CN101862647A - Preparation method for preparing titanium dioxide photochemical catalyst by ionic liquid - Google Patents
Preparation method for preparing titanium dioxide photochemical catalyst by ionic liquid Download PDFInfo
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Abstract
The invention discloses a preparation method for preparing titanium dioxide photochemical catalyst by ionic liquid, which comprises the following steps: solution A is obtained by adding absolute ethyl alcohol, tetrabutyl orthotita and methyl ethyl diketone to an agitated reactor with mechanical stirring in sequence and then stirring; solution B is obtained by adding absolute ethyl alcohol, 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid, distilled water and concentrated hydrochloric acid to an agitated reactor with mechanical stirring in sequence and then stirring; transparent light yellow collosol is obtained by mixing the solution A with the solution B and then stirring; the light yellow collosol is stoved at 100 DEG C in a vacuum drying oven with heat in a muffle furnace being preserved for 1 hour, the muffle furnace is heated and then heat is preserved for 2 hours, finally the light yellow collosol taken out from the muffle furnace to reach indoor temperature by natural cooling to obtain the titanium dioxide photochemical catalyst. The invention takes 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as organic solution medium so as to obtain a high efficient titanium dioxide photochemical catalyst which has uniform granularity, good crystallization, increscent exciting light wavelength coverage and ampliative light absorption coverage.
Description
Technical field
The invention belongs to the environmental chemical engineering environmental technology field, especially relate to the preparation method that a kind of ionic liquid participates in the titanium dioxide optical catalyst of preparation.
Background technology
In recent years, the sustainability pollutant of the difficult degradation in the water body and hypertoxicity pollutant have caused sizable pollution threat to the environment of human survival, the hazardous contaminant of how effectively degrading, and do not bring secondary pollution to environment, be the research emphasis and the focus of present water technology.
By discovering TiO
2Have good photocatalytic and can promote water body purification and effective simultaneously degraded hazardous contaminant, become a big focus of current water technology research at present already.But because TiO
2Photochemical catalyst band gap broad (Eg=3.2eV, λ=387nm), only under the ultraviolet excitation of incident light λ less than 387nm, the valence band electronics just can transit on the conduction band and to form light induced electron and separate with the hole, and then generation redox reaction, and the recombination rate height in light induced electron and hole, photo-quantum efficiency is low, has limited its practical application.
For overcoming above-mentioned shortcoming, can adopt to change organic solvent medium to TiO
2Carry out the method for modification, so that TiO
2Photochemical catalyst has good degree of crystallinity, little particle size and high specific area, and reduces TiO
2Energy gap, enlarge its light abstraction width, improve the excitation wavelength scope.
Compare with conventional organic solvents, ionic liquid at room temperature is having the following advantages aspect the preparation of nano material: (1) its surface tension is low, can make the nucleation rate of inorganic material higher, obtains less particle and crystal grain thinning; (2) its lower surface can make material have good stability therein, has also strengthened multiple molecule solvability therein; (3) its stability is high, and reaction can be carried out in the vessels not under pressure more than 100 ℃; (4) anhydrous or have under the condition of minor amount of water, the polar reaction thing is down auxiliary it, helps the synthetic of inorganic material, can avoid the generation of hydroxide and some amorphous substances; (5) under liquid state, formed the hydrogen bond of " prolongation ", formed structural system preferably, so, ionic liquid can be used as closely related driving form spontaneously tissue well, the nanostructured of long-range order.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, provides a kind of ionic liquid to participate in the preparation method of the titanium dioxide optical catalyst of preparation.The titanium dioxide optical catalyst that uses this preparation method to obtain, sustainability pollutant and hypertoxicity pollutant that can the difficult degradation in the efficient degradation water body in visible-range, and using method is easy, can reuse, and can not bring secondary pollution.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of ionic liquid participates in the preparation method of the titanium dioxide optical catalyst of preparation, it is characterized in that, the raw material of preparation titanium dioxide optical catalyst is formed by volume percentage and is counted: absolute ethyl alcohol 45%～54%, butyl titanate 30%～35%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 10%～14%, distilled water 4%～5%, acetylacetone,2,4-pentanedione 1%～1.6%, concentrated hydrochloric acid 0.2%～0.4%; Wherein, the mass fraction of described concentrated hydrochloric acid is 20%～22%;
The preparation method may further comprise the steps:
(1) has in the churned mechanically reactor one, add absolute ethyl alcohol, butyl titanate and acetylacetone,2,4-pentanedione successively, obtain solution A after the stirring;
(2) again in another has churned mechanically reactor, add absolute ethyl alcohol, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, distilled water and concentrated hydrochloric acid successively, obtain solution B after the stirring;
(3) with in the solution A in the slow impouring step of the solution B in the step (2) (1), mixing the back continues to stir, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, again in Muffle furnace 300 ℃ the insulation 1 hour, then furnace temperature is risen to 600 ℃ of insulations 2 hours, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Mixing time in the above-mentioned steps (1) is 1 hour.
Mixing time in the above-mentioned steps (2) is 0.5 hour.
Mixing time in the above-mentioned steps (3) is 0.5 hour.
The present invention compared with prior art has the following advantages: the present invention is by adding ionic liquid at room temperature---and 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid has obtained the titanium dioxide optical catalyst efficiently of a kind of epigranular, well-crystallized, the increase of excitation wavelength scope, light abstraction width expansion as the organic solution medium; The titanium dioxide optical catalyst that uses this preparation method to obtain, sustainability pollutant and hypertoxicity pollutant that can the difficult degradation in the efficient degradation water body in visible-range, and using method is easy, can reuse, and can not bring secondary pollution.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is the X-ray diffractogram of the titanium dioxide optical catalyst of the present invention's preparation.
Fig. 2 adds the titanium dioxide optical catalyst of the present invention's preparation and does not add the degradation curve schematic diagram of the formalin of titanium dioxide optical catalyst under the visible light condition.
Fig. 3 adds the titanium dioxide optical catalyst of the present invention's preparation and does not add the degradation curve schematic diagram of the phenol solution of titanium dioxide optical catalyst under the visible light condition.
Fig. 4 is titanium dioxide optical catalyst that adds the present invention's preparation under the visible light condition and the degradation curve schematic diagram that does not add the aniline solution of titanium dioxide optical catalyst.
Fig. 5 is titanium dioxide optical catalyst that adds the present invention's preparation under the visible light condition and the degradation curve schematic diagram that does not add the cyanide ion solution of titanium dioxide optical catalyst.
The specific embodiment
Embodiment 1
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following raw material:
Absolute ethyl alcohol 45%, butyl titanate 35%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 13%, distilled water 5%, acetylacetone,2,4-pentanedione 1.6%, mass fraction are 20%～22% concentrated hydrochloric acid 0.4%.
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 25ml, butyl titanate 35ml and acetylacetone,2,4-pentanedione 1.6ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 20ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 13ml, distilled water 5ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.4ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Embodiment 2
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following component:
Absolute ethyl alcohol 46%, butyl titanate 34%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 14%, distilled water 4.8%, acetylacetone,2,4-pentanedione 1%, concentrated hydrochloric acid (mass fraction is 20%～22%) 0.2%.
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 26ml, butyl titanate 34ml and acetylacetone,2,4-pentanedione 1ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 20ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 14ml, distilled water 4.8ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.2ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Embodiment 3
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following component:
Absolute ethyl alcohol 48%, butyl titanate 34%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 12%, distilled water 4.6%, acetylacetone,2,4-pentanedione 1.1%, concentrated hydrochloric acid (mass fraction is 20%～22%) 0.3%.
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 25ml, butyl titanate 34ml and acetylacetone,2,4-pentanedione 1.1ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 23ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 13ml, distilled water 4.6ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.3ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Embodiment 4
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following component:
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 25ml, butyl titanate 32ml and acetylacetone,2,4-pentanedione 1.6ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 25ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 12ml, distilled water 4ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.4ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following component:
Absolute ethyl alcohol 51%, butyl titanate 32%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 11%, distilled water 4.2%, acetylacetone,2,4-pentanedione 1.5%, concentrated hydrochloric acid (mass fraction is 20%～22%) 0.3%.
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 25ml, butyl titanate 32ml and acetylacetone,2,4-pentanedione 1.5ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 26ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 11ml, distilled water 4.2ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.3ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Embodiment 6:
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following component:
Absolute ethyl alcohol 49%, butyl titanate 33%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 12%, distilled water 4.4%, acetylacetone,2,4-pentanedione 1.2%, concentrated hydrochloric acid (mass fraction is 20%～22%) 0.4%.
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 25ml, butyl titanate 33ml and acetylacetone,2,4-pentanedione 1.2ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 24ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 12ml, distilled water 4.4ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.4ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Embodiment 7
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following component:
Absolute ethyl alcohol 52%, butyl titanate 31%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 11%, distilled water 4.5%, acetylacetone,2,4-pentanedione 1.3%, concentrated hydrochloric acid (mass fraction is 20%～22%) 0.2%.
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 25ml, butyl titanate 31ml and acetylacetone,2,4-pentanedione 1.3ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 27ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 11ml, distilled water 4.5ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.2ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Embodiment 8
The highly efficient titania photocatalyst of present embodiment, by volume percentage is made up of following component:
Absolute ethyl alcohol 54%, butyl titanate 30%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 10%, distilled water 4.8%, acetylacetone,2,4-pentanedione 1%, concentrated hydrochloric acid (mass fraction is 20%～22%) 0.2%.
The preparation method of present embodiment:
(1) in suitable the having in the churned mechanically reactor of a volume, adds absolute ethyl alcohol 25ml, butyl titanate 30ml and acetylacetone,2,4-pentanedione 1ml successively, stirred 1 hour, obtain solution A.
(2) again in having of another volume adequacy churned mechanically reactor, add absolute ethyl alcohol 29ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 10ml, distilled water 4.8ml and concentrated hydrochloric acid (mass fraction is 20%～22%) 0.2ml successively, stirred 0.5 hour, and obtained solution B.
(3) with in the slow impouring solution A of solution B, after the mixing, continue to stir 0.5 hour, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, 300 ℃ of insulations 1 hour in Muffle furnace again rise to furnace temperature 600 ℃ of insulations 2 hours then, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
Fig. 1 is the X-ray diffractogram of the titanium dioxide optical catalyst for preparing of the present invention, according to the diffraction result, and this sample TiO as can be known
2The main component of powder-type photochemical catalyst is rutile crystal type and anatase crystal, and the mass ratio of rutile crystal type and anatase crystal is 1: 4.Hence one can see that, and the crystal formation of titanium dioxide optical catalyst is all right.
Fig. 2 adds the titanium dioxide optical catalyst of the present invention's preparation and does not add the degradation curve of the formalin of titanium dioxide optical catalyst under the visible light condition, reaction condition is that content of formaldehyde is 40mg/L, TiO
2The photochemical catalyst consumption is light-catalyzed reaction 20 hours under the situation of 5g/L, and as seen from the figure, after 20 hours degraded, the formalin degradation rate that adds titanium dioxide reaches 94.56%, and the formalin of not adding titanium dioxide then is not degraded basically.
Fig. 3 adds the titanium dioxide optical catalyst of the present invention's preparation and does not add the degradation curve of the phenol solution of titanium dioxide optical catalyst under the visible light condition, reaction condition is that phenol content is 30mg/L, TiO
2The photochemical catalyst consumption is light-catalyzed reaction 32 hours under the situation of 5g/L, and as seen from the figure, after 32 hours degraded, the phenol solution degradation rate that adds titanium dioxide reaches 96.83%, and the phenol solution of not adding titanium dioxide then is not degraded basically.
Fig. 4 is the titanium dioxide optical catalyst and the degradation curve that does not add the aniline solution of titanium dioxide optical catalyst that adds the present invention's preparation under the visible light condition, and reaction condition is 45mg/L for aniline content, TiO
2The photochemical catalyst consumption is light-catalyzed reaction 24 hours under the situation of 5g/L, and as seen from the figure, after 24 hours degraded, the aniline solution degradation rate that adds titanium dioxide reaches 97.12%, and the aniline solution that does not add titanium dioxide then is not degraded basically.
Fig. 5 is the titanium dioxide optical catalyst and the degradation curve that does not add the cyanide ion solution of titanium dioxide optical catalyst that adds the present invention's preparation under the visible light condition, and reaction condition is 10mg/L for cyanide ion content, TiO
2The photochemical catalyst consumption is light-catalyzed reaction 12 hours under the situation of 5g/L, as seen from the figure, after 12 hours degraded, the cyanide ion solution degradation rate of adding titanium dioxide reaches 99.12%, and the cyanide ion solution that does not add titanium dioxide then is not degraded basically.
The above; it only is preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, everyly any simple modification that above embodiment did, change and equivalent structure changed, all still belong in the protection domain of technical solution of the present invention according to the technology of the present invention essence.
Claims (4)
1. an ionic liquid participates in the preparation method of the titanium dioxide optical catalyst of preparation, it is characterized in that, the raw material of preparation titanium dioxide optical catalyst is formed by volume percentage and is counted: absolute ethyl alcohol 45%～54%, butyl titanate 30%～35%, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid 10%～14%, distilled water 4%～5%, acetylacetone,2,4-pentanedione 1%～1.6%, concentrated hydrochloric acid 0.2%～0.4%; Wherein, the mass fraction of described concentrated hydrochloric acid is 20%～22%;
The preparation method may further comprise the steps:
(1) has in the churned mechanically reactor one, add absolute ethyl alcohol, butyl titanate and acetylacetone,2,4-pentanedione successively, obtain solution A after the stirring;
(2) again in another has churned mechanically reactor, add absolute ethyl alcohol, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, distilled water and concentrated hydrochloric acid successively, obtain solution B after the stirring;
(3) with in the solution A in the slow impouring step of the solution B in the step (2) (1), mixing the back continues to stir, obtain transparent faint yellow colloidal sol, 100 ℃ of oven dry in vacuum drying chamber earlier, again in Muffle furnace 300 ℃ the insulation 1 hour, then furnace temperature is risen to 600 ℃ of insulations 2 hours, naturally cool to room temperature after the taking-up, obtain titanium dioxide optical catalyst.
2. participate in the preparation method of the titanium dioxide optical catalyst of preparation according to the described ionic liquid of claim 1, it is characterized in that: the mixing time in the step (1) is 1 hour.
3. participate in the preparation method of the titanium dioxide optical catalyst of preparation according to the described ionic liquid of claim 1, it is characterized in that: the mixing time in the step (2) is 0.5 hour.
4. participate in the preparation method of the titanium dioxide optical catalyst of preparation according to the described ionic liquid of claim 1, it is characterized in that: the mixing time in the step (3) is 0.5 hour.
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| CN102059107A (en) * | 2010-11-26 | 2011-05-18 | 长安大学 | Method for preparing modified serpentine loaded titanium dioxide photocatalyst |
| CN102079542A (en) * | 2011-01-11 | 2011-06-01 | 福建农林大学 | Method for synthesizing meso-porous TiO2 by cellulose template in ionic liquid / water medium |
| CN102125861A (en) * | 2011-01-21 | 2011-07-20 | 福建农林大学 | F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof |
| CN102266786A (en) * | 2011-06-14 | 2011-12-07 | 福建农林大学 | SiO2 supported s-doped TiO2 visible light catalyst and preparation method thereof |
| CN102658110A (en) * | 2012-05-10 | 2012-09-12 | 西安科技大学 | Method for preparing modified hedenbergite supported titanium dioxide photocatalyst |
| CN105316953A (en) * | 2015-11-04 | 2016-02-10 | 长安大学 | Preparation method and application of SnS2-attached textile |
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| CN105831154A (en) * | 2016-04-07 | 2016-08-10 | 济南钛盾生物科技有限公司 | Titanium dioxide antibacterial sol and preparation method thereof |
| CN113441182A (en) * | 2021-06-29 | 2021-09-28 | 安徽农业大学 | Preparation method of core-shell titanium dioxide @ carboxyl chitosan nanoparticles |
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| CN102059107B (en) * | 2010-11-26 | 2012-06-27 | 长安大学 | Method for preparing modified serpentine loaded titanium dioxide photocatalyst |
| CN102059107A (en) * | 2010-11-26 | 2011-05-18 | 长安大学 | Method for preparing modified serpentine loaded titanium dioxide photocatalyst |
| CN102079542A (en) * | 2011-01-11 | 2011-06-01 | 福建农林大学 | Method for synthesizing meso-porous TiO2 by cellulose template in ionic liquid / water medium |
| CN102125861A (en) * | 2011-01-21 | 2011-07-20 | 福建农林大学 | F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof |
| CN102125861B (en) * | 2011-01-21 | 2012-12-05 | 福建农林大学 | F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof |
| CN102266786B (en) * | 2011-06-14 | 2013-11-13 | 福建农林大学 | SiO2 supported s-doped TiO2 visible light catalyst and preparation method thereof |
| CN102266786A (en) * | 2011-06-14 | 2011-12-07 | 福建农林大学 | SiO2 supported s-doped TiO2 visible light catalyst and preparation method thereof |
| CN102658110B (en) * | 2012-05-10 | 2014-10-22 | 西安科技大学 | Method for preparing modified hedenbergite supported titanium dioxide photocatalyst |
| CN102658110A (en) * | 2012-05-10 | 2012-09-12 | 西安科技大学 | Method for preparing modified hedenbergite supported titanium dioxide photocatalyst |
| CN105316953A (en) * | 2015-11-04 | 2016-02-10 | 长安大学 | Preparation method and application of SnS2-attached textile |
| CN105421029A (en) * | 2015-11-04 | 2016-03-23 | 长安大学 | Preparation method and application of attachment SnS2 nonwoven fabric |
| CN105421029B (en) * | 2015-11-04 | 2017-12-15 | 长安大学 | One kind attachment SnS2The preparation method and applications of non-woven fabrics |
| CN105316953B (en) * | 2015-11-04 | 2018-02-13 | 长安大学 | One kind attachment SnS2The preparation method and applications of textile |
| CN105831154A (en) * | 2016-04-07 | 2016-08-10 | 济南钛盾生物科技有限公司 | Titanium dioxide antibacterial sol and preparation method thereof |
| CN105831154B (en) * | 2016-04-07 | 2018-08-24 | 济南钛盾生物科技有限公司 | A kind of titanium dioxide antibiotic colloidal sol and preparation method thereof |
| CN113441182A (en) * | 2021-06-29 | 2021-09-28 | 安徽农业大学 | Preparation method of core-shell titanium dioxide @ carboxyl chitosan nanoparticles |
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