CN1321742C - Visible light response photocatalyst and application thereof - Google Patents
Visible light response photocatalyst and application thereof Download PDFInfo
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- CN1321742C CN1321742C CNB2003101062806A CN200310106280A CN1321742C CN 1321742 C CN1321742 C CN 1321742C CN B2003101062806 A CNB2003101062806 A CN B2003101062806A CN 200310106280 A CN200310106280 A CN 200310106280A CN 1321742 C CN1321742 C CN 1321742C
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- 239000011941 photocatalyst Substances 0.000 title abstract description 8
- 230000004298 light response Effects 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 66
- 238000000354 decomposition reaction Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003426 co-catalyst Substances 0.000 claims description 12
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- 229910052748 manganese Inorganic materials 0.000 claims description 3
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- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
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- 229910052697 platinum Inorganic materials 0.000 claims description 2
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- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 8
- 229910005855 NiOx Inorganic materials 0.000 description 7
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-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
- 230000000052 comparative effect Effects 0.000 description 3
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- 206010013786 Dry skin Diseases 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical group [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 Co x Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides highly active photocatalysts for efficiently adsorbing middle ultraviolet light and visual light in sunlight, and a method for using the photocatalysts to decompose harmful chemical substances and decompose water to prepare hydrogen. The photocatalysts are composite oxide semiconductors formed from indium, an element in 5A of the periodic table of elements and a transition metal element M. Oxide semiconductors represented by InAO4(A is an element in 5A), and composite oxide semiconductors expressed by the formula of In<1-x>MxAO4 derived by displacing part of indium with the transitional metal M, wherein the total mole number of indium to M equals to the mole number of A. Under the irradiation of sunlight containing ultraviolet light and visual light, the photocatalysts can decompose harmful chemical substances and decompose water to prepare hydrogen.
Description
One, technical field:
The present invention relates to ultraviolet and visible light-responded photochemical catalyst and application thereof, especially relate to the highly active photochemical catalyst that the indium system complex oxide semiconductor of the ultraviolet ray that can absorb efficiently in the sunshine and visible light is formed, and utilize the application that its decomposes harmful chemical and make hydrogen.
Two, technical background
At present, the deep environment and the energy problem that cause because of restriction and its a large amount of consumption of fossil resource, as global warming, ecological deterioration or the like, directly influenced the improvement of human existence and quality of life, the mankind press for green, the safe new forms of energy of exploitation.As the source of new forms of energy, though nuclear energy power generation comes into operation, the problem of aspects such as security and waste disposal has appearred.
One of approach of dealing with problems is to utilize solar energy.In the period of one, the solar energy that arrives earth surface is huge, and it is equivalent to catabiotic 10,000 times more than of human year.One of purpose of being engaged in the visible light Study on photocatalyst is the photosynthesis of simulating plant, development artificial light synthetic technology, thus utilize inexhaustible sunshine and water, directly make hydrogen and oxygen as green fuel.The decomposition reaction of water is the reaction of energy reservoir type shown in (1), considers the bright reaction condition of the necessity that only produces oxygen, and photosynthetic reaction is identical with it, also is such decomposition reaction:
H
2O=H
2+ 1/2O
2Formula (1)
Photochemical catalyst has generated hole and electronics after having absorbed the photon that is higher than its band-gap energy.These holes and electronics carry out oxidation reaction and reduction reaction respectively, produce oxygen and hydrogen.Consider the practicality of photochemical catalyst, utilizing sunshine is indispensable as light source.Irradiation is near sunshine medium wavelength visible light intensity maximum 500nm on the face of land, and wavelength is that the energy of the visible region of 400nm-750nm approximately is 43% of a sunshine gross energy.On the other hand, be ultraviolet ray less than 5% then below the 440nm at wavelength.So, seek the photochemical catalyst that under visible light, has catalyst activity in order to utilize solar spectrum, people to wish efficiently.
But though semiconductor light-catalyst in the past can produce hydrogen and oxygen having under the high-octane ultraviolet ray irradiation, it is very limited to utilize visible light-responded semiconductor light-catalyst to realize making the example of hydrogen, and activity is also very low.And make full use of visible light is the basic premise that efficiently utilizes sunshine.
In recent years, the research of application photochemical catalyst decomposition harmful chemical had caused people's attention.Though occurred utilizing titanium dioxide in the water and organic matters such as agricultural chemicals in the atmosphere and odorant decompose and be coated in the surface of solids and carry out application such as automatically cleaning, titanium dioxide almost can not utilize visible light.If the visible-light photocatalyst that can support utilization is arranged, can improve the efficient of above-mentioned application greatly so.The hole of valence band has very strong oxidability in the oxide semiconductor, can oxidize water and electron donor such as most of organic matters, thus discharge oxygen.And conduction band electron has reducing power, the water reduction can be generated hydrogen.That is to say that conduction level is than the oxidizing potential height of oxygen, and valence-band level lower than the reduction potential of hydrogen be the essential condition of realizing water decomposition.The photochemical catalyst that the energy decomposition water produces hydrogen and oxygen has strong oxidation and reducing power, therefore can expect to be applied in above-mentioned field.
Three, summary of the invention
The objective of the invention is: the highly active photochemical catalyst that the indium system complex oxide semiconductor of efficient absorption sunshine middle-ultraviolet lamp and visible light constituted is provided and utilizes its to decompose harmful chemical and make the method for hydrogen.
The object of the present invention is achieved like this:
1. visible light-responded photochemical catalyst, by indium and A element, and the combined oxidation semiconductor of divalent transition metal M formation: In
1-xM
XAO
4, the A element is Nb, Ta, that selects among the V is at least a, described divalent transition metal M is from Cr, Mn, Fe, Co, Ni, Cu, select in the Zn element at least a, 0＜x＜1, these composite oxide semiconductors are as photochemical catalyst.
2. the oxide semiconductor InAO that constitutes by A element in the indium and the periodic table of elements
4Represented oxide semiconductor and wherein a part of indium are replaced into the Formula I n after the transition metal M
1-xM
XAO
4Represented composite oxide semiconductor, request 1 photochemical catalyst that is write down exactly with wolfranite type crystal structure.
3. be the photochemical catalyst that writes down among the above-mentioned 1-3 as visible light-responded oxide semiconductor.
4. adopt Formula I n
1-xNi
xTaO
4Or In
1-xNi
xNbO
4Represented composite oxide semiconductor is as the photochemical catalyst of above-mentioned 1-4 record.
5. the photochemical catalyst of the co-catalyst that writes down among the above-mentioned 1-5.
6. the method that is contained the light irradiation decomposition harmful chemical of ultraviolet ray and visible light with the photochemical catalyst among the above-mentioned 1-6.
7. contained ultraviolet ray with the photochemical catalyst among the above-mentioned 1-6 and the light of visible light shines the method for making hydrogen.
8. to shine complete decomposition water be the method that hydrogen and oxygen are made hydrogen to the light that is contained ultraviolet ray or visible light with the photochemical catalyst among the above-mentioned 1-6.
In the present invention, employed photochemical catalyst is that expression formula is In
1-xM
XAO
4Oxide, wherein M is the metallic element of divalent, is from Cr, Mn, Fe, Co, Ni, Cu, select in the elements such as Zn, A is the element of 5 valencys, selects from elements such as V, Nb, Ta, with 4 atoms, the result who in fact obtains is less than 4 owing to defectives such as having the oxygen room to oxygen in the chemical formula in form.Can think that the quantity of oxygen will become and be less than 4 if the M of divalent becomes many.X is bigger than 1 little numeral than 0.Basic molecular formula is expressed as general expression B
3-A
5-O
4, having the wolfranite crystal structure, x is just passable in keeping the stable scope of its crystal structure in the compound.Composite oxide semiconductor of the present invention can be synthetic by general solid reaction process, promptly mixes the oxide that respectively has each metal ingredient according to stoichiometric proportion, calcines to form under the air normal pressure.For the raw material of easy distillation, on deal, need to add a bit slightly.In addition, also can use metal alkoxide or slaine to be several different methods such as various collosol and gels (sol-gel) method of raw material, citric acid complex method.
In order to effectively utilize light more, wish among the present invention photochemical catalyst be shaped as particulate, to obtain bigger surface area.
With the oxide of solid reaction process preparation, its particle is big and surface area is less, but can particle diameter be diminished by pulverizing means such as ball mills.General particle size is about 10 μ m-200 μ m, preferably below the 50 μ m.In addition, particulate can also be pressed into tabular the use.The method of solid phase reaction can be referring to the applicant's related invention 92107282,98111231 inventors: the new spring of Xin etc.
Can modify co-catalyst commonly used at semiconductor surface of the present invention, as transition metal, NiO and IrO2, NiO such as noble metals such as Pt, Pd, Ni, Co
x, RuO
2Deng oxide, as photochemical catalyst with micro-structural.The preparation method can be infusion process or electrodeposition process etc.Infusion process is exactly that the aqueous solution that conductor oxidate is put into the compound such as chloride, nitrate of this oxide spike is flooded, following dry about 2-5 hour at 100-200 ℃ then, at (preferably between 200-500 ℃) below 800 ℃, calcining is 2-5 hour under reducibility gas and/or oxidizing gas.The co-catalyst consumption is 0.01-10wt%, 0.1-5wt% preferably.
In addition, the employed reaction solution of complete decomposition reaction that carries out water is not limited in pure water.In general, the decomposition reaction of water is taken place.
In the above-mentioned aqueous solution, add photochemical catalyst of the present invention.The addition of catalyst should be to guarantee that the light of incident can be by the amount of efficient absorption basically.To irradiated area is 25cm
2Situation, the amount of the photochemical catalyst of interpolation is 0.05-10g, preferably 0.2-3g.By decomposing the aqueous solution with catalyst and carry out illumination and penetrate, can make water decomposition and produce oxygen like this having added light.For example, can in pure water, add photochemical catalyst of the present invention, make water decomposition, generate stoichiometric proportion simultaneously and be 2: 1 oxygen and hydrogen by the irradiation visible light.The spectrum that is used to shine the light of water must contain the wavelength that can be absorbed by semiconductor.Also can shine sunshine in the present invention.
The mode of concrete reaction can be turbidly to carry out illumination penetrate in comprising aqueous organic catalyst is outstanding, also can be that catalyst is fixed on the base, and liquid slowly flows on its surface, the gas-phase reaction that also can decompose odorant in the vaporizer bed.
Photochemical catalyst of the present invention not only can be used for the decomposition fully of water, can also be applied to multiple light-catalyzed reaction.For example, when decomposing complicated organic molecule, the molecule of polluters such as alcohol or agricultural chemicals, dyestuff, intermediate, stench generally plays the effect of electron donor, they are decomposed by the hole oxidation, meanwhile, perhaps produced hydrogen by electron reduction, perhaps oxygen is by electron reduction.The device of concrete reaction can be turbidly to carry out illumination penetrate in comprising aqueous organic catalyst is outstanding, also can be that catalyst is fixed on the base, also can be the gas-phase reaction when decomposing odorant.
The effect of invention also comprises: about the photochemical catalyst that directly utilizes solar energy that water is decomposed fully, the photochemical catalyst that uses only has activity under ultraviolet ray at present, accounts for the visible light that accounts for the overwhelming majority in the solar energy and can not effectively utilize.Then can utilize visible light to split water into hydrogen and oxygen by the present invention.Just might be paved with photochemical catalyst future in cistern, by a large amount of hydrogen of making in endless solar energy highly effective rate ground, this provides an approach likely for solving energy problem.
Four, the specific embodiment
Embodiment 1
At Formula I n of the present invention
1-xM
xAO
4In, use indium, element M and A to synthesize In
1-xM
xAO
4According to stoichiometric proportion, by the oxide of the synthetic various compositions of solid phase method.This catalyst is to utilize stoichiometric proportion to regulate (1-x) mol In
2O
3X=(0-1), x mol NiO (x=0-1) and 1 mol Ta
2O
5(table 1).For example, during x=0.2, In
0.8Ni
0.2TaO
4Be respectively weighing In
2O
83.201g, NiO 0.431g, Ta
2O
56.368g.These raw materials are put into the alumina crucible, in air under the normal pressure in electric furnace through after 900 ℃, 24 hours the presintering, repeat 3 calcinings of 1200 ℃, 50 hours again.After calcining finishes, this calcined material is ground to form big or small powder below the 10 μ m in grinding alms bowl.Use the chemical composition and the crystal structure of XRD and SEM-EDS research light reaction front and back catalyst.Resolve by Rietveld, this type oxide has monoclinic crystal structure, space group is P2/C, and crystal configuration is a stratiform Wolframite structure.Semiconductor with Wolframite type crystal structure, its electronics ratio is easier to move.Measure by the UV Absorption spectrum, can obtain its energy gap below 2.5Ev, therefore have the response of visible light.
The method of mixing the 1.0wt%NiOx co-catalyst in the above-mentioned oxide semiconductor is by Ni (NO
3)
2The dipping of the aqueous solution, 200 ℃ of following 5 hours dryings, 500 ℃ of following hydrogen reductions, realize 200 ℃ of following oxidations again.
The NiOx/In of 0.5g
1-xNi
xTaO
4Outstanding turbid in pure water 250ml, make it that photolysis reactions of water take place.Use closed circulation class catalyst reaction device, stir Yi Bian carry out magnetic, Yi Bian from the external irradiation visible light.Light source uses the xenon lamp of 300W, the vessel that reactive tank uses pyrex to make.(wavelength＞420nm) obtains long wavelength's light, irradiates light catalyst then by the copped wave wave filter to make light.Carry out with gas chromatography the detection of the hydrogen that produced and oxygen with quantitatively.
Experimental result shows: the stoichiometric proportion of hydrogen and oxygen is 2: 1, thus proof: rely on visible light to realize the decomposition fully of water.The speed of hydrogen and generation thereof is as shown in table 1.This performance when the part of In is replaced with Ni is greatly different.In this based semiconductor, active maximum during x=0.1.
In
1-xM
xAO
4In, the foregoing description roughly the same is respectively from using IrO
2, CoO, NiO
x, RuO
2, oxides such as CuO, ZnO replace NiO, can obtain similar composite oxides, effect is also similar.
In like manner, V
2O
5, Nb
2O
5Replace Ta
2O
5, roughly the same the foregoing description can obtain similar composite oxides, and effect is also similar.
Embodiment 2
Use RuO
2NiOx among the replacement embodiment 1 is as co-catalyst.In
1-xNi
xTaO
4Semiconductor mixes 1.0wt%RuO
2Method be to pass through RuCl
4The dipping of the aqueous solution, 200 ℃ of following 5 hours dryings, the calcining in following 2 hours of 500 ℃ of following oxidizing gases realize.Its result is as shown in table 1.Also can learn this moment: water decomposes fully under visible light.The embodiment of IrO2 is the same.
Electrodeposition process is that electrolysis process is deposited on In with Pt noble metal, Co transition metal
1-xNi
xTaO
4On the semiconductor, obtain as photochemical catalyst with micro-structural.Its result is close with table 1.Also can use Pt carbon to accumulate in In
1-xNi
xTaO
4On similar semiconductor.
Embodiment 3
In order to confirm that organic decomposition can carry out more efficiently under visible light, in the aqueous solution, carry out the decomposition of methyl alcohol.Use Pt (0.1wt%) as In
0.9Ni
0.1TaO
4Co-catalyst.With the photochemical catalyst of 0.5g put into the mixed liquor of 240ml pure water and 10ml methyl alcohol outstanding turbid, make it that photolysis reactions take place.Use closed circulation class catalyst reaction device, stir Yi Bian carry out magnetic, Yi Bian from the external irradiation visible light.Light source uses the xenon lamp of 300W, the vessel that reactive tank uses pyrex to make.From the light of light source, (wavelength＞420nm) obtains long wavelength's light to light, shines test portion (photochemical catalyst) then by the copped wave wave filter.Carry out with gas chromatography the detection of the hydrogen that produced and oxygen with quantitatively.Experimental result shows that hydrogen produces with the velocity-stabilization of 146 μ mol/h, does not produce oxygen.This shows that under visible light radiation following reaction has taken place: methanol oxidation is decomposed in the hole, the electron reduction water generates hydrogen.
Decomposition to organic pollutant matter: be used for removing complicated chemical materials such as waste water phenol, acid, ketone, aldehyde, can be referring to titanium dioxide method processing method: the CN01238388 of Southeast China University " administers the photo catalysis reactor of waste water and gas.
Present embodiment is used for the processing to phenol wastewater (factory effluent of terephthalic acid (TPA)), uses above-mentioned condition, and the photochemical catalyst of 0.5g is put into 250ml waste water, xenon lamp direct irradiation 2 hours, and the COD clearance reaches more than 80%.
Present embodiment is used for the photochemical catalyst of the processing to the imperial sour waste water of Gu: 0.5g and put into 250ml waste water xenon lamp direct irradiation 2 hours, and the perusal decolorizing effect is obvious.
Embodiment 4
In embodiment 3, use Pt (1wt%) as In
0.8Cu
0.2TaO
4Co-catalyst, Pt (1wt%) is as In
0.8Fe
0.2TaO
4Co-catalyst.The mixed liquor of the photochemical catalyst of 0.5g being put into 240ml pure water and 10ml methyl alcohol hangs turbid, as to make its generation water photolysis reactions.Use closed circulation class catalyst reaction device, stir Yi Bian carry out magnetic, Yi Bian from the external irradiation visible light.Light source uses the high-pressure mercury-vapor lamp of 400W, the vessel that reactive tank uses pyrex to make, irradiation visible light and ultraviolet ray.The hydrogen that produces with gas chromatography and the detection of oxygen with quantitatively.Experimental result shows that hydrogen produces with the velocity-stabilization of 100 μ mol/h and 80 μ mol/h, does not produce oxygen.This shows following reaction has taken place: methanol oxidation is decomposed in the hole, the electron reduction water generates hydrogen.
Comparative example 1
In embodiment 1, to not replacing the NiOx/InTaO of Ni
4And RuO2/InTaO
4Activity estimate, but it compares NiOx/In
L-xNi
xTaO
4And RuO2/In
1-xNi
xTaO
4The activity of embodiment 1 low.
Comparative example 2
In representational photochemical catalyst Pt-TiO2, only under radiation of visible light, without any reaction.
Table 1: photocatalyst activity
| Example | Semiconductor | Co-catalyst | Reaction | Light source | Gas produces speed (μ mol/h) | |
| H | 0 | |||||
| Embodiment 1 embodiment 2 | In 1-xNi xTaO 4(x＝0.05) (x＝0.1) (x＝0.15 ) In 1-xNi xTaO 4(x＝0.05) (x＝0.1) | NiOx RuO2 | The decomposition of the decomposition water of water | The Xe lamp (＞420nm) the Xe lamp (＞420nm) | 4.2 17.0 8.3 2.0 8.7 4.8 | 2.1 8.1 4.1 1.0 4.3 2.3 |
| Comparative example 1 | InTaO4 TiO2 | NiOx RuO2 Pt | The decomposition of water | The Xe lamp (＞420nm) the Xe lamp (＞420nm) | 3.2 0.8 tr | 1.1 0.4 0 |
Claims (9)
1, visible light-responded photochemical catalyst is characterized in that by indium and A element, and the composite oxide semiconductor that forms of divalent transition metal M: In
1-xM
xAO
4, the A element is Nb, Ta, that selects among the V is at least a, described divalent transition metal M is from Cr, Mn, Fe, Co, Ni, Cu, select in the Zn element at least a, 0＜x＜1, these composite oxide semiconductors are as photochemical catalyst.
2,, it is characterized in that the co-catalyst that described composite oxide semiconductor finishing is used is Pt, Pd, Ni, Co, NiO, IrO by the described visible light-responded photochemical catalyst of claim 1
2, NiO
xOr RuO
2
3,, it is characterized in that described co-catalyst consumption is 0.01-10wt% by the described visible light-responded photochemical catalyst of claim 2.
4,, it is characterized in that described co-catalyst consumption is 0.1-5wt% by the described visible light-responded photochemical catalyst of claim 3.
5, by the described visible light-responded photochemical catalyst of claim 1, it is characterized in that adopting Formula I n
1-xNi
xTaO
4Or In
1-xNi
xNbO
4
6,, it is characterized in that this catalyst is contained the light irradiation decomposition harmful chemical of ultraviolet ray and visible light by the purposes of claim 1 or 2 described visible light-responded photochemical catalysts.
7, by the purposes of the described visible light-responded photochemical catalyst of claim 6: it is characterized in that: the mode of reaction is turbidly to carry out illumination penetrate in comprising aqueous organic catalyst is outstanding, or catalyst is fixed on the base, liquid slowly flows on its surface, or the gas-phase reaction when being used for vaporizer and decomposing odorant.
8,, it is characterized in that light that this catalyst is contained ultraviolet ray and visible light shines to make hydrogen by the purposes of claim 1 or 2 described visible light-responded photochemical catalysts.
9,, it is characterized in that the mode of reacting turbidly carries out illumination and penetrate catalyst is outstanding in comprising aqueous organic, or catalyst be fixed on the base that water slowly flows on its surface by the purposes of the described visible light-responded photochemical catalyst of claim 8.
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| CN100423293C (en) * | 2006-04-30 | 2008-10-01 | 南京大学 | Solar cell and its preparing method |
| CN102872853A (en) * | 2012-09-26 | 2013-01-16 | 北京工业大学 | Three-dimensional ordered macroporous InVO4 visible light-responsive photocatalyst, preparation and application |
| CN106732717B (en) * | 2013-05-31 | 2019-03-05 | 天津大学 | Application in water generation hydrogen and oxygen is decomposed by the catalyst that element tantalum indium nickel oxygen and nitrogen form under visible light |
| CN104307527A (en) * | 2014-10-24 | 2015-01-28 | 桂林理工大学 | Visible light responding photocatalyst InFeZn5O8 and preparation method thereof |
| CN104841440B (en) * | 2015-05-07 | 2017-12-12 | 北京化工大学 | A kind of heterojunction type tri compound semiconductor light-catalyst and preparation method thereof |
| CN107376960A (en) * | 2017-07-11 | 2017-11-24 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of nickel doping phosphoric acid indium photochemical catalyst |
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| CN1422694A (en) * | 2001-12-06 | 2003-06-11 | 中国科学院大连化学物理研究所 | Catalyst for reduction of nitrogen oxide, its preparation method and use |
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