CN103894218B - A kind of nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material and preparation method thereof - Google Patents
A kind of nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of nitrogen of responding to visible light, fluorin-doped titanium dioxide mesoporous microsphere catalysis material and preparation method thereof, first be dissolved in hydrochloric acid with titanium tetrafluoride and obtain reaction precursor liquid, precursor liquid is atomization at ultrasonic atomizer, the aerosol being rich in fine droplet generated, aerosol enters high temperature process furnances reaction under ammonia drives, generate pressed powder, collect with distilled water, washing, in 75 ~ 85 DEG C of oven dry after centrifugal, obtain pressed powder, continue to calcine 1.5 ~ 2.5 hours at 450 ~ 550 DEG C in Muffle furnace, obtained fluorine, nitrogen co-doped titanium dioxide mesoporous photocatalytic material, this material crystalline phase is Anatase, fluorine-containing 1.5-3%, nitrogenous 0.8-5.2%, surplus is titanium dioxide.This fluorine, nitrogen co-doped titanium dioxide have mesoporous microsphere particle shape, and ultraviolet-visible spectrum just starts to absorb at below 600nm.Its preparation method is simple, production is continuous, is conducive to the large-scale production and application in industrialization.
Description
Technical field
The invention belongs to material preparation and environmental photocatlytsis field, be specifically related to a kind of nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material and preparation method thereof.
Background technology
TiO
2the advantages such as the stable and bio-compatible performance of abundance, nonpoisonous and tasteless, physicochemical properties is good become modal photochemical catalyst.But, TiO
2in light-catalyzed reaction process light induced electron and the photohole life-span extremely short, very easily compound in light-catalyzed reaction process, makes its quantum efficiency in photocatalytic process lower; TiO
2bandwidth be about 3.2eV, can not responding to visible light, only less than 5% can be utilized in solar energy, this makes TiO
2commercial Application is subject to very big restriction widely.In order to address these problems, a large amount of research work is around titanium deoxide catalyst Optimal flattening.First direction is TiO
2the modification (comprising various doped with metal elements, precious metal surface deposition, semiconductors coupling, change surface acidity etc.) of photochemical catalyst; Second direction is the photocatalysis of synthesizing various nano-scale different-shapes.A large amount of research work achieves certain progress, but fundamentally solves this great difficult problem of photocatalytic process efficiency not yet.In a period of current and expected future, exploitation can responding to visible light, efficient, cheap, nontoxic and stable photochemical catalyst, and raising photocatalytic process solar energy utilization ratio and quantum efficiency remain one of the focus and key problem of photocatalysis field.
The doping of titanium dioxide has been proved to be a kind of effective optimization titanium dioxide can be with that obtain can the method for photochemical catalyst of responding to visible light.In various element doping, of greatest concern with the research of the titanium dioxide of N doping, but the photochemical catalyst quantum efficiency only obtained with N doping is still not high enough.Therefore wish other elements that simultaneously adulterate, improve sunshine utilization rate and the course of reaction quantum efficiency of catalyst further.In addition the pattern of catalyst is also proved to be remarkable on the light-catalysed catalytic efficiency impact of catalyst, there are some researches show that the catalyst of ball-type can improve the light utilization efficiency of catalyst, therefore can improve the catalytic efficiency of catalyst.
The catalyst that current preparation has the doping of pattern can use hydro-thermal method, solvent-thermal method, the precipitation method etc., but these usually need reaction time length, high temperature, high pressure, and needs additional template agent, therefore not easily applies in industrialization.In the present invention, ultrasonic atomizatio method is applied to preparation N by us, the catalyst of F codope, the catalyst of synthesis has mesoporous sphere structure, nitrogen and fluorine are doped in catalyst effectively, obtain the photochemical catalyst of energy responding to visible light, and this preparation method have simple for process, generate continuously, be conducive to the feature of the extensive generation application in industrialization.
Summary of the invention
The object of the present invention is to provide a kind of nitrogen of responding to visible light, fluorin-doped titanium dioxide mesoporous microsphere catalysis material and preparation method thereof.The method technique is simple, and cost is low, and productive rate is high, realistic need of production, has larger application potential.
For achieving the above object, the present invention adopts following technical scheme:
A kind of nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, the mass fraction of described catalysis material fluorine is 1.5-3%, and the mass fraction of nitrogen is 0.8-5.2%, and surplus is titanium dioxide.
Described catalysis material is Detitanium-ore-type.
The mass fraction of described catalysis material fluorine is 1.2%, and the mass fraction of nitrogen is 4.7%, and surplus is titanium dioxide.
In described catalysis material, fluorine, nitrogen two kinds of elements can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band.
Described catalysis material is piled up by nanocrystalline material and is formed.
Described catalysis material is spherical particles, and the diameter of its spherical particles is 100nm-1000nm.
A preparation method for nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material,
Described preparation method is ultrasonic atomizatio method, and it comprises the steps:
1) titanium tetrafluoride being dissolved in concentration is in 1.0mol/L hydrochloric acid solution, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid passes through atomization under ultrasonic atomizer effect in reaction bulb, and form the aerosol being rich in fine droplet together with ammonia, described ultrasonic atomizer frequency is 1.7MHz;
3) aerosol enters high temperature process furnances under vavuum pump drives, each aerosol forms a microreactor in tube furnace, reaction temperature is 500-600 DEG C, ammonia flow velocity is at 10-30L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, fluorine two kinds of element dopings enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4) under the drive of vavuum pump, pressed powder step 3) obtained is extracted in distilled water to be collected, and washing, after centrifugal, in 75 ~ 85 DEG C of oven dry;
5) continue the pressed powder through step 4) process with the temperature calcination 1.5 ~ 2.5 hours of 450 ~ 550 DEG C in Muffle furnace, programming rate is 1-5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
One prepares nitrogen, the device of fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it comprises ammonia generating bottle and ultrasonic atomizer, ammoniacal liquor is loaded with in described ammonia generating bottle, described ammonia generating bottle comprises air inlet pipe and escape pipe, one end of described air inlet pipe is connected with outside air, the other end extends into below ammonia generating bottle liquid level, one end of described escape pipe extends into ammonia generating bottle, remain on liquid level, the other end of described escape pipe comprises two interfaces, one of them orifice responds bottle, another orifice has high temperature process furnances, described reaction bulb is placed on ultrasonic atomizer, the port of export of described high temperature process furnances is communicated with the vial being loaded with distilled water by glass tube, described vial sidewall is provided with an outlet nozzle, described outlet nozzle is communicated with vavuum pump.
Catalysis material of the present invention is mesoporous ball shape structure, and its crystal structure is piled up by nanocrystalline material to form.
In this catalysis material, fluorine, nitrogen two kinds of elements can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band, change the crystal structure of titanium dioxide, fluorine, nitrogen co-doped titanium dioxide are when reacting as catalyst, and can reduce reaction can be with, can the generation of catalytic reaction under visible light, improve the utilization rate of solar energy.
Catalysis material energy response wave length prepared by the present invention, at the visible ray of below 600nm, has higher photocatalytic activity, and the TiO 2 visible light photocatalytic activity adulterated than the single element of fluorine, nitrogen is high.
Remarkable advantage of the present invention is:
(1) excusing from death atomization is used for titanium dioxide nitrogen, fluorin-doped modification by the present invention first, and the catalyst of synthesis has mesoporous ball shape structure, and under visible light illumination, photo-generated carrier can effectively be separated, and be a kind of novel photochemical catalyst, its catalytic efficiency is high.
(2) whole technical process of the present invention is simple and easy to control, and energy consumption is low, and productive rate is high, and cost is low, and realistic need of production is conducive to large-scale popularization.
(3) catalyst of the present invention's synthesis pollutant that can produce in the degraded gas phase of efficient stable and liquid-phase assay process, has good activity stability simultaneously.Can carry out separating treatment easily in light-catalyzed reaction system, recycling rate of waterused is high, has very high practical value and application prospect widely.
Accompanying drawing explanation
The reaction unit sketch that Fig. 1 is nitrogen of the present invention, prepared by fluorin-doped titanium dioxide mesoporous microsphere catalysis material;
Fig. 2 is the nitrogen of the embodiment of the present invention 3 gained, the x-ray diffractogram of powder of fluorin-doped titanium dioxide mesoporous microsphere catalysis material;
Fig. 3 is the nitrogen of the embodiment of the present invention 3 gained, the scanning electron microscope (SEM) photograph of fluorin-doped titanium dioxide mesoporous microsphere catalysis material;
Fig. 4 is the nitrogen of the embodiment of the present invention 3 gained, the UV-Vis diffuse reflection spectroscopy figure of fluorin-doped titanium dioxide mesoporous microsphere catalysis material;
Fig. 5 is the F1sX X-ray photoelectron spectroscopy X figure of the Fluorin doped mesoporous titanium dioxide microspheres catalysis material of the embodiment of the present invention 3 gained;
Fig. 6 is the N1sX X-ray photoelectron spectroscopy X figure of the nitrogen-doped titanium dioxide mesoporous microsphere catalysis material of the embodiment of the present invention 3 gained.
Detailed description of the invention
Be below several embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
The nitrogen of responding to visible light, a fluorin-doped titanium dioxide mesoporous microsphere catalysis material, the mass fraction of described catalysis material fluorine is 1.5-3%, and the mass fraction of nitrogen is 0.8-5.2%, and surplus is titanium dioxide.
Described catalysis material is Detitanium-ore-type.
The mass fraction of described catalysis material fluorine is 1.2%, and the mass fraction of nitrogen is 4.7%, and surplus is titanium dioxide.
In described catalysis material, fluorine, nitrogen two kinds of elements can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band.
Described catalysis material is piled up by nanocrystalline material and is formed.
Described catalysis material is spherical particles, and the diameter of its spherical particles is 100nm-1000nm.
The nitrogen of responding to visible light, a preparation method for fluorin-doped titanium dioxide mesoporous microsphere catalysis material,
Described preparation method is ultrasonic atomizatio method, and it comprises the steps:
1) titanium tetrafluoride being dissolved in concentration is in 1.0mol/L hydrochloric acid solution, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid passes through atomization under ultrasonic atomizer effect in reaction bulb, and form the aerosol being rich in fine droplet together with ammonia, described ultrasonic atomizer frequency is 1.7MHz;
3) aerosol enters high temperature process furnances under vavuum pump drives, each aerosol forms a microreactor in tube furnace, reaction temperature is 500-600 DEG C, ammonia flow velocity is at 10-30L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, fluorine two kinds of element dopings enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4) under the drive of vavuum pump, pressed powder step 3) obtained is extracted in distilled water to be collected, and washing, after centrifugal, in 75 ~ 85 DEG C of oven dry;
5) pressed powder through step 4) process is continued in Muffle furnace with 450 ~ 550
othe temperature calcination of C 1.5 ~ 2.5 hours, programming rate is 1-5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
Prepare a device for nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material,
It comprises ammonia generating bottle 7 and ultrasonic atomizer, ammoniacal liquor is loaded with in described ammonia generating bottle 7, described ammonia generating bottle 7 comprises air inlet pipe 71 and escape pipe 72, one end of described air inlet pipe 71 is connected with outside air, the other end extends into below ammonia generating bottle 7 liquid level, one end of described escape pipe 72 extends into ammonia generating bottle 7, remain on liquid level, the other end of described escape pipe 72 comprises two interfaces, one of them orifice responds bottle 2, another orifice has high temperature process furnances 4, described reaction bulb 2 is placed on ultrasonic atomizer 3, the port of export of described high temperature process furnances 4 is communicated with the vial 5 being loaded with distilled water by glass tube, described vial 5 sidewall is provided with an outlet nozzle 6, described outlet nozzle 6 is communicated with vavuum pump.
Embodiment 1
It is in 1.0mol/L hydrochloric acid solution that 1.5g titanium tetrafluoride is dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution is atomization at ultrasonic atomizer, and frequency is 1.7MHz, by carrier gas, aerosol band is entered high temperature process furnances (500 DEG C) and reacts; The flow velocity of carrier gas is 10L/min, and carrier gas, without ammonia spirit, collects the pressed powder generated after tube furnace with distilled water, through washing, in 85 DEG C of oven dry after centrifugal; The powder solid obtained, continue to calcine 2.5 hours at 550 DEG C in Muffle furnace, programming rate is 5 DEG C/min, obtains Fluorin doped mesoporous titanium dioxide microspheres catalysis material, as the comparative example of fluorine, nitrogen co-doped titanium dioxide mesoporous microsphere.
Embodiment 2
It is in 1.0mol/L hydrochloric acid solution that 1.5g titanium tetrachloride is dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution is atomization at ultrasonic atomizer, and ultrasonic atomizer frequency is 1.7MHz, by carrier gas, aerosol band is entered high temperature process furnances (500 DEG C) and reacts; The flow velocity of carrier gas is 10L/min, and carrier gas is first the ammonia spirit of 5mol/L by concentration, makes to be rich in ammonia in carrier gas; The pressed powder generated is collected with distilled water, through washing, in 85 DEG C of oven dry after centrifugal after tube furnace; The powder solid obtained, continue to calcine 2.5 hours at 550 DEG C in Muffle furnace, programming rate is 5 DEG C/min, obtains yellow nitrogen-doped titanium dioxide mesoporous microsphere catalysis material, as the comparative example of fluorine, nitrogen co-doped titanium dioxide mesoporous microsphere.
Embodiment 3
It is in 1.0mol/L hydrochloric acid solution that 1.5g titanium tetrafluoride is dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution forms aerosol under ultrasonic atomizer effect, and ultrasonic atomizer frequency is 1.7MHz, by carrier gas, aerosol band is entered high temperature process furnances (500 DEG C) and reacts; The flow velocity of carrier gas is 10L/min, and carrier gas is first the ammonia spirit of 5mol/L by concentration, makes to be rich in ammonia in carrier gas; The pressed powder generated is collected with distilled water, through washing, in 85 DEG C of oven dry after centrifugal after reaction; Continue to calcine 2.5 hours at 550 DEG C in Muffle furnace, programming rate is 5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
Embodiment 4
It is in 1.0mol/L hydrochloric acid solution that 1.5g titanium tetrafluoride is dissolved in concentration, after 3 hours stir, obtains transparent solution; Solution forms aerosol under ultrasonic atomizer effect, and ultrasonic atomizer frequency is 1.7MHz, by carrier gas, aerosol band is entered high temperature process furnances (550 DEG C) and reacts; The flow velocity of carrier gas is 20L/min, and carrier gas is first the ammonia spirit of 2mol/L by concentration, makes to be rich in ammonia in carrier gas; The pressed powder generated is collected with distilled water, through washing, in 80 DEG C of oven dry after centrifugal after reaction; Continue to calcine 2.5 hours at 500 DEG C in Muffle furnace, programming rate is 4 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
Embodiment 5
It is in 1.0mol/L hydrochloric acid solution that 1.5g titanium tetrafluoride is dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution forms aerosol under ultrasonic atomizer effect, and ultrasonic atomizer frequency is 1.7MHz, by carrier gas, aerosol band is entered high temperature process furnances (600 DEG C) and reacts; The flow velocity of carrier gas is 30L/min, and carrier gas is first the ammonia spirit of 0.5mol/L by concentration, makes to be rich in ammonia in carrier gas; The pressed powder generated is collected with distilled water, through washing, in 75 DEG C of oven dry after centrifugal after reaction; Continue to calcine 2.5 hours at 450 DEG C in Muffle furnace, programming rate is 3 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
Embodiment 6
Respectively with rhodamine B (RhB) aqueous solution (1 × 10
-5the photocatalytic activity of the photochemical catalytic oxidation efficiency rating catalyst of the nitric oxide (concentration 400ppb, flow velocity 4L/min) mol/L) and in gas phase, the light source of use is artificial light source, and wavelength is 400-800nm, and active testing the results are shown in Table 1.
The Photocatalytic oxidation activity of table 1 different catalysts compares
| Sequence number | Catalyst sample | Oil repellent (%) | Nitrogen content (%) | RhB degradation rate a | Conversion of nitric oxide gas rate b |
| 1 | Embodiment 1 | 3.1 | 0 | 35% | 16.5% |
| 2 | Embodiment 2 | 0 | 4.8 | 51% | 28.5% |
| 3 | Embodiment 3 | 1.2 | 4.7 | 100% | 42.5% |
| 4 | Embodiment 4 | 1.2 | 1.9 | 91% | 39.2% |
| 5 | Embodiment 5 | 1.3 | 0.9 | 86% | 37.5% |
Note:
RhB degradation rate a is (C
o-C
t)/C
o× 100%,
C in formula
ofor the initial concentration of rhodamine B (RhB), C
tfor the concentration of light-catalyzed reaction RhB after 4 hours;
Conversion of nitric oxide gas rate b is (C
in-C
out)/C
in× 100%,
C in formula
infor the concentration of NO in air inlet, C
outfor the concentration of the NO after photocatalysis Gas-phase reactor.
As can be seen from Table 1, shown by photocatalytic activity test, use fluorine, nitrogen co-doped photocatalysis material of titanium dioxide prepared by this method, higher than the photocatalytic activity of titanium dioxide in gas phase and liquid phase of nitrogen and the doping of fluorine single element.
Claims (7)
1. a preparation method for nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: the mass fraction of described catalysis material fluorine is 1.2%, and the mass fraction of nitrogen is 4.7%, and surplus is titanium dioxide;
Described preparation method is ultrasonic atomizatio method, and it comprises the steps:
1) titanium tetrafluoride being dissolved in concentration is in 1.0mol/L hydrochloric acid solution, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid passes through atomization under ultrasonic atomizer effect in reaction bulb, and form the aerosol being rich in fine droplet together with ammonia, described ultrasonic atomizer frequency is 1.7MHz;
3) aerosol enters high temperature process furnances under vavuum pump drives, each aerosol forms a microreactor in tube furnace, reaction temperature is 500-600 DEG C, ammonia flow velocity is at 10-30L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, fluorine two kinds of element dopings enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4) under the drive of vavuum pump, pressed powder step 3) obtained is extracted in distilled water to be collected, and washing, after centrifugal, in 75 ~ 85 DEG C of oven dry;
5) continue the pressed powder through step 4) process with the temperature calcination 1.5 ~ 2.5 hours of 450 ~ 550 DEG C in Muffle furnace, programming rate is 1-5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
2. a preparation method for nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: the mass fraction of described catalysis material fluorine is 1.2%, and the mass fraction of nitrogen is 1.9%, and surplus is titanium dioxide;
Described preparation method is ultrasonic atomizatio method, and it comprises the steps:
1) titanium tetrafluoride being dissolved in concentration is in 1.0mol/L hydrochloric acid solution, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid passes through atomization under ultrasonic atomizer effect in reaction bulb, and form the aerosol being rich in fine droplet together with ammonia, described ultrasonic atomizer frequency is 1.7MHz;
3) aerosol enters high temperature process furnances under vavuum pump drives, each aerosol forms a microreactor in tube furnace, reaction temperature is 500-600 DEG C, ammonia flow velocity is at 10-30L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, fluorine two kinds of element dopings enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4) under the drive of vavuum pump, pressed powder step 3) obtained is extracted in distilled water to be collected, and washing, after centrifugal, in 75 ~ 85 DEG C of oven dry;
5) continue the pressed powder through step 4) process with the temperature calcination 1.5 ~ 2.5 hours of 450 ~ 550 DEG C in Muffle furnace, programming rate is 1-5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
3. a preparation method for nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: the mass fraction of described catalysis material fluorine is 1.3%, and the mass fraction of nitrogen is 0.9%, and surplus is titanium dioxide;
Described preparation method is ultrasonic atomizatio method, and it comprises the steps:
1) titanium tetrafluoride being dissolved in concentration is in 1.0mol/L hydrochloric acid solution, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid passes through atomization under ultrasonic atomizer effect in reaction bulb, and form the aerosol being rich in fine droplet together with ammonia, described ultrasonic atomizer frequency is 1.7MHz;
3) aerosol enters high temperature process furnances under vavuum pump drives, each aerosol forms a microreactor in tube furnace, reaction temperature is 500-600 DEG C, ammonia flow velocity is at 10-30L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, fluorine two kinds of element dopings enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4) under the drive of vavuum pump, pressed powder step 3) obtained is extracted in distilled water to be collected, and washing, after centrifugal, in 75 ~ 85 DEG C of oven dry;
5) continue the pressed powder through step 4) process with the temperature calcination 1.5 ~ 2.5 hours of 450 ~ 550 DEG C in Muffle furnace, programming rate is 1-5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
4., according to the preparation method of a kind of nitrogen one of claim l-3 Suo Shu, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it is characterized in that: described catalysis material is Detitanium-ore-type.
5. according to the preparation method of a kind of nitrogen one of claim l-3 Suo Shu, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it is characterized in that: in described catalysis material, fluorine, nitrogen two kinds of elements can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band.
6. according to the preparation method of a kind of nitrogen one of claim l-3 Suo Shu, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it is characterized in that: described catalysis material is piled up by nanocrystalline material and formed.
7. according to the preparation method of a kind of nitrogen one of claim l-3 Suo Shu, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it is characterized in that: described catalysis material is spherical particles, the diameter of its spherical particles is 100nm-1000nm.
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| CN104475137B (en) * | 2014-11-04 | 2016-05-25 | 陕西科技大学 | In-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst and preparation method thereof |
| CN104399505B (en) * | 2014-11-04 | 2016-04-20 | 陕西科技大学 | Fluorine, nitrogen co-doped bismuth phosphate-cuprous oxide catalysis material and preparation method thereof |
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| CN104399504B (en) * | 2014-11-04 | 2016-05-11 | 陕西科技大学 | Fluorine, nitrogen co-doped bismuth phosphate-tin oxide composite photo-catalyst and preparation method thereof |
| CN104624217B (en) * | 2015-01-16 | 2016-05-25 | 陕西科技大学 | In-situ doping type bismuth phosphate-nickel oxide composite photocatalyst material and preparation method thereof |
| CN106192373A (en) * | 2016-08-31 | 2016-12-07 | 朱凤兮 | A kind of dacron aculeus filtering felt surface coating process |
| CN108452787B (en) * | 2018-02-07 | 2020-12-01 | 中南民族大学 | Titanium dioxide hollow microsphere with high visible light activity and preparation method and application thereof |
| CN113937257B (en) * | 2021-08-27 | 2023-05-30 | 山东大学 | Nitrogen and fluorine co-doped titanium dioxide/carbon microsphere material, preparation method thereof and application thereof in sodium ion battery |
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