CN101024168A - Carbou doped titanium-oxide graded hole photocatalytic material and preparing method - Google Patents
Carbou doped titanium-oxide graded hole photocatalytic material and preparing method Download PDFInfo
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- CN101024168A CN101024168A CN 200710056968 CN200710056968A CN101024168A CN 101024168 A CN101024168 A CN 101024168A CN 200710056968 CN200710056968 CN 200710056968 CN 200710056968 A CN200710056968 A CN 200710056968A CN 101024168 A CN101024168 A CN 101024168A
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Abstract
This invention relates to TiO2 photocatalysis materials preparation, particularly relates to a classification carbon-doped titanium dioxide catalyst material and preparation method. This invention is a kind of the carbon-doped titanium dioxide with mesoporous - macroporous grade pore structure, carbon 3-25%, anatase phase, the big channel pore size of 300-1000nm, mesoporous aperture 2.0-24nm, the specific surface area can be as high as 691m2/g. The described material is prepared by titanate and carbon mixture hydrolysis product of the roasting 300-600deg.C, and preparation of equipment used simple, the described materials in organic dye molecules have good catalytic properties on the photodegradation.
Description
Technical field
The present invention relates to the preparation of titanium oxide photochemical catalyst material, particularly a kind of Carbou doped titanium-oxide graded hole photocatalytic material and preparation method thereof, novel mesopore-macropore classification hole Carbou doped titanium-oxide catalyst is applied to the photocatalytic degradation of dye molecule.
Background technology
Since rising of Tokyo Univ Japan in 1972 led clear and since the strong professor of tutor Duo Ben finds photocatalysis principle and effect for the first time, the research of optically catalytic TiO 2 is very active always, be widely used in the exploitation of solar cell, gas sensor, the solar energy preparing hydrogen by decomposing, the photocatalytic degradation of sewage and waste water, photo-catalyst, self-cleaning and antifog etc.But TiO
2Forbidden band broad (Eg=3.2eV), (λ≤387.5nm) ultraviolet light excites can only only to be accounted for about 5% in the sunshine.Thereby, improve its quantum yield, widen TiO
2To the response of the visible light that accounts for solar radiation 46%, thereby full range utilizes solar energy, is TiO
2The developing direction of catalysis material.The spectral sensitization of organic dyestuff, noble metal support and transient metal doped, though can improve utilization rate, also make photocatalytic titania film ultraviolet light light reaction reduce to sunshine, a little less than the photo-catalysis capability, the photo and thermal stability variation, cost improves.Asahi etc. have calculated C, N, F, P or S doping back TiO respectively
2State density (DDSs), show TiO
2After anion doped, can make its light absorption edge to being shifted than low-lying level, the exciting light threshold values can be expanded to visible region (Science 2001,293,269).Because carbon has suitable electrical conductivity, density is very low, and carbon can enter in the titanium dioxide by organic carbonization of preference temperature, has changed the absorption of visible light, thereby obtains good photocatalysis effect.Khan etc. at the flame calcination titanium sheet of 850 degree, obtain the titanium dioxide (Science2002,297,2243) that carbon mixes by control methane and oxygen flow.But, mainly be that the form of rutile exists after the titanium dioxide high-temperature roasting that carbon mixes, and may cause TiO
2Nanocrystal is reunited and is grown up.Irie etc. are to TiC 600 degree oxidizing annealings in Oxygen Flow, and the Carbou doped titanium-oxide that obtains becomes display light catalytic activity (Chem.Lett.2003,32,772) in the reaction of CO2 under visible light (400-530nm) radiation isopropyl alcohol being decomposed through acetone.Li Yuanzhi etc. are to TiCl
4Hydrolysate contains the temperature programming carbonization in the cyclohexane air-flow of K anatase, makes Carbou doped titanium-oxide (Chem.Phys.Lett.2005,404,25).Ren Wenjie etc. mix back 160 degree hydrothermal treatment consists with isopropyl titanate hydrolysate in the mixture of the KCl aqueous solution and ethanol and obtain Carbou doped titanium-oxide with glucose, the mesoporous property in particle gap (Appl.Catal.B2007,69,138) is arranged.The method of employing gas reaction magnetron sputterings such as Ye Qin has prepared carbon doped Ti O2 film (artificial lens journal, 2006,35,1257) at 350 degree.Under hot conditions, the synthetic report of a small amount of low temperature needs the participation of potassium ion mostly in above-mentioned carbon doped Ti O2 preparation, the preparation condition harshness, and complex process, and the carbon doped Ti O2 of preparation is dense non-porous mostly, idol has report that mesoporous property is arranged.If introduce mesopore-macropore classification pore structure in catalyst, the then effectively diffusion of intensified response thing and product molecule reduces resistance to mass tranfer, improves catalytic activity.The introducing of the macropore that the aperture is identical with light wavelength also helps the transmission of light at the catalyst particles intragranular, and then improves active.
We have synthesized a kind of carbon titanium oxide photochemical catalyst material that mix, that have mesopore-macropore classification pore structure under the low temperature, not only have high-specific-surface mesoporous hole wall, and TiO has more been improved in its macropore duct
2Absorption property to organic dyestuff, and effectively improve mass transfer, photo-generated carrier and semiconductor recombination probability have been increased, simultaneously, after carbon mixes, not only titanium dioxide absorbs the sideband red shift to visible region, and has effectively improved it to the photodegradative catalytic activity of organic dye molecule (methyl orange and rhodamine B etc.).
Summary of the invention
The object of the present invention is to provide a kind of Carbou doped titanium-oxide graded hole photocatalytic material and preparation method thereof, can overcome the shortcoming of prior art.Synthesis device of the present invention is simple, and is easy to operate, and condition is loose, the energy is saved in of low pollution, and raw material is simple and easy to, and is with low cost.The photochemical catalyst of the present invention's preparation has the classification pore structure of two kinds of pore passage structures that interconnect of mesopore-macropore, and the specific surface height is good to the performance of organic dye molecule catalytic degradation.
Carbou doped titanium-oxide of the present invention has not only kept anatase phase fully, and average grain size is less than 50nm, have higher heat endurance and quantum efficiency, under ultraviolet light and visible light, all can excite, the more important thing is, macropore that this material has concurrently and meso-hole structure, can effectively reduce the liquid diffusional resistance, increase photon and semiconductor effect probability, reduce energy gap, strengthen photocatalytic activity.
The objective of the invention is to reach by following technical measures:
The present invention is with titanate esters (comprising other various alkoxide etc.), lauryl amine (DDA), and vitamin B6 etc. are raw material, the titanium-oxide graded hole material that the synthetic carbon of one-step method mixes.This preparation method comprises following two kinds of schemes:
Under (1) 80 ℃ with titanate esters and carbon source (as lauryl amine DDA, DDA/TiO
2The ratio 0.05～1 of amount) in conical flask, mix, the mixed liquor of ethanol and deionized water (volume ratio is 10: 1～5: 1) is joined in the reactant liquor fast, stir, aging, washing, suction filtration, drying obtains white powder.The white powder solid in tube furnace under the nitrogen protection 300～600 ℃ of following roasting 2-8h promptly obtain yellowish carbon doped porous titanium dioxide powder.
(2) under the room temperature 5.8～8.0g titanate esters, 15～30ml deionized water, 4.0～8.0g carbon source (as vitamin B6) are mixed; stir; aging; 60 ℃ dry down; get white powder, white powder 300～600 ℃ of following roasting 2-8h under the condition of nitrogen protection promptly obtain yellowish carbon doped porous titanium dioxide powder.
Described titanate esters can be tetraethyl titanate [Ti (OC
2H
5)
4], metatitanic acid n-propyl [Ti (OC
3H
7)
4], isopropyl titanate [Ti (iso-OC
3H
7)
4] or butyl titanate [Ti (OC
4H
9)
4].
Described carbon source can be lauryl amine, urea, tetrabutylammonium, cyclohexylamine, vitamin B6.
Adopt above prescription and reaction condition,, can prepare and have foramen magnum-mesoporous hierarchical porous structure through above-mentioned processing step, single anatase phase, the absorption spectrum expansion is wide, has the titania meterial that the highly active carbon of ultraviolet and visible light catalytic mixes.
Characteristics of the present invention are:
1. this method makes the oxygen in the simple effectively replacement of the carbon titanium oxide lattice and forms the titanium oxide that carbon mixes.
2. the carbon dope titanium oxide of this method preparation has tangible foramen magnum-mesoporous structure, and the macropore duct is of a size of 300-1000nm, and mesoporous aperture is 2.0-24nm, and specific area can be up to 691m
2/ g.
3. the Carbou doped titanium-oxide carbon containing 3.0%-25.0% of this method gained, its UV-vis absorption spectrum to more than the 440nm, have high photocatalytic activity from 393 red shifts in the experiment of the radiation of visible light degraded methyl orange of the above wave band of 400nm and rhodamine B.
4. this method preparation technology and equipment are simple, and great industrial production prospects is arranged.
Specific embodiment
Embodiment one
Add 10.0ml tetrabutyl titanate and 0.688g DDA under 80 ℃ in the volumetric flask of 100ml, their amount ratio is 0.075.Add the 40ml volume ratio then fast and be 7: 1 ethanol water, slowly stir 3h after, at 80 ℃ of down aging 48h; filter washing, drying; obtain the powder solid of white, primary product are 400 ℃ of roasting 8h under the nitrogen protection of Guan Shi stove, and cooling obtains yellowish powder solid.Stereoscan photograph demonstrates the regularly arranged big hole path that sample has 0.5-1 μ m pore size.Nitrogen adsorption isotherm is the IV type, and mesoporous pore diameter range is between 2.3～13.5nm.Transmission electron microscope photo shows that mesoporous pore structure is vermiform.X-ray diffraction spectrum figure shows that sample is single anatase phase oxidation titanium.Ultraviolet-visible absorption spectroscopy shows that the absorption sideband red shift of carbon doping rear oxidation titanium material is to the 450nm place.
Embodiment two
In the volumetric flask of 100ml, add 20ml deionized water and 6.8g tetrabutyl titanate under the room temperature, after slowly stirring 1h, add the 4.007g vitamin B6, continue to stir slowly 3h, static at normal temperatures 24h, drying gets the white pressed powder that gets, carbonization was carried out in the 400 ℃ of heating under nitrogen atmosphere of white powder solid in 6 hours, and cooling obtains the Carbou doped titanium-oxide material.This product has the big hole path of aperture size 0.3～1 μ m, anatase phase.Nitrogen adsorption-desorption isotherm is the IV type, and corresponding BJH pore-size distribution has two mesoporous distributions at 2.0nm and 24.0nm, and specific surface is up to 691m
2/ g.
Embodiment three
Get embodiment one and example two synthetic sample 0.02g and make catalyst, be suspended in the rhodamine B aqueous solution of 100 milliliter of 4.8 mg/litre, using by wavelength is that the 125W high-pressure sodium lamp of 365nm is done light source, tests its catalytic performance.Use unadulterated TiO simultaneously
2Powder sample is done the contrast experiment.The result shows, under same experimental conditions, behind UV-irradiation 1h, the catalyst of example one and example two preparations makes rhodamine B that degraded more than 95% all be arranged, and doped Ti O not
2Sample is lower than 60% to the degraded of rhodamine B.When the incandescent light of using 500W instead is done light source, the carbon doped Ti O that example one and example two are synthetic
2The photocatalytic activity of catalyst degradation rhodamine B is doped Ti O not
22-3 doubly.
Claims (7)
1. Carbou doped titanium-oxide multi-stage aperture photocatalysis material, it is characterized in that it has mesopore-macropore classification pore structure, (aperture 0.3-1 μ m) is regularly arranged in the macropore duct, and the hole wall of macropore is mesoporous, the mesoporous 2.0-24.0nm that is of a size of, specific area can be up to 691m
2/ g; In the described Carbou doped titanium-oxide material carbon content 3-25% is arranged, crystalline phase is single anatase phase.
2. preparation method who prepares the described Carbou doped titanium-oxide graded hole photocatalytic material of claim 1 is characterized in that it comprises following two kinds of schemes:
(1) titanate esters is mixed in conical flask with carbon source under 20-80 ℃, add fast in the mixed liquor of ethanol and deionized water, stir, aging, washing, suction filtration, drying obtains white powder.The white powder solid promptly obtains yellowish carbon doped porous titanium dioxide powder behind the uniform temperature roasting certain hour under the nitrogen protection in tube furnace.
(2) under the room temperature titanate esters, deionized water and carbon source are mixed, stir, aging, drying gets white powder, and white powder promptly obtains yellowish carbon doped porous titanium dioxide powder behind uniform temperature roasting certain hour under the condition of nitrogen protection.
3. according to the preparation method of the described a kind of Carbou doped titanium-oxide graded hole photocatalytic material of claim 2, it is characterized in that described titanate esters can be tetraethyl titanate [Ti (OC
2H
5)
4], metatitanic acid n-propyl [Ti (OC
3H
7)
4], isopropyl titanate [Ti (iso-OC
3H
7)
4] or butyl titanate [Ti (OC
4H
9)
4]; Described carbon source is lauryl amine, urea, cyclohexylamine, vitamin B6, glucose, sucrose etc.
4. according to the preparation method of the described a kind of Carbou doped titanium-oxide graded hole photocatalytic material of claim 2, it is characterized in that the pH value of solution can be 1-12.
5. according to the preparation method of the described a kind of Carbou doped titanium-oxide graded hole photocatalytic material of claim 2, it is characterized in that described aging temperature is 60-80 ℃; Time is 0-72h.
6. according to the preparation method of the described a kind of Carbou doped titanium-oxide graded hole photocatalytic material of claim 2, it is characterized in that described sintering temperature is 300-600 ℃, roasting time is 2-8h.
7. according to the preparation method of the described a kind of Carbou doped titanium-oxide graded hole photocatalytic material of claim 2, it is characterized in that the mass ratio of carbon source and titanate esters is 0.05～1; The volume ratio of ethanol and water is 10: 1～5: 1.
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| CN102389787A (en) * | 2011-09-21 | 2012-03-28 | 中国科学院城市环境研究所 | Carbon-doped titanium dioxide hollow spherical photocatalyst and preparation method thereof |
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| CN109896574A (en) * | 2018-09-30 | 2019-06-18 | 福建省农业科学院农业工程技术研究所 | A kind of carbon ferrite-titanium oxide Multifunctional water purification material and preparation method thereof |
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Application publication date: 20070829 Assignee: Tianjin Yuetai Petro-Chemical Technology Co., Ltd. Assignor: Tianjin Shenneng Science and Technology Co., Ltd. Contract record no.: 2014120000077 Denomination of invention: Carbou doped titanium-oxide graded hole photocatalytic material and preparing method Granted publication date: 20100127 License type: Exclusive License Record date: 20140923 |
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