CN101862668A - Surface gaseous penetration modification method of nanometer titanium dioxide film photocatalyst - Google Patents
Surface gaseous penetration modification method of nanometer titanium dioxide film photocatalyst Download PDFInfo
- Publication number
- CN101862668A CN101862668A CN201010213903A CN201010213903A CN101862668A CN 101862668 A CN101862668 A CN 101862668A CN 201010213903 A CN201010213903 A CN 201010213903A CN 201010213903 A CN201010213903 A CN 201010213903A CN 101862668 A CN101862668 A CN 101862668A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- dioxide film
- nano
- penetration
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a surface gaseous penetration modification method of a nanometer titanium dioxide film photocatalyst, which relates to the penetration modification method of the nanometer titanium dioxide film photocatalyst. The invention solves the problem of low hydrogen production efficiency of the titanium dioxide film used for catalysis hydrogen preparation. The method of the invention comprises the following steps: using an anodic oxidation method for preparing the nanometer titanium dioxide film on a titanium substrate; then, heating a dripping penetration furnace to 500 to 800 DEG C; dripping methanol into the dripping penetration furnace for exhausting the air in the dripping penetration furnace; then, placing the treated titanium substrate into the dripping penetration furnace; and next, dripping penetration agents into the dripping penetration furnace. The method of the invention modifies the carbon, the carbon and the nitrogen, the carbon and the rare earth elements, or the carbon, and the nitrogen and the rare earth elements onto the surface of the nanometer titanium dioxide film and into the crystal lattices, the hydrogen production speed of the photocatalysis hydrogen production of the obtained modified nanometer titanium dioxide photocatalyst is 1.16 to 1.48 times of that of the titanium dioxide film without carrying out gaseous penetration treatment, and the photocatalysis hydrogen production performance is greatly improved.
Description
Technical field
The present invention relates to a kind of penetration modification method of nano-titanium dioxide film photocatalyst.
Background technology
Along with the mankind enter 21 century, the quickening of social development, traditional resources such as coal, natural gas, oil face the gesture of exhaustion, and the environmental problem that these energy of while bring also is on the rise.One with energy savings and resource, preserve the ecological environment, reduce environmental pollution, realize that sustainable development is that the new industrial revolution of target is risen.Solar energy is as a kind of new forms of energy of cleaning, have inexhaustible, nexhaustible, can not cause the advantage of any pollution again.Since 1972, fujishima and honda found TiO
2Optical Electro-Chemistry can produce H by decomposition water
2Since, around utilizing solar energy, by developing the focus that work that high efficiency photocatalyst prepares Hydrogen Energy becomes current scientific research.
At present, the multichip semiconductor that is used as catalyst is the chalcogen semiconductor material, as TiO
2, ZnO, CdS, WO
3, SnO etc.TiO
2With advantages such as its stable chemical property, strong redox ability, anti-photocathode corrosivity, indissoluble, nontoxic, cheapnesss, be widely used as photochemical catalyst.Especially along with the combining closely of nanometer technology and material science, the nanostructured TiO that preparation has specific modality and function
2Become once more that the material field is the most basic, one of most active research contents, also be to implement TiO
2The prerequisite of nano-functional material property research and technological development.Utilize the physicochemical characteristics such as small-size effect, skin effect, quantum size effect of nano material uniqueness, the research nano-TiO
2Aspect photocatalysis hydrogen production, cause the concern of scientific circles.For powder TiO
2, exist to separate, reclaim problems such as difficulty, and with sunshine during as light source and since only account for solar energy seldom the ultraviolet light of a part (＜5%) could directly excite TiO
2, efficient is very low.These effects limit TiO
2The industrial applications of photocatalysis technology.Therefore, how to improve TiO
2Visible light catalysis activity and realization TiO
2Immobilization be the tool challenging two big problems of photocatalysis research field.
Anodizing is nearly ten years a kind of preparation TiO that grow up
2The new technology of nano-tube array can be at titanium surface in situ growth TiO
2Nano thin-film is containing on the titanium alloy of heterogeneity composition by regulation and control electrolyte, is applying voltage and reaction time and can prepare the TiO of different structure
2Nanotube has been realized TiO
2Immobilization and nanometer, and improve TiO by methods such as ion doping modification, loaded with heavy metals, semiconductor couplings
2The catalytic activity of visible light.With TiO
2The nano particle perforated membrane is compared, in order the TiO that arranges
2Nano-tube array has tangible quantum confined effect, high-sequential orientation texture and big specific area, can improve the interfacial separation in electronics-hole and the directional transmissions efficient of carrier effectively, make it important application prospects be arranged in photo catalytic reduction hydrogen producing technology field.
At present, on pure titanium matrix, preparing TiO
2The nano-array method of modifying is generally methods such as carried noble metal, doped metal ion, doped with non-metals anion, dye sensitization, semiconductor coupling, and Photocatalytic Performance Study is many to be degraded to the master, research aspect photo catalytic reduction hydrogen manufacturing also seldom, and the efficient of photo catalytic reduction hydrogen manufacturing is also very low, and the efficient of visible light catalytic reductive water hydrogen manufacturing is also very low, yet there are no report for the research in the nano-tube array photocatalysis hydrogen production performance of TC4 body upper surface growth.
Summary of the invention
The objective of the invention is to the invention provides a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification method in order to solve the existing low problem of hydrogen generation efficiency that is used for the titanium deoxid film of photocatalysis hydrogen production.
Nano-titanium dioxide film photocatalyst surface gaseous penetration modification method of the present invention is realized by following steps: one, prepare nano-titanium dioxide film on the titanium matrix: the titanium matrix is carried out preliminary treatment remove surface film oxide, then pretreated titanium matrix is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 10 ~ 30V, carry out constant voltage anodic oxidation 20 ~ 120min, promptly obtain nano-titanium dioxide film on the titanium matrix, wherein electrolyte consists of: the NaF of 5 ~ 6g/L and volumetric concentration are 2% ~ 5% H
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ~ 800 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10 ~ 30min, then the titanium matrix after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 50 ~ 200mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is that mass concentration is that the methanol solution or the mass concentration of the rare earth compound of 0 ~ 12g/L is the formamide solution of the rare earth compound of 0 ~ 12g/L in the step 2, and described rare earth compound is rare earth-iron-boron or rare earth nitrades.
Titanium matrix described in the step 1 of the present invention is industrially pure titanium, TC4 titanium alloy, Ti-Ni alloy or titanium niobium alloy; All can be used for the present invention as long as can realize anodised titanium matrix thereon.The nano-titanium dioxide film that step 1 obtains is a nano tube structure, has very big specific area.
Splash into methyl alcohol in the step 2 of the present invention earlier, ooze dripping of high temperature that methanol gasifying is a gas in the stove, drain dripping an air that oozes in the stove.Then penetration enhancer is splashed into and ooze in the stove, after methyl alcohol or formamide pyrolysis, carbon in the methyl alcohol or the carbon in the formamide and nitrogen element expanded ooze to nano-titanium dioxide film surface and lattice, rare earth element also expands under high temperature action and oozes to the lattice of nano-titanium dioxide film, has realized the gaseous penetration modification of nano-titanium dioxide film.
The dropping time of penetration enhancer is determined jointly by drop rate and dripping quantity in the step 2 of the present invention.
Nano-titanium dioxide film photocatalyst surface gaseous penetration modification method technology of the present invention is simple, operate simple and easy, be modified with carbon and rare earth element in the modified nano-titanium dioxide thin film that obtains, perhaps be modified with carbon, nitrogen and rare earth element, changed the absorption intensity of modified nano-titanium dioxide thin film, and the efficient of photocatalytic degradation water hydrogen manufacturing improves to visible light.
The present invention adopt to be dripped and to be oozed furnace apparatus and be implemented in and realize gaseous penetration on the nano-titanium dioxide film, the nano-titanium dioxide film that the step 1 anodic oxidation is prepared directly places to drip and oozes stove and carry out gaseous penetration, omitted the prior heat treatment process of carrying out separately, heat treatment and gaseous penetration process are finished synchronously, simplified preparation technology, and the effect of the good photocatalysis hydrogen production of obtaining, the hydrogen-producing speed of the nano-titanium dioxide film photocatalyst that obtains (21.0 ~ 26.4 μ L/hcm
2) be hydrogen-producing speed (17.1 ~ 19.5 μ L/hcm that do not carry out the titanium deoxid film of gaseous penetration processing
2) 1.16 ~ 1.48 times, the photocatalysis hydrogen production performance improves greatly.
The TiO that the present invention prepares on the titanium matrix
2Ooze through expanding by ooze the method for gaseous penetration carbon in the stove (perhaps carbon and nitrogen) and rare earth in expansion on the nano-tube array surface, and rete increases greatly to the absorption of visible light, and the efficient of photocatalysis hydrogen production also has significantly raising simultaneously.
Description of drawings
Fig. 1 drips the device simple diagram of oozing stove in the specific embodiment one; Fig. 2 is the microscopic appearance figure of the SEM (SEM) of the nano-titanium dioxide film that obtains on TA1 titanium sheet of the step 1 of the specific embodiment 17; Fig. 3 is the microscopic appearance figure of the SEM (SEM) of the nano-titanium dioxide film photocatalyst that obtains of the specific embodiment 17; Fig. 4 is the ultraviolet-visible absorption spectroscopy figure of the nano-titanium dioxide film photocatalyst for preparing of the specific embodiment 17 to the specific embodiment 19; Fig. 5 is the photocatalytic degradation time of nano-titanium dioxide film photocatalyst of the specific embodiment 17 and 18 and the graph of relation of hydrogen output; Fig. 6 is that the x-ray photoelectron of the nano-titanium dioxide film photocatalyst that obtains of the specific embodiment 17 can spectrogram; Fig. 7 is the Raman spectrum spectrogram of the nano-titanium dioxide film photocatalyst that obtains of the specific embodiment 17 to 19; Fig. 8 is the photocatalytic degradation time of nano-titanium dioxide film photocatalyst of the specific embodiment 19 and the graph of relation of hydrogen output; Fig. 9 is the photocatalytic degradation time of the nano-titanium dioxide film photocatalyst that obtains of the specific embodiment 20 and 21 and the graph of relation of hydrogen output; Figure 10 is the photocatalytic degradation time of the nano-titanium dioxide film photocatalyst that obtains of the specific embodiment 22 and 23 and the graph of relation of hydrogen output; Figure 11 is the ultraviolet-visible absorption spectroscopy figure of the nano-titanium dioxide film photocatalyst for preparing of the specific embodiment 24 to 27; Figure 12 is that the x-ray photoelectron of the nano-titanium dioxide film photocatalyst that obtains of the specific embodiment 24 can spectrogram; Figure 13 is the photocatalytic degradation time of the nano-titanium dioxide film photocatalyst for preparing of the specific embodiment 24 to 27 and the graph of relation of hydrogen output; Figure 14 is the photocatalytic degradation time of the nano-titanium dioxide film photocatalyst that obtains of the specific embodiment 28 to 31 and the graph of relation of hydrogen output.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method of present embodiment is realized by following steps: one, on the titanium matrix, prepare nano-titanium dioxide film: the titanium matrix is carried out preliminary treatment remove surface film oxide, then pretreated titanium matrix is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 10 ~ 30V, carry out constant voltage anodic oxidation 20 ~ 120min, promptly obtain nano-titanium dioxide film on the titanium matrix, wherein electrolyte consists of: the NaF of 5 ~ 6g/L and volumetric concentration are 2% ~ 5% H
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ~ 800 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10 ~ 30min, then the titanium matrix after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 50 ~ 200mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is that mass concentration is that the methanol solution or the mass concentration of the rare earth compound of 0 ~ 12g/L is the formamide solution of the rare earth compound of 0 ~ 12g/L in the step 2, and described rare earth compound is rare earth-iron-boron or rare earth nitrades.
The device simple diagram that dripping of adopting in the present embodiment oozed stove as shown in Figure 1.Penetration enhancer drops to by the sepage instillation system and oozes in the stove, and the penetration enhancer after the gasification is lighted at exhaust port, and the burning back drains into extract system with the form of inorganic gas, and the injury to human body is reduced in the discharging operation space.
Preparation method's technology of present embodiment is simple, operate simple and easy, be modified with carbon and rare earth element in the modified nano-titanium dioxide thin film that obtains, perhaps be modified with nitrogen and rare earth element, make the absorption intensity grow of modified nano-titanium dioxide thin film to visible light, the efficient of photocatalytic degradation water hydrogen manufacturing improves.The hydrogen-producing speed of the nano-titanium dioxide film photocatalyst that obtains is 1.16 ~ 1.48 times of hydrogen-producing speed that do not carry out the titanium deoxid film that gaseous penetration handles, and the photocatalysis hydrogen production performance improves greatly.
The specific embodiment two: what present embodiment and the specific embodiment one were different is that the titanium matrix is industrially pure titanium, TC4 titanium alloy, Ti-Ni alloy or titanium niobium alloy in the step 1.Other step and parameter are identical with the specific embodiment one.
Industrially pure titanium is TA1 or TA2 in the present embodiment.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is that the control response voltage is 15 ~ 25V in the step 1.Other step and parameter are identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different with the specific embodiment one or two is that the control response voltage is 20V in the step 1.Other step and parameter are identical with the specific embodiment one or two.
The specific embodiment five: what present embodiment was different with one of specific embodiment one to five is to carry out constant voltage anodic oxidation 30 ~ 90min in the step 1.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment six: what present embodiment was different with one of specific embodiment one to five is to carry out constant voltage anodic oxidation 60min in the step 1.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: what present embodiment was different with one of specific embodiment one to six is that electrolyte consists of in the step 1: the NaF of 5.88g/L and volumetric concentration are 2.28% H
3PO
4Solution.
The specific embodiment eight: what present embodiment was different with one of specific embodiment one to seven is in the step 2 carburizer to be heated to 500 ~ 700 ℃.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment nine: what present embodiment was different with one of specific embodiment one to seven is in the step 2 carburizer to be heated to 600 ℃.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment ten: what present embodiment was different with one of specific embodiment one to nine is to stop to drip methyl alcohol after continuing in the step 2 to drip 20min.Other step and parameter are identical with one of specific embodiment one to nine.
The specific embodiment 11: present embodiment is different with one of specific embodiment one to ten is to begin in the step 2 to drip penetration enhancer with the 3 seconds/speed of dripping in carburizer again, and the penetration enhancer of 100mL is dropwised.Other step and parameter are identical with one of specific embodiment one to ten.
The specific embodiment 12: what present embodiment was different with one of specific embodiment one to 11 is that penetration enhancer is methyl alcohol or formamide in the step 2.Other step and parameter are identical with one of specific embodiment one to 11.
Adopt the penetration enhancer of present embodiment, can obtain expansion and be impregnated with carbon, the perhaps modified nano-titanium dioxide thin film of carbon and nitrogen.
The specific embodiment 13: present embodiment is different with one of specific embodiment one to 11 is that penetration enhancer is that mass concentration is that the methanol solution or the mass concentration of the rare earth compound of 5 ~ 12g/L is the formamide solution of the rare earth compound of 5 ~ 12g/L in the step 2.Other step and parameter are identical with one of specific embodiment one to 11.
The specific embodiment 14: present embodiment is different with one of specific embodiment one to 11 is that penetration enhancer is that mass concentration is that the methanol solution or the mass concentration of the rare earth compound of 10g/L is the formamide solution of the rare earth compound of 10g/L in the step 2.Other step and parameter are identical with one of specific embodiment one to 11.
The specific embodiment 15: what present embodiment was different with one of specific embodiment one to 14 is that the described penetration enhancer middle rare earth of step 2 compound is a kind of or wherein several mixture in cerium chloride, ytterbium chloride, neodymium chloride, Europium chloride, samarium trichloride, lanthanum chloride, cerous nitrate, ytterbium nitrate, lanthanum nitrate and the europium nitrate.Other step and parameter are identical with one of specific embodiment one to 14.
In the present embodiment when rare earth compound is wherein several mixture, for arbitrarily than mixing.
The specific embodiment 16: present embodiment is different with one of specific embodiment one to 15 is in the step 1 titanium matrix to be carried out preliminary treatment to remove the concrete operations of surface film oxide and be: with hydrofluoric acid and red fuming nitric acid (RFNA) according to volume ratio be the ratio of 1:1 mix mixed acid solution, then the titanium matrix is immersed in the mixed acid solution, parked 1 ~ 2s in mixed acid solution, take out then, rinse well with deionized water, and then with in the titanium matrix immersion mixed acid solution, parked 1 ~ 2s, take out then, repeat aforesaid operations 1 ~ 4 time.Other step and parameter are identical with one of specific embodiment one to 15.
Concrete repetitive operation number of times can be by the light decision that become of titanium matrix surface in the present embodiment.
The specific embodiment 17: present embodiment nano-titanium dioxide film photocatalyst surface gaseous penetration modification method is realized by following steps: one, on TA1 titanium sheet, prepare nano-titanium dioxide film: TA1 titanium sheet is carried out preliminary treatment remove surface film oxide, then pretreated TA1 titanium sheet is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 20V, carry out constant voltage anodic oxidation 30min, promptly obtain nano-titanium dioxide film on TA1 titanium sheet, wherein electrolyte consists of: volume is the H that contains 1.47gNaF and 5.7mL in the electrolyte of 250mL
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10min, then the TA1 titanium sheet after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 100mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is that mass concentration is the cerium chloride of 10g/L and the methanol solution of lanthanum chloride mixture in the step 2.
The response area of the TA1 titanium sheet of present embodiment step 1 is 2.5 * 4cm
2, the top of conversion zone is wrapped with sealing with adhesive tape, and purpose is prevent electrolyte soaring.To dropwise required time be 1 ~ 2h to penetration enhancer in the step 2.In the step 1 TA1 titanium sheet being carried out preliminary treatment removes the concrete operations of surface film oxide and is: with hydrofluoric acid and red fuming nitric acid (RFNA) according to volume ratio be the ratio of 1:1 mix mixed acid solution, then the titanium matrix is immersed in the mixed acid solution, parked 1 ~ 2s in mixed acid solution, take out then, rinse well with deionized water, and then the titanium matrix is immersed in the mixed acid solution parked 1 ~ 2s, take out then, repeat aforesaid operations 2 times.
The present embodiment step 1 obtains nano-titanium dioxide film on TA1 titanium sheet be titania nanotube, the microscopic appearance figure of its SEM (SEM) as shown in Figure 2, titanium dioxide exists with the nano-tube array form in the nano-titanium dioxide film, has increased the surface area of nano-titanium dioxide film greatly; The microscopic appearance figure of the SEM (SEM) of the nano-titanium dioxide film photocatalyst that obtains after the step 2 gaseous penetration is handled handles TiO in the rete through 500 ℃ as shown in Figure 3 in the different cracking atmosphere of methyl alcohol
2It is big that crystal grain becomes, and is filled with fine particulate material in the space between nanotube.
Present embodiment is carried out the uv-vis spectra test to the nano-titanium dioxide film photocatalyst for preparing, and the ultraviolet-visible absorption spectroscopy curve that obtains is shown in curve among Fig. 41; As a comparison, present embodiment obtains nano-titanium dioxide film (handling without the step 2 gaseous penetration) to step 1 and carries out the uv-vis spectra test on TA1 titanium sheet, and the ultraviolet-visible absorption spectroscopy curve that obtains is shown in curve among Fig. 44; In the comparison diagram 4 curve 1 and curve 4 as seen, the nano-titanium dioxide film photocatalyst after the gaseous penetration modification doping treatment of present embodiment has stronger absorption at visible light wave range.
Present embodiment is carried out the photocatalysis hydrogen production performance test to the nano-titanium dioxide film photocatalyst for preparing, and method of testing is: with the quartz glass tube reactor, and 0.1mol/LNa
2S and 0.02mol/LNa
2SO
3The aqueous solution for the reaction target, under the irradiation of 500W xenon lamp, the hydrogen that collect to produce, the distance of xenon lamp and quartz glass tube is 10cm, the reactivity of evaluation photochemical catalyst.The photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Fig. 51, and hydrogen-producing speed is 21.5 μ L/hcm
2As a comparison, present embodiment obtains nano-titanium dioxide film (handling without the step 2 gaseous penetration) to step 1 and carries out the test of photocatalytic degradation hydrogen production by water decomposition effect on TA1 titanium sheet, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Fig. 53.Hydrogen-producing speed is 17.2 μ L/hcm
2By curve among Fig. 51 and curve 3 as can be known, after the gaseous penetration of present embodiment was handled, it is big that the hydrogen output of its photocatalytic degradation hydrogen production by water decomposition becomes, and it is big that hydrogen-producing speed becomes, and hydrogen-producing speed is not have gaseous penetration to handle 1.25 times of film.
Present embodiment is carried out x-ray photoelectron power spectrum (XPS) test to the nano-titanium dioxide film photocatalyst that obtains, and test structure as shown in Figure 6.The Nano tube array of titanium dioxide probing surface goes out Ti, O, three kinds of elements of C, and C goes out the peak position at 484.2eV, and this is typical carbon graphite peak, and the atomic percentage conc of C illustrates and surperficial absorption of TNTs gone up carbon up to 56.8%." atom% " refers to atomic percent among the figure, just atom number percentage.As shown in Figure 6, successfully carbon is expanded in the nano-titanium dioxide film photocatalyst that obtains and ooze to nano-titanium dioxide film; Regrettably do not detect the peak of rare-earth element cerium, the analysis reason is that the amount of film middle rare earth elemental cerium and lanthanum is too little, and XPS detects not come out.
Present embodiment is carried out the Raman spectrum test to the nano-titanium dioxide film photocatalyst that obtains, and test result is shown in curve among Fig. 71.As a comparison, present embodiment obtains nano-titanium dioxide film (handling without the step 2 gaseous penetration) to step 1 and carries out the Raman spectrum test on TA1 titanium sheet, and test result is shown in curve among Fig. 74.The peak position of A mark is an anatase titanium dioxide among the figure, and the peak position of R mark is a rutile titanium dioxide.The G mark be the G peak, by E
2gSymmetric vibration produces (E
2gBe the stretching vibration in the graphite lattice wire side), corresponding 1580cm
-1Raman peaks; The D mark be the D peak, be by A
1gSymmetric vibration (this may be because the partial structurtes of crystallization are shifted to lower symmetry or lost symmetry fully by six side's symmetry and form, and the relative intensity of D band is the reflection of crystalline texture disorder degree) that produce.In the comparison diagram 7 curve 1 and curve 4 as can be known, behind gaseous penetration, anatase has appearred in nanometer titanium dioxide carbon film photocatalyst, the appearance at D peak and G peak illustrates that the carbon in the nanometer titanium dioxide carbon film photocatalyst exists with the form of amorphous carbon.
The specific embodiment 18: what present embodiment and the specific embodiment 17 were different is in the step 2 carburizer to be heated to 600 ℃.Other step and parameter are identical with the specific embodiment 17.
Present embodiment is carried out the uv-vis spectra test to the nano-titanium dioxide film photocatalyst for preparing, and the ultraviolet-visible absorption spectroscopy curve that obtains is shown in curve among Fig. 42; In the comparison diagram 4 curve 2 and curve 4 as seen, the nano-titanium dioxide film photocatalyst after the gaseous penetration modification doping treatment of present embodiment has stronger absorption at visible light wave range.
Take the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Fig. 52, and hydrogen-producing speed is 25.3 μ L/hcm
2, be hydrogen output (the 17.2 μ L/hcm that do not pass through the carbon dioxide film of gaseous penetration processing
2) 1.48 times.
Present embodiment is carried out the Raman spectrum test to the nano-titanium dioxide film photocatalyst that obtains, test result is shown in curve among Fig. 72, as seen, behind gaseous penetration, anatase and rutile have appearred in the nanometer titanium dioxide carbon film photocatalyst, the appearance at D peak and G peak illustrates that the carbon in the nanometer titanium dioxide carbon film photocatalyst exists with the form of amorphous carbon.
The specific embodiment 19: what present embodiment and the specific embodiment 17 were different is in the step 2 carburizer to be heated to 700 ℃.Other step and parameter are identical with the specific embodiment 17.
Present embodiment is carried out the uv-vis spectra test to the nano-titanium dioxide film photocatalyst for preparing, and the ultraviolet-visible absorption spectroscopy curve that obtains is shown in curve among Fig. 43; As seen from Figure 4, the nano-titanium dioxide film photocatalyst after the gaseous penetration modification doping treatment of present embodiment descends to some extent in the absorption intensity of visible light wave range.
Take the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Fig. 81, and hydrogen-producing speed is 21.7 μ L/hcm
2Curve 2 is that step 1 obtains the photocatalytic degradation time of nano-titanium dioxide film (handling without the step 2 gaseous penetration) and the relation curve of hydrogen output on TA1 titanium sheet among Fig. 8.The hydrogen-producing speed of the nano-titanium dioxide film photocatalyst of present embodiment is hydrogen output (the 17.2 μ L/hcm that do not pass through the carbon dioxide film of gaseous penetration processing
2) 1.26 times.
Present embodiment is carried out the Raman spectrum test to the nano-titanium dioxide film photocatalyst that obtains, test result is shown in curve among Fig. 73, as seen, behind gaseous penetration, anatase disappears in the nanometer titanium dioxide carbon film photocatalyst, all become the rutile phase, the appearance at D peak and G peak illustrates that the carbon in the nanometer titanium dioxide carbon film photocatalyst exists with the form of amorphous carbon, but compares with curve 2 with curve 1, emphasizing to die down in the peak, illustrates that the carbon of absorption tails off.
The specific embodiment 20: present embodiment nano-titanium dioxide film photocatalyst surface gaseous penetration modification method is realized by following steps: one, on TC4 titanium alloy sheet, prepare nano-titanium dioxide film: TC4 titanium alloy sheet is carried out preliminary treatment remove surface film oxide, then pretreated TC4 titanium alloy sheet is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 15V, carry out constant voltage anodic oxidation 30min, promptly obtain nano-titanium dioxide film on TC4 titanium alloy sheet, wherein electrolyte consists of: volume is the H that contains 1.47gNaF and 5.7mL in the electrolyte of 250mL
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10min, then the TC4 titanium alloy sheet after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 100mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is that mass concentration is the cerium chloride of 10g/L and the methanol solution of lanthanum chloride mixture in the step 2.
The response area of the TC4 titanium alloy sheet of present embodiment step 1 is 2.5 * 4cm
2, the top of conversion zone is wrapped with sealing with adhesive tape, and purpose is prevent electrolyte soaring.To dropwise required time be 1 ~ 2h to penetration enhancer in the step 2.In the step 1 TC4 titanium alloy sheet being carried out preliminary treatment removes the concrete operations of surface film oxide and is: with hydrofluoric acid and red fuming nitric acid (RFNA) according to volume ratio be the ratio of 1:1 mix mixed acid solution, then the titanium matrix is immersed in the mixed acid solution, parked 1 ~ 2s in mixed acid solution, take out then, rinse well with deionized water, and then the titanium matrix is immersed in the mixed acid solution parked 1 ~ 2s, take out then, repeat aforesaid operations 3 times.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Fig. 91, and hydrogen-producing speed is 24.7 μ L/hcm
2As a comparison, as a comparison, present embodiment obtains nano-titanium dioxide film (handling without the step 2 gaseous penetration) to step 1 and carries out the test of photocatalytic degradation hydrogen production by water decomposition effect on TC4 titanium alloy sheet, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Fig. 93.Hydrogen-producing speed is 17.1 μ L/hcm
2By curve among Fig. 91 and curve 3 as can be known, after the gaseous penetration of present embodiment was handled, it is big that the hydrogen output of its photocatalytic degradation hydrogen production by water decomposition becomes, and it is big that hydrogen-producing speed becomes, and hydrogen-producing speed is not have gaseous penetration to handle 1.44 times of film.
The specific embodiment 21: what present embodiment and the specific embodiment 20 were different is in the step 2 carburizer to be heated to 600 ℃.Other step and parameter are identical with the specific embodiment 20.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Fig. 92, and hydrogen-producing speed is 25.3 μ L/hcm
2, be 1.48 times of the nano-titanium dioxide film (shown in curve among Figure 10 3) do not handled through gaseous penetration.
The specific embodiment 22: what present embodiment and the specific embodiment 20 were different is in the step 2 carburizer to be heated to 700 ℃.Other step and parameter are identical with the specific embodiment 20.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Figure 10 1, and hydrogen-producing speed is 23.7 μ L/hcm
2, be 1.39 times of hydrogen-producing speed (shown in curve among Figure 10 3) of the nano-titanium dioxide film do not handled through gaseous penetration.
The specific embodiment 23: what present embodiment and the specific embodiment 20 were different is in the step 2 carburizer to be heated to 800 ℃.Other step and parameter are identical with the specific embodiment 20.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Figure 10 2, and hydrogen-producing speed is 23.4 μ L/hcm
2, be 1.37 times of hydrogen-producing speed (shown in curve among Figure 10 3) of the nano-titanium dioxide film do not handled through gaseous penetration.
The specific embodiment 24: present embodiment nano-titanium dioxide film photocatalyst surface gaseous penetration modification method is realized by following steps: one, on TA1 titanium sheet, prepare nano-titanium dioxide film: TA1 titanium sheet is carried out preliminary treatment remove surface film oxide, then pretreated TA1 titanium sheet is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 20V, carry out constant voltage anodic oxidation 30min, promptly obtain nano-titanium dioxide film on TA1 titanium sheet, wherein electrolyte consists of: volume is the H that contains 1.47gNaF and 5.7mL in the electrolyte of 250mL
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10min, then the TA1 titanium sheet after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 100mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is that mass concentration is the cerium chloride of 10g/L and the formamide solution of Europium chloride mixture in the step 2.
The response area of the TA1 titanium sheet of present embodiment step 1 is 2.5 * 4cm
2, the top of conversion zone is wrapped with sealing with adhesive tape, and purpose is prevent electrolyte soaring.To dropwise required time be 1 ~ 2h to penetration enhancer in the step 2.In the step 1 TA1 titanium sheet being carried out preliminary treatment removes the concrete operations of surface film oxide and is: with hydrofluoric acid and red fuming nitric acid (RFNA) according to volume ratio be the ratio of 1:1 mix mixed acid solution, then the titanium matrix is immersed in the mixed acid solution, parked 1 ~ 2s in mixed acid solution, take out then, rinse well with deionized water, and then the titanium matrix is immersed in the mixed acid solution parked 1 ~ 2s, take out then, repeat aforesaid operations 2 times.
Present embodiment is carried out the uv-vis spectra test to the nano-titanium dioxide film photocatalyst for preparing, and the ultraviolet-visible absorption spectroscopy curve that obtains is shown in curve among Figure 11 1; As a comparison, present embodiment obtains nano-titanium dioxide film (handling without the step 2 gaseous penetration) to step 1 and carries out the uv-vis spectra test on TA1 titanium sheet, and the ultraviolet-visible absorption spectroscopy curve that obtains is shown in curve among Figure 11 5; As seen from Figure 11, the nano-titanium dioxide film photocatalyst after the gaseous penetration modification doping treatment of present embodiment has stronger absorption at visible light wave range.
Present embodiment is carried out x-ray photoelectron power spectrum (XPS) test to the nano-titanium dioxide film photocatalyst that obtains, and the XPS spectrum that obtains as shown in figure 12.As can be known, carbon in the formamide and nitrogen element all are doped in the nano-titanium dioxide film photocatalyst, detect Ti, O, C, Al, five kinds of elements of N in the nano-titanium dioxide film array surface, N goes out the peak position at 400.2eV, produce by Ti-N-O, can determine that nitrogen-doping in the formamide is to nano-titanium dioxide film photocatalyst.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output as among Figure 13-■-curve shown in, hydrogen-producing speed is 24.2 μ L/hcm
2As a comparison, present embodiment obtains nano-titanium dioxide film (handling without the step 2 gaseous penetration) to step 1 and carries out the test of photocatalytic degradation hydrogen production by water decomposition effect, curve among the photocatalytic degradation time that obtains and the relation curve of hydrogen output such as Figure 13 on TA1 titanium sheet
Shown in.Hydrogen-producing speed is 19.5 μ L/hcm
2As can be known, after the gaseous penetration of present embodiment was handled, it is big that the hydrogen output of its photocatalytic degradation hydrogen production by water decomposition becomes, and it is big that hydrogen-producing speed becomes, and hydrogen-producing speed is not have gaseous penetration to handle 1.24 times of film.
The specific embodiment 25: what present embodiment and the specific embodiment 24 were different is in the step 2 carburizer to be heated to 600 ℃.Other step and parameter are identical with the specific embodiment 24.
The ultraviolet-visible absorption spectroscopy of the nano-titanium dioxide film photocatalyst of present embodiment is shown in curve among Figure 11 2.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, in the photocatalytic degradation time that obtains and the relation curve such as Figure 13 of hydrogen output-● shown in-the curve, hydrogen-producing speed is 26.4 μ L/hcm
2, be not have gaseous penetration to handle 1.35 times of hydrogen-producing speed of film.
The specific embodiment 26: what present embodiment and the specific embodiment 24 were different is in the step 2 carburizer to be heated to 700 ℃.Other step and parameter are identical with the specific embodiment 24.
The ultraviolet-visible absorption spectroscopy of the nano-titanium dioxide film photocatalyst of present embodiment is shown in curve among Figure 11 3.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output as among Figure 13-▲-curve shown in, hydrogen-producing speed is 25.6 μ L/hcm
2, be not have gaseous penetration to handle 1.31 times of hydrogen-producing speed of film.
The specific embodiment 27: what present embodiment and the specific embodiment 24 were different is in the step 2 carburizer to be heated to 800 ℃.Other step and parameter are identical with the specific embodiment 24.
The ultraviolet-visible absorption spectroscopy of the nano-titanium dioxide film photocatalyst of present embodiment is shown in curve among Figure 11 4.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output as among Figure 13-▼-curve shown in, hydrogen-producing speed is 22.7 μ L/hcm
2, be not have gaseous penetration to handle 1.16 times of hydrogen-producing speed of film.
The specific embodiment 28: present embodiment nano-titanium dioxide film photocatalyst surface gaseous penetration modification method is realized by following steps: one, on TC4 titanium alloy sheet, prepare nano-titanium dioxide film: TC4 titanium alloy sheet is carried out preliminary treatment remove surface film oxide, then pretreated TC4 titanium alloy sheet is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 15V, carry out constant voltage anodic oxidation 30min, promptly obtain nano-titanium dioxide film on TC4 titanium alloy sheet, wherein electrolyte consists of: volume is the H that contains 1.47gNaF and 5.7mL in the electrolyte of 250mL
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10min, then the TC4 titanium alloy sheet after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 100mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is that mass concentration is the cerium chloride of 10g/L and the formamide solution of europium nitrate mixture in the step 2.
The response area of the TC4 titanium alloy sheet of present embodiment step 1 is 2.5 * 4cm
2, the top of conversion zone is wrapped with sealing with adhesive tape, and purpose is prevent electrolyte soaring.To dropwise required time be 1 ~ 2h to penetration enhancer in the step 2.In the step 1 TC4 titanium alloy sheet being carried out preliminary treatment removes the concrete operations of surface film oxide and is: with hydrofluoric acid and red fuming nitric acid (RFNA) according to volume ratio be the ratio of 1:1 mix mixed acid solution, then the titanium matrix is immersed in the mixed acid solution, parked 1 ~ 2s in mixed acid solution, take out then, rinse well with deionized water, and then the titanium matrix is immersed in the mixed acid solution parked 1 ~ 2s, take out then, repeat aforesaid operations 3 times.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Figure 14 1, and hydrogen-producing speed is 21.0 μ L/hcm
2As a comparison, present embodiment obtains nano-titanium dioxide film (handling without the step 2 gaseous penetration) to step 1 at TC4 titanium alloy sheet and carries out the test of photocatalytic degradation hydrogen production by water decomposition effect, and the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Figure 14 5.Hydrogen-producing speed is 17.9 μ L/hcm
2As can be known, after the gaseous penetration of present embodiment was handled, it is big that the hydrogen output of its photocatalytic degradation hydrogen production by water decomposition becomes, and it is big that hydrogen-producing speed becomes, and hydrogen-producing speed is not have gaseous penetration to handle 1.17 times of film.
The specific embodiment 29: what present embodiment and the specific embodiment 28 were different is in the step 2 carburizer to be heated to 600 ℃.Other step and parameter are identical with the specific embodiment 28.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Figure 14 2, and hydrogen-producing speed is 24.8 μ L/hcm
2, be not have gaseous penetration to handle 1.39 times of hydrogen-producing speed of film.
The specific embodiment 30: what present embodiment and the specific embodiment 28 were different is in the step 2 carburizer to be heated to 700 ℃.Other step and parameter are identical with the specific embodiment 28.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Figure 14 3, and hydrogen-producing speed is 23.5 μ L/hcm
2, be not have gaseous penetration to handle 1.31 times of hydrogen-producing speed of film.
The specific embodiment 31: what present embodiment and the specific embodiment 28 were different is in the step 2 carburizer to be heated to 800 ℃.Other step and parameter are identical with the specific embodiment 28.
Adopt the method for testing of the specific embodiment 17 described photocatalysis hydrogen production performance tests that the nano-titanium dioxide film photocatalyst that present embodiment obtains is tested, the photocatalytic degradation time that obtains and the relation curve of hydrogen output are shown in curve among Figure 14 4, and hydrogen-producing speed is 21.7 μ L/hcm
2, be not have gaseous penetration to handle 1.21 times of hydrogen-producing speed of film.
The specific embodiment 32: present embodiment nano-titanium dioxide film photocatalyst surface gaseous penetration modification method is realized by following steps: one, on TA1 titanium sheet, prepare nano-titanium dioxide film: TA1 titanium sheet is carried out preliminary treatment remove surface film oxide, then pretreated TA1 titanium sheet is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 20V, carry out constant voltage anodic oxidation 30min, promptly obtain nano-titanium dioxide film on TA1 titanium sheet, wherein electrolyte consists of: volume is the H that contains 1.47gNaF and 5.7mL in the electrolyte of 250mL
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10min, then the TA1 titanium sheet after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 100mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is a methyl alcohol in the step 2.
The response area of the TA1 titanium sheet of present embodiment step 1 is 2.5 * 4cm
2, the top of conversion zone is wrapped with sealing with adhesive tape, and purpose is prevent electrolyte soaring.To dropwise required time be 1 ~ 2h to penetration enhancer in the step 2.In the step 1 TA1 titanium sheet being carried out preliminary treatment removes the concrete operations of surface film oxide and is: with hydrofluoric acid and red fuming nitric acid (RFNA) according to volume ratio be the ratio of 1:1 mix mixed acid solution, then the titanium matrix is immersed in the mixed acid solution, parked 1 ~ 2s in mixed acid solution, take out then, rinse well with deionized water, and then the titanium matrix is immersed in the mixed acid solution parked 1 ~ 2s, take out then, repeat aforesaid operations 2 times.
The ultraviolet-visible absorption spectroscopy of the nano-titanium dioxide film photocatalyst of present embodiment as shown in figure 14.As seen from Figure 14, the nano-titanium dioxide film photocatalyst of present embodiment has very strong absorption to the visible region, the absorption intensity basically identical when its absorption intensity and penetration enhancer are the methanol solution of rare earth compound.
Present embodiment can expand carbon oozes to nano-titanium dioxide film photocatalyst, obtains the nano-titanium dioxide film photocatalyst of the carbon modification of gaseous penetration modification.
Claims (10)
1. nano-titanium dioxide film photocatalyst surface gaseous penetration modification method, it is characterized in that the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method realizes by following steps: one, on the titanium matrix, prepare nano-titanium dioxide film: the titanium matrix is carried out preliminary treatment remove surface film oxide, then pretreated titanium matrix is placed electrolyte as working electrode, the copper sheet conduct is to electrode, the control response voltage is 10 ~ 30V, carry out constant voltage anodic oxidation 20 ~ 120min, promptly obtain nano-titanium dioxide film on the titanium matrix, wherein electrolyte consists of: the NaF of 5 ~ 6g/L and volumetric concentration are 2% ~ 5% H
3PO
4Solution, solvent are water; Two, carburizer is heated to 500 ~ 800 ℃, insulation, in carburizer, splash into methyl alcohol then, stop to drip methyl alcohol after continuing to drip 10 ~ 30min, then the titanium matrix after step 1 is handled is put on the specimen holder of carburizer, begin again in carburizer, to drip penetration enhancer, the penetration enhancer of 50 ~ 200mL is dropwised, promptly finish the nano-titanium dioxide film photocatalyst surface gaseous penetration modification method with 2 ~ 4 seconds/speed of dripping; Wherein penetration enhancer is that mass concentration is that the methanol solution or the mass concentration of the rare earth compound of 0 ~ 12g/L is the formamide solution of the rare earth compound of 0 ~ 12g/L in the step 2, and described rare earth compound is rare earth-iron-boron or rare earth nitrades.
2. a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification method according to claim 1 is characterized in that the titanium matrix is industrially pure titanium, TC4 titanium alloy, Ti-Ni alloy or titanium niobium alloy in the step 1.
3. a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification method according to claim 1 and 2 is characterized in that the control response voltage is 15 ~ 25V in the step 1.
4. a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification method according to claim 3 is characterized in that carrying out in the step 1 constant voltage anodic oxidation 30 ~ 90min.
5. according to claim 1,2 or 4 described a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification methods, it is characterized in that in the step 2 carburizer being heated to 500 ~ 700 ℃.
6. according to claim 1,2 or 4 described a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification methods, it is characterized in that in the step 2 carburizer being heated to 600 ℃.
7. a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification method according to claim 5 is characterized in that beginning in the step 2 dripping penetration enhancer with the 3 seconds/speed of dripping in carburizer again, and the penetration enhancer of 100mL is dropwised.
8. according to claim 1,2,4 or 7 described a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification methods, it is characterized in that penetration enhancer is methyl alcohol or formamide in the step 2.
9. according to claim 1,2,4 or 7 described a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification methods, it is characterized in that penetration enhancer in the step 2 is that mass concentration is that the methanol solution or the mass concentration of the rare earth compound of 5 ~ 12g/L is the formamide solution of the rare earth compound of 5 ~ 12g/L.
10. a kind of nano-titanium dioxide film photocatalyst surface gaseous penetration modification method according to claim 9 is characterized in that the described penetration enhancer middle rare earth of step 2 compound is a kind of or wherein several mixture in cerium chloride, ytterbium chloride, neodymium chloride, Europium chloride, samarium trichloride, lanthanum chloride, cerous nitrate, ytterbium nitrate, lanthanum nitrate and the europium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010213903XA CN101862668B (en) | 2010-06-30 | 2010-06-30 | Surface gaseous penetration modification method of nanometer titanium dioxide film photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010213903XA CN101862668B (en) | 2010-06-30 | 2010-06-30 | Surface gaseous penetration modification method of nanometer titanium dioxide film photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101862668A true CN101862668A (en) | 2010-10-20 |
| CN101862668B CN101862668B (en) | 2012-01-18 |
Family
ID=42954705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010213903XA Active CN101862668B (en) | 2010-06-30 | 2010-06-30 | Surface gaseous penetration modification method of nanometer titanium dioxide film photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101862668B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140049A (en) * | 2015-07-28 | 2015-12-09 | 哈尔滨工业大学 | Method for loading carbon on titania nanotube by gas-phase permeation method |
| CN106621807A (en) * | 2017-02-15 | 2017-05-10 | 中南大学 | Flue gas treatment method for realizing desulphurization and denitrification simultaneously by using lanthanum-cerium oxide-loaded titanium dioxide nanotube array for catalytic reduction |
| CN111155147A (en) * | 2020-01-15 | 2020-05-15 | 浙江大学 | Lanthanum chloride molten salt mediated tantalum nitride photo-anode and preparation method thereof |
| CN115896895A (en) * | 2022-12-06 | 2023-04-04 | 哈尔滨工业大学 | Anti-static high-absorption and high-emission composite thermal control coating prepared on surface of TC4 titanium alloy and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10130887A (en) * | 1996-09-04 | 1998-05-19 | Nikon Corp | Production of porous titanium oxide film, porous titanium oxide film and photocatalyst for decomposing gaseous nox |
| CN1936082A (en) * | 2006-09-07 | 2007-03-28 | 复旦大学 | Method for preparing carbon-doped nano titanium dioxide film |
| CN101596457A (en) * | 2009-07-06 | 2009-12-09 | 宁波山泉建材有限公司 | The nano titanium dioxide photocatalyst and the preparation method of boron and other element codope |
-
2010
- 2010-06-30 CN CN201010213903XA patent/CN101862668B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10130887A (en) * | 1996-09-04 | 1998-05-19 | Nikon Corp | Production of porous titanium oxide film, porous titanium oxide film and photocatalyst for decomposing gaseous nox |
| CN1936082A (en) * | 2006-09-07 | 2007-03-28 | 复旦大学 | Method for preparing carbon-doped nano titanium dioxide film |
| CN101596457A (en) * | 2009-07-06 | 2009-12-09 | 宁波山泉建材有限公司 | The nano titanium dioxide photocatalyst and the preparation method of boron and other element codope |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Physics and Chemistry of Solids》 20071231 Wu Xiaohong.et al "Photocatalytic activity of Eu-doped TiO2 ceramic films prepared by microplasma oxidation method" 第2387-2393页 1-10 第68卷, 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140049A (en) * | 2015-07-28 | 2015-12-09 | 哈尔滨工业大学 | Method for loading carbon on titania nanotube by gas-phase permeation method |
| CN105140049B (en) * | 2015-07-28 | 2017-09-26 | 哈尔滨工业大学 | A kind of method that utilization gaseous penetration method loads carbon on titanium oxide nanotubes |
| CN106621807A (en) * | 2017-02-15 | 2017-05-10 | 中南大学 | Flue gas treatment method for realizing desulphurization and denitrification simultaneously by using lanthanum-cerium oxide-loaded titanium dioxide nanotube array for catalytic reduction |
| CN106621807B (en) * | 2017-02-15 | 2020-02-04 | 中南大学 | Flue gas treatment method for catalytic reduction, desulfurization and denitrification of titanium dioxide nanotube array loaded with lanthanum-cerium oxide |
| CN111155147A (en) * | 2020-01-15 | 2020-05-15 | 浙江大学 | Lanthanum chloride molten salt mediated tantalum nitride photo-anode and preparation method thereof |
| CN111155147B (en) * | 2020-01-15 | 2021-05-18 | 浙江大学 | Lanthanum chloride molten salt mediated tantalum nitride photo-anode and preparation method thereof |
| CN115896895A (en) * | 2022-12-06 | 2023-04-04 | 哈尔滨工业大学 | Anti-static high-absorption and high-emission composite thermal control coating prepared on surface of TC4 titanium alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101862668B (en) | 2012-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Suarez et al. | BiVO4 as photocatalyst for solar fuels production through water splitting: a short review | |
| Li et al. | Visible light driven hydrogen evolution by photocatalytic reforming of lignin and lactic acid using one-dimensional NiS/CdS nanostructures | |
| CN104835648B (en) | The preparation method of bismuth oxide nanoparticles/Nano tube array of titanium dioxide | |
| CN101653728A (en) | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst | |
| CN108525667A (en) | Metal organic frame derives the preparation method of the TiO 2 nanotubes modified array of cobaltosic oxide | |
| CN103506142B (en) | A kind of Molybdenum disulfide/silver phosphate composite visible light photocatalytic material and preparation method thereof | |
| CN101844077B (en) | Preparation method of carbon and nitrogen modified nano-titanium dioxide thin film with visible light activity | |
| CN104911639B (en) | A kind of supported silver nano net and its preparation method and application | |
| CN104313637A (en) | Metal sulfide electrode with hydrogen reduction activity and preparation method of metal sulfide electrode | |
| CN102965710A (en) | Preparation of silver/cadmium sulfide-nanoparticle-comodified titanium dioxide nanotube array | |
| CN105044180A (en) | Preparation method and application of heterojunction photoelectrode | |
| CN102701312A (en) | Method for producing hydrogen by using dye-sensitized photocatalytic fuel cell and degrading organic dye wastewater simultaneously | |
| CN101862668B (en) | Surface gaseous penetration modification method of nanometer titanium dioxide film photocatalyst | |
| CN104120443A (en) | Visible light layered array electrode of composite structure and preparation method thereof | |
| CN102764650A (en) | Modified titanium dioxide/ bamboo charcoal composite material and preparation method thereof | |
| CN107723777A (en) | The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot | |
| CN102218332B (en) | Sulfur-doped titanium dioxide nano-tube film loading indium-zinc-silver-sulfide solid solution, its preparation method and application | |
| Jang et al. | CO2 reduction by photocatalytic and photoelectrocatalytic approaches over Eu (III)-ZnGa2O4 nanoparticles and Eu (III)-ZnGa2O4/ZnO nanorods | |
| CN103320839B (en) | Go the preparation method of the titanium dioxide nanotube array photoelectrode of removal organic polluter | |
| CN102660763A (en) | Preparation method for TiO2 nanotube array film with high catalytic properties and application of TiO2 nanotube array film | |
| CN104117366B (en) | A kind of heterogeneous nano array structure material of ZnO/ZnSe, preparation method and application thereof | |
| CN108057451B (en) | One-dimensional zinc oxide/cadmium sulfide/molybdenum disulfide nano array photocatalytic composite material and preparation method and application thereof | |
| CN104549400A (en) | Visible light response type TiO2 nanotube array, as well as preparation method and applications thereof | |
| CN108273486B (en) | Carbon nano tube/secondary anode oxidized TiO2Nanotube photocatalyst material and preparation method and application thereof | |
| CN104399503B (en) | Iron-nitrogen-fluorine co-doped titanium dioxide nanotube array photocatalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |