CN102407107A - Metal/TiO2 composite multilayer film photocatalyst and preparation method thereof - Google Patents
Metal/TiO2 composite multilayer film photocatalyst and preparation method thereof Download PDFInfo
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- CN102407107A CN102407107A CN201110354462XA CN201110354462A CN102407107A CN 102407107 A CN102407107 A CN 102407107A CN 201110354462X A CN201110354462X A CN 201110354462XA CN 201110354462 A CN201110354462 A CN 201110354462A CN 102407107 A CN102407107 A CN 102407107A
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Abstract
The invention relates to a metal/TiO2 composite multilayer film photocatalyst and a preparation method thereof. The method comprises the following steps of: (1) putting a carrier into a vacuum reaction cavity, and controlling pressure in the vacuum reaction cavity in a first pressure range; (2) introducing argon into the vacuum reaction cavity, and controlling pressure in the vacuum reaction cavity in a second pressure range; (3) respectively depositing a first TiO2 film layer, a Pt film layer and a second TiO2 film layer on the surface of the carrier by a magnetron sputtering method to obtain a photocatalyst with a three-layer film structure; and (4) sintering the photocatalyst obtained in the step (3) in air, and naturally cooling to room temperature. The photocatalyst has the advantages of high catalytic activity and low cost.
Description
Technical field
The present invention relates to a kind of metal/TiO
2Composite multi-layer film photocatalyst and preparation method thereof relates in particular to a kind of TiO
2/ Pt/TiO
2Composite multi-layer film photocatalyst and preparation method thereof.
Background technology
In recent years, water environmental problems has become one of subject matter of restriction human survival and development, utilizes that organic pollution is one of important means of working as the pre-treatment water environment pollution in the conductor photocatalysis technology degradation water.Its principle is that the electronics on the catalyst valence band obtains the energy of photon, thereby transits to conduction band, forms light induced electron, then correspondingly forms photohole on the valence band when adopting energy to penetrate its surface greater than the illumination of semiconductor light-catalyst energy gap.The hole can with the hydrone or the OH of semiconductor surface absorption
-Oxidation reaction takes place, and generates hydroxyl radical free radical; Electronics then can with the oxygen molecule generation reduction reaction of semiconductor surface absorption, generate hydroxyl radical free radical, superoxide ion free radical and HO
2Free radical.These free radicals all have extremely strong oxidisability, can various organic dyestuff be direct oxidation into water, CO
2Deng inorganic molecules, thereby reduce its harm to environment.
The research of photochemical catalyst at present mainly concentrates on TiO
2Yet, have highly active TiO
2Photochemical catalyst all is pulverous, but powder catalyst in the aqueous solution, be easy to reunite and use after can't reclaim, this is increasing cost virtually, has influenced the business-like process of photocatalysis technology.Simultaneously because TiO
2Have narrower spectral response range (energy gap is 3.2eV, and its spectral response range is at ultraviolet region) and lower birth defects such as quantum efficiency as photochemical catalyst.Therefore, in practical application, exploitation has the two-dimentional TiO that higher electronics-hole utilization rate is easy to reclaim
2Film photocatalyst has become the main direction of current photocatalyst material research.
In order to solve the compound problem in light induced electron and hole, method such as the researcher mainly takes to mix, and semiconductor is compound and noble metal decorated is to TiO
2Carry out modification.Wherein, noble metal nano particles is adsorbed on TiO
2The compound system that the surface is constituted has special contact interface structure because of it and the electron transfer characteristic receives people's attention always.For example the researcher is attached to TiO with sheet metal
2On the ceramic target, adopt the method for cosputtering to prepare metal/TiO
2Laminated film, find these metal/TiO
2Laminated film degradating organic dye more efficiently.
At the metal/TiO that studies before
2Compound system in, mostly metallic particles is to be embedded in the TiO2 film.Yet except this Embedded structure, artificial layer structure also can be used as a kind of raising TiO
2The approach of film light catalytic performance.For example the researcher is with TiO
2Film is combined with each other with the network structure of silver, finds that this compound layer structure can improve TiO significantly
2The photo-catalysis capability of film.
Summary of the invention
To the deficiency of prior art, the technical problem that the present invention solves provides metal/TiO that a kind of catalytic activity is high, cost is low
2Composite multi-layer film photocatalyst and preparation method thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is achieved in that a kind of metal/TiO
2The composite multi-layer film photocatalyst is deposited on carrier surface, and wherein, said photochemical catalyst comprises a TiO
2Thin layer, Pt thin layer and the 2nd TiO
2Thin layer, a said TiO
2Thin layer is deposited on said carrier surface, and said Pt thin layer is deposited on a said TiO
2The thin layer surface, said the 2nd TiO
2Thin layer is deposited on said Pt thin layer surface.
Preferably, said carrier is a quartz plate.
For solving the problems of the technologies described above, technical scheme of the present invention can also realize like this:
A kind of metal/TiO
2The preparation method of composite multi-layer film photocatalyst comprises the steps:
(1) carrier is positioned in the vacuum reaction chamber, the pressure in the vacuum reaction chamber is controlled at first pressure limit;
(2) in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at second pressure limit;
(3) deposit a TiO through magnetron sputtering method respectively in said carrier surface
2Thin layer, Pt thin layer and the 2nd TiO
2Thin layer, thereby the photochemical catalyst of acquisition trilamellar membrane structure;
(4) photochemical catalyst that obtains in the said step (3) is carried out sintering in air, naturally cool to room temperature then.
Preferably, said first pressure limit is 1 * 10
-4Pa-3 * 10
-4Pa.
Preferably, said second pressure limit is 1Pa-2Pa.
Preferably, also comprise a rf magnetron sputtering appearance in the said step (3), the operating frequency of said rf magnetron sputtering appearance is 13.56MHz.
Preferably, deposition the one TiO in the said step (3)
2Thin layer and deposition the 2nd TiO
2The sputtering power of thin layer is 180-220W, and the sputtering power of deposition Pt thin layer is 25-35W in the said step (3).
Preferably, a said TiO
2Thin layer and the 2nd TiO
2The sedimentation time of thin layer is 5 minutes, and the sedimentation time of said Pt thin layer is 0-80s.
Preferably, the sintering temperature of in the said step (4) photochemical catalyst being carried out sintering in air is 250 ℃-500 ℃, and sintering time is 30 minutes-2 hours.
Preferably, also comprise TiO in the said step (3)
2Ceramic target and Pt target, said TiO
2The diameter of ceramic target and Pt target is 50mm.
Compared with prior art, the invention has the beneficial effects as follows:
(1) adopt radio-frequency magnetron sputter method to prepare metal/TiO
2Composite multilayer membrane can be realized effective regulation and control of structure, component and metal deposition to the TiO2 film, and utilizes the film of this method preparation on different substrates, to deposit, have bigger flexibility with can be handling.
(2) the simple TiO that compares
2Film, metal/TiO
2Composite multilayer membrane can improve the ability of degradating organic dye effectively, can more effectively utilize solar energy to reach the purpose of the depollution of environment.
(3) metal/TiO
2Composite multilayer membrane can not only improve photocatalytic activity, and helps recycling, and has practiced thrift use cost.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the invention; To do to introduce simply to the accompanying drawing of required use among the embodiment below; Obviously, the accompanying drawing relevant of the present invention in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Shown in Figure 1 is to prepare metal/TiO among the present invention
2The step sketch map of composite multi-layer film photocatalyst;
Shown in Figure 2 for utilizing the TiO of radio-frequency magnetron sputter method preparation in the embodiment of the invention one
2/ Pt/TiO
2The X ray diffracting spectrum of composite multi-layer film photocatalyst;
Shown in Figure 3 for utilizing the TiO of radio-frequency magnetron sputter method preparation in the embodiment of the invention one
2/ Pt/TiO
2The AFM photo of composite multi-layer film photocatalyst;
Shown in Figure 4 for utilizing the TiO of radio-frequency magnetron sputter method preparation in the embodiment of the invention one
2/ Pt/TiO
2The ultraviolet-visible absorption spectra of composite multi-layer film photocatalyst;
Shown in Figure 5 for utilizing the TiO of radio-frequency magnetron sputter method preparation in the embodiment of the invention one
2/ Pt/TiO
2The composite multi-layer film photocatalyst is to the degraded situation sketch map of methylene blue;
Shown in Figure 6 for utilizing the TiO of radio-frequency magnetron sputter method preparation in the embodiment of the invention one
2/ Pt/TiO
2The sketch map of the photocatalysis circulation experiment of composite multi-layer film photocatalyst.
The specific embodiment
The present invention relates to a kind of metal/TiO
2The composite multi-layer film photocatalyst, it is deposited on carrier surface, comprises a TiO
2Thin layer, Pt thin layer and the 2nd TiO
2Thin layer.Wherein, a TiO
2Thin layer is deposited on carrier surface, and the Pt thin layer is deposited on a TiO
2The thin layer surface, the 2nd TiO
2Thin layer is deposited on Pt thin layer surface.The multi-layer film structure of this photochemical catalyst can be by multiple preparation method's realization, for example: chemical vapour deposition technique, sol-gal process and magnetron sputtering method etc.
Chemical vapour deposition technique, sol-gal process and magnetron sputtering ratio juris are distinguished as follows:
Chemical vapour deposition technique: utilize gas-phase reaction, under conditions such as high temperature, plasma or laser is auxiliary, control factors such as reacting gas, airflow rate, substrate material temperature, thus the nucleating growth process of control nanoparticle film.The temperature of reacting required in this method is too high, generally requires about 1000 ℃, has therefore limited the practical application of this method.
Sol-gal process: the compound with containing high chemism component is made presoma; Under liquid phase, these raw materials are evenly mixed, and be hydrolyzed, the condensation chemical reaction, in solution, form stable vitreosol system; Colloidal sol is through slow polymerization; Form the gel of three-dimensional space network structure, be full of the solvent that loses flowability between gel network, form gel.Whole sol-gel process required time is longer, has a large amount of micropores in the gel, in dry run, can overflow many gases and organic matter, contaminated environment.
Magnetron sputtering method: the characteristics that have certain kinetic energy after utilizing the ion that has electric charge in electric field, to quicken; Ion is guided into the target electrode of desiring by sputter; Under the suitable situation of ion energy, the ion of incident with the collision process of the atom on target surface in the latter is sputtered out.These atoms by sputter have certain kinetic energy, and can be along certain direction directive substrate, thereby realize the deposition of film on substrate.The film of this kind method preparation has high-quality, high density, and characteristics such as good binding property and intensity, and also device performance is stable, is convenient to operation, and technology is controlled easily, produces good reproducibility.
The carrier that is adopted among the present invention can be selected from silica gel, active carbon, activated alumina, glass fiber mesh, hollow ceramic ball, sea sand, hollow glass micro-ball, quartz glass plate (pipe), simple glass sheet, wave carrier piece, optical fiber, bead, lamellar graphite, the block electrodeless carriers such as earth, ceramic tile, zeolite, stainless steel, refractory brick, alloy, nickel foam that mix; Also can adopt some natural minerals, like zeolite, bentonite, diatomite etc.; Also can select organic carriers such as perfluorinated sulfonic acid film, celluloid film, polyethylene, fluororesin for use.
Be that example is further set forth technical scheme of the present invention below with the magnetron sputtering method:
Embodiment one:
TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst utilizes repeatedly, and radio-frequency magnetron sputter method is prepared from.Wherein, TiO
2The diameter of ceramic target and Pt target is 50mm, TiO
2The sputtering power of target and Pt target is respectively 200W and 30W, and the operating frequency of rf magnetron sputtering appearance is 13.56MHz.
Join shown in Figure 1, TiO
2/ Pt/TiO
2The preparation process of composite multi-layer film photocatalyst comprises the steps:
(1), with quartz plate carrier (1.5 * 1cm
2) be positioned in the vacuum reaction chamber, at room temperature place apart from target (TiO the quartz plate carrier is parallel
2Ceramic target or Pt target) on the sample stage of 60mm;
(2), through mechanical rotation pump or eddy current molecular pump the pressure in the vacuum reaction chamber is reduced to 1 * 10
-4Pa;
(3), in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at 1.5Pa;
(4), deposition the one TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and the surface that these ions accumulate in the quartz plate carrier forms a TiO
2Thin layer, a said TiO
2The time of thin layer deposition is 5 minutes;
(5), deposition Pt thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon Pt target surface with very high speed, generate plasma sputter, these ions accumulate in a TiO
2The thin layer surface forms the Pt thin layer, and the time of said Pt thin layer deposition is 20 seconds;
(6), deposition the 2nd TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and these ions accumulate in Pt thin layer surface and form the 2nd TiO
2Thin layer, the 2nd TiO
2The time of thin layer deposition is 5 minutes;
(7), three-layer thin-film layer deposition forms TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst, with photochemical catalyst in air with 300 ℃ of sintering 1 hour, naturally cool to room temperature then.
In step (4), step (5) and step (6), before each sputter, target all will be in argon gas sputter 3min in advance.
Below in conjunction with TiO
2/ Pt/TiO
2The performance of prepared sample in the photocatalysis performance method of testing of composite multi-layer film photocatalyst sample and the experimental data illustrative embodiment one:
One, experiment purpose
For research institute prepares sample (TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst) photocatalysis performance, the experiment of degradation of dye methylene blue (MB) under the design ultraviolet light.Utilize the character of methylene blue photocatalytic degradation decolouring,, observe the variation of solution colour, and then obtain percent of decolourization through the absorbance of ultraviolet/visible absorbance spectrometry solution at 664nm.
Two, experiment content
The concrete photocatalysis performance of material is tested as follows: with TiO
2/ Pt/TiO
2Film is placed on 4ml MB solution (2 * 10 is housed
-5M) in the rectangular tank, before illumination, the dye solution that contains film catalyst stirs two hours to reach the adsorption equilibrium between film catalyst, MB, the water in the darkroom.Utilize visible/ultraviolet/near infrared spectrometer to record the concentration of the MB solution after the adsorption equilibrium, and with it as intrinsic concentration value (C
0), the light source of light-catalyzed reaction be apart from the low pressure mercury lamp at container 10cm place (λ=256nm, 30W), TiO
2/ Pt/TiO
2Film has that one side of film to place towards light source, and the temperature in the reaction unit to remain on room temperature, is avoided the generation of heat catalysis through fan control, after the certain hour section, get reacted solution a little, measure the concentration (C) of MB in the solution at this moment.Be testing film stability of sample and reuse, after the MB that adds all degrades fully, film catalyst repeatedly washed with deionized water, then baking 30min under 150 ℃.Sample with oven dry is placed in the new MB solution then, and the degradation process of MB was circulated as the second time, and this process repeats several times.
Three, analysis of experimental data and conclusion
Join shown in Figure 2ly, utilize the TiO of radio-frequency magnetron sputter method preparation among the embodiment one
2/ Pt/TiO
2The X ray diffracting spectrum of composite multilayer membrane is thanked through XRD constituent analysis and debye and to be reined in formula and calculate, and that experiment obtains is Pt/TiO
2Composite construction, TiO
2Film is that anatase and The grain size are about about 75nm.
Join shown in Figure 3ly, utilize the TiO of radio-frequency magnetron sputter method preparation among the embodiment one
2/ Pt/TiO
2The AFM photo of composite multilayer membrane, as can be seen from the figure, The grain size is about 80nm, and the root-mean-square value of the roughness on top layer (RMS) is 1.97nm.
Join shown in Figure 4ly, utilize the TiO of radio-frequency magnetron sputter method preparation among the embodiment one
2/ Pt/TiO
2The ultraviolet-visible absorption spectra of composite multilayer membrane, as can be seen from the figure this photochemical catalyst pure TiO that compares
2The film red shift, the estimation band gap is 3.10ev.
Join shown in Figure 5ly, utilize the TiO of radio-frequency magnetron sputter method preparation among the embodiment one
2/ Pt/TiO
2Composite multilayer membrane is to the degradation rate situation of methylene blue (MB).The MB solution that does not add any catalyst had only the degraded about 25% in 2.5 hours at UV-irradiation, added photochemical catalyst and did not still add under the situation of illumination, and MB solution only has fainter degraded, and this explains TiO
2/ Pt/TiO
2Composite multilayer membrane has reached adsorption equilibrium in dyestuff.Add pure TiO
2Film is as photochemical catalyst, illumination 2.5 hours, and the degradation rate of MB solution is 35%.But adding TiO
2/ Pt/T TiO
2After the composite multilayer membrane, equally at UV-irradiation after 2.5 hours, MB shows tangible degradation effect, arrives about 96% degraded.
Join shown in Figure 6: the TiO that utilizes the radio-frequency magnetron sputter method preparation among the embodiment one
2/ Pt/TiO
2Any change as can be seen from the figure, does not take place through structures of samples after four cyclic tests in the photocatalysis loop test experiment of composite multilayer membrane, and interpret sample can be recycled.
At other embodiments, step (2) but in air pressure value in the vacuum reaction chamber in 1 * 10
-4Pa-3 * 10
-4Pa; Step (3) but in vacuum reaction chamber, feed argon gas back cavity internal gas pressure also value in 1Pa-2Pa; Depositing Ti O in step (4) and the step (6)
2The desirable 180-220W of the sputtering power of film; The desirable 25-35W of sputtering power of deposition Pt film in the step (5); Desirable 250 ℃-500 ℃ of sintering temperature in the step (7), sintering time can be 30 minutes-2 hours.
Embodiment two (time of Pt thin layer deposition is 0 second):
TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst utilizes repeatedly, and radio-frequency magnetron sputter method is prepared from.Wherein, TiO
2The diameter of ceramic target and Pt target is 50mm, TiO
2The sputtering power of target and Pt target is respectively 200W and 30W, and the operating frequency of rf magnetron sputtering appearance is 13.56MHz.
TiO
2/ Pt/TiO
2The preparation process of composite multi-layer film photocatalyst comprises the steps:
(1), with quartz plate carrier (1.5 * 1cm
2) be positioned in the vacuum reaction chamber, at room temperature place apart from target (TiO the quartz plate carrier is parallel
2Ceramic target or Pt target) on the sample stage of 60mm;
(2), through mechanical rotation pump or eddy current molecular pump the pressure in the vacuum reaction chamber is reduced to 1 * 10
-4Pa;
(3), in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at 1.5Pa;
(4), deposition the one TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and the surface that these ions accumulate in the quartz plate carrier forms a TiO
2Thin layer, a said TiO
2The time of thin layer deposition is 5 minutes;
(5), deposition Pt thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon Pt target surface with very high speed, generate plasma sputter, these ions accumulate in a TiO
2The thin layer surface forms the Pt thin layer, and the time of said Pt thin layer deposition is 0 second;
(6), deposition the 2nd TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and these ions accumulate in Pt thin layer surface and form the 2nd TiO
2Thin layer, the 2nd TiO
2The time of thin layer deposition is 5 minutes;
(7), three-layer thin-film layer deposition forms TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst, with photochemical catalyst in air with 300 ℃ of sintering 1 hour, naturally cool to room temperature then.
In step (4), step (5) and step (6), before each sputter, target all will be in argon gas sputter 3min in advance.
Embodiment two can be used for preparing pure TiO2 film.
Embodiment three (time of Pt thin layer deposition is 3 seconds):
TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst utilizes repeatedly, and radio-frequency magnetron sputter method is prepared from.Wherein, TiO
2The diameter of ceramic target and Pt target is 50mm, TiO
2The sputtering power of target and Pt target is respectively 200W and 30W, and the operating frequency of rf magnetron sputtering appearance is 13.56MHz.
TiO
2/ Pt/TiO
2The preparation process of composite multi-layer film photocatalyst comprises the steps:
(1), with quartz plate carrier (1.5 * 1cm
2) be positioned in the vacuum reaction chamber, at room temperature place apart from target (TiO the quartz plate carrier is parallel
2Ceramic target or Pt target) on the sample stage of 60mm;
(2), through mechanical rotation pump or eddy current molecular pump the pressure in the vacuum reaction chamber is reduced to 1 * 10
-4Pa;
(3), in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at 1.5Pa;
(4), deposition the one TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and the surface that these ions accumulate in the quartz plate carrier forms a TiO
2Thin layer, a said TiO
2The time of thin layer deposition is 5 minutes;
(5), deposition Pt thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon Pt target surface with very high speed, generate plasma sputter, these ions accumulate in a TiO
2The thin layer surface forms the Pt thin layer, and the time of said Pt thin layer deposition is 3 seconds;
(6), deposition the 2nd TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and these ions accumulate in Pt thin layer surface and form the 2nd TiO
2Thin layer, the 2nd TiO
2The time of thin layer deposition is 5 minutes;
(7), three-layer thin-film layer deposition forms TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst, with photochemical catalyst in air with 300 ℃ of sintering 1 hour, naturally cool to room temperature then.
In step (4), step (5) and step (6), before each sputter, target all will be in argon gas sputter 3min in advance.
Embodiment four (time of Pt thin layer deposition is 6 seconds):
TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst utilizes repeatedly, and radio-frequency magnetron sputter method is prepared from.Wherein, TiO
2The diameter of ceramic target and Pt target is 50mm, TiO
2The sputtering power of target and Pt target is respectively 200W and 30W, and the operating frequency of rf magnetron sputtering appearance is 13.56MHz.
TiO
2/ Pt/TiO
2The preparation process of composite multi-layer film photocatalyst comprises the steps:
(1), with quartz plate carrier (1.5 * 1cm
2) be positioned in the vacuum reaction chamber, at room temperature place apart from target (TiO the quartz plate carrier is parallel
2Ceramic target or Pt target) on the sample stage of 60mm;
(2), through mechanical rotation pump or eddy current molecular pump the pressure in the vacuum reaction chamber is reduced to 1 * 10
-4Pa;
(3), in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at 1.5Pa;
(4), deposition the one TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and the surface that these ions accumulate in the quartz plate carrier forms a TiO
2Thin layer, a said TiO
2The time of thin layer deposition is 5 minutes;
(5), deposition Pt thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon Pt target surface with very high speed, generate plasma sputter, these ions accumulate in a TiO
2The thin layer surface forms the Pt thin layer, and the time of said Pt thin layer deposition is 6 seconds;
(6), deposition the 2nd TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and these ions accumulate in Pt thin layer surface and form the 2nd TiO
2Thin layer, the 2nd TiO
2The time of thin layer deposition is 5 minutes;
(7), three-layer thin-film layer deposition forms TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst, with photochemical catalyst in air with 300 ℃ of sintering 1 hour, naturally cool to room temperature then.
In step (4), step (5) and step (6), before each sputter, target all will be in argon gas sputter 3min in advance.
Embodiment five (time of Pt thin layer deposition is 50 seconds):
TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst utilizes repeatedly, and radio-frequency magnetron sputter method is prepared from.Wherein, TiO
2The diameter of ceramic target and Pt target is 50mm, TiO
2The sputtering power of target and Pt target is respectively 200W and 30W, and the operating frequency of rf magnetron sputtering appearance is 13.56MHz.
TiO
2/ Pt/TiO
2The preparation process of composite multi-layer film photocatalyst comprises the steps:
(1), with quartz plate carrier (1.5 * 1cm
2) be positioned in the vacuum reaction chamber, at room temperature place apart from target (TiO the quartz plate carrier is parallel
2Ceramic target or Pt target) on the sample stage of 60mm;
(2), through mechanical rotation pump or eddy current molecular pump the pressure in the vacuum reaction chamber is reduced to 1 * 10
-4Pa;
(3), in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at 1.5Pa;
(4), deposition the one TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and the surface that these ions accumulate in the quartz plate carrier forms a TiO
2Thin layer, a said TiO
2The time of thin layer deposition is 5 minutes;
(5), deposition Pt thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon Pt target surface with very high speed, generate plasma sputter, these ions accumulate in a TiO
2The thin layer surface forms the Pt thin layer, and the time of said Pt thin layer deposition is 50 seconds;
(6), deposition the 2nd TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and these ions accumulate in Pt thin layer surface and form the 2nd TiO
2Thin layer, the 2nd TiO
2The time of thin layer deposition is 5 minutes;
(7), three-layer thin-film layer deposition forms TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst, with photochemical catalyst in air with 300 ℃ of sintering 1 hour, naturally cool to room temperature then.
In step (4), step (5) and step (6), before each sputter, target all will be in argon gas sputter 3min in advance.
Embodiment six (time of Pt thin layer deposition is 80 seconds):
TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst utilizes repeatedly, and radio-frequency magnetron sputter method is prepared from.Wherein, TiO
2The diameter of ceramic target and Pt target is 50mm, TiO
2The sputtering power of target and Pt target is respectively 200W and 30W, and the operating frequency of rf magnetron sputtering appearance is 13.56MHz.
TiO
2/ Pt/TiO
2The preparation process of composite multi-layer film photocatalyst comprises the steps:
(1), with quartz plate carrier (1.5 * 1cm
2) be positioned in the vacuum reaction chamber, at room temperature place apart from target (TiO the quartz plate carrier is parallel
2Ceramic target or Pt target) on the sample stage of 60mm;
(2), through mechanical rotation pump or eddy current molecular pump the pressure in the vacuum reaction chamber is reduced to 1 * 10
-4Pa;
(3), in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at 1.5Pa;
(4), deposition the one TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and the surface that these ions accumulate in the quartz plate carrier forms a TiO
2Thin layer, a said TiO
2The time of thin layer deposition is 5 minutes;
(5), deposition Pt thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon Pt target surface with very high speed, generate plasma sputter, these ions accumulate in a TiO
2The thin layer surface forms the Pt thin layer, and the time of said Pt thin layer deposition is 80 seconds;
(6), deposition the 2nd TiO
2Thin layer: argon ion (Ar in the argon gas
+) under electromagnetic field effect, impinge upon TiO with very high speed
2The ceramic target surface generates plasma sputter, and these ions accumulate in Pt thin layer surface and form the 2nd TiO
2Thin layer, the 2nd TiO
2The time of thin layer deposition is 5 minutes;
(7), three-layer thin-film layer deposition forms TiO
2/ Pt/TiO
2The composite multi-layer film photocatalyst, with photochemical catalyst in air with 300 ℃ of sintering 1 hour, naturally cool to room temperature then.
In step (4), step (5) and step (6), before each sputter, target all will be in argon gas sputter 3min in advance.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and under the situation that does not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other concrete form.Therefore; No matter from which point; All should regard embodiment as exemplary; And be nonrestrictive, scope of the present invention is limited accompanying claims rather than above-mentioned explanation, therefore is intended to the implication of the equivalents that drops on claim and all changes in the scope are included in the present invention.Should any Reference numeral in the claim be regarded as limit related claim.
In addition; Describing according to embodiment though should be appreciated that this specification, is not that each embodiment only comprises an independently technical scheme; This narrating mode of specification only is for clarity sake; Those skilled in the art should make specification as a whole, and the technical scheme among each embodiment also can form other embodiments that it will be appreciated by those skilled in the art that through appropriate combination.
Claims (10)
1. metal/TiO
2The composite multi-layer film photocatalyst is deposited on carrier surface, it is characterized in that: said photochemical catalyst comprises a TiO
2Thin layer, Pt thin layer and the 2nd TiO
2Thin layer, a said TiO
2Thin layer is deposited on said carrier surface, and said Pt thin layer is deposited on a said TiO
2The thin layer surface, said the 2nd TiO
2Thin layer is deposited on said Pt thin layer surface.
2. metal/TiO according to claim 1
2The composite multi-layer film photocatalyst is characterized in that: said carrier is a quartz plate.
3. metal/TiO according to claim 1 or claim 2
2The preparation method of composite multi-layer film photocatalyst is characterized in that comprising the steps:
(1) carrier is positioned in the vacuum reaction chamber, the pressure in the vacuum reaction chamber is controlled at first pressure limit;
(2) in vacuum reaction chamber, feed argon gas and the pressure in the vacuum reaction chamber is controlled at second pressure limit;
(3) deposit a TiO through magnetron sputtering method respectively in said carrier surface
2Thin layer, Pt thin layer and the 2nd TiO
2Thin layer, thereby the photochemical catalyst of acquisition trilamellar membrane structure;
(4) photochemical catalyst that obtains in the said step (3) is carried out sintering in air, naturally cool to room temperature then.
4. metal/TiO according to claim 3
2The preparation method of composite multi-layer film photocatalyst is characterized in that: said first pressure limit is 1 * 10
-4Pa-3 * 10
-4Pa.
5. metal/TiO according to claim 3
2The preparation method of composite multi-layer film photocatalyst is characterized in that: said second pressure limit is 1Pa-2Pa.
6. metal/TiO according to claim 3
2The preparation method of composite multi-layer film photocatalyst is characterized in that: also comprise a rf magnetron sputtering appearance in the said step (3), the operating frequency of said rf magnetron sputtering appearance is 13.56MHz.
7. metal/TiO according to claim 3
2The preparation method of composite multi-layer film photocatalyst is characterized in that: deposition the one TiO in the said step (3)
2Thin layer and deposition the 2nd TiO
2The sputtering power of thin layer is 180-220W, and the sputtering power of deposition Pt thin layer is 25-35W in the said step (3).
8. metal/TiO according to claim 3
2The preparation method of composite multi-layer film photocatalyst is characterized in that: a said TiO
2Thin layer and the 2nd TiO
2The sedimentation time of thin layer is 5 minutes, and the sedimentation time of said Pt thin layer is 0-80s.
9. metal/TiO according to claim 3
2The preparation method of composite multi-layer film photocatalyst is characterized in that: the sintering temperature of in the said step (4) photochemical catalyst being carried out sintering in air is 250 ℃-500 ℃, and sintering time is 30 minutes-2 hours.
10. metal/TiO according to claim 3
2The preparation method of composite multi-layer film photocatalyst is characterized in that: said step also comprises TiO in (3)
2Ceramic target and Pt target, said TiO
2The diameter of ceramic target and Pt target is 50mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007931A (en) * | 2012-11-22 | 2013-04-03 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN109457227A (en) * | 2018-12-14 | 2019-03-12 | 五邑大学 | A kind of method that direct current magnetron sputtering process prepares photoelectrocatalysioxidization oxidization Ti electrode |
| CN110560136A (en) * | 2019-09-24 | 2019-12-13 | 桂林理工大学 | Photocatalytic film and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11300878A (en) * | 1998-04-24 | 1999-11-02 | Yazaki Corp | Anti-fogging and anti-fouling meter cover and its production |
| CN1502405A (en) * | 2002-11-26 | 2004-06-09 | 中国科学院广州能源研究所 | TiO2 photocatalyst film with inhomogeneously-doped metal ions on base body and preparation process thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11300878A (en) * | 1998-04-24 | 1999-11-02 | Yazaki Corp | Anti-fogging and anti-fouling meter cover and its production |
| CN1502405A (en) * | 2002-11-26 | 2004-06-09 | 中国科学院广州能源研究所 | TiO2 photocatalyst film with inhomogeneously-doped metal ions on base body and preparation process thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007931A (en) * | 2012-11-22 | 2013-04-03 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN103007931B (en) * | 2012-11-22 | 2014-05-21 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN109457227A (en) * | 2018-12-14 | 2019-03-12 | 五邑大学 | A kind of method that direct current magnetron sputtering process prepares photoelectrocatalysioxidization oxidization Ti electrode |
| CN110560136A (en) * | 2019-09-24 | 2019-12-13 | 桂林理工大学 | Photocatalytic film and preparation method and application thereof |
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