CN102580708B - Method for preparing nitrogen modified titanium dioxide sol with visible-light catalytic activity - Google Patents
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Abstract
The invention relates to a method for preparing a nitrogen modified titanium dioxide sol with visible-light catalytic activity. The method comprises the steps of: dispersing an organic titanium compound in an alcoholic solution according to a certain proportion to obtain a uniform dispersion liquid A, dispersing a stabilizing agent in a nitric acid solution to obtain a uniform dispersion liquid B, and mixing the solution A with the solution B to obtain a transparent precursor solution; gradually dripping organic amine to adjust pH value of the solution, heating the solution after being mixed at a room temperature for a heat treatment, and ultrasonically dispersing the obtained solution to obtain the nitrogen modified titanium dioxide sol. Compared with the prior art, the preparation method disclosed by the invention is simple and low in cost; and the prepared sol applied in the surface modification can enable the modified surface to have photo-catalytic activity under the irradiation of visible lights, so that the method realizes wide-spectrum response to the solar spectrum and is more suitable for practical large-scale application.
Description
Technical field
The invention belongs to the crossing domain of inorganic nano material, chemistry and environmental science, especially relate to a kind of method of preparing the nitrogen modified titanium dioxide sol with visible light catalysis activity.
Background technology
Titanium dioxide semiconductor photocatalysis oxidation technique is subject to common concern.The features such as that the titanium dioxide raw material of this utilization has is cheap, stable performance, nontoxic non-corrosiveness; This technology can utilize green clean solar energy as the energy on the other hand, and reaction condition gentleness, easy and simple to handle, non-secondary pollution etc., so the various application technologies based on titanium dioxide have broad application prospects.In the practical application of present stage, photocatalysis material of titanium dioxide for fields such as the purifier of water and air, self-cleaning glass surface, antibacterial photocatalysis ceramics face bricks, has produced huge economy, environmental and social benefits.
TiO 2 sol has significant application value, can need for various exterior decorations, external wall, fiber cloth, ceramic tile and other surface treatment of cleaning objects.But the optical wavelength range that the simple anatase with photocatalytic activity or rutile ore titanium dioxide can respond is confined to ultraviolet portion, and ultraviolet portion energy in sunshine only accounts for approximately 5%, therefore in application, needs to adopt extra ultraviolet source just can produce a desired effect.Self-cleaning in application, the antibacterial and air clearing product simple titanium dioxide of employing mostly at present, the photocatalysis effect under sunshine or natural daylight is very limited.
The wavelength that titanium dioxide can be responded by the method for doping vario-property is extended to visible-range." visible light photocatalysis of nitrogen-doped titanium dioxide " (Asahi, the R. for example delivering on document < < science > > magazine 2001,293,269; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y., Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides.Science), reported a kind of method that by ion sputtering method, nitrogen-doping is entered to titanium dioxide lattice.Document < < Germany applied chemistry > > magazine 2003,42, " the carbon modification TiO delivering on 4908-4911
2daylight photocatalysis " (S.Sakthivel; H.Kisch; Daylight Photocatalysis by Carbon-Modified Titanium Dioxide; Angew.Chem.Int.Ed.); reported interpolation TBAH hydrolysis titanium tetrachloride, the carbon that obtains highlight catalytic active after roasting is titania-doped.Nitrogen take urea, ammoniacal liquor etc. as nitrogenous source doping in recent years or carbon doping modification method all can obtain visible light-responded nitrogen or carbon titania-doped, but these experimental techniques are all employing high-temperature roasting methods, preparation be modifying titanium dioxide nano-powder.Although these nano-powders have visible light-responded activity, nano-powder is again distributed in solution and is difficult to obtain uniform colloidal sol, in photocatalytic self-cleaning or the application of other surface-treated, be also difficult to obtain uniform film or coating.
Summary of the invention
Object of the present invention is exactly to provide a kind of preparation at a lower temperature to have the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity in order to overcome the defect that above-mentioned prior art exists, and realizes and adopts this colloidal sol surface after treatment under visible ray illumination, to have photocatalysis.
Object of the present invention can be achieved through the following technical solutions: employing organic titanic compound is raw material, by introducing stabilizing agent and organic nitrogen source, solution is through processing lower than the temperature of 160 ℃, in the process that nitrogen element is grown up in titania, enter lattice, obtain the uniform and stable nitrogen modified titanium dioxide sol with visible light catalysis activity.
Preparation has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, comprises the following steps:
(1) organic titanic compound is dispersed in and in alcohol, obtains uniform dispersion liquid A;
(2) stabilizing agent is dispersed in salpeter solution, obtains uniform dispersion liquid B;
(3) solution A and B are uniformly mixed, obtain transparent precursor liquid; Dropwise add organic amine, with nitric acid regulator solution pH value be 3-12, after stirring at room 1-72h, solution is warmed up to 90-160 ℃ and heat-treats 1-72h, the solution obtaining obtain nitrogen modified titanium dioxide sol through ultrasonic dispersion.
Described organic titanic compound is butyl titanate, tetraisopropyl titanate or tetraethyl titanate; Described alcohol is all alcohol that the carbon number of methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or the tert-butyl alcohol is less than 5; The volume ratio of described organic titanic compound and alcohol is 0.01-1.
Described stabilizing agent is glycolic, acetylacetone,2,4-pentanedione, EDTA or citric acid, and the mol ratio of stabilizing agent and organic titanic compound is between 0.01-10.
The concentration of described salpeter solution is 0.01-1mol/L, and the volume ratio of dispersion liquid A and dispersion liquid B is 0.1-10, during mixing, dispersion liquid A is dropwise added in dispersion liquid B, or dispersion liquid B is dropwise added in dispersion liquid A, or by dispersion liquid A and dispersion liquid B rapid mixing.
Described organic amine is diethylamine, triethylamine, trimethylamine, diethylenetriamines, propane diamine or triethylene tetramine, organic amine and organic titanic compound mole be 0.01-10.
Described heat treatment is the stirring and refluxing reaction under water under high pressure thermal response or normal pressure.
The solid concentration of the nitrogen modified titanium dioxide sol preparing is 0.1 grams per liter-100 grams per liter; Wherein nitrogen content accounts for the 0.1-10wt% of solid, and titanium dioxide nano-particle is the crystal formation that mixes that mixes crystal formation or anatase and brockite of anatase type or anatase and rutile ore.
The nitrogen modified titanium dioxide sol preparing can be applicable to deodorizing, the sterilization of family, hospital and public arena, be applied to the self-cleaning functionalization of exterior decoration, exterior wall, glass surface, be applied to the clean functionalization of clean surfaces of the clothes such as cotton, silk, wool, staple fibre, be applied to the removal of decomposing the persistent organic pollutants in liquid phase or gas phase, and be applied to photocatalysis heavy-metal ion removal, photochemical catalyzing, photo catalytic reduction nitrate or fixed nitrogen.
Compared with prior art, the present invention has the following advantages:
(1) by adding stabilizing agent and organic amine, control hydrolysis and the gel process of organic titanic compound, make in the propagation process of titanium dioxide nano-particle, nitrogen element is incorporated among crystal grain, obtains the stable sol that contains nitrogen modified titanium dioxide nano particle.Colloidal sol can obtain nitrogen modifying titanium dioxide nanometer powder after super-dry, carrying out washing treatment; Also can directly colloidal sol be loaded to cotton fiber surface and obtain modified cotton fiber.Methyl orange is a kind of typical hardly degraded organic substance.By nano-powder or modified cotton fiber, under visible ray shines, methyl orange degradation is decoloured to characterize colloidal sol visible light catalysis activity.It can be natural daylight that light source used is tested in photocatalysis, manual simulation's sunshine or room lighting light source.
(2) can realize the nitrogen modified titanium dioxide sol of preparing at a lower temperature the stable and uniform with visible light catalysis activity, and preparation flow is succinct, production cost is low, prepared TiO 2 sol can be realized the wide range response to visible ray, significantly improves catalytic response performance and the catalytic efficiency of the relevant modified product of modifying titanium dioxide under sunshine.
(3) at aspects such as photocatalysis water body purification, air cleaning, self-cleaning ceramic tile, the clean clothing of antibiosis and self-cleaning, self-cleaning exterior wall, glass, combination with decorative surfaces, antibiotic and sterilizings, have broad application prospects.Specifically can be applicable to deodorizing, the sterilization of family, hospital and various public arenas, be applied to the persistent organic pollutants of decomposing in liquid phase or gas phase, be applied to the self-cleaning functionalization on various surfaces, and be applied to photochemical catalyzing, photo catalytic reduction nitrate, fixed nitrogen and relative photo catalytic applications, be particularly suitable for the condition take sunshine, indoor natural light as light source.
Accompanying drawing explanation
Fig. 1 is the x-ray diffractogram of powder spectrum after the nitrogen modified titanium dioxide sol drying washing prepared of embodiment 1;
Fig. 2 is ultraviolet-visible diffuse reflection abosrption spectrogram corresponding to powder sample after the nitrogen modified titanium dioxide sol drying washing prepared of embodiment 3.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Get in the isopropyl alcohol that 10 milliliters of tetraisopropyl titanates are dispersed in 5 milliliters and obtain uniform dispersion A; 0.3 gram of ethylenediamine tetra-acetic acid is dissolved in the dilute nitric acid solution of 100 milliliter of 0.1 mol/L, obtains uniform dispersion B; Under vigorous stirring state, solution A is dropwise added in solution B, be uniformly mixed 12 hours, obtain clear solution.Dropwise add again 2 milliliters of diethylamine, by nitric acid regulator solution pH value to 5, under normal temperature, first stir 12 hours, solution back flow reaction 12 hours in the oil bath of 120 degree subsequently, the solution obtaining, can obtain nitrogen modified titanium dioxide sol through ultrasonic dispersion.Colloidal sol is faint yellow transparent colloidal solution.The colloidal sol of getting certain volume obtains nitrogen modifying titanium dioxide powder after being dried and washing, and for the methyl orange degradation under visible ray, within two hours, methyl orange rate reaches 73%.Colloidal sol is loaded to cotton fiber, and under methyl orange visible ray, to reach 40%, Fig. 1 be the x-ray diffractogram of powder spectrum after the washing of nitrogen modified titanium dioxide sol drying for two hours percent of decolourizations, can determine it is mainly anatase phase from collection of illustrative plates.
Embodiment 2
Get in the isopropyl alcohol that 5 milliliters of butyl titanates are dispersed in 5 milliliters and obtain uniform dispersion A; 3 milliliters of acetylacetone,2,4-pentanediones are dispersed in the dilute nitric acid solution of 50 milliliter of 0.08 mol/L, obtain uniform dispersion B; Under vigorous stirring state, solution B is dropwise added in solution A, be uniformly mixed 24 hours, obtain clear solution; Dropwise add 3 milliliters of triethylamines, by nitre acid for adjusting pH value to 9, stirring at normal temperature 12 hours, solution is 150 degree reaction 24 hours in autoclave subsequently again, and the solution obtaining can obtain nitrogen modified titanium dioxide sol through ultrasonic dispersion.Colloidal sol is yellow transparent colloidal solution.The colloidal sol of getting certain volume obtains nitrogen modifying titanium dioxide powder after being dried and washing, and for the methyl orange degradation under visible ray, within two hours, methyl orange rate reaches 91%.Colloidal sol is loaded to cotton fiber, and under methyl orange visible ray, two hours percent of decolourizations reach 62%.
Embodiment 3
Get in the isopropyl alcohol that 5 milliliters of tetraisopropyl titanates are dispersed in 5 milliliters and obtain uniform dispersion A; 1 milliliter of acetylacetone,2,4-pentanedione is dissolved in the dilute nitric acid solution of 80 milliliter of 0.5 mol/L, obtains uniform dispersion B; Under vigorous stirring state, solution A is directly mixed with solution B, continue to stir 12 hours, obtain clear solution; Dropwise add again 1 milliliter of triethylamine, by nitre acid for adjusting pH value to 10, stirring at normal temperature 12 hours, solution back flow reaction 12 hours in the oil bath of 110 degree subsequently, the solution obtaining can obtain nitrogen modified titanium dioxide sol through ultrasonic dispersion.Colloidal sol is light yellow transparent colloidal solution.The colloidal sol of getting certain volume obtains nitrogen modifying titanium dioxide powder after being dried and washing, and for the methyl orange degradation under visible ray, within two hours, methyl orange rate reaches 82%.Colloidal sol is loaded to cotton fiber, under methyl orange visible ray, two hours percent of decolourizations reach 54%, Fig. 2 is ultraviolet-visible diffuse reflection abosrption spectrogram corresponding to powder sample after the washing of nitrogen modified titanium dioxide sol drying, can see that absorbing cutoff wavelength is extended to 500nm.Measuring instrument is VARIAN Cary 500UV-vis spectrophotometer.
Embodiment 4
Get in the ethanol that 5 milliliters of butyl titanates are dispersed in 10 milliliters and obtain uniform dispersion A; 0.2 gram of glycolic is dissolved in the dilute nitric acid solution of 100 milliliter of 0.1 mol/L, obtains uniform dispersion B; Under vigorous stirring state, solution A is directly mixed with solution B, continue to stir 24 hours, obtain clear solution; Dropwise add again 3 milliliters of triethylamines, by nitre acid for adjusting pH value to 8, stirring at normal temperature 12 hours, solution back flow reaction 24 hours in the oil bath of 100 degree subsequently, the solution obtaining can obtain nitrogen modified titanium dioxide sol after ultrasonic dispersion.Colloidal sol is light yellow transparent colloidal solution.The colloidal sol of getting certain volume obtains nitrogen modifying titanium dioxide powder after being dried and washing, and for the methyl orange degradation under visible ray, within two hours, methyl orange rate reaches 90%.Colloidal sol is loaded to cotton fiber, and under methyl orange visible ray, two hours percent of decolourizations reach 55%.
Embodiment 5
Preparation has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, comprises the following steps:
(1) butyl titanate is dispersed in propyl alcohol and obtains uniform dispersion liquid A, the volume ratio of butyl titanate and propyl alcohol is 0.01;
(2) stabilizing agent acetylacetone,2,4-pentanedione is dispersed in the dilute nitric acid solution that concentration is 0.01mol/L, obtains uniform dispersion liquid B, the mol ratio of acetylacetone,2,4-pentanedione and butyl titanate is 0.01;
(3) solution A and B are uniformly mixed, the volume ratio of dispersion liquid A and dispersion liquid B is 0.1, during mixing, dispersion liquid A is dropwise added in dispersion liquid B, obtain transparent precursor liquid, dropwise add trimethylamine, trimethylamine and butyl titanate mole be 0.01, with nitric acid regulator solution pH value be 3, after stirring at room 1h, solution is warmed up to 90 ℃, adopt water under high pressure thermal response to heat-treat 1h, the solution obtaining obtain nitrogen modified titanium dioxide sol through ultrasonic dispersion, solid concentration be 0.1 grams per liter/liter, wherein nitrogen content accounts for the 0.1wt% of solid, titanium dioxide nano-particle is the crystal formation that mixes of anatase and brockite.
The nitrogen modified titanium dioxide sol preparing can be applicable to deodorizing, the sterilization of family, hospital and public arena, be applied to the self-cleaning functionalization of exterior decoration, exterior wall, glass surface, be applied to the clean functionalization of clean surfaces of the clothes such as cotton, silk, wool, staple fibre, be applied to the removal of decomposing the persistent organic pollutants in liquid phase or gas phase, and be applied to photocatalysis heavy-metal ion removal, photochemical catalyzing, photo catalytic reduction nitrate or fixed nitrogen.
Embodiment 6
Preparation has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, comprises the following steps:
(1) tetraethyl titanate is dispersed in the tert-butyl alcohol and obtains uniform dispersion liquid A, the volume ratio of tetraethyl titanate and the tert-butyl alcohol is 1;
(2) stabilizing agent EDTA is dispersed in the dilute nitric acid solution that concentration is 1mol/L, the mol ratio of stabilizing agent EDTA and tetraethyl titanate is 10, obtains uniform dispersion liquid B;
(3) solution A and B are uniformly mixed, the volume ratio of dispersion liquid A and dispersion liquid B is 0.1, during mixing, dispersion liquid B is dropwise added in dispersion liquid A, obtain transparent precursor liquid, dropwise add diethylenetriamines, with nitric acid regulator solution pH value be 12, after stirring at room 72h, solution is warmed up to 160 ℃, adopts the stirring and refluxing reaction under normal pressure to heat-treat 72h, the solution obtaining obtain nitrogen modified titanium dioxide sol through ultrasonic dispersion, and solid concentration is 100 grams per liters; Wherein nitrogen content accounts for the 10wt% of solid, and titanium dioxide nano-particle is the crystal formation that mixes of anatase and rutile ore.
The nitrogen modified titanium dioxide sol preparing can be applicable to deodorizing, the sterilization of family, hospital and public arena, be applied to the self-cleaning functionalization of exterior decoration, exterior wall, glass surface, be applied to the clean functionalization of clean surfaces of the clothes such as cotton, silk, wool, staple fibre, be applied to the removal of decomposing the persistent organic pollutants in liquid phase or gas phase, and be applied to photocatalysis heavy-metal ion removal, photochemical catalyzing, photo catalytic reduction nitrate or fixed nitrogen.
Claims (8)
1. preparation has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, the method comprises the following steps:
(1) organic titanic compound is dispersed in and in alcohol, obtains uniform dispersion liquid A;
(2) stabilizing agent is dispersed in salpeter solution, obtains uniform dispersion liquid B;
(3) solution A and B are uniformly mixed, obtain transparent precursor liquid; Dropwise add organic amine, with nitric acid regulator solution pH value be 3-12, after stirring at room 1-72h, solution is warmed up to 90-160 ℃ and heat-treats 1-72h, the solution obtaining obtain nitrogen modified titanium dioxide sol through ultrasonic dispersion.
2. preparation according to claim 1 has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, described organic titanic compound is butyl titanate, tetraisopropyl titanate or tetraethyl titanate; Described alcohol is all alcohol that the carbon number of methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or the tert-butyl alcohol is less than 5; The volume ratio of described organic titanic compound and alcohol is 0.01-1.
3. preparation according to claim 1 has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, described stabilizing agent is glycolic, acetylacetone,2,4-pentanedione, EDTA or citric acid, and the mol ratio of stabilizing agent and organic titanic compound is between 0.01-10.
4. preparation according to claim 1 has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, the concentration of described salpeter solution is 0.01-1mol/L, the volume ratio of dispersion liquid A and dispersion liquid B is 0.1-10, during mixing, dispersion liquid A is dropwise added in dispersion liquid B, or dispersion liquid B is dropwise added in dispersion liquid A, or by dispersion liquid A and dispersion liquid B rapid mixing.
5. preparation according to claim 1 has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, described organic amine is diethylamine, triethylamine, trimethylamine, diethylenetriamines, propane diamine or triethylene tetramine, organic amine and organic titanic compound mole be 0.01-10.
6. preparation according to claim 1 has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, described heat treatment is the stirring and refluxing reaction under water under high pressure thermal response or normal pressure.
7. preparation according to claim 1 has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, the solid concentration of described nitrogen modified titanium dioxide sol is 0.1 grams per liter-100 grams per liter; Wherein nitrogen content accounts for the 0.1-10wt% of solid, and titanium dioxide nano-particle is the crystal formation that mixes that mixes crystal formation or anatase and brockite of anatase type or anatase and rutile ore.
8. preparation according to claim 1 has the method for the nitrogen modified titanium dioxide sol of visible light catalysis activity, it is characterized in that, described nitrogen modified titanium dioxide sol can be applicable to family, the deodorizing of hospital and public arena, sterilization, be applied to exterior decoration, exterior wall, the self-cleaning functionalization of glass surface, be applied to cotton, silk, wool, the clean functionalization of clean surfaces of the clothes such as staple fibre, be applied to the removal of decomposing the persistent organic pollutants in liquid phase or gas phase, and be applied to photocatalysis heavy-metal ion removal, photochemical catalyzing, photo catalytic reduction nitrate or fixed nitrogen.
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| CN103055837B (en) * | 2013-01-14 | 2015-05-20 | 中国科学院生态环境研究中心 | Titanium dioxide catalyst for photo-catalytic oxidation NOx (nitric oxide) in visible light, and preparation method as well as application of titanium dioxide |
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| CN107570193A (en) * | 2017-08-25 | 2018-01-12 | 华南理工大学 | One kind has high visible-light activity N doping N TiO2Preparation method |
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