CN104030345B - A kind of mixed phase nano-TiO of different colours 2preparation method - Google Patents
A kind of mixed phase nano-TiO of different colours 2preparation method Download PDFInfo
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- 239000003086 colorant Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 62
- 239000012071 phase Substances 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000005457 ice water Substances 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- 238000007669 thermal treatment Methods 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 14
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 4
- -1 Huang Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 230000008092 positive effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 34
- 230000000694 effects Effects 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002159 nanocrystal Substances 0.000 description 4
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229910003089 Ti–OH Inorganic materials 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- WZRZTHMJPHPAMU-UHFFFAOYSA-L disodium;(3e)-3-[(4-amino-3-sulfonatophenyl)-(4-amino-3-sulfophenyl)methylidene]-6-imino-5-methylcyclohexa-1,4-diene-1-sulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(=N)C(C)=CC1=C(C=1C=C(C(N)=CC=1)S([O-])(=O)=O)C1=CC=C(N)C(S(O)(=O)=O)=C1 WZRZTHMJPHPAMU-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of mixed phase nano-TiO of different colours
2preparation method, its gordian technique is the armorphous nano TiO to aqueous phase one-step synthesis
2heat-treat at different temperatures.Concrete grammar is: first by Ti (SO
4)
2solution and ammoniacal liquor hybrid reaction under ice-water bath condition obtains TiO
2unformed hydrate colloidal sol, centrifuge washing, then by colloidal sol low temperature evaporate to dryness, what obtain is the nano-TiO of unformed phase
2, respectively at different temperatures to the unformed phase nano-TiO of evaporate to dryness
2solid is heat-treated, and obtains the unformed of different colours and anatase octahedrite mixed phase nano-TiO
2.The present invention is the mixed phase nano-TiO adopting gradient heat-treating methods to obtain a series of different colours first
2, the method is simple to operate, and raw material is easy to get, with low cost, environmentally friendly, the mixed phase nano-TiO of the different colours of preparation
2achieve the continuous regulation and control to energy band structure, in photocatalysis degradation organic contaminant, have excellent performance and positive effect, have a good application prospect.
Description
Technical field
The invention belongs to the preparation field of metal oxide functional material, particularly a kind of mixed phase nano-TiO of different colours
2preparation method.
Background technology
Nano-TiO
2be a kind of novel inorganic functional materials, there is the performance of the uniquenesses such as specific surface area is large, surfactivity is high, absorbing properties is good.Nano-TiO
2valuable optical property makes it all demonstrate good development prospect in automotive industry and numerous areas.Nano-TiO
2also there is very high chemical stability, thermostability, nontoxicity, Superhydrophilic, non-migratory, and completely can with Food Contact, so be widely used in anti-ultraviolet material, weaving, photochemical catalysis catalyst, glass with clean, sunscreen, coating, ink, packaging material for food, paper industry, space industry, lithium cell.
At organic solvent middle synthesis of nano TiO mutually
2, nanoparticle is adsorbed on organic macromolecule, and sluggish occurs, and is conducive to like this controlling the growth of particle in reaction process, obtains the nanocrystal of required desirable pattern, therefore the TiO of major part synthesis at present
2method how much all can be with an organic solvent.But the method often produces malicious byproduct, simultaneously because nanocrystal and the macromolecular combination of organism, the subsequent disposal that nanocrystal is synthesized becomes complicated.And adopt synthesis in water nano-TiO
2method, easy and simple to handle, with low cost, toxic side effect is little, and subsequent disposal is simple, but more difficult to the control ratio of product structure, current synthesis in water TiO
2because the application prospect of broadness, receive increasing concern.
Anatase-phase nano TiO
2as a kind of optical function material, it is mainly employed photocatalyst.But common anatase octahedrite nano-TiO
2because energy gap is at more than 3.3eV, only could transition of electron be produced under the ultraviolet excitation only accounting for solar radiation 5%, lower to the efficiency of light energy utilization, and also photo-generate electron-hole is fast to association rate, and all can to nano-TiO
2photocatalytic activity have an impact.For this problem, many research and propose various terms of settlement both at home and abroad, comprised to TiO
2in mix the impurity such as C, N, S, to TiO
2carry out hydrogen treatment and introduce grain surface nonsequential bed etc.These methods are to nano-TiO
2structure reinvent, what have can improve its photocatalytic activity really, but all have passed through more complicated step, and experiment condition is very harsh, and natural cost is high.
Thermal treatment as a kind of conventional means, to TiO
2modification in also have extensive utilization, but generally all just choose a specified temp (mostly being 400 DEG C-500 DEG C), as the transition step of in experimentation, the change of the simple thermal treatment temp of systematic study can nano-TiO to synthesis in water
2what kind of impact sample produces.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of mixed phase nano-TiO of different colours
2preparation method.
The technical solution used in the present invention is:
The mixed phase nano-TiO of a series of different colours
2, they are by the white amorphous nano-TiO after aqueous phase one-step synthesis
2obtain after carrying out the thermal treatment of differing temps, described mixed phase is amorphous and anatase octahedrite mixed phase, and thermal treatment temp is higher, and unformed phase proportion is lower.
Described aqueous phase one-step synthesis is titanium sulfate solution and ammoniacal liquor single step reaction in aqueous phase.
Described thermal treatment temp is 200-800 DEG C, and under differing temps, process obtains the pressed powder comprising palm fibre, Huang, ash, white colour.
When described thermal treatment temp is 700 DEG C, the mixed phase nano-TiO obtained
2under solar irradiation, there is the highest photocatalytic activity.
When described thermal treatment temp is 600 DEG C, the mixed phase nano-TiO obtained
2under visible ray shines, there is the highest photocatalytic activity.
Nano-TiO
2energy gap with thermal treatment temp raise and increase, specific surface area with thermal treatment temp raise and reduce.
Concrete steps are:
1) join in deionized water by titanium sulfate solution and ammoniacal liquor under ice-water bath condition, this single step reaction, through being uniformly mixed 2h, obtains TiO
2the colloidal sol of unformed hydrate;
2) the colloidal sol centrifugation that step 1) obtains, solid precipitation deionized water wash;
3) by step 2) in washing after colloidal sol evaporate to dryness at low temperatures, obtain white amorphous nano-TiO
2solid, respectively through heat treatments at different, obtains the mixed phase nano-TiO of different colours
2.
In step 1), the concentration of titanium sulfate solution is 8.0g/100mL, and the concentration of ammoniacal liquor is 4mol/L, and the pH of reaction system maintains 9-10.
Step 2) middle centrifugation rate at least 5500rpm, more than washing time 20min.
Low temperature evaporate to dryness described in step 3) is 60-80 DEG C of constant temperature evaporate to dryness in air dry oven, then the solid of evaporate to dryness is put into retort furnace, respectively at 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C and 800 DEG C of thermal treatment 3h, temperature rise rate 10 DEG C/min, obtains the mixed phase nano-TiO of different colours
2.
Beneficial effect of the present invention: have employed gradient temperature heat-treating methods first, to the white amorphous nano-TiO of aqueous phase one-step synthesis
2crystallization degree control, obtain the unformed of different colours and anatase octahedrite mixed phase nano-TiO
2, along with thermal treatment temp raises, nano-TiO
2degree of crystallinity increase, color shoals gradually.The method preparation technology is simple, with low cost, and experimental result shows, TiO
2the hydroxyl of nanocrystal surface is the major reason causing crystalline structure unordered.Unformed TiO
2hydroxy radical content is large, causes band curvature, energy gap is narrowed.Thermal treatment temp is higher, and hydroxyl is sloughed with the form of water gradually, TiO
2changed by the anatase octahedrite of height disordering to complete rule, band curvature fades away, thus achieves nano-TiO
2structure and the continuous regulation and control that can be with.TiO after thermal treatment
2photoabsorption enhancing in the scope of visible and near infrared light, consistent with the result of their different colours macroscopically and band curvature.Nano-TiO prepared by heat treatments at different
2there is different activity in photocatalysis degradation organic contaminant, wherein 700 DEG C of heat treated TiO
2there is the highest sunlight catalytic active; 600 DEG C of heat treated TiO
2have the highest visible light catalysis activity, this method prepares excellent photocatalyst material, efficient extn nano-TiO
2range of application.
Accompanying drawing explanation
Fig. 1 is the different colours nano-TiO that thermal treatment obtains
2sample photo;
Fig. 2 is the different colours mixed phase nano-TiO that thermal treatment obtains
2xRD figure spectrum.Collection of illustrative plates shows along with thermal treatment temp raises, nano-TiO
2anatase degree of crystallinity increase;
Fig. 3 is the different colours mixed phase nano-TiO that thermal treatment obtains
2part HRTEM photo: before (a) thermal treatment; (b) 200 DEG C of thermal treatments; (c) 400 DEG C of thermal treatments; (d) 800 DEG C of thermal treatments.Photo shows along with thermal treatment temp raises, nano-TiO
2occur by unformed mutually in Anatase crystal nucleation grow up, until all unformed phases are all by process that regular lattice replaces;
Fig. 4 is the different colours mixed phase nano-TiO that thermal treatment obtains
2o1sXPS collection of illustrative plates: before (a) thermal treatment; (b) 200 DEG C of thermal treatments; (c) 400 DEG C of thermal treatments; (d) 500 DEG C of thermal treatments; (e) 600 DEG C of thermal treatments; (f) 700 DEG C of thermal treatments; (g) 800 DEG C of thermal treatments; .The Gaussian peak being positioned at 530eV after collection of illustrative plates swarming represents Ti-O key, and another Gaussian peak represents Ti-OH key, and peak area size shows along with thermal treatment temp raises, mixed phase nano-TiO
2the ratio of middle Ti-O/Ti-OH is by increase, and namely anatase crystalline phase increases gradually with the ratio of unformed phase;
Fig. 5 is the different colours mixed phase nano-TiO that thermal treatment obtains
2part ultraviolet-visible absorption spectroscopy.Collection of illustrative plates shows the nano-TiO that color is darker
2, have more visible absorption and larger band curvature.Thermal treatment temp is higher, the nano-TiO obtained
2energy gap is larger, and visible absorption is less.Dotted line represents 400 DEG C of heat treated nano-TiOs
2the position of the interband energy level produced;
Fig. 6 is the different colours mixed phase nano-TiO that thermal treatment obtains
2part VBXPS collection of illustrative plates.Collection of illustrative plates shows the impact being subject to mixed phase structure, nano-TiO
2top of valence band position can there is blue shift, cause band curvature, energy gap narrowed.The position of the magnetic tape trailer of top of valence band and band curvature formation has been marked in figure;
Fig. 7 is the different colours mixed phase nano-TiO that thermal treatment obtains
2part energy band structure schematic diagram.White TiO before thermal treatment
2only has discrete energy level, the TiO after thermal treatment
2have band curvature in various degree and interband energy level, along with thermal treatment temp raises, the magnetic tape trailer that can be with is less, and energy gap is larger;
Fig. 8 a is the different colours mixed phase nano-TiO that thermal treatment obtains
2at the degradation curve of xenon lamp simulated solar irradiation to the acid fuchsine solution;
Fig. 8 b is the different colours mixed phase nano-TiO that thermal treatment obtains
2degradation curve to the acid fuchsine solution under xenon lamp simulated solar irradiation adds the catalysis of spectral filter simulated visible light.
Collection of illustrative plates shows that the ratio regular meeting of anatase octahedrite and unformed phase is to nano-TiO
2photocatalytic activity impact, but be not monotone variation, the mixed phase nano-TiO that 700 DEG C of thermal treatment obtains
2under solar irradiation, there is the highest photocatalytic activity.And the mixed phase nano-TiO that 600 DEG C of thermal treatment obtains
2under visible ray shines, there is the highest photocatalytic activity, illustrate that amorphous phase is more conducive to nano-TiO
2visible light catalysis activity, and by adjustment thermal treatment temp, the desired light catalytic material needed for us can be obtained.
Embodiment
Below in conjunction with embodiment, the present invention is elaborated.
embodiment 1
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, the white nano-TiO before drying obtains thermal treatment at 80 DEG C
2solid (Fig. 1).This nano-TiO
2belong to unformed shape (Fig. 2), do not form crystalline structure (a part of Fig. 3), microtexture is TiO
6octahedral aggregate, according to quantum size effect, this TiO
2only have discrete energy level, do not possess quasi-continuous energy band structure, therefore energy gap very large (Fig. 7).Its specific surface area size is up to 328.55m
2/ g, therefore has very strong adsorption to the organism in solution, but due to crystallinity very poor, energy gap is large, does not almost have photocatalytic activity.Be applicable to making sorbent material instead of photocatalyst.
embodiment 2
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, at 80 DEG C, drying obtains white nano-TiO
2solid, then by its constant temp. heating process 3h at 200 DEG C, obtains brown mixed phase nano-TiO
2(Fig. 1).This nano-TiO
2major part belongs to unformed shape (Fig. 2), and Anatase crystal starts forming core, the b part of median size 1.44nm(Fig. 3 simultaneously), specific surface area size reaches 281.88m
2/ g.This TiO
2there is the highest and continuous print visible absorption (Fig. 5), therefore have maximum band curvature, cause its energy gap the narrowest (Fig. 7).This product also has certain adsorptive power, but due to degree of crystallinity also very poor, photocatalytic activity is not high, is not very desirable to the degraded of organic solution.
embodiment 3
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, at 80 DEG C, drying obtains white nano-TiO
2solid, then by its constant temp. heating process 3h at 400 DEG C, obtains Yellow nanometer TiO
2(Fig. 1).This nano-TiO
2belong to anatase octahedrite and unformed shape mixed phase (Fig. 2), Anatase crystal is grown up gradually, and median size increases to the c part of 8.90nm(Fig. 3), specific surface area size is 161.18m
2/ g.This TiO
2occur a boss (Fig. 5) in visible absorption spectrum, representing that it has an interband energy level (Fig. 7), is also the major cause that its energy gap narrows.The adsorptive power of this product is not high, but has suitable degree of crystallinity and energy gap, therefore has higher sunlight and visible light catalysis activity (Fig. 8 a, b) simultaneously.
embodiment 4
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, at 80 DEG C, drying obtains white nano-TiO
2solid, then by its constant temp. heating process 3h at 500 DEG C, obtains faint yellow nano-TiO
2(Fig. 1).This nano-TiO
2belong to anatase octahedrite and unformed shape mixed phase (Fig. 2), Anatase crystal continues to grow up, and median size increases to 12.68nm.The energy band structure of this product and 400 DEG C of heat treated TiO
2similar, and its degree of crystallinity is higher than the latter, therefore its under solar irradiation to the degradation rate of fuchsin solution higher than 400 DEG C of heat treated nano-TiOs
2, visible ray according under then contrary (Fig. 8 a, b).
embodiment 5
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, at 80 DEG C, drying obtains white nano-TiO
2solid, then by its constant temp. heating process 3h at 600 DEG C, obtains yellow-white nano-TiO
2(Fig. 1).This nano-TiO
2belong to anatase octahedrite and unformed shape mixed phase (Fig. 2) because its degree of crystallinity is higher, median size 15.11nm, under solar irradiation to the degradation rate of fuchsin solution higher than 500 DEG C of heat treated nano-TiOs
2(Fig. 8 a); Simultaneously also have certain band curvature (Fig. 7) due to it, in structure, unformed and ratio that is anatase octahedrite is conducive to visible light catalytic most, the TiO therefore after all thermal treatment
2in there is the highest visible light catalysis activity (Fig. 8 b).
embodiment 6
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, at 80 DEG C, drying obtains white nano-TiO
2solid, then by its constant temp. heating process 3h at 700 DEG C, obtains white nano-TiO
2(Fig. 1).This nano-TiO
2belong to anatase octahedrite and unformed shape mixed phase, the brilliant median size 16.43nm of anatase-phase nano, illustrates this product highly crystallized.Because its high degree of crystallinity, still have a small amount of unformed shape to exist, in its structure, unformed and ratio that is anatase octahedrite is conducive to sunlight catalytic most simultaneously, therefore under solar irradiation to the nano-TiO of fuchsin solution after all thermal treatment
2in have the highest degradation rate (Fig. 8 a), but visible ray according under catalytic degradation activity lower (Fig. 8 b).
embodiment 7
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, at 80 DEG C, drying obtains white nano-TiO
2solid, then by its constant temp. heating process 3h at 800 DEG C, obtains white nano-TiO
2(Fig. 1).This nano-TiO
2the overwhelming majority belongs to the anatase octahedrite (Fig. 2) of highly crystalline, and also have a small amount of unformed shape, Anatase average crystal grain diameter has been grown up to 31.05nm(Fig. 3), specific surface area size reduces to 19.35m
2/ g.Although this product has maximum degree of crystallinity, there is not band curvature, energy gap wider (Fig. 7), therefore not high (Fig. 8 a, b) of sunlight and visible light photocatalysis active.
embodiment 8
Under ice-water bath condition, in 100mL deionized water, add 8.0g/100mL titanium sulfate solution and 4mol/L ammoniacal liquor that 12mL and 20mL prepare respectively, reaction system magnetic agitation 2h; By centrifugal for the colloidal sol after stirring, solid precipitation deionized water supersound washing; Get the colloidal sol after 100mL washing, at 80 DEG C, drying obtains white nano-TiO
2solid, then by its constant temp. heating process 3h at 1000 DEG C, obtains khaki color nano-TiO
2.This nano-TiO
2belong to the rutile (Fig. 2) of highly crystalline.
Claims (2)
1. the mixed phase nano-TiO of a different colours
2preparation method, it is characterized in that,
Described mixed phase nano-TiO
2by to the white amorphous nano-TiO after aqueous phase one-step synthesis
2obtain after carrying out the thermal treatment of differing temps, described mixed phase is amorphous and anatase octahedrite mixed phase, and thermal treatment temp is higher, and unformed phase proportion is lower; Nano-TiO
2energy gap with thermal treatment temp raise and increase, specific surface area with thermal treatment temp raise and reduce;
Described aqueous phase one-step synthesis is titanium sulfate solution and ammoniacal liquor single step reaction in aqueous phase;
Described thermal treatment temp is 200-800 DEG C, and under differing temps, process obtains the pressed powder comprising palm fibre, Huang, ash, white colour;
The concrete steps of preparation are:
1) join in deionized water by titanium sulfate solution and ammoniacal liquor under ice-water bath condition, this single step reaction, through being uniformly mixed 2h, obtains TiO
2the colloidal sol of unformed hydrate;
2) the colloidal sol centrifugation that step 1) obtains, solid precipitation deionized water wash;
3) by step 2) in washing after colloidal sol evaporate to dryness at low temperatures, obtain white amorphous nano-TiO
2solid, respectively through heat treatments at different, obtains the mixed phase nano-TiO of different colours
2;
In step 1), the concentration of titanium sulfate solution is 8.0g/100mL, and the concentration of ammoniacal liquor is 4mol/L, and the pH of reaction system maintains 9-10;
Step 2) middle centrifugation rate at least 5500rpm, more than washing time 20min.
2. according to claim
1the mixed phase nano-TiO of described a kind of different colours
2preparation method, it is characterized in that, low temperature evaporate to dryness described in step 3) is 60-80 DEG C of constant temperature evaporate to dryness in air dry oven, then the solid of evaporate to dryness is put into retort furnace, respectively at 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C and 800 DEG C of thermal treatment 3h, temperature rise rate 10 DEG C/min, obtains the mixed phase nano-TiO of different colours
2.
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| CN201410261175.8A CN104030345B (en) | 2014-06-13 | 2014-06-13 | A kind of mixed phase nano-TiO of different colours 2preparation method |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295977A (en) * | 2000-12-19 | 2001-05-23 | 中国科学院上海硅酸盐研究所 | Simple method for preparing titanium dioxide collosol |
| CN1594101A (en) * | 2004-07-05 | 2005-03-16 | 华东理工大学 | Method for preparing titanium dioxide mesoporous material |
| CN1898160A (en) * | 2003-11-13 | 2007-01-17 | 阿尔泰纳米材料公司 | Process to make rutile pigment from aqueous titanium solutions |
| CN101049962A (en) * | 2007-05-18 | 2007-10-10 | 广东省生态环境与土壤研究所 | Method for preparing sol of neutral Nano titanium dioxide |
| CN102107907A (en) * | 2009-12-28 | 2011-06-29 | 中国科学院金属研究所 | Porous nano hydrated titanium dioxide dearsenifying material and preparation method thereof |
| CN102784633A (en) * | 2011-05-17 | 2012-11-21 | 王东宁 | Preparation method for photocatalyst TiO2 supporter and manufacturing method for photocatalyst air cleaner |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06172127A (en) * | 1992-12-02 | 1994-06-21 | Kanebo Ltd | Coloring agent and its cosmetic |
| JP2011225396A (en) * | 2010-04-19 | 2011-11-10 | National Institute Of Advanced Industrial Science & Technology | Method for producing porous transparent thin film comprising anatase nanocrystal of titanium oxide, porous transparent thin film and porous transparent thin film photocatalyst |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295977A (en) * | 2000-12-19 | 2001-05-23 | 中国科学院上海硅酸盐研究所 | Simple method for preparing titanium dioxide collosol |
| CN1898160A (en) * | 2003-11-13 | 2007-01-17 | 阿尔泰纳米材料公司 | Process to make rutile pigment from aqueous titanium solutions |
| CN1594101A (en) * | 2004-07-05 | 2005-03-16 | 华东理工大学 | Method for preparing titanium dioxide mesoporous material |
| CN101049962A (en) * | 2007-05-18 | 2007-10-10 | 广东省生态环境与土壤研究所 | Method for preparing sol of neutral Nano titanium dioxide |
| CN102107907A (en) * | 2009-12-28 | 2011-06-29 | 中国科学院金属研究所 | Porous nano hydrated titanium dioxide dearsenifying material and preparation method thereof |
| CN102784633A (en) * | 2011-05-17 | 2012-11-21 | 王东宁 | Preparation method for photocatalyst TiO2 supporter and manufacturing method for photocatalyst air cleaner |
Non-Patent Citations (1)
| Title |
|---|
| 纳米二氧化钛的制备及其在皮革涂饰剂中的应用展望;王全杰等;《中国皮革》;20041231;第33卷(第23期);11-15 * |
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