CN110280274A - One kind being based on TiO2Wide spectrum responsible photocatalytic material of array optical waveguide and the preparation method and application thereof - Google Patents
One kind being based on TiO2Wide spectrum responsible photocatalytic material of array optical waveguide and the preparation method and application thereof Download PDFInfo
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- CN110280274A CN110280274A CN201910705588.3A CN201910705588A CN110280274A CN 110280274 A CN110280274 A CN 110280274A CN 201910705588 A CN201910705588 A CN 201910705588A CN 110280274 A CN110280274 A CN 110280274A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 111
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 claims abstract description 20
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- 229940038773 trisodium citrate Drugs 0.000 claims description 6
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- 239000004408 titanium dioxide Substances 0.000 claims description 4
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052719 titanium Inorganic materials 0.000 abstract description 2
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- 230000008569 process Effects 0.000 description 9
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to one kind to be based on TiO2Wide spectrum responsible photocatalytic material of array optical waveguide and the preparation method and application thereof, the catalysis material include optical fiber, and the optical fiber surface growth in situ has TiO2Array；The TiO2Growth in situ has visible-light photocatalyst or/and near infrared light catalyst on array.The present invention passes through in optical fiber surface growth in situ TiO2Array, Lai Shixian catalysis material it is immobilized, the aggregation of titanium deoxide catalyst is avoided, the problem of being easy to fall off.By growing TiO in optical fiber surface in situ2Array and the WS that building is responded on array with visible light-responded CdS and near infrared light2For the secondary structure of representative, realizes continuous photocatalysis and degraded efficiently under full spectrum sunlight using methyl orange as the organic dyestuff of representative, it, being capable of effective degradating organic dye by continuous photocatalytic degradation system.
Description
Technical field
The present invention relates to one kind to be based on TiO2Wide spectrum responsible photocatalytic material of array optical waveguide and preparation method thereof belongs to
In catalysis material technical field.
Background technique
In recent years, water body and the seriously polluted of atmosphere affect society and expanding economy.It is asked to solve environmental pollution
Topic, many means, such as Fenton process, combustion method, microbiological treatment, film process, are developed and utilized.With conductor photocatalysis
Research carry out, photocatalysis technology solves the technological means of problem of environmental pollution, studied as light degradation organic pollutant
The degree of concern of person greatly improves.The means such as various structure regulatings, Morphological control are in the research for preparing high-efficiency photocatalysis material
It is applied.As the catalysis material found earliest, TiO2It is considered most industrial practical application value and obtains most extensively
Research and application.Current stage TiO2As catalysis material the most stable, mass technology of preparing can be real
Existing, it is the catalysis material for most possibly realizing practical application at this stage that performance regulation, which also has significant progress,.However, existing
There are conflicts to limit its industrial applications, i.e. TiO in reality2The promotion of photocatalysis efficiency needs more active faces, limit
Make the size of catalyst material, and the TiO of small size2Separation of solid and liquid and recycling after reacting for catalysis bring huge
Big difficulty, then, people are based on TiO in exploitation2Catalysis material during, propose a variety of by immobilized mode
To avoid the demand to separation of solid and liquid process.Such as catalysis material is supported on glass mat, is supported on filter membrane, directly
It connects and is loaded on container wall, in zeolite structured middle load catalysis material etc..This structure solves photocatalysis really
The separation problem of material and treatment liquid, but it is not only that inherently lighttight substrate can absorb light, sewage itself for these
It is a large amount of to absorb light, cause photocatalysis very low to the utilization rate of light source, simultaneously as TiO2Forbidden bandwidth limit it in the sun
To visible light and near-infrared absorption under light, the utilization rate to sunlight is reduced.By effectively in TiO2Secondary structure
It is to improve TiO that upper load visible light or near infrared light catalyst, which form and expand the composite construction of spectral absorption,2Light abstraction width
Effective means, but how in its composite construction preferably using the sunlight of different wave length be still one challenge.
Optical fiber is the widely known important access for optical propagation, then passes through and constructs catalysis material on optical fiber
Composite material be also suggested, and carried out research.Propagation path of light based on optical fiber can overcome the damage of invalid light absorption
Consumption.The design of this structure has Marinangeli and Ollis to propose first, and has carried out theoretical research, then, utilizes silica gel etc.
The TiO2 experiment for being attached on optical fiber is also obtained into success, has carried out basic application study in water process.In addition, passing through titanium
Hydrolysis of alkoxide after the mode calcined or the mode calcined after sol-gel coating, also obtain the heavy of catalyst on optical fiber
Product.
But above method be all chemistry stick or be sintered stick by way of be supported on optical fiber, catalyst appearance
Aggregating state is easily presented, the exposure of its active site is limited, in addition, the aggregate of nano particle, will lead to internal production
Raw photo-generated carrier is not easy to be transported to catalyst surface, limits the promotion of its catalytic efficiency.This load model, obtains
Catalyst film there are a large amount of residual stress, cause using be easy in fall off so that composite catalyzing material failure.
On the other hand, it is only to be utilized to wave band a certain in spectrum using single catalysis material, seriously affects
The utilization efficiency of light, therefore design studies can be realized the catalysis material that multiband can utilize in spectrum, improve the utilization of light
Rate is those skilled in the art's technical problem urgently to be resolved.For this purpose, proposing the present invention.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of based on TiO2The wide spectrum responsible photocatalytic of array optical waveguide
Material and preparation method thereof.The present invention is by growing TiO in optical fiber surface2Array, Lai Shixian catalysis material it is immobilized, and realize
Light is exported from optical fiber enters TiO2Array, and pass through TiO2The visible lights such as secondary structure CdS, WS are constructed on array2Equal near-infrareds
Photochemical catalyst makes light from optical fiber to TiO2Crystal array, then arrive CdS visible light catalyst or WS2This light of near-infrared catalyst
Propagation path realizes the promotion of material light catalysis active site and the utilization rate for widening spectrum, obtains light passing light in efficient and urges
Change composite material.
Technical scheme is as follows:
One kind being based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide, including optical fiber, the optical fiber surface
Growth in situ has TiO2Array；The TiO2Growth in situ has visible-light photocatalyst or/and near infrared light catalysis on array
Agent.
, according to the invention it is preferred to, the visible-light photocatalyst is CdS, and the near infrared light catalyst is
WS2。
, according to the invention it is preferred to, the optical fiber is silica fibre.
, according to the invention it is preferred to, the TiO25-20 in the nanometer rods and nanometer rods that array is length 0.5-2 microns
The nanometer branch crystalline substance composition of nanometer, and be uniformly grown on silicon fiber, pass through TiO2Nanometer rods with thereon formed
CdS/WS2The TiO of nanometer branch crystalline substance building2Secondary structure array.
, according to the invention it is preferred to, the TiO2Array carries out hydro-thermal load in the case where excessively synthesizing concentration, to guarantee
TiO2Array can be full and uniform be supported in light guide quartz fiber surface, be absorbed and utilized in full spectrum to the greatest extent
Ultraviolet light carries out degradation catalysis reaction.Preferably, the TiO on optical fiber surface2Uniform fold with a thickness of 5-10 microns.
, according to the invention it is preferred to, TiO2、CdS、WS2The mass ratio of three is 1:(0.1-0.5): (0.1-0.5), with most
The visible and near infrared light of big degree being absorbed and utilized in full spectrum carries out degradation catalysis reaction.
According to the present invention, above-mentioned to be based on TiO2The preparation method of the wide spectrum responsible photocatalytic material of array optical waveguide, packet
It includes:
Titanium salt solution is provided, optical fiber is placed in titanium salt solution, in 160-200 DEG C of hydro-thermal reaction 3h-9h, obtains TiO2Array
Active optical fiber；
Cadmium salt soln is provided, by TiO2Array functional optical fiber, which is placed in cadmium salt soln, to be impregnated, and ammonium hydroxide and thiocarbamide is then added,
70-90 DEG C of water-bath, obtains CdS/TiO2Array functional optical fiber；
Or/and tungsten salt solution is provided, by TiO2Array functional optical fiber or CdS/TiO2It is molten that array functional optical fiber is placed in tungsten salt
In liquid, is calcined under an inert atmosphere in 400-600 DEG C again after dipping, obtain WS2/TiO2Array functional optical fiber or WS2/CdS/TiO2
Array functional optical fiber.
, according to the invention it is preferred to, the titanium salt is K2TiO(C2O4)2；Preferably, the solvent of titanium salt solution be water with
The mixed solvent of diethylene glycol (DEG) (DEG), it is further preferred that the volume ratio of water and diethylene glycol (DEG) is 1:3；
Preferably, the concentration of titanium salt solution is 0.04-0.06mol/L.
, according to the invention it is preferred to, the cadmium salt soln is the mixed aqueous solution of trisodium citrate and caddy；It is preferred that
, the concentration of cadmium salt aqueous solution is 0.05mol/L；Preferably, trisodium citrate, caddy, ammonium hydroxide, thiocarbamide molar ratio be
(2-2.5): 1:0.2:4.
, according to the invention it is preferred to, the tungsten salt solution is (NH4)2WS4Aqueous solution, concentration 4-6mmol/L.It is preferred that
, inert gas is argon gas；Calcination time is 4-6 hours.
, according to the invention it is preferred to, fiber perpendicular is placed in titanium salt solution.Titanium dioxide is in optical fiber surface growth in situ.
, according to the invention it is preferred to, it is pre-processed as follows before YAG Fiber Growth:
The method for being made and being etched of array prepares the optical fiber with needle-shaped incidence end, then in sulfuric acid and hydrogen peroxide
Immersion treatment in mixed solution.This process is to carry out the activation processing of optical fiber surface, is easy to implement TiO2Growth on surface,
Rather than simple deposition.Preferably, the mass concentration of sulfuric acid is 70%, and the mass concentration of hydrogen peroxide is 30%.Preferably, it impregnates
Temperature is 80-100 DEG C；Preferably, preparation has the method for the optical fiber of needle-shaped incidence end are as follows: gathers into bundles optical fiber, uses gelatin
It pours, is cut into plane at aggregation end, subsequently into 5wt%HF aqueous solution, by 1-2 hours, takes out after cleaning, dissolve by heating
Gelatin is removed, the optical fiber with needle point structure is obtained.
According to the present invention, described based on TiO2The preparation method of the wide spectrum responsible photocatalytic material of array optical waveguide,
A kind of preferred embodiment, comprises the following steps that
(1) business is impregnated 12 hours or more in acetone with optical fiber (G652D), after removing covering, by the quartz of naked leakage
Optical fiber is successively cleaned by ultrasonic in acetone, ethyl alcohol, pure water；
(2) optical fiber is gathered into bundles, is poured with gelatin, plane is cut at aggregation end, subsequently into 5wt%HF aqueous solution
In, it by 1-2 hours, takes out after cleaning, dissolves by heating removal gelatin, obtain the optical fiber with needle point structure；
(3) optical fiber is immersed in 70wt% sulfuric acid and the H of 30wt%2O2Mixed solution impregnates 1 hour in 90 DEG C, it
It is thoroughly cleaned with clear water afterwards；This process is to carry out the activation processing of optical fiber surface, is easy to implement TiO2Growth on surface, rather than
Simple deposition；
(4) by 8mmolK2TiO(C2O4)2The in the mixed solvent of 160mL deionized water and diethylene glycol (DEG) (DEG), volume is added
For 1:3；Solution is transferred in 200 milliliters of polytetrafluoroethyllining lining stainless steel autoclaves；Quartz fibre one end polytetrafluoroethylene (PTFE)
Adhesive tape is tied up, and is disposed vertically in polytetrafluoroethyllining lining, ties up side downward；Sample is used after 180 DEG C of hydro-thermal process 3h-9h
Deionized water is thoroughly cleaned, and dry a whole night, obtains TiO at 80 DEG C2Array functional optical fiber；
(5) citric acid (0.03g/ml) trisodium and caddy (0.01g/ml) are added in 30 ml deionized waters, it is former
Position growth TiO2The optical fiber of array was steeped into wherein 1 small time, and 1.5 milliliters of 28wt% ammonium hydroxide and 14 milliliters of thiocarbamide are added later
(0.015g/ml), it is 80 DEG C of water-bath light to stir 3 hours, it is thoroughly cleaned with deionized water, is dried in vacuo a whole night at 60 DEG C, obtains
CdS/TiO is arrived2Array functional optical fiber；
(6) by CdS/TiO2Array functional optical fiber is immersed in 30mL, and concentration is the (NH of 5mM4)2WS420h in solution, later
60 DEG C drying 2 hours again, then by the active optical fiber full of argon gas atmosphere under 500 DEG C of 5 hours of calcining, obtain WS2/CdS/
TiO2Array functional optical fiber.
According to the present invention, described to be based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide is at photocatalysis sewage
Application in reason.Preferably, application method are as follows:
By WS2/CdS/TiO2Array functional fiber optic tip one end gathers into bundles, and is coupled by silica gel with LED light, carries out light
It is catalyzed sewage treatment.Preferably, multiple coupled structures can be connected, using multistage homogeneous structure, realizes continuous photocatalysis treatment.
Processing unit after assembling, as shown in Figure 5.
Beneficial effects of the present invention:
1, the present invention is by optical fiber surface growth in situ TiO2Array, Lai Shixian catalysis material it is immobilized, avoid two
The aggregation of titanium oxide catalyst, the problem of being easy to fall off.
2, the present invention passes through TiO2The visible light catalysts such as secondary structure CdS, WS are constructed on array2Equal near infrared lights catalysis
Agent makes light from optical fiber to TiO2Crystal array, then arrive CdS visible light catalyst or WS2This light propagation road of near-infrared catalyst
Diameter realizes the promotion of material light catalysis active site and the utilization rate for widening spectrum, it is compound to obtain light passing photocatalysis in efficient
Material.
3, the present invention is by growing TiO in optical fiber surface in situ2Array and on array building with visible light-responded
CdS and near infrared light response WS2For the secondary structure of representative, continuous photocatalysis is realized efficiently in full spectrum sunlight
Lower degradation, being capable of effective degradating organic dye by continuous photocatalytic degradation system using methyl orange as the organic dyestuff of representative.
Detailed description of the invention
Fig. 1 is the TiO that embodiment 1 obtains2TiO in array functional optical fiber2The scanning electron microscope of different enlargement ratios is shone
Piece (SEM).
Fig. 2 is the TiO that embodiment 1 obtains2Array functional optical fiber light propagation image.
Fig. 3 is the TiO that embodiment 1 obtains2Array functional optical fiber light propagation analog simulation figure.
Fig. 4 is the WS that embodiment 1 obtains2/CdS/TiO2The schematic diagram of array functional optical fiber.
Fig. 5 is the continuous photocatalysis apparatus photo of integration in test example 1.
Fig. 6 is the continuous photocatalysis apparatus degradation of contaminant performance data results figure of integration in test example 1.
Specific embodiment
Below by specific embodiment and in conjunction with attached drawing the invention will be further described book, but not limited to this.
Embodiment 1
One kind being based on TiO2The preparation method of the wide spectrum responsible photocatalytic material of array optical waveguide, comprises the following steps that
(1) business is impregnated 12 hours or more in acetone with optical fiber (G652D), after removing covering, by the quartz of naked leakage
Optical fiber is successively cleaned by ultrasonic in acetone, ethyl alcohol, pure water；
(2) optical fiber is gathered into bundles, is poured with gelatin, plane is cut at aggregation end, subsequently into 5wt%HF aqueous solution
In, it by 1-2 hours, takes out after cleaning, dissolves by heating removal gelatin, obtain the optical fiber with needle point structure；
(3) optical fiber is immersed in 70wt% sulfuric acid and the H of 30wt%2O2Mixed solution impregnates 1 hour in 90 DEG C, it
It is thoroughly cleaned with clear water afterwards；This process is to carry out the activation processing of optical fiber surface, is easy to implement TiO2Growth on surface, rather than
Simple deposition；
(4) by 8mmol K2TiO(C2O4)2The in the mixed solvent of 160mL deionized water and diethylene glycol (DEG) (DEG), volume is added
For 1:3；Solution is transferred in 200 milliliters of polytetrafluoroethyllining lining stainless steel autoclaves；Quartz fibre one end polytetrafluoroethylene (PTFE)
Adhesive tape is tied up, and is disposed vertically in polytetrafluoroethyllining lining, ties up side downward；Sample is used after 180 DEG C of hydro-thermal process 3h-9h
Deionized water is thoroughly cleaned, and dry a whole night, obtains TiO at 80 DEG C2Array functional optical fiber；
(5) trisodium citrate (0.03g/ml) and caddy (0.01g/ml) is added in 30 ml deionized waters, it is former
Position growth TiO2The optical fiber of array is steeped into wherein 1 hour, and 1.5 milliliters of 28wt% ammonium hydroxide and 14 milliliters of thiocarbamide are added later
(0.015g/ml), it is 80 DEG C of water-bath light to stir 3 hours, it is thoroughly cleaned with deionized water, is dried in vacuo a whole night at 60 DEG C, obtains
CdS/TiO is arrived2Array functional optical fiber；
(6) by CdS/TiO2Array functional optical fiber is immersed in 30mL, and concentration is the (NH of 5mM4)2WS420h in solution, later
60 DEG C drying 2 hours again, then by the active optical fiber full of argon gas atmosphere under 500 DEG C of 5 hours of calcining, obtain WS2/CdS/
TiO2Array functional optical fiber.
The TiO that the present embodiment obtains2TiO in array functional optical fiber2Electron scanning micrograph (SEM) and WS2/CdS/
TiO2Transmission electron microscope (TEM) is as shown in Figure 1.TiO as shown in Figure 12Nano-array realizes silicon fiber to be covered entirely
Lid, TiO2About 7 microns of the thickness of uniform fold, wherein TiO2Array is long in 1 micron of nanometer rods and nanometer rods by length
It forms for the small nanometer branch crystalline substance of 10 rans, and is uniformly grown on silicon fiber, pass through TiO2Nanometer rods and its
The CdS/WS of upper formation2The TiO of nanometer branch crystalline substance building2Secondary structure array.
The TiO that the present embodiment is obtained2Array functional optical fiber carries out light propagation image measurement, as shown in Figure 2.It can by Fig. 2
Know TiO2The light propagation approach of the silicon fiber of array covering is single lit sideways, and coating of titanium dioxide fiber has white
Appearance has the release of light, this is because for naked quartz with the increase of incident light on the quartz fibre of titanium dioxide effect
Optical fiber, since silica refractive index is higher (~1.54), most of light is reflected into quartz in silica-Air Interface.
Equally, for TiO2The silicon fiber of covering, TiO2Refractive index it is higher, light can be in TiO2-SiO2Interfacial refraction is to TiO2
In, incident light and outgoing optical analog are as shown in figure 3, there is TiO2In the quartz fibre of covering, fiber-TiO2Interface guide light to
TiO2It propagates, a large amount of light is caused to escape from fiber.This with light in naked silica fibre and titania functional silica fibre
Optical transport research under red laser effect is consistent.Its light propagation analog simulation figure is as shown in Figure 3.
The WS that the present embodiment obtains2/CdS/TiO2The schematic diagram of array functional optical fiber is as shown in Figure 4.As shown in Figure 4, this hair
The bright wide spectrum that can be realized ultraviolet, visible light, near-infrared utilizes catalysis, light utilization efficiency height.
Embodiment 2
A kind of secondary structure TiO2The preparation method of the optical fiber catalysis material of load, comprises the following steps that
(1) business is impregnated 12 hours or more in acetone with optical fiber (G652D), after removing covering, by the quartz of naked leakage
Optical fiber is successively cleaned by ultrasonic in acetone, ethyl alcohol, pure water；
(2) optical fiber is gathered into bundles, is poured with gelatin, plane is cut at aggregation end, subsequently into 5wt%HF aqueous solution
In, it by 2 hours, takes out after cleaning, dissolves by heating removal gelatin, obtain the optical fiber with needle point structure；
(3) optical fiber is immersed in 70wt% sulfuric acid and the H of 30wt%2O2Mixed solution impregnates 1 hour in 90 DEG C, it
It is thoroughly cleaned with clear water afterwards；This process is to carry out the activation processing of optical fiber surface, is easy to implement TiO2Growth on surface, rather than
Simple deposition；
(4) by 6.5mmol K2TiO(C2O4)2It is 1:3 that 160mL is added by deionized water and diethylene glycol (DEG) (DEG) by volume
The in the mixed solvent of composition；Solution is transferred in 200 milliliters of polytetrafluoroethyllining lining stainless steel autoclaves；It uses quartz fibre one end
Polytetrafluoroethylene (PTFE) adhesive tape is tied up, and is disposed vertically in polytetrafluoroethyllining lining, ties up side downward；Sample is through 160 DEG C of hydro-thermal process
It after 9h, is thoroughly cleaned with deionized water, dry a whole night, obtains TiO at 90 DEG C2Array functional optical fiber；
(5) trisodium citrate (0.03g/ml) and caddy (0.01g/ml) is added in 30 ml deionized waters, it is former
Position growth TiO2The optical fiber of array is steeped into wherein 1 hour, and 1.5 milliliters of 28wt% ammonium hydroxide and 14 milliliters of thiocarbamide are added later
(0.015g/ml), it is 80 DEG C of water-bath light to stir 3 hours, it is thoroughly cleaned with deionized water, is dried in vacuo a whole night at 60 DEG C, obtains
CdS/TiO is arrived2Array functional optical fiber.
Embodiment 3
A kind of secondary structure TiO2The preparation method of the optical fiber catalysis material of load, comprises the following steps that
(1) business is impregnated 12 hours or more in acetone with optical fiber (G652D), after removing covering, by the quartz of naked leakage
Optical fiber is successively cleaned by ultrasonic in acetone, ethyl alcohol, pure water；
(2) optical fiber is gathered into bundles, is poured with gelatin, plane is cut at aggregation end, subsequently into 5wt%HF aqueous solution
In, it by 2 hours, takes out after cleaning, dissolves by heating removal gelatin, obtain the optical fiber with needle point structure；
(3) optical fiber is immersed in 70wt% sulfuric acid and the H of 30wt%2O2Mixed solution impregnates 1 hour in 90 DEG C, it
It is thoroughly cleaned with clear water afterwards；This process is to carry out the activation processing of optical fiber surface, is easy to implement TiO2Growth on surface, rather than
Simple deposition；
(4) by 9mmol K2TiO(C2O4)2It is 1:3 group that 160mL is added by deionized water and diethylene glycol (DEG) (DEG) by volume
At in the mixed solvent；Solution is transferred in 200 milliliters of polytetrafluoroethyllining lining stainless steel autoclaves；Use poly- in quartz fibre one end
Tetrafluoroethene adhesive tape is tied up, and is disposed vertically in polytetrafluoroethyllining lining, ties up side downward；Sample is through 190 DEG C of hydro-thermal process 4h
Afterwards, it is thoroughly cleaned with deionized water, dry a whole night, obtains TiO at 70 DEG C2Array functional optical fiber；
(5) by TiO2Array functional optical fiber is immersed in 30mL, and concentration is the (NH of 5mM4)2WS420h in solution, later again 60
DEG C dry 2 hours, then by the active optical fiber under the atmosphere full of argon gas 500 DEG C of 5 hours of calcining, obtain WS2/TiO2Array
Active optical fiber.
Comparative example 1
On the basis of absorption, to a kind of P25 (TiO2Nano particle) it is coated on light guide quartz fibre, it will locate in advance
The silica fibre of reason is immersed in two hours in NaOH solution, by the more-OH of its surface modification, with ultrasonic wave by 50mgP25
It is dispersed in water, the silica fibre of surface modification-OH is immersed in 12h in the dispersion liquid of P25, slightly rinsed with deionized water,
The silica fibre of P25 covering is obtained after drying.
Comparative example 2
Butyl titanate (8.5mL) and diethanol amine (2.5mL) is dissolved in 35.5ml ethyl alcohol, is stirred at room temperature later
Continue stirring 1 hour after 0.5ml water is added after 10min.Optical fiber is with the speed dip-coating of 1mm/s.Finally, the optical fiber after dip-coating exists
6h is calcined in 600 DEG C of air, obtains TiO2Functional fibre.
Comparative example 3
As described in Example 1, unlike:
It omits step (5) and (6), obtains TiO2Array functional optical fiber.
Test example 1
By WS made from embodiment 12/CdS/TiO2Array functional fiber optic tip one end gathers into bundles, and passes through silica gel and LED
Lamp coupling carries out the continuous photocatalysis sewage processing of integration.Integrated continuous photocatalysis apparatus photo is as shown in Figure 5.
Integrated continuous photocatalysis apparatus forms (i.e. TiO by six light-catalyzed reaction systems2The optical fiber tip of load
One end gathers into bundles and passes through silica gel and LED light is coupled as a reaction system).By peristaltic pump by methyl orange solution with 5mL/
The speed of min flows through in the reaction unit of assembling.The color of methyl orange is constantly decolourized in flowing through photocatalytic reaction device, is being flowed
Methyl orange is essentially colourless after crossing the 6th coupled system.The photo of Fig. 4 is the figure clapped after the reaction unit is run 1 hour
Picture shows that the reaction unit has certain stability.
Test results are shown in figure 6.
Test results are shown in figure 6 for the quantitative degradation of the continuous photo-catalytic degradation of methyl-orange of each coupled system.Each
Photocatalysis coupled system can make methyl orange degradation 20% during methyl orange flows through.
Test example 2
Whether silica fibre can be uniformly grown in by scanning electron microscope come comparing embodiment 1 and comparative example 1,2
In, it is demonstrated experimentally that the TiO that embodiment 1 is grown2Structure can be in surface homoepitaxial, and comparative example 1, and 2 are reunited, raw
Long non-uniform situation.Meanwhile by loading TiO to distinct methods2Quartz fibre carries out the method for slight ultrasound to judge this
The secured situation of three kinds of samples, experiment show the slight ultrasound in water of embodiment 1, and do not fall off TiO2, aqueous solution presents clear
It is clear, no white nano particle, and comparative example 1,2 there is the case where nano particle falls off, and it is muddy to go out a little whites in aqueous solution
It is turbid, it was demonstrated that embodiment 1 and comparative example 1,2 are compared, stronger.
Test example 3
Pass through the TiO for forming embodiment 1 and 1,2,3 growth pattern of comparative example2The silica fibre building one of secondary structure
The continuous photocatalysis apparatus of bodyization forms (i.e. same as Example 1,1,2,3 method of comparative example general by six light-catalyzed reaction systems
With TiO2Optical fiber tip one end for the secondary structure load of base building gathers into bundles and passes through silica gel and full-spectrum LED lamp
It is coupled as a reaction system).Methyl orange solution is flowed through to the reaction unit of assembling by peristaltic pump with the speed of 5mL/min
In.By testing the degradation amount of methyl orange, carry out the continuous photocatalytic reaction device that comparing embodiment 1 and comparative example 1,2,3 form
Degradation property.
The results show that comparative example 1,2 is degraded under full spectrum sunlight under conditions of the methyl orange of 20mg/L, five hours
Degradation rate be 50%, the degradation rate of comparative example 3 under the same conditions is 80%, and for embodiment 1, under the same conditions its
Degradation rate is 100%.Compared to comparative example 1,2, its degradation efficiency improves 50% under the same conditions；Compared with comparative example 3,
Embodiment 1 carries out photocatalysis under full spectrum, further improves degradation rate.
Claims (10)
1. one kind is based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide, which is characterized in that the catalysis material includes
Optical fiber, the optical fiber surface growth in situ have TiO2Array；The TiO2Growth in situ has visible-light photocatalyst on array
Or/and near infrared light catalyst.
2. according to claim 1 be based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide, which is characterized in that
The visible-light photocatalyst is CdS, and the near infrared light catalyst is WS2。
3. according to claim 1 be based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide, which is characterized in that
The optical fiber is silica fibre.
4. according to claim 1 be based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide, which is characterized in that
The TiO25-20 nanometers of nanometer branch crystalline substance composition in the nanometer rods and nanometer rods that array is length 0.5-2 microns, and uniformly
Be grown on silicon fiber, pass through TiO2Nanometer rods and the CdS/WS formed thereon2The TiO of nanometer branch crystalline substance building2Second level
Array of structures.
5. according to claim 1 be based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide, which is characterized in that
The TiO on optical fiber surface2Uniform fold with a thickness of 5-10 microns；
Preferably, TiO2、CdS、WS2The mass ratio of three is 1:(0.1-0.5): (0.1-0.5).
6. claim 1-5 is described in any item to be based on TiO2The preparation side of the wide spectrum responsible photocatalytic material of array optical waveguide
Method, comprising:
Titanium salt solution is provided, optical fiber is placed in titanium salt solution, in 160-200 DEG C of hydro-thermal reaction 3h-9h, obtains TiO2Array functional
Optical fiber；
Cadmium salt soln is provided, by TiO2Array functional optical fiber, which is placed in cadmium salt soln, to be impregnated, and ammonium hydroxide and thiocarbamide, 70-90 is then added
DEG C water-bath, obtains CdS/TiO2Array functional optical fiber；
Or/and tungsten salt solution is provided, by TiO2Array functional optical fiber or CdS/TiO2Array functional optical fiber is placed in tungsten salt solution,
It is calcined under an inert atmosphere in 400-600 DEG C again after dipping, obtains WS2/TiO2Array functional optical fiber or WS2/CdS/TiO2Array
Active optical fiber.
7. according to claim 6 be based on TiO2The preparation method of the wide spectrum responsible photocatalytic material of array optical waveguide,
It is characterized in that, the titanium salt is K2TiO(C2O4)2；Preferably, the solvent of titanium salt solution is the mixing of water and diethylene glycol (DEG) (DEG)
The volume ratio of solvent, water and diethylene glycol (DEG) is 1:3；
Preferably, the concentration of titanium salt solution is 0.04-0.06mol/L.
8. according to claim 6 be based on TiO2The preparation method of the wide spectrum responsible photocatalytic material of array optical waveguide,
It is characterized in that, the cadmium salt soln is the mixed aqueous solution of trisodium citrate and caddy, and the concentration of cadmium salt aqueous solution is
0.05mol/L；Preferably, trisodium citrate, caddy, ammonium hydroxide, thiocarbamide molar ratio be (2-2.5): 1:0.2:4；
Preferably, the tungsten salt solution is (NH4)2WS4Aqueous solution, concentration 4-6mmol/L；
Preferably, fiber perpendicular is placed in titanium salt solution, and titanium dioxide is in optical fiber surface growth in situ.
9. according to claim 6 be based on TiO2The preparation method of the wide spectrum responsible photocatalytic material of array optical waveguide,
It is characterized in that, is pre-processed as follows before YAG Fiber Growth:
The method for being made and being etched of array prepares the optical fiber with needle-shaped incidence end, then mixes in sulfuric acid and hydrogen peroxide
Immersion treatment in solution；
Prepare the method with the optical fiber of needle-shaped incidence end are as follows: optical fiber is gathered into bundles, is poured with gelatin, is cut at aggregation end flat
Face, by 1-2 hours, is taken out after cleaning subsequently into 5wt%HF aqueous solution, dissolves by heating removal gelatin, obtaining has needle
The optical fiber of sharp structure.
10. claim 1-5 is described in any item to be based on TiO2The wide spectrum responsible photocatalytic material of array optical waveguide is in photocatalysis
Application in sewage treatment.
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