered sulfur-doped titanium dioxide photocatalyst.
Example 6
According to Cu60Ti40Weighing Cu and Ti metal element raw materials with the purity of 99.9 percent as target components, and preparing Cu through vacuum arc melting and vacuum melt spinning30Ti70Amorphous alloy ribbon.
Ammonium persulfate is prepared to be 1mol L in deionized water-1In the preparation process of the solution, sodium hydroxide is added, and the concentration is 0.5mol L-1。
25ml of the prepared ammonium persulfate solution and 200mg of prepared Cu30Ti70Transferring the amorphous alloy strip into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at 150 ℃, and cooling along with the furnace after the reaction is finished.
And taking the cooled strip out of the solution, repeatedly soaking and cleaning the strip by using deionized water and absolute ethyl alcohol in sequence, and drying the strip for 1h in a drying oven at the temperature of 45 ℃ to obtain the dried strip.
And grinding the dried strips into powder to obtain the powdered sulfur-doped titanium dioxide photocatalyst.
Example 7
According to Cu80Ti20Weighing Cu and Ti metal element raw materials with the purity of 99.9 percent as target components, and preparing Cu through vacuum arc melting and vacuum melt spinning80Ti20Amorphous alloy ribbon.
Ammonium persulfate is prepared to be 1mol L in deionized water-1In the preparation process of the solution, sodium hydroxide is added, and the concentration is 0.5mol L-1。
25ml of the prepared ammonium persulfate solution and 200mg of prepared Cu80Ti20Transferring the amorphous alloy strip into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at 150 ℃, and cooling along with the furnace after the reaction is finished.
And taking the cooled strip out of the solution, repeatedly soaking and cleaning the strip by using deionized water and absolute ethyl alcohol in sequence, and drying the strip for 1h in a drying oven at the temperature of 45 ℃ to obtain the dried strip.
And grinding the dried strips into powder to obtain the powdered sulfur-doped titanium dioxide photocatalyst.
The above examples are only preferred embodiments of the present invention, but not limiting the scope of the invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and equivalents can be made without departing from the spirit of the invention, and it is intended that all such modifications and equivalents fall within the scope of the invention as defined in the claims.
Claims (6)
1. A preparation method of a sulfur-doped titanium dioxide photocatalyst is characterized in that the preparation method takes a copper-titanium amorphous alloy as a precursor, and prepares the sulfur-doped anatase titanium dioxide photocatalyst through selective corrosion reaction, and specifically comprises the following steps:
step 1: preparing amorphous Cu from pure copper and pure titaniumxTiyAn alloy strip;
step 2: amorphous state of CuxTiyThe alloy strip is placed in a container with the concentration of 0.5-2 mol L-1Keeping the temperature of a hydrothermal reaction kettle of ammonium persulfate solution at 120-180 ℃ for 10-30 h;
and step 3: cooling, taking out the reaction product, repeatedly soaking and cleaning with deionized water and alcohol, drying, and grinding to obtain amorphous CuxTiyAnd grinding the alloy strip into powder to obtain the sulfur-doped titanium dioxide photocatalyst.
2. The method for preparing the sulfur-doped titanium dioxide photocatalyst according to claim 1, wherein the obtained sulfur-doped titanium dioxide photocatalyst obtained in the step 3 is subjected to heat treatment at 400 to 700 ℃ for 1 to 3 hours to adjust the morphology, sulfur content and crystal type of the catalyst.
3. The method for preparing a sulfur-doped titanium dioxide photocatalyst according to claim 1, wherein the sodium hydroxide concentration in the ammonium persulfate solution is 0.1-1 mol L-1。
4. The method of claim 1, wherein the sulfur-doped titanium dioxide photocatalyst is a microsphere having an average particle size of 2 μm formed by stacking particles having a particle size of 50 to 100nm, and sulfur element is present in the titanium dioxide in a doped form.
5. The method of claim 1, wherein the amorphous Cu is doped with titanium dioxidexTiyX and y in the alloy strip respectively correspond to the atomic percentages of Cu and Ti elements, wherein x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, and x + y is equal to 100.
6. The preparation method of the sulfur-doped titanium dioxide photocatalyst according to claim 1, wherein in the preparation process, the ratio of the mass of the used amorphous alloy strip to the volume of the ammonium persulfate solution is 5-10 g/L.
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