CN101791562B - Method for preparing ferrum-fluorine-codoped nano-titanium dioxide visible light photocatalyst - Google Patents
Method for preparing ferrum-fluorine-codoped nano-titanium dioxide visible light photocatalyst Download PDFInfo
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- CN101791562B CN101791562B CN2010101324160A CN201010132416A CN101791562B CN 101791562 B CN101791562 B CN 101791562B CN 2010101324160 A CN2010101324160 A CN 2010101324160A CN 201010132416 A CN201010132416 A CN 201010132416A CN 101791562 B CN101791562 B CN 101791562B
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Abstract
The invention relates to a method for preparing a ferrum-fluorine-codoped nano-titanium dioxide visible light photocatalyst. The method comprises the following steps: (1) at the room temperature, adding nitric acid into the ethanol solution of tetrabutyl titanate dropwise, adding ferrum-fluorine-containing ethanol solution into the mixed solution with stirring, and stirring the mixed solution at the room temperature for 0.5 to 2 hours to perform a hydrolysis reaction to obtain light yellow titanium dioxide sol; (2) ageing the obtained titanium dioxide sol at the room temperature to obtain titanium dioxide gel, and drying the titanium dioxide gel to obtain dried titanium dioxide gel; and (3) grinding, screening and sintering the dried titanium dioxide gel to obtain the ferrum-fluorine-codoped nano-titanium dioxide visible light photocatalyst. The method has the characteristics of mild reaction conditions, easy control, simple equipment and rich raw material resources, simple synthetic process and high yield, and can be used for large-scale production; and the prepared ferrum-fluorine-codoped nano-titanium dioxide visible light photocatalyst has high performance.
Description
Technical field
The invention belongs to the preparation field of nano-titanium dioxide visible light photocatalyst, the preparation method of particularly a kind of iron, fluorin-doped nano-titanium dioxide visible light photocatalyst.
Background technology
Titanium dioxide is a kind of extremely important and the most promising catalysis material, compares with other semi-conducting materials, has advantages such as photocatalysis performance is good, chemical stability is good, nontoxic, cheap.But titanium dioxide as catalysis material exist two point out inadequate: on the one hand, titanium dioxide is a kind of wide bandgap semiconductor, band-gap energy big (～3.2eV), can only the less ultraviolet light of absorbing wavelength, solar energy utilization ratio is low.On the other hand, light induced electron and photohole are very easily compound, and photo-generated carrier efficient is low.
The present invention carries out the codope study on the modification to titanium dioxide; Expectation can be expanded its response range and its photochemical catalyst performance of raising to visible light simultaneously, thereby it is found broad application in many fields such as environmental pollution prevention and control, water treatment, air cleaning, preparation automatically cleaning materials.
According to pertinent literature, iron mixes and can make the spectral absorption limit red shift of titanium dioxide, helps absorption of visible light, and an amount of doping simultaneously can reduce the recombination probability in electronics and hole, and the photocatalysis performance of titanium dioxide is obviously improved.The doped with non-metals ion not only can be with TiO
2The photoresponse wavelength expand to the visible region, can also remain on the photocatalytic activity of ultraviolet region, can effectively utilize sunshine and carry out photocatalysis.For example: Sakatani etc. have prepared Fe
3+, K
+, Ca
2+, Sr
2+, Ba
2+, Nb
5+, Zn
2+, Al
3+With the titanium dioxide that nitrogen is mixed altogether, XPS and ESR show that nitrogen-atoms is positioned at the interstitial void position, make titanium dioxide show as paramagnetic properties, and induce visible light activity; Simultaneously, photocatalytic degradation acetaldehyde explanation Sr
2+Mix altogether with N and to have higher visible light photocatalysis active.
So, Fe
3+With F
-The nano-titanium dioxide visible light photocatalyst of codope correspondingly also has photocatalysis performance and visible light-responded property preferably.Fe is not arranged at present as yet
3+With F
-The nano-titanium dioxide visible light photocatalyst preparation and the report that characterizes of codope.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of iron, fluorin-doped nano-titanium dioxide visible light photocatalyst, the gentle and control easily of reaction condition in this Preparation of catalysts process; Equipment is simple, and raw material sources are abundant; Building-up process is simple, and output is higher, can be used for large-scale production; Prepared iron, fluorin-doped nano titanium dioxide photocatalyst have good performance, such as: particle size is little, specific surface is high, crystalline phase purity is high, visible light-responded, photocatalysis performance is good.
The preparation method of a kind of iron of the present invention, fluorin-doped nano-titanium dioxide visible light photocatalyst comprises:
(1) at room temperature, in the ethanolic solution of butyl titanate, dropwise add nitric acid; When stirring; Add the ethanolic solution of iron content and fluorine, and at room temperature stir 0.5～2h, hydrolytic reactions; Obtain flaxen TiO 2 sol; Wherein raw materials used mol ratio is: butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 10～25: 1～6: 0.1～0.8, and wherein the mole ratio of iron and titanium is: 0.00071: 1～0.0029: 1, the mole ratio of fluorine and titanium was: 0.05: 1～0.10: 1;
(2) with the TiO 2 sol that obtains ageing 24～60h at room temperature, obtain titania gel, then with titania gel at 70～100 ℃ of baking 8～15h, obtain the titanium dioxide xerogel;
(3) xerogel that obtains is ground, 200 orders sieve, and obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst at 400～600 ℃ of calcining 1.5～3h then.
In the iron in the said step (1) and the ethanolic solution of fluorine, the solute of iron ion is a ferric sesquichloride, and concentration is 0.0014M～0.0056M, and the solute of fluorine ion is an ammonium fluoride, and concentration is 0.10M～0.20M.
Raw materials used mol ratio in the said step (1) is a butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 23: 2.24: 0.6.
Raw materials used mol ratio in the said step (1) is a butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 18: 2.24: 0.3.
Raw materials used mol ratio in the said step (1) is a butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 23: 2.24: 0.15.
Raw materials used mol ratio in the said step (1) is a butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 18: 2.24: 0.3.
Raw materials used mol ratio in the said step (1) is a butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 14: 2.24: 0.15.
Raw materials used mol ratio in the said step (1) is a butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 23: 2.24: 0.44.
The mole ratio of mole ratio through regulating iron and titanium and fluorine, titanium obtains the different compositions and the iron of photocatalysis performance, fluorin-doped nano-titanium dioxide visible light photocatalyst.
The present invention is raw material with butyl titanate, ferric sesquichloride, ammonium fluoride, earlier ferric sesquichloride and ammonium fluoride is dissolved in low amounts of water and the alcohol mixeding liquid.Then above-mentioned solution is added drop-wise under condition of stirring in the ethanolic solution that contains butyl titanate, at room temperature continues to stir certain hour and be hydrolyzed, obtain TiO 2 sol.Form titania gel after at room temperature leaving standstill a period of time.Calcining can obtain corresponding nano titanium dioxide photocatalyst under different temperature.
Beneficial effect
(1) first with Fe
3+With F
-Two kinds of ions mix to titanium dioxide simultaneously, obtain the TiO 2 visible light catalyst of highlight catalytic active;
(2) the gentle and control easily of reaction condition in the Preparation of catalysts process among the present invention; Equipment is simple, and raw material sources are abundant; Building-up process is simple, and output is higher, can be used for large-scale production;
(3) prepared iron, fluorin-doped nano titanium dioxide photocatalyst have good performance; Such as: particle size is little, specific surface is high, crystalline phase purity is high, visible light-responded, photocatalysis performance is good; Improved the utilization rate of visible light; Energy savings has reached good photocatalysis performance, can extensively apply to many fields such as environmental pollution prevention and control, water treatment, air cleaning, preparation automatically cleaning material.
Description of drawings
Fig. 1 is the X-ray diffractogram of iron, fluorin-doped nano titanium oxide;
Fig. 2 is the transmission electron microscope photo of iron, fluorin-doped nano titanium oxide;
Fig. 3 is the ultraviolet-visible of iron, the fluorin-doped nano titanium oxide spectrogram that diffuses;
Fig. 4 is the visible light photocatalysis performance map of iron, fluorin-doped nano titanium oxide;
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The practical application (degradation of methylene blue) of the visible-light photocatalyst of iron of the present invention, fluorin-doped nano titanium oxide: as excitation source, photocatalytic reaction conditions is photochemical catalyst with the light of xenon lamp:
(1) above-mentioned codope photochemical catalyst adding concentration is 1g/L;
(2) electric current of xenon lamp is 15A, catalyst adsorbs 30min in methylene blue solution after, and light source direct irradiation solution.
Embodiment 1
At room temperature, the ethanolic solution of measuring 45.8ml 0.8M butyl titanate stirs in reactor.Dropwise slowly add 1.00ml nitric acid (analyze pure, 65～68wt%), continue to stir 30min.Measure the ferric sesquichloride of 18ml 0.0014M and the ammonium fluoride ethanolic solution of 0.10M, dropwise join in the reactor, and at room temperature stir 30min, hydrolytic reactions obtains flaxen TiO 2 sol.With the TiO 2 sol that obtains ageing 60h at room temperature, obtain titania gel then.Again titania gel is dried by the fire 15h at 70 ℃, obtain the titanium dioxide xerogel.At last the xerogel that obtains is ground refinement, 200 orders sieve; 400 ℃ down calcining 3h obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst.In the present embodiment, raw materials used mol ratio is: butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 23: 2.24: 0.6, and the mole ratio of iron and titanium is: 0.00071: 1, the mole ratio of fluorine and titanium was: 0.05: 1.
The iron that present embodiment synthesizes, fluorin-doped nano titanium oxide X-ray diffractogram show: the crystalline phase of this sample mainly is the titanium dioxide of anatase phase, is 12.8nm through calculating the synthetic sample particle diameter of present embodiment.The degradation rate of this sample degradation of methylene blue (after 110 minutes) under visible light reaches 42.5%.
At room temperature, the ethanolic solution of measuring 35.8ml 1.0M butyl titanate stirs in reactor.Dropwise slowly add 0.50ml nitric acid (analyze pure, 65～68wt%), continue to stir 30min.Measure the ferric sesquichloride of 18ml 0.0014M and the ammonium fluoride ethanolic solution of 0.10M, dropwise join in the reactor, and at room temperature stir 30min, hydrolytic reactions obtains flaxen TiO 2 sol.With the TiO 2 sol that obtains ageing 60h at room temperature, obtain titania gel then.Again titania gel is dried by the fire 12h at 80 ℃, obtain the titanium dioxide xerogel.At last the xerogel that obtains is ground refinement, 200 orders sieve; 500 ℃ down calcining 2h obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst.In the present embodiment, raw materials used mol ratio is: butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 18: 2.24: 0.3, and the mole ratio of iron and titanium is: 0.00071: 1, the mole ratio of fluorine and titanium was: 0.05: 1.
The iron that present embodiment synthesizes, fluorin-doped nano titanium oxide X-ray diffractogram show: the crystalline phase of this sample mainly is the titanium dioxide of anatase phase, is 15.6nm through calculating the synthetic sample particle diameter of present embodiment.The degradation rate of this sample degradation of methylene blue (after 110 minutes) under visible light reaches 88.9%.
Embodiment 3
At room temperature, the ethanolic solution of measuring 45.8ml 0.8M butyl titanate stirs in reactor.Dropwise slowly add 0.25ml nitric acid (analyze pure, 65～68wt%), continue to stir 30min.Measure the ferric sesquichloride of 18ml 0.0014M and the ammonium fluoride ethanolic solution of 0.10M, dropwise join in the reactor, and at room temperature stir 30min, hydrolytic reactions obtains flaxen TiO 2 sol.With the TiO 2 sol that obtains ageing 48h at room temperature, obtain titania gel then.Again titania gel is dried by the fire 15h at 70 ℃, obtain the titanium dioxide xerogel.At last the xerogel that obtains is ground refinement, 200 orders sieve; 600 ℃ down calcining 2h obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst.In the present embodiment, raw materials used mol ratio is: butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 23: 2.24: 0.15, and the mole ratio of iron and titanium is: 0.00071: 1, the mole ratio of fluorine and titanium was: 0.05: 1.
Fig. 1 is the synthetic iron of present embodiment, fluorin-doped nano titanium oxide X-ray diffractogram, and the diffraction maximum among the figure shows: the crystalline phase of this sample is the titanium dioxide of anatase phase.Fig. 2 is the transmission electron microscope photo of sample, can find out that the synthetic sample particle diameter of present embodiment is 16.0nm and utilizes 17.3nm that the Scherrer formula calculates ten minutes approaching.The uv-visible absorption spectra (a) of the iron that Fig. 3 synthesizes for present embodiment, fluorin-doped titanium dioxide, can find out: red shift phenomenon has slightly taken place in its absorption spectrum.Fig. 4 is the curve of this sample degradation of methylene blue under visible light, and its degradation rate reaches 90.4% after 110 minutes.
Embodiment 4
At room temperature, the ethanolic solution of measuring 35.8ml 1.0M butyl titanate stirs in reactor.Dropwise slowly add 0.50ml nitric acid (analyze pure, 65～68wt%), continue to stir 30min.Measure the ferric sesquichloride of 18ml 0.0014M and the ammonium fluoride ethanolic solution of 0.20M, dropwise join in the reactor, and at room temperature stir 30min, hydrolytic reactions obtains flaxen TiO 2 sol.With the TiO 2 sol that obtains ageing 24h at room temperature, obtain titania gel then.Again titania gel is dried 10h at 90 ℃, obtain the titanium dioxide xerogel.At last the xerogel that obtains is ground refinement, 200 orders sieve; 600 ℃ down calcining 2h obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst.In the present embodiment, raw materials used mol ratio is: butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 18: 2.24: 0.3, and the mole ratio of iron and titanium is: 0.00071: 1, the mole ratio of fluorine and titanium was: 0.10: 1.
The iron that present embodiment synthesizes, fluorin-doped nano titanium oxide X-ray diffractogram show: the crystalline phase of this sample mainly is the titanium dioxide of anatase phase.Through calculating the synthetic sample particle diameter of present embodiment is 14.1nm.The uv-visible absorption spectra of the iron that present embodiment synthesizes, fluorin-doped titanium dioxide shows: certain red shift has taken place in its absorption spectrum.The degradation rate of this sample degradation of methylene blue (after 110 minutes) under visible light reaches 87.8%.
Embodiment 5
At room temperature, the ethanolic solution of measuring 25.8ml 1.4M butyl titanate stirs in reactor.Dropwise slowly add 0.25ml nitric acid (analyze pure, 65～68wt%), continue to stir 30min.Measure the ferric sesquichloride of 18ml 0.0028M and the ammonium fluoride ethanolic solution of 0.10M, dropwise join in the reactor, and at room temperature stir 30min, hydrolytic reactions obtains flaxen TiO 2 sol.With the TiO 2 sol that obtains ageing 48h at room temperature, obtain titania gel then.Again titania gel is dried 12h at 80 ℃, obtain the titanium dioxide xerogel.At last the xerogel that obtains is ground refinement, 200 orders sieve; 600 ℃ down calcining 1.5h obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst.In the present embodiment, raw materials used mol ratio is: butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 14: 2.24: 0.15, and the mole ratio of iron and titanium is: 0.00142: 1, the mole ratio of fluorine and titanium was: 0.05: 1.
The iron that present embodiment synthesizes, fluorin-doped nano titanium oxide X-ray diffractogram show: the crystalline phase of this sample mainly is the titanium dioxide of anatase phase.Fig. 3 has shown the uv-visible absorption spectra (b) of the synthetic iron of present embodiment, fluorin-doped titanium dioxide, shows that certain red shift has taken place its absorption spectrum.The degradation rate of this sample degradation of methylene blue (after 110 minutes) under visible light reaches 58.4%.
Embodiment 6
At room temperature, the ethanolic solution of measuring 45.8ml 0.8M butyl titanate stirs in reactor.Dropwise slowly add 0.75ml nitric acid (analyze pure, 65～68wt%), continue to stir 30min.Measure the ferric sesquichloride of 18ml 0.0056M and the ammonium fluoride ethanolic solution of 0.10M, dropwise join in the reactor, and at room temperature stir 30min, hydrolytic reactions obtains flaxen TiO 2 sol.With the TiO 2 sol that obtains ageing 36h at room temperature, obtain titania gel then.Again titania gel is dried 8h at 100 ℃, obtain the titanium dioxide xerogel.At last the xerogel that obtains is ground refinement, 200 orders sieve; 600 ℃ down calcining 1.5h obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst.In the present embodiment, raw materials used mol ratio is: butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 23: 2.24: 0.44, and the mole ratio of iron and titanium is: 0.0029: 1, the mole ratio of fluorine and titanium was: 0.05: 1.
The iron that present embodiment synthesizes, fluorin-doped nano titanium oxide X-ray diffractogram show: the crystalline phase of this sample mainly is the titanium dioxide of anatase phase.Fig. 3 has shown the uv-visible absorption spectra (c) of the synthetic iron of present embodiment, fluorin-doped titanium dioxide, shows that certain red shift has taken place its absorption spectrum.The degradation rate of this sample degradation of methylene blue (after 110 minutes) under visible light reaches 66.0%.
Claims (1)
1. the preparation method of an iron, fluorin-doped nano-titanium dioxide visible light photocatalyst comprises:
At room temperature, the ethanolic solution of measuring 45.8ml 0.8M butyl titanate stirs in reactor, dropwise slowly adds the nitric acid that 0.25ml analyzes pure 65～68wt%, continues to stir 30min; Measure the ferric sesquichloride of 18ml 0.0014M and the ammonium fluoride ethanolic solution of 0.10M, dropwise join in the reactor, and at room temperature stir 30min, hydrolytic reactions obtains flaxen TiO 2 sol; With the TiO 2 sol that obtains ageing 48h at room temperature, obtain titania gel then; Again titania gel is dried by the fire 15h at 70 ℃, obtain the titanium dioxide xerogel; At last the xerogel that obtains is ground refinement, 200 orders sieve; 600 ℃ down calcining 2h obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst; Wherein, raw materials used mol ratio is butyl titanate: absolute ethyl alcohol: water: nitric acid=1: 23: 2.24: 0.15, and the mole ratio of iron and titanium is: 0.00071: 1, the mole ratio of fluorine and titanium was: 0.05: 1.
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| CN104588048B (en) * | 2015-01-14 | 2017-06-13 | 武汉理工大学 | The preparation method of the efficient iron fluorine co-modified photocatalysis material of titanium dioxide of double auxiliary agents |
| CN108452803B (en) * | 2017-02-22 | 2020-06-09 | 中国科学院福建物质结构研究所 | Nb-Rh codoped titanium dioxide photocatalyst and preparation method and application thereof |
| CN109772398B (en) * | 2017-11-13 | 2021-11-23 | 广州中国科学院沈阳自动化研究所分所 | Immobilized F, N, Ag co-doped titanium dioxide photocatalyst and preparation method and application thereof |
| CN109701566B (en) * | 2019-02-26 | 2020-09-04 | 中国矿业大学 | Co-doped TiO2Photocatalyst and preparation method thereof |
| CN109876764A (en) * | 2019-03-15 | 2019-06-14 | 西安工程大学 | A kind of preparation method of aluminum oxide/titanium dioxide composite adsorbing material |
| CN110219011A (en) * | 2019-07-09 | 2019-09-10 | 广州市健崎电子科技有限公司 | A kind of oxygen conduction liquid processed |
| CN111921516B (en) * | 2020-09-18 | 2023-03-14 | 哈尔滨师范大学 | Preparation method of photocatalyst with super-strong degradation effect |
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