CN107497413A - A kind of preparation method of black titanium dioxide coating - Google Patents
A kind of preparation method of black titanium dioxide coating Download PDFInfo
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- CN107497413A CN107497413A CN201710622273.3A CN201710622273A CN107497413A CN 107497413 A CN107497413 A CN 107497413A CN 201710622273 A CN201710622273 A CN 201710622273A CN 107497413 A CN107497413 A CN 107497413A
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- titanium dioxide
- black titanium
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- dioxide coating
- coating
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000001307 helium Substances 0.000 claims abstract description 7
- 229910052734 helium Inorganic materials 0.000 claims abstract description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 238000000151 deposition Methods 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 210000002381 plasma Anatomy 0.000 description 35
- 238000000034 method Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 208000003351 Melanosis Diseases 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
Abstract
The present invention relates to a kind of preparation method of black titanium dioxide coating, including：(1) normal pressure, room temperature in reaction cavity, are passed through TiCl under conditions of 200 DEG C4、O2With the mixed gas of discharge gas, normal pressure kHz radio frequency plasma power supplys are opened, deposition obtains TiO2Coating；(2) above-mentioned power supply is replaced by normal pressure MHz radio frequency plasma power supplys, is passed through the mixed gas of helium and hydrogen, opened radio-frequency power supply and produce hydrogen plasma, handled under normal temperature, obtain black titanium dioxide coating.The energy band and photoresponse scope of the invention for greatly changing titanic oxide material, the black TiO of acquisition2Coating improves in the absorption of visible ray, infrared light district, it is seen that/infrared photocatalytic activity greatly improves；Simultaneously because can deposit coated in material surfaces such as polymer, there is important value in the practical applications such as DSSC, visible ray hydrogen manufacturing and environmental improvement.
Description
Technical field
The invention belongs to field of photocatalytic material, more particularly to a kind of preparation method of black titanium dioxide coating.
Background technology
Titanium dioxide has the characteristic such as photocatalytic activity height, chemical property stabilization, in clean energy resource, environmental improvement etc.
Have a wide range of applications, be always the focus of catalysis material research application.But as a kind of broad-band gap indirect semiconductor material,
It absorbs threshold value in below 387nm, in the solar spectrum based on visible ray (44%) and infrared ray (53%), its sunshine
Absorption rate is extremely low.Therefore, its band structure is widened, improves its absorption in visible ray, near infrared region, and photocatalysis
Response characteristic, is very necessary, utilizes photocatalysis material of titanium dioxide also particularly significant on a large scale to the energy, environmental area.
It is relatively more to the method for visible absorption value to improve titanic oxide material, including element doping method, such as metal ion
Doping is nonmetallic ion-doped.Wonyong Choi (J.Phys.Chem.1994,98,13669-13679) pass through research
Fe3+,Mo5+,Ru3+,Os3+,Re5+,V4+And Rh3+Visible light-responded titanium dioxide is prepared Deng various metals ion and analyzes it
Mechanism.Open peak etc. and have studied absorption of the metal-doped discovery of Rh, V, Ni, Cd, Cu and Fe in titanium dioxide at 400~600nm
Improve.The H that Chongyin Yang (J.Am.Chem.Soc.2013,135,17831-17838) pass through 1000Pa2Under S atmosphere
600 DEG C are handled 4 hours, are prepared the titanium deoxid film of sulfur doping, have effectively been widened the absorption region of visible ray.Using
More than 420nm light source carries out photocatalysis test, and sample is degradable by degraded solutions at 4 hours, and control sample just completes hundred
Less than/ten degraded.Visible light-responded titanium dioxide can also be prepared using the method for the nonmetal dopings such as N, B, C, Cl
Titanium material.
Hydrogen reduction method can prepare the visible light-responded titanic oxide material of black.(the Xiaobo such as Xiaobo Chen
Chen, Lei Liu, Peter Y.Yu, Samuel S.Mao, Science, 2011, Vol 331,746) existed using hydrogen reduction method
Under 20bar atmosphere of hydrogen, carried out at a temperature of 200 DEG C, by the processing of 5 days, prepare black titanium dioxide powder.Due to depositing
In substantial amounts of Ti3+So that there is auto-doping phenomenon in titanic oxide material, effectively raises the suction of visible region titanium dioxide
Receive, there is good photocatalytic activity.Plasma asistance hydrogen reducing (Y.K.Chae, S.Mori, M.Suzuki, Thin
Solid Films 517,2009,4260-4263) it is similarly applied to prepare black titanium dioxide material, but generally such side
The plasma of formula application is in vacuum hypobaric.Under plasmaassisted, the time of titanic oxide material melanism is big
Width foreshortens to several hours, and titanic oxide material prepared by such a mode possesses good visible light-responded and photocatalysis characteristic.
The methods of above-mentioned doping, hydrogen reducing, plasmaassisted hydrogen reducing, prepares black titanium dioxide material, typically
Process is complex, it is necessary to high temperature hyperbar long time treatment, or vacuum low pressure long time treatment, the possibility of continuous processing
Property is not high, influences practical application.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of black titanium dioxide coating, this method pole
The big energy band and photoresponse scope that change titanic oxide material, the black TiO of acquisition2Coating is in visible ray, infrared light district
Absorption improve, it is seen that/infrared photocatalytic activity greatly improves；Simultaneously because it can deposit coated in the material table such as polymer
Face, there is important value in the practical applications such as DSSC, visible ray hydrogen manufacturing and environmental improvement.
The invention provides a kind of preparation method of black titanium dioxide coating, including：
(1) normal pressure, room temperature in reaction cavity, are passed through TiCl under conditions of 200 DEG C4、O2With the mixing of discharge gas
Gas, opens normal pressure kHz radio frequency plasma power supplys, and deposition obtains TiO2Coating；
(2) above-mentioned power supply is replaced by normal pressure MHz radio frequency plasma power supplys, is passed through the mixed gas of helium and hydrogen,
Open radio-frequency power supply and produce hydrogen plasma, handled 1~60 minute under normal temperature, obtain black titanium dioxide coating.
TiCl in the step (1)4、O2Flow-rate ratio with discharge gas is 1000:10:25~200:1:2(sccm)；
Wherein, TiCl4It is passed through under the protection of argon gas.
The discharge gas is one or both of argon gas, helium, preferably argon gas.
The frequency of normal pressure kHz radio frequency plasma power supplys in the step (1) is 10kHz~300kHz, preferably 10kHz
~100kHz, voltage are 1000~30000v.Depending on sedimentation time is with coating layer thickness.
The flow-rate ratio of helium and hydrogen in the step (2) is 2~50:1.Argon gas, flow now can also be included
Than for 2~50:1~20:1.
The frequency of normal pressure MHz radio frequency plasma power supplys in the step (2) is 1MHz~300MHz, preferably 10MHz
~50MHz, power are 40~200W.
The deposition and the block media of processing are in quartz, aluminium oxide ceramics, polytetrafluoroethylene (PTFE), glass, mica
It is one or more of.It is preferred that quartz, aluminium oxide ceramics and combinations thereof.
The discharging gap of the dielectric barrier discharge plasma reactor is 0.5-5mm.
TiCl of the invention first with normal pressure kHz scopes4/O2The plasma-deposited acquisition TiO of/Ar2Coating, and then
Coating is sent into the inert gas plasmas such as normal pressure MHz radio frequencies He, a certain proportion of hydrogen is passed through, produces the work of high concentration
Property hydrogen ion, by the acceleration of radio frequency sheaths, bombard coating surface, whole course of reaction effectively accelerated, relatively low
Deposition and treatment temperature under, within several minutes, obtain black TiO2Coating, change TiO2Band structure and light absorbs it is special
Property.Handle the black titanium dioxide obtained by the method has higher ultraviolet light, visible ray and infrared Absorption special simultaneously
Property.
Atmospheric pressure MHz plasma pyrolysis hydrogen molecule can provide higher reactive hydrogen ions concentration.Pass through
Campbell thermally decomposes formula, and in 500K, the heat resolve velocity constant of hydrogen is：
K (500K)=2.20 × 10-53cm3/s。
And under plasma conditions, pass through Bolsig+Software simulates RF-plasma processing procedures, and the decomposition of hydrogen is anti-
The velocity constant is answered to be：
K (50W)=5.27 × 10-17cm3/s。
So in atmospheric plasma environment, can be under relatively low discharge power, there is provided the work of a high concentration
Property hydrogen ion atmosphere and relatively low substrate temperature, effectively accelerate whole course of reaction.Simultaneously as using plasma medium
The mode of barrier discharge, H+Ion can be accelerated in the sheaths close to material and coating surface, promote it with higher energy
Amount is reacted with surface, promotes the progress of reduction reaction.
Beneficial effect
(1) present invention is especially suitable for the materials such as the poor polymer of temperature tolerance, textile because depositing temperature is less than 200 DEG C
Material surface prepares black TiO2Coating；
(2) present invention is carried out at ambient pressure due to depositing and handling, and reduction reaction speed is fast, can apply to black
TiO2Prepared by the on-line continuous of coating, have good actual application value；
(3) present invention promotes it using the atmosphere of high concentration reactive hydrogen ions and the sheaths acceleration of plasma
Surface reduction is carried out with higher speed, greatly changes the energy band and photoresponse scope of titanic oxide material, is obtained
Black TiO2Coating improves in the absorption of visible ray, infrared light district, it is seen that/infrared photocatalytic activity greatly improves；While by
In that can deposit coated in material surfaces such as polymer, in DSSC, visible ray hydrogen manufacturing and environmental improvement etc.
There is important value in practical application.
Brief description of the drawings
Fig. 1 is the schematic diagram that atmospheric pressure plasma discharge prepares coating of titanium dioxide；
Optical photographs and visible uv absorption spectra of the Fig. 2 for coating of titanium dioxide before and after RF plasma processing；
Wherein, (a) is the coating of titanium dioxide prepared at 200 DEG C on quartz plate；(b) it is the two of the discoloration of 50W RF plasma processings
Titania coating, 10 minutes processing times；
Fig. 3 a-b are that the coating of titanium dioxide XPS-REELS before and after 50W RF plasma processings tests H atom content
Figure；
Fig. 4 is 200 DEG C and prepared and the optical photograph of the titanium deoxid film of 160W RF plasma processings and visible purple
Outer abosrption spectrogram；Wherein, (a) is the coating of titanium dioxide prepared at 200 DEG C on quartz plate；(b) it is 160W radio frequency plasmas
The coating of titanium dioxide of body processing discoloration, 30 minutes processing times；
Fig. 5 is under the optical photograph and xenon lamp irradiation of coating of titanium dioxide in nickel foam before and after RF plasma processing
The photocatalytic degradation methylene blue empirical curve of (below 400nm ultraviolet lights have filtered out).
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
At 200 DEG C of quartz substrate temperature (discharging gap of barrier discharge plasma reactor is 2mm), first using normal
Press plasma gas phase deposition coating of titanium dioxide, Ar:O2:Ar(TiCl4) flow is respectively 950:10:20 (sccm), during deposition
Between 20min, the frequency of plasma is 60kHz, voltage 10000v.
Deposition terminates, and closes kHz power supplys and deposition reaction gas, is cooled to room temperature, changes 13.56MHz radio frequency plasmas
Body power supply, by He/H2Gaseous mixture is according to 50:1 ratio is passed through in reaction cavity, and 50W is handled 10 minutes, takes out black titanium dioxide
Coating.
The optical picture of coating of titanium dioxide is as shown in Figure 2.By ultraviolet-uisible spectrophotometer to titanium dioxide before and after the processing
The absorbance of titanium coating is characterized.As can be seen that depositing untreated coating of titanium dioxide as white, reflect TiO2Allusion quotation
The visible ultraviolet spectra of type, do not absorbed higher than 320nm light area.And existed by the coating of 10 minutes RF plasma processings
Have greatly increased in visible absorption value.Simultaneously coating spectral absorption threshold value also have it is very big widen, from 387nm lifting to
655nm wavelength, changes TiO2The band gap of material.Fig. 3 show the before processing of the REELS functional measurements in being tested by XPS
The H loss of coating of titanium dioxide afterwards, as a result have found, 32% H loss occurs in the sample by 50W corona treatments,
Illustrate the doping for H occurred.
Embodiment 2
At 180 DEG C of quartz substrate temperature (discharging gap of barrier discharge plasma reactor is 2mm), first using normal
Press plasma gas phase deposition coating of titanium dioxide, Ar:O2:Ar(TiCl4) flow is respectively 500:10:10 (sccm), during deposition
Between 30min, the frequency of plasma is 30kHz, voltage 20000v.
Deposition terminates, and closes kHz power supplys and deposition reaction gas, is cooled to room temperature, changes 1MHz radio frequency plasmas electricity
Source, by He/H2Gaseous mixture is according to 15:1 ratio is passed through in reaction cavity, and 160W is handled 30 minutes, is taken out black titanium dioxide and is applied
Layer.
Optical photograph and visible ultra-violet absorption spectrum such as Fig. 4 before and after the processing, it is seen then that deposition of titanium oxide coating is visible
Light and infrared part only have extremely low absorption, and treated black titanium dioxide coating is in visible region and infrared part
It is obviously improved, the absorption threshold value of sample is changed into 901.8nm.It can be seen that after by atmospheric pressure plasma jet treatment, two
The absorption threshold value of titania coating is obviously improved, while also has great lifting between visible ray and near infrared region.This shows
The very big change that the gap structure of titanium dioxide occurs.
Embodiment 3
By metal nickel foam at 100 DEG C of temperature (discharging gap of barrier discharge plasma reactor is 2mm), first adopt
With normal pressure plasma gas phase deposition coating of titanium dioxide, Ar:O2:Ar(TiCl4) flow is respectively 300:2:10 (sccm), sink
Product time 40min, the frequency of plasma is 100kHz, voltage 10000v.
Deposition terminates, and closes kHz power supplys and deposition reaction gas, is cooled to room temperature, changes 27MHz radio frequency plasmas electricity
Source, by He/H2Gaseous mixture is according to 30:1 ratio is passed through in reaction cavity, and 100W is handled 30 minutes, is taken out black titanium dioxide and is applied
Layer.
Shown in Fig. 5, the optical photograph of metal foam coating of titanium dioxide before and after the processing is shown, processing Front-coating mirror is white
Color, the obvious melanism of coating after processing.
From Fig. 5 it has been also found that when light source uses xenon lamp, and filter out the ultraviolet portion light source less than 400nm, methylene
During the degradation product that blue solution is tested as photocatalysis, possessed significantly by the metal nickel foam coating of titanium dioxide for handling blackening
Photocatalysis performance, have outstanding visible ray (or natural to the degradation rate of methylene blue far above untreated white as former state
Light) photocatalytic activity.
Claims (8)
1. a kind of preparation method of black titanium dioxide coating, including：
(1) normal pressure, room temperature in reaction cavity, are passed through TiCl under conditions of 200 DEG C4、O2With the mixed gas of discharge gas,
Normal pressure kHz radio frequency plasma power supplys are opened, deposition obtains TiO2Coating；
(2) above-mentioned power supply is replaced by normal pressure MHz radio frequency plasma power supplys, is passed through the mixed gas of helium and hydrogen, opened
Radio-frequency power supply produces hydrogen plasma, is handled 1~60 minute under normal temperature, obtains black titanium dioxide coating.
A kind of 2. preparation method of black titanium dioxide coating according to claim 1, it is characterised in that：The step
(1) TiCl in4、O2Flow-rate ratio with discharge gas is 1000:10:25~200:1:2；Wherein, TiCl4In the protection of argon gas
Under be passed through.
A kind of 3. preparation method of black titanium dioxide coating according to claim 1 or 2, it is characterised in that：It is described to put
Electric body is one or both of argon gas, helium.
A kind of 4. preparation method of black titanium dioxide coating according to claim 1, it is characterised in that：The step
(1) frequency of the normal pressure kHz radio frequency plasma power supplys in is 10kHz~300kHz, and voltage is 1000~30000v.
A kind of 5. preparation method of black titanium dioxide coating according to claim 1, it is characterised in that：The step
(2) flow-rate ratio of helium and hydrogen in is 2~50:1.
A kind of 6. preparation method of black titanium dioxide coating according to claim 1, it is characterised in that：The step
(2) frequency of the normal pressure MHz radio frequency plasma power supplys in is 1MHz~300MHz, and power is 40~200W.
A kind of 7. preparation method of black titanium dioxide coating according to claim 1, it is characterised in that：It is described deposition and
The block media of processing is the one or more in quartz, aluminium oxide ceramics, polytetrafluoroethylene (PTFE), glass, mica.
A kind of 8. preparation method of black titanium dioxide coating according to claim 7, it is characterised in that：The medium resistance
The discharging gap for keeping off discharging plasma reactor is 0.5-5mm.
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