CN110436558B - Insertion type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array visible-light-driven photocatalyst and preparation method and application thereof - Google Patents
Insertion type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array visible-light-driven photocatalyst and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000002071 nanotube Substances 0.000 title claims abstract description 90
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 62
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003780 insertion Methods 0.000 title claims description 8
- 230000037431 insertion Effects 0.000 title claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010936 titanium Substances 0.000 claims abstract description 70
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 23
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
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- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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 discloses a molybdenum sulfide inserted-type gap-doped porous-wall titanium dioxide nanotube array visible-light-driven photocatalyst, and a preparation method and application thereof. The method comprises the following steps: the preparation method comprises the steps of firstly carrying out anodic oxidation on a pure titanium sheet, then calcining the pure titanium sheet in a muffle furnace, regulating and controlling the parameters of the calcining conditions to prepare the porous-wall titanium dioxide nanotube, then inserting molybdenum sulfide into part of the porous side wall in a sheet form by a solvothermal method, widening the photoresponse range of the porous-wall titanium dioxide nanotube array while not hindering the adsorption and mass transfer functions of the porous wall, and finally preparing the inserted-sheet type molybdenum sulfide gap-doped porous-wall titanium dioxide nanotube array visible-light-induced photocatalyst. The photocatalyst has a multi-stage pore canal of a canal wall, a regular canal wall array structure, good visible light response, capability of providing a rapid electron transmission channel and better adsorption mass transfer performance, remarkably enhanced visible light catalytic performance compared with a pure titanium dioxide nanotube array and molybdenum sulfide powder, and greatly improved sunlight utilization efficiency and photoproduction electron hole separation capability.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials, and particularly relates to a preparation method of an insert type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array visible-light-driven photocatalyst and application thereof in environmental pollution treatment.
Background
One of the major problems facing and urgently needing to be solved by human beings in the 21 st century is environmental pollution and energy shortage, namely TiO2Photocatalytic technology represented by the following uses solar energy to driveThe unique performances of dynamic reaction, room temperature deep reaction and the like are provided, and the method becomes an ideal environmental pollution treatment technology and a clean energy production technology. The morphology structure of the semiconductor photocatalyst obviously influences the maximum catalytic effect. In recent years, TiO with various morphological structures2Materials such as wires, hollow spheres, nanotubes, sheets, and three-dimensional interconnect structures have been developed in succession. Among them, titanium nanotubes are widely favored by researchers because of their highly controllable structure, large specific surface area, and fast electron channel.
Anodic oxidation, electrostatic spinning and template hydrothermal methods are the main preparation methods of the titanium nanotube at present. Compared with electrostatic spinning and template hydrothermal preparation methods, the anodic oxidation method has simple process, and the prepared TiO is2The nano tube has regular and uniform growth, extremely high order of nano structure, extremely low agglomeration degree and larger specific surface area. However, most of the existing anodic oxidation technologies adopt a pure titanium foil electrode as an anode and a platinum sheet as a cathode, so that the cost is very high, the prepared pure titanium nanotube array can only absorb ultraviolet light excitation, the compact tube wall of the pure titanium nanotube array can prevent light from reaching the inner tube wall, so that the utilization rate of sunlight is further reduced, and the factors obviously limit the large-scale practical application of the nanotube array. Therefore, the key problem is expected to be solved by utilizing the visible light response and the porous structure of the visible light photocatalyst of the insert-type molybdenum sulfide gap-doped porous-wall titanium dioxide nanotube array.
The invention adopts an anodic oxidation method and a solvothermal method, takes a pure titanium sheet as a cathode, carries out anodic oxidation in fluorine-containing glycol electrolyte to obtain an amorphous titanium dioxide nanotube array, and creates a multistage pore canal of the nanotube wall after calcining in a muffle furnace. And then inserting the molybdenum sulfide into part of the porous side wall in a sheet shape by a solvothermal method to prepare the insert-type molybdenum sulfide gap-doped porous-wall titanium dioxide nanotube array visible-light-driven photocatalyst. Due to the existence of the multi-stage pore channel structure, the inserted molybdenum sulfide gap-doped titanium dioxide nanotube with the porous tube wall is further beneficial to the adsorption and mass transfer of reactants, and simultaneously, incident light can enter the interior of the tube through the multi-stage pore channel of the tube wall, so that the utilization rate of the inner surface of the nanotube array to light is greatly improved, and on the other hand, the uniform gap doping of molybdenum sulfide enlarges the sunlight absorption range of the nanotube array, and the photocatalysis efficiency of the nanotube array is further improved. The preparation method adopted by the invention provides a new direction for preparing the visible light photochemical novel nanotube array material.
Disclosure of Invention
The invention aims to overcome the defects that the cost is high when a noble metal electrode is adopted in the prior anodic oxidation technology, a pure titanium dioxide nanotube array only has sunlight utilization rate, compact tube wall, low ultraviolet response and the like, and provides a simple preparation method of a plug-in type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array visible-light-induced photocatalyst and application thereof in environmental pollution treatment.
The invention is realized by the following technical scheme:
the preparation method of the plug-in type molybdenum sulfide gap doped porous titanium dioxide nanotube array visible-light-driven photocatalyst is characterized in that molybdenum sulfide is inserted into the side wall of a part of porous titanium dioxide nanotubes in a sheet shape, and visible-light response is realized. The porous pore structure is realized by adopting a pure titanium sheet as a working electrode and a pure titanium sheet as a cathode, carrying out anodic oxidation in fluorine-containing glycol electrolyte, then carrying out muffle furnace calcination, and regulating and controlling anodic oxidation parameters. The photocatalyst is placed in a reaction kettle after being calcined in a muffle furnace, molybdenum sulfide is doped on the porous side wall through a solvothermal method, and then N is added2And calcining in a tube furnace in the atmosphere, so that the visible light catalyst with the plug-in type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array with visible light response is prepared on the side wall of the porous titanium dioxide nanotube in which the molybdenum sulfide in a sheet form is inserted.
A preparation method of an inserted molybdenum sulfide gap doped porous wall titanium dioxide nanotube array visible-light-driven photocatalyst comprises the following steps:
(1) pretreatment: taking a pure titanium sheet, sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water for ultrasonic treatment, drying the pure titanium sheet at room temperature in the air, then polishing a sample by adopting an electrochemical method, taking a self-made pure titanium sheet as a cathode, taking the cleaned and dried pure titanium sheet as an anode, taking a polishing solution which is an Ethylene Glycol (EG) solution containing sodium chloride, polishing the pure titanium sheet under a direct current constant voltage until the titanium sheet is bright and traceless, finally ultrasonically cleaning the pure titanium sheet by using the absolute ethyl alcohol and the deionized water, and drying the pure titanium sheet at room temperature to obtain a pretreated pure titanium sheet;
(2) anodic oxidation: adopting a two-electrode system, wherein the cathode is a pure titanium sheet, the anode is the pretreated pure titanium sheet obtained in the step (1), and the electrolyte is ammonium fluoride (NH)4F) And a solution of deionized water in Ethylene Glycol (EG); carrying out anodic oxidation under a direct current constant voltage without maintaining the temperature of the electrolyte and stirring; after reaction, the mixture is placed into absolute ethyl alcohol to be soaked for 20-40 min and then is naturally dried at room temperature to obtain amorphous TiO2A nanotube array; the NH4The concentration of F is 0.3wt% -1.0 wt%; the volume of the deionized water is 1-5 vol%; the volume of the electrolyte is 65-75 mL;
(3) and (3) calcining: adding amorphous TiO2Placing the nanotube array in a muffle furnace for high-temperature calcination in air atmosphere to obtain porous wall TiO2An array of nanotubes.
(4) Preparing an insertion piece type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array: TiO porous wall2Placing the nanotube array in a reaction kettle, and adding sodium molybdate (Na)2MoO4·2H2O), thioacetamide (C)2H5NS) and deionized water. Taking out after reacting for a period of time, washing with deionized water and absolute ethyl alcohol in sequence, and drying at room temperature for later use; placing the dried sample in a tube furnace for high-temperature calcination, N2Performing atmosphere to obtain an inserted molybdenum sulfide doped porous wall titanium dioxide nanotube array; the addition amount of the sodium molybdate is 5-50 mg; the addition amount of the thioacetamide is 10-100 mg; the addition amount of the deionized water is 10-30 mL;
in the above method, in the step (1), the pure titanium sheet; the thickness of the titanium sheet is 1-3 mm, and the mass fraction of the titanium element is not less than 99.9%; the ultrasonic cleaning time is 10-30 min, the drying temperature at room temperature is 20-30 ℃, and the drying time is 1-2 h.
In the above method, the step (1) In the method, the effective area of the cathode pure titanium sheet is 350-450 mm2(the back is covered by adhesive tape), the effective area of the anode pure titanium sheet is 2 multiplied by 350-450 mm2(ii) a The distance between the cathode and the anode is 1-4 cm; the direct current voltage is 30-70V.
In the method, in the step (2), the anodic oxidation voltage range is 30-70V, the oxidation time is 1-3 h, the anodic oxidation temperature at room temperature is 20-30 ℃, the temperature of the electrolyte does not need to be maintained, and the stirring speed of stirring is 30-60 r/min.
In the method, in the step (2), the drying temperature at room temperature is 20-35 ℃, and the drying time is 10-20 h.
In the method, in the step (3), the calcination temperature is 400-600 ℃, the calcination time is 1-3 h, and the temperature rise rate is 1-5 ℃/min.
In the above method, the calcination method specifically comprises: the temperature raising procedure comprises the steps of raising the temperature from room temperature to 240-260 ℃ at the speed of 2-4 ℃/min, keeping the temperature constant at 240-260 ℃ for 25-35 min, raising the temperature to 400-600 ℃ at the speed of 0.5-1.5 ℃/min, keeping the temperature constant for 1-4 h, and finally lowering the temperature to room temperature at the speed of 1-5 ℃/min.
In the method, in the step (4), the reaction temperature is 150-250 ℃; the reaction time is 20-40 h; the calcining temperature of the tubular furnace is 350-850 ℃;
in the method, the specific method for calcining in the tube furnace comprises the following steps: n is a radical of2The temperature raising program under the atmosphere is as follows: the temperature is kept constant at 20-30 ℃ for 30-60 min, the temperature is increased from the room temperature to 400-450 ℃ at the speed of 3-6 ℃/min, the temperature is kept constant at 400-450 ℃ for 25-35 min, the temperature is increased to 400-500 ℃ at the speed of 0.5-1.5 ℃/min, the temperature is kept constant for 1-3 h, and finally the temperature is reduced to the room temperature at the speed of 1-5 ℃/min.
An insert-type molybdenum sulfide gap-doped porous-wall titanium dioxide nanotube array visible-light-driven photocatalyst is applied to wastewater treatment or atmosphere purification.
The invention improves and innovates on the basis of the existing sulfide-doped titanium dioxide nanotube array, the invention adopts an anodic oxidation technology to prepare the porous-wall titanium dioxide nanotube array, and then molybdenum sulfide is inserted into the side wall of a part of the porous titanium dioxide nanotube in a flaky form by a solvothermal method, so that the photoresponse range of the porous-wall titanium dioxide nanotube array is widened while the adsorption mass transfer of the porous wall is not hindered. The simple preparation of the inserted sheet type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array with high visible light catalytic activity is realized. The photocatalyst has larger specific surface area, higher light utilization rate and adsorption mass transfer efficiency, and the visible light catalytic activity of the photocatalyst is greatly improved.
Compared with the prior art, the invention has the following advantages:
the preparation method has the advantages of simple operation, low cost, construction of the multistage pore channels of the tube wall, doping of visible light elements while not obstructing the adsorption and mass transfer of the porous wall, widening of the photoresponse range and the like, and has more regular and uniform appearance and more abundant pore channel structures compared with visible light response nanotube arrays prepared by other methods, thereby having higher light utilization rate. The catalyst can be widely applied to the aspects of photocatalytic treatment of polluted wastewater, purification of atmospheric pollution and the like.
Drawings
FIG. 1 is an XRD pattern of a plug-in sheet type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array visible light catalyst, a pure titanium dioxide nanotube array and molybdenum sulfide powder of the present invention;
FIG. 2 is a field emission scanning electron microscope FE-SEM of the top of the visible light catalyst of the inserted molybdenum sulfide gap doped porous wall titanium dioxide nanotube array of the present invention;
FIG. 3 is a field emission scanning electron microscope FE-SEM of the visible light catalyst sidewall of the inserted sheet type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array of the present invention;
FIG. 4 is an ultraviolet-visible diffuse reflectance spectrum DRS of an insert-type molybdenum sulfide gap-doped porous-wall titanium dioxide nanotube array visible-light-induced photocatalyst, a pure titanium dioxide nanotube array and molybdenum sulfide powder according to the present invention;
FIG. 5 is a diagram of the visible light catalytic degradation effect of the inserted molybdenum sulfide gap doped porous wall titanium dioxide nanotube array visible light catalyst, pure titanium dioxide nanotube array and molybdenum sulfide powder on DBP.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
(1) Pretreatment: taking a pure titanium sheet (the thickness of the titanium sheet is 1 mm, the mass fraction of titanium element is not less than 99.9%), sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water for ultrasonic treatment for 10 min, drying the pure titanium sheet for 1 h at room temperature of 20 ℃ in the air, then polishing a sample by adopting an electrochemical method, taking a self-made pure titanium sheet as a cathode, taking a clean and dried pure titanium sheet as an anode, polishing the pure titanium sheet at the distance of 1 cm between the two electrodes by using Ethylene Glycol (EG) solution containing 0.1mol/L sodium chloride, polishing the pure titanium sheet under the condition of 20V of direct current constant voltage until the pure titanium sheet is bright and traceless, finally ultrasonically cleaning the pure titanium sheet for 10 min by using absolute ethyl alcohol and deionized water, and drying the pure titanium sheet for 1 h at room temperature to obtain a pretreated pure titanium sheet;
(2) anodic oxidation: adopting a two-electrode system, wherein the distance between a cathode and an anode is 1 cm, the cathode is a pure titanium sheet, the anode is the pretreated pure titanium sheet obtained in the step (1), and the electrolyte is ammonium fluoride (NH) containing 0.4 wt percent4F) And 2 vol% deionized water in Ethylene Glycol (EG); anodizing for 1 h under the DC constant voltage of 40V without maintaining the temperature of the electrolyte, wherein the stirring speed is 30 r/min; after reaction, the mixture is put into absolute ethyl alcohol for soaking for 20 min and then is naturally dried for 15 h at the room temperature of 20 ℃ to obtain amorphous TiO2A nanotube array;
(3) and (3) calcining: adding amorphous TiO2The nanotube array is placed in a muffle furnace for high-temperature calcination in air atmosphere, and the temperature rise procedure comprises the steps of firstly raising the temperature from room temperature to 240 ℃ at the speed of 2 ℃/min, keeping the temperature at 240 ℃ for 25 min, then raising the temperature to 400 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 2h, and finally lowering the temperature to room temperature at the speed of 4 ℃/min. Obtaining porous wall TiO2An array of nanotubes.
(4) Preparing an insertion piece type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array: TiO with porous wall obtained in the step (3)2The nanotube array was placed in a reaction kettle and 5mg sodium molybdate (Na) was added2MoO4·2H2O), 10mg of thioacetamide (C)2H5NS) and 10mL deionized water. The reaction temperature is 180 ℃, the mixture is taken out after 20 hours of reaction, washed by deionized water and absolute ethyl alcohol in sequence and dried at room temperature of 20 ℃ for later use; placing the dried sample in a tube furnace for high-temperature calcination, N2The temperature raising program under the atmosphere is as follows: the temperature is kept at 20 ℃ for 30min at room temperature, the temperature is increased from the room temperature to 400 ℃ at the speed of 3 ℃/min, the temperature is kept at 400 ℃ for 25 min, the temperature is increased to 400 ℃ at the speed of 0.5 ℃/min, the temperature is kept for 1 h, and finally the temperature is reduced to the room temperature at the speed of 4 ℃/min. And obtaining the inserted molybdenum sulfide doped porous wall titanium dioxide nanotube array.
Example 2
(1) Pretreatment: taking a pure titanium sheet (the thickness of the titanium sheet is 2 mm, the mass fraction of titanium element is not less than 99.9%), sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water for ultrasonic treatment for 20 min, drying the pure titanium sheet for 2h at room temperature of 25 ℃ in the air, then polishing a sample by adopting an electrochemical method, taking a self-made pure titanium sheet as a cathode, taking a clean and dried pure titanium sheet as an anode, polishing a polishing solution with the distance of 2 cm between the two electrodes as an Ethylene Glycol (EG) solution containing 0.15 mol/L sodium chloride, polishing the pure titanium sheet under a direct current constant voltage of 30V until the pure titanium sheet is bright and traceless, finally ultrasonically cleaning the pure titanium sheet for 20 min by using absolute ethyl alcohol and deionized water, and drying the pure titanium sheet for 2h at room temperature to obtain a pretreated pure titanium sheet;
(2) anodic oxidation: adopting a two-electrode system, wherein the distance between a cathode and an anode is 2 cm, the cathode is a pure titanium sheet, the anode is the pretreated pure titanium sheet obtained in the step (1), and the electrolyte is ammonium fluoride (NH) containing 0.7wt percent4F) And 3vol% deionized water in Ethylene Glycol (EG); anodizing for 2h under the DC constant voltage of 50V without maintaining the temperature of the electrolyte, wherein the stirring speed is 40 r/min; after reaction, the mixture is put into absolute ethyl alcohol for soaking for 30min and then is naturally dried for 20h at the room temperature of 20 ℃ to obtain amorphous TiO2A nanotube array;
(3) and (3) calcining: the amorphous TiO obtained in the step (2)2The nanotube array is placed in a muffle furnace for high-temperature calcination in air atmosphere, the temperature rise procedure is that the temperature is raised from room temperature to 250 ℃ at the speed of 3 ℃/min, the temperature is kept at 250 ℃ for 30min, then the temperature is raised to 500 ℃ at the speed of 1 ℃/min,keeping the temperature for 1 h, and finally cooling to room temperature at the speed of 5 ℃/min to obtain the porous wall TiO2An array of nanotubes.
(4) Preparing an insertion piece type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array: TiO with porous wall obtained in the step (3)2The nanotube array was placed in a reaction kettle and 15 mg sodium molybdate (Na) was added2MoO4·2H2O), 30 mg of thioacetamide (C)2H5NS) and 20 mL deionized water. The reaction temperature is 200 ℃, the mixture is taken out after 24 hours of reaction, washed by deionized water and absolute ethyl alcohol in sequence and dried at the room temperature of 25 ℃ for later use; placing the dried sample in a tube furnace for high-temperature calcination, N2The temperature raising program under the atmosphere is as follows: the temperature is kept at 20 ℃ for 60 min at room temperature, the temperature is increased from room temperature to 450 ℃ at the speed of 5 ℃/min, the temperature is kept at 450 ℃ for 30min, the temperature is increased to 500 ℃ at the speed of 1 ℃/min, the temperature is kept for 2h, and finally the temperature is reduced to room temperature at the speed of 5 ℃/min. And obtaining the inserted molybdenum sulfide doped porous wall titanium dioxide nanotube array.
FIG. 1 is an XRD (X-ray diffraction) diagram of a plug-in molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array, a pure titanium dioxide nanotube array and molybdenum sulfide powder, FIGS. 2 and 3 are a field emission scanning electron microscope (FE-SEM) diagram of the top and the side wall of the plug-in molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array, and FIG. 4 is an ultraviolet visible diffuse reflectance spectrum DRS of the plug-in molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array, the pure titanium dioxide nanotube array and the molybdenum sulfide powder. The insertion type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array has excellent crystallinity, a special shape structure, uniform and obvious tubular shape, and the photoresponse range is widened from ultraviolet to full spectrum.
Example 3
Photocatalytic oxidation activity evaluation, as shown in fig. 5: the visible light catalytic oxidation activity of various photocatalysts is compared by adopting a nondegradable endocrine disrupter dibutyl phthalate (DBP) as a model pollutant. The photocatalytic degradation reaction is carried out in a self-made photocatalytic circulating condensation reaction device, and the effective illumination area of the catalyst is 400 mm2The initial concentration of DBP model contaminants is5 mg/L, the total volume of the solution is 100 mL, and the light intensity of the light source is visible light AM1.5G (100 mW/cm)2) Dark adsorption is carried out for 60 min before the light source is started; the concentration of remaining DBP in the solution was determined by high performance liquid chromatography. The DBP removal rate of the catalyst is the ratio of the DBP concentration of the catalyst degradation to the initial concentration of the solution. The results show that: insert type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array (marked as MoS)2@TiO2NTAs) photocatalysts showed a better than pure titanium dioxide nanotube array (denoted as TiO)2NTAs) and molybdenum sulfide powder (noted MoS)2) Higher visible light catalytic activity. The prepared insertion type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array has excellent environmental benefit.
The above examples are only intended to illustrate the technical solution of the present invention and not to be restrictive in strict terms, and it will be understood by those skilled in the art that various changes in the details or forms thereof may be made without departing from the spirit and scope of the present invention as defined in the claims.
Claims (9)
1. A preparation method of a plug-in type molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array visible-light-induced photocatalyst is characterized in that a pure titanium sheet is subjected to anodic oxidation and then is calcined in a muffle furnace, the calcination condition parameters are regulated and controlled, porous wall titanium dioxide nanotubes are prepared, molybdenum sulfide is inserted into partial porous side walls in a plug-in type manner by utilizing a solvothermal method, the photoresponse range of the porous wall titanium dioxide nanotube array visible-light-induced photocatalyst is widened while the adsorption and mass transfer functions of the porous walls are not hindered, and the plug-in type molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array visible-light-induced photocatalyst is prepared;
the method comprises the following steps:
(1) pretreatment: taking a pure titanium sheet, sequentially putting the pure titanium sheet into absolute ethyl alcohol and deionized water for ultrasonic treatment, drying the pure titanium sheet at room temperature in the air, then polishing a sample by adopting an electrochemical method, taking the pure titanium sheet as a cathode, taking the cleaned and dried pure titanium sheet as an anode, taking a polishing solution which is an Ethylene Glycol (EG) solution containing sodium chloride, polishing the pure titanium sheet under a direct current constant voltage until the titanium sheet is bright and traceless, finally ultrasonically cleaning the pure titanium sheet by using the absolute ethyl alcohol and the deionized water, and drying the pure titanium sheet at room temperature to obtain a pretreated pure titanium sheet;
(2) anodic oxidation: adopting a two-electrode system, wherein a cathode is a pure titanium sheet, an anode is the pretreated pure titanium sheet obtained in the step (1), and an electrolyte is a glycol solution containing ammonium fluoride and deionized water; carrying out anodic oxidation under a direct current constant voltage without maintaining the temperature of the electrolyte and stirring; after reaction, the mixture is placed into absolute ethyl alcohol to be soaked for 20-40 min and then is naturally dried at room temperature to obtain amorphous TiO2A nanotube array; the concentration of the ammonium fluoride is 0.3-1.0 wt%; the volume of the deionized water is 1-5 vol%; the volume of the electrolyte is 65-75 mL;
(3) and (3) calcining: the amorphous TiO obtained in the step (2)2Placing the nanotube array in a muffle furnace for high-temperature calcination in air atmosphere to obtain porous wall TiO2A nanotube array;
(4) preparing an insertion piece type molybdenum sulfide gap doped porous wall titanium dioxide nanotube array: TiO with porous wall obtained in the step (3)2Placing the nanotube array in a reaction kettle, adding sodium molybdate, thioacetamide and deionized water, taking out after reaction, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying at room temperature for later use; placing the dried sample in a tube furnace for high-temperature calcination, N2Performing atmosphere to obtain an inserted molybdenum sulfide doped porous wall titanium dioxide nanotube array; the addition amount of the sodium molybdate is 5-50 mg; the addition amount of the thioacetamide is 10-100 mg; the addition amount of the deionized water is 10-30 mL.
2. The method for preparing the plug-in molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array visible light catalyst according to claim 1, wherein in the step (1), the pure titanium sheet; the thickness of the titanium sheet is 1-3 mm, and the mass fraction of the titanium element is not less than 99.9%; the ultrasonic cleaning time is 10-30 min, the drying temperature at room temperature is 20-30 ℃, and the drying time is 1-2 h.
3. The insert-type molybdenum sulfide gap-doped porous wall titanium dioxide nano-meter according to claim 1The preparation method of the tube array visible-light-driven photocatalyst is characterized in that in the step (1), the effective area of the cathode pure titanium sheet is 350-450 mm2The back surface of the cathode pure titanium sheet is covered by an adhesive tape, and the effective area of the anode pure titanium sheet is 2 multiplied by 350-450 mm2(ii) a The distance between the cathode and the anode is 1-4 cm; the direct current voltage is 30-70V.
4. The preparation method of the plug-in molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array visible light catalyst according to claim 1, wherein in the step (2), the anodic oxidation voltage is in a range of 30-70V, the oxidation time is 1-3 h, the anodic oxidation temperature at room temperature is 20-30 ℃, the temperature of the electrolyte is not required to be maintained, and the stirring speed is 30-60 r/min.
5. The preparation method of the plug-in molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array visible light catalyst according to claim 1, wherein in the step (2), the drying temperature at room temperature is 20-35 ℃, and the drying time is 10-20 h.
6. The preparation method of the plug-in type molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array visible light catalyst according to claim 1, wherein in the step (3), the calcination temperature is 400-600 ℃, the calcination time is 1-3 h, and the temperature rise rate is 1-5 ℃/min;
the specific calcining method comprises the following steps: the temperature raising procedure comprises the steps of raising the temperature from room temperature to 240-260 ℃ at the speed of 2-4 ℃/min, keeping the temperature constant at 240-260 ℃ for 25-35 min, raising the temperature to 400-600 ℃ at the speed of 0.5-1.5 ℃/min, keeping the temperature constant for 1-4 h, and finally lowering the temperature to room temperature at the speed of 1-5 ℃/min.
7. The preparation method of the plug-in molybdenum sulfide gap-doped porous-wall titanium dioxide nanotube array visible-light-driven photocatalyst according to claim 1, wherein in the step (4), the reaction temperature is 150-250 ℃; the reaction time is 20-40 h; the calcining temperature of the tubular furnace is 350-850 ℃;
the specific calcining method of the tubular furnace comprises the following steps: n is a radical of2The temperature raising program under the atmosphere is as follows: the temperature is kept constant at 20-30 ℃ for 30-60 min, the temperature is increased from the room temperature to 400-450 ℃ at the speed of 3-6 ℃/min, the temperature is kept constant at 400-450 ℃ for 25-35 min, the temperature is increased to 400-500 ℃ at the speed of 0.5-1.5 ℃/min, the temperature is kept constant for 1-3 h, and finally the temperature is reduced to the room temperature at the speed of 1-5 ℃/min.
8. The visible light catalyst of the inserted molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array prepared by the preparation method of any one of claims 1 to 7.
9. The visible light photocatalyst of the inserted molybdenum sulfide gap-doped porous wall titanium dioxide nanotube array of claim 8 is applied to wastewater treatment or atmosphere purification.
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