CN1833773A - Radiant energy photocatalysis combiner - Google Patents
Radiant energy photocatalysis combiner Download PDFInfo
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- CN1833773A CN1833773A CN 200510055423 CN200510055423A CN1833773A CN 1833773 A CN1833773 A CN 1833773A CN 200510055423 CN200510055423 CN 200510055423 CN 200510055423 A CN200510055423 A CN 200510055423A CN 1833773 A CN1833773 A CN 1833773A
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Abstract
A radiation energy enabled composite photocatalyst for photocatalytic reaction is composed of a photocatalyst for UV photocatalytic reaction, a promoter for absorbing radiation energy and releasing photons, and a porous material as carrier.
Description
Technical field
The present invention relates to a kind of radiant energy photocatalysis combiner that can utilize radiant energy as the photocatalysis energy, and manufacturing and using method.
Background technology
Photocatalyst has become one of surrounding purifying material that attracts most attention at present.It can effectively handle polluters such as chlorobenzene organic matter in the pollutant, chlorophenol compound, cyanide, metal ion, for nitrogen oxide (NO
x), sulfur oxide (SO
x) wait the processing of gaseous contamination that good effect is also arranged.In addition, photocatalyst is only played the part of the role of catalyst in reaction, and itself can't be consumed, and can not cause other bad reaction to environment, so the exploitation of photocatalyst has become one of the widest goal in research of potentiality with application.
The material of photocatalyst has a variety of, for example TiO
2, ZnO, SnO
2, ZrO
2Deng oxide and CdS, ZnS sulfides.The wherein the most representative and the most extensive person of application surely belongs to titanium dioxide (TitaniumDioxide, TiO
2),, chemical property strong because of its oxidability stablized, and nontoxic, finds so far from 1972, has been widely used in various people's livelihood purposes, for example coating, mouth mask, household electrical appliances, cloth etc.
Titanium dioxide itself is a kind of semiconductor, and it can provide energy via solar radiation or ultraviolet ray irradiation, and makes titanium dioxide surface carry out redox reaction.Titanium dioxide can form electronics (e after absorbing energy
-) and electric hole (h
+) two kinds of carriers, electric hole can will be adsorbed on the hydrone oxidation of titanium dioxide surface, forms the hydroxyl radical free radical (OH) of strong oxidizing force; The oxygen of electronics in can reducing atmosphere, and become superoxide anion (O
2 -), then form hydrogen peroxide (H
2O
2), become H at last
2O.In addition, because the oxidizing force in electric hole much larger than organic molecule, when hydroxyl radical free radical contact organic matter, can destroy bonds such as the C-C in the organic molecule, C-H, C-N, C-O, O-H, N-H to capture the mode of electronics, impel organic matter to decompose or fracture.Pollutant or pathogen in the general environment mostly are carbohydrate, through with the titanium dioxide effect after, can resolve into harmless water and carbon dioxide, therefore can reach scrubbing, sterilization, and make the target of the depollution of environment.
In addition, in the photocatalyst of titanium dioxide reaction, can be via the photosynthetic mechanism of similar plants, with transform light energy is chemical energy, impel water to be broken down into oxygen and hydrogen, wherein hydrogen can be used as the main fuel of fuel cell, therefore is regarded as the free of contamination energy of new generation.Though the application of hydrogen energy source still is in conceptual phase at present, the following energy that can become alternative oil most probably, so the using value of photocatalyst reaction is limitless.
Make the electronics of titanium dioxide transit to conduction band (conduction band), must rely on external light source enough energy are provided by valence band (valence band) leap energy gap (band gap).The width of titanium dioxide energy gap is 3.2eV, and its corresponding wavelength is 380nm, and this wavelength is just belonging to the wave-length coverage of ultraviolet light.In other words, have only and use the light source of wavelength, just can make titanium dioxide carry out photocatalyst reaction less than 380nm (being that energy is greater than 3.2eV).The photocatalyst of titanium dioxide of present commercial extensive use, how with ultraviolet light or solar radiation as light source.With ultraviolet lamp during as light source, must with extremely low efficient with the electric energy conversion after, just can carry out photocatalyst reaction.Moreover because the penetration power of ultraviolet light is limited, if meet with the obstruct that ultraviolet light can't penetrate, the light penetration range is long, or photocatalyst material medium itself is non-when being transparent, all will influence the carrying out of photocatalyst reaction.As light source, though need not provide extra light source, natural energy resources can be limited by the influence of factors such as weather, season, indoor, night with solar radiation, and photocatalyst reaction can't be carried out in the area that solar radiation can't shine.Moreover the ultraviolet source that can provide photocatalyst reaction in the solar radiation only accounts for about 5% of solar radiation, and the usefulness of using photocatalyst reaction is very limited.
In order to enlarge the light source applications scope of photocatalyst, the equal active development in countries in the world with visible light (390～780nm) photocatalysts as light source, with the efficient that improves photocatalyst reaction with and application.For example, make titanium dioxide absorb some have color as chromium (Cr), vanadium (V), manganese (Mn), iron (Fe) or nickel (Ni) etc. metal ion, these metal ions are in excitation state after absorbing visible light, be injected in the titanic oxide material, radiation produces oxygen defect and causes photocatalyst reaction by the electricity slurry, but the shortcoming of this mode not only influences the usefulness of reaction, and expends quite high cost for being difficult to form inhomogeneity dispersity.
Summary of the invention
In order to solve the shortcoming that conventional art produces, and improve the reaction efficiency of known photocatalyst, the applicant is with known TiO
2Add to discharge in the material and excite TiO
2The promoter of light-catalyzed reaction, and with the exciting energy resource of radiant energy (for example using the radiation source of higher-energy) as photocatalyst, and reach the better photocatalyst reaction of reaction efficiency.Fig. 1 be with barium fluoride as promoter, and utilize free radiation as exciting the energy of photocatalyst reaction to be example, make photocatalyst TiO
2Carry out the schematic diagram of light-catalyzed reaction.Because material is subjected to the mechanism of action after the radiation, as photoelectric effect or Compton effect, the atomic number (Z) of its light productive rate and material is tied to form the progression ratio, is generally Z
3-Z
5And inorganic scintillator contains the element of heavy atom preface usually, by the heavy atom on the scintillator particulate, as barium (Ba), lanthanum (La), yttrium elements such as (Y), can increase absorption and effect probability for radiation, therefore be suitable as the promoter that excites photocatalyst reaction.As shown in Figure 1, behind barium fluoride nano particle absorbed radiation energy, the barium atom is subjected to radiation effects and transits to conduction band (C.B.), and produce the excite state electronics, and this excite state electronics is alleviated to the process of crystal valence band (V.B.) by conduction band (C.B.) in the barium atom, can can trap catch by fluorine ion, and to emit the light energy wavelength be 220 and the emittance of 315nm that the light energy of this kind wavelength is and causes the effective energy that titanium dioxide produces the photocatalysis effect.Because the penetration power of radiant energy is strong, therefore can overcome the not good problem of traditional UV light source penetrability, unlikelyly, photon influences photocatalyst reaction because being subjected to the obstruct of matrix or material.In addition, radioactive wastes such as nuclear energy power generation or industrial resin that produces or organic liquid waste, often face and to solidify or problem such as extremely difficult, radial pattern photocatalyst complex of the present invention, can directly utilize the radiant energy of waste material itself to decompose or the decrement waste material, for relevant discarded object in the environment provides a kind of new utilization and processing mode, change radiant energy into can regenerate the energy, even can be used as the renewable sources of energy of producing hydrogen as energy source.
Therefore, one of purpose of the present invention provides a kind of radiant energy photocatalysis combiner, and this photocatalyst complex can utilize the excitation energy of radiant energy as photocatalyst reaction, and it comprises a photocatalyst, and this photocatalyst can carry out photocatalyst reaction; One promoter, its energy absorbed radiation energy, and discharge the luminous energy that this photocatalyst of sening as an envoy to carries out photocatalyst reaction; And porous material, this material can provide the absorption position of reactants such as photocatalyst and promoter, those reactants is fixed thereon, and becomes the kenel of a species complex, and promote its light-catalyzed reaction.Wherein the shared percentage by weight of this photocatalyst and promoter is preferable with 1～40% respectively respectively.
Another object of the present invention provides a kind of method of making radiant energy photocatalysis combiner, and the method comprises the following step at least: (i) a synthetic photocatalyst and a promoter; And (ii) this photocatalyst and this promoter fixedly are attached on the porous material; Wherein, this photocatalyst can carry out photocatalyst reaction via exciting of particular energy photon; This promoter energy absorbed radiation energy, and discharge the photon that this photocatalyst of sening as an envoy to carries out photocatalyst reaction; This porous matrix material can provide the position of particulates such as fixed light catalyst and promoter, with the kenel of a species complex, is applied to light-catalyzed reaction.
The present invention provides a kind of method of using radiant energy photocatalysis combiner simultaneously, and the method comprises the following step at least: (1) obtains a radiant energy photocatalysis combiner that comprises photocatalyst and promoter; (2) this radiant energy photocatalysis combiner is contacted with an object; (3) make promoter absorbed radiation energy in this radiant energy photocatalysis combiner; And (4) this promoter discharges a photon, makes photocatalyst and object in this radiant energy photocatalysis combiner carry out redox reaction.
Radiant energy photocatalysis combiner of the present invention, wherein there is no particular restriction for the photocatalyst that is comprised, but be preferable with titanium dioxide.Also there is no particular restriction for promoter, as long as can absorbed radiation energy for it, and the release light energy that this photocatalyst carries out photocatalyst reaction of sening as an envoy to gets final product.Because many inorganic scintillators after absorbing energy, can discharge the light wave of specific wavelength, therefore be suitable as the promoter among the present invention.For reach purpose of the present invention, can select for use be subjected to radiant energy and excite after, it discharges the scintillator of wavelength less than 380nm, be shown in the table 1 absorb energy after, discharge wavelength some inorganic scintillator materials less than 380nm.If consideration can be fixed in porous material and can be promoted the usefulness of photocatalyst reaction, the preferably is a barium fluoride.The compound of baric or higher atomic number very easily is subjected to exciting of energy-rich radiation, even under no optical condition, be attached to barium fluoride crystal particulate on the base material and also can gulp down the radiation sink effect of effect by photoelectric effect or Kang Pu, disengaging is enough to photon that photocatalyst is reacted, finishes relevant photocatalytic effect.
In order to improve the efficient of photocatalyst reaction, the particle diameter of employed titanium dioxide and promoter is preferable with nano level particulate among the present invention.The grain size of photocatalyst and promoter is preferably and is no more than 100nm.
Porous substrate can select to be easy to adsorb and to make photocatalyst and promoter bond micron order material thereon, relatively poor but the ceramic powder that adsorption effect is preferable of clear glass powder or light transmittance for example, and light tight but activated carbon that adsorption effect is good etc.Radiant energy photocatalysis combiner provided by the present invention is immobilized onto photocatalyst and promoter on the porous substrate, forms a species complex kenel, therefore is convenient to reclaim and reuse.In addition, the grain size of porous material is preferred with the micron, can provide bigger absorption and immobilized surface area like this, and so as to bigger reaction table area is provided, its specific area is preferably minimum 50m
2/ g.Simultaneously, if be used nano level photocatalyst and promoter particulate in the porous material that uses micron-scale, because of its particle diameter is little, surface area is big, and can be covered in the made from porous material surface each other alternately, therefore can significantly promote the reaction efficiency of photocatalyst.
When making radiant energy photocatalysis combiner, can be directly with the promoter of baric and the powder of dioxide photocatalyst titanium, this mixed-powder is adsorbed and be immobilized onto on the porous material.Also can promoter, TiO will be comprised
2, and the powder of porous material, and react respectively, generate promoter and dioxide photocatalyst titanium.By this course of reaction, simultaneously promoter and photocatalyst absorption are fixed on the porous material.Can further add coupler during reaction and improve immobilized effect, this coupler can adopt citric acid or EDTA, and the preferably is EDTA.Because EDTA can combine with the metal ion in the porous material originally as metal-chelator; On the other hand, the carboxyl on the EDTA can combine with promoter or photocatalyst, and reaches preferable immobilization effect.After previous reaction and adsorption process are finished,, can obtain radiant energy photocatalysis combiner of the present invention via 400～600 ℃ high-temperature calcination.Finished product through aforementioned preparation method's gained, can utilize different characteristic analysis methods to be identified, for example with XRD analysis its whether grow up to crystalline phase be anatase (anatase), observe its particle diameter and surface morphology distribution with SEM, or carry out the concentration of element analysis with XRF, confirm titanium, barium weight ratio of constituents example in the photocatalyst powder via digestion step and icp analysis more at last.
When using radiant energy photocatalysis combiner, can utilize different free and non-free radiation such as ultraviolet ray, gamma-rays, X ray or β ray respectively, also can the visual response condition and treating capacity utilize above-mentioned radiation simultaneously, as the exciting energy resource of photocatalyst.The mode that can adopt the outside to penetrate the source is shone radiant energy photocatalysis combiner and is produced photocatalyst reaction, also direct the contact with object and radiant energy photocatalysis combiner mixing of radiation source can be carried out photocatalyst reaction.
Description of drawings
Fig. 1 is the reaction schematic diagram of radial pattern photocatalyst complex of the present invention.
Fig. 2 is the schematic flow sheet of preparation radiant energy photocatalysis combiner of the present invention.
Fig. 3 is (a) SEM photo of radiant energy photocatalysis combiner of the present invention, and scale is represented 0.5m among the figure; Analyze collection of illustrative plates with (b) EDS.
Fig. 4 carries out photocatalyst catalyst reaction device schematic diagram for utilizing radiant energy photocatalysis combiner of the present invention.
Among the figure
1 air 2Co-60,3 mixtures
5 lead screens of 4 agitating devices
The specific embodiment
Below will further specify embodiments of the present invention with specific embodiment and more detailed the explanation.
It is emphasized that; following embodiment is used for illustrating the present invention; be not in order to limit scope of the present invention; any those of ordinary skill in the art; without departing from the spirit and scope of the present invention; can do a little change and retouching, so protection scope of the present invention should be as the criterion with claim institute restricted portion.
Figure 2 shows that the schematic flow sheet of preparation radiant energy photocatalysis combiner of the present invention.As shown in Figure 2, when preparing radiant energy photocatalysis combiner of the present invention, can be with barium nitrate, sodium fluoride, titanium tetrachloride and porous material powder such as (as ceramic powder, glass dust or activated carbon), make barium fluoride and the dioxide photocatalyst titanium of its reaction generation as promoter, and be adsorbed on the porous material, through high-temperature calcination (400-600 ℃), can make radiant energy photocatalysis combiner of the present invention.Can use at last XRD analysis its whether grow up to crystalline phase be preferable anatase (anatase), observe its particle diameter with SEM and distribute, or utilize XRF to carry out elementary analysis and carry out the various characteristics analysis.
Below will further specify embodiments of the present invention with specific embodiment.
The preparation of embodiment 1. radiant energy photocatalysis combiners
In alkaline aqueous solution, add an amount of EDTA at normal temperatures, barium nitrate, sodium fluoride are added and dissolving, add powder such as quantitative ceramic powder,, dropwise added titanium tetrachloride and stir about 2 hours through evenly stirring.Secondly, utilize thermal source to make behind the solution evaporate to dryness, dried powder in baking oven, and through high temperature about 400 ℃ of calcination promptly obtain the photocatalyst powder.Above-mentioned barium nitrate, sodium fluoride, titanium tetrachloride and porous material (ceramic powder, glass dust or activated carbon) wait the mixed weight of each reactant to be respectively 1～5: 0.7～1.8: 0.4～2.0: 2～7 than (is unit with the gram), and the molal quantity of EDTA is the summation of barium nitrate and titanium tetrachloride molal quantity.Reaction is finished the back and is generated as the barium fluoride of promoter and as the titanium dioxide of photocatalyst, and the while absorption profiles is on the ceramic powder of porous material.Through behind the high-temperature calcination, the molecule of promoter and photocatalyst crystal process rearranges, and obtains can repeating to reclaim using and the strong radiant energy photocatalysis combiner of catalytic.
The photocatalyst complex that preparation is finished is confirmed titanium, barium weight ratio of constituents example in the photocatalyst powder via digestion step and icp analysis again.Its analysis result is as shown in table 2.List the prepared photocatalyst complex of finishing of 6 kinds (C1-C6) titanium tetrachloride, barium nitrate, sodium fluoride in varing proportions in the table 2, behind digestion step and icp analysis, resulting titanium, barium component content.This result shows, in 6 kinds of photocatalyst complexs of C1-C6, all contains the composition of titanium and barium really, and the content of these two kinds of compositions, can increase and increase along with titanium tetrachloride, barium nitrate and sodium fluoride consumption.
In addition, observe Ba, the distribution of Ti diameter of particle of above-mentioned photocatalyst complex with SEM.Observe behind high temperature sintering the TiO in the photocatalyst complex with XRD
2Whether be anatase (anatase) crystal formation, and BaF
2Whether be present in simultaneously in the photocatalyst complex.Moreover, utilize XPS to observe particulate bond kenel, and also with the grain size on the AFM observation porous material.With the C6 in the table 2 is example, and it is with the reactant usage ratio shown in the table 2, at the synthetic photocatalyst complex of the carbon porous material of graphitiferous.In the analysis result of SEM, can see, contain Ba and Ti composition simultaneously in the structural nanoparticle of the flake graphite of 10 μ m.With the XRD analysis specific crystal formation, the peak position of pure activated carbon is to be positioned at about 26 ° of 2 θ in collection of illustrative plates again, and TiO
2The main peak position of anatase crystal is to be positioned at about 25.2 ° of 2 θ, as for BaF
22 θ peak values be located at 23.9 ° of 2 θ, 28.5 °, 41.2 °, 66.1 °, 67.9 °, it belongs to flange Ke Dikesuo Nat (frankdicksonite) class crystal formation.And utilize X-ray photoelectric spectrum (XPS) to observe, then find TiO
2Characteristic absorption such as middle Ti 2p, O 1s, Ba+2 (Ba 3d5/2and Ba 3d3/2), F 1s are respectively 458.7eV, 530eV, 780eV and 795eV, 684eV.As for the acicular texture of observing with AFM on the carbon, its micro-crystal type size is about 6～10nm.Show the photocatalyst complex that the present invention synthesized by The above results, its particulate has the nanometer particle size size, and has the TiO of anatase crystal
2And the BaF of flange Ke Dikesuo Nat crystal formation
2The SEM photo and the EDS that Figure 3 shows that photocatalyst complex of the present invention analyze collection of illustrative plates.The employed porous material of this photocatalyst complex is a ceramic powder, and the contained titanium dioxide and the particle diameter of barium fluoride are less than the nanoparticle below the 100nm in the display light catalyst complex as a result.
The methyl blue solution that to prepare 6 groups of concentration be 10ppm, respectively that embodiment 1 is prepared and photocatalyst complex (C1-C6) 0.2g that obtain adds in the methyl blue solution, and penetrate the source radiation irradiation with the Co-60 γ of 25Gy.Because methyl blue at the about 663nm of visible-range wavelength place, has one greatly to reach sensitive absworption peak, therefore can measure change of absorption peak strength herein by photoelectric colorimeter.In addition, methyl blue solution is blue when oxidation state, and is colourless when going back ortho states, and the therefore variation that also can be inspected solution colour simply by naked eyes judges whether solution example has carried out redox reaction.
Device when reacting can be as shown in Figure 4, the object that desire is handled (for example spent resin or industrial wastewater, and herein for methyl blue solution) mix with radiant energy photocatalysis combiner and to be mixture (3), the radiation source of Co-60 (2) is positioned in this mixture (3), the outside is provided with lead screen (5), can be provided with an agitating device (4) in addition, and fresh air is fed (1) in the reactor.
The result is as shown in table 3, A
0The light absorption value at the wavelength 663nm place before representative is still handled without the photocatalyst complex, the light absorption value of At representative after the photocatalyst complex is handled, so At/A
0Numerical value low more, represent the catalytic reaction of photocatalyst good more.By in the table 3 as can be known, listed C1-C6 photocatalyst complex all can cause the photo catalytic reduction reaction of methyl blue via the Co-60 radiation, and observes its fading effect.In addition, if with Ti content, compared to the lower C1-C3 of titaniferous amount, the higher C4-C6 of titaniferous amount has preferable catalytic effect.And in the identical photocatalyst complex of titaniferous amount, barium content is high more, and catalytic effect is good more.
The radiation source of above-mentioned Co-60 (2) can outer setting mode provide, also can replace by the X-ray irradiation apparatus.
In addition, because of methyl blue is a kind of azo based dye, therefore, the result of embodiment 2 can know by inference thus, and photocatalyst complex of the present invention can be used for handling the industrial wastewater that contains the azo based dye.
Reaction unit is as described in the embodiment 2, is that handled object changes actual used Purolite company of institute of Taiwan nuclear plant cationic ion-exchange resin into.1 gram resin, 1 is restrained the water of C6 photocatalyst complex (preparation method such as embodiment 1), 70ml and contains activity 5 * 10
6The Co-60 of Bq inserts in the reaction vessel of Fig. 4, and the maximum absorbed dose rate of solution is about 4mGy/h.Test with different exposure doses, and measure postradiation total carbon (TOC) content with elemental analyser.The result is as shown in table 4, and exposure dose 1-9Gy all can make resin decompose, and along with exposure dose increases, resin becomes the little molecule in the solution at last gradually by the granular powdery that transfers to.Can be observed the dosage that resin decomposes fully when listed exposure dose is visual in the table 4.When exposure dose increases, the TOC in the solution will obviously reduce, and behind the irradiation 9Gy, TOC approximately only is left original 1%.Hence one can see that, and photocatalyst complex of the present invention can be under unglazed environment, utilizes free radiation to decompose resin fully, and can expect the purpose that reaches permineralization.
In aforesaid explanation and embodiment, can confirm that radiant energy photocatalysis combiner provided by the present invention can utilize radiant energy to carry out photocatalyst reaction really, and its manufacture method is easy.Low and the stable in properties of employed promoter cost, this kind radiant energy photocatalysis combiner can repeat to reclaim and use simultaneously.
This kind radiant energy photocatalysis combiner also can utilize traditional UV light and free radiation as excitation source simultaneously, and increases its service efficiency.Utilize the excitation source of free radiation, because of it has high-penetrability and does not need characteristic such as extra power consumption, so can be applied to large-scale industrial treatment, and not be subjected to the restriction of weather, place and time as photocatalyst.This kind radiant energy photocatalysis combiner is applicable to the processing of commonly industrial wastewater waste gas, organic liquid waste, used oil etc.In addition, the present invention as new energy purposes, not only can solve the handling problem of radioactive waste with radioactive waste, even can environment purification, or produce the free of contamination energy of new generation, be to serve multiple in fact.
Maximum after table 1, some inorganic scintillator are stimulated is disengaged wavelength
| Scintillator | Maximum after being stimulated is disengaged wavelength (nm) |
| NaI (sodium iodide) | 303 |
| CsI (cesium iodide) | 310 |
| BaF 2(barium fluoride) | 190/220；310 |
| CeF 3(cerium fluoride) | 300；340 |
| YAP | 370 |
The icp analysis result (N=5) of table 2, photocatalyst complex of the present invention
| The photocatalyst complex | The reactant consumption | Content (mg/g) | |||
| TiCl 4(g) | Ba(NO 3) 2(g) | NaF(g) | Ti | Ba | |
| C1 | 0.4 | 1.0 | 0.7 | 15.3±1.5 | 43.2±2.6 |
| C2 | 0.4 | 3.1 | 1.1 | 16.2±1.6 | 105±5 |
| C3 | 0.4 | 5.1 | 1.8 | 18.1±1.4 | 156±5 |
| C4 | 2.0 | 1.0 | 0.7 | 45.2±2.5 | 38.1±2.1 |
| C5 | 2.0 | 3.1 | 1.1 | 44.5±2.6 | 102±4 |
| C6 | 2.0 | 5.1 | 1.8 | 41.1±2.3 | 140±5 |
Table 3, utilize the reduction reaction of Co-60 for radiant energy and photocatalyst complex catalysis methyl blue of the present invention
| The photocatalyst complex | At/Ao |
| C1 | 0.62 |
| C2 | 0.53 |
| C3 | 0.41 |
| C4 | 0.35 |
| C5 | 0.33 |
| C6 | 0.20 |
Table 4, utilize the reaction of Co-60 for radiant energy and photocatalyst complex catalysed cationic exchanger resin of the present invention
| Exposure dose (Gy) | TOC(ppm) |
| 0 | 336,000 |
| 1 | 3,480 |
| 3 | 2,664 |
| 5 | 2,135 |
| 9 | 2,046 |
Claims (27)
1. radiant energy photocatalysis combiner, this photocatalyst complex can utilize the excitation energy of radiant energy as photocatalyst reaction, and its composition comprises:
One photocatalyst, this photocatalyst can carry out photocatalyst reaction;
One promoter, its energy absorbed radiation energy, and discharge the photon that this photocatalyst of sening as an envoy to carries out photocatalyst reaction; And
One porous material, this material can make this photocatalyst and the absorption of this promoter and be fixed thereon;
Wherein the shared percentage by weight of this photocatalyst is 1～40%, and this promoter is 1～40%.
2. radiant energy photocatalysis combiner according to claim 1, wherein this radiant energy be selected from group that ultraviolet ray, gamma-rays, X ray, β ray formed at least one of them.
3. radiant energy photocatalysis combiner according to claim 1, wherein this promoter is the inorganic scintillator material.
4. radiant energy photocatalysis combiner according to claim 1, wherein this promoter is selected from NaI (sodium iodide), CsI (cesium iodide), BaF
2(barium fluoride), CeF
3(cerium fluoride), group that YAP formed at least one of them.
5. radiant energy photocatalysis combiner according to claim 1, wherein this promoter is barium fluoride.
6. radiant energy photocatalysis combiner according to claim 1, wherein this photocatalyst is a titanium dioxide.
7. radiant energy photocatalysis combiner according to claim 1, wherein this porous material be selected from group that ceramic powder, glass dust and activated carbon form at least one of them.
8. radiant energy photocatalysis combiner according to claim 1, wherein the grain size of this photocatalyst and promoter is 100nm to the maximum.
9. radiant energy photocatalysis combiner according to claim 1, wherein the grain size of this porous material is a micron order, and its specific area minimum be 50m
2/ g.
10. method of making radiant energy photocatalysis combiner, it comprises the following step at least:
(i) a synthetic photocatalyst and a promoter; And
This photocatalyst and this promoter fixedly are attached on the porous material;
Wherein, the photon that this photocatalyst can specific wavelength carries out photocatalyst reaction; This promoter can absorb free radiation, and disengages and make this photocatalyst carry out the photon of photocatalyst reaction; And this porous material can make this photocatalyst and this promoter adhere to and be fixed thereon.
11. the method for manufacturing radiant energy photocatalysis combiner according to claim 10, wherein this photocatalyst is a titanium dioxide.
12. the method for manufacturing radiant energy photocatalysis combiner according to claim 10, wherein this promoter is the inorganic scintillator material.
13. the method for manufacturing radiant energy photocatalysis combiner according to claim 10, wherein this promoter is selected from NaI (sodium iodide), CsI (cesium iodide), BaF
2(barium fluoride), CeF
3(cerium fluoride), group that YAP formed at least one of them.
14. the method for manufacturing radiant energy photocatalysis combiner according to claim 10, wherein this promoter is barium fluoride.
15. the method for manufacturing radiant energy photocatalysis combiner according to claim 10, wherein this porous material be selected from group that ceramic powder, glass dust and activated carbon form at least one of them.
16. the method for manufacturing radiant energy photocatalysis combiner according to claim 10, wherein step (i) comprises barium nitrate, sodium fluoride, titanium tetrachloride, coupler, and the mixing of porous material powder, and react, to obtain barium fluoride and titanium dioxide.
17. the method for manufacturing radiant energy photocatalysis combiner according to claim 16, wherein this coupler is EDTA.
18. the method for manufacturing radiant energy photocatalysis combiner according to claim 17, wherein mixed weight part ratio of barium nitrate, sodium fluoride, titanium tetrachloride and ceramic powder is respectively 1～5: 0.7～1.8: 0.4～2.0: 2～7, and the molal quantity of EDTA is the summation of barium nitrate and titanium tetrachloride molal quantity.
19. the method for manufacturing radiant energy photocatalysis combiner according to claim 10, wherein step (ii) comprises the step of a high-temperature calcination, and calcination temperature is 400～600 ℃.
20. a method of using radiant energy photocatalysis combiner, the method comprises the following step at least:
(1) a synthetic radiant energy photocatalysis combiner according to claim 1;
(2) this radiant energy photocatalysis combiner is contacted with an object;
(3) make the promoter in this radiant energy photocatalysis combiner absorb free radiant energy; And
(4) this promoter discharges a photon, makes photocatalyst and object in this radiant energy photocatalysis combiner carry out redox reaction.
21. the method for use radiant energy photocatalysis combiner according to claim 20, wherein this object is the azo based dye.
22. the method for use radiant energy photocatalysis combiner according to claim 20, wherein this object is industrial spent resin.
23. the method for use radiant energy photocatalysis combiner according to claim 20, wherein this radiant energy system be selected from group that ultraviolet ray, gamma-rays, X ray, β ray formed at least one of them.
24. the method for use radiant energy photocatalysis combiner according to claim 20, wherein this photocatalyst is a titanium dioxide.
25. the method for use radiant energy photocatalysis combiner according to claim 20, wherein this promoter is the inorganic scintillator material.
26. the method for use radiant energy photocatalysis combiner according to claim 20, wherein this promoter is selected from NaI (sodium iodide), CsI (cesium iodide), BaF
2(barium fluoride), CeF
3(cerium fluoride), group that YAP formed at least one of them.
27. the method for use radiant energy photocatalysis combiner according to claim 20, wherein this promoter is barium fluoride.
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| CNB2005100554234A CN100443162C (en) | 2005-03-17 | 2005-03-17 | Radiant energy photocatalysis combiner |
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|---|---|---|---|
| CNB2005100554234A CN100443162C (en) | 2005-03-17 | 2005-03-17 | Radiant energy photocatalysis combiner |
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| CN1833773A true CN1833773A (en) | 2006-09-20 |
| CN100443162C CN100443162C (en) | 2008-12-17 |
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| CNB2005100554234A Expired - Fee Related CN100443162C (en) | 2005-03-17 | 2005-03-17 | Radiant energy photocatalysis combiner |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144963A1 (en) * | 2007-06-01 | 2008-12-04 | Microvast, Inc. | Photodegradation catalyst and photodegradation catalyst precursor comprising metal halide or metal oxyhalide |
| CN102320791A (en) * | 2011-05-20 | 2012-01-18 | 福建耀中建材实业有限公司 | Method for preparing photocatalyst ecological bricks |
| CN108889263A (en) * | 2018-07-06 | 2018-11-27 | 上海济旦水科技有限公司 | The filler and preparation method thereof that can be generated free radicals |
| CN110526209A (en) * | 2019-08-16 | 2019-12-03 | 中国原子能科学研究院 | A kind of method of β irradiation Photocatalyzed Hydrogen Production |
| CN117943069A (en) * | 2024-01-31 | 2024-04-30 | 广州市政鑫橡塑有限公司 | CsBr-TiO2Composite photodegradation catalyst and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3233842B2 (en) * | 1995-11-17 | 2001-12-04 | 三菱重工業株式会社 | Hydrogen production method and apparatus |
| JP2002239397A (en) * | 2001-02-19 | 2002-08-27 | Hitachi Ltd | Method and apparatus for converting radiation energy |
| JP4635190B2 (en) * | 2001-07-09 | 2011-02-16 | 独立行政法人 日本原子力研究開発機構 | Photocatalyst-based hydrogen / oxygen production method and apparatus using a nuclear reactor |
| JP2003054902A (en) * | 2001-08-09 | 2003-02-26 | Japan Atom Energy Res Inst | Photocatalyst use type hydrogen/oxygen manufacturing method using radiation and apparatus therefor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144963A1 (en) * | 2007-06-01 | 2008-12-04 | Microvast, Inc. | Photodegradation catalyst and photodegradation catalyst precursor comprising metal halide or metal oxyhalide |
| CN101743060B (en) * | 2007-06-01 | 2014-03-12 | 微宏公司 | Photodegradation catalyst and photodegradation catalyst precursor comprising metal halide or metal oxyhalide |
| US8748335B2 (en) | 2007-06-01 | 2014-06-10 | Microvast, Inc. | Photodegradation catalyst and photodegradation catalyst precursor comprising metal halide or metal oxyhalide |
| CN102320791A (en) * | 2011-05-20 | 2012-01-18 | 福建耀中建材实业有限公司 | Method for preparing photocatalyst ecological bricks |
| CN102320791B (en) * | 2011-05-20 | 2013-03-27 | 福建耀中建材实业有限公司 | Method for preparing photocatalyst ecological bricks |
| CN108889263A (en) * | 2018-07-06 | 2018-11-27 | 上海济旦水科技有限公司 | The filler and preparation method thereof that can be generated free radicals |
| CN110526209A (en) * | 2019-08-16 | 2019-12-03 | 中国原子能科学研究院 | A kind of method of β irradiation Photocatalyzed Hydrogen Production |
| CN117943069A (en) * | 2024-01-31 | 2024-04-30 | 广州市政鑫橡塑有限公司 | CsBr-TiO2Composite photodegradation catalyst and preparation method thereof |
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| CN100443162C (en) | 2008-12-17 |
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