CN101214432A - Supported type titanium dioxide visible light photocatalyst - Google Patents
Supported type titanium dioxide visible light photocatalyst Download PDFInfo
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- CN101214432A CN101214432A CNA2007101730586A CN200710173058A CN101214432A CN 101214432 A CN101214432 A CN 101214432A CN A2007101730586 A CNA2007101730586 A CN A2007101730586A CN 200710173058 A CN200710173058 A CN 200710173058A CN 101214432 A CN101214432 A CN 101214432A
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Abstract
The invention relates to a titanium dioxide photocatalyst with photocatalytic activity of visible light. The titanium dioxide photocatalyst is a load catalyst with one nano titanium dioxide in metals in I B to VIIB and VIII of the doping element periodic table as the active component, and one of the metals in I B to VIIB and VIII of Period 5 and 6 in the element periodic table as the carrier. The titanium dioxide photocatalyst prepared by the invention has quite high quantum yield of titanium dioxide photocatalytic reaction and wider light response range (i.e. ''red shift'' of the light response range), which lays foundation for the titanium dioxide photocatalytic technology to enter into the stage of practicality.
Description
Technical field
The present invention relates to a kind of titanium dioxide (TiO
2) photochemical catalyst, specifically, relate to a kind of TiO with visible light photocatalysis active
2Photochemical catalyst.
Background technology
Photocatalysis technology is an emerging green technology that progressively grows up from the seventies in 20th century.It utilizes the conductor oxidate material can be subjected to the characteristic of activation at the illumination lower surface, utilizes luminous energy oxidation Decomposition organic matter, reducing heavy metal ion, kill bacteria and elimination peculiar smell effectively.Because it is simple to operate that it has, only need to carry out at normal temperature and pressure; And can thoroughly destroy pollutant in the empty G﹠W, making it permineralization is innocuous substances such as carbon dioxide, water, avoids advantages such as secondary pollution, is a kind of green environment improvement technology with broad prospect of application.At present, the multiphase photocatalysis material of academia's research photocatalytic degradation environmental contaminants mostly concentrates on metal oxide and the metal sulfide semiconductor material, as titanium dioxide, zinc oxide, tungstic acid, tin ash, di-iron trioxide and cadmium sulfide etc.In numerous conductor photocatalysis materials, titanium dioxide is because of characteristics such as its catalytic activity height, safety non-toxic, chemical property are stable, with low cost, is acknowledged as the environment-friendly type catalysis material of the tool exploitation future in environment pollution treatment field.
Yet the energy gap of titanium dioxide is 3.2eV, light abstraction width only be confined to ultraviolet region (wavelength for＜380nm).But this part light does not still reach and shines 5% of ground surface sunlight gross energy, has therefore limited its utilization to solar energy greatly.In addition, the quantum yield of optically catalytic TiO 2 reaction is low, because it is compound very easily again and cause inactivation to be subjected to produce after the light radiation excitation state valence band hole and conduction band electron.Therefore, improving the quantum yield of optically catalytic TiO 2 reaction and the photoresponse scope of prolongation titanium dioxide and become the key that the optically catalytic TiO 2 technology enters the practicality stage, also is the technical issues that need to address of the present invention simultaneously.
Summary of the invention
To titanium dioxide (TiO
2) carry out nonmetally or metal-doped, can in titanium dioxide crystal lattice, introduce impurity energy level, reduce TiO
2Energy gap; With TiO
2Be carried on metal, can more effectively carry out electronics and shift, reduce the compound of electronics-hole, prolong the life-span in hole, thereby improve the quantum yield of light-catalyzed reaction.In view of the above, the present inventor provides a kind of have visible light photocatalysis active and TiO with practical value after a large amount of experiments
2Photochemical catalyst.
The said titanium dioxide optical catalyst of the present invention, it is an active component with nano titanium oxide a kind of in the metal that IB～VIIB and VIII were comprised in the doped chemical periodic table (particle diameter of titanium dioxide is less than 100nm), with a kind of in the periodic table of elements the 5th and IB～VIIB and VIII were comprised in the 6th cycle the metal be the loaded catalyst of carrier.
In optimized technical scheme of the present invention, with nano titanium oxide a kind of in the metal that IB～VIIB was comprised in the doped chemical periodic table is active component, the molal quantity that with the mole percent is titanium in measurement unit, the nano titanium oxide is to calculate benchmark, and said metal doping amount is 0.1%～2%; Preferred doping metals is a kind of in the metal that VB comprised in the periodic table of elements; Best doping metals is vanadium metal (V).
In another optimal technical scheme of the present invention, with a kind of in the periodic table of elements the 5th and VIII was comprised in the 6th cycle the metal be carrier, the gross weight (the weight sum of active component and carrier) that with the percetage by weight is measurement unit, said catalyst is for calculating benchmark, and the load capacity of said metal (carrier) is 0.5%～8%; More preferably metal platinum (Pt) or Metal Palladium (Pd) are as the carrier of the said catalyst of the present invention.
The key step of preparation the present invention said titanium dioxide optical catalyst is: at first make by sol-gel process and hydrothermal crystallizing and be mixed with a kind of nano titanium oxide in the metal that IB～VIIB and VIII comprise; The method (specifically referring to Journal of Physics Chemistry B 106 (2002) 7635) that adopts deposition-precipitation (urea) then is carried on prepared nano titanium oxide in the periodic table of elements the 5th and IB～VIIB and VIII comprised in the 6th cycle the metal a kind of, promptly gets object.
Description of drawings
Mix nano titanium oxide photocatalytic activity schematic diagram under visible light of vanadium metals of different amounts of Fig. 1,
Wherein: transverse axis is a vanadium metal different theories doping, and the longitudinal axis is the nano titanium oxide of the vanadium metals of the different amounts of the mixing degradation rate to 10mg/l methyl orange after 2.5 hours.
Fig. 2 different catalysts is the photocatalytic activity schematic diagram under visible light,
Wherein: a in the transverse axis is pure TiO
2Catalyst, b are 0.57%V-TiO
2Catalyst, c are 2%Pt/TiO
2Catalyst, d are 2%Pt/0.57%V-TiO
2Catalyst; The longitudinal axis is that different catalysts is to 2.5 hours degradation rate of 20mg/l methyl orange solution.
The specific embodiment
With doping metals vanadium (V) and loaded metal platinum (Pt) is example, sets forth the method for preparing the said titanium dioxide optical catalyst of the present invention.Said preparation method comprises the steps:
(1) alkyl titanate and absolute ethyl alcohol are mixed, get mixture A; Ethanol, water, vanadium chloride or nitric acid vanadium and nitric acid are mixed, get mixture B.Is that 3～4 droplets/second speed is added drop-wise to by among the continuous stirred mixture B with mixture A to drip speed.Dropwise, under 20 ℃～40 ℃ conditions, kept 3～5 hours, get vitreosol.Gained colloidal sol was placed 1～2 day under 20 ℃～60 ℃ conditions, got wet gel.With the gained wet gel after hydrothermal crystallizing (temperature of hydrothermal crystallizing is that 100 ℃～240 ℃, time are 5-30 hour), washing and drying, the nano titanium oxide that mixes of vanadium metal.
Wherein, said alkyl titanate is butyl titanate, metatitanic acid isopropyl ester, metatitanic acid second fat and/or metatitanic acid formicester, and the consumption of vanadium chloride or nitric acid vanadium can get by theoretical calculating according to the molal quantity (combining target doping) of titanium in the used alkyl titanate.
(2) behind the method loaded metal platinum (" platinum source " is water miscible platinum salt) of the nano titanium oxide that will mix by document Journal of Physics ChemistryB 106 (2002) 7635 described depositions-precipitation (urea), get object by the vanadium metal that step (1) makes.
The titanium dioxide optical catalyst that the present invention is prepared, it has the quantum yield and the more wide in range photoresponse scope (being photoresponse scope " red shift ") of higher optically catalytic TiO 2 reaction, lays a good foundation for the optically catalytic TiO 2 technology enters the practicality stage.
The present invention is further elaborated below by embodiment.Protection scope of the present invention is not limited by the cases cited.
Said in embodiment or the Comparative Examples below " investigation photocatalytic activity " is meant sample characterized the degradation and decolorization situation of methyl orange solution.Specific operation process is as follows: the sample that takes by weighing 0.06g, measure the certain density methyl orange solution of 60ml (the pH value of solution value is 6.4-6.7) in teat glass, put into magnetic stir bar again, made suspension in ultrasonic 10 minutes, place on the magnetic stirring apparatus pre-absorption to make it to reach the adsorption-desorption balance in 30 minutes in test tube, sampling is carried out light-catalyzed reaction then as the light degradation initial concentration under 1000W iodine-tungsten lamp (JB420 type filter plate elimination ultraviolet light).Reacting took a sample after 2.5 hours places centrifuge tube centrifugal, gets supernatant liquor again and tests its absorbance with the ultraviolet-visible diffuse reflection spectrum, calculates its degradation rate.
Embodiment
The preparation of transient metal doped, noble metal load nano-titanium dioxide:
With 6ml butyl titanate and 17ml absolute ethyl alcohol mix solution A; With the 34ml absolute ethyl alcohol, 0-1.6ml water, 1.6-0ml 0.1175M vanadium chloride solution (vanadium chloride solution+water=1.6ml), 0.4ml the mixed solution B that gets of nitric acid, then A is added drop-wise in the solution B that is constantly stirred with the speed of 3d/s, after dropwising, continues reaction and got vitreosol in 0.5 hour, colloidal sol was transferred in 40 ℃ of water-baths gel 24 hours, wet gel is directly changed over to has in the teflon-lined autoclave 180 ℃ of hydrothermal crystallizings 10 hours.Then precipitate with deionized water is washed be placed on to the neutrality in the IR bake after dry 12 hours the titania-doped sample of vanadium.Change the addition of vanadium chloride, make the titanium dioxide of different vanadium doping contents, divide to be designated as 0.1%V-TiO
2, 0.3%V-TiO
2, 0.5%V-TiO
2, 0.57%V-TiO
2, 0.7%V-TiO
2, 0.9%V-TiO
2And 2.0%V-TiO
2Investigate the visible light photocatalysis active of different vanadium dopings, the results are shown in Figure 1.As shown in Figure 1: 0.57%V-TiO
2Visible light activity the highest.Therefore choosing this sample carries out the noble metal load.The method that adopts document Journal ofPhysics Chemistry B 106 (2002) 7635 described depositions-precipitation (urea) is to the above-mentioned 0.57%V-TiO that makes
2The load gold.The platinum load capacity is 2%, and the sample note is 2%Pt/0.57%V-TiO
2
Comparative Examples
The preparation of noble metal load nano-titanium dioxide:
With 6ml butyl titanate and 17ml absolute ethyl alcohol mix solution A; With the 34ml absolute ethyl alcohol, 1.6ml water, 0.4ml the mixed solution B that gets of nitric acid, then A is added drop-wise in the solution B that is constantly stirred with the speed of 3d/s, after dropwising, continue reaction 0.5 hour vitreosol, colloidal sol was transferred in 40 ℃ of water-baths gel 24 hours, wet gel directly changed over to have in the teflon-lined autoclave 180 ℃ of hydrothermal crystallizings 10 hours.Then precipitate with deionized water is washed be placed on to the neutrality in the IR bake after dry 12 hours the pure titinium dioxide sample, note is pure TiO
2The method that adopts document Journal ofPhysics Chemistry B 106 (2002) 7635 described depositions-precipitation (urea) then is to the above-mentioned pure titinium dioxide load platinum that makes.Platinum theoretical negative carrying capacity is 2%, and the sample note is 2%Pt/TiO
2
Get by embodiment and Comparative Examples and prepare pure TiO
2(a), 0.57%V-TiO
2(b), 2%Pt/TiO
2(c) and 2%Pt/0.57%V-TiO
2(d) sample is investigated its visible light photocatalysis active, the results are shown in Figure 2.As shown in Figure 2: the photocatalytic activity of sample d is the highest.
Claims (7)
1. titanium dioxide optical catalyst, it is characterized in that, it is an active component with nano titanium oxide a kind of in the metal that IB～VIIB and VIII were comprised in the doped chemical periodic table for said titanium dioxide optical catalyst, with a kind of in the periodic table of elements the 5th and IB～VIIB and VIII were comprised in the 6th cycle the metal be the loaded catalyst of carrier.
2. as the said titanium dioxide optical catalyst of claim 1, it is characterized in that, be active component wherein with nano titanium oxide a kind of in the metal that IB～VIIB was comprised in the doped chemical periodic table, the molal quantity that with the mole percent is titanium in measurement unit, the nano titanium oxide is to calculate benchmark, and said metal doping amount is 0.1%～2%.
3. as the said titanium dioxide optical catalyst of claim 2, it is characterized in that wherein the metal that is mixed is a kind of in the metal that VB comprised in the periodic table of elements.
4. as the said titanium dioxide optical catalyst of claim 3, it is characterized in that wherein the metal that is mixed is a vanadium metal.
5. as the said titanium dioxide optical catalyst of claim 1, it is characterized in that, wherein with a kind of in the periodic table of elements the 5th and VIII was comprised in the 6th cycle the metal be carrier, the gross weight that with the percetage by weight is measurement unit, said catalyst is to calculate benchmark, and the load capacity of said metal is 0.5%～8%.
6. as the said titanium dioxide optical catalyst of claim 5, it is characterized in that wherein the metal as carrier is metal platinum or Metal Palladium.
7. as any said titanium dioxide optical catalyst in the claim 1～6, it is characterized in that said titanium dioxide optical catalyst is an active component with the nano titanium oxide of doping 0.57mol% vanadium metal, is carrier with the metal platinum.
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| CNA2007101730586A CN101214432A (en) | 2007-12-26 | 2007-12-26 | Supported type titanium dioxide visible light photocatalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008247A (en) * | 2011-05-04 | 2017-08-04 | 斯图尔特·本森·阿沃雷特 | Titanium dioxide optical catalyst composition and its application |
| CN108993538A (en) * | 2018-07-28 | 2018-12-14 | 天津大学 | A kind of preparation method of rhenium disulfide nanometer sheet/titanium dioxide nanofiber composite photocatalyst material |
-
2007
- 2007-12-26 CN CNA2007101730586A patent/CN101214432A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008247A (en) * | 2011-05-04 | 2017-08-04 | 斯图尔特·本森·阿沃雷特 | Titanium dioxide optical catalyst composition and its application |
| CN108993538A (en) * | 2018-07-28 | 2018-12-14 | 天津大学 | A kind of preparation method of rhenium disulfide nanometer sheet/titanium dioxide nanofiber composite photocatalyst material |
| CN108993538B (en) * | 2018-07-28 | 2021-07-06 | 天津大学 | Preparation method of rhenium disulfide nanosheet/titanium dioxide nanofiber composite photocatalytic material |
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Open date: 20080709 |