CN103170357A - High-activity two-dimensional doped modified titanium dioxide nanometer powder photocatalytic material and preparation method thereof - Google Patents
High-activity two-dimensional doped modified titanium dioxide nanometer powder photocatalytic material and preparation method thereof Download PDFInfo
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- CN103170357A CN103170357A CN2013101022821A CN201310102282A CN103170357A CN 103170357 A CN103170357 A CN 103170357A CN 2013101022821 A CN2013101022821 A CN 2013101022821A CN 201310102282 A CN201310102282 A CN 201310102282A CN 103170357 A CN103170357 A CN 103170357A
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Abstract
The invention discloses a high-activity two-dimensional doped modified titanium dioxide nanometer powder photocatalytic material and a preparation method thereof. Two-dimensional doping modification of the TiO2 nanometer powder photocatalytic material is realized by adopting a one-step wet-type chemical method, so that quantum yield of the material within a visible spectrum range is improved, the recombination rate of photo-produced electron cavities is effectively restrained and the utilization range of the material to the solar spectrum is expanded. According to the high-activity two-dimensional doped modified titanium dioxide nanometer powder photocatalytic material and the preparation method thereof disclosed by the invention, the preparation method is simple to implement and the process is easy to control; moreover, the prepared TiO2 nanometer powder photocatalytic material is intensively distributed between 13nm and 15nm; the crystal form is an anatase type. Compared with the photocatalytic material prepared by the conventional method, the photocatalytic activity of the high-activity two-dimensional doped modified titanium dioxide nanometer powder photocatalytic material disclosed by the invention is remarkably improved.
Description
Technical field
The present invention relates to the photocatalysis technology field, more particularly, relate to a kind of novel nano catalysis material and preparation method thereof, relate in particular to a kind of high activity two dimension doping vario-property TiO
2Nano-powder catalysis material and preparation method thereof.
Background technology
About visible light-responded based on TiO
2The preparation of one-dimensional doping modified nano powder catalysis material appears in the newspapers in the world frequently, but the present material of reporting or be subject to high recombination rate and the low quantum yield in light induced electron hole in the solar spectrum scope or be difficult to utilizing scope or having the factor such as serious photoetch and make its photochemical catalytic oxidation efficient in the solar spectrum scope be difficult to improve of broadening solar spectrum model.Therefore, how to prepare in the solar spectrum scope and have high activity, the TiO of high stability
2The nanoscale catalysis material is still the Research Challenges in this area.In recent years, based on the two-dimentional doping vario-property TiO of metal-metal, nonmetal-nonmetal, metal-nonmetalloid
2Nano-photocatalyst material becomes study hotspot gradually.Two-dimentional doping vario-property TiO at metal-nonmetalloid
2In nano-photo catalytic material research field, rare earth element (Ln)-N codope is because of its 4f electronic shell and TiO
2Conduction band between electron transition cause light induced electron hole right effective separation, particularly Ce and N codope because of Ce
3+/ Ce4
+And the existence of hybridized orbit (N2p and O2p orbital hybridization) can effectively improve its under sunshine Photocatalytic oxidation activity and receive much concern.But about Ce and the codoping modified TiO of N
2The low energy consumption of nano-powder catalysis material, one-step synthesis there is not yet report so far cheaply.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, for overcoming existing sunshine response TiO
2The defective that the photocatalytic nanometer powder body material exists, namely improve its quantum yield in limit of visible spectrum, effectively suppress its scope of utilizing to solar spectrum of broadening in the recombination rate in light induced electron hole, and have good photocatalysis stability and the photochemical catalyst of heat endurance, and it is low low with cost to prepare required energy consumption, the invention discloses a kind of low power consuming, one goes on foot the standby high activity two dimension of wet chemistry legal system doping vario-property TiO cheaply
2Nano-powder catalysis material and preparation method thereof.
Technical purpose of the present invention is achieved by following technical proposals:
A kind of high activity two dimension doping vario-property TiO
2Nano-powder catalysis material and preparation method thereof, carry out according to following step:
(1) (1-x) volume ratio is with butyl titanate, alcohols solvent and aqueous solution of nitric acid configuration mixed solution according to 17x:120x:3, add the polyvinyl alcohol that accounts for mixed solution quality 35%-50% again in above-mentioned mixed solution, and be stirred to its Uniform Dispersion, wherein 0.3≤x≤0.8 under 20-50 ℃;
(2) according to the mol ratio of Ti:Ce:N in 1:(0.001-0.02): in (0.001-0.15) interval, add soluble-salt and the nitrogen substance that contains Ce elements in solution of preparation in (1), be stirred to its Uniform Dispersion;
(3) drip the mixed solution of distilled water and alcohol organic solvent in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 25-60 ℃ of mechanical agitation 8-14 hours; forming vitreosol is placed in drying box in 90-120 ℃ of dryings after 10-24 hours; calcining 1-8 hours under 450-750 ℃ He under inert gas shielding; heat up under room temperature; programming rate is controlled at 2.5-10 ℃/minutes; cooling rate is controlled at 1-7 ℃/minutes, is cooled to room temperature, namely obtains final photocatalyst material.
In described step (1), use a kind of as in methyl alcohol, absolute ethyl alcohol, n-butanol or isobutanol of alcohols solvent.
In described step (1), the concentration of the aqueous solution of nitric acid of use is 0.05-0.15mol/L.
In described step (1), the number-average molecular weight of the polyvinyl alcohol of use is 600-20000.
In described step (1), the difference by adding nitric acid quantity is so that the pH of the solution of final preparation is 2.0-5.5.
In described step (2), the mol ratio of Ti:Ce:N preferred 1:(0.01-0.02): (0.01-0.15), when determining two kinds of element mol ratios in step (2), the nitrogen element is not considered the N that in step (1), existing nitric acid is brought into, only considers the nitrogen element that adds in step (2).
In described step (2), the nitrogen substance that uses is urea or guanidine.
In described step (2), the soluble-salt that contains Ce elements is nitrate or the chloride that contains Ce elements, for example CeCl
37H
2O, Ce(NO
3) 36H
2O。
In described step (3), in mixed solution, the volume ratio of distilled water and alcohol organic solvent is in (1:10)-(1:50) interval, and described alcohol organic solvent is a kind of in methyl alcohol, absolute ethyl alcohol, n-butanol or isobutanol.
In described step (4), a kind of as in nitrogen, helium or argon gas of the inert gas that uses.
In described step (4), preferably calcining 2-4 hours under 450-550 ℃ He under inert gas shielding.
Be 20-25 ℃ in the room temperature described in each step.
Adopt polyvinyl alcohol that sol solutions viscosity is increased in the present invention, and can play the effect of antioxidant.The effect that short distance is disperseed is played in ultrasonic dispersion, makes in sol solutions each material reach nanoscale and disperses.The present invention can also adopt temperature programmed control Gel heat-treatment Process Design and optimization and control in calcination process and heat up and rate of temperature fall, can guarantee material in heat treatment process substantially without reunion, the minimizing sintering subside and crystallization all right.Can prepare anatase by the pH value of controlling course of reaction and account for the nanocrystal that main phase forms, make simultaneously highly active (101) face account for main crystal face and form.By controlling as shown in attached Fig. 1 and 2, the catalysis material particle diameter concentrate be distributed between 13-15nm, crystallization is all right and to the obvious broadening of utilization rate of solar spectrum.
The atomic absorption spectrum of group of the lanthanides (Ln) element derives from electron transition and the electron transition between configuration and the electric charge transition in the fn configuration, and namely the electronics of f-f, 4f-5d, 4f-6s, 4f-6p, ligand ion is to/Ln
4+/ Ln
3+The transition of ion etc. can effectively suppress the recombination probability in light induced electron hole.In addition, the absorption spectrum of lanthanide series is distributed widely in ultra-violet (UV) band, near infrared region and visible region, therefore can make its absorption spectrum Einstein shift through the catalysis material of lanthanide series modification, can partly utilize visible light (λ＜450nm).Mixing of nitrogen (N) element can reach the nano-TiO that effectively narrows by broadening conduction band or hydridization N2p track and O2p track
2The purpose of energy gap, improve its utilization ratio to sunshine (λ～600nm).The Ce that passes through to adulterate and the cooperative effect of N can increase the light induced electron hole productive rate of prepared material under sunshine excites, simultaneously by the electron transition between 4f and conduction band and Ce
3+/ Ce
4+Between redox reaction can effectively suppress the compound of light induced electron hole, produce simultaneously OH and the O that has in a large number strong oxidizing property
2 -, and then improve its Photocatalytic oxidation activity under solar light irradiation.Heat up and the cooling processing by accurate control program, make prepared catalysis material have good photocatalysis stability and heat endurance, can reuse.
Aqueous solution of methylene blue take initial concentration as 15ppm is the degraded object, carry out the recycling experimental study of photocatalytic oxidation degradation experimental study and prepared material take the 30W fluorescent lamp as light source, as shown in accompanying drawing 3 and 4, the illumination reaction time is 10 hours, use the concentration (752 spectrophotometers, Instr Ltd. is analysed by Shanghai unit) with the spectrophotometer measurement reaction system.The titanium dioxide of non-modified is 30.6% to the water-soluble degradation rate of methylene blue, only the titanium dioxide of rare earth Ce doping modification is 35% to the degradation rate of aqueous solution of methylene blue, can degradable aqueous solution of methylene blue when 3h is carried out in reaction with the titanium dioxide of doping vario-property through nitrogen and rare earth element ce, as seen utilize this method can effectively improve photocatalytic activity.Prepared catalysis material as visible in accompanying drawing 4 through the experiment of the recycling under five the same terms (the illumination reaction time is 120 minutes) after, photocatalytic activity only slightly has reduction.
The invention process is easy, and process is easy to control, and the TiO for preparing
2The nano-powder catalysis material has good crystallinity, photocatalysis stability, heat endurance and the high Photocatalytic oxidation activity under sunshine excites.The catalysis material particle diameter is concentrated and is distributed between 13-15nm; The crystal crystal formation is Detitanium-ore-type; Comparing photocatalytic activity than the catalysis material of conventional method preparation obviously improves.
Description of drawings
Fig. 1 is nitrogen and the rare earth element codoping titanium dioxide nano powder TEM figure (JEM-2100F type transmission electron microscope, company of NEC) that utilizes the technical solution of the present invention preparation.
Fig. 2 is XRD figure (the D8-Focus type X-ray diffractometer of the catalysis material of preparation, Germany Brooker AXS Co., Ltd produces), wherein 1 is the titanium dioxide of non-modified (being pure titinium dioxide), 2 are the titanium dioxide of rare earth element ce modification (namely not adding the N element in step (2)), and 3 for utilizing Ce and the N modifying titanium dioxide catalysis material of technical solution of the present invention preparation.
Fig. 3 is that catalysis material is to the degradation efficiency comparison diagram of aqueous solution of methylene blue, wherein 1 is the titanium dioxide of non-modified (being pure titinium dioxide), 2 are the titanium dioxide of rare earth element ce modification (namely not adding the N element in step (2)), and 3 for utilizing Ce and the N modifying titanium dioxide catalysis material of technical solution of the present invention preparation.
Fig. 4 is the catalysis material for preparing of the present invention through the recycling lab diagram (the illumination reaction time is 120 minutes) under five the same terms.
The specific embodiment
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment one
(1) according to the volume ratio of 17x:120x:3 (1-x) with butyl titanate, methyl alcohol and 0.05M(mol/L, lower same) aqueous solution of nitric acid configuration mixed solution, add the polyvinyl alcohol (number-average molecular weight 20 that accounts for mixed solution quality 35% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 20 ℃, x=0.3 wherein, pH=5.5;
(2) add Ce(NO in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.001:0.001 to (1)
3)
36H
2The mixture of O and urea is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:10) of distilled water and methyl alcohol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 25 ℃ of mechanical agitation 8 hours; forming vitreosol is placed in drying box in 90 ℃ of dryings after 10 hours; calcining 1 hour under 450 ℃ and under nitrogen protection; heat up under 20 ℃ of room temperatures; programming rate is controlled at 2.5 ℃/minutes; cooling rate is controlled at 1 ℃/minute, is cooled to 20 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment two
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, absolute ethyl alcohol and 0.15M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 600) that accounts for mixed solution quality 50% again in above-mentioned mixed solution, and be stirred to its Uniform Dispersion under 50 ℃, x=0.8 wherein, pH=2.0;
(2) add Ce(NO in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.02:0.15 to (1)
3)
36H
2The mixture of O and urea is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:50) of distilled water and absolute ethyl alcohol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 60 ℃ of mechanical agitation 14 hours; forming vitreosol is placed in drying box in 120 ℃ of dryings after 24 hours; calcining 8 hours under 750 ℃ and under argon shield; heat up under 25 ℃ of room temperatures; programming rate is controlled at 10 ℃/minutes; cooling rate is controlled at 7 ℃/minutes, is cooled to 25 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment three
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, n-butanol and 0.10M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 4 that accounts for mixed solution quality 45% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 40 ℃, x=0.5 wherein, pH=3.5;
(2) add Ce(NO in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.008:0.089 to (1)
3)
36H
2The mixture of O and urea is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:30) of distilled water and n-butanol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 35 ℃ of mechanical agitation 10 hours; forming vitreosol is placed in drying box in 100 ℃ of dryings after 12 hours; calcining 3.5 hours under 550 ℃ and under the helium protection; heat up under 25 ℃ of room temperatures; programming rate is controlled at 4 ℃/minutes; cooling rate is controlled at 2.5 ℃/minutes, is cooled to 25 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment four
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, isobutanol and 0.05M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 20 that accounts for mixed solution quality 50% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 30 ℃, x=0.3 wherein, pH=5.5;
(2) add in the solution of preparation in 1:0.001:0.001 to (1) according to the mol ratio of Ti:Ce:N and contain CeCl
37H
2The mixture of O and guanidine is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:10) of distilled water and isobutanol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 25 ℃ of mechanical agitation 8 hours; forming vitreosol is placed in drying box in 90 ℃ of dryings after 10 hours; calcining 1 hour under 450 ℃ and under nitrogen protection; heat up under 25 ℃ of room temperatures; programming rate is controlled at 2.5 ℃/minutes; cooling rate is controlled at 1 ℃/minute, is cooled to 20 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment five
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, methyl alcohol and 0.15M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 10 that accounts for mixed solution quality 40% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 25 ℃, x=0.8 wherein, pH=2.0;
(2) add CeCl in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.02:0.15 to (1)
37H
2The mixture of O and guanidine is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:50) of distilled water and absolute ethyl alcohol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 50 ℃ of mechanical agitation 10 hours; forming vitreosol is placed in drying box in 120 ℃ of dryings after 24 hours; calcining 8 hours under 550 ℃ and under nitrogen protection; heat up under 20 ℃ of room temperatures; programming rate is controlled at 5 ℃/minutes; cooling rate is controlled at 5 ℃/minutes, is cooled to 25 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment six
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, absolute ethyl alcohol and 0.12M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 10 that accounts for mixed solution quality 45% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 35 ℃, x=0.4 wherein, pH=4.6;
(2) add CeCl in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.012:0.011 to (1)
37H
2The mixture of O and guanidine is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:40) of distilled water and n-butanol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 50 ℃ of mechanical agitation 12 hours; forming vitreosol is placed in drying box in 100 ℃ of dryings after 15 hours; calcining 2.5 hours under 600 ℃ and under nitrogen protection; heat up under 20 ℃ of room temperatures; programming rate is controlled at 3.5 ℃/minutes; cooling rate is controlled at 1.5 ℃/minutes, is cooled to 25 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment seven
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, methyl alcohol and 0.05M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 800) that accounts for mixed solution quality 50% again in above-mentioned mixed solution, and be stirred to its Uniform Dispersion under 50 ℃, x=0.3 wherein, pH=5.5;
(2) add Ce(NO in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.001:0.05 to (1)
3)
36H
2The mixture of O and guanidine is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:30) of distilled water and absolute ethyl alcohol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 25 ℃ of mechanical agitation 8 hours; forming vitreosol is placed in drying box in 90 ℃ of dryings after 10 hours; calcining 6 hours under 650 ℃ and under argon shield; heat up under 20 ℃ of room temperatures; programming rate is controlled at 2.5 ℃/minutes; cooling rate is controlled at 1 ℃/minute, is cooled to 25 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment eight
(1) according to the volume ratio of 17x:120x:3 (1-x) with butyl titanate, n-butanol and and 0.15M aqueous solution of nitric acid configuration mixed solution, add the polyvinyl alcohol (number-average molecular weight 1 that accounts for mixed solution quality 40% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 50 ℃, x=0.8 wherein, pH=2.0;
(2) add Ce(NO in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.015:0.01 to (1)
3)
36H
2The mixture of O and guanidine is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:50) of distilled water and methyl alcohol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 60 ℃ of mechanical agitation 14 hours; forming vitreosol is placed in drying box in 120 ℃ of dryings after 24 hours; calcining 8 hours under 700 ℃ and under nitrogen protection; heat up under 25 ℃ of room temperatures; programming rate is controlled at 10 ℃/minutes; cooling rate is controlled at 7 ℃/minutes, is cooled to 25 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment nine
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, absolute ethyl alcohol and 0.12M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 10 that accounts for mixed solution quality 40% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 25 ℃, x=0.6 wherein, pH=2.9;
(2) add Ce(NO in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.010:0.009 to (1)
3)
36H
2The mixture of O and guanidine is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:20) of distilled water and absolute ethyl alcohol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 55 ℃ of mechanical agitation 12 hours; forming vitreosol is placed in drying box in 100 ℃ of dryings after 15 hours; calcining 5.5 hours under 550 ℃ and under the helium protection; heat up under 25 ℃ of room temperatures; programming rate is controlled at 7 ℃/minutes; cooling rate is controlled at 3 ℃/minutes, is cooled to 25 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment ten
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, absolute ethyl alcohol and 0.05M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 20 that accounts for mixed solution quality 35% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 35 ℃, x=0.3 wherein, pH=5.5;
(2) add CeCl in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.001:0.001 to (1)
37H
2The mixture of O and urea is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:25) of distilled water and absolute ethyl alcohol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 25 ℃ of mechanical agitation 8 hours; forming vitreosol is placed in drying box in 90 ℃ of dryings after 10 hours; calcining 1 hour under 450 ℃ and under the helium protection; heat up under 20 ℃ of room temperatures; programming rate is controlled at 2.5 ℃/minutes; cooling rate is controlled at 1 ℃/minute, is cooled to 20 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment 11
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, n-butanol and 0.15M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 8 that accounts for mixed solution quality 40% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 50 ℃, x=0.8 wherein, pH=2.0;
(2) add CeCl in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.02:0.15 to (1)
37H
2The mixture of O and urea is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:50) of distilled water and n-butanol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 60 ℃ of mechanical agitation 14 hours; forming vitreosol is placed in drying box in 120 ℃ of dryings after 24 hours; calcining 8 hours under 700 ℃ and under the helium protection; heat up under 20 ℃ of room temperatures; programming rate is controlled at 10 ℃/minutes; cooling rate is controlled at 7 ℃/minutes, is cooled to 20 ℃ of room temperatures, namely obtains final photocatalyst material.
Embodiment 12
(1) volume ratio according to 17x:120x:3 (1-x) configures mixed solution with butyl titanate, methyl alcohol and 0.12M aqueous solution of nitric acid, add the polyvinyl alcohol (number-average molecular weight 10 that accounts for mixed solution quality 45% again in above-mentioned mixed solution, 000), and be stirred to its Uniform Dispersion under 50 ℃, x=0.7 wherein, pH=2.2;
(2) add CeCl in the solution of preparation according to the mol ratio of Ti:Ce:N in 1:0.010:0.009 to (1)
37H
2The mixture of O and urea is stirred to its Uniform Dispersion;
(3) drip the mixed solution (both volume ratios are 1:40) of distilled water and isobutanol in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 40 ℃ of mechanical agitation 12 hours; forming vitreosol is placed in drying box in 100 ℃ of dryings after 15 hours; calcining 2.5 hours under 550 ℃ and under argon shield; heat up under 20 ℃ of room temperatures; programming rate is controlled at 4 ℃/minutes; cooling rate is controlled at 2.5 ℃/minutes, is cooled to 20 ℃ of room temperatures, namely obtains final photocatalyst material.
Above the present invention has been done exemplary description; should be noted that; in the situation that do not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. high activity two dimension doping vario-property TiO
2The nano-powder catalysis material is characterized in that, particle diameter is concentrated and is distributed between 13-15nm; The crystal crystal formation is Detitanium-ore-type, carries out according to following step:
(1) (1-x) volume ratio is with butyl titanate, alcohols solvent and aqueous solution of nitric acid configuration mixed solution according to 17x:120x:3, add the polyvinyl alcohol that accounts for mixed solution quality 35%-50% again in above-mentioned mixed solution, and be stirred to its Uniform Dispersion, wherein 0.3≤x≤0.8 under 20-50 ℃;
(2) according to the mol ratio of Ti:Ce:N in 1:(0.001-0.02): in (0.001-0.15) interval, add soluble-salt and the nitrogen substance that contains Ce elements in solution of preparation in (1), be stirred to its Uniform Dispersion;
(3) drip the mixed solution of distilled water and alcohol organic solvent in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 25-60 ℃ of mechanical agitation 8-14 hours; forming vitreosol is placed in drying box in 90-120 ℃ of dryings after 10-24 hours; calcining 1-8 hours under 450-750 ℃ He under inert gas shielding; heat up under room temperature; programming rate is controlled at 2.5-10 ℃/minutes; cooling rate is controlled at 1-7 ℃/minutes, is cooled to room temperature, namely obtains final photocatalyst material.
2. a kind of high activity two dimension doping vario-property TiO according to claim 1
2The nano-powder catalysis material is characterized in that, in described step (1), uses a kind of as in methyl alcohol, absolute ethyl alcohol, n-butanol or isobutanol of alcohols solvent; In described step (1), the concentration of the aqueous solution of nitric acid of use is 0.05-0.15mol/L; In described step (1), the number-average molecular weight of the polyvinyl alcohol of use is 600-20000; In described step (1), the difference by adding nitric acid quantity is so that the pH of the solution of final preparation is 2.0-5.5.
3. a kind of high activity two dimension doping vario-property TiO according to claim 1
2The nano-powder catalysis material is characterized in that, in described step (2), and the mol ratio of Ti:Ce:N preferred 1:(0.01-0.02): (0.01-0.15); Described nitrogen substance is urea or guanidine; The described soluble-salt that contains Ce elements is nitrate or the chloride that contains Ce elements, for example CeCl
37H
2O, Ce(NO
3)
36H
2O。
4. a kind of high activity two dimension doping vario-property TiO according to claim 1
2The nano-powder catalysis material, it is characterized in that, in described step (3), in mixed solution, the volume ratio of distilled water and alcohol organic solvent is in (1:10)-(1:50) interval, and described alcohol organic solvent is a kind of in methyl alcohol, absolute ethyl alcohol, n-butanol or isobutanol.
5. a kind of high activity two dimension doping vario-property TiO according to claim 1
2The nano-powder catalysis material is characterized in that, in described step (4), described inert gas is a kind of in nitrogen, helium or argon gas; In described step (4), preferably calcining 2-4 hours under 450-550 ℃ He under inert gas shielding.
6. high activity two dimension doping vario-property TiO
2The preparation method of nano-powder catalysis material is characterized in that, carries out according to following step:
(1) (1-x) volume ratio is with butyl titanate, alcohols solvent and aqueous solution of nitric acid configuration mixed solution according to 17x:120x:3, add the polyvinyl alcohol that accounts for mixed solution quality 35%-50% again in above-mentioned mixed solution, and be stirred to its Uniform Dispersion, wherein 0.3≤x≤0.8 under 20-50 ℃;
(2) according to the mol ratio of Ti:Ce:N in 1:(0.001-0.02): in (0.001-0.15) interval, add soluble-salt and the nitrogen substance that contains Ce elements in solution of preparation in (1), be stirred to its Uniform Dispersion;
(3) drip the mixed solution of distilled water and alcohol organic solvent in (2) in solution of preparation, be stirred to its Uniform Dispersion;
(4) with mixed liquor in 25-60 ℃ of mechanical agitation 8-14 hours; forming vitreosol is placed in drying box in 90-120 ℃ of dryings after 10-24 hours; calcining 1-8 hours under 450-750 ℃ He under inert gas shielding; heat up under room temperature; programming rate is controlled at 2.5-10 ℃/minutes; cooling rate is controlled at 1-7 ℃/minutes, is cooled to room temperature, namely obtains final photocatalyst material.
7. a kind of high activity two dimension doping vario-property TiO according to claim 6
2The preparation method of nano-powder catalysis material is characterized in that, in described step (1), uses a kind of as in methyl alcohol, absolute ethyl alcohol, n-butanol or isobutanol of alcohols solvent; In described step (1), the concentration of the aqueous solution of nitric acid of use is 0.05-0.15mol/L; In described step (1), the number-average molecular weight of the polyvinyl alcohol of use is 600-20000; In described step (1), the difference by adding nitric acid quantity is so that the pH of the solution of final preparation is 2.0-5.5.
8. a kind of high activity two dimension doping vario-property TiO according to claim 6
2The preparation method of nano-powder catalysis material is characterized in that, in described step (2), and the mol ratio of Ti:Ce:N preferred 1:(0.01-0.02): (0.01-0.15); Described nitrogen substance is urea or guanidine; The described soluble-salt that contains Ce elements is nitrate or the chloride that contains Ce elements, for example CeCl
37H
2O, Ce(NO
3)
36H
2O。
9. a kind of high activity two dimension doping vario-property TiO according to claim 6
2The preparation method of nano-powder catalysis material, it is characterized in that, in described step (3), in mixed solution, the volume ratio of distilled water and alcohol organic solvent is in (1:10)-(1:50) interval, and described alcohol organic solvent is a kind of in methyl alcohol, absolute ethyl alcohol, n-butanol or isobutanol.
10. a kind of high activity two dimension doping vario-property TiO according to claim 6
2The preparation method of nano-powder catalysis material is characterized in that, in described step (4), described inert gas is a kind of in nitrogen, helium or argon gas; In described step (4), preferably calcining 2-4 hours under 450-550 ℃ He under inert gas shielding.
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| CN115558130A (en) * | 2022-09-29 | 2023-01-03 | 清华大学深圳国际研究生院 | Optical hydrogel with adjustable birefringence and preparation method and application thereof |
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