CN110280274B - Based on TiO2Wide-spectral-response photocatalytic material of array optical waveguide and preparation method and application thereof - Google Patents
Based on TiO2Wide-spectral-response photocatalytic material of array optical waveguide and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
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Abstract
The invention relates to a method for preparing a catalyst based on TiO2The wide-spectrum response photocatalytic material of the array optical waveguide comprises an optical fiber, wherein TiO grows on the surface of the optical fiber in situ2An array; the TiO is2Visible light photocatalyst or/and near infrared photocatalyst is grown in situ on the array. The invention grows TiO on the surface of the optical fiber in situ2The array realizes the immobilization of the catalytic material, and avoids the problems of aggregation and easy shedding of the titanium dioxide catalyst. By growing TiO in situ on the surface of the optical fibre2Array and visible light response CdS and near infrared light response WS constructed on array2The organic dye represented by methyl orange is efficiently degraded under full-spectrum sunlight by continuous photocatalysis, and the organic dye can be effectively degraded by a continuous photocatalytic degradation system.
Description
Technical Field
The invention relates to a method for preparing a catalyst based on TiO2A wide-spectrum response photocatalytic material of an array optical waveguide and a preparation method thereof belong to the technical field of photocatalytic materials.
Background
In recent years, social and economic development is seriously affected by pollution of water and the atmosphere. In order to solve the problem of environmental pollution, various means such as fenton's method, combustion method, microbial treatment, membrane treatment, etc. have been developed and utilized. With the development of semiconductor photocatalysis research, a photocatalysis technology is used as a technical means for photodegrading organic pollutants to solve the problem of environmental pollution, and the attention degree of researchers is greatly improved. Various means such as structure regulation and control, morphology regulation and control and the like are applied to the research of preparing the high-efficiency photocatalytic material. MakingTiO, the earliest discovered photocatalytic material2Is considered to have the most practical industrial application value and is researched and applied most widely. Current stage TiO2As the most stable photocatalytic material, the mass preparation technology can be realized, the performance regulation and control of the photocatalytic material also have remarkable progress, and the photocatalytic material is the photocatalytic material which is most likely to realize practical application at present. However, there is a practical conflict that limits its industrial application, i.e. TiO2The increase in photocatalytic efficiency requires more active surface, limits the size of the catalyst material, and the small size of TiO2The solid-liquid separation and recycling after the catalytic reaction are very difficult, and therefore, the development of the catalyst based on TiO is under way2In the process of the photocatalytic material, various solid-liquid separation processes are avoided by adopting an immobilization mode. Such as loading the photocatalytic material on a glass fiber felt, loading on a filter membrane, directly loading on the wall of a container, loading the photocatalytic material in a zeolite structure, and the like. This structure does solve the problem of separation of the photocatalytic material from the treatment liquid, but not only the substrates, which are themselves opaque, absorb light, but also the sewage itself absorbs a large amount of light, resulting in a low utilization rate of the light source by photocatalysis, and at the same time, because of the TiO2The forbidden band width limits the absorption of visible light and near infrared light under sunlight, and reduces the utilization rate of the sunlight. By effectively in TiO2The secondary structure is loaded with visible light or near infrared light catalyst to form a composite structure for expanding spectrum absorption, which is to improve TiO2Effective means of light absorption range, but how to better utilize different wavelengths of sunlight in their composite structures remains a challenge.
Optical fibers are well known as important pathways for optical propagation, and thus composites by constructing photocatalytic materials on optical fibers have been proposed and studied. Based on the optical propagation path of the optical fiber, the loss of ineffective light absorption can be overcome. This structural design was first proposed by Marinangeli and Ollis and theoretical studies were carried out, and then experiments for adhering TiO2 to an optical fiber using silica gel or the like were also successful and fundamental application studies on water treatment were carried out. Furthermore, the deposition of the catalyst on the optical fiber is also obtained by means of calcination after hydrolysis of the alkoxide of titanium, or by means of calcination after sol-gel coating.
However, the above methods are all loaded on the optical fiber by a chemical adhesion or sintering adhesion manner, the catalyst is easily in an agglomerated state, and the exposure of the catalytic active sites is limited, and in addition, the agglomeration of the nanoparticles can cause that photogenerated carriers generated inside are not easily transported to the surface of the catalyst, and the improvement of the catalytic efficiency is limited. In the loading mode, a large amount of residual stress exists in the obtained catalyst membrane, so that the catalyst membrane is easy to fall off in use, and the composite catalytic material is ineffective.
On the other hand, the single photocatalytic material is only used for a certain wavelength band in the spectrum, and the utilization efficiency of light is seriously affected, so that the design and research of the photocatalytic material capable of being used in multiple wavelength bands in the spectrum are realized, the utilization rate of light is improved, and the technical problem to be solved by the technical personnel in the field is urgently needed. The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a TiO-based material2A wide-spectrum response photocatalytic material of an array optical waveguide and a preparation method thereof. The invention grows TiO on the surface of the optical fiber2Array to realize the immobilization of catalytic material and the light is led out from the optical fiber and enters into TiO2Arrayed and deposited by TiO2Visible light, WS, with secondary structure CdS and the like constructed on the array2The near infrared photocatalyst allows light to pass from the optical fiber to the TiO2Single crystal arrays to CdS visible light catalyst or WS2The near-infrared catalyst is a light propagation path, so that the promotion of the photocatalytic active sites of the material and the utilization rate of the broadened spectrum are realized, and the high-efficiency internally-communicated photocatalytic composite material is obtained.
The technical scheme of the invention is as follows:
based on TiO2The wide-spectrum response photocatalytic material for the array optical waveguide comprises an optical fiber, wherein TiO is grown on the surface of the optical fiber in situ2An array; the TiO is2Visible light photocatalyst grown in situ on the array orAnd/or near infrared photocatalyst.
According to the invention, preferably, the visible light photocatalyst is CdS, and the near infrared photocatalyst is WS2。
According to the present invention, preferably, the optical fiber is a silica optical fiber.
According to the invention, preferably, the TiO is2The array is composed of nano rods with the length of 0.5-2 microns and nano dendrites with the length of 5-20 nanometers on the nano rods, and the nano dendrites uniformly grow on the quartz optical fiber and pass through TiO2Nanorod and CdS/WS formed thereon2TiO constructed by nano-dendrite2An array of secondary structures.
According to the invention, preferably, the TiO is2The array is subjected to hydrothermal loading at excess synthesis concentration to ensure TiO2The array can be fully and uniformly loaded on the surface of the optical quartz fiber, so that the degradation catalytic reaction is carried out by utilizing ultraviolet light in a full spectrum in a maximum absorption manner. Preferably, TiO on the surface of the optical fiber2The thickness of the uniform coverage is 5-10 microns.
According to the invention, preferably, TiO2、CdS、WS2The mass ratio of the three components is 1: (0.1-0.5): (0.1-0.5), and the visible light and near infrared light in a full spectrum are utilized to carry out degradation catalytic reaction with maximum absorption.
According to the invention, the above-mentioned TiO-based material2The preparation method of the wide spectral response photocatalytic material of the array optical waveguide comprises the following steps:
providing a titanium salt solution, placing the optical fiber in the titanium salt solution, and carrying out hydrothermal reaction at 160-2An array functional optical fiber;
providing a solution of cadmium salt, adding TiO2Soaking the array functional fiber in cadmium salt solution, adding ammonia water and thiourea, and reacting in 70-90 deg.C water bath to obtain CdS/TiO2An array functional optical fiber;
or/and providing a tungsten salt solution and adding TiO2Array functional fiber or CdS/TiO2Placing the array functional fiber in a tungsten salt solution, impregnating, and calcining at 400-600 ℃ in an inert atmosphere to obtain WS2/TiO2Array functional fiber, or WS2/CdS/TiO2And (4) array functional optical fibers.
According to the invention, preferably, the titanium salt is K2TiO(C2O4)2(ii) a Preferably, the solvent of the titanium salt solution is a mixed solvent of water and diethylene glycol (DEG), and more preferably, the volume ratio of water to diethylene glycol is 1: 3;
preferably, the concentration of the titanium salt solution is 0.04-0.06 mol/L.
According to the invention, preferably, the cadmium salt solution is a mixed aqueous solution of trisodium citrate and cadmium chloride; preferably, the concentration of the cadmium salt aqueous solution is 0.05 mol/L; preferably, the mole ratio of the trisodium citrate to the cadmium chloride to the ammonia water to the thiourea is (2-2.5): 1:0.2:4.
According to the present invention, preferably, the tungsten salt solution is (NH)4)2WS4The concentration of the aqueous solution is 4-6 mmol/L. Preferably, the inert gas is argon; the calcination time is 4-6 hours.
According to the invention, the optical fiber is preferably placed vertically in a titanium salt solution. Titanium dioxide grows in situ on the surface of the optical fiber.
According to the invention, the optical fiber is preferably pretreated before growing as follows:
an optical fiber with a needle-shaped incident end is prepared by an array manufacturing and etching method, and then is soaked in a mixed solution of sulfuric acid and hydrogen peroxide. The process is to carry out the activation treatment of the surface of the optical fiber, so as to conveniently realize TiO2Growth on the surface, not simple deposition. Preferably, the mass concentration of the sulfuric acid is 70% and the mass concentration of the hydrogen peroxide is 30%. Preferably, the soaking temperature is 80-100 ℃; preferably, the method for preparing the optical fiber having the needle-shaped incident end comprises the following steps: gathering the optical fibers into bundles, pouring the optical fibers with gelatin, cutting the gathered ends into planes, then putting the planes into 5wt% HF aqueous solution, taking the planes out for 1 to 2 hours, and heating and dissolving the planes to remove the gelatin to obtain the optical fibers with the pinpoint structure.
According to the invention, said TiO-based material2Preparation method of wide spectral response photocatalytic material of array optical waveguide, and application thereofA preferred embodiment, comprises the steps of:
(1) soaking a commercial optical fiber (G652D) in acetone for more than 12 hours, removing a cladding, and sequentially ultrasonically cleaning the bare quartz optical fiber in acetone, ethanol and pure water;
(2) gathering the optical fibers into bundles, pouring the optical fibers with gelatin, cutting the gathered ends into planes, then putting the planes into 5wt% of HF aqueous solution, taking the optical fibers out and cleaning the optical fibers after 1 to 2 hours, and heating and dissolving the optical fibers to remove the gelatin to obtain the optical fibers with the pinpoint structure;
(3) the optical fiber was immersed in 70 wt% sulfuric acid and 30 wt% H2O2Soaking the mixed solution at 90 deg.C for 1 hr, and cleaning with clear water; the process is to carry out the activation treatment of the surface of the optical fiber, thereby being convenient for realizing TiO2Growth on the surface, rather than simple deposition;
(4) adding 8mmol K2TiO(C2O4)2Adding 160mL of deionized water and diethylene glycol (DEG) mixed solvent in a volume of 1: 3; transferring the solution into a 200 ml stainless steel autoclave with a polytetrafluoroethylene lining; one end of the quartz fiber is bundled by a polytetrafluoroethylene adhesive tape and is vertically placed in a polytetrafluoroethylene lining, and the bundling side faces downwards; subjecting the sample to hydrothermal treatment at 180 deg.C for 3-9 h, thoroughly washing with deionized water, and drying at 80 deg.C overnight to obtain TiO2An array functional optical fiber;
(5) adding trisodium citrate (0.03g/ml) and cadmium chloride (0.01g/ml) into 30ml of deionized water, and growing TiO in situ2The arrayed optical fibers were immersed for 1 hour, then 1.5 ml of 28 wt% ammonia water and 14 ml of thiourea (0.015g/ml) were added, gently stirred in a water bath at 80 ℃ for 3 hours, thoroughly washed with deionized water, and vacuum-dried at 60 ℃ overnight to obtain CdS/TiO2An array functional optical fiber;
(6) CdS/TiO2The array functional fiber was soaked in 30mL of 5mM (NH)4)2WS4After 20h in the solution, drying at 60 ℃ for 2h, calcining the functional optical fiber at 500 ℃ for 5 h in an argon-filled atmosphere to obtain WS2/CdS/TiO2And (4) array functional optical fibers.
According to the invention, said TiO-based material2The wide-spectrum response photocatalytic material of the array optical waveguide is applied to photocatalytic sewage treatment. Preferably, the application method comprises the following steps:
let WS be2/CdS/TiO2One end of the array functional optical fiber tip is gathered into a bundle and is coupled with the LED lamp through silica gel to carry out photocatalytic sewage treatment. Preferably, a plurality of coupling structures can be connected in series, and continuous photocatalytic treatment is realized by utilizing a multi-stage similar structure. The assembled processing device is shown in fig. 5.
The invention has the beneficial effects that:
1. the invention grows TiO on the surface of the optical fiber in situ2The array realizes the immobilization of the catalytic material, and avoids the problems of aggregation and easy shedding of the titanium dioxide catalyst.
2. According to the invention, by TiO2Constructing visible light catalyst, WS, with secondary structure, such as CdS2The near infrared photocatalyst allows light to pass from the optical fiber to the TiO2Single crystal arrays to CdS visible light catalyst or WS2The near-infrared catalyst is a light propagation path, so that the promotion of the photocatalytic active sites of the material and the utilization rate of the broadened spectrum are realized, and the high-efficiency internally-communicated photocatalytic composite material is obtained.
3. The invention grows TiO on the surface of the optical fiber in situ2Array and visible light response CdS and near infrared light response WS constructed on array2The organic dye represented by methyl orange is efficiently degraded under full-spectrum sunlight by continuous photocatalysis, and the organic dye can be effectively degraded by a continuous photocatalytic degradation system.
Drawings
FIG. 1 shows TiO obtained in example 12TiO in array functional optical fiber2Scanning Electron Micrographs (SEM) at different magnifications.
FIG. 2 shows TiO obtained in example 12The array function fiber optic propagates the image.
FIG. 3 shows TiO obtained in example 12And (3) an array functional optical fiber light propagation simulation diagram.
FIG. 4 shows WS obtained in example 12/CdS/TiO2Schematic diagram of array functional fiber.
FIG. 5 is a photograph of the integrated continuous photocatalytic device in test example 1.
FIG. 6 is a graph showing the results of pollutant degradation performance data of the integrated continuous photocatalytic device in test example 1.
Detailed Description
The invention is further described, but not limited to, by the following examples in conjunction with the accompanying drawings.
Example 1
Based on TiO2The preparation method of the wide spectral response photocatalytic material of the array optical waveguide comprises the following steps:
(1) soaking a commercial optical fiber (G652D) in acetone for more than 12 hours, removing a cladding, and sequentially ultrasonically cleaning the bare quartz optical fiber in acetone, ethanol and pure water;
(2) gathering the optical fibers into bundles, pouring the optical fibers with gelatin, cutting the gathered ends into planes, then putting the planes into 5wt% of HF aqueous solution, taking the optical fibers out and cleaning the optical fibers after 1 to 2 hours, and heating and dissolving the optical fibers to remove the gelatin to obtain the optical fibers with the pinpoint structure;
(3) the optical fiber was immersed in 70 wt% sulfuric acid and 30 wt% H2O2Soaking the mixed solution at 90 deg.C for 1 hr, and cleaning with clear water; the process is to carry out the activation treatment of the surface of the optical fiber, thereby being convenient for realizing TiO2Growth on the surface, rather than simple deposition;
(4) adding 8mmol of K2TiO(C2O4)2Adding 160mL of deionized water and diethylene glycol (DEG) mixed solvent in a volume of 1: 3; transferring the solution into a 200 ml stainless steel autoclave with a polytetrafluoroethylene lining; one end of the quartz fiber is bundled by a polytetrafluoroethylene adhesive tape and is vertically placed in a polytetrafluoroethylene lining, and the bundling side faces downwards; subjecting the sample to hydrothermal treatment at 180 deg.C for 3-9 h, thoroughly washing with deionized water, and drying at 80 deg.C overnight to obtain TiO2An array functional optical fiber;
(5) trisodium citrate (0.03g/ml) and cadmium chloride (0.01g/ml) were added to 30ml of deionized waterIn-situ growth of TiO2The arrayed optical fibers were immersed for 1 hour, then 1.5 ml of 28 wt% ammonia water and 14 ml of thiourea (0.015g/ml) were added, gently stirred in a water bath at 80 ℃ for 3 hours, thoroughly washed with deionized water, and vacuum-dried at 60 ℃ overnight to obtain CdS/TiO2An array functional optical fiber;
(6) CdS/TiO2The array functional fiber was soaked in 30mL of 5mM (NH)4)2WS4After 20h in the solution, drying at 60 ℃ for 2h, calcining the functional optical fiber at 500 ℃ for 5 h in an argon-filled atmosphere to obtain WS2/CdS/TiO2And (4) array functional optical fibers.
TiO obtained in this example2TiO in array functional optical fiber2Scanning Electron Microscope (SEM) and WS2/CdS/TiO2A Transmission Electron Microscope (TEM) is shown in FIG. 1. From FIG. 1, it can be seen that TiO2The nano array realizes full coverage on quartz optical fiber, TiO2The thickness of the uniform coating is about 7 μm, wherein the TiO2The array consists of nanorods with the length of 1 micron and micro nano-crystals growing on the nanorods with the length of about 10 nanometers, and the micro-nano-crystals grow on the quartz optical fiber uniformly and pass through TiO2Nanorod and CdS/WS formed thereon2TiO constructed by nano-dendrite2An array of secondary structures.
The TiO obtained in this example was added2The array functional fiber was subjected to light propagation image testing as shown in fig. 2. From FIG. 2, it can be seen that TiO2The light propagation path of the array-covered quartz optical fiber is single-sided light irradiation, the titanium dioxide coated fiber has a white appearance, and as the incident light increases, there is a release of light on the silica fiber acted on by the titanium dioxide, because, for bare silica fibers, most of the light is reflected into the silica at the silica-air interface due to the higher refractive index of silica (-1.54). Also for TiO2Coated quartz optical fibre, TiO2Has a higher refractive index, light will be in TiO2-SiO2Refraction to TiO at the interface2In the middle, incident light and emergent light are simulated in the presence of TiO as shown in FIG. 32Of covered quartz fibres, fibre-TiO2Interface directs light toward the TiO2Propagating, causing a significant amount of light to escape from the fiber. This is consistent with the study of light transmission under red laser in bare silica fibers and titania functional silica fibers. The simulation diagram of light propagation is shown in fig. 3.
WS obtained in this example2/CdS/TiO2A schematic diagram of an arrayed functional fiber is shown in fig. 4. As can be seen from fig. 4, the present invention can realize the utilization and catalysis of ultraviolet, visible light, and near-infrared broad spectrum, and has a high light utilization rate.
Example 2
TiO with secondary structure2The preparation method of the supported optical fiber photocatalytic material comprises the following steps:
(1) soaking a commercial optical fiber (G652D) in acetone for more than 12 hours, removing a cladding, and sequentially ultrasonically cleaning the bare quartz optical fiber in acetone, ethanol and pure water;
(2) gathering the optical fibers into bundles, pouring the optical fibers with gelatin, cutting the gathered ends into planes, then putting the planes into 5wt% of HF aqueous solution, taking the planes out for 2 hours, cleaning the planes, and heating and dissolving the planes to remove the gelatin to obtain the optical fibers with the pinpoint structure;
(3) the optical fiber was immersed in 70 wt% sulfuric acid and 30 wt% H2O2Soaking the mixed solution at 90 deg.C for 1 hr, and cleaning with clear water; the process is to carry out the activation treatment of the surface of the optical fiber, thereby being convenient for realizing TiO2Growth on the surface, rather than simple deposition;
(4) 6.5mmol of K2TiO(C2O4)2Adding 160mL of mixed solvent consisting of deionized water and diethylene glycol (DEG) according to the volume ratio of 1: 3; transferring the solution into a 200 ml stainless steel autoclave with a polytetrafluoroethylene lining; one end of the quartz fiber is bundled by a polytetrafluoroethylene adhesive tape and is vertically placed in a polytetrafluoroethylene lining, and the bundling side faces downwards; subjecting the sample to hydrothermal treatment at 160 deg.C for 9h, thoroughly washing with deionized water, and drying at 90 deg.C overnight to obtain TiO2An array functional optical fiber;
(5) trisodium citrate (0.03g/ml) and cadmium chloride (0.01g/ml) were added to 30ml of deionised waterIn-situ growth of TiO in water2The arrayed optical fibers were immersed for 1 hour, then 1.5 ml of 28 wt% ammonia water and 14 ml of thiourea (0.015g/ml) were added, gently stirred in a water bath at 80 ℃ for 3 hours, thoroughly washed with deionized water, and vacuum-dried at 60 ℃ overnight to obtain CdS/TiO2And (4) array functional optical fibers.
Example 3
TiO with secondary structure2The preparation method of the supported optical fiber photocatalytic material comprises the following steps:
(1) soaking a commercial optical fiber (G652D) in acetone for more than 12 hours, removing a cladding, and sequentially ultrasonically cleaning the bare quartz optical fiber in acetone, ethanol and pure water;
(2) gathering the optical fibers into bundles, pouring the optical fibers with gelatin, cutting the gathered ends into planes, then putting the planes into 5wt% of HF aqueous solution, taking the planes out for 2 hours, cleaning the planes, and heating and dissolving the planes to remove the gelatin to obtain the optical fibers with the pinpoint structure;
(3) the optical fiber was immersed in 70 wt% sulfuric acid and 30 wt% H2O2Soaking the mixed solution at 90 deg.C for 1 hr, and cleaning with clear water; the process is to carry out the activation treatment of the surface of the optical fiber, thereby being convenient for realizing TiO2Growth on the surface, rather than simple deposition;
(4) adding 9mmol of K2TiO(C2O4)2Adding 160mL of mixed solvent consisting of deionized water and diethylene glycol (DEG) according to the volume ratio of 1: 3; transferring the solution into a 200 ml stainless steel autoclave with a polytetrafluoroethylene lining; one end of the quartz fiber is bundled by a polytetrafluoroethylene adhesive tape and is vertically placed in a polytetrafluoroethylene lining, and the bundling side faces downwards; subjecting the sample to hydrothermal treatment at 190 deg.C for 4 hr, thoroughly washing with deionized water, and drying at 70 deg.C overnight to obtain TiO2An array functional optical fiber;
(5) adding TiO into the mixture2The array functional fiber was soaked in 30mL of 5mM (NH)4)2WS4After 20h in the solution, drying at 60 ℃ for 2h, calcining the functional optical fiber at 500 ℃ for 5 h in an argon-filled atmosphere to obtain WS2/TiO2And (4) array functional optical fibers.
Comparative example 1
On the basis of adsorption, P25 (a TiO)2Nanoparticles) are coated on a light guide quartz fiber, the pretreated quartz fiber is soaked in NaOH solution for two hours, the surface of the quartz fiber is modified with more-OH, 50mgP25 is dispersed in water by ultrasonic waves, the quartz fiber with the surface modified with-OH is soaked in P25 dispersion liquid for 12 hours, the quartz fiber is slightly washed by deionized water and dried to obtain the quartz fiber covered by P25.
Comparative example 2
Tetrabutyltitanate (8.5mL) and diethanolamine (2.5mL) were dissolved in 35.5mL ethanol, followed by stirring at room temperature for 10min, followed by addition of 0.5mL water and subsequent stirring for 1 h. The optical fiber was dip coated at a rate of 1 mm/s. Finally, calcining the optical fiber after dip coating in the air at 600 ℃ for 6h to obtain TiO2And (3) functional fibers.
Comparative example 3
As shown in example 1, except that:
omitting steps (5) and (6) to obtain TiO2And (4) array functional optical fibers.
Test example 1
WS obtained in example 12/CdS/TiO2One end of the array functional optical fiber tip is gathered into a bundle and is coupled with the LED lamp through silica gel to carry out integrated continuous photocatalytic sewage treatment. A photograph of the integrated continuous photocatalytic device is shown in FIG. 5.
The integrated continuous photocatalytic device consists of six photocatalytic reaction systems (namely TiO)2The loaded fiber optic tips are gathered into a bundle at one end and coupled to an LED lamp via silica gel to form a reaction system). The methyl orange solution was flowed through the assembled reaction apparatus by a peristaltic pump at a rate of 5 mL/min. The color of the methyl orange is continuously decolored in the photocatalytic reaction device, and the methyl orange is basically colorless after flowing through the sixth coupling system. The photograph of FIG. 4 is an image taken after the reaction apparatus was operated for 1 hour, indicating that the reaction apparatus had some stability.
The test results are shown in fig. 6.
The results of the quantitative degradation test for the continuous photocatalytic degradation of methyl orange by each coupled system are shown in fig. 6. Each photocatalytic coupling system can degrade methyl orange by 20% in the process of flowing methyl orange.
Test example 2
The experiment of comparing whether example 1 and comparative examples 1 and 2 can be uniformly grown in the silica fiber by a scanning electron microscope proves that the TiO grown in example 12The structure can grow uniformly on the surface, while the comparative examples 1 and 2 have the condition of agglomeration and non-uniform growth. At the same time, loading TiO by different methods2The quartz fiber is slightly ultrasonically treated to judge the firmness of the three samples, and experiments show that the example 1 is slightly ultrasonically treated in water and does not shed TiO2The aqueous solution was clear with no white nanoparticles, whereas comparative examples 1,2 showed exfoliation of the nanoparticles, with some white turbidity in the aqueous solution, demonstrating that example 1 was more robust than comparative examples 1, 2.
Test example 3
TiO formed by growing example 1 and comparative examples 1,2, 32The integrated continuous photocatalysis device constructed by the quartz optical fiber with the secondary structure consists of six photocatalytic reaction systems (namely, the method is the same as that of the embodiment 1, and the methods of the comparative examples 1,2 and 3 adopt TiO2The ends of the tips of the optical fibers loaded by the secondary structure constructed for the base are gathered into a bundle and are coupled with a full-spectrum LED lamp through silica gel to form a reaction system). The methyl orange solution was flowed through the assembled reaction apparatus by a peristaltic pump at a rate of 5 mL/min. The degradation performance of the continuous photocatalytic reaction device composed of the example 1 and the comparative examples 1,2 and 3 is compared by testing the degradation amount of methyl orange.
The results show that comparative examples 1,2 have a degradation rate of 50% for five hours, comparative example 3 has a degradation rate of 80% under the same conditions, and example 1 has a degradation rate of 100% under the same conditions, under the conditions of 20mg/L methyl orange degradation under full spectrum sunlight. Compared with comparative examples 1 and 2, the degradation efficiency is improved by 50% under the same conditions; example 1 was photocatalytic at full spectrum, further increasing the degradation rate compared to comparative example 3.
Claims (7)
1. Based on TiO2The wide-spectrum response photocatalytic material of the array optical waveguide is characterized by comprising an optical fiber, wherein TiO is grown on the surface of the optical fiber in situ2An array; the TiO is2Visible light photocatalyst and near infrared photocatalyst grow in situ on the array;
the visible light photocatalyst is CdS, and the near infrared photocatalyst is WS2；
The TiO is2The array is composed of nano rods with the length of 0.5-2 microns and nano dendrites with the length of 5-20 nanometers on the nano rods, and the nano dendrites uniformly grow on the quartz optical fiber and pass through TiO2Nanorod and CdS/WS formed thereon2TiO constructed by nano-dendrite2A secondary structure array;
TiO on the surface of optical fiber2The thickness of the uniform covering is 5-10 microns, TiO2、CdS、WS2The mass ratio of the three components is 1: (0.1-0.5): (0.1-0.5).
2. The TiO-based according to claim 12The wide-spectrum response photocatalytic material of the array optical waveguide is characterized in that the optical fiber is a quartz optical fiber.
3. The TiO-based material according to any one of claims 1 to 22The preparation method of the wide spectral response photocatalytic material of the array optical waveguide comprises the following steps:
providing a titanium salt solution, placing the optical fiber in the titanium salt solution, and carrying out hydrothermal reaction at 160-2An array functional optical fiber;
providing a solution of cadmium salt, adding TiO2Soaking the array functional fiber in cadmium salt solution, adding ammonia water and thiourea, and reacting in 70-90 deg.C water bath to obtain CdS/TiO2An array functional optical fiber;
providing a tungsten salt solution, and adding CdS/TiO2Placing the array functional fiber in a tungsten salt solution, impregnating, and calcining at 400-600 ℃ in an inert atmosphere to obtain WS2/CdS/TiO2And (4) array functional optical fibers.
4. TiO-based according to claim 32The preparation method of the wide spectral response photocatalytic material of the array optical waveguide is characterized in that the titanium salt is K2TiO(C2O4)2(ii) a The solvent of the titanium salt solution is a mixed solvent of water and diethylene glycol (DEG), and the volume ratio of the water to the diethylene glycol is 1: 3; the concentration of the titanium salt solution is 0.04-0.06 mol/L.
5. TiO-based according to claim 32The preparation method of the wide spectral response photocatalytic material of the array optical waveguide is characterized in that the cadmium salt solution is a mixed aqueous solution of trisodium citrate and cadmium chloride, and the concentration of the cadmium salt aqueous solution is 0.05 mol/L; the mole ratio of trisodium citrate, cadmium chloride, ammonia water and thiourea is (2-2.5): 1:0.2: 4;
the tungsten salt solution is (NH)4)2WS4The concentration of the aqueous solution is 4-6 mmol/L;
the optical fiber is vertically placed in a titanium salt solution, and titanium dioxide grows in situ on the surface of the optical fiber.
6. TiO-based according to claim 32The preparation method of the wide spectral response photocatalytic material of the array optical waveguide is characterized in that the following pretreatment is carried out before the optical fiber grows:
preparing an optical fiber with a needle-shaped incident end by adopting an array manufacturing and etching method, and then soaking the optical fiber in a mixed solution of sulfuric acid and hydrogen peroxide;
the method for preparing the optical fiber with the needle-shaped incident end comprises the following steps: gathering the optical fibers into bundles, pouring the optical fibers with gelatin, cutting the gathered ends into planes, then putting the planes into 5wt% HF aqueous solution, taking the planes out for 1 to 2 hours, and heating and dissolving the planes to remove the gelatin to obtain the optical fibers with the pinpoint structure.
7. The TiO-based material according to any one of claims 1 to 22The wide-spectrum response photocatalytic material of the array optical waveguide is applied to photocatalytic sewage treatment.
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