CN102266792A - Synthesis method for visible photocatalyst by modifying titanium dioxide by using ammonium fluoride - Google Patents
Synthesis method for visible photocatalyst by modifying titanium dioxide by using ammonium fluoride Download PDFInfo
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- CN102266792A CN102266792A CN201110158002XA CN201110158002A CN102266792A CN 102266792 A CN102266792 A CN 102266792A CN 201110158002X A CN201110158002X A CN 201110158002XA CN 201110158002 A CN201110158002 A CN 201110158002A CN 102266792 A CN102266792 A CN 102266792A
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Abstract
The invention relates to a synthesis method for a visible photocatalyst by modifying titanium dioxide (TiO2) by using ammonium fluoride (NH4F). The synthesis method comprises three steps of: preparing a mesocellular foam silica (MCF) molecular sieve, preparing an MCF carrying TiO2 catalyst and modifying MCF/TiO2 by using the NH4F. Compared with the prior art, the carrying catalyst MCF/TiO2 is subjected to NH4F hydrophobic modification through a hydrothermal process and a low-temperature vacuum activation method; as a mesoporous material has extremely high absorption capability, the visible photocatalyst has outstanding absorption performance and catalyzing and degrading performance on ultraviolet and visible light of high-concentration organic pollutants during degrading of organic compounds, such as rhodamine B and the like; furthermore, during hydrophobic modification, if isopropyl alcohol is found to be a solvent, the NH4F hydrophobic modification effect of the prepared catalyst is the optimal and the hydrophobic stability is quite good; moreover, the synthesis method is simple in operation and low in cost, and the raw materials are easily obtainable.
Description
Technical field
The present invention relates to the nano-photocatalyst material field, especially relating to a kind of mesoporous MCF is carrier, at its duct internal burden TiO
2, utilize the synthetic method of ammonium fluoride modifying titanium dioxide visible light catalyst.
Background technology
Along with the development of society, environmental pollution becomes a great difficult problem that hinders survival and development of mankind.The mode that people press for a kind of cleaning solves environmental pollution.Photocatalysis can effectively utilize sunshine, the degraded environmental contaminants.And TiO
2Nontoxic with it, safety, efficient, cheap and easy to get, become the catalysis material of the tool potentiality in environment pollution treatment field.TiO
2Because the good He strong oxidisability of practicality is widely used as photochemical catalyst.Many researchs are paid close attention to TiO
2Carry out finishing to improve its ultraviolet light and visible light activity, such as doping metals or nonmetalloid, surface fluorination, surface sensitizing and semiconductor load.Yet, bibliographical information is seldom arranged by improving TiO
2To the adsorption capacity of organic pollution thing, thereby further improve the photocatalytic activity of catalyst.Matthews etc. find by improving TiO
2To the organic pollutant adsorption ability, help to improve its photocatalytic activity.At present, improve TiO
2The effective ways of adsorption capacity are the hydrophobic properties of the surface that improve catalyst.In recent years, the super-hydrophobicity material has caused numerous researchers' very big interest, because its unique character can be applied to fields such as self-cleaning coating, antiseptic, microfluid, biocompatible material.In addition, also there is great potentiality to be exploited in super hydrophobic material in fields such as national defense industry, agricultural, shipbuilding industry.Yet, up to the present, seldom have the research report that super hydrophobic material is applied to photocatalysis field.In fact, mesoporous materials such as zeolite molecular sieve as HMS, SBA-15, MCF etc., owing to itself have big specific area and nano pore structure, have good adsorption capacity to organic matter, can eliminate the organic pollution in the water and air.Therefore, at the duct internal burden TiO of the mesoporous material of hydrophobic type
2, the novel supported photochemical catalyst that obtains can effectively improve its ultraviolet and visible light activity.
But the stability of hydrophobic material is to limit the important difficult problem that it is used in photocatalysis field always.Traditional hydrophobically modified agent comprises the organosilan coupling reagent that contains organic hydrophobic grouping and contains the silane coupler of inorganic atoms such as F.These organo-functional groups are easy under illumination by TiO
2Decompose, thereby greatly reduce the hydrophobic stability of hydrophobic material.In addition, the silane coupler of many F of containing is poisonous and cost an arm and a leg, and does not have actual application value.Therefore, seek inorganic hydrophobically modified agent a kind of cheapness, that chemical stability is good, prepare the good hydrophobic type mesoporous material of photochemical stability, extremely important to its application in photocatalysis field.This novel super hydrophobic material with high photochemical stability is by load TiO
2, can improve TiO greatly
2To the organic pollutant adsorption ability, thereby further improve its photocatalytic activity.The novel supported photochemical catalyst of this kind has very big using value in photocatalysis field.
Summary of the invention
Purpose of the present invention is exactly the synthetic method that the ammonium fluoride modifying titanium dioxide visible light catalyst of a kind of simple to operate, raw material is easy to get, energy resource consumption is few, synthetic product has good adsorption organic pollution rhodamine B performance and high ultraviolet and visible light catalysis activity is provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of synthetic method of ammonium fluoride modifying titanium dioxide visible light catalyst is characterized in that, this method may further comprise the steps:
(1) foam-like mesopore molecular sieve (mesocellular foam silica, preparation MCF)
(PEO-PPO-PEO P123), is dissolved in the hydrochloric acid solution, adds NH again to take by weighing a certain amount of triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene under 37 ℃
4F and 1,3,5-trimethylbenzene (TMB) stirred 1 hour, the synthermal ethyl orthosilicate (TEOS) that adds down, stirred 20 hours, the gained slurry is transferred in the autoclave, 100 ℃ of following hydro-thermals 24 hours, washing precipitation, dry 12h in 60 ℃ of vacuum drying chambers calcined 6 hours down at 550 ℃ again, obtained the MCF molecular sieve;
(2) MCF load TiO
2Preparation of catalysts
Weighing titanium sulfate (Ti (SO
4)
2) solid, add redistilled water, stirred 30 minutes, treat that titanium sulfate dissolves fully after, the MCF molecular sieve that adding step (1) prepares stirred 4 hours, solution to be mixed is even, changes in the autoclave, puts to 120 ℃ of baking ovens hydro-thermal 7 hours; After the isolated washing of precipitate, 60 ℃ of vacuum drying 12 hours obtain MCF load TiO
2Catalyst is labeled as MCF/TiO
2
(3) NH
4F is to MCF/TiO
2Modification
Take by weighing a certain amount of NH
4F is added in the solvent, stirs 1 hour, after the dissolving, adds the MCF/TiO that step (2) prepares fully
2, stirring 1 hour, above-mentioned solution is transferred in the autoclave and puts into 120 ℃ of baking ovens, hydro-thermal 20 hours, isolated precipitation is washed three times with distilled water, and 200 ℃ of vacuum activate 3 hours in vacuum drying chamber, promptly obtain ammonium fluoride modifying titanium dioxide visible light catalyst.
The concentration of the hydrochloric acid solution described in the step (1) is 1.5～2mol/L.
(PEO-PPO-PEO, P123) concentration in hydrochloric acid solution is 0.02～0.03g/ml to triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene described in the step (1).
Triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene described in the step (1) (PEO-PPO-PEO, P123), NH
4F and 1,3, the weight ratio of 5-trimethylbenzene is 8: 0.1: 4.
5. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the ethyl orthosilicate (TEOS) described in the step (1) is 1 with the volume ratio of hydrochloric acid solution: (16～17).
The concentration of titanium sulfate in redistilled water described in the step (2) is 0.04～0.05g/ml.
The weight ratio of titanium sulfate described in the step (2) and MCF molecular sieve is 3: 2.
Solvent described in the step (3) is isopropyl alcohol, methyl alcohol, ethanol or water.
The preferred isopropyl alcohol of solvent described in the step (3).
NH described in the step (3)
4F and MCF/TiO
2Weight ratio be (0.05～1.0): 1.
Compared with prior art, the present invention has the following advantages:
(1) synthetic operation is simple;
(2) the hydrophobically modified agent ammonium fluoride of selecting for use is cheap and easy to get, and toxicity is less relatively;
(3) at NH
4In the F hydrophobically modified process, the catalyst that makes when only selecting isopropyl alcohol as solvent for use possesses super-hydrophobicity, and when adopting other solvent such as methyl alcohol, ethanol, water, the catalyst of preparation does not possess hydrophobic performance substantially;
(4) whole technical process is controlled easily, is easy to enlarge use;
(5) Zhi Bei catalyst has super-hydrophobicity and good hydrophobic stability;
(6) Zhi Bei catalyst has organic pollution good adsorption performance, and has very high ultraviolet and visible light activity.
Description of drawings
Fig. 1 is the TEM photo of different samples;
Fig. 2 is the UV, visible light diffuse reflection spectrum of different samples;
Fig. 3 is the EPR collection of illustrative plates of different samples;
Fig. 4 prepares the XPS photoelectron spectroscopy of sample for embodiment 1;
Fig. 5 is that the photocatalytic activity of different samples under ultraviolet and radiation of visible light is investigated the result.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
A kind of synthetic method of ammonium fluoride modifying titanium dioxide visible light catalyst may further comprise the steps:
(1) preparation of MCF
8.0g P123 joins in 40mL watery hydrochloric acid and the 260ml distilled water, is stirred to dissolving under 37 ℃.Add 0.1g NH again
4The TMB of F and 4.0g (1,3, the 5-trimethylbenzene), mechanical agitation 1 hour.37 ℃ of TEOS that drip down 18.3ml, and mechanical agitation 20 hours, 100 ℃ of following hydro-thermals of gained slurry 24 hours, washing precipitation, 60 ℃ of vacuum drying 12 hours 550 ℃ of calcinings 6 hours down, obtain the MCF mesopore molecular sieve again.
(2) MCF load TiO
2Preparation of catalysts
Take by weighing titanium sulfate (Ti (SO
4)
2) solid 1.2g, join in the 25ml redistilled water magnetic agitation 30min, after treating that titanium sulfate dissolves fully, add the MCF mesopore molecular sieve that 0.8g prepares again, stirred 4 hours, treat that solution mixes, change in the autoclave, and put to 120 ℃ of baking ovens hydro-thermal 7 hours.After the precipitation that obtains is washed through secondary water washing, 60 ℃ of following vacuum drying 12 hours, the loaded catalyst that obtains is labeled as MCF/TiO
2
(3) NH
4F is to MCF-TiO
2Modification
A certain amount of NH of weighing
4F adds 70ml isopropyl alcohol (methyl alcohol, ethanol or water), and magnetic agitation added 0.5g loaded catalyst MCF/TiO after 1 hour
2, magnetic agitation is after 1 hour, is transferred to solution in the autoclave and puts into 120 ℃ of baking ovens, hydro-thermal 20 hours.The precipitation of preparation is with second distillation water washing three times, and is transferred in the vacuum drying chamber 200 ℃ of activation 3 hours down, promptly obtains NH
4Novel load photochemical catalyst after the F modification, identified as samples is designated as: m-MCF/TiO
2, m represents to add NH
4The molar content of F.
Photocatalytic activity evaluation method provided by the invention is as follows:
By rhodamine B (RhB, the ultraviolet catalytic activity of the catalyst after 20mg/L) the degraded situation under UV-irradiation is estimated after the negative ammonium fluoride modification.Rhodamine B is artificial synthetic dyestuffs, has very strong fluorescence, occupies very big proportion in environmental contaminants.Under the neutrallty condition, the maximum absorption peak of rhodamine B is 554nm.The visible light activity of the catalyst of phenol after estimating modification by degraded 20mg/L under visible light.Get the 0.0700g sample at every turn and put into the quartzy light reaction test tube of 100ml, add 70ml rhodamine B solution or phenol solution again.At first agitating solution 120min under the dark state makes rhodamine B or phenol molecule reach adsorption equilibrium at sample surfaces.(average luminous intensity is about 1230 μ Wcm to the high-pressure sodium lamp of using 300W then respectively as the transmitting illuminant of ultraviolet ray (365nm)
-2), the halogen tungsten lamp of 1000W (adds optical filter and makes wavelength X＞420nm) as visible light source.Fluorescent tube is put into the cylindrical quartz sleeve pipe, logical condensed water cooling in the cover outer tube layer interlayer, and the environment temperature during the maintenance light reaction is constant substantially, and the distance of light source and reaction tube is 10cm.Sample analysis in the time interval of subscribing, carry out centrifugal immediately, with 0.22 μ m filtering with microporous membrane, isolate catalyst, filtrate is measured the absorption intensity of solution in the 200-800nm scope with Cary 100 ultraviolet-visible spectrophotometers, according to the relation curve of concentration and absorbance, calculate its degradation rate.
The molecular sieve that common MCF molecular sieve, load are had titanium dioxide and through NH
4The load of F modification has the molecular sieve of titanium dioxide to detect, the transmission electron microscope photo of different samples as shown in Figure 1, wherein, (A) (B) is pure MCF; (C) (D) be loaded catalyst MCF/TiO
2(E) (F) be into ammonium fluoride modification and cryogenic vacuum catalyst activated 0.4-MCF/TiO
2Can see TiO from Fig. 1 (D) figure
2Particle has been dispersed in the duct of MCF.From Fig. 1 (F) figure, can see NH
4The modification of F does not change pore canal structure of catalyst and configuration of surface.
Fig. 2 is the ultraviolet-visible diffuse reflection spectrum of the different samples of embodiment 1 preparation, and the curve of below is not pass through NH
4The sample MCF/TiO of F hydrophobically modified and 200 ℃ of vacuum activation
2The curve of top is through NH
4The sample 0.4-MCF/TiO of F hydrophobically modified and 200 ℃ of vacuum activation
2, pass through catalyst after the modification as can be seen at the obvious grow of the absorption of visible region.
Fig. 3 is the EPR spectrogram of the different samples of embodiment 1 preparation, through NH
4The catalyst of F modification signal peak occurred at g=1.977 and g=1.944, and Ti has been described
3+Formation and XPS photoelectron spectroscopy; Fig. 4 is the XPS photoelectron spectroscopy that embodiment 1 prepares sample, and the 686.2-688.8eV place goes out the peak among the figure, and the formation of surperficial Ti-F and Si-F key has been described.
Fig. 5 is that the photocatalytic activity of different samples under ultraviolet and radiation of visible light is investigated the result, and wherein A figure is the result that different samples are degraded after illumination to rhodamine B solution, and B figure is the result that the Pyrogentisinic Acid carries out illumination degrading.C
0Be the original concentration of rhodamine B solution, C
tBe the concentration of dark absorption back rhodamine B.From figure as can be seen, catalyst has demonstrated better absorption property after the modification; Through NH
4The catalyst of F modification also is significantly increased than the catalyst that does not have modification to the degradation effect of rhodamine B and phenol.
Embodiment 2
A kind of synthetic method of ammonium fluoride modifying titanium dioxide visible light catalyst, this method may further comprise the steps:
(1) foam-like mesopore molecular sieve (mesocellular foam silica, preparation MCF)
Take by weighing a certain amount of triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO under 37 ℃, P123), be dissolved in the hydrochloric acid solution, the concentration of hydrochloric acid is 1.5mol/L, the concentration of P123 in the mixed solution of hydrochloric acid and distilled water is 0.02g/ml, adds NH again
4F and 1,3,5-trimethylbenzene (TMB), P123, NH
4F and 1,3, the weight ratio of 5-trimethylbenzene is 8: 0.1: 4, stirred 1 hour, the synthermal ethyl orthosilicate (TEOS) that adds down, ethyl orthosilicate (TEOS) is 1: 16 with the volume ratio of hydrochloric acid solution, stirs 20 hours, the gained slurry is transferred in the autoclave, 100 ℃ of following hydro-thermals 24 hours, washing precipitation, dry 12h in 60 ℃ of vacuum drying chambers, calcined 6 hours down at 550 ℃ again, obtain the MCF molecular sieve;
(2) MCF load TiO
2Preparation of catalysts
Weighing titanium sulfate (Ti (SO
4)
2) solid, add redistilled water, the concentration of titanium sulfate in redistilled water is 0.04g/ml, stirs 30 minutes, treat that titanium sulfate dissolves fully after, add the MCF molecular sieve that step (1) prepares, the weight ratio of titanium sulfate and MCF molecular sieve is 3: 2, stirs 4 hours, and solution to be mixed is even, change in the autoclave, put to 120 ℃ of baking ovens hydro-thermal 7 hours; After the isolated washing of precipitate, 60 ℃ of vacuum drying 12 hours obtain MCF load TiO
2Catalyst is labeled as MCF/TiO
2
(3) NH
4F is to MCF/TiO
2Modification
Take by weighing a certain amount of NH
4F is added in the methyl alcohol, stirs 1 hour, after the dissolving, adds the MCF/TiO that step (2) prepares fully
2, NH
4F and MCF/TiO
2Weight ratio be 1: 1, stirred 1 hour, above-mentioned solution is transferred in the autoclave and puts into 120 ℃ of baking ovens, hydro-thermal 20 hours, isolated precipitation is washed three times with distilled water, and 200 ℃ of vacuum activate 3 hours in vacuum drying chamber, promptly obtain ammonium fluoride modifying titanium dioxide visible light catalyst.
Embodiment 3
A kind of synthetic method of ammonium fluoride modifying titanium dioxide visible light catalyst, this method may further comprise the steps:
(1) foam-like mesopore molecular sieve (mesocellular foam silica, preparation MCF)
Take by weighing a certain amount of triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO under 37 ℃, P123), be dissolved in the hydrochloric acid solution, the concentration of hydrochloric acid is 1.8mol/L, triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO, P123) concentration in the mixed solution of hydrochloric acid and distilled water is 0.03g/ml, adds NH again
4F and 1,3,5-trimethylbenzene (TMB), the triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO, P123), NH
4F and 1,3, the weight ratio of 5-trimethylbenzene is 8: 0.1: 4, stirred 1 hour, the synthermal ethyl orthosilicate (TEOS) that adds down, ethyl orthosilicate (TEOS) is 1: 17 with the volume ratio of hydrochloric acid solution, stirs 20 hours, the gained slurry is transferred in the autoclave, 100 ℃ of following hydro-thermals 24 hours, washing precipitation, dry 12h in 60 ℃ of vacuum drying chambers, calcined 6 hours down at 550 ℃ again, obtain the MCF molecular sieve;
(2) MCF load TiO
2Preparation of catalysts
Weighing titanium sulfate (Ti (SO
4)
2) solid, add redistilled water, the concentration of titanium sulfate in redistilled water is 0.05g/ml, stirs 30 minutes, treat that titanium sulfate dissolves fully after, add the MCF molecular sieve that step (1) prepares, the weight ratio of titanium sulfate and MCF molecular sieve is 3: 2, stirs 4 hours, and solution to be mixed is even, change in the autoclave, put to 120 ℃ of baking ovens hydro-thermal 7 hours; After the isolated washing of precipitate, 60 ℃ of vacuum drying 12 hours obtain MCF load TiO
2Catalyst is labeled as MCF/TiO
2
(3) NH
4F is to MCF/TiO
2Modification
Take by weighing a certain amount of NH
4F is added in the water, stirs 1 hour, after the dissolving, adds the MCF/TiO that step (2) prepares fully
2, NH
4F and MCF/TiO
2Weight ratio be 0.05: 1, stirred 1 hour, above-mentioned solution is transferred in the autoclave and puts into 120 ℃ of baking ovens, hydro-thermal 20 hours, isolated precipitation is washed three times with distilled water, and 200 ℃ of vacuum activate 3 hours in vacuum drying chamber, promptly obtain ammonium fluoride modifying titanium dioxide visible light catalyst.
Embodiment 4
A kind of synthetic method of ammonium fluoride modifying titanium dioxide visible light catalyst, this method may further comprise the steps:
(1) foam-like mesopore molecular sieve (mesocellular foam silica, preparation MCF)
Take by weighing a certain amount of triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO under 37 ℃, P123), be dissolved in the hydrochloric acid solution, the concentration of hydrochloric acid is 2mol/L, triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO, P123) concentration in the mixed solution of hydrochloric acid and distilled water is 0.02g/ml, adds NH again
4F and 1,3,5-trimethylbenzene (TMB), P123, NH
4F and 1,3, the weight ratio of 5-trimethylbenzene is 8: 0.1: 4, stirred 1 hour, the synthermal ethyl orthosilicate (TEOS) that adds down, ethyl orthosilicate (TEOS) is 1: 16 with the volume ratio of hydrochloric acid solution, stirs 20 hours, the gained slurry is transferred in the autoclave, 100 ℃ of following hydro-thermals 24 hours, washing precipitation, dry 12h in 60 ℃ of vacuum drying chambers, calcined 6 hours down at 550 ℃ again, obtain the MCF molecular sieve;
(2) MCF load TiO
2Preparation of catalysts
Weighing titanium sulfate (Ti (SO
4)
2) solid, add redistilled water, the concentration of titanium sulfate in redistilled water is 0.04g/ml, stirs 30 minutes, treat that titanium sulfate dissolves fully after, add the MCF molecular sieve that step (1) prepares, the weight ratio of titanium sulfate and MCF molecular sieve is 3: 2, stirs 4 hours, and solution to be mixed is even, change in the autoclave, put to 120 ℃ of baking ovens hydro-thermal 7 hours; After the isolated washing of precipitate, 60 ℃ of vacuum drying 12 hours obtain MCF load TiO
2Catalyst is labeled as MCF/TiO
2
(3) NH
4F is to MCF/TiO
2Modification
Take by weighing a certain amount of NH
4F is added in the isopropyl alcohol, stirs 1 hour, after the dissolving, adds the MCF/TiO that step (2) prepares fully
2, NH
4F and MCF/TiO
2Weight ratio be 0.1: 1, stirred 1 hour, above-mentioned solution is transferred in the autoclave and puts into 120 ℃ of baking ovens, hydro-thermal 20 hours, isolated precipitation is washed three times with distilled water, and 200 ℃ of vacuum activate 3 hours in vacuum drying chamber, promptly obtain ammonium fluoride modifying titanium dioxide visible light catalyst.
Claims (10)
1. the synthetic method of an ammonium fluoride modifying titanium dioxide visible light catalyst is characterized in that, this method may further comprise the steps:
(1) preparation of foam-like mesopore molecular sieve (MCF molecular sieve)
(PEO-PPO-PEO P123), is dissolved in the hydrochloric acid solution, adds NH again to take by weighing a certain amount of triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene under 37 ℃
4F and 1,3,5-trimethylbenzene (TMB) stirred 1 hour, the synthermal ethyl orthosilicate (TEOS) that adds down, stirred 20 hours, the gained slurry is transferred in the autoclave, 100 ℃ of following hydro-thermals 24 hours, washing precipitation, dry 12h in 60 ℃ of vacuum drying chambers calcined 6 hours down at 550 ℃ again, obtained the MCF molecular sieve;
(2) MCF load TiO
2Preparation of catalysts
Weighing titanium sulfate (Ti (SO
4)
2) solid, add redistilled water, stirred 30 minutes, treat that titanium sulfate dissolves fully after, the MCF molecular sieve that adding step (1) prepares stirred 4 hours, solution to be mixed is even, changes in the autoclave, puts to 120 ℃ of baking ovens hydro-thermal 7 hours; After the isolated washing of precipitate, 60 ℃ of vacuum drying 12 hours obtain MCF load TiO
2Catalyst is labeled as MCF/TiO
2
(3) NH
4F is to MCF/TiO
2Modification
Take by weighing a certain amount of NH
4F is added in the solvent, stirs 1 hour, after the dissolving, adds the MCF/TiO that step (2) prepares fully
2, stirring 1 hour, above-mentioned solution is transferred in the autoclave and puts into 120 ℃ of baking ovens, hydro-thermal 20 hours, isolated precipitation is washed three times with distilled water, and 200 ℃ of vacuum activate 3 hours in vacuum drying chamber, promptly obtain ammonium fluoride modifying titanium dioxide visible light catalyst.
2. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the concentration of the hydrochloric acid solution described in the step (1) is 1.5～2mol/L.
3. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1, it is characterized in that the concentration of triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene in hydrochloric acid solution described in the step (1) is 0.02～0.03g/ml.
4. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, triblock polymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the NH described in the step (1)
4F and 1,3, the weight ratio of 5-trimethylbenzene is 8: 0.1: 4.
5. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the ethyl orthosilicate (TEOS) described in the step (1) is 1 with the volume ratio of hydrochloric acid solution: (16～17).
6. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the concentration of titanium sulfate in redistilled water described in the step (2) is 0.04～0.05g/ml.
7. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the weight ratio of titanium sulfate described in the step (2) and MCF molecular sieve is 3: 2.
8. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the solvent described in the step (3) is isopropyl alcohol, methyl alcohol, ethanol or water.
9. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the preferred isopropyl alcohol of solvent described in the step (3).
10. the synthetic method of a kind of ammonium fluoride modifying titanium dioxide visible light catalyst according to claim 1 is characterized in that, the NH described in the step (3)
4F and MCF/TiO
2Weight ratio be (0.05～1.0): 1.
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