CN100464846C - Method for preparing solid solution light catalyst capable of responding visible light - Google Patents

Method for preparing solid solution light catalyst capable of responding visible light Download PDF

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CN100464846C
CN100464846C CNB2006100294015A CN200610029401A CN100464846C CN 100464846 C CN100464846 C CN 100464846C CN B2006100294015 A CNB2006100294015 A CN B2006100294015A CN 200610029401 A CN200610029401 A CN 200610029401A CN 100464846 C CN100464846 C CN 100464846C
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photochemical catalyst
load
visible light
ruo
oxide
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CN1899689A (en
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刘恢
上官文峰
袁坚
施建伟
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Shanghai Jiaotong University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

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Abstract

The preparation of light catalyst capable of responding visible light is used in semiconductor light catalysis. The light catalyst is compound of chemical expression of BixM2-xV2O8, where, M is one of Y, La, Ce, Pr, Nd and Sm, 0<x<2, and the atom ratio of (Bi+M) to V to O is 1 to 1 to 4. The preparation process of the light catalyst includes the following steps: mixing the oxides or salts containing Bi, M and V in the ratio of x to (2-x) to 2, where 0<x<2, in ethanol; drying at 80deg.c for 12 hr, and final high temperature solid state reaction at 800-1000deg.c for over 1 hr to produce the target product. The catalyst of the present invention can absorb visible light and ultraviolet ray of wavelength smaller than 600 nm, and after loading NiOx, or Pt and/or RuO2, it may catalyze the decomposition of water to produce H2 and O2, and raise solar energy utilization rate.

Description

The preparation method of the mischcrystal photocatalyst of energy responding to visible light
Technical field
The present invention relates to a kind of preparation method of photochemical catalyst, particularly a kind of preparation method of mischcrystal photocatalyst of energy responding to visible light.Be used for the conductor photocatalysis technical field.
Background technology
Photocatalysis is a kind of new technique that utilizes luminous energy (particularly solar energy) to carry out the depollution of environment and energy conversion.Because it can utilize natural energy source---solar energy widely, and have that energy consumption is low, reaction condition is gentle, easy and simple to handle, can reduce outstanding feature such as secondary pollution and come into one's own day by day, have broad application prospects.Under illumination condition, photochemical catalyst can generate light induced electron and hole, and reduction takes place for they and water and oxidation generates hydrogen and oxygen, thereby solar energy directly is converted to Hydrogen Energy, realize the artificial photosynthesis, for from now on global energy and environmental problem provides splendid solution route.
TiO 2Be a kind of typical photochemical catalyst, energy gap is about 3.2eV, and light abstraction width is confined to ultra-violet (UV) band (optical wavelength＜380nm).But this part light only accounts for 4% of whole sunshine gross energy, and present TiO 2Quantum efficiency is not higher than 28%, so the utilization ratio of solar energy has only about 1%, has limited the utilization to solar energy greatly.Although the whole bag of tricks is arranged to TiO 2Carry out modification, so that it can work in visible-range (account for solar radiation 65%), but because these methods can be at TiO 2In mix atom or in crystal, form defective and cause the compound of light induced electron and hole so that on the contrary to some extent decline of over-all quantum efficiency.
Exploitation high-quantum efficiency, visible light-responded new catalysis material are the keys of photocatalysis technology.The exploitation of new material has three kinds of approach to realize: (1) forms new donor energy level by the method such as transient metal doped in semi-conductive forbidden band; (2) in semiconductor, form new valence band by methods such as nonmetal dopings; (3) by solid-solution approach the semi-conductive valence band of two kinds of different band structures and conduction band are coupled respectively and form new valence band and conduction band.Because method (3) can be regulated valence band and the conduction band position of material simultaneously, has bigger technology space and application prospect, therefore paid attention to by the researcher in recent years.
Find that by literature search the Chinese invention patent application number is 03140525.8, name is called: nitrogenous optically catalytic TiO 2 film and preparation method thereof, this patent disclosure a kind of at O 2/ N 2In the reacting gas, adopt magnetically controlled sputter method to prepare nitrogenous optically catalytic TiO 2 film.The magnetically controlled sputter method unit scale is big, price is high, is not suitable for simultaneously preparation and the doping vario-property of nano-powder material.Utilize NH 3Same TiO 2Reaction also can be synthesized the titanium dioxide optical catalyst of nitrating, but NH 3Danger and contaminative are big.In addition, owing to improve titanium dioxide by nitrogen-doping method visible Optical Absorption and utilization are remained limited, in recent years have some synthetic metal oxynitride photochemical catalyst of report that visible light is had good response characteristic.But, no matter be nitrogen-doped titanium dioxide or metal oxynitride, all have unstability, nitrogen will be overflowed under higher temperature or some condition, thereby loses the responding ability to visible light.
Summary of the invention
The object of the invention is to overcome the deficiency of above technical problem, has proposed a kind of preparation method of mischcrystal photocatalyst of energy responding to visible light.The photochemical catalyst of the present invention preparation can absorbing wavelength less than visible light and the ultraviolet light of 600nm, by Pt or RuO 2Or single load or Pt and the RuO of NiOx (0＜x＜1) 2Common load, possessed photocatalytic activity, can be in its absorption spectrum ranges effectively degradation of contaminant and photolysis water hydrogen gas and oxygen, that has improved solar energy utilizes scope and transformation efficiency.
The present invention is achieved by the following technical solutions, and photochemical catalyst of the present invention is that a kind of chemical formula that is made of Bi, M, four kinds of elements of V, O is Bi xM 2-xV 2O 8Solid solution compound, a kind of among M=Y, La, Ce, Pr, Nd, the Sm wherein, 0＜x＜2, (Bi+M): the atomic ratio of V:O is 1:1:4, and Bi and M can replace mutually continuously, this photochemical catalyst adopts high temperature solid state reaction synthetic, specific as follows:
The oxide or its esters that will contain Bi, M (M=Y, La, Ce, Pr, Nd, Sm), V, in x:(2-x): 2 ratios are measured, and wherein 0＜x＜2 add a spot of ethanol pressed powder is mixed, dry 12h under 80 ℃ is then through the synthetic object of high temperature solid state reaction.The parameter of high temperature solid state reaction is: firing temperature is 800-1000 ℃, and the solid phase reaction time is more than 1 hour.When temperature is lower than 800 ℃, also has a small amount of unreacted raw material in the object.Can sinter piece into when temperature is higher than 1000 ℃, be not easy to use.
The described Bi of containing compound comprises a kind of in bismuth nitrate, bismuth oxide, the waltherite.
The compound of the described V of containing is a kind of in ammonium metavanadate, the vanadic anhydride.
The described M of containing (M=Y, La, Ce, Pr, Nd, Sm) compound comprises in oxide, nitrate, the carbonate a kind of.
The described Y of containing compound is any one in yittrium oxide, yttrium nitrate, the yttrium carbonate.
The described La of containing compound is any one in lanthana, lanthanum nitrate, the lanthanum carbonate.
The described Ce of containing compound is any one in the inferior cerium of oxidation, cerous nitrate, the cerous carbonate.
The described Pr of containing compound is any one in praseodymium oxide, praseodymium nitrate, the praseodymium carbonate.
The described Nd of containing compound is any one in neodymia, neodymium nitrate, the neodymium carbonate.
The described Sm of containing compound is any one in samarium oxide, the samaric nitrate.
Described by carrying method with Pt or RuO 2Or NiO x(0＜x＜1) is carried on Bi xM 2-xV 2O 8(M=Y, La, Ce, Pr, Nd, Sm; 0＜x＜2) concrete grammar on surface is respectively as follows:
The load of Pt can realize by following two kinds of methods: (1) is with Bi xM 2-xV 2O 8Powder impregnated in chloroplatinic acid H 2PtCl 6In the aqueous solution, in whipping process, utilize ultra violet lamp to make the Pt reduction, form the Bi of Pt load xM 2-xV 2O 8Photochemical catalyst, a kind of among M=Y, La, Ce, Pr, Nd, the Sm, 0＜x＜2; (2) with Bi xM 2-xV 2O 8Powder impregnated in chloroplatinic acid H 2PtCl 6In the aqueous solution, by heating evaporation, drying and calcining, form the Bi of Pt load xM 2-xV 2O 8Photochemical catalyst, a kind of among M=Y, La, Ce, Pr, Nd, the Sm, 0＜x＜2.
RuO 2Load can realize by the following method: with Bi xM 2-xV 2O 8Powder impregnated in ruthenic chloride (RuCl 3) in the aqueous solution, by heating evaporation, drying and calcining, form RuO 2Load with Bi xM 2-xV 2O 8Photochemical catalyst.
Pt-RuO 2The method of load is altogether: earlier by the above method load RuO 2After, again by the above method supporting Pt.
NiO xThe load of (0＜x＜1) can realize by the following method: with Bi xM 2-xV 2O 8Powder impregnated in nickel nitrate (Ni (NO 3) 2) in the aqueous solution, by heating with water evaporation, drying, at H 2The lower 500 ℃ of calcining 2h of atmosphere are then at O 2The lower 200 ℃ of calcining 1h of atmosphere form NiO x(0＜x＜1) load with Bi xM 2-xV 2O 8Photochemical catalyst.
The load capacity of above-described loaded optic catalyst is controlled at following scope: Pt:0.1～0.5wt%, RuO 2: 0.5～3.0wt%, NiO x(0＜x＜1): 0.1～3.0wt%.
The energy that the sun discharged arrives earth surface in 1 year total amount is 5.5X10 26J is 10,000 times of present 1 year institute of whole mankind consumed energy summation.The low-density of solar energy and unstability thereof are unfavorable for the direct utilization to it.The technology of photochemical catalyzing can utilize solar energy to split water into hydrogen and oxygen, thereby converts solar energy into chemical energy, is convenient to store, transports and utilizes.After using hydrogen, hydrogen becomes again the form of water, can not pollute environment.Simultaneously, water and sunlight are inexhaustible materials, and therefore the hydrogen that obtains by photochemical catalyzing is a kind of energy of sustainable development and utilization completely.But can photodissociation water practicability depend on that the most at last conversion of solar energy is the efficient of chemical energy.Up to now, people find and develop the photochemical catalyst great majority that are used for photodissociation water only can be in the ultraviolet ray range work of wavelength less than 400nm.And accounting for about about 4%, 65% energy of gross energy, the energy of sunshine middle-ultraviolet lamp all belongs to visible-range.Therefore, photochemical catalyst provided by the present invention can absorbing wavelength less than visible light and the ultraviolet light of 600nm, and decomposition water generates hydrogen and oxygen simultaneously in visible light and ultraviolet light range, thereby improved the transformation efficiency of solar energy, had positive meaning solving the following energy and environmental problem.
In addition, aspect the depollution of environment, the photochemical catalyst that can absorb visible light provided by the present invention can be widely used in the surfaces such as indoor and outdoor body of wall of various buildings, can utilize natural daylight to purify pollutant in the atmosphere effectively, purify waste water, improve environmental quality, will bring great social benefit and economic benefit.
Specific embodiment
Content in conjunction with the inventive method provides following examples:
Embodiment 1:
1. with Bi (NO 3) 35H 2O gets 4.8507g as the bismuth source, uses Y 2O 3As the yttrium source, get 1.1254g, as the vanadium source, get 2.3395g with ammonium metavanadate, put into agate mortar, add absolute ethyl alcohol 10mL as dispersant, grind, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 800 ℃ with the speed of 10 ℃/min, insulation 12h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 900 ℃ with the speed of 10 ℃/min, insulation 12h.Take out after the cooling and grind acquisition object BiYV 2O 8
4. take by weighing 2g BiYV 2O 8Powder impregnated in 5ml chloroplatinic acid (H 2PtCl 6) in the aqueous solution (0.00205mol/L), by 300w Xenon light shining 2h, form the BiYV of Pt load 2O 8Photochemical catalyst, the amount of the Pt of institute's load is 0.1wt%.
5. take by weighing the BiYV of load 0.1wt%Pt 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is used with the gas chromatograph of thermal conductance detector and done quantitative analysis, BiYV 2O 8Product hydrogen and produce oxygen speed and be respectively 126 μ mol/gh and 65.3 μ mol/gh.With behind the following wavelength light wave of optical filter elimination 420nm, produce hydrogen under the same terms and be respectively 12.3 μ mol/gh and 6.2 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.With behind the following wavelength light wave of optical filter elimination 510nm, produce hydrogen under the same terms and be respectively 3.2 μ mol/gh and 2 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.
Embodiment 2:
1. with Bi (NO 3) 35H 2O gets 0.4851g as the bismuth source, uses Ce 2O 3As the cerium source, get 3.1182g, as the vanadium source, get 2.3395g with ammonium metavanadate, put into agate mortar, add absolute ethyl alcohol 10mL as dispersant, grind, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 900 ℃ with the speed of 10 ℃/min, insulation 5h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 1000 ℃ with the speed of 10 ℃/min, insulation 10h.Take out after the cooling and grind acquisition object Bi 0.1Ce 1.9V 2O 8
4. take by weighing 2g Bi 0.1Ce 1.9V 2O 8Powder impregnation is in 5ml chloroplatinic acid (H 2PtCl 6) in the aqueous solution (0.01025mol/L), according to 2h, form the Bi of Pt load by the 300w xenon lamp 0.1Ce 1.9V 2O 8Photochemical catalyst, the amount of the Pt of institute's load is 0.5wt%.
5. take by weighing the Bi of load 0.5wt%Pt 0.1Ce 1.9V 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis, BiYV with the gas chromatograph that has the thermal conductance detector 2O 8Product hydrogen and produce oxygen speed and be respectively 44 μ mol/gh and 21.8 μ mol/gh, with behind the following wavelength light wave of optical filter elimination 420nm, the same terms produces hydrogen down and product oxygen speed is respectively 6.3 μ mol/gh and 2.0 μ mol/gh in the above-mentioned photocatalytic reaction device.
Embodiment 3:
1. with Bi (NO 3) 35H 2O gets 9.2169g as the bismuth source, uses La 2O 3As the lanthanum source, get 0.1629g, as the vanadium source, get 2.3395g with ammonium metavanadate, put into agate mortar, add absolute ethyl alcohol 10mL as dispersant, grind, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 850 ℃ with the speed of 10 ℃/min, insulation 8h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 950 ℃ with the speed of 10 ℃/min, insulation 8h.Take out after the cooling and grind acquisition object Bi 1.9La 0.1V 2O 8
4. take by weighing 2g Bi 1.9La 0.1V 2O 8Powder impregnation is in 5ml chloroplatinic acid (H 2PtCl 6) in the aqueous solution (0.01025mol/L),, form the Bi of Pt load by heating evaporation, drying and calcining 0.1Ce 1.9V 2O 8Photochemical catalyst, the amount of the Pt of institute's load is 0.5wt%.
5. take by weighing the Bi of load 0.5wt% Pt 1.9La 0.1V 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is done quantitative analysis, BiYV with the gas chromatograph that has the thermal conductance detector 2O 8Product hydrogen and produce oxygen speed and be respectively 67.5 μ mol/gh and 33.4 μ mol/gh.With behind the following wavelength light wave of optical filter elimination 420nm, produce hydrogen under the same terms and be respectively 2.8 μ mol/gh and 1.2 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.
Embodiment 4:
1. with Bi (NO 3) 35H 2O gets 4.8507g as the bismuth source, uses Pr 2O 3As the praseodymium source, get 1.6491g, as the vanadium source, get 2.3395g with ammonium metavanadate, put into agate mortar, add absolute ethyl alcohol 10mL as dispersant, grind, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 850 ℃ with the speed of 10 ℃/min, insulation 10h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 950 ℃ with the speed of 10 ℃/min, insulation 10h.Take out after the cooling and grind acquisition object BiPrV 2O 8
4. take by weighing 2g BiPrV 2O 8Powder impregnation is in 5ml ruthenic chloride (RuCl 3) in the aqueous solution (0.09mol/L), by heating evaporation, drying and calcining,, form RuO 2The Bi of load 0.1Ce 1.9V 2O 8Photochemical catalyst, the load RuO of institute 2Amount be 3wt%.
5. take by weighing load 3wt% RuO 2BiPrV 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is used with the gas chromatograph of thermal conductance detector and done quantitative analysis, BiYV 2O 8Product hydrogen and produce oxygen speed and be respectively 32.4 μ mol/gh and 14.6 μ mol/gh.With behind the following wavelength light wave of optical filter elimination 420nm, produce hydrogen under the same terms and be respectively 2.1 μ mol/gh and 1.2 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.
Embodiment 5:
1. with Bi (NO 3) 35H 2O gets 4.8507g as the bismuth source, with Nd (NO 3) 36H 2O gets 4.3834g as the neodymium source, as the vanadium source, gets 2.3395g with ammonium metavanadate, puts into agate mortar, adds absolute ethyl alcohol 10mL as dispersant, grinds, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 800 ℃ with the speed of 10 ℃/min, insulation 12h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 900 ℃ with the speed of 10 ℃/min, insulation 12h.Take out after the cooling and grind acquisition object BiNdV 2O 8
4. take by weighing 2g BiNdV 2O 8Powder impregnated in 10ml ruthenic chloride (RuCl 3) in the aqueous solution (0.0075mol/L), by heating evaporation, drying and calcining,, form RuO 2The BiNdV of load 2O 8Photochemical catalyst, the load RuO of institute 2Amount be 0.5wt%.
5. take by weighing load 0.5wt%RuO 2BiNdV 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is used with the gas chromatograph of thermal conductance detector and done quantitative analysis, BiYV 2O 8Product hydrogen and produce oxygen speed and be respectively 22.4 μ mol/gh and 10.5 μ mol/gh.With behind the following wavelength light wave of optical filter elimination 420nm, produce hydrogen under the same terms and be respectively 3.4 μ mol/gh and 1.4 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.
Embodiment 6:
1. use Bi 2O 3As the bismuth source, get 2.3298g, use Sm 2O 3As the samarium source, get 1.7436g, use V 2O 5As the vanadium source, get 1.8188g, put into agate mortar, add absolute ethyl alcohol 10mL as dispersant, grind, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 850 ℃ with the speed of 10 ℃/min, insulation 12h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 950 ℃ with the speed of 10 ℃/min, insulation 12h.Take out after the cooling and grind acquisition object BiSmV 2O 8
4. take by weighing 2g BiNdV 2O 8Powder impregnated in 5ml nickel nitrate (Ni (NO 3) 3) in the aqueous solution (0.00535mol/L), after heating evaporation, drying, at H 2The lower 500 ℃ of calcining 2h of atmosphere are then at O 2The lower 200 ℃ of calcining 1h of atmosphere form NiO x(x＜1) load BiSmV 2O 8Photochemical catalyst, the load NiO of institute xAmount be 0.1wt%.
5. take by weighing load 0.1wt%NiO xThe BiNdV of (x＜1) 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is used with the gas chromatograph of thermal conductance detector and done quantitative analysis, BiYV 2O 8Product hydrogen and produce oxygen speed and be respectively 25.6 μ mol/gh and 12.5 μ mol/gh.With behind the following wavelength light wave of optical filter elimination 420nm, produce hydrogen under the same terms and be respectively 6.1 μ mol/gh and 3.1 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.
Embodiment 7:
1. use Bi 2O 3As the bismuth source, get 2.3298g, use Y 2O 3As the yttrium source, get 1.1254g, as the vanadium source, get 2.3395g with ammonium metavanadate, put into agate mortar, add absolute ethyl alcohol 10mL as dispersant, grind, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 900 ℃ with the speed of 10 ℃/min, insulation 6h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 1000 ℃ with the speed of 10 ℃/min, insulation 1h.Take out after the cooling and grind acquisition object BiYV 2O 8
4. take by weighing 2g BiYV 2O 8Powder impregnated in 10ml nickel nitrate (Ni (NO 3) 3) in the aqueous solution (0.08025mol/L), by heating evaporation, do at H 2The lower 500 ℃ of calcining 2h of atmosphere are then at O 2The lower 200 ℃ of calcining 1h of atmosphere form NiO x(x＜1) load BiSmV 2O 8Photochemical catalyst, the amount of the load NiOx of institute is 3wt%.
5. take by weighing load 3wt%NiO xThe BiYV of (x＜1) 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is used with the gas chromatograph of thermal conductance detector and done quantitative analysis, BiYV 2O 8Product hydrogen and produce oxygen speed and be respectively 89.4 μ mol/gh and 42.3 μ mol/gh.With behind the following wavelength light wave of optical filter elimination 420nm, produce hydrogen under the same terms and be respectively 8.9 μ mol/gh and 4.2 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.
Embodiment 8:
1. use Bi 2O 3As the bismuth source, get 2.3298g, use Y 2O 3As the yttrium source, get 1.1254g, as the vanadium source, get 2.3395g with ammonium metavanadate, put into agate mortar, add absolute ethyl alcohol 10mL as dispersant, grind, till volatilizing fully to absolute ethyl alcohol.
Will above obtain solid-like 80 ℃ of dry 12h in vacuum drying chamber, grind 10min after removing cooling, obtain dry powder solid sample.
3. the powder solid sample is put into the porcelain crucible that volume is 50mL, the porcelain crucible that will adorn sample then places Muffle furnace, is warming up to 900 ℃ with the speed of 10 ℃/min, insulation 12h.The cooling back is taken out and is ground, and the porcelain crucible that will adorn sample again places Muffle furnace to be warming up to 1000 ℃ with the speed of 10 ℃/min, insulation 1h.Take out after the cooling and grind acquisition object BiYV 2O 8
4. take by weighing 2g BiYV 2O 8Powder impregnated in 5ml ruthenic chloride (RuCl 3) in the aqueous solution (0.045mol/L), by heating evaporation, drying and calcining, form RuO 2The BiYV of load 2O 8Photochemical catalyst, the load RuO of institute 2Amount be 1.5wt%.Again powder be impregnated in 5ml chloroplatinic acid (H 2PtCl 6) in the aqueous solution (0.01025mol/L), by 300w Xenon light shining 2h, form the BiYV of Pt load 2O 8Photochemical catalyst, the amount of the Pt of institute's load is 0.5wt%.
5. take by weighing common load 1.5wt%RuO 2BiYV with 0.5wt%Pt 2O 8Catalyst 0.4g is scattered in the 150ml water, and placing material is the photo catalysis reactor of Pyrex glass, and direct external irradiation is 4 hours under the 300W xenon lamp, and the gas that light-catalyzed reaction produces is used with the gas chromatograph of thermal conductance detector and done quantitative analysis, BiYV 2O 8Product hydrogen and produce oxygen speed and be respectively 79 μ mol/gh and 44.3 μ mol/gh.With behind the following wavelength light wave of optical filter elimination 420nm, produce hydrogen under the same terms and be respectively 5.6 μ mol/gh and 3.0 μ mol/gh with product oxygen speed in the above-mentioned photocatalytic reaction device.

Claims (10)

1, a kind of preparation method of photochemical catalyst of energy responding to visible light is characterized in that described photochemical catalyst is that a kind of chemical formula that is made of Bi, M, four kinds of elements of V, O is Bi xM 2-xV 2O 8Solid solution compound, a kind of among M=Y, La, Ce, Pr, Nd, the Sm wherein, 0＜x＜2, (Bi+M): the atomic ratio of V:O is 1:1:4, by Pt or RuO 2Or NiO ySingle load, wherein 0＜y＜1, or Pt and RuO 2Common load, possessed photocatalytic activity, this photochemical catalyst adopts high temperature solid state reaction synthetic, specific as follows:
The oxide or its esters that will contain Bi, M, V are in x:(2-x): 2 ratios are measured, and wherein 0＜x＜2 add ethanol pressed powder is mixed, and 80 ℃ of following dry 12h are then through the synthetic object of high temperature solid state reaction; The parameter of high temperature solid state reaction is: firing temperature is 800-1000 ℃, and the solid phase reaction time is more than 1 hour.
2, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that, and is described by Pt or RuO 2Or NiO ySingle load, wherein 0＜y＜1, perhaps Pt and RuO 2Common load, further improve photocatalytic activity, the load capacity of loaded optic catalyst is controlled at following scope: Pt:0.1-0.5wt%, RuO 2: 0.5-3.0wt%, NiO x: 0.1-3.0wt%.
3, the preparation method of photochemical catalyst that can responding to visible light according to claim 2 is characterized in that, the method for supporting Pt is any in following two kinds:
(1) with Bi xM 2-xV 2O 8Powder impregnated in chloroplatinic acid H 2PtCl 6In the aqueous solution, in whipping process, utilize ultra violet lamp to make the Pt reduction, form the Bi of Pt load xM 2-xV 2O 8Photochemical catalyst, a kind of among M=Y, La, Ce, Pr, Nd, the Sm, 0＜x＜2 wherein;
(2) with Bi xM 2-xV 2O 8Powder impregnated in chloroplatinic acid H 2PtCl 6In the aqueous solution, by heating evaporation, drying and calcining, form the Bi of Pt load xM 2-xV 2O 8Photochemical catalyst, a kind of among M=Y, La, Ce, Pr, Nd, the Sm, 0＜x＜2 wherein.
4, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 2 is characterized in that load RuO 2Method specific as follows:
With Bi xM 2-xV 2O 8Powder impregnated in ruthenic chloride RuCl 3In the aqueous solution, by heating evaporation, drying and calcining, form RuO 2The Bi of load xM 2-xV 2O 8Photochemical catalyst, a kind of among M=Y, La, Ce, Pr, Nd, the Sm, 0＜x＜2 wherein.
5, according to the preparation method of claim 2 or 3 or 4 described photochemical catalysts that can responding to visible light, it is characterized in that Pt and RuO 2Common carrying method be:
Earlier according to the above method load RuO 2After, again according to the above method supporting Pt, form RuO 2Bi with the common load of Pt xM 2-xV 2O 8Photochemical catalyst, a kind of among M=Y, La, Ce, Pr, Nd, the Sm, 0＜x＜2.
6, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 2 is characterized in that load NiO yMethod specific as follows:
With Bi xM 2-xV 2O 8Powder impregnated in nitric acid nickel (NO 3) 2In the aqueous solution, by heating evaporation, drying, at H 2The lower 500 ℃ of calcining 2h of atmosphere are then at O 2The lower 200 ℃ of calcining 1h of atmosphere form NiO yThe Bi of load xM 2-xV 2O 8Photochemical catalyst, a kind of among M=Y, La, Ce, Pr, Nd, the Sm, 0＜x＜2.
7, the preparation method of photochemical catalyst that can responding to visible light according to claim 1 is characterized in that, any one in the bismuth nitrate of described oxide that contains Bi or its esters, bismuth oxide, the waltherite; The compound of the described V of containing is a kind of in ammonium metavanadate, the vanadic anhydride.
8, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that the oxide of the described Y of containing or its esters are any one in yittrium oxide, yttrium nitrate, the yttrium carbonate; The oxide of the described La of containing or its esters are any one in lanthana, lanthanum nitrate, the lanthanum carbonate.
9, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that, the oxide of the described Ce of containing or its esters are any one in the inferior cerium of oxidation, cerous nitrate, the cerous carbonate; The oxide of the described Pr of containing or its esters are any one in praseodymium oxide, praseodymium nitrate, the praseodymium carbonate.
10, the preparation method of the photochemical catalyst of energy responding to visible light according to claim 1 is characterized in that the oxide of the described Nd of containing or its esters are any one in neodymia, neodymium nitrate, the neodymium carbonate; The oxide of the described Sm of containing or its esters are any one in samarium oxide, the samaric nitrate.
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