CN102949985B - For substrate fixed titanium dioxide nano thread and the manufacture method thereof of water treatment technology, and utilize the method for treating water of substrate fixed titanium dioxide nano thread - Google Patents
For substrate fixed titanium dioxide nano thread and the manufacture method thereof of water treatment technology, and utilize the method for treating water of substrate fixed titanium dioxide nano thread Download PDFInfo
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- CN102949985B CN102949985B CN201210240806.9A CN201210240806A CN102949985B CN 102949985 B CN102949985 B CN 102949985B CN 201210240806 A CN201210240806 A CN 201210240806A CN 102949985 B CN102949985 B CN 102949985B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 280
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 135
- 239000000758 substrate Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000005516 engineering process Methods 0.000 title claims description 24
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 238000007731 hot pressing Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229920005596 polymer binder Polymers 0.000 claims description 5
- 239000002491 polymer binding agent Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 230000005283 ground state Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- VMXUWOKSQNHOCA-LCYFTJDESA-N ranitidine Chemical compound [O-][N+](=O)/C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-LCYFTJDESA-N 0.000 description 6
- 229960000620 ranitidine Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002070 nanowire Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- -1 hydroxyl free radical Chemical class 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention provides substrate fixed titanium dioxide nano thread and manufacture method thereof, and utilize the method for treating water of substrate fixed titanium dioxide nano thread, by electrojet method and pressure sintering, titanium dioxide is fixed on substrate, thus without separation and recovery titanium dioxide when carrying out water treatment, regulate the ratio of titanium dioxide crystal form to be best, photocatalytic activity is reached to greatest extent.
Description
Technical field
The present invention relates to substrate fixed titanium dioxide nano thread and manufacture method thereof, and utilize the method for treating water of substrate fixed titanium dioxide nano thread.Be specifically related to electrojet method and titanium dioxide is fixed on substrate by pressure sintering, thus, separation and recovery need not be carried out to titanium dioxide when carrying out water treatment, simultaneously, titanium dioxide crystal form ratio can be regulated to be optimal proportion, make photocatalytic activity reach substrate fixed titanium dioxide nano thread and manufacture method thereof to greatest extent, and utilize the method for treating water of this substrate fixed titanium dioxide nano thread.
Background technology
Photochemical catalyst is the material causing catalytic reaction under light (300 ~ 400nm) irradiates, and light-catalyzed reaction comes from semiconductor and produces duplet and the electron transition on interface by absorbing band-gap energy.By light-catalyzed reaction, produce and there is the hydroxyl free radical of Strong oxdiative ability and super cloudy oxonium ion, organic pollution materials is finally decomposed into water and carbon dioxide.
The soild oxide with photocatalysis usefulness has ZrO
2, ZnO, SnO
2, V
2o
3, TiO
2deng, CdS, WO
3deng also using as photochemical catalyst.The photochemical catalyst material that utilization rate is high, not only will have good optical activity, and not have photoetch, makes its durable excellent in abrasion resistance, and meanwhile, at biology and be chemically inactive, and itself is non-toxic, high to the security of environment.Can meet above-mentioned photochemical catalyst feature, and cheap, that earth resource is abundant mainstream product is exactly white powder titanium dioxide (TiO
2).
Usual titanium dioxide utilizes with film morphology when gas-phase reaction, during liquid phase reactor mainly with colloid form utilize or on supporter plated for film use.On environmental area, the air of titanium dioxide and water purification technology exploitation and correlative study become main flow.Especially, the VOC (VOCs) in room air and nitrogen oxide (NO
x) to remove the exploitation of technology very active, reaches commercialization step.
On the contrary, in the field relevant to water purification technology, from nineteen ninety, carry out a lot of research, but still do not have a technology successfully to realize commercialization at present.Its reason can illustrate according to two backgrounds substantially, and first, the water standard of the sewage and waste water process of current legal provisions is not too strict, to such an extent as to does not also need to use photochemical catalyst.
But, estimate in the future to there will be more micro-harmful organic substances newly, and the earth is on the rise because of insufficient water phenomenon, will popularize by improving water cycle system and expand the regeneration of water, the technology that the biology water treatment of therefore current sewage and waste water realizes high-quality is the problem awaiting solving.
Meanwhile, on water purification technology field, although the outstanding treatment effeciency of photochemical catalyst obtains demonstration, the maximum reason that can not be widely used is the shortcoming being difficult to after it has use be separated from water and reclaim.The photochemical catalyst size of general use is about 50nm, because of particle agglomeration (agglomeration) phenomenon in water, its magnitude range is about within the scope of 0.5 ~ 1 μm, in order to the recycling of titanium oxide, in order to recovery titanium oxide complete during water treatment produces clean process water, necessarily require the technology of the costlinesses such as additional input film process (membrane).
In the middle of No. 886906th, Korean granted patent, propose the titanium diffusion barrier and manufacture method thereof with nano porous titanium dioxide surface, but its shortcoming is the pollution (fouling) that nano-porous surface occurs to be caused operating continuously, requires periodic cleaning.
Summary of the invention
The present invention is conceived to solve the problem, its object is to provide electrojet method and pressure sintering to be fixed on substrate by titanium dioxide, separation and recovery need not be carried out to titanium dioxide when carrying out water treatment, and titanium dioxide crystal form ratio can be regulated for best, make photocatalytic activity reach substrate fixed titanium dioxide nano thread and manufacture method thereof to greatest extent, and utilize the method for treating water of this substrate fixed titanium dioxide nano thread.
In order to achieve the above object, the regulating step of the substrate fixed titanium dioxide nano thread of the present invention step and titanium dioxide nano thread crystal form ratio that are fixed on substrate by titanium dioxide nano thread has come; The step that above-mentioned titanium dioxide nano thread is fixed on substrate is made up of following three processes: comprise the mixed solution of TiO 2 precursor and the set-up procedure of substrate; Titanium dioxide nano thread to be plated in the process on substrate by above-mentioned mixed solution through electrojet; By hot-pressing processing titanium dioxide nano thread is fixed on the process on substrate: the regulating step of the crystal form ratio of above-mentioned titanium dioxide nano thread is, the substrate of above-mentioned fixing titanium dioxide nano thread regulates the Detitanium-ore-type crystallization of titanium dioxide nano thread and the ratio of rutile-type crystallization through after-baking.
In the middle of the crystal form ratio regulating step of above-mentioned titanium dioxide nano thread, the ratio of above-mentioned Detitanium-ore-type and rutile-type crystallization is preferably adjusted to 8:2 to 7:3, and above-mentioned after-baking temperature can be 500 ~ 600 DEG C.
Above-mentioned mixed solution through the process of electrojet evaporation titanium dioxide nano thread on substrate is, come by electrojet equipment, above-mentioned electrojet equipment is made up of the precursor mixed solution supply unit of the mixed solution supplied containing TiO 2 precursor, electrojet shower nozzle, collector (chamber) and high-voltage generator; Above-mentioned collector inside is provided with the substrate forming titanium film, while above-mentioned precursor mixed solution is fed to above-mentioned electrojet shower nozzle by above-mentioned precursor mixed solution supply unit, the high voltage that above-mentioned high-voltage generator produces is applied on above-mentioned electrojet shower nozzle, titanium dioxide nano thread is changed into according to the precursor mixed solution in electrojet principle electrojet shower nozzle, be ejected into collector inner space, the titanium dioxide nano thread evaporation of collector inside is on titanium film.Now, the titanium film on aforesaid substrate is in ground state.
The above-mentioned mixed solution containing TiO 2 precursor is made up of the high polymer binder of titania precursor body, ethanol and adjusting viscosity.And aforesaid substrate can be silicon substrate or quartz base plate.
Substrate fixed titanium dioxide nano thread of the present invention is made up of the titanium dioxide nano thread that the titanium film that substrate, aforesaid substrate are formed and above-mentioned titanium film are formed, the crystal type of above-mentioned titanium dioxide nano thread is, the ratio of Detitanium-ore-type and rutile-type is 8:2 to 7:3.
The method for treating water utilizing substrate fixed titanium dioxide nano thread of the present invention, is characterized in that, is the method for treating water utilizing substrate fixed titanium dioxide nano thread; Aforesaid substrate fixed titanium dioxide nano thread is made up of the titanium dioxide nano thread that the titanium film that substrate, aforesaid substrate are formed, above-mentioned titanium film are formed; The Detitanium-ore-type of the crystal type of above-mentioned titanium dioxide nano thread and the ratio of rutile-type are 8:2 to 7:3; Aforesaid substrate fixed titanium dioxide nano thread is arranged in the water treatment pipeline that former water passes through or the reactive tank removing former impurities in water, decomposes according to the organic pollution materials that the photocatalytic activity of above-mentioned titanium dioxide nano thread will contain in former water.
Ultraviolet lamp can also be provided with in above-mentioned water treatment pipeline or reactive tank.
Invention effect
Substrate fixed titanium dioxide nano thread of the present invention and manufacture method thereof, and utilize the method for treating water of substrate fixed titanium dioxide nano thread to have following effect.
Electricity consumption gunite by titanium dioxide nano thread evaporation on substrate time, substrate is pre-formed titanium film, can make titanium film be used as conduct electricity earth plate while, the adhesion of titanium dioxide nano thread can be increased.And make the Detitanium-ore-type of the crystal type of titanium dioxide nano thread and rutile-type crystal area proportion reach best, photocatalytic activity reaches to greatest extent, improves water treatment efficiency.Simultaneously, titanium dioxide nano thread in the state being fixed on substrate, therefore, need not separation and recovery titanium dioxide nano thread again when carrying out water treatment, can repeatedly re-use.
Accompanying drawing explanation
Fig. 1 is the structural map of electrojet equipment.
Fig. 2 is the present invention in conjunction with the flow chart of the manufacture method of Benq's plate fixed titanium dioxide nano thread an embodiment.
Fig. 3 is the sample photo of heat pressing process have to have no contrast.
Fig. 4 is the photo of the titanium dioxide nano thread of each step in the manufacture method of the substrate fixed titanium dioxide nano thread that the present invention carries out in conjunction with an embodiment.
Fig. 5 shows the XRD result of after-baking temperature on the impact that crystal form ratio changes.
Fig. 6 shows the collection of illustrative plates of after-baking temperature on the impact of the photocatalysis Decomposition velocity variations of ranitidine (ranitidine).
Fig. 7 is that display after-baking temperature is on the collection of illustrative plates of the impact of the photocatalysis Decomposition velocity variations of parachlorophenol (4-chlorophenol).
Detailed description of the invention
Feature of the present invention utilizes electrojet method (electrospinning) and pressure sintering to be fixed on substrate by titanium dioxide nano thread, and the crystal form ratio of titanium dioxide is controlled by after-baking, when making to carry out water treatment, the photocatalytic activity of titanium dioxide nano thread reaches to greatest extent, does not need separation and recovery titanium dioxide nano thread.
The manufacture method of substrate fixed titanium dioxide nano thread of the present invention, is divided into the step of substrate being fixed titanium dioxide nano thread and the step regulating titanium dioxide nano thread crystal form ratio substantially.
Aforesaid substrate is fixed the step of titanium dioxide nano thread, can 1 be subdivided into) set-up procedure, 2 of mixed solution containing TiO 2 precursor and substrate) above-mentioned mixed solution is through the process and 3 of electrojet evaporation titanium dioxide nano thread on substrate) by hot-pressing processing titanium dioxide nano thread is fixed on process on substrate.
Above-mentioned 1) set-up procedure (S201 in Fig. 2) of the mixed solution containing TiO 2 precursor and substrate, is described in detail as follows.
Mixed solution containing TiO 2 precursor comprises the high polymer binder of titania precursor body (TTIP, titaniumtetra-isopropoxide), ethanol, adjusting viscosity.Above-mentioned ethanol serves the effect improving presoma viscosity, suppress foaming, and the high polymer binder of above-mentioned adjusting viscosity can use polyvinylpyrrolidone (PVP; Polyvinylpyrrolidone).Further, can also comprise in above-mentioned mixed solution promote titanium dioxide crystal play catalyst action-glacial acetic acid.Above-mentioned mixed solution preferably stirs 30 minutes ~ 1 hour at 50 ~ 70 DEG C of temperature.
Aforesaid substrate can use silicon (Si) substrate or quartz (SiO
2) substrate, aforesaid substrate to be pre-formed certain thickness titanium film.Above-mentioned titanium film, by ground connection conducting surface when being used as mixed solution electrojet described later, plays the effect of the adhesion increasing titanium dioxide nano thread fixing on substrate simultaneously.Because of titanium (Ti) and titanium dioxide (TiO
2) grid system similar, can farthest prevent titanium dioxide nano thread from coming off from substrate.
Titanium film as above by electron beam evaporation plating machine (E-beamevaporator) preferably with the thickness evaporation of 50 ~ 150nm on substrate, except electron beam evaporation plating machine, plasma enhanced chemical vapor deposition method (PECVD can also be passed through; Plasmaenhancedchemicalvapordeposition), sputter (sputtering) technique forms titanium film.
Below, above-mentioned 2 are illustrated) titanium dioxide nano thread is plated on process (S202) on substrate by mixed solution electrostatic spray.
Mixed solution containing TiO 2 precursor is through electrojet, and process titanium dioxide nano thread being plated in substrate has been come by electrojet equipment.Electrojet equipment as shown in Figure 1, is made up of the precursor mixed solution supply unit (120) of mixed solution of supply containing TiO 2 precursor, electrojet shower nozzle (130), collector (110) and high-voltage generator (140), in above-mentioned collector (110), is provided with the substrate (150) of formation titanium film (151).
In this case, in above-mentioned precursor mixed solution supply unit (120) supply precursor mixed solution to above-mentioned electrojet shower nozzle (130), by above-mentioned high-voltage generator (140), high voltage is applied on above-mentioned electrojet shower nozzle (130) simultaneously, changes titanium dioxide nano thread into according to the precursor mixed solution in electrojet (electrospinning) principle electrojet shower nozzle (130) and be ejected into above-mentioned collector (110) inner space.Now, the solvent composition of precursor mixed solution vapors away because of the high voltage applied, and titanium dioxide nano thread is that (+) or (-) one pole is charged.And be located at the titanium film (151) of the substrate (150) of collector (110) bottom in ground state, thus the titanium dioxide nano thread of collector (110) inside is plated on titanium film (151).
Under the state that titanium dioxide nano thread is plated in substrate, carrying out above-mentioned 3) titanium dioxide nano thread is fixed on process (S203) on substrate by hot-pressing processing.Above-mentioned heat pressing process is the process of with punch press, substrate being carried out to hot pressing under uniform temperature and pressure, pressure and temperature be now respectively 10 ~ 15MPa, 100 ~ 150 DEG C, sustainable 5 ~ 15 minutes of heat pressing process.By above-mentioned heat pressing process, the adhesion of substrate and titanium dioxide nano thread increases, and is completed step titanium dioxide nano thread being fixed on substrate by this series of processes.
After the step that above-mentioned titanium dioxide nano thread is fixed on substrate completes, carry out the regulating step (S204) of titanium dioxide nano thread crystal form ratio, the crystal form ratio of the titanium dioxide nano thread be fixed on substrate can be controlled by this step, and select best crystal form ratio, the photocatalytic activity of titanium dioxide nano thread is reached to greatest extent.
Specifically, under the state that titanium dioxide nano thread is fixed on substrate, in 500 ~ 900 DEG C of temperature ranges, after-baking is carried out to aforesaid substrate.The Detitanium-ore-type of the crystal type of titanium dioxide and the crystal form ratio of rutile-type is regulated by thereafter heat process.Relatively low temperature that is about 500 DEG C time Detitanium-ore-type ratio large, along with the ratio regular meeting of temperature rising rutile-type is risen.Aftermentioned experimental result shows, when the ratio of Detitanium-ore-type and rutile-type is 7:3, photocatalytic activity reaches the highest, and therefore the control ratio of Detitanium-ore-type and rutile-type is preferably 7:3 to 8:2, and now after-baking temperature is 500 ~ 600 DEG C.
By manufacture method as above, can manufacture substrate fixed titanium dioxide nano thread, the substrate fixed titanium dioxide nano thread produced can be applicable to water treatment field.
Specifically, constructed in accordance go out substrate fixed titanium dioxide nano thread, be positioned in the water treatment pipeline that former water passes through or the reactive tank removing former impurities in water, decomposable asymmetric choice net is contained in the polluter in former water, can add and arrange ultraviolet lamp to promote the decomposition efficiency of polluter in above-mentioned water treatment pipeline or reactive tank.The titanium dioxide nano thread being fixed on substrate generates hydroxyl free radical by the irradiation of visible light or ultraviolet (300 ~ 400nm), changes and be decomposed into carbon dioxide and water after the hydroxyl radical reaction of the organic pollution materials in former water and generation.
Below, the present invention manufactures substrate fixed titanium dioxide nano thread in conjunction with an embodiment, and understands its feature.
The manufacture of embodiment 1 substrate fixed titanium dioxide nano thread and signature analysis thereof
The high polymer binder PVP1g of mixing glacial acetic acid 4ml, ethanol 14ml, adjusting viscosity and TiO 2 precursor TTIP2g, stirs 30 minutes at 50 DEG C of temperature, preparation precursor mixed solution.
After utilizing electron beam evaporation plating machine to form 100nm titanium film on a quartz substrate, above-mentioned precursor solution 2ml carries out electrojet with the speed of 50 μm/min, is plated on substrate by titanium dioxide nano thread.Then at 120 DEG C of temperature and 15MPa pressure, punch press pressure substrate carries out hot-pressing processing 10 minutes, is fixed on substrate by titanium dioxide nano thread.
Fig. 3 is when separately display manufactures substrate fixed titanium dioxide nano thread, does not carry out hot-pressing processing and directly carries out the sample ((a) in Fig. 3) of after-baking and carry out the picture of sample ((b) in Fig. 3) of hot-pressing processing and after-baking.As shown in Figure 3, after hot-pressing processing, carry out the sample of after-baking, can confirm that titanium dioxide nano thread is stably fixed on a quartz substrate.
The photo of Fig. 4 for utilizing SEM (SEM) to observe the titanium dioxide nano thread in each manufacturing step respectively, after Fig. 4 (a) can be observed electrojet, nanowire diameter is approximately about 300nm; The diametric shrinkage that omission heat pressing process directly carries out the nano wire of after-baking at 600 DEG C as shown in figure (c) is 1/2, but its pattern is closely similar with (a).And, b () and (d) is the photo respectively carrying out the titanium dioxide of hot pressing and after-baking under 15MPa and 20MPa, b diameter that () observes nano wire is about 100nm, and (d) can confirm that nano wire melts.(b) and (d) with reference to figure 4 is known, adds that the pressure of more than 15MPa can cause titanium dioxide nano thread pattern to deform.
The hot-pressing processing that is through of Fig. 5 display fixes titanium dioxide nano thread on a quartz substrate, carries out the XRD analysis result after after-baking under varying temperatures.Known with reference to figure 5, when after-baking temperature is more than more than 500 DEG C, titanium dioxide nano thread starts crystallization, along with the crystallization of the increase titanium dioxide nano thread of temperature becomes rutile-type mutually from Detitanium-ore-type.That is 500 DEG C time titanium dioxide nano thread crystallization major part be Detitanium-ore-type, and more than 800 DEG C major part can phase transfers be rutile-type.And the ratio of after-baking temperature Detitanium-ore-type and rutile-type when being 600 DEG C is approximately 7:3.
Embodiment 2 is according to the photocatalytic activity analysis of crystal form ratio
Observe the decomposition efficiency of the organic pollution materials of the substrate fixed titanium dioxide nano thread produced by embodiment 1.Fig. 6 is the change collection of illustrative plates of the photocatalysis Decomposition speed of the ranitidine that display after-baking variations in temperature causes.Quartz base plate used by experiment is each 2cm of length and width, and ranitidine is organic pollution materials.And the initial concentration of ranitidine is 100 μMs, that the light source of light decomposition experiment utilizes is 4WBLBlamp (emission wavelength: 350 to 400nm, PhilipsCo.).
Known with reference to figure 6, the photocatalysis Decomposition effect of ranitidine is best when 600 DEG C of after-baking, and after-baking temperature its decomposition rate different is also different.Observed by front, can confirm that after-baking temperature and crystal form ratio have correlation, the ratio along with crystal formation changes its photocatalysis Decomposition speed and also can change, and when the ratio of Detitanium-ore-type and rutile-type is 7:3 as shown in Figure 6, photocatalysis Decomposition is fastest.
Fig. 7 is the organic pollution materials that 4-chlorophenol decomposes as needs, observes the result of its photocatalysis Decomposition speed with Fig. 6 under identical conditions.As shown in Figure 7, when can reaffirm that the photocatalysis Decomposition of 4-chlorophenol be also the after-baking temperature of nano wire is 600 DEG C, most effective when namely Detitanium-ore-type and rutile-type ratio are 7:3.
Symbol description
110: collector 120: precursor mixed solution supply unit
130: electrojet shower nozzle 140: high-voltage generator
150: substrate 151: titanium film
Claims (12)
1., for a manufacture method for the substrate fixed titanium dioxide nano thread of water treatment technology, it is characterized in that,
The regulating step of the step and titanium dioxide nano thread crystal form ratio that are fixed on substrate by titanium dioxide nano thread is formed,
Above-mentioned titanium dioxide nano thread is fixed on the step of substrate, comprise following three processes: through electrojet titanium dioxide nano thread to be plated in the process on substrate containing TiO 2 precursor mixed solution and the set-up procedure of substrate, above-mentioned mixed solution, with the process by hot-pressing processing titanium dioxide nano thread is fixed on substrate
Above-mentioned hot-pressing processing is carried out 5 to 15 minutes at the temperature of the pressure of 10 ~ 15MPa and 100 ~ 150 DEG C,
The regulating step of the crystal form ratio of above-mentioned titanium dioxide nano thread is, the substrate of above-mentioned fixing titanium dioxide nano thread regulates the Detitanium-ore-type crystallization of titanium dioxide nano thread and the ratio of rutile-type crystallization through after-baking,
Aforesaid substrate fixed titanium dioxide nano thread is used in water treatment technology.
2. the manufacture method of the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 1, it is characterized in that, in the regulating step of the crystal form ratio of above-mentioned titanium dioxide nano thread, the proportion adjustment of above-mentioned Detitanium-ore-type and rutile-type is 8:2 to 7:3.
3. the manufacture method of the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 1, is characterized in that, in the regulating step of the crystal form ratio of above-mentioned titanium dioxide nano thread, above-mentioned after-baking temperature is 500 ~ 600 DEG C.
4. the manufacture method of the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 1, it is characterized in that, titanium dioxide nano thread is plated in the process of substrate by above-mentioned mixed solution through electrojet, come by electrojet equipment,
Above-mentioned electrojet equipment is made up of the precursor mixed solution supply unit of the mixed solution supplied containing TiO 2 precursor, electrojet shower nozzle, collector and high-voltage generator, is provided with the substrate forming titanium film in above-mentioned collector,
Above-mentioned precursor mixed solution supply unit supply precursor mixed solution is on above-mentioned electrojet shower nozzle, by above-mentioned high-voltage generator, high voltage is applied on above-mentioned electrojet shower nozzle simultaneously, then change titanium dioxide nano thread into according to the precursor mixed solution in electrojet principle electrojet shower nozzle and be ejected into above-mentioned collector inner space, the titanium dioxide nano thread evaporation of collector inside is on titanium film.
5. the manufacture method of the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 4, it is characterized in that, the titanium film on aforesaid substrate is ground state.
6. the manufacture method of the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 1, it is characterized in that, the above-mentioned mixed solution containing TiO 2 precursor comprises the high polymer binder of titania precursor body, ethanol and adjusting viscosity.
7. the manufacture method of the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 1, it is characterized in that, aforesaid substrate is silicon substrate or quartz base plate.
8. for a substrate fixed titanium dioxide nano thread for water treatment technology, it is characterized in that, adopt the manufacture method manufacture of the substrate fixed titanium dioxide nano thread for water treatment technology in claim 1 to 7 described in any one,
Comprise the titanium dioxide nano thread that titanium film and above-mentioned titanium film that substrate, aforesaid substrate are formed are formed, the Detitanium-ore-type of above-mentioned titanium dioxide nano thread crystal formation and rutile-type ratio are 8:2 to 7:3,
Aforesaid substrate fixed titanium dioxide nano thread is used in water treatment technology.
9. the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 8, it is characterized in that, above-mentioned titanium film can be utilized as conductive earth plate when electrojet.
10. the substrate fixed titanium dioxide nano thread for water treatment technology according to claim 8, it is characterized in that, aforesaid substrate is silicon substrate or quartz base plate.
11. 1 kinds of method for treating water, it is the method for treating water utilizing substrate fixed titanium dioxide nano thread, it is characterized in that, the substrate fixed titanium dioxide nano thread of the manufacture method manufacture of the substrate fixed titanium dioxide nano thread for water treatment technology as claimed in any of claims 1 to 7 is arranged in the water treatment pipeline that former water passes through or the reactive tank removing former impurities in water, is decomposed the organic pollution materials contained in former water by the photocatalytic activity of above-mentioned titanium dioxide nano thread.
12. method for treating water according to claim 11, is characterized in that, in above-mentioned water treatment pipeline or reactive tank, also comprise ultraviolet lamp.
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| CN103469291B (en) * | 2013-08-23 | 2016-03-30 | 中山大学 | A kind of method of low-temperature growth rutile titanium dioxide monocrystal nano line array under normal pressure |
| WO2017085590A1 (en) * | 2015-11-16 | 2017-05-26 | Sabic Global Technologies B.V. | Multi-layered water- splitting photocatalyst having a plasmonic metal layer with optimized plasmonic effects |
| CN106587249B (en) * | 2016-11-15 | 2019-06-11 | 西安交通大学 | A kind of interdigitated organic pollutant light degradation device and preparation method thereof |
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| Development of photocatalytic TiO2 nanofibers by electrospinning and its application to degradation of dye pollutants;Seok Joo Doh等;《Journal of Hazardous Materials》;20071006;第154卷;第118-127页 * |
| Enhanced Photocatalytic Activity of Electrospun TiO2 Nanofibers with Optimal Anatase/Rutile Ratio;Heping Li等;《 J. Am. Ceram. Soc.》;20111031;第94卷(第10期);第3184-3187页 * |
| Processing-Microstructure-Properties Correlation of Ultrasensitive Gas Sensors Produced by Electrospinning;Osnat Landau等;《Chem. Mater.》;20081216;第21卷(第1期);第9-11页 * |
| Structural and Optical Properties of Electrospun TiO2 Nanofibers;A. Kumar等;《 Chem. Mater.》;20071130;第19卷(第26期);第6536-6542页 * |
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