CN101856618A - Method for preparing platinum/semiconductor oxide catalyst having photo-thermal synergistic effect - Google Patents
Method for preparing platinum/semiconductor oxide catalyst having photo-thermal synergistic effect Download PDFInfo
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- chloroplatinic acid
- uviol lamp
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Abstract
The invention relates to a method for preparing a catalyst capable of degrading gaseous phase volatile organic pollutant. The method for preparing a platinum/semiconductor oxide catalyst having a photo-thermal synergistic effect comprises the steps of: 1) adding the semiconductor oxide into a solvent, 2) performing the ultrasonic processing for 1 to 2 hours, 3) adding chloroplatinic acid aqueous solution into the suspension of the semiconductor oxide, stirring at dark place and then stirring under light, 4) coating on the surface of an UV lamp, 5) drying and 6) utilizing the luminous energy and thermal energy emitted by the UV lamp to steam for 2 to 5 h under the mixture steam of water and alcohol, in order to catalytically reduce the chloroplatinic acid into nanometer platinum grain through the luminous energy, opening a gaseous phase catalytic reactor, going on illuminating for 1 to 3 h and volatilizing the residual alcohol and water. The method for preparing the product has simple technique, is easily industrialized, and is capable of efficiently photo-thermal concerted catalyzing to degrade the gaseous phase volatile organic pollutant, with high catalytic stability.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method of the gas phase volatile organic contaminant of degrading.
Background technology
At present, volatile organic matter gas (as: formaldehyde, benzene,toluene,xylene etc.) is the main component of indoor air pollutants and industry air pollution (as industries such as chemical industry, pharmacy, printing and dyeing, leathers), they produce harmful effect even cause serious consequence human health, it is the importance that influences the PE safe and sanitary, it also is the generation root of a lot of occupational diseases, therefore, develop a kind of catalyst of efficient, stable degraded gas phase volatile organic contaminant, be the difficult point in the environmental improvement always.
In the past few decades, people have studied a large amount of resolutions, and from the absorption method in past, bioanalysis goes so far as nearest photocatalysis technology.Studies have shown that, be catalyst with the conductor oxidate, utilize in the photocatalytic oxidation degradation place water organic pollution particularly waste water from dyestuff be efficient and simple method, wherein a TiO
2Catalyst is because its high activity, stability, characteristic such as inexpensive and nontoxic become an important technology handling organic pollution in the water.In recent years, the scholar of all circles is devoted to adopt the photocatalysis technology gas phase volatile organic contaminant that goes to degrade.Adopt slurry dipping, gel-sol technology with TiO among the China invention CN02112266.0
2Nano particle or film are carried on the woven wire, and itself and uviol lamp are formed catalytic reactor, pernicious gases such as the formaldehyde in the sealing storehouse, benzene series row can be eliminated, and its clearance is greater than 80%.China invention CN01134335.4 utilizes magnetron sputtering to form TiO on carriers such as glass, metal, pottery
2Photocatalysis film, this film is photocatalytic degradation pernicious gas such as formaldehyde, phenol etc. effectively.(Qiancheng Zhang, Fengbao Zhang et al.ChinaEnvironmental Science 2003,23 (6): 661～664.) the know clearly gas-phase photocatalysis degraded of benzene of research in a circulating photoreaction system such as Zhang.Although photocatalysis technology has been obtained certain effect, TiO in the application of gas-phase benzene catalytic degradation
2Photochemical catalyst rapid deactivation in photocatalytic process but is a problem that is difficult to overcome, and its main cause is that the intermediate product that produces in course of reaction is deposited on catalyst surface and can reduces its activity, makes the photochemical catalyst rapid deactivation and can't recycle.How to solve the rapid deactivation of photochemical catalyst, prolong the life-span of photochemical catalyst, improve its activity simultaneously and become problem demanding prompt solution.
In order to solve photochemical catalyst inactivation problem in the gas-phase photocatalysis reaction, and further improve the photochemical catalytic oxidation activity of benzene, people have carried out a large amount of experimental studies.Studies show that and in photochemical catalytic oxidation, add photocatalytic degradation catalytic activity (J.Jeong, K.Sekiguchi, W.Lee, K.Sakamoto, J.Photochem.Photobio.A2005,169,279. that ozone can obviously improve benzene and toluene; Yu K P, Grace W M.Appl.Catal.B, 2007,75 (1-2), 29-38.), but ozone equally also is a kind of pollutant, must have equipment for after-treatment to remove redundant ozone, just can reach effective pollution control.Also have research to invent the plasma of designing as the alternative traditional ultraviolet source of light source with plasma and drive photocatalytic system (B.Y.Lee, S.H.Park, S.C.Lee, M.Kang, S.J.Choung, Catal.Today, 2004,93-95,769.), this method can improve the catalytic degradation activity of benzene effectively, can also suppress TiO simultaneously
2The formation of surface intermediate product, but this appliance arrangement is somewhat expensive, is difficult to realize large-scale industrialization.Therefore develop a great problem that a kind of effective and inexpensive volatile organic contaminant degradation process method has become depollution of environment field.Invented a kind of preparation method in China's invention invention (200910272895.3) with semiconductor oxide catalyst of light heat synergetic action, this method is applied to the uviol lamp surface with semiconductor oxide catalyst, make full use of heat and luminous energy that the uviol lamp surface is given out, realized that the efficient photo-thermal concerted catalysis of gas phase volatile organic contaminant purifies.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action, this preparation method's technology is simple, be easy to industrialization, the platinum/semiconductor oxide catalyst of this method preparation is photo-thermal concerted catalysis degraded gas phase volatile organic contaminant efficiently, and catalytic stability is good.
To achieve these goals, the technical solution used in the present invention is: have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it is characterized in that it comprises the steps:
1) proportioning of pressing conductor oxidate and solvent is (0.1～2) g: (10～40) mL, choose conductor oxidate and solvent, and conductor oxidate is joined in the solvent, mix, obtain the suspension of conductor oxidate;
2) beaker that the suspension of conductor oxidate will be housed is positioned in the ultrasonic device, and ultrasonic processing 1～2 hour obtains the suspension of ultrasonic good conductor oxidate;
3) proportioning of pressing conductor oxidate and chloroplatinic acid aqueous solution is (0.1～2) g: (0.6～10) mL, choose chloroplatinic acid aqueous solution; Chloroplatinic acid aqueous solution is added in the suspension of ultrasonic good conductor oxidate, in the dark stirs 5～15min, under illumination, stir 5～15min then, obtain the suspension of chloroplatinic acid and conductor oxidate;
4) then the suspension of chloroplatinic acid and conductor oxidate is coated in the uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) dry under infrared lamp on the uviol lamp surface that will scribble chloroplatinic acid and conductor oxidate, makes solvent (as ethanol, the water) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid and conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding entry and ethanol, close the gas phase catalytic reaction device, open uviol lamp, the luminous energy and the heat energy that utilize uviol lamp to send, under the mixed vapour of water and ethanol, steam 2～5h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal, open the gas phase catalytic reaction device then, continue illumination 1～3h, make residual second alcohol and water volatilization, obtain having the platinum/semiconductor oxide catalyst of light heat synergetic action.
Described conductor oxidate is TiO
2, SnO
2, CeO
2, ZnO, CuO, Bi
2O
3, Fe
2O
3Or V
2O
5
Described solvent is the mixed solvent of any one or two kinds in water, the organic solvent, and two kinds is any proportioning when mixing.
Organic solvent is ethanol or acetone etc.
The frequency of described ultrasonic processing is 20～150KHz, and power is 100～1800W.
The concentration of chloroplatinic acid aqueous solution is 0.001～0.005mol/L (the best 0.0048mol/L of being).
The power of described uviol lamp is 4～1000W.
The volume proportion of water and ethanol is 10: 3～4 in the step 6), the addition of water and ethanol for the gas phase catalytic reaction body long-pending 0.001～10%.
Described catalyst is the Pt/TiO of different loads amount
2, Pt/SnO
2, Pt/CeO
2, Pt/ZnO, Pt/CuO, Pt/Bi
2O
3, Pt/Fe
2O
3Or Pt/V
2O
5Platinum/semiconductor oxide catalyst, load capacity (wt%) is 0.05%～5%.
Gas phase volatile organic contaminants such as the present invention's energy efficient degradation benzene, toluene, n-hexane or acetone, pollutant levels are 10～1 * 10
6Mg/m
3
The present invention is further invention on the basis of China's invention (200910272895.3), the small amounts of platinum nano particle is carried on the semiconductor oxide catalyst surface, and it is applied to the uviol lamp surface, adopt this method can increase substantially the catalytic purification efficient of gas phase volatile organic contaminant.
The invention has the beneficial effects as follows:
1) this preparation method's technology simple, be easy to industrialization.
2) the support type platinum/semiconductor oxide catalyst of this preparation method's preparation, can make full use of heat energy and luminous energy light intensity that the uviol lamp surface is given out, need not to use external heater just can realize that efficient photo-thermal concerted catalysis purifies the gas phase volatile organic contaminant.Photo-thermal concerted catalysis at this platinum/semiconductor oxide catalyst purifies in the reaction, it or not the simple combination of the thermocatalytic process of the photo-thermal concerted catalysis purification process of semiconductor oxide catalyst and loaded platinum catalyst, but there is a kind of new synergy between, this light heat synergetic action has greatly improved the catalytic activity of catalytic purification gas phase volatile organic contaminant, that is: oxygen molecule dissociates to adsorb on the nm Pt catalyst surface and forms the ADSORPTION STATE oxygen atom with high oxidation activity, thereby these ADSORPTION STATE oxygen atoms not only can the catalytic oxidation organic pollutant molecule be realized the heat catalytic oxidation function of conventional loaded platinum catalyst, but also overflow to the semiconductor catalyst surface, the photo-thermal concerted catalysis oxidizing process of remarkable accelerated semiconductor oxide catalyst.
3) prepared platinum/semiconductor oxide catalyst can efficient catalytic degraded benzene, gas phase volatile organic contaminants such as toluene, n-hexane, acetone, its photo-thermal concerted catalysis purifies the active not only active and thermocatalytic purification activity far above simple light catalytic purifying, and purifies active far above the photo-thermal concerted catalysis of semiconductor oxide catalyst; The photo-thermal concerted catalysis excellent in stability of this platinum/semiconductor oxide catalyst, inactivation not yet after the reaction of photo-thermal concerted catalysis oxidation gas phase organic matter repeatedly.
4) load capacity of noble metal platinum is low in the platinum/semiconductor oxide catalyst of this method preparation, because its catalytic purification efficient efficiently, the catalyst use amount is few, thereby catalyst is with low cost.
Description of drawings
Fig. 1 is the embodiment of the invention 1 resulting 0.1wt%Pt/TiO with light heat synergetic action
2Catalyst is used 0.1wt%Pt/TiO in degraded benzene (be the A among Fig. 1, be photo-thermal catalytic degradation benzene), the Comparative Examples 1
20.1wt%Pt/TiO in photocatalytic degradation benzene (be the B among Fig. 1, be photocatalytic degradation benzene) and the Comparative Examples 2
2Catalyst is at thermocatalytic degrade benzene (be the C among Fig. 1, be thermocatalytic degraded benzene) degradation rate and time chart.
Fig. 2 is embodiment 1 resulting 0.1wt%Pt/TiO with light heat synergetic action
2Catalyst is used, the degradation rate of photo-thermal concerted catalysis Oxybenzene and the graph of a relation of catalyst circulation access times.
Fig. 3 is embodiment 2 resulting 0.5wt%Pt/TiO with light heat synergetic action
2Catalyst is at photo-thermal concerted catalysis and thermocatalytic comparison diagram.
Fig. 4 is embodiment 3 resulting 1.0wt%Pt/TiO with light heat synergetic action
2Catalyst is at photo-thermal concerted catalysis and thermocatalytic comparison diagram.
Fig. 5 is embodiment 6 resulting 0.5wt%Pt/Fe with light heat synergetic action
2O
3Catalyst is at photo-thermal concerted catalysis and thermocatalytic comparison diagram.
Fig. 6 is embodiment 7 resulting 0.5wt%Pt/CeO with light heat synergetic action
2Catalyst is at photo-thermal concerted catalysis and thermocatalytic comparison diagram.
Fig. 7 is embodiment 8 resulting 0.5wt%Pt/V with light heat synergetic action
2O
5Catalyst is at photo-thermal concerted catalysis and thermocatalytic comparison diagram.
Fig. 8 is embodiment 9 resulting 0.5wt%Pt/Bi with light heat synergetic action
2O
3Catalyst is at photo-thermal concerted catalysis and thermocatalytic comparison diagram
The specific embodiment
Further set forth substantive distinguishing features of the present invention and obvious improvement below in conjunction with embodiment, but the cited case does not limit protection domain of the present invention.
Embodiment 1:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with TiO
2, water is raw material, takes by weighing the TiO of 0.5g
2Powder joins in the 10mL water, and both are mixed, and obtains TiO
2Suspension;
2) TiO will be housed
2The beaker of suspension be positioned in the ultrasonic device, ultrasonic processing 2 hours obtains ultrasonic good TiO
2Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 0.663mL is added to above-mentioned ultrasonic good TiO
2Suspension in, in the dark stir 10min, stir 10min in illumination then, obtain chloroplatinic acid and TiO
2Suspension; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and TiO
2Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (TiO
2) the uviol lamp surface under infrared lamp, dry, make solvent (as the water) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3m L ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 0.1wt%Pt/TiO of light heat synergetic action
2Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 1:
With the embodiment of the invention 1 resulting 0.1wt%Pt/TiO with light heat synergetic action
2Catalyst is applied to catalytic degradation benzene, and its experimental procedure is as follows: with the 0.1wt%Pt/TiO that scribbles of the embodiment of the invention 1 gained
2The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 40uL benzene, the initial concentration of benzene is 4863mg/m
3, open uviol lamp, the active testing that utilizes luminous energy that this uviol lamp sends and heat energy (the lamp surface temperature is 240 ℃) to carry out photo-thermal concerted catalysis degraded benzene, degradation rate and time relation are seen the A among Fig. 1, the complete degradation time of benzene is 30min.
Comparative Examples 1: with the TiO of 0.5g
2Powder joins in the beaker that 10mL water is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 0.663mL is added to ultrasonic good TiO
2Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in reactor wall, dry with infrared lamp in the process that is coated with; The reactor that scribbles chloroplatinic acid/conductor oxidate is dried under infrared lamp, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 0.1wt%Pt/TiO
2Catalyst.
Reactor is placed on carries out photocatalytic degradation benzene active testing in the ice-water bath, when active testing, inject 40uL benzene in 7.2L gas phase catalytic reaction device, the initial concentration of benzene is 4863mg/m
3, light source is the 125W uviol lamp, and the reactor wall catalyst temperature is a room temperature, and degradation rate and time relation are seen the B among Fig. 1, and the degradation rate of benzene in 30min only is 22.1%.
Comparative Examples 2: with the TiO of 0.5g
2Powder joins in the beaker that 10mL water is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 0.663mL is added to ultrasonic good TiO
2Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in the culture dish, dry with infrared lamp in the process that is coated with; Then this culture dish is placed catalytic reactor, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 0.1wt%Pt/TiO
2Catalyst.Close uviol lamp then, reactor is placed the catalytic activity of measuring this catalyst thermocatalytic degraded benzene on the electric hot plate, inject 40uL benzene in 7.2L gas phase catalytic reaction device, the initial concentration of benzene is 4863mg/m
3, under no optical condition, make the temperature of catalyst remain on 240 ℃ (uviol lamp surface temperatures), degradation rate and time relation are seen the C among Fig. 1, the degradation rate of benzene in 30min only is 47.3%.
By active comparison diagram 1 as can be known, the degradation rate constant (0.19378min of photo-thermal concerted catalysis oxidation
-1) be the degradation rate constant (0.02445min of heat catalytic oxidation
-1) 7.9 times; Be the degradation rate constant (0.00734min of photochemical catalytic oxidation
-1) 26.4 times; Be the degradation rate constant and the (0.03179min of heat catalytic oxidation and photochemical catalytic oxidation
-1) 6.1 times.Shown 0.1wt%Pt/TiO
2The photo-thermal concerted catalysis oxidation of catalyst is to the efficient catalytic degradation capability of benzene.
Application example 2:
With the embodiment of the invention 1 resulting 0.1wt%Pt/TiO with light heat synergetic action
2Catalyst is applied to the cyclic test of catalytic degradation benzene, and its experimental procedure is as follows: with the 0.1wt%Pt/TiO that scribbles of the embodiment of the invention 1 gained
2The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 40uL benzene, the initial concentration of benzene is 4863mg/m
3Open uviol lamp, benzene begins catalytic degradation, behind the 30min, close this uviol lamp, and open reactor and make product in the fresh air metathesis reactor, close reactor, again to wherein injecting 40ul benzene, after the repetition above-mentioned steps 40 times, benzene catalysis degradation modulus when 30min still is 100%, and the result has shown the photo-thermal concerted catalysis stability that it is good as shown in Figure 2 thus.
Embodiment 2:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with TiO
2, water is raw material, takes by weighing the TiO of 0.5g
2Powder joins in the 10mL water, and both are mixed, and obtains TiO
2Suspension;
2) TiO will be housed
2The beaker of suspension be positioned in the ultrasonic device, ultrasonic processing 2 hours obtains ultrasonic good TiO
2Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 3.319mL is added to above-mentioned ultrasonic good TiO
2Suspension in, in the dark stir 10min, stir 10min in illumination then, obtain chloroplatinic acid and TiO
2Suspension; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and TiO
2Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (TiO
2) the uviol lamp surface under infrared lamp, dry, make solvent (as the water) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 0.5wt%Pt/TiO of light heat synergetic action
2Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 3:
With the embodiment of the invention 2 resulting 0.5wt%Pt/TiO with light heat synergetic action
2Catalyst is applied to catalytic degradation benzene, and its experimental procedure is as follows: with the 0.5wt%Pt/TiO that scribbles of the embodiment of the invention 2 gained
2The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 40uL benzene, the initial concentration of benzene is 4863mg/m
3, open uviol lamp, the active testing that utilizes luminous energy that this uviol lamp sends and heat energy (the lamp surface temperature is 240 ℃) to carry out photo-thermal concerted catalysis degraded benzene, degradation rate and time relation are seen the A among Fig. 3, the complete degradation time of benzene is 20min.
Comparative Examples 3: with the TiO of 0.5g
2Powder joins in the beaker that 10mL water is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 3.319mL is added to ultrasonic good TiO
2Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in the culture dish, dry with infrared lamp in the process that is coated with; Then this culture dish is placed catalytic reactor, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 0.5wt%Pt/TiO
2Catalyst.Close uviol lamp then, reactor is placed the catalytic activity of measuring this catalyst thermocatalytic degraded benzene on the electric hot plate, the initial concentration of benzene is 4863mg/m
3, under no optical condition, make the temperature of catalyst remain on 240 ℃ (uviol lamp surface temperatures), degradation rate and time relation are seen the B among Fig. 3, benzene catalysis degradation modulus when 20min is 87.7%.
By active comparison diagram 3 as can be known, the degradation rate constant (0.2442min of photo-thermal concerted catalysis oxidation
-1) be the degradation rate constant (0.0885min of heat catalytic oxidation
-1) 2.8 times, shown 0.5wt%Pt/TiO
2The photo-thermal concerted catalysis oxidation of catalyst is to the efficient catalytic degradation capability of benzene.
Application example 4:
With the embodiment of the invention 2 resulting 0.5wt%Pt/TiO with light heat synergetic action
2Catalyst carries out the active testing of photo-thermal concerted catalysis degraded benzene, acetone, toluene and n-hexane, and the initial concentration of benzene, acetone, toluene and n-hexane is respectively 4863mg/m
3, 4360mg/m
3, 4791mg/m
3, 3646mg/m
3, light source is the 125W uviol lamp, and the lamp surface temperature is 240 ℃, and degradation time sees Table 1 fully.
Table 1
| The pollutant title | Benzene | Acetone | Toluene | N-hexane |
| Complete degradation time | ??20min | ??15min | ??25min | ??35min |
As can be seen from Table 1, the 0.5wt%Pt/TiO that has light heat synergetic action
2Catalyst is to the efficient catalytic degradation capability of gaseous-phase organic pollutant.
Embodiment 3:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with TiO
2, water is raw material, takes by weighing the TiO of 0.5g
2Powder joins in the 10mL water, and both are mixed, and obtains TiO
2Suspension;
2) TiO will be housed
2The beaker of suspension be positioned in the ultrasonic device, ultrasonic processing 2 hours obtains ultrasonic good TiO
2Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 6.638mL is added to above-mentioned ultrasonic good TiO
2Suspension in, in the dark stir 10min, stir 10min in illumination then, obtain chloroplatinic acid and TiO
2Suspension; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and TiO
2Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (TiO
2) the uviol lamp surface under infrared lamp, dry, make solvent (as the water) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3m L ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 1.0wt%Pt/TiO of light heat synergetic action
2Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 5:
With the embodiment of the invention 3 resulting 1.0wt%Pt/TiO with light heat synergetic action
2Catalyst carries out the active testing of photo-thermal concerted catalysis degraded benzene, acetone, toluene and n-hexane, and the initial concentration of benzene, acetone, toluene and n-hexane is respectively 4863mg/m
3, 4360mg/m
3, 4791mg/m
3, 3646mg/m
3, light source is the 125W uviol lamp, and the lamp surface temperature is 240 ℃, and degradation time sees Table 2 fully.
Table 2
| The pollutant title | Benzene | Acetone | Toluene | N-hexane |
| Complete degradation time | ??10min | ??15min | ??25min | ??20min |
As can be seen from Table 2, the 1.0wt%Pt/TiO that has light heat synergetic action
2Catalyst is to the efficient catalytic degradation capability of gaseous-phase organic pollutant.
Application example 6:
With the embodiment of the invention 3 resulting 1.0wt%Pt/TiO with light heat synergetic action
2Catalyst is applied to catalytic degradation benzene, and its experimental procedure is as follows: with the 1.0wt%Pt/TiO that scribbles of the embodiment of the invention 3 gained
2The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 100uL benzene, the initial concentration of benzene is 1.216 * 10
4Mg/m
3, open uviol lamp, the active testing that utilizes luminous energy that this uviol lamp sends and heat energy (the lamp surface temperature is 240 ℃) to carry out photo-thermal concerted catalysis degraded benzene, degradation rate and time relation are seen the A among Fig. 4, the complete degradation time of benzene is 20min.
Comparative Examples 4: with the TiO of 0.5g
2Powder joins in the beaker that 10mL water is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 6.638mL is added to ultrasonic good TiO
2Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in the culture dish, dry with infrared lamp in the process that is coated with; Then this culture dish is placed catalytic reactor, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 1.0wt%Pt/TiO
2Catalyst.Close uviol lamp then, reactor is placed the catalytic activity of measuring this catalyst thermocatalytic degraded benzene on the electric hot plate, inject 100uL benzene in 7.2L gas phase catalytic reaction device, the initial concentration of benzene is 1.216 * 10
4Mg/m
3, under no optical condition, make the temperature of catalyst remain on 240 ℃ (uviol lamp surface temperatures), degradation rate and time relation are seen the B among Fig. 4, the degradation rate of benzene in 20min only is 40.1%
By active comparison diagram 4 as can be known, the degradation rate constant (0.29733min of photo-thermal concerted catalysis oxidation
-1) be the degradation rate constant (0.04443min of heat catalytic oxidation
-1) 6.7 times, shown 1.0wt%Pt/TiO
2The photo-thermal concerted catalysis oxidation of catalyst is to the efficient catalytic degradation capability of benzene.
Embodiment 4:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with TiO
2, water is raw material, takes by weighing the TiO of 0.5g
2Powder joins in the 10mL water, and both are mixed, and obtains TiO
2Suspension;
2) TiO will be housed
2The beaker of suspension be positioned in the ultrasonic device, ultrasonic processing 2 hours obtains ultrasonic good TiO
2Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 13.276mL is added to above-mentioned ultrasonic good TiO
2Suspension in, in the dark stir 10min, stir 10min in illumination then, obtain chloroplatinic acid and TiO
2Suspension; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and TiO
2Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (TiO
2) the uviol lamp surface under infrared lamp, dry, make solvent (as the water) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3m L ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 2.0wt%Pt/TiO of light heat synergetic action
2Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 7:
With the embodiment of the invention 4 resulting 2.0wt%Pt/TiO with light heat synergetic action
2Catalyst carries out the active testing of photo-thermal concerted catalysis degraded benzene, acetone, toluene and n-hexane, and the initial concentration of benzene, acetone, toluene and n-hexane is respectively 4863mg/m
3, 4360mg/m
3, 4791mg/m
3, 3646mg/m
3, light source is the 125W uviol lamp, and the lamp surface temperature is 240 ℃, and degradation time sees Table 3 fully.
Table 3
| The pollutant title | Benzene | Acetone | Toluene | N-hexane |
| Complete degradation time | ??15min | ??15min | ??20min | ??25min |
As can be seen from Table 3, the 2.0wt%Pt/TiO that has light heat synergetic action
2Catalyst is to the efficient catalytic degradation capability of gaseous-phase organic pollutant.
Embodiment 5:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with TiO
2, water is raw material, takes by weighing the TiO of 0.5g
2Powder joins in the 10mL water, and both are mixed, and obtains TiO
2Suspension;
2) TiO will be housed
2The beaker of suspension be positioned in the ultrasonic device, ultrasonic processing 2 hours obtains ultrasonic good TiO
2Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 33.19mL is added to above-mentioned ultrasonic good TiO
2Suspension in, in the dark stir 10min, stir 10min in illumination then; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and TiO
2Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (TiO
2) the uviol lamp surface under infrared lamp, dry, make solvent (as the water) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 5.0wt%Pt/TiO of light heat synergetic action
2Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 8:
With the embodiment of the invention 5 resulting 5.0wt%Pt/TiO with light heat synergetic action
2Catalyst carries out the active testing of photo-thermal concerted catalysis degraded benzene, acetone, toluene and n-hexane, and the initial concentration of benzene, acetone, toluene and n-hexane is respectively 4863mg/m
3, 4360mg/m
3, 4791mg/m
3, 3646mg/m
3, light source is the 125W uviol lamp, and the lamp surface temperature is 240 ℃, and degradation time sees Table 4 fully.
Table 4
| The pollutant title | Benzene | Acetone | Toluene | N-hexane |
| Complete degradation time | ??10min | ??15min | ??30min | ??25min |
As can be seen from Table 4, the 5.0wt%Pt/TiO that has light heat synergetic action
2Catalyst is to the efficient catalytic degradation capability of gaseous-phase organic pollutant.
Sample (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action) to embodiment 1～5 carries out photo-thermal concerted catalysis degraded benzene active testing, and the initial concentration of benzene is 4863mg/m
3, light source is the 125W uviol lamp, the lamp surface temperature is 240 ℃, the results are shown in Table 5.
Table 5:
| The embodiment sequence number | The load capacity of Pt (wt%) | The degradation rate (%) of the collaborative benzene of photo-thermal (reaction 10min) |
| Embodiment 1 | ??0.1 | ?81.6 |
| The embodiment sequence number | The load capacity of Pt (wt%) | The degradation rate (%) of the collaborative benzene of photo-thermal (reaction 10min) |
| Embodiment 2 | ??0.5 | ?91.3 |
| Embodiment 3 | ??1 | ?98.1 |
| Embodiment 4 | ??2 | ??98.5 |
| |
??5 | ??100.0 |
Embodiment 6:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with Fe
2O
3, alcohol (ethanol) is raw material, takes by weighing the Fe of 0.5g
2O
3Powder joins in the 40mL alcohol, and both are mixed, and obtains Fe
2O
3Suspension;
2) Fe will be housed
2O
3Suspension (Fe
2O
3And alcohol) beaker is positioned in the ultrasonic device, and ultrasonic processing 2 hours obtains ultrasonic good Fe
2O
3Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 3.319mL is added to above-mentioned ultrasonic good Fe
2O
3Suspension in, in the dark stir 10min, under illumination, stir 10min then, obtain chloroplatinic acid and Fe
2O
3Suspension; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and Fe
2O
3Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (Fe
2O
3) the uviol lamp surface under infrared lamp, dry, make solvent (as the alcohol) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 0.5wt%Pt/Fe of light heat synergetic action
2O
3Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 9:
With the embodiment of the invention 6 resulting 0.5wt%Pt/Fe with light heat synergetic action
2O
3Catalyst is applied to catalytic degradation benzene, and its experimental procedure is as follows: with the 0.5wt%Pt/Fe that scribbles of the embodiment of the invention 6 gained
2O
3The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 40uL benzene, the initial concentration of benzene is 4863mg/m
3, open uviol lamp, the active testing that utilizes luminous energy that this uviol lamp sends and heat energy (the lamp surface temperature is 240 ℃) to carry out photo-thermal concerted catalysis degraded benzene, degradation rate and time relation are seen the A among Fig. 5, the degradation rate of benzene in 20min is 97.3%
Comparative Examples 5: with the Fe of 0.5g
2O
3Powder joins in the beaker that 40mL alcohol is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 3.319mL is added to ultrasonic good Fe
2O
3Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in the culture dish, dry with infrared lamp in the process that is coated with; Then this culture dish is placed catalytic reactor, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 0.5wt%Pt/Fe
2O
3Catalyst.Close uviol lamp then, reactor is placed the catalytic activity of measuring this catalyst thermocatalytic degraded benzene on the electric hot plate, inject 40uL benzene in 7.2L gas phase catalytic reaction device, the initial concentration of benzene is 4863mg/m
3, under no optical condition, make the temperature of catalyst remain on 240 ℃ (uviol lamp surface temperatures), degradation rate and time relation are seen the B among Fig. 5, the degradation rate of benzene in 20min is 84.6%.
By active comparison diagram 5 as can be known, the degradation rate constant (0.18198min of photo-thermal concerted catalysis oxidation
-1) be the degradation rate constant (0.12488min of heat catalytic oxidation
-1) 1.46 times, shown 0.5wt%Pt/Fe
2O
3The photo-thermal concerted catalysis of catalyst is to the efficient catalytic degradation capability of benzene.
Embodiment 7:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with CeO
2, alcohol is raw material, takes by weighing the CeO of 0.5g
2Powder joins in the 40mL alcohol, and both are mixed;
2) CeO will be housed
2Be positioned in the ultrasonic device with the beaker of alcohol, ultrasonic processing obtained ultrasonic good CeO in 2 hours
2Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 3.319mL is added to above-mentioned ultrasonic good CeO
2Suspension in, in the dark stir 10min, stir 10min in illumination then, obtain chloroplatinic acid and CeO
2Suspension; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and CeO
2Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (CeO
2) the uviol lamp surface under infrared lamp, dry, make solvent (as the alcohol) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 0.5wt%Pt/CeO of light heat synergetic action
2Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 10:
With the embodiment of the invention 7 resulting 0.5wt%Pt/CeO with light heat synergetic action
2Catalyst is applied to catalytic degradation benzene, and its experimental procedure is as follows: with the 0.5wt%Pt/CeO that scribbles of the embodiment of the invention 7 gained
2The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 40uL benzene, the initial concentration of benzene is 4863mg/m
3, open uviol lamp, the active testing that utilizes luminous energy that this uviol lamp sends and heat energy (the lamp surface temperature is 240 ℃) to carry out photo-thermal concerted catalysis degraded benzene, degradation rate and time relation are seen the A among Fig. 6, the degradation rate of benzene in 20min is 85.6%.
Comparative Examples 6: with the CeO of 0.5g
2Powder joins in the beaker that 10mL water is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 3.319mL mL is added to ultrasonic good CeO
2Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in the culture dish, dry with infrared lamp in the process that is coated with; Then this culture dish is placed catalytic reactor, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 0.5wt%Pt/CeO
2Catalyst.Close uviol lamp then, reactor is placed the catalytic activity of measuring this catalyst thermocatalytic degraded benzene on the electric hot plate, inject 40uL benzene in 7.2L gas phase catalytic reaction device, the initial concentration of benzene is 4863mg/m
3, under no optical condition, make the temperature of catalyst remain on 240 ℃ (uviol lamp surface temperatures), degradation rate and time relation are seen the B among Fig. 6, the degradation rate of benzene in 20min is 60.3%.
By active comparison diagram 6 as can be known, the degradation rate constant (0.1153min of photo-thermal concerted catalysis oxidation
-1) be the degradation rate constant (0.0978min of heat catalytic oxidation
-1) 1.18 times, shown 0.5wt%Pt/CeO
2The photo-thermal concerted catalysis of catalyst is to the efficient catalytic degradation capability of benzene.
Embodiment 8:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with V
2O
5, alcohol is raw material, takes by weighing the V of 0.5g
2O
5Powder joins in the 40mL alcohol, and both are mixed;
2) V will be housed
2O
5Be positioned in the ultrasonic device with the beaker of alcohol, ultrasonic processing 2 hours obtains ultrasonic good V
2O
5Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 3.319mL is added to above-mentioned ultrasonic good V
2O
5Suspension in, in the dark stir 10min, stir 10min in illumination then, obtain chloroplatinic acid and V
2O
5Suspension; The concentration of chloroplatinic acid aqueous solution is 0.0048mol/L;
4) then with above-mentioned chloroplatinic acid and V
2O
5Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (V
2O
5) the uviol lamp surface under infrared lamp, dry, make solvent (as the alcohol) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 0.5wt%Pt/V of light heat synergetic action
2O
5Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 11:
With the embodiment of the invention 8 resulting 0.5wt%Pt/V with light heat synergetic action
2O
5Catalyst is applied to catalytic degradation benzene, and its experimental procedure is as follows: with the 0.5wt%Pt/V that scribbles of the embodiment of the invention 8 gained
2O
5The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 40uL benzene, the initial concentration of benzene is 4863mg/m
3, open uviol lamp, the active testing that utilizes luminous energy that this uviol lamp sends and heat energy (the lamp surface temperature is 240 ℃) to carry out photo-thermal concerted catalysis degraded benzene, degradation rate and time relation are seen the A among Fig. 7, the degradation rate of benzene in 20min is 41.0%
Comparative Examples 7: with the V of 0.5g
2O
5Powder joins in the beaker that 10mL water is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 0.663mL is added to ultrasonic good V
2O
5Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in the culture dish, dry with infrared lamp in the process that is coated with; Then this culture dish is placed catalytic reactor, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 0.5wt%Pt/V
2O
5Catalyst.Close uviol lamp then, reactor is placed the catalytic activity of measuring this catalyst thermocatalytic degraded benzene on the electric hot plate, inject 40uL benzene in 7.2L gas phase catalytic reaction device, the initial concentration of benzene is 4863mg/m
3, under no optical condition, make the temperature of catalyst remain on 240 ℃ (uviol lamp surface temperatures), degradation rate and time relation are seen the B among Fig. 7, the degradation rate of benzene in 20min is 7.5%.
By active comparison diagram 7 as can be known, the degradation rate constant (0.03622min of photo-thermal concerted catalysis oxidation
-1) be the degradation rate constant (0.01487min of heat catalytic oxidation
-1) 2.44 times, shown 0.5wt%Pt/V
2O
5The photo-thermal concerted catalysis of catalyst is to the efficient catalytic degradation capability of benzene.
Embodiment 9:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) with Bi
2O
3, alcohol is raw material, takes by weighing the Bi of 0.5g
2O
3Powder joins in the 40mL alcohol, and both are mixed;
2) Bi will be housed
2O
3Be positioned in the ultrasonic device with the beaker of alcohol, ultrasonic processing 2 hours obtains ultrasonic half good Bi
2O
3Suspension; The frequency of described ultrasonic processing is 80KHz, and power is 500W;
3) the chloroplatinic acid aqueous solution amount with 3.319mL is added to above-mentioned ultrasonic half good Bi
2O
3Suspension in, in the dark stir 10min, stir 10min in illumination then, obtain chloroplatinic acid and Bi
2O
3Suspension; Is the concentration of chloroplatinic acid aqueous solution? mol/L;
4) then with above-mentioned chloroplatinic acid and Bi
2O
3Suspension be evenly coated in 125W uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) will scribble chloroplatinic acid and conductor oxidate (Bi
2O
3) the uviol lamp surface under infrared lamp, dry, make solvent (as the alcohol) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid/conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open uviol lamp, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal; Open catalytic reactor then, continue illumination 1h, make the second alcohol and water volatilization that remains in catalyst surface, obtain having the 0.5wt%Pt/Bi of light heat synergetic action
2O
3Catalyst (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action).
Application example 12:
With the embodiment of the invention 9 resulting 0.5wt%Pt/Bi with light heat synergetic action
2O
3Catalyst is applied to catalytic degradation benzene, and its experimental procedure is as follows: with the 0.5wt%Pt/Bi that scribbles of the embodiment of the invention 9 gained
2O
3The uviol lamp of catalyst places catalytic reactor, the off-response device, and to wherein injecting 40uL benzene, the initial concentration of benzene is 4863mg/m
3, open uviol lamp, the active testing that utilizes luminous energy that this uviol lamp sends and heat energy (the lamp surface temperature is 240 ℃) to carry out photo-thermal concerted catalysis degraded benzene, degradation rate and time relation are seen the A among Fig. 8, the degradation rate of benzene in 20min is 20.3%.
Comparative Examples 8: with the Bi of 0.5g
2O
3Powder joins in the beaker that 10mL water is housed, ultrasonic processing 2 hours, and the frequency of described ultrasonic processing is 80KHz, power is 500W; The chloroplatinic acid aqueous solution of 3.319mL is added to ultrasonic good Bi
2O
3Suspension in (concentration of chloroplatinic acid aqueous solution is 0.0048mol/L), in the dark stir 10min, stir 10min in illumination again; Then the suspension of chloroplatinic acid and conductor oxidate is coated with and is evenly coated in the culture dish, dry with infrared lamp in the process that is coated with; Then this culture dish is placed catalytic reactor, and to wherein adding 10mL water and 3mL ethanol, close catalytic reactor, open the uviol lamp in the reactor, utilize its luminous energy that sends and heat energy, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open catalytic reactor then, continue illumination 1h by photo-thermal, make the second alcohol and water volatilization that remains in catalyst surface, obtain 0.5wt%Pt/Bi
2O
3Catalyst.Close uviol lamp then, reactor is placed the catalytic activity of measuring this catalyst thermocatalytic degraded benzene on the electric hot plate, inject 40uL benzene in 7.2L gas phase catalytic reaction device, the initial concentration of benzene is 4863mg/m
3, under no optical condition, make the temperature of catalyst remain on 240 ℃ (uviol lamp surface temperatures), degradation rate and time relation are seen the B among Fig. 8, the degradation rate of benzene in 20min is 3.3%.
By active comparison diagram 8 as can be known, the degradation rate constant (0.01039min of photo-thermal concerted catalysis oxidation
-1) be the degradation rate constant (0.0049min of heat catalytic oxidation
-1) 2.12 times, shown 0.5wt%Pt/Bi
2O
3The photo-thermal concerted catalysis of catalyst is to the efficient catalytic degradation capability of benzene.
Sample (platinum/semiconductor oxide catalyst that promptly has light heat synergetic action) to embodiment 2,6～9 carries out collaborative heat of photo-thermal and thermocatalytic degraded benzene active testing, and the initial concentration of benzene is 4863mg/m
3, light source is the 125W uviol lamp, the lamp surface temperature is 240 ℃, the results are shown in Table 5.
Table 5
| The embodiment sequence number | Catalyst | The degradation rate of photo-thermal Oxybenzene (reaction 20min) | The degradation rate of heat catalytic oxidation benzene (reaction 20min) |
| Embodiment 2 | ??0.5wt％Pt/TiO 2 | ??100％ | ??87.7％ |
| Embodiment 6 | ??0.5wt％Pt/Fe 2O 3 | ??97.3％ | ??84.6％ |
| Embodiment 7 | ??0.5wt％Pt/CeO 2 | ??85.6％ | ??60.3％ |
| Embodiment 8 | ??0.5wt％Pt/V 2O 5 | ??41.0％ | ??7.5％ |
| Embodiment 9 | ??0.5wt％Pt/Bi 2O 3 | ??20.3％ | ??3.3％ |
Embodiment 10:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) proportioning by conductor oxidate and solvent is 0.1g: 10mL, chooses conductor oxidate and solvent, and conductor oxidate is joined in the solvent, mixes, and obtains the suspension of conductor oxidate; Described conductor oxidate is ZnO; The solvent of stating is water and ethanol mixed solvent, and the volume of water, ethanol respectively accounts for solvent volume 50%;
2) beaker that the suspension of conductor oxidate will be housed is positioned in the ultrasonic device, and ultrasonic processing 1 hour obtains the suspension of ultrasonic good conductor oxidate; The frequency of described ultrasonic processing is 20KHz, and power is 100W;
3) proportioning by conductor oxidate and chloroplatinic acid aqueous solution is 0.1g: 0.6mL, chooses chloroplatinic acid aqueous solution; Chloroplatinic acid aqueous solution is added in the suspension of ultrasonic good conductor oxidate, in the dark stirs 5min, under illumination, stir 5min then, obtain the suspension of chloroplatinic acid and conductor oxidate; The concentration of chloroplatinic acid aqueous solution is 0.001mol/L;
4) then the suspension of chloroplatinic acid and conductor oxidate is coated in the uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp; The power of described uviol lamp is 4W;
5) dry under infrared lamp on the uviol lamp surface that will scribble chloroplatinic acid and conductor oxidate, makes solvent (as the second alcohol and water) volatilization that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid and conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding entry and ethanol, the volume proportion of water and ethanol is 10: 3, the addition of water and ethanol for the gas phase catalytic reaction body long-pending 0.001%; Close the gas phase catalytic reaction device, open uviol lamp, the luminous energy and the heat energy that utilize uviol lamp to send, under the mixed vapour of water and ethanol, steam 2h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open the gas phase catalytic reaction device then, continue illumination 1h by photo-thermal, make residual second alcohol and water volatilization, obtain having the platinum/semiconductor oxide catalyst of light heat synergetic action.
Embodiment 11:
Have the preparation method of the platinum/semiconductor oxide catalyst of light heat synergetic action, it comprises the steps:
1) proportioning by conductor oxidate and solvent is 2g: 40mL, chooses conductor oxidate and solvent, and conductor oxidate is joined in the solvent, mixes, and obtains the suspension of conductor oxidate; Described conductor oxidate is CuO; The solvent of stating is the mixed solvent of water and acetone, and the volume of water, acetone respectively accounts for solvent volume 50%;
2) beaker that the suspension of conductor oxidate will be housed is positioned in the ultrasonic device, and ultrasonic processing 2 hours obtains the suspension of ultrasonic good conductor oxidate; The frequency of described ultrasonic processing is 150KHz, and power is 1800W;
3) proportioning by conductor oxidate and chloroplatinic acid aqueous solution is 2g: 10mL, chooses chloroplatinic acid aqueous solution; Chloroplatinic acid aqueous solution is added in the suspension of ultrasonic good conductor oxidate, in the dark stirs 15min, under illumination, stir 15min then, obtain the suspension of chloroplatinic acid and conductor oxidate; The concentration of chloroplatinic acid aqueous solution is 0.005mol/L;
4) then the suspension of chloroplatinic acid and conductor oxidate is coated in the uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp; The power of described uviol lamp is 1000W;
5) dry under infrared lamp on the uviol lamp surface that will scribble chloroplatinic acid and conductor oxidate, makes the solvent evaporates that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid and conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding entry and ethanol, the volume proportion of water and ethanol is 10: 4, the addition of water and ethanol for the gas phase catalytic reaction body long-pending 10%; Close the gas phase catalytic reaction device, open uviol lamp, the luminous energy and the heat energy that utilize uviol lamp to send, under the mixed vapour of water and ethanol, steam 5h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle, open the gas phase catalytic reaction device then, continue illumination 3h by photo-thermal, make residual second alcohol and water volatilization, obtain having the platinum/semiconductor oxide catalyst of light heat synergetic action.
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of technological parameter (as temperature, time etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (8)
1. the preparation method who has the platinum/semiconductor oxide catalyst of light heat synergetic action is characterized in that it comprises the steps:
1) proportioning of pressing conductor oxidate and solvent is (0.1～2) g: (10～40) mL, choose conductor oxidate and solvent, and conductor oxidate is joined in the solvent, mix, obtain the suspension of conductor oxidate;
2) beaker that the suspension of conductor oxidate will be housed is positioned in the ultrasonic device, and ultrasonic processing 1～2 hour obtains the suspension of ultrasonic good conductor oxidate;
3) proportioning of pressing conductor oxidate and chloroplatinic acid aqueous solution is (0.1～2) g: (0.6～10) mL, choose chloroplatinic acid aqueous solution; Chloroplatinic acid aqueous solution is added in the suspension of ultrasonic good conductor oxidate, in the dark stirs 5～15min, under illumination, stir 5～15min then, obtain the suspension of chloroplatinic acid and conductor oxidate;
4) then the suspension of chloroplatinic acid and conductor oxidate is coated in the uviol lamp surface, the process that is coated with is carried out under the illumination of infrared lamp;
5) dry under infrared lamp on the uviol lamp surface that will scribble chloroplatinic acid and conductor oxidate, makes the solvent evaporates that remains in the uviol lamp surface;
6) uviol lamp that will scribble chloroplatinic acid and conductor oxidate at last places in the gas phase catalytic reaction device, and to wherein adding entry and ethanol, close the gas phase catalytic reaction device, open uviol lamp, the luminous energy and the heat energy that utilize uviol lamp to send, under the mixed vapour of water and ethanol, steam 2～5h, make chloroplatinic acid be catalysed and reduced into nano-platinum particle by photo-thermal, open the gas phase catalytic reaction device then, continue illumination 1～3h, make residual second alcohol and water volatilization, obtain having the platinum/semiconductor oxide catalyst of light heat synergetic action.
2. the preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action according to claim 1 is characterized in that: described conductor oxidate is TiO
2, SnO
2, CeO
2, ZnO, CuO, Bi
2O
3, Fe
2O
3Or V
2O
5
3. the preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action according to claim 1 is characterized in that: described solvent is the mixed solvent of any one or two kinds in water, the organic solvent, and two kinds is any proportioning when mixing.
4. the preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action according to claim 3 is characterized in that: organic solvent is ethanol or acetone.
5. the preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action according to claim 1 is characterized in that: the frequency of described ultrasonic processing is 20～150KHz, and power is 100～1800W.
6. the preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action according to claim 1 is characterized in that: the concentration of chloroplatinic acid aqueous solution is 0.001～0.005mol/L.
7. the preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action according to claim 1 is characterized in that: the power of described uviol lamp is 4～1000W.
8. the preparation method with platinum/semiconductor oxide catalyst of light heat synergetic action according to claim 1, it is characterized in that: the volume proportion of water and ethanol is 10: 3～4 in the step 6), the addition of water and ethanol for the gas phase catalytic reaction body long-pending 0.001～10%.
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