Controllable one-pan method for preparing high-efficient titanic oxide mixed crystal photocatalyst

The controllable tank preparation method of high-efficiency titanium dioxide mixed photocatalyst crystal

technical field

The crystal titanium dioxide according the invention relates to a high-efficiency titanium dioxide crystal mixed photocatalyst and synthetic method, obtains for brookite and rutile titanium dioxide, with high photocatalytic activeness.

background technology

The recent years the semiconductor photocatalyst the temperature-preserving pollutant and solar energy and hydrocarbon degrading environment conversion the radius applied to receive the worldwide scale wide for because of comprising a (l) Fujishima, A;. Smoothness, T-SHAPED. N;. Tryk, D.A/. corpse /wtocAe and .i^oto&o/.

C; corpse totoc/z a rivet fixer. /? ev. 2000, 厶 1. (2) Kawahara, T-SHAPED;. Konishi, THE;. Tada, H-SHAPED;. Tohge, N;. Nishii, J;. Ito, S-SHAPED. A 戸. C7z seam/the r. AND 2002, 仏 2811. (3) Mills, A;. LeHunte, S-SHAPED. 乂 P/iofoc/? Decorative vessel force. to surface. A' C& joint .1997, or friend, l). . The numerous semiconductor photochemical, wherein the titanium dioxide is a ideal environmental friendly photocatalyst, comprising a chemical property stably jetting, difficult to dissolving, non-toxic, low cost state PDC (Fujishima, A;. Smoothness, T-SHAPED. N;. Tryk, D. A/. corpse /zotoc/? ew. PORT and o prestige o/. C;. corpse/? method otocA the i? ev. 2000, 7, L). .

The titanium dioxide with different structure; the inside of the rutile, anatase, brookite and a crystal seeds, the non-isomorphism's titanium dioxide with different application performance. The three seeds' crystal titanium dioxide, the rutile is considered of the thermodynamics stablest crystalling phase, and with the highest density and refractive-rate locating. Anatase of the grinding report of photocatalytic the titanium dioxide generally which rutile the reaction activeness of titanium dioxide is higher than the. Because of the actual process is less difficult to prepare purely the brookite titanium dioxide, therefore the grinding of measuring titanium block type titanium dioxide is a bracket. Further - literature part report brookite titanium dioxide when the degradation with isopropyl alcohol of the silver deposits the display of the anatase better photocatalytic (activeness (l) Ovenstone, J;. Yanagisawa, K-SHAPED. CAem. 1999, I people 2770. (2) Ohtani, AN;. Handa, J.I;. Nishimoto, S-SHAPED. I;.

Kagiya, T-SHAPED. 1985, a 0, 292). .

The titanium dioxide upper part and photocatalyst ability the solar conversion is a chemical energy. When the titanium dioxide absorption is more than light emitting of semiconductor energy the energy; the electronic is stimulated to four transmission belt from the valence belt, rear of the positive power on the valence of the hole. /A grounding with each other, and electronic hole to a mainly composite, comprising and lower phototransformation efficiency and lower photocatalytic activeness. Further the small part and electronic hole shifted the surface, or with the reaction of the upper chemical composite with the absorption directly, or jumped the pressure centre sounding composite (Hurum, D.C;. Agrios, A BACK.;. Grey, K-SHAPED. A. corpse, A CAem. 5 To 2003, myo- 4545). .

A for and is 1990; the scientist claims for preparing through the anatase and rutile mixed crystal titanium dioxide improving the photocatalytic activeness, wherein the upper activeness turning counting to the stimulated type can stop four from the anatase surface of the rutile surface, a efficient and type composite hole, which can the photocatalytic activeness. Tank two planting crystal titanium dioxide's Fermi grades of different, and two interphases with Schottky (Schottky) positioning barrier, which can turn the shifting of electric and holes, and migrates to the catalyst surface (i.e. the crystal effect). Electronic and holes for separating tank also two limit contact elevates, a enables the mixed nanometre crystal titanium dioxide powder with higher photocatalytic efficiency (Bickley, R.J./. The So/WSto 1991, W, 178). . For example, now commercialization titanium dioxide powder P25 (is made anatases 70% and 30%) rutiles the mixing cooperative effect of the logistics for with good photocatalytic activeness because of a [Bickley, R.J. fo/W/

1991,92,178). . And some grinding reported of the anatase deals with a rutile the closed contact surface of the coins type to four from the anatase to the rutile only needs the lower activating energy. For example, part of reported of the minor rutile crystal promiscuous parts of the anatase wherein the type of the shifting of rutiles and anatase two interactions, and is formed so-called the catalytic movable part. At the same time, part grinding reported in the device for mixed crystal titanium dioxide, the interface structure of optimization and a block-shaped Body is a spot, comprising a active existence is confirmed of non-default photocatalytic (activeness, And A.H-SHAPED;. Dimitrijevic, N. AND;. Chen, an l-shaped;. Nichols, J. AND;. Rajh, T-SHAPED;. Grey, K-SHAPED. A J.J and .CAe connector .2008, a 0, 5402). . The circular workpiece reported in mixed crystal titanium dioxide the different crystalling phase proportion with different photocatalytic activeness, the best photocatalytic activeness is corresponding to a proportion of optimization, therefore of the simple and method for preparing a proportion adjustable for mixed crystal titanium dioxide with less vital significance.

The beforehand grinding tool with the left synthesizing method for mixed crystal titanium dioxide, for example, the reaction spitting method is used to synthesize the mixed crystal titanium dioxide film effectively (Chen, an l-shaped;. Graham, AND. AN; And, BAFFLES; Grey, K-SHAPED. A. J7? /A F a certain carriage (2006,575, 1176)., part topic-based groups of reported synthesized a group of anatases/rutile/brookite mixed crystalling phase titanium dioxide, they synthesized the pilot through the solvent and method for first clip, comprising of K-SHAPED 773 calcine 2 hours (, And A.H-SHAPED;. Grey, K-SHAPED. A. C7/e joint. Tkfater 2007, 79, 1143). . Tank anatases, brookite and rutile three crystal seeds the thermostability is different, therefore the traditional preparing mixed crystal titanium dioxide for high-temperature calcine method. The invention taking inorganic salt titanium and titanium supply, a alkyl set amines is a conditioner, adopts a simple low temperature can direct to synthesize the brookite and rutile proportion adjustable efficient titanium dioxide mixed photocatalyst crystal. A variable the proportion of water and alkyl set amines, a knob of the mixed crystal comprise much conveniently the proportion of brookite and rutile. Without requirement any thermal treatment following steps. The mixed crystal titanium dioxide photocatalyst of the connecting Rodin composite B to simulate the organic pollutant and connecting simulating the sunlight and radiating light source, comprising on the light degradation experiment, and discussed the different the proportion of light degradation activeness. The utility model are of the mass percent is 38% brookite with the best photocatalytic activeness with a mixed crystal titanium dioxide according 62% rutiles electronic, capable of realizing the closed 100% degradation of contaminants of 150 minutes, wherein photocatalytic activeness is can six times of P25 powder marketability German Degussa Corporation production, the production technique is simple. Moreover the cost is low, the industrial amplifying factor is small, claims a novel chute is a large production photocatalytic material.

The gift; two and ejector report of the crystal titanium dioxide, and a nanometre crystal mixed photocatalyst Ti02 emulsion and preparation method for ejector Hebei is University Box Shiwen the topic-based set reported device and method for preparing high stable neutral mixed of nanometer Ti02 hydrosol is blocks University the resolute topic-based set reported. Compared to the upper be; the ejector of invention has two diversities: (1). The mixed crystal titanium dioxide according formerly be reported between the rutile and anatase the crystallizer, and mixed crystal of the ejector of invention refers to a rutile and brookite mixed; crystal(2). The mixed crystallizer according formerly be prepared of the emulsion perhaps the sol, and mixed crystal of the ejector of invention referred to is a powder, compared with the emulsion perhaps sol's application in industrial, the powder titanium dioxide wherein the bottom of catalyst and is then. The meshes of the invention is invention claims a high-efficiency titanium dioxide mixed crystal photochemical catalyst and preparation method thereof, wherein preparation method for controllable tank; the inner the inorganic titanium salt the water, a circulating the ration the Alkylamine, the adjusting the solvent thermal treatment device obtains the corresponding titanium dioxide the crystallizer, the mass percent is 38% brookite lower simulating the sunlight with high photocatalytic activeness with a mixed crystal titanium dioxide according 62% rutiles electronic.

The invention claims a high-efficiency titanium dioxide mixed photocatalyst crystallizer for brookite and rutile titanium dioxide mixed crystal powder, comprising a calculates according to the is 1-20%, the brookite having is 38%; the rutile having is 62%.

The invention for preparing steps of high-efficiency titanium dioxide crystal mixed photocatalyst and a: a歩 and l of the inorganic titanium salt of the distilled water mutation, wherein the liquid is made of titanium ion is 0.1~0.5 mole/; liter Step 2, wherein the step 1) matches with the oil solution to add the dike bottom pipeline; the Alkylamine and water volume ratio is 10-15: 2~1: 5, The step 3, which is a plates the solvent thermal treatment, the processing temperature is 100 to 220 +, the time is 24 to 72; hours Rear 歩 4, 3 歩 with ended mutation concave; the filter, and solid product of the filter obtains with the distilled water and ethanol compound leaching, wherein the product (lower TC the vacuum drying 12 hours of IO, then obtains the brookite and rutile mixed crystal titanium dioxide.

Inorganic titanium salt is titanium chloride, sulphate or orthophosphate; Alkyl set amines is triethylamine, diethylamine or ethylenediamine.

Superiority of the invention Is-one and adopts a tank method to synthesize the brookite and rutile proportion adjustable efficient titanium dioxide photocatalyst under low temperature; the combined sequence without requirement any thermal treatment following steps.

2nd, Wherein the weight separator of synthetic 38% and 62% rutile mixed crystal titanium dioxide with the interface structure for brookite; the semiconductor photocatalyst lower simulating the sunlight with high photocatalytic activeness, capable of realizing pollutant Rodin bright AND closed hydrocarbon degrading 100% and 150 minutes, which can P25 powder movable which can according commercialization German Degussa Corporation production.

3rd, The whole combined process for a tank to the whole, the process of synthetic is simple, the whole technological in easily controller, the raw material is convenient, the cost is low, the production rate is high, wherein the real requirement production.

Brief description for drawings

Work 1) is installed on the sample the XRD atlas.

Work 1 indicated sample preparation device is JCPDS (73-1765) and brookite (JCPDS 3-380) composed of a rutile. And 2^=27.5, 36.1 and 54.4° of the top corresponding to the rutile (JCPDS 73-1765); and 6=25.6 2, 31.0, 37.6, 48.4 and . The top are corresponding to the brookite (JCPDS 3-380 (lll), (121), (201), a (231) and crystal. The rutile and brookite's weight separator in mixed crystal 'p/^4/(A+i: b^b) computer through the obtains. And 'b field of the mixed crystal the weight separator of brookite. A and A field the rutile (110) is the intensity of brookite (121) is respectively corresponding. Optimized correlative A thermal is 2.721.

Work 2) is installed on the sample the brush type microscope picture (amplifying factor is 80,000) can.

Work 3) is installed on the sample the transmission type microscope picture (amplifying factor is 150,000) can.

Work 4) is installed on the sample the ultraviolet diffuse reflection atlas, type shows compares to P25, sample wave absorbing length of visible light displacement direction to (420 nanometers.

Section is 5 of the different time stimulation sunlight light source to prepare, the sample and market DegussaP25 degrade Rodin bright AND the respectively; the titanium dioxide sampling conveniently according of seats the invention preparing heads is higher catalyzed degradation activeness protection Degussa P25. The detailed description of illustrated embodiments implementation carrying 1 rutile and brookite mixed crystal powder preparing, wherein preparing steps of a as follows: Further connected and for drop into the titanium tetrachloride a IO milliliter water machine, the titanium ion concentration of the O.l mole/a liter solution storing; Step 2, wherein the step 1) matches with the oil solution to 3 which milliliters; triethylamine

The step 3 and 2 of the oil solution is provided on the first solvent the thermal treatment, the temperature is 100 +, the time is 24; hours Rear end 4, reactor is ended, the solid product filter, and a distilled water or the ethanol compound leaching product; the product IO (TC the dry 12 hours of the vacuum condition, then obtains the white titanium dioxide powder (powder). The sample preparation XRD made of analyzing as shown in work 1.

Implementation carrying 2 rutile and brookite mixed crystal powder preparing, wherein preparing steps of a as follows: 歩 connected and for drop into the titanium tetrachloride (10 milliliters water mutation, forming the titanium ion and is 0.3 mole/a liter solution storing; 歩 mutation 2, wherein 歩 1) matches with the oil solution to add 2 milliliters diethylamine concave; The step 3 and 2 of the oil solution is provided on the first solvent the thermal treatment, the temperature is 120 'C; the time is 30; hours Rear end 4, reactor is ended, the solid product filter, and a distilled water or the ethanol compound leaching product; the product IO (TC the dry 12 hours of the vacuum condition, then obtains the white titanium dioxide powder. The sample brush type microscope picture and transmission type microscope picture of preparing work to 2 and shown in work 3. Implementation carrying 3 rutile and brookite mixed crystal powder preparing, wherein preparing end of a as follows one.

Further connected and for drop into the phosphoric acid titanium and a IO milliliter water machine, the titanium ion and is 0.4 mole/a liter solution storing; Step 2, wherein the step 1) matches with the oil solution to add 5 milliliters; ethylenediamine歩 3 and 2 of the oil solution is provided on the first concave the solvent thermal treatment, the temperature is 220 +, the time is 48; hours Rear 歩 4, reactor is ended mutation, the solid product filter, and a distilled water or the ethanol compound leaching product; the product the IOO'C dry 12 hours of the vacuum condition, then obtains the white titanium dioxide powder. Preparation sample ultraviolet diffuse reflection atlas result as shown in work 4.

Implementation carrying 4 rutile and brookite mixed crystal powder preparing, wherein preparing steps of a as follows: Further connected and for drop into the titanium sulphate a IO milliliter water machine, the density is 0.3 mole/a liter solution storing; Step 2, wherein the step 1) matches with the oil solution to 3 which milliliters; triethylamineThe step 3 and 2 of the oil solution is provided on the first solvent the thermal treatment, the temperature is 200 " TYPE, the time is 72; hours Rear end 4, reactor is ended, the solid product filter, and a distilled water or the ethanol compound leaching product; the product IO (TC the dry 12 hours of the vacuum condition, then obtains the white titanium dioxide powder.

Implementation carrying 5 rutile and brookite mixed crystal powder preparing, wherein preparing steps of a as follows: 歩 connected and for drop into the titanium sulphate a IO milliliter water mutation, forming the density is 0.5 mole/a liter solution storing; Step 2, wherein the step 1) matches with the oil solution to 3.5 which milliliters; triethylamineThe step 3 and 2 of the oil solution is provided on the first solvent the thermal treatment, the temperature is (18 TC, the time is 60; hours Rear end 4, reactor is ended, the solid product filter, and a distilled water or the ethanol compound leaching product; the product IO (TC the dry 12 hours of the vacuum condition, then obtains the white titanium dioxide powder.

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