CN100553769C - Tungstenic acid/silver chloride visible light photocatalyst and preparation method thereof - Google Patents
Tungstenic acid/silver chloride visible light photocatalyst and preparation method thereof Download PDFInfo
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- CN100553769C CN100553769C CNB2008100166124A CN200810016612A CN100553769C CN 100553769 C CN100553769 C CN 100553769C CN B2008100166124 A CNB2008100166124 A CN B2008100166124A CN 200810016612 A CN200810016612 A CN 200810016612A CN 100553769 C CN100553769 C CN 100553769C
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- wolframic acid
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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
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides a kind of Tungstenic acid/silver chloride visible light photocatalyst, this photochemical catalyst is made of wolframic acid and silver chlorate, and chemical formula is H
2WO
4/ AgCl, silver chlorate load on the wolframic acid surface, and silver chlorate accounts for the 34.9-69.8% of gross weight.This Preparation of catalysts method may further comprise the steps: (1) configuration concentration is the sodium tungstate aqueous solution of 0.1mol/l, 1: 1 by volume ratio with joining sodium tungstate solution put into the nitric acid that concentration is 6mol/l, after refluxing under the 150-200 ℃ of temperature, resultant sediment washes to pH=7, makes wolframic acid; (2) obtained wolframic acid is put into the Muffle furnace heating anneal; (3) wolframic acid is joined in the silver nitrate aqueous solution, add chloric ethane, gained sediment undergoes washing, filtration, oven dry.The Tungstenic acid/silver chloride photochemical catalyst that the present invention makes have the photocatalytic activity height, easily separated, solar energy is utilized high characteristics, can be used for photodissociation water, decomposing organic matter and sterilization etc., its effect is better than catalysis material P25.
Description
Technical field
The present invention relates to a kind of photochemical catalyst that is applied to hydrogen production by water decomposition or decomposition air and water pollutant and preparation method thereof, belong to the catalysis material technical field.
Background technology
Along with increasing the weight of of excessive development and use of resource and environmental pollution, human available resources are shortage more and more, and living environment is subjected to more and more serious destruction, and the energy and environmental problem become the two big subject matters that the world today pays close attention to.At present world energy sources mainly relies on non-renewable fossil resource, China's energy wastage in bulk or weight be non-renewable fossil energy more than 90%.How to solve current energy crisis? solar energy resources is abundant, and 1 year arrives earth total amount is 5.5 * 1026J, is 10,000 times of whole world energy resource consumption in a year now; If can prepare catalysis material efficiently, utilize solar energy to prepare hydrogen and come alleviating energy crisis that great Practical significance will be arranged; Often contain more organic pollution in industry and family expenses waste gas and the waste water, the waste water of this class eutrophication and waste gas can bring seriously to ecological environment and destroy.Along with international environment standard (ISO 14001, and October 1996) requires increasingly stringentization, the improvement technology of organic contamination also is rapidly developed.The application of photocatalysis in recent years in energy development and environmental protection is subject to people's attention day by day.
Catalysis material is one of focus of scientific research always.Last century early seventies, Fujishima of Tokyo Univ Japan and Honda discover, utilize the titanium dioxide single crystalline light-catalyzed reaction to make water resolve into hydrogen and oxygen.After this, the various countries scholar has carried out extensive studies around photocatalysis material of titanium dioxide.Light-catalysed principle can be explained with semi-conductive band theory: when the illumination that is equal to or higher than the energy gap of semi-conducting material with energy was penetrated, the valence band electronics was stimulated and transits to conduction band, produced corresponding hole simultaneously on valence band, formed electron hole pair; Light induced electron, hole are separated under the internal electric field effect and are moved to material surface, and redox reaction takes place.Light-catalyzed reaction is the physical and chemical process under photoinduction, can realize the light hydrogen production by water decomposition and purifies air and the effect of water.
Realize photocatalytic hydrogen production by water decomposition or decompose pollutant in the empty G﹠W, catalysis material must satisfy two conditions: at first, its energy gap is greater than the decomposition voltage of water or pollutant, and secondly valence band location should compare O
2/ H
2The current potential corrigendum of O, and H should be compared in the position of conduction band
+/ H
2More negative.The tradition catalysis material satisfies above-mentioned two conditions, but its can band gap greater than 3.0eV, so can only utilize ultraviolet light in the sunshine.Yet the energy of ultraviolet light only accounts for 4% of solar energy, and visible light accounts for 43%.
Current, the applied main catalysis material of people is the titanium dioxide with specific crystalline form, is called for short P25, and it has been widely used in purifying air.Because it is higher that it can be with, too low to the utilization rate of solar energy, so each state is all endeavouring and is seeking visible-light photocatalyst efficiently.
Can expand the absorption region of visible light effectively based on the modified photocatalytic material of titanium dioxide, but cationic modification significantly reduces the light quantum conversion efficiency, anionic modification (N or C) under illumination easily light decompose, have unstability.Therefore, to have visible light-responded high-efficiency photocatalysis material of new generation be to improve solar energy photocatalytic hydrogen manufacturing, purify air and the key of the effect of water in research and development.
Wolframic acid is that the hydration tungstic acid is a kind of well behaved photochromic material, but its unstability has restricted its application in photocatalysis field.Silver chlorate has good response as a kind of light-sensitive material to light, but its can be with than higher, can only absorb ultraviolet light, and unstable under illumination.
Summary of the invention
The present invention is directed to that at present general catalysis material P25 exists low to solar energy utilization rate, be difficult to problem such as separation in the use repeatedly, a kind of photocatalytic activity height, easily separated is provided, solar energy is utilized high Tungstenic acid/silver chloride visible light photocatalyst, and a kind of this Preparation of catalysts method is provided.
Tungstenic acid/silver chloride visible light photocatalyst of the present invention is made of wolframic acid and silver chlorate, and chemical formula is H
2WO
4/ AgCl, silver chlorate load on the wolframic acid surface.Silver chlorate accounts for the 34.9-69.8% of gross weight.
The preparation method of above-mentioned Tungstenic acid/silver chloride visible light photocatalyst may further comprise the steps:
(1) preparation wolframic acid: configuration concentration is the sodium tungstate aqueous solution of 0.1mol/l, 1: 1 by volume ratio with joining the sodium tungstate aqueous solution put into the nitric acid that concentration is 6mol/l, fully stirring dissolves solution fully, solution is transferred in the microwave reflux again, under 150 ℃ of-200 ℃ of temperature, refluxed 3 hours-5 hours, obtain blue sediment, to pH=7, make wolframic acid with deionized water rinsing;
(2) wolframic acid post processing: with the prepared wolframic acid of step (1), put into Muffle furnace and be heated to 200 ℃-900 ℃ of temperature, annealed 2 hours-3 hours;
(3) preparation Tungstenic acid/silver chloride photochemical catalyst: the wolframic acid after step (2) annealing in process is joined in the silver nitrate aqueous solution that concentration is 0.05mol/l, every 0.1g wolframic acid joins in the 20ml-40ml silver nitrate aqueous solution, stirred 2 hours-3 hours, dropwise add chloric ethane, to precipitating fully, the gained sediment, cleans one time with ethanol to pH=7.0 then with washed with de-ionized water, filter back 60 ℃ of oven dry, promptly get the Tungstenic acid/silver chloride photochemical catalyst.
The present invention is directed to the shortcoming of tungstic acid and silver chlorate, utilize wolframic acid to follow the compound of silver chlorate, the decomposition of silver chlorate and self reducing of tungstic acid have been suppressed effectively, guaranteed its stability under illumination, utilize the wolframic acid band gap narrow simultaneously, the characteristics that can effectively absorb visible light have strengthened its absorption to visible light, can utilize the energy of sunshine more fully, the Tungstenic acid/silver chloride photochemical catalyst that makes has the photocatalytic activity height, easily separated, solar energy is utilized high characteristics, can be used for photodissociation water, decomposing organic matter and sterilization etc., its effect are much better than the current catalysis material P25 that generally uses.
The specific embodiment
Embodiment 1
(1) preparation of wolframic acid: configuration concentration is the sodium tungstate aqueous solution of 0.1mol/l, get sodium tungstate solution that 50ml joins and put into the nitric acid that 50ml concentration is 6mol/l, stir and solution was dissolved fully in 5 minutes-10 minutes, again solution is transferred in the microwave reflux and refluxed 5 hours at 150 ℃.The blue precipitate with deionized water flushing of gained makes wolframic acid up to pH=7.
(2) post processing of wolframic acid:, put into Muffle furnace and be heated to 200 ℃ of annealing 3 hours with the obtained wolframic acid of step (1).
(3) preparation of Tungstenic acid/silver chloride photochemical catalyst: get the made wolframic acid 0.5g of step (2) and join in the silver nitrate aqueous solution that 100ml concentration is 0.05mol/l and to stir 2 hours, dropwise add chloric ethane, to precipitation fully.The gained sediment, cleans one time with ethanol all over to pH=7.0 then with the washed with de-ionized water number, filters back 60 ℃ of oven dry, promptly gets the Tungstenic acid/silver chloride photochemical catalyst.
Embodiment 2
(1) preparation of wolframic acid: configuration concentration is the sodium tungstate aqueous solution of 0.1mol/l, get sodium tungstate solution that 50ml joins and put into the nitric acid that 50ml concentration is 6mol/l, stir and solution was dissolved fully in 5 minutes-10 minutes, again solution is transferred in the microwave reflux and refluxed 4.5 hours at 160 ℃.The flushing of the blue precipitation of gained water makes wolframic acid up to pH=7.
(2) post processing of wolframic acid: the obtained wolframic acid of step (1) is put into Muffle furnace be heated to 400 ℃ of annealing 3 hours.
(3) preparation of Tungstenic acid/silver chloride photochemical catalyst: get the made wolframic acid 0.5g of step (2) and join in the silver nitrate aqueous solution that 150ml concentration is 0.05mol/l and to stir 2 hours, dropwise add chloric ethane, to precipitation fully.The gained sediment, cleans one time with ethanol all over to pH=7.0 then with the washed with de-ionized water number, filters, and 60 ℃ of oven dry promptly get the Tungstenic acid/silver chloride photochemical catalyst.
Embodiment 3
(1) preparation of wolframic acid: configuration concentration is the sodium tungstate aqueous solution of 0.1mol/l, get sodium tungstate solution that 50ml joins and put into the nitric acid that 50ml concentration is 6mol/l, stir and solution was dissolved fully in 5 minutes-10 minutes, again solution is transferred in the microwave reflux and refluxed 4 hours at 180 ℃.The flushing of the blue precipitation of gained water makes wolframic acid up to pH=7.
(2) post processing of wolframic acid: the obtained wolframic acid of step (1) is put into Muffle furnace be heated to 600 ℃ of annealing 2.5 hours.
(3) preparation of Tungstenic acid/silver chloride photochemical catalyst: get the made wolframic acid 0.5g of step (2) and join in the silver nitrate aqueous solution that 180ml concentration is 0.05mol/l and to stir 2.5 hours, dropwise add chloric ethane, to precipitation fully.The gained sediment, cleans one time with ethanol all over to pH=7.0 then with the washed with de-ionized water number, filters, and 60 ℃ of oven dry promptly get the Tungstenic acid/silver chloride photochemical catalyst.
Embodiment 4
(1) preparation of wolframic acid: configuration concentration is the sodium tungstate aqueous solution of 0.1mol/l, get sodium tungstate solution that 50ml joins and put into the nitric acid that 50ml concentration is 6mol/l, stir and solution was dissolved fully in 5 minutes-10 minutes, again solution is transferred in the microwave reflux and refluxed 3 hours at 200 ℃.The flushing of the blue precipitation of gained water makes wolframic acid up to pH=7.
(2) post processing of wolframic acid: the obtained wolframic acid of step (1) is put into Muffle furnace be heated to 900 ℃ of annealing 2 hours.
(3) preparation of Tungstenic acid/silver chloride photochemical catalyst: get the made wolframic acid 0.5g of step (2) and join in the silver nitrate aqueous solution that 200ml concentration is 0.05mol/l and to stir 3 hours, dropwise add chloric ethane, to precipitation fully.The gained sediment, cleans one time with ethanol all over to pH=7.0 then with the washed with de-ionized water number, filters, and 60 ℃ of oven dry promptly get the Tungstenic acid/silver chloride photochemical catalyst.
Claims (3)
1. a Tungstenic acid/silver chloride visible light photocatalyst is characterized in that, is made of wolframic acid and silver chlorate, and chemical formula is H
2WO
4/ AgCl, silver chlorate load on the wolframic acid surface.
2. according to the described Tungstenic acid/silver chloride visible light photocatalyst of claim 1, it is characterized in that silver chlorate accounts for the 34.9-69.8% of gross weight.
3. the preparation method of the described Tungstenic acid/silver chloride visible light photocatalyst of claim 1 is characterized in that, may further comprise the steps:
(1) preparation wolframic acid: configuration concentration is the sodium tungstate aqueous solution of 0.1mol/l, 1: 1 by volume ratio with joining the sodium tungstate aqueous solution put into the nitric acid that concentration is 6mol/l, fully stirring dissolves solution fully, solution is transferred in the microwave reflux again, under 150 ℃ of-200 ℃ of temperature, refluxed 3 hours-5 hours, obtain blue sediment, to pH=7, make wolframic acid with deionized water rinsing;
(2) wolframic acid post processing: with the prepared wolframic acid of step (1), put into Muffle furnace and be heated to 200 ℃-900 ℃ of temperature, annealed 2 hours-3 hours;
(3) preparation Tungstenic acid/silver chloride photochemical catalyst: the wolframic acid after step (2) annealing in process is joined in the silver nitrate aqueous solution that concentration is 0.05mol/l, every 0.1g wolframic acid joins in the 20ml-40ml silver nitrate aqueous solution, stirred 2 hours-3 hours, dropwise add chloric ethane, to precipitating fully, the gained sediment, cleans one time with ethanol to pH=7.0 then with washed with de-ionized water, filter back 60 ℃ of oven dry, promptly get the Tungstenic acid/silver chloride photochemical catalyst.
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| CN1528514A (en) * | 2003-10-10 | 2004-09-15 | 广西大学 | Preparation of tungstate phatocatalyst and use of catalytic degradation of molasses alcohol waste water thereof |
| CN1775349A (en) * | 2005-12-14 | 2006-05-24 | 中国科学院上海硅酸盐研究所 | Wolfram oxide modified visible light activity nano titanium oxide photocatalyst and its method |
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| CN1528514A (en) * | 2003-10-10 | 2004-09-15 | 广西大学 | Preparation of tungstate phatocatalyst and use of catalytic degradation of molasses alcohol waste water thereof |
| CN1775349A (en) * | 2005-12-14 | 2006-05-24 | 中国科学院上海硅酸盐研究所 | Wolfram oxide modified visible light activity nano titanium oxide photocatalyst and its method |
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