CN103894218A - Titanium dioxide mesoporous microsphere photocatalytic material co-doped with nitrogen and fluorine and preparation method of material - Google Patents
Titanium dioxide mesoporous microsphere photocatalytic material co-doped with nitrogen and fluorine and preparation method of material Download PDFInfo
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Abstract
The invention discloses a titanium dioxide mesoporous microsphere photocatalytic material co-doped with nitrogen and fluorine in response to visible light and a preparation method of the material. The preparation method of the material comprises the following steps: firstly dissolving titanium tetrafluoride in hydrochloric acid to obtain a reaction precursor solution, atomizing the precursor solution in an ultrasonic atomizer to generate aerosol rich in tiny droplets, introducing the aerosol into a high-temperature tubular furnace in the presence of ammonia gas to react and generate solid powder, collecting the solid powder by using distilled water, washing, centrifuging and then drying at the temperature of 75-85 DEG C to obtain the solid powder, sequentially roasting for 1.5-2.5 hours in a muffle furnace at the temperature of 450-550 DEG C to prepare the titanium dioxide mesoporous microsphere photocatalytic material co-doped with nitrogen and fluorine. A crystalline phase of the material is an anatase phase; the material comprises the following components by weight percent: 1.5-3.0% of fluorine, 0.8-5.2% of nitrogen and the balance being titanium dioxide; the titanium dioxide co-doped with nitrogen and fluorine has a mesoporous microsphere particle shape; an ultraviolet-visible light spectrum begins to absorb when being below 600nm. The preparation method of the material is simple, practicable and capable of continuously producing, and facilitating the large-scale production and application in industrialization.
Description
Technical field
The invention belongs to material preparation and surround lighting catalytic 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 abundant, nonpoisonous and tasteless, the physicochemical properties of originating is good become modal photochemical catalyst.But, TiO
2in light-catalyzed reaction process light induced electron and photohole life-span extremely short, very easily compound in light-catalyzed reaction process, make its quantum efficiency in photocatalytic process lower; TiO
2bandwidth be 3.2 about eV, can not responding to visible light, in solar energy, only less than 5% can be utilized, 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 (comprise that various doped with metal elements, precious metal surface deposit, semiconductor is compound, 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 have obtained certain progress, but fundamentally do not solve yet this great difficult problem of photocatalytic process efficiency.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 of photocatalysis field and key problem.
The doping of titanium dioxide has been proved to be a kind of effective optimization titanium dioxide can be with the method that obtains photochemical catalyst that can responding to visible light.In various element dopings, of greatest concern with the research of the titanium dioxide of nitrogen doping, however only still not high enough with the adulterate photochemical catalyst quantum efficiency that obtains of nitrogen.Therefore wish to adulterate other elements simultaneously, further improve sunshine utilization rate and the course of reaction quantum efficiency of catalyst.In addition the pattern of catalyst is also proved to be on the light-catalysed catalytic efficiency impact of catalyst significantly, 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 preparation at present has the doping of pattern can use hydro-thermal method, solvent-thermal method, the precipitation method etc., but these are conventionally to need reaction time length, high temperature, high pressure, and needs additional template agent, is therefore difficult for applying in industrialization.In the present invention, ultrasonic atomizatio method is applied to preparation N by we, the catalyst of F codope, synthetic catalyst has mesoporous sphere structure, nitrogen and fluorine are doped in catalyst effectively, obtain the photochemical catalyst of energy responding to visible light, and that this preparation method has is 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 nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material of a kind of responding to visible light and preparation method thereof.The method technique is simple, and cost is low, and productive rate is high, and 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, two kinds of elements of nitrogen can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band.
Described catalysis material is piled up and is formed by nanocrystalline material.
Described catalysis material is spherical particles, and the diameter of its spherical particles is 100 nm-1000 nm.
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 to concentration is in 1. 0 mol/L hydrochloric acid solutions, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid process atomization in reaction bulb under ultrasonic atomizer effect forms the aerosol that is rich in fine droplet together with ammonia, and described ultrasonic atomizer frequency is 1.7 MHz;
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 10-30 L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, two kinds of element dopings of fluorine enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4), under the drive of vavuum pump, the pressed powder that step 3) is obtained is extracted in distilled water to be collected, washing, centrifugal after, in 75 ~ 85 DEG C of oven dry;
5) pressed powder through step 4) processing is continued to the temperature with 450 ~ 550 DEG C in Muffle furnace and calcine 1.5 ~ 2.5 hours, programming rate is 1-5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
One is prepared nitrogen, the device of fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it comprises ammonia generating bottle and ultrasonic atomizer, in described ammonia generating bottle, be loaded with ammoniacal liquor, 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 interface is communicated with reaction bulb, another interface is communicated with 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 that is 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 to be piled up and formed by nanocrystalline material.
In this catalysis material, fluorine, two kinds of elements of nitrogen can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band, changed the crystal structure of titanium dioxide, fluorine, nitrogen co-doped titanium dioxide, in the time reacting as catalyst, can reduce reaction and can be with, can, in the generation of catalytic reaction under visible ray, improve the utilization rate of solar energy.
Catalysis material energy response wave length prepared by the present invention visible ray below 600 nm, has higher photocatalytic activity, and higher than the TiO 2 visible light photocatalytic activity of the single element doping of fluorine, nitrogen.
Remarkable advantage of the present invention is:
(1) the present invention will have children outside the state plan atomization first for titanium dioxide nitrogen, fluorin-doped modification, and synthetic catalyst has mesoporous ball shape structure, and under radiation of visible light, photo-generated carrier can effectively separate, and is a kind of novel photochemical catalyst, and 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) pollutant producing in the degraded gas phase that the synthetic catalyst of the present invention can efficient stable and liquid phase experimentation has good activity stability simultaneously.In light-catalyzed reaction system, can carry out easily separating treatment, recycling rate of waterused is high, has very high practical value and application prospect widely.
Brief description of the drawings
Fig. 1 is reaction unit sketch prepared by nitrogen of the present invention, 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 DRS spectrogram of fluorin-doped titanium dioxide mesoporous microsphere catalysis material;
Fig. 5 is the F 1s x-ray photoelectron energy spectrogram of the titania-doped mesoporous microsphere catalysis material of fluorine of the embodiment of the present invention 3 gained;
Fig. 6 is the N1s x-ray photoelectron energy spectrogram 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, two kinds of elements of nitrogen can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band.
Described catalysis material is piled up and is formed by nanocrystalline material.
Described catalysis material is spherical particles, and the diameter of its spherical particles is 100 nm-1000 nm.
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 to concentration is in 1. 0 mol/L hydrochloric acid solutions, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid process atomization in reaction bulb under ultrasonic atomizer effect forms the aerosol that is rich in fine droplet together with ammonia, and described ultrasonic atomizer frequency is 1.7 MHz;
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 10-30 L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, two kinds of element dopings of fluorine enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4), under the drive of vavuum pump, the pressed powder that step 3) is obtained is extracted in distilled water to be collected, washing, centrifugal after, in 75 ~ 85 DEG C of oven dry;
5) pressed powder through step 4) processing is continued in Muffle furnace with 450 ~ 550
othe temperature calcining 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, in described ammonia generating bottle 7, be loaded with ammoniacal liquor, 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 levels, 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 interface is communicated with reaction bulb 2, another interface is communicated with 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 that is loaded with distilled water by glass tube, described vial 5 sidewalls are provided with an outlet nozzle 6, described outlet nozzle 6 is communicated with vavuum pump.
Embodiment 1
It is in 1. 0 mol/L hydrochloric acid solutions that 1.5 g titanium tetrafluorides are dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution is atomization in ultrasonic atomizer, and frequency is 1.7 MHz, by carrier gas, aerosol band is entered to high temperature process furnances (500 DEG C) reaction; The flow velocity of carrier gas is 10 L/min, and carrier gas is without ammonia spirit, after tube furnace, collects with distilled water the pressed powder generating, through washing, centrifugal after in 85 DEG C of oven dry; The powder solid obtaining, continues at 550 DEG C, to calcine 2.5 hours in Muffle furnace, and programming rate is 5 DEG C/min, obtains the titania-doped mesoporous microsphere catalysis material of fluorine, as the comparative example of fluorine, nitrogen co-doped titanium dioxide mesoporous microsphere.
Embodiment 2
It is in 1. 0 mol/L hydrochloric acid solutions that 1.5 g titanium tetrachlorides are dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution is atomization in ultrasonic atomizer, and ultrasonic atomizer frequency is 1.7 MHz, by carrier gas, aerosol band is entered to high temperature process furnances (500 DEG C) reaction; The flow velocity of carrier gas is 10 L/min, and carrier gas is first the ammonia spirit of 5 mol/L by concentration, makes to be rich in carrier gas ammonia; After tube furnace with distilled water collect generate pressed powder, through washing, centrifugal after in 85 DEG C of oven dry; The powder solid obtaining, continues at 550 DEG C, to calcine 2.5 hours in Muffle furnace, and 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. 0 mol/L hydrochloric acid solutions that 1.5 g titanium tetrafluorides are dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution forms aerosol under ultrasonic atomizer effect, and ultrasonic atomizer frequency is 1.7 MHz, by carrier gas, aerosol band is entered to high temperature process furnances (500 DEG C) reaction; The flow velocity of carrier gas is 10 L/min, and carrier gas is first the ammonia spirit of 5 mol/L by concentration, makes to be rich in carrier gas ammonia; After reaction with distilled water collect generate pressed powder, through washing, centrifugal after in 85 DEG C of oven dry; Continue at 550 DEG C, to calcine 2.5 hours 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 solutions that 1.5 g titanium tetrafluorides are dissolved in concentration, after 3 hours stir, obtains transparent solution; Solution forms aerosol under ultrasonic atomizer effect, and ultrasonic atomizer frequency is 1.7 MHz, by carrier gas, aerosol band is entered to high temperature process furnances (550 DEG C) reaction; The flow velocity of carrier gas is 20 L/min, and carrier gas is first the ammonia spirit of 2 mol/L by concentration, makes to be rich in carrier gas ammonia; After reaction with distilled water collect generate pressed powder, through washing, centrifugal after in 80 DEG C of oven dry; Continue at 500 DEG C, to calcine 2.5 hours 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 solutions that 1.5 g titanium tetrafluorides are dissolved in concentration, after 2 hours stir, obtains transparent solution; Solution forms aerosol under ultrasonic atomizer effect, and ultrasonic atomizer frequency is 1.7 MHz, by carrier gas, aerosol band is entered to high temperature process furnances (600 DEG C) reaction; The flow velocity of carrier gas is 30 L/min, and carrier gas is first the ammonia spirit of 0.5 mol/L by concentration, makes to be rich in carrier gas ammonia; After reaction with distilled water collect generate pressed powder, through washing, centrifugal after in 75 DEG C of oven dry; Continue at 450 DEG C, to calcine 2.5 hours 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 400 ppb, flow velocity 4 L/min) mol/L) and in gas phase, the light source of use is artificial light source, and wavelength is 400-800 nm, and active testing the results are shown in Table 1.
The Photocatalytic oxidation activity comparison of table 1 different catalysts
| Sequence number | Catalyst sample | Fluorine content (%) | Nitrogen content (%) | RhB degradation rate a | Nitric oxide conversion ratio 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;
Nitric oxide conversion ratio 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, test and show by photocatalytic activity, fluorine prepared by use this method, nitrogen co-doped photocatalysis material of titanium dioxide, the photocatalytic activity than the titanium dioxide of nitrogen and the doping of fluorine single element in gas phase and liquid phase is higher.
Claims (8)
1. nitrogen, a fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: the mass fraction of described catalysis material fluorine is 1.5-3%, the mass fraction of nitrogen is 0.8-5.2%, and surplus is titanium dioxide.
2. according to the nitrogen of the responding to visible light described in claim l, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it is characterized in that: described catalysis material is Detitanium-ore-type.
3. nitrogen according to claim 1, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: the mass fraction of described catalysis material fluorine is 1.2 %, the mass fraction of nitrogen is 4.7 %, and surplus is titanium dioxide.
4. nitrogen according to claim 1, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: in described catalysis material, fluorine, two kinds of elements of nitrogen can replace TiO simultaneously effectively
2the O of lattice position forms doped energy-band.
5. nitrogen according to claim 1, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: described catalysis material is piled up and formed by nanocrystalline material.
6. nitrogen according to claim 1, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: described catalysis material is spherical particles, the diameter of its spherical particles is 100 nm-1000 nm.
7. a preparation method for nitrogen as claimed in claim 1, fluorin-doped titanium dioxide mesoporous microsphere catalysis material, is characterized in that: described preparation method is ultrasonic atomizatio method, and it comprises the steps:
1) titanium tetrafluoride being dissolved in to concentration is in 1. 0 mol/L hydrochloric acid solutions, after 1-3 hour stirs, obtains transparent precursor liquid;
2) precursor liquid process atomization in reaction bulb under ultrasonic atomizer effect forms the aerosol that is rich in fine droplet together with ammonia, and described ultrasonic atomizer frequency is 1.7 MHz;
3) aerosol enters high temperature process furnances under vavuum pump DEG C drive, each aerosol forms a microreactor in tube furnace, reaction temperature is 500-600 DEG C, ammonia flow velocity is at 10-30 L/min, titanium tetrafluoride hydrolysis in course of reaction, form titanium dioxide, nitrogen, two kinds of element dopings of fluorine enter in titanium dioxide crystal, and form the pressed powder of spherical particles shape;
4), under the drive of vavuum pump, the pressed powder that step 3) is obtained is extracted in distilled water to be collected, washing, centrifugal after, in 75 ~ 85 DEG C of oven dry;
5) pressed powder through step 4) processing is continued to the temperature with 450 ~ 550 DEG C in Muffle furnace and calcine 1.5 ~ 2.5 hours, programming rate is 1-5 DEG C/min, obtains yellow nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material.
8. prepare nitrogen as claimed in claim 1 for one kind, the device of fluorin-doped titanium dioxide mesoporous microsphere catalysis material, it is characterized in that: it comprises ammonia generating bottle and ultrasonic atomizer, in described ammonia generating bottle, be loaded with ammoniacal liquor, 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 interface is communicated with reaction bulb, another interface is communicated with 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 that is loaded with distilled water by glass tube, described vial sidewall is provided with an outlet nozzle, described outlet nozzle is communicated with vavuum pump.
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| CN104475137A (en) * | 2014-11-04 | 2015-04-01 | 陕西科技大学 | In-situ doped type bismuth phosphate-cuprous oxide composite photocatalyst and preparation method thereof |
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| CN104399505A (en) * | 2014-11-04 | 2015-03-11 | 陕西科技大学 | Fluorine-nitrogen co-doped bismuth phosphate- cuprous oxide photocatalytic material and preparation method thereof |
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| CN103894218B (en) | 2016-03-23 |
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