CN1214864C - Visible light responding photocatalyst of alkali metal and Ag-Bi oxide and its application - Google Patents
Visible light responding photocatalyst of alkali metal and Ag-Bi oxide and its application Download PDFInfo
- Publication number
- CN1214864C CN1214864C CN03158264.8A CN03158264A CN1214864C CN 1214864 C CN1214864 C CN 1214864C CN 03158264 A CN03158264 A CN 03158264A CN 1214864 C CN1214864 C CN 1214864C
- Authority
- CN
- China
- Prior art keywords
- photochemical catalyst
- visible light
- alkali metal
- bismuth
- application
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 title abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000004065 semiconductor Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000005286 illumination Methods 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a visible light responding photocatalyst of alkali metals and Ag-Bi composite oxide, which is prepared from a composite oxide semiconductor represented by the general formula of MBiO3. nH2O, wherein M represents at least one element of Li, Na, K and Ag, and n is not less than 0 and not greater than 2. When the photocatalyst prepared from the composite oxide semiconductor and used for decomposing harmful chemical substances is used, the photocatalyst has the characteristic that the harmful chemical substances are removed by irradiation with ultraviolet rays and visible rays.
Description
One, technical field
The present invention is relevant with photochemical catalyst.Especially visible light-responded photochemical catalyst, this photochemical catalyst are the composite oxide semiconductors that comprises the specific composition of alkali metal or Ag and bismuth, can effectively absorb the ultraviolet ray and the luminous ray that comprise in the sunshine, and optical Response is very superior.Content of the present invention comprises the very capable high activity decomposable harmful substances photochemical catalyst of decomposition harmful chemical, and uses this photochemical catalyst to decompose, remove the method for harmful chemical.
Two, background technology
The negative effect that the economic growth rapidly of 20th century brings---earth environment problem, increasingly serious.Environmental Hormone problems such as diox needless to say, agricultural chemicals in water and the atmosphere and odorant are also threatening people's safety and comfortable life.Therefore, we need carry on technical development, and control the generation of harmful substance, and remove the harmful substance that has produced as early as possible.People proposed to utilize in the photochemical catalyst decomposition water and atmosphere in agricultural chemicals and organic matter such as odorant, and application examples such as self-cleaning that scribble the surface of solids of photochemical catalyst, wherein major part has been used titanium dioxide.The band gap of titanium dioxide is 3.2eV, only just can manifest activity under the ultraviolet irradiation shorter than 400nm, so the photochemical catalyst of present use can only be outdoor or the local work of uviol lamp arranged.
The present invention is used for providing the ultraviolet ray that comprises except that the absorption sunshine, can also effectively absorb the novel photocatalysis agent of visible light.By using this catalyst, harmful substance is carried out illumination, decompose this harmful substance, thereby provide the method for innocent treatment of harmful substances.The research group that comprises the inventor is devoted to the research of the environmental cure of earth scope always, has then proposed the various schemes of relevant photochemical catalyst as wherein a ring, has carried out various inventions.According to the order of applying for a patent, briefly introduce the formation of each invention: proposed BVO below
1The photochemical catalyst (patent documentation 1) that the represented composite oxide semiconductor that contains vanadium constitutes; RVO
1The photochemical catalyst (patent documentation 2) that the represented composite oxide semiconductor that contains vanadium constitutes; (BaO)
2(In
2O
3) photochemical catalyst (patent documentation 3) that constitutes of the represented composite oxide semiconductor of m; MIn
2O
1The photochemical catalyst that represented composite oxide semiconductor constitutes; ABO
3The photochemical catalyst that the composite oxide semiconductor of represented Ca-Ti ore type constitutes; And MBiO
1The visible light-responded a series of like this photochemical catalysts such as photochemical catalyst that represented composite oxide semiconductor constitutes.
The present invention is the ring in these researchs, it is characterized in that developing with the diverse novel photocatalysis agent of photochemical catalyst that proposed in the past and has obtained success.But it is to be based upon on the successful in the past basis.It is as follows that Japan Patent discloses the document of above-mentioned prior art:
1, Japanese publication patent 2001-221148
2, Japanese publication patent 2002-59804
3, Japanese publication patent 2002-225296
The content of Japanese patent application 1 is: BVO
4(B=Al, Ga In) contain the compound of vanadium, and the content of Japanese patent application 2 is: RVO
4(R=terres rares and Y) contains the compound of vanadium: (BaO)
2, (In
2O
3) m (m=0-6) lamellar compound.
Three, summary of the invention
Absorbed the photon of the energy that surpasses its band gap when photochemical catalyst after, generate hole and electronics, because have powerful oxidation and reducing power, so can be with chemical substance oxidation or the reduction around it.In recent years, aspect the application study of photochemical catalyst, use it to decompose harmful chemical, and become the effective environmental scavenging material by expectation by extensive discussions.
Inject the sunshine on the face of land, reach maximum radiant intensity near visible wavelength is 500nm, the energy of the visible-range of wavelength 400～750nm is 43% of whole solar energies.And the energy in the ultraviolet ray below the wavelength 400nm is less than 5%.The application of above-mentioned titanium dioxide has limitation, although its weatherability fabulous be its major reason of applying.Therefore, in order effectively to utilize sunshine spectrum, need exploitation under visible light, also to have the photochemical catalyst of catalyst activity.
Therefore, in above-mentioned application study, developed the photochemical catalyst that can utilize visible light.If can effectively utilize visible light, the wavelength field will enlarge, and efficient will significantly improve.The titanium dioxide that uses is not having ultraviolet indoor being difficult to use at present, if can utilize visible light, so adaptable market will significantly enlarge.
Here, the key property of oxide semiconductor photochemical catalyst is the size of its band gap and the energy level in conduction band and forbidden band.The hole of oxide semiconductor valence band has very strong oxidability, can be the electron donor oxidation of water and multiple organic matter and so on, and the conduction band electronics that generates simultaneously need be consumed by the oxygen in the reducing atmosphere.That is to say that conduction level must be lower than the reduction potential of oxygen.
The present invention seeks to: propose a kind of catalyst,, can also effectively absorb the novel photocatalysis agent of visible light except that being used for providing the ultraviolet ray that comprises except that the absorption sunshine.By using this catalyst, harmful substance is carried out illumination, decompose this harmful substance, thereby provide the purifying treatment method of harmful substances.Comprise the research group that proposes the present invention, be devoted to the research of the environmental cure of earth scope always,, proposed the various schemes of relevant photochemical catalyst, carried out various inventions as a ring wherein.
The present invention is the ring in these researchs, it is characterized in that developing with the diverse novel photocatalysis agent of photochemical catalyst that proposed in the past and has obtained success.But it is to be based upon on the successful in the past basis.
The result of researchs such as the inventor is by adopting the method for following (1)～(3), successfully to solve above-mentioned problem.
(1) by general expression (I): MBiO
3NH
2The photochemical catalyst that composite oxide semiconductor constituted that O represents.In formula, M must represent at least one element among Li, Na, K, the Ag.N is between 0～2.
(2) put down in writing in above-mentioned 1 by composite oxide semiconductor constituted, combined oxidation bismuth semiconductor especially is used to decompose the photochemical catalyst of harmful chemical.
(3) exist in above-mentioned 2 record be used to decompose the photochemical catalyst of harmful chemical the time, be characteristics with the illumination that harmful chemical is comprised ultraviolet ray and luminous ray, decompose, remove the method for harmful chemical.
As implied above, by general expression (I): MBiO
3NH
2(in formula, M must represent at least one element among Li, Na, K, the Ag to the photochemical catalyst that composite oxide semiconductor constituted that O represents.0≤n≤2。), it can realize that the wavelength of photoresponse is the visible light of 700nm to the maximum.The photochemical catalyst that adopts can only work in ultraviolet ray range at present, so it is very great to enlarge the meaning of the visible wavelength range that can effectively utilize.Rely on the present invention, can utilize visible light energy, expeditiously dyestuff such as decomposition of methyl indigo plant.In addition, such photochemical catalyst also can be used in other chemical reaction.For example can be applied in the reaction of Environmental Hormone such as diox and organic decomposition reaction or reduction of metal ion.Can also contribute for environment purification.
Composite oxide semiconductor photochemical catalyst of the present invention as mentioned above, has activity in wide spectrum, the condition of use is not harsh, can durablely use.Because this characteristic, we can expect it not only in above-mentioned example, and can be employed in other multiple uses, we can say that it will bring into play great role from now on.
Four, the specific embodiment:
To be specifically described the present invention below.These all are the concrete practical operation examples of the present invention, and the present invention is not limited only to this.
1, the composite oxides MBiO of record in the application of the present invention the 1st
3NH
2The photochemical catalyst that is made of composite oxide semiconductor that O is represented, wherein M comprises a kind of or two or more elements among Li, Na, K, the Ag, and LiBiO is for example arranged specifically
3NH
2O, NaBiO
3NH
2O, KBiO
3NH
2O or AgBiO
3NH
2O, in addition, M comprises that above-mentioned a plurality of elements also are effective.Do not contain (n=0) or contain a small amount of (n is about 0.5) crystallization water H
2The material of O belongs to trigonal system, and lattice paprmeter is a=0.562, c=1.605nm approximately.And the material that contains 2 above crystallizations water belongs to hexagonal crystal, and lattice paprmeter is a=0.560, c=0.742nm.M comprises above-mentioned a plurality of elements, as dual element Li
yNa
1-yBiO
3NH
2O, Ag
yNa
1-yBiO
3NH
2O, Ag
yK
1-yBiO
3NH
2O, Li
yK
1-yBiO
3NH
2O.
2, in order to obtain the composite oxide semiconductor among the present invention, use solid state reaction usually, promptly the ratio of forming according to target as the oxide of each metal ingredient of raw material is mixed, burning in air, synthetic under normal pressure again.If the raw material of easy distillation, then the ratio of constituent is higher, promptly needs to increase the deal of raw material.
In addition, can also use several different methods such as ion-exchange, the method for changing mutually as the various colloidal sols and the gel state of raw material with metal complex or slaine, coprecipitation, citric acid complex method.Wherein also comprise the method for synthesizing by modulation nucleation, combustion oxidation thing presoma.
3, in order effectively to utilize light, the shape of the photochemical catalyst among the present invention preferably micron, nano particle and specific area is bigger.Oxide in solid state reaction after the modulation nucleation, particle is big, specific area is little, can pulverize with ball mill pulverizer, to dwindle particle diameter.The size of particle is generally 10nm～2000nm and the diameter of best results is below the 10nm.In addition, the particulate moulding is used as tabular, perhaps in other materials, be processed into film and use.
4, the photochemical catalyst among the present invention can be applied to multiple photochemical catalyst reaction.For example when organic matter decomposed, alcohol, agricultural chemicals, odorant etc. generally played electron donor, also produced hydrogen in the time of by the hole oxidation Decomposition because of electronics or oxygen reduction.Its reaction form is, makes catalyst outstanding turbid and carry out illumination in comprising aqueous organic, perhaps catalyst is fixed on the substrate.Also can as decomposing, odorant carry out vapor reaction.
Embodiment
Serve as that the present invention is described in detail on the basis with concrete practical operation example below.In following practical operation example, LiBiO
3And AgBiO
3Synthesize with ion-exchange.
Embodiment 1,
Use the NaBiO of X-ray diffraction (XRD) to selling on the market
3Raw material has carried out the detection of catalyst junction crystal structure.Determine this material and contain the crystallization water more than 2, belong to hexagonal crystal, space group P3, lattice paprmeter a=0.560, c=0.742nm.By NaBiO
32H
2O forms.
According to ultraviolet---the mensuration of visible absorption spectra analyzer, this photochemical catalyst can absorb the light from ultraviolet field to the visible-range that is limited to 500nm.Estimate that band gap below 2.5eV, has the response of visible light.
Make the NaBiO of 0.3 gram
32H
2O is outstanding turbid in the methyl blue aqueous solution 100ml of 15.3mg/l, carries out the photolysis reactions of methyl blue.Stir on one side with magnetism stick, from outside carry out illumination on one side.Light source adopts the lamp of 300WXe, and reactor adopts heat resistant glass (corning company product).In order to remove thermal effect, Yi Bian in cold water, make the reactor cooling, Yi Bian carry out the photochemical catalyst reaction test.Then between lamp and reactor, insert the optical filter of 420nm, only shine with the light of wavelength greater than filter.Passing through ultraviolet---the visible absorption spectra analyzer can detect because the light of methyl blue decomposes the change in concentration that produces.
As a result, under the visible light radiation of wavelength greater than 420nm, only used 15 minutes, methyl blue solution just fades fully.Its result is as shown in table 1.
Use KBiO
3Result that raw material obtains and above-mentioned NaBiO
3Basic identical.Dual element Li
yNa
1-yBiO
3, Ag
yNa
1-yBiO
3, Ag
yK
1-yBiO
3, Li
yK
1-yBiO
3Basic identical.
Embodiment 2
In air under the normal pressure, above-mentioned NaBiO
32H
2O estimates with the material that 120～250 ℃ temperature combustion formed after 5 hours in electric furnace.
Use XRD to detect the crystalline texture of catalyst.Can determine this material is not contain or contain a small amount of (n is about 0.5) crystallization water H
2The material of O belongs to three prismatic crystals, space group R-3, and lattice paprmeter is a=0.556, c=1.605nm.
According to the mensuration of ultraviolet-visible absorption spectra analyzer, this photochemical catalyst can absorb from ultraviolet field to the light in the visible light field that is limited to 500nm.Estimate that band gap below 2.5eV, has the responsiveness of visible light.
Make the NaBiO of 0.3 gram
32H
2O is outstanding turbid in the methyl blue aqueous solution 100ml of 15.3mg/l, carries out the photolysis reactions of methyl blue.Stir with magnetism stick on the limit, and illumination is carried out on the limit from the outside.Light source adopts the lamp of 300WXe, and reactor adopts heat resistant glass (product of corning company).In order to remove thermal effect, the limit makes reactor cooling limit carry out the photochemical catalyst reaction test in cold water.In addition,, between lamp and reactor, insert the interception filter of 420nm～580nm, only shine with the light of wavelength greater than filter in order to detect the interdependence of light wave length in the photochemical catalyst reaction.Can detect because the light of methyl blue decomposes the change in concentration that produces by the uv-visible absorption spectra analyzer.
As a result, by under the visible light radiation of 420nm filter, only used 9 minutes, methyl blue solution just fades fully, becomes complete white.When using the filter of 460nm, 480nm, the degrading activity of methyl blue is basic identical.Passing through under the visible light radiation of 580nm filter, methyl blue solution fades fully after 30 minutes.At this moment, except NaBiO
3Photochemical catalyst carries out beyond the light absorption, and the light absorption function of methyl blue self has played the effect of sensitizer, and the light of the decomposition reaction scope of replying enlarges more.Its result is as shown in table 1.
In addition, in order to determine the stability of compound, according to identical style, above-mentioned by the methyl blue solution decomposition run repeatable operation under the radiation of visible light of 420nm filter 5 times, result viewing is basic identical to its activity, determines that simultaneously the crystalline texture of photocatalyst material does not change yet.
The relation of research methyl blue degrading activity and incendiary material temperature found that the activity of material is the highest after 120 ℃ of burnings.
Embodiment 3
Carry out LiBiO with ion-exchange
32H
2Synthesizing of O photochemical catalyst.As original material, use NaBiO
32H
2O and LiNO
3According to the ratio of mol ratio 1 to 4 NaBiO
32H
2O and LiNO
3Mix, be dissolved in then in the water of 400ml, under 70 ℃ through 48 hours chemical reaction after, filter, again 60 ℃ dry down, thereby obtain.
Use XRD to detect the crystal structure of catalyst.Can determine it and belong to hexagonal crystal, space group P3, Lattice constant and above-mentioned NaBiO
32H
2O is approaching.Measure according to the uv-visible absorption spectra analyzer, this photochemical catalyst can absorb from ultraviolet field to the light in the visible light field that is limited to 500nm.Estimate that band gap below 2.5eV, has the responsiveness of visible light.
Make the LiBiO of 0.3 gram
32H
2O is outstanding turbid in the methyl blue aqueous solution 100ml of 15.3mg/l, carries out the photolysis reactions of methyl blue.Stir with magnetism stick on the limit, and illumination is carried out on the limit from the outside.Light source adopts the lamp of 300WXe, and reactor adopts heat resistant glass (corning company product).In order to remove thermal effect, Yi Bian in cold water, make reactor cooling limit carry out the photochemical catalyst reaction test.In addition,, between lamp and reactor, insert the interception filter of 420nm～500nm, only shine with the light of wavelength greater than filter in order to detect the interdependence of light wave length in the photochemical catalyst reaction.Passing through ultraviolet---the visible absorption spectra analyzer can detect because the light of methyl blue decomposes the change in concentration that produces.
As a result, by under the visible light radiation of 420nm filter, only used 10 minutes, methyl blue solution just fades fully, becomes complete white.Passing through under the visible light radiation of 500nm filter, methyl blue solution fades fully after 20 minutes.Its result is as shown in table 1.
Embodiment 4
Carry out AgBiO with ion-exchange
32H
2Synthesizing of O photochemical catalyst.As original material, use NaBiO
32H
2O and AgNO
3According to the ratio of mol ratio 1 to 4 NaBiO
32H
2O and AgNO
3Mix, be dissolved in then in the water of 400ml, under 70 ℃ through 48 hours chemical reaction after, filter, again 60 ℃ dry down, thereby obtain.
Use XRD to detect the crystal structure of catalyst.Can determine it and belong to hexagonal crystal, space group P3, Lattice constant and above-mentioned NaBiO
32H
2O is approaching.According to ultraviolet---the mensuration of visible absorption spectra analyzer, this photochemical catalyst can absorb from ultraviolet field to the light in the visible light field that is limited to 700nm, have the responsiveness of tangible visible light.
Make the AgBiO of 0.3 gram
32H
2O is outstanding turbid in the methyl blue aqueous solution 100ml of 15.3mg/l, carries out the photolysis reactions of methyl blue.Stir with magnetism stick on the limit, and illumination is carried out on the limit from the outside.Light source adopts the lamp of 300WXe, and reactor adopts heat resistant glass (product of corning company).In order to remove thermal effect, the limit makes reactor cooling limit carry out the photochemical catalyst reaction test in cold water.In addition,, between lamp and reactor, insert the interception filter of 420nm～500nm, only shine with the light of wavelength greater than filter in order to detect the interdependence of light wave length in the photochemical catalyst reaction.Passing through ultraviolet---the visible absorption spectra analyzer can detect because the light of methyl blue decomposes the change in concentration that produces.
As a result, passing through under the visible light radiation of 420nm filter, about 30 minutes, methyl blue solution faded fully, became complete white.Passing through under the visible light radiation of 500nm filter, methyl blue solution fades fully after about 40 minutes.Its result is as shown in table 1.
About above result, that is summed up in the table 1 is as implied above.That is to say, in table 1, sum up and listed the time that the photochemical catalyst composition that uses, the kind (purpose of reaction) of reaction, the light source that uses and wavelength, methyl blue fade fully and need.
The plastics work of embodiment 5, indoor use adds agent and is used to prepare aseptic appliance shell, and kitchen plastics, addition are the 0.5%NaBiO of plastics and filler total amount
32H
2O contrasts the same plastics that do not add photochemical catalyst, and the inhibiting rate of bacterium is obviously improved, and under the same environmental condition, the former has only below 20% of consequence person by the bacterium of unit are.
According to The above results, the scope that the bismuth-system compound oxide photocatalyst of alkali metal of the present invention and Ag is used is unqualified, for example environment and the photochemical catalyst that is used to decompose harmful chemical.As make nano level better effects if, purposes as: the plastics work of outdoor coating, indoor use adds agent and is used to prepare aseptic appliance shell, and kitchen plastics, addition are the 0.2-2% of plastics and filler total amount, more effective than titanium dioxide, be used to prepare the utensil of various food, medical treatment use.Harmful chemical is comprised that the illumination of ultraviolet ray and luminous ray is characteristics, decompose, remove the method for harmful chemical, handle the organic chemistry waste water of high concentration as if having found a treasure: as above-mentioned embodiment, the need of addition are handled more than 0.1% of the water yield, promptly can reach more than 90% by the COD clearance through illumination (ultraviolet light is better).Add LiBiO
32H
2O and KBiO
32H
2The O same amount can obtain effect same.
Table 1, photocatalyst activity The performance test results
| Semiconductor | Reaction | Light source | MB decomposes the needed time (branch) fully | |
| Embodiment 1 | NaBiO 3·2H 2O | Methyl blue decomposes | 300W Xe lamp (＞420nm) | 15 |
| Embodiment 2 | NaBiO 3·xH 2O | Methyl blue decomposes | 300W Xe lamp (＞420nm) | 8 |
| (x＜0.5) | 300W Xe lamp (＞460nm) | 9 | ||
| 300W Xe lamp (＞480nm) | 10 | |||
| 300W Xe lamp (＞580nm) | 30 | |||
| Embodiment 3 | LiBiO 3·2H 2O | Methyl blue decomposes | 300W Xe lamp (＞420nm) | 10 |
| 300W Xe lamp (＞500nm) | 20 | |||
| Embodiment 4 | AgBiO 3·2H 2O | Methyl blue decomposes | 300W Xe lamp (＞420nm) | 30 |
| 300W Xe lamp (＞500nm) | 40 |
MB: methyl blue
Claims (5)
1, the visible light-responded photochemical catalyst of the bismuth-system compound oxide of alkali metal and Ag is characterized in that by following formula: MBiO
3NH
2The photochemical catalyst that composite oxide semiconductor constituted that O represents, in formula, M represents at least one element among Li, Na, K, the Ag, 0≤n≤2.
2, by the visible light-responded photochemical catalyst of bismuth-system compound oxide of described alkali metal of claim 1 and Ag, the size that it is characterized in that combined oxidation bismuth semiconductor particle is 10nm～2000nm.
3,, it is characterized in that using in the outdoor coating addition 0.2-2% by the application of the visible light-responded photochemical catalyst of the bismuth-system compound oxide of described alkali metal of claim 1 and Ag.
4, by the application of the visible light-responded photochemical catalyst of the bismuth-system compound oxide of described alkali metal of claim 1 and Ag, it is characterized in that indoorly being used for plastics work and adding agent and prepare aseptic appliance shell, the kitchen plastics, the utensil that food, medical treatment are used, addition is the 0.2-2% of plastics and filler total amount.
5, by the application of the visible light-responded photochemical catalyst of the bismuth-system compound oxide of described alkali metal of claim 1 and Ag, it is characterized in that being used for organic chemistry wastewater treatment to the harmful chemical high concentration, addition is to need to handle more than 0.1% of the water yield, and through illumination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03158264.8A CN1214864C (en) | 2003-09-19 | 2003-09-19 | Visible light responding photocatalyst of alkali metal and Ag-Bi oxide and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03158264.8A CN1214864C (en) | 2003-09-19 | 2003-09-19 | Visible light responding photocatalyst of alkali metal and Ag-Bi oxide and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1526475A CN1526475A (en) | 2004-09-08 |
| CN1214864C true CN1214864C (en) | 2005-08-17 |
Family
ID=34287206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN03158264.8A Expired - Fee Related CN1214864C (en) | 2003-09-19 | 2003-09-19 | Visible light responding photocatalyst of alkali metal and Ag-Bi oxide and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1214864C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560027B (en) * | 2009-04-10 | 2011-07-20 | 南京大学 | Method for rapid degradation of triphenylmethane dye waste water |
| CN102527383B (en) * | 2012-02-18 | 2014-11-26 | 桂林理工大学 | Composite oxide photocatalyst LiAg3O2 with visible light response and preparation method for composite oxide photocatalyst |
| CN107162052B (en) * | 2017-06-15 | 2019-03-12 | 成都大学 | Bismuthic acid silver nanowires and preparation method thereof |
| WO2020042125A1 (en) * | 2018-08-30 | 2020-03-05 | 南通纺织丝绸产业技术研究院 | Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof |
| CN114160134B (en) * | 2021-12-16 | 2024-03-29 | 郑州航空工业管理学院 | In-situ synthesis of flower-like AgBiO 3 /NaBiO 3 Photocatalytic material and application thereof |
-
2003
- 2003-09-19 CN CN03158264.8A patent/CN1214864C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1526475A (en) | 2004-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Borate particulate photocatalysts for photocatalytic applications: a review | |
| Jing et al. | Engineering of g-C3N4 nanoparticles/WO3 hollow microspheres photocatalyst with Z-scheme heterostructure for boosting tetracycline hydrochloride degradation | |
| Zhang et al. | Facile in situ chemical transformation synthesis, boosted charge separation, and increased photocatalytic activity of BiPO4/BiOCl pn heterojunction photocatalysts under simulated sunlight irradiation | |
| Dong et al. | Species, engineering and characterizations of defects in TiO2-based photocatalyst | |
| CN107866234B (en) | High-activity ZnIn2S4/TiO2Preparation method of Z-system catalyst material | |
| CN107008467B (en) | Preparation method and application of heterojunction photocatalyst | |
| CN108465477A (en) | The Preparation method and use of Three-element composite photocatalyst | |
| CN1799690A (en) | Visible light responsible photocatalysis material of AgTO2 type composite oxide and its application | |
| CN110721698B (en) | Bismuth vanadate/copper vanadate composite photocatalyst and preparation method and application thereof | |
| CN1736584A (en) | Method for preparing nitrogen doped nano titanium dioxide photocatalyst with visible light activity by direct heat treatment method | |
| CN109364951B (en) | Visible light catalytic composite material and preparation method and application thereof | |
| CN103894177A (en) | Method for synthesizing rare earth doped potassium titanate powder with photocatalytic activity | |
| CN103301833B (en) | Yb<3+>-Tm<3+>-Li<+> triple-doped Bi2WO6/CNTs (carbon nanotubes) upconversion photocatalytic material | |
| CN107262132A (en) | A kind of sulfur doping g C3N4The preparation method of/zinc-cadmium sulfide composite photo-catalyst | |
| CN110624595A (en) | Calcium-indium-sulfur/titanium carbide photocatalytic composite material and preparation method thereof | |
| Karidas et al. | Photodegradation of methylene blue (MB) using cerium-doped zinc oxide nanoparticles | |
| CN111036272B (en) | C3N4/LaVO4Composite photocatalyst and preparation method thereof | |
| CN106925258A (en) | A kind of new Mo-Ti monocrystalline oxides nano material and its preparation and application | |
| CN1214864C (en) | Visible light responding photocatalyst of alkali metal and Ag-Bi oxide and its application | |
| CN102211019A (en) | Visible light-responsive composite oxide photochemical catalyst Ba1-xSrxLi2Ti6O14 and preparation method thereof | |
| CN111558389B (en) | BiVO4Protonated g-C3N4AgI ternary composite photocatalyst and preparation method thereof | |
| CN111558382B (en) | Preparation method and application of bismuth sulfide/bismuth molybdate oxygen defect hollow sphere composite photocatalyst | |
| CN108525695A (en) | A kind of graphene/carbon nitrence of two-dimensional layered structure/bromine oxygen bismuth composite Nano catalysis material and its preparation method and application | |
| CN110575841A (en) | Novel photocatalyst material for degrading methylene blue light and preparation method thereof | |
| CN102836720A (en) | Preparation method of zinc oxide nano-composite material and application of material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |