CN102764649B - Metal-silver-supported titanium dioxide photocatalyst and preparation method thereof - Google Patents
Metal-silver-supported titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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- CN102764649B CN102764649B CN201210234760.XA CN201210234760A CN102764649B CN 102764649 B CN102764649 B CN 102764649B CN 201210234760 A CN201210234760 A CN 201210234760A CN 102764649 B CN102764649 B CN 102764649B
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Abstract
The invention discloses a metal-silver-supported titanium dioxide photocatalyst and a preparation method thereof. The photocatalyst material is composed of metal-silver-supported titanium dioxide microspheres, wherein the diameter of the titanium dioxide microspheres is 300-500nm; the supported metal silver is dispersed in the titanium dioxide microspheres in a bulk phase homogenization manner; the diameter of the metal silver particles is 5-15nm; and the photocatalyst material has very high photocatalysis efficiency for simulated organic pollutant rhodamine B in water body under the irradiation of ultraviolet and visible light. The preparation method is simple in process, safe to operate and low in cost; and all the used reagents are cheap and accessible, and are free of substances poisonous/harmful to human body or environment.
Description
Technical field
The invention belongs to composite preparing technical field, relate to a kind of titanium dioxide based photocatalytic material, be specifically related to a kind of argent load type titania photocatalyst, the invention still further relates to the preparation method of this argent load type titania photocatalyst.
Background technology
In recent years titanium dioxide semiconductor catalysis material because of its cheapness having, be easy to get, the characteristic development such as nontoxic, stable chemical nature, anti-photoetch are strong rapidly, and obtain huge economic benefit in practical application area such as water pollution control, air cleaning and anti-bacteria ceramics.But, TiO in actual application
2photocatalysis degradation organic contaminant exists that photo-generated carrier recombination rate is high, quantum yield is low and itself can not effectively utilize the shortcomings such as visible ray compared with wide band gap and become the bottleneck of its large-scale industrial application of restriction.
Research shows, modifies TiO with nano-noble metal material
2can promote effective separation of electron-hole Deng conductor photocatalysis material, improve photocatalytic activity, the service time of extending catalyst.After its area load nano metal material, due to metal and semiconductor TiO
2there is different fermi levels, in light-catalyzed reaction process, semiconductor TiO
2valence band electronics is by induced transition to empty conduction band, and because the effect of Fermi level, electronics will finally transit to fermi level, thereby make TiO
2hole-duplet occurs effectively to separate, and forming semiconductor valence band will be take hole as main, and Fermi level is take electronics as main system; In photocatalytic process, the organic group (hydroxyl, carboxyl) that is adsorbed onto semiconductor surface is oxidized with valence band hole generation redox reaction, simultaneously will accept the electronics that fermi level provides as the group of electron acceptor and be reduced, improving light-catalyzed reaction efficiency with this.The load of metal simultaneously can also improve the effective absorption of TiO 2-base optical catalyst material to visible ray, and its range of application is expanded to visible region.
The existing method of preparing argent load type titania photocatalyst material mainly contains electronation, light deposition and high-temperature calcination three classes, (1) chemical reduction method, the method of mainly reducing by the reduction of silver-colored source precursor solution dipping, the reduction of high energy light source irradiation or reducing agent, but its efficiency is lower, not easy to operate; (2) high-temperature calcination, mainly by slaine is decomposed in hot environment, and realizes the apposition growth of metal nanoparticle at titanium dioxide surface, this method power consumption is high and be difficult for realizing the uniform load of noble metal; (3) Photodeposition, mainly adopts the light source irradiation precious metal salt of different-energy, and it is decomposed, and reaches the effect of deposition, and this method is loaded down with trivial details, it is strict that reaction condition is required.
Summary of the invention
The object of this invention is to provide a kind of argent load type titania photocatalyst material, realized argent nano particle at TiO
2uniform load on microballoon, and the particle diameter of titanium dioxide and argent is controlled, and the reagent using is all cheap and easy to get, and does not contain human body or environment poisonous and harmful substances.
Another object of the present invention is to provide the preparation method of above-mentioned argent load type titania photocatalyst.
The technical solution adopted in the present invention is, a kind of argent load type titania photocatalyst, this photocatalyst material is made up of the titanium dioxide microballoon sphere of argent load, wherein the diameter of titanium dioxide microballoon sphere is 300 ~ 500nm, it is mutually dispersed that the argent of institute's load is body in titanium dioxide microballoon sphere, and the particle diameter of metallic silver particles is 5 ~ 15nm.
Another technical scheme of the present invention is, a kind of method of preparing argent load type titania photocatalyst, the photocatalyst material preparing, titanium dioxide microballoon sphere by argent load forms, wherein the diameter of titanium dioxide microballoon sphere is 300 ~ 500nm, it is mutually dispersed that the argent of institute's load is body in titanium dioxide microballoon sphere, and the particle diameter of metallic silver particles is 5 ~ 15nm;
Specifically implement according to following steps,
Step 1: be that the inorganic salt solution that 1-2:300 is 0.1 ~ 1.0mmol/L by molar concentration joins in absolute ethyl alcohol according to volume ratio, magnetic agitation 20min, slowly splash into tetrabutyl titanate, the volume ratio of tetrabutyl titanate and inorganic salt solution is 1-2:5.4, vigorous stirring reaction 10min, ageing 1 ~ 6h, centrifugation is also cleaned successively by absolute ethyl alcohol and deionized water, obtains pure white powder;
Step 2: be that the pure white powder that 1/400-1/600g/ml makes step 1 is dispersed in absolute ethyl alcohol according to quality-volumetric concentration, ultrasonic dispersion 20min, adding wherein concentration is the AgNO of 0.1 ~ 1.5g/100mL
3solution, AgNO
3the volume ratio of solution and absolute ethyl alcohol is 1:2-12, and under 30 ~ 50 ℃ of conditions, temperature constant magnetic stirring, to solution evaporate to dryness, obtains sepia powder;
Step 3: the sepia powder that step 2 is obtained is placed in Muffle furnace in air atmosphere calcination processing, makes argent load type titania photocatalyst.
Feature of the present invention is also,
Calcination processing in step 3 wherein, temperature increasing schedule is: before 300 ℃, heating rate is 2 ℃/min, and 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cools to subsequently room temperature.
Inorganic salt solution in step 1 is wherein selected the one or more kinds of mixtures in LiCl, KCl or NaCl.
The invention has the beneficial effects as follows: successfully prepared a kind of argent load type titania photocatalyst material, realized argent nano particle at TiO
2uniform load on microballoon, and the particle diameter of titanium dioxide and argent is controlled, and the reagent using is all cheap and easy to get, and does not contain human body or environment poisonous and harmful substances.In addition, this photocatalyst material is simulated organic pollution rhodamine B in to water body and is all had very high photocatalysis efficiency under Uv and visible light irradiates.
In the present invention, amount and the digestion time etc. of positive four butyl esters of metatitanic acid, absolute ethyl alcohol, inorganic salt solution, deionized water have considerable influence to the pattern of titanium dioxide microballoon sphere.Size and the pattern of addition, the constant temperature whipping temp etc. of liquor argenti nitratis ophthalmicus to silver-colored particle also has certain influence.
Accompanying drawing explanation
Fig. 1 be the argent load type titania photocatalyst different amplification that makes of the embodiment of the present invention 1 transmission electron microscope photo;
Fig. 2 is the X ray diffracting spectrum of the argent load type titania photocatalyst that makes of the embodiment of the present invention 2;
Fig. 3 is the degradation curve of argent load type titania photocatalyst rhodamine B in UV-irradiation goes down except water body of making of the embodiment of the present invention 3;
Fig. 4 is the degradation curve of argent load type titania photocatalyst rhodamine B in radiation of visible light goes down except water body of making of the embodiment of the present invention 3.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Argent load type titania photocatalyst of the present invention, titanium dioxide microballoon sphere by argent load forms, wherein the diameter of titanium dioxide microballoon sphere is 300 ~ 500nm, it is mutually dispersed that the argent of institute's load is body in titanium dioxide microballoon sphere, the particle diameter of metallic silver particles is 5 ~ 15nm, and this photocatalyst material is simulated organic pollution rhodamine B in to water body and all had very high photocatalysis efficiency under Uv and visible light irradiates.
The present invention prepares the method for argent load type titania photocatalyst, specifically carries out according to following steps:
Step 1: be that 0.1 ~ 1.0mmol/L inorganic salt solution joins in 300mL absolute ethyl alcohol by 1 ~ 2mL concentration, magnetic agitation 20min, slowly splash into the tetrabutyl titanate of 5.4mL, vigorous stirring reaction 10min, ageing 1 ~ 6h, centrifugation is also cleaned successively by absolute ethyl alcohol and deionized water, obtains a kind of pure white powder.
Step 2: prepared 0.1g step 1 pure white powder is dispersed in 40 ~ 60mL absolute ethyl alcohol, ultrasonic dispersion 20min, adding wherein 5 ~ 15mL concentration is the AgNO of 0.1 ~ 1.5g/100mL
3solution, under 30 ~ 50 ℃ of conditions, temperature constant magnetic stirring, to solution evaporate to dryness, obtains sepia powder.
Step 3: the brown powder that step 2 is obtained is placed in Muffle furnace in air atmosphere calcination processing.Wherein temperature increasing schedule is that before 300 ℃, heating rate is 2 ℃/min, and 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cools to subsequently room temperature, can make argent load type titania photocatalyst material.
Wherein in step 1, inorganic salt solution used can be a kind of or its mixture in LiCl, KCl and NaCl.
Embodiment 1
Be that 0.1mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.0mL concentration, magnetic agitation 20min, slowly splashes into the butyl titanate of 5.4mL, vigorous stirring reaction 10min, ageing 2h, centrifugal and clean successively by absolute ethyl alcohol and deionized water, obtain lily powder.Above-mentioned obtained pure white powder is dispersed in 50mL absolute ethyl alcohol, ultrasonic dispersion 20min, adding wherein 10mL concentration is the AgNO of 0.1g/100mL
3solution, under 35 ℃ of conditions, temperature constant magnetic stirring certain hour, to solution evaporate to dryness, obtains tan powder.Above-mentioned obtained brown powder is placed in to Muffle furnace in air atmosphere calcination processing.Wherein temperature increasing schedule is that before 300 ℃, heating rate is 2 ℃/min, and 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cools to subsequently room temperature, can obtain Ag-carried nanometer titanium dioxide photochemical catalyst.Fig. 1 be the argent load type titania photocatalyst different amplification that makes transmission electron microscope photo.
Embodiment 2
Be that 0.8mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.3mL concentration, magnetic agitation 20min, slowly splashes into the butyl titanate of 5.4mL, vigorous stirring reaction 10min, ageing 1h, centrifugal and clean successively by absolute ethyl alcohol and deionized water, obtain lily powder.Above-mentioned obtained pure white powder is dispersed in 40mL absolute ethyl alcohol, ultrasonic dispersion 20min, adding wherein 12mL concentration is the AgNO of 1.3g/100mL
3solution, under 40 ℃ of conditions, temperature constant magnetic stirring certain hour, to solution evaporate to dryness, obtains tan powder.Above-mentioned obtained brown powder is placed in to Muffle furnace in air atmosphere calcination processing.Wherein temperature increasing schedule is that before 300 ℃, heating rate is 2 ℃/min, and 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cools to subsequently room temperature, can obtain Ag-carried nanometer titanium dioxide photochemical catalyst.Fig. 2 is the X ray diffracting spectrum of the argent load type titania photocatalyst that makes.
Embodiment 3
Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 20min, slowly splashes into the butyl titanate of 5.4mL, vigorous stirring reaction 10min, ageing 3h, centrifugal and clean successively by absolute ethyl alcohol and deionized water, obtain lily powder.Above-mentioned obtained pure white powder is dispersed in 45mL absolute ethyl alcohol, ultrasonic dispersion 20min, adding wherein 14mL concentration is the AgNO of 0.8g/100mL
3solution, under 30 ℃ of conditions, temperature constant magnetic stirring certain hour, to solution evaporate to dryness, obtains tan powder.Above-mentioned obtained brown powder is placed in to Muffle furnace in air atmosphere calcination processing.Wherein temperature increasing schedule is that before 300 ℃, heating rate is 2 ℃/min, and 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cools to subsequently room temperature, can obtain Ag-carried nanometer titanium dioxide photochemical catalyst.Fig. 3 is the degradation curve of argent load type titania photocatalyst rhodamine B in UV-irradiation goes down except water body of making, and Fig. 4 is the degradation curve of argent load type titania photocatalyst rhodamine B in radiation of visible light goes down except water body of making.
Embodiment 4
Be that 0.2mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.8mL concentration, magnetic agitation 20min, slowly splashes into the butyl titanate of 5.4mL, vigorous stirring reaction 10min, ageing 5h, centrifugal and clean successively by absolute ethyl alcohol and deionized water, obtain lily powder.Above-mentioned obtained pure white powder is dispersed in 55mL absolute ethyl alcohol, ultrasonic dispersion 20min, adding wherein 5mL concentration is the AgNO of 0.2g/100mL
3solution, under 50 ℃ of conditions, temperature constant magnetic stirring certain hour, to solution evaporate to dryness, obtains tan powder.Above-mentioned obtained brown powder is placed in to Muffle furnace in air atmosphere calcination processing.Wherein temperature increasing schedule is that before 300 ℃, heating rate is 2 ℃/min, and 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cools to subsequently room temperature, can obtain Ag-carried nanometer titanium dioxide photochemical catalyst.
Be that 1.0mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 2.0mL concentration, magnetic agitation 20min, slowly splashes into the butyl titanate of 5.4mL, vigorous stirring reaction 10min, ageing 6h, centrifugal and clean successively by absolute ethyl alcohol and deionized water, obtain lily powder.Above-mentioned obtained pure white powder is dispersed in 60mL absolute ethyl alcohol, ultrasonic dispersion 20min, adding wherein 15mL concentration is the AgNO of 1.5g/100mL
3solution, under 45 ℃ of conditions, temperature constant magnetic stirring certain hour, to solution evaporate to dryness, obtains tan powder.Above-mentioned obtained brown powder is placed in to Muffle furnace in air atmosphere calcination processing.Wherein temperature increasing schedule is that before 300 ℃, heating rate is 2 ℃/min, and 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cools to subsequently room temperature, can obtain Ag-carried nanometer titanium dioxide photochemical catalyst.
Claims (3)
1. prepare the method for argent load type titania photocatalyst for one kind, it is characterized in that, the photocatalyst material preparing, titanium dioxide microballoon sphere by argent load forms, wherein the diameter of titanium dioxide microballoon sphere is 300～500nm, it is mutually dispersed that the argent of institute's load is body in titanium dioxide microballoon sphere, and the particle diameter of metallic silver particles is 5～15nm;
Specifically implement according to following steps,
Step 1: be that the inorganic salt solution that 1-2:300 is 0.1～1.0mmol/L by molar concentration joins in absolute ethyl alcohol according to volume ratio, magnetic agitation 20min, slowly splash into tetrabutyl titanate, the volume ratio of tetrabutyl titanate and inorganic salt solution is 1-2:5.4, vigorous stirring reaction 10min, ageing 1～6h, centrifugation is also cleaned successively by absolute ethyl alcohol and deionized water, obtains pure white powder;
Step 2: be that the pure white powder that 1/400-1/600g/ml makes step 1 is dispersed in absolute ethyl alcohol according to quality-volumetric concentration, ultrasonic dispersion 20min, adding wherein concentration is the AgNO of 0.1～1.5g/100mL
3solution, AgNO
3the volume ratio of solution and absolute ethyl alcohol is 1:2-12, and under 30～50 ℃ of conditions, temperature constant magnetic stirring, to solution evaporate to dryness, obtains sepia powder;
Step 3: the sepia powder that step 2 is obtained is placed in Muffle furnace in air atmosphere calcination processing, makes argent load type titania photocatalyst.
2. the method for preparing argent load type titania photocatalyst according to claim 1, it is characterized in that, calcination processing in described step 3, temperature increasing schedule is: before 300 ℃, heating rate is 2 ℃/min, 300 ℃ to 500 ℃ heating rates are 1 ℃/min, and in 500 ℃ of maintenances 2 hours, naturally cool to subsequently room temperature.
3. the method for preparing argent load type titania photocatalyst according to claim 1, is characterized in that, the inorganic salt solution in described step 1 is selected the one or more kinds of mixtures in LiCl, KCl or NaCl.
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| CN103394343B (en) * | 2013-08-16 | 2015-06-03 | 河海大学 | Preparation method and application of metal-doped titanium dioxide material |
| JP6510782B2 (en) * | 2014-09-18 | 2019-05-08 | 国立大学法人 筑波大学 | Photocatalyst, coating film and sterilization device |
| CN109529823A (en) * | 2018-12-07 | 2019-03-29 | 武汉工程大学 | A kind of silver carried titanium dioxide hollow sphere and preparation method thereof |
| CN109529832B (en) * | 2018-12-07 | 2021-10-12 | 武汉工程大学 | Silver-loaded titanium dioxide/yttrium oxide double-shell hollow sphere and preparation method thereof |
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