CN1814348A - Solid-phase photocatalyst utilizing visible light and its preparing method - Google Patents

Solid-phase photocatalyst utilizing visible light and its preparing method Download PDF

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CN1814348A
CN1814348A CNA2005100112883A CN200510011288A CN1814348A CN 1814348 A CN1814348 A CN 1814348A CN A2005100112883 A CNA2005100112883 A CN A2005100112883A CN 200510011288 A CN200510011288 A CN 200510011288A CN 1814348 A CN1814348 A CN 1814348A
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exchange resin
metal compound
oxo
anion exchange
heteropoly acid
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赵进才
雷鹏翔
马万红
陈春城
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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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
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Abstract

This invention belongs to solid phase catalyst field, especially relates to solid phase catalyst consisted by carrier and yang collaterals transition metal compound with photocatalysis activity. The catalyst is consisted by negative ion exchange resin and yang collaterals transition metal compound, they linkage with each other and there quality ratio is 1:0.01-1.5. The compound is isopoly acid, heteropoly acid or tertiary heteropoly acid, and they all have light activity. The catalyst can use visible light activate H<SUB>2</SUB>O<SUB>2</SUB> to clear and process the organic fuel pollutant in dye printing industrial waste water.

Description

Utilize solid-phase photocatalyst of visible light and preparation method thereof
Technical field
The invention belongs to the solid-phase photocatalyst field, particularly solid-phase photocatalyst of forming by carrier and oxo transistion metal compound and preparation method thereof with photocatalytic activity.
Background technology
As everyone knows, along with industrial expansion, problem of environmental pollution is very serious.According to statistics, the river of China nearly 1/2 is subjected to the pollution of toxic organic compound, and 1.6 hundred million people drink the serious water of organic contamination, and many urban air pollutions are serious.In these pollutants, some contained in the waste water with printing and dyeing industry discharging dyestuff contaminant toxicity are bigger, can't be handled with existing microbial technique, or can't thoroughly remove, and are particularly outstanding to the harm that natural environment brings.
In recent years, the photocatalysis technology of polyacid compound has been obtained very big progress in environmental applications, many isopolyacids and heteropoly acid are found the poisonous organic pollution of can degrading under ultraviolet excitation, the article that this type of document has American Chemical Society's " environmental science and technology " magazine (2000 the 34th volume 2024～2028 pages) to deliver " utilizes phosphotungstic acid photoinduction degraded monochloro and multi-chlorophenol in the aqueous solution: as 2; 4; the 6-trichlorophenol " (Androulaki, E.; Hiskia, A.; Dimotikali, D.; Minero, C.; Calza, P.; Pelezzetti, E.; Papaconstantinou, E.Light induced Elimination of Mono-andPolychlorinated Phenols from Aqueous Solutions by PW 12O 40 3-.The case of2,4,6-trichlorophenol); " the mechanism research of heteropoly acid photochemical catalytic oxidation chlorinatedorganic " (Ozer, R.R. that " physical chemistry " magazine (volume was 9444～9448 pages in 2000 the 104th) is delivered; Ferry, J.L.Kinetic Probes of the Mechanism of Polyoxometalate-mediated PhotocatalyticOxidation of Chlorinated Organics.).Wherein, isopolyacid and heteropoly acid are as the inorganic anion of the nano-scale of solubility, has non-oxidizability, can when keeping self structure not to be destroyed, carry out electron rich oxidation-reduction reaction, under the effect of ultraviolet light, show the character of similar semiconductor light-catalyst, caused widely and paid close attention to.In addition, the composite catalyst that isopolyacid or loaded by heteropoly acid are formed to the carrier not only is beneficial to the recycling of catalyst, and different carriers can also give composite catalyst some special nature, improves the catalytic activity of isopolyacid or heteropoly acid." the molecular sieve carried heteropoly acid of NaY in aqueous phase photochemical catalytic oxidation 1,2-dichloro-benzenes " (Ozer, R.R. that this type of document has that " physical chemistry " magazine (2002 the 36th volume 1325～1329 pages) delivers; Ferry, J.L.PhotocatalyticOxidation of Aqueous 1,2-Dichlorobenzene by Polyoxometalates Supported on theNaY Zeolite); " photocatalysis of heteropoly acid/TiO2 co-catalyst: intermediate and mechanism research " (Chen, C. that " environmental science and technology " magazine (volume was 329～337 pages in 2004 the 38th) inventor delivers; Lei, P.; Ji, H.; Ma, W.; Zhao, J.Photocatalysis by Titanium Dioxide andPolyoxometalate/TiO 2Cocatalysts.Intermediates and Mechanistic Study.).
Yet, the absorption region to light of isopolyacid and heteropoly acid mainly is in the ultra-violet (UV) band, have only wavelength could effectively excite the vibration υ (M=O) of metallic atom and terminal oxygen less than the ultraviolet light of 350nm, and ultraviolet light only occupies 3～5% ratio in sunshine, as use artificial ultraviolet source can expend a large amount of electric energy, therefore, attempt handling waste water to environmental protection with energy-conservationly all have and important meaning with low price, visible light with low cost or sunshine.There is the researcher to utilize dyestuff the characteristics of very strong absorption to be arranged recently,, proposes isopolyacid and heteropoly acid and can utilize visible light photoactivated degradation of dye in conjunction with the redox characteristic of isopolyacid and heteropoly acid at visible region." heteropoly acid solution and TiO under the visible light that this type of document has the inventor to deliver at " Europe chemistry " magazine (volume was 1956～1965 pages in 2004 the 10th) 2The sensitization degradation of dye to mechanism research when " (Chen, C.; Zhao, W.; Lei, P.; Zhao, J.; Serpone, N.Photosensitized degradation of dyes in polyoxometalate solutions versus TiO 2Dispersions under visible-light irradiation:mechanistic implications.).But, most of isopolyacid or heteropoly compound be ability stable existence in the aqueous solution of pH value lower (pH＜3.5) only, catalyst is difficult to separate in the homogeneous system simultaneously, and dye molecule only decomposes to a certain extent under radiation of visible light, and mineralising takes place hardly.
Summary of the invention
The object of the present invention is to provide solid-phase photocatalyst, can be under radiation of visible light and H 2O 2Effect efficient catalytic degradation of dye pollutant can not only make dyestuff decompose and fade, and mineralising to a certain degree can also take place, and catalyst is easy to reclaim and recycling simultaneously.
Two of purpose of the present invention provides a kind of preparation method who utilizes the solid-phase photocatalyst of visible light.
The solid-phase photocatalyst that utilizes visible light of the present invention, by polymer support and with it the oxo transistion metal compound of bonding form, it is characterized in that: described polymer support is an anion exchange resin, particle diameter is 0.05～200 micron; Described oxo transistion metal compound loads on the anion exchange resin by electrostatic interaction, and the mass ratio of described oxo transistion metal compound and polymer support is 0.01～1.5: 1.
Described anion exchange resin is selected from a kind of in the reinforcing yin essence ion exchange resin, band amino group weak anion exchange resin that styrene/divinylbenzene is EVA of reinforcing yin essence ion exchange resin, band quaternary amines that styrene/divinylbenzene is EVA of band quaternary amines of weak anion exchange resin, polystyrene type of the band amino group of polystyrene type.
The used anion exchange resin of the present invention is the commercially available prod, and manufacturer can be U.S. Aldrich reagent company, Anhui Samsung resin Science and Technology Ltd. and Chemical Plant of Nankai Univ..
The weak anion exchange resin of the band amino group of described polystyrene type is as the D301R type ion exchange resin of Chemical Plant of Nankai Univ.'s production.
The reinforcing yin essence ion exchange resin of the band quaternary amines of described polystyrene type is as the D201 type ion exchange resin of Chemical Plant of Nankai Univ.'s production.
Described styrene/divinylbenzene is the reinforcing yin essence ion exchange resin of the band quaternary amines of EVA, as the Amberlite IRA 900 of U.S. Aldrich company.
Described styrene/divinylbenzene is the band amino group weak anion exchange resin of EVA, as the D301 type anion exchange resin of Anhui Samsung resin Science and Technology Ltd. production.
Described oxo transistion metal compound is for having photoactive isopolyacid, heteropoly acid or ternary heteropoly acid.
Described isopolyacid is selected from many molybdic acid (H 2Mo 6O 19), many wolframic acid (H 4W 10O 32) and corresponding lithium salts (Li 2Mo 6O 19, Li 2W 10O 32), sodium salt (Na 2Mo 6O 19, Na 2W 10O 32) in a kind of;
Described heteropoly acid is selected from phosphomolybdic acid (H 3PMo 12O 40), phosphotungstic acid (H 3PW 12O 40), silico-tungstic acid (H 4SiW 12O 40) and lithium salts (Li 3PMo 12O 40, Li 3PW 12O 40, Li 4SiW 12O 40), sodium salt (Na 3PMo 12O 40, Na 3PW 12O 40, Na 4SiW 12O 40) in a kind of;
Described ternary heteropoly acid is for being the ternary heteropoly acid of matrix with phosphomolybdic acid, phosphotungstic acid, is that to be selected from general formula be H 3(PW xMo 12-xO 40) a kind of in the acid, wherein x=1～6.Described oxo transistion metal compound can be the commercially available prod, or the reference literature method is synthetic, and document is " Catalysis by Polyoxometalates ", JohnWiley and sons, 2002,47～59 pages.
The preparation method of the solid-phase photocatalyst of visible light that utilizes of the present invention may further comprise the steps:
(1) pre-treatment of anion exchange resin
Adopt conventional method, anion exchange resin is carried out pickling and alkali cleaning after, to neutral, after the vacuum drying, grind to form particle diameter and be 0.05～200 micron single-size with deionized water drip washing, place drier standby.Described anion exchange resin is selected from a kind of in the reinforcing yin essence ion exchange resin of the weak anion exchange resin of the band amino group of polystyrene type, the band quaternary amines reinforcing yin essence ion exchange resin of polystyrene type and the band quaternary amines that styrene/divinylbenzene is EVA and the band amino group weak anion exchange resin that styrene/divinylbenzene is EVA.
(2) configuration of oxo transistion metal compound storing solution
Configuration concentration scope 1 * 10 -4～1 * 10 -2The oxo transistion metal compound storing solution of M, standby.
Described oxo transistion metal compound is a kind of have photoactive isopolyacid, heteropoly acid or ternary heteropoly acid.
Described isopolyacid is selected from many molybdic acid (H 2Mo 6O 19), many wolframic acid (H 4W 10O 32) and corresponding lithium salts (Li 2Mo 6O 19, Li 4W 10O 32), sodium salt (Na 2Mo 6O 19, Na 4W 10O 32) in a kind of;
Described heteropoly acid is selected from phosphomolybdic acid (H 3PMo 12O 40), phosphotungstic acid (H 3PW 12O 40), silico-tungstic acid (H 4SiW 12O 40) and lithium salts (Li 3PMo 12O 40, Li 3PW 12O 40, Li 4SiW 12O 40), sodium salt (Na 3PMo 12O 40, Na 3PW 12O 40, Na 4SiW 12O 40) in a kind of;
Described ternary heteropoly acid is for being the ternary heteropoly acid of matrix with phosphomolybdic acid, phosphotungstic acid, is that to be selected from general formula be H 3(PW xMo 12-xO 40) a kind of in the acid, wherein x=1～6.Described oxo transistion metal compound can be the commercially available prod, or the reference literature method is synthetic, and document is " Catalysis by Polyoxometalates ", JohnWiley and sons, 2002,47～59 pages.
(3) loading process of oxo transistion metal compound on resin
In a glass container that electromagnetic mixing apparatus is housed, put into the resin that step (1) was handled, add a kind of oxo transistion metal compound of step (2) preparation, wherein, the mass ratio of oxo transistion metal compound and resin is 0.01～1.5: 1; HClO with 0.1M 4Transfer to pH 3.90～4.60, stirred at least 48 hours under the room temperature, supernatant liquor is removed in centrifugation, deionized water washing, centrifugation again, deionized water washing.Repetitive operation detects less than oxo transistion metal compound in supernatant liquor.Vacuum drying 30～40 hours under 10～50 ℃ of low temperature then.
Described acid is selected from HCl, H 2SO 4, HNO 3Deng in a kind of.
Described alkali is selected from a kind of among NaOH, the LiOH etc.
The invention provides a kind of novel, have a solid-phase photocatalyst high photocatalytic activity, stable.Its technology of preparing main points be select a kind of contain can with the high molecular polymer of the functional group of isopolyacid, heteropoly acid or the effective complexing of ternary heteropoly acid, with a kind of suitable isopolyacid, heteropoly acid or ternary heteropolyacid catalyst, combine by electrostatic attraction.
The purposes of photochemical catalyst of the present invention:
Photochemical catalyst of the present invention can utilize visible light cheap and easy to get or sunshine, activation H 2O 2Decompose, dyestuff contaminant in the mineralising dyeing waste water, solved the problem that isopolyacid in the homogeneous system or heteropoly acid ion are difficult to separate, avoid secondary pollution, can reuse, reduce operating cost.Simultaneously also can be applied to the selective oxidation anthropogenics.
Specify effect of the present invention below in conjunction with accompanying drawing.
Description of drawings
Fig. 1, rhodamine B dyestuff 2 * 10 -5The photocatalytic degradation reaction result of M under radiation of visible light.
Curve 1-100mg heteropoly acid (H 3PW 12O 40)/liter and H 2O 2Light reaction
Curve 2-100mg catalyst/liter and H 2O 2Dark reaction (by among the embodiment 2 preparation)
The blank resin of curve 3-100mg/liter and H 2O 2Light reaction
Curve 4-100mg catalyst/liter light reaction (by among the embodiment 2 preparation)
Curve 5-100mg catalyst/liter and H 2O 2Light reaction (by among the embodiment 2 preparation)
Illumination experiment condition a: halogen lamp is placed in the double glazing condensation sleeve pipe, on every side around recirculated cooling water.(λ＞450nm) place the chuck outside to excise the following light of 450nm fully guarantees only to react and carries out under visible light a cut-off type optical filter.Following experiment condition is identical.
Fig. 2, catalyst (the 100mg catalyst/liter) (by preparation among the embodiment 2) rhodamine B (2 * 10 of degrading for 4 times of circulating continuously -5M) photocatalytic activity result.
The variation of body phase TOC in Fig. 3, catalyst (100mg catalyst/liter) (by preparation among the embodiment 6) degraded rhodamine B process.
Curve 1 among Fig. 1 is heteropoly acid (H under the radiation of visible light 3PW 12O 40) and H 2O 2Blank light reaction, the concentration of illumination 240min rhodamine B has reduced about 10%; Curve 2 is catalyst (by preparation among the embodiment 2) and H 2O 2Dark reaction, rhodamine B is not almost degraded; Curve 3 is blank resin and H 2O 2Light reaction, the change in concentration of illumination 240min rhodamine B is very little; Curve 4 is in the presence of catalyst (preparation in by embodiment 2), and radiation of visible light 240min rhodamine B has degraded about 15%; Curve 5 is at catalyst (preparation in by embodiment 2) and H 2O 2Existence under, radiation of visible light 240min rhodamine B has degraded about 98%.
Fig. 2 has provided catalyst (the 100mg/ liter is by preparation among the embodiment 2) under the visible light effect, activation H 2O 2, the result of 4 the degraded rhodamine Bs of circulating.The circulation light reaction that the back is three times, the degraded of radiation of visible light 240min rhodamine B all can reach more than 95%, and activity of such catalysts does not have to reduce substantially.
Fig. 3 has provided the variation of body phase TOC in catalyst (100mg catalyst/liter) (by preparation among the embodiment 6) degraded rhodamine B process, reacts after 15 hours, and the TOC clearance reaches about 21.5%.
The specific embodiment
Embodiment 1
Styrene/divinylbenzene of getting selected particle diameter and being 0.05～0.45 micron is reinforcing yin essence ion exchange resin (the Amberlite IRA of the U.S. Aldrich reagent company 900 types) 1.0g of the band quaternary amines of EVA, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 61.2 milliliter 1 * 10 -4Phosphomolybdic acid (the H of M 3PMo 12O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 3.90, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till the phosphomolybdic acid radical ion with rinsed with deionized water, centrifugation then 10 ℃ of low-temperature vacuum dryings 36 hours, promptly obtains the catalyst of load.
Embodiment 2
Get selected particle diameter and be reinforcing yin essence ion exchange resin (Chemical Plant of Nankai Univ. of band quaternary amines of 0.5～1.8 micron polystyrene type, the D201 type) 1.0g, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 58.4 milliliter 1 * 10 -2Sodium phosphotungstate (the Na of M 3PW 12O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till the phosphotungstic acid radical ion with rinsed with deionized water, centrifugation then 50 ℃ of low-temperature vacuum dryings 36 hours, promptly obtains the catalyst of load.
Embodiment 3
Styrene/divinylbenzene of getting selected particle diameter and being 30～200 microns is band amino group weak anion exchange resin (the Anhui Samsung of EVA, the D301 type) 1.0g, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 50 milliliter 1 * 10 -3Silico-tungstic acid lithium (the Li of M 4SiW 12O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till the silico-tungstic acid radical ion with rinsed with deionized water, centrifugation then 40 ℃ of low-temperature vacuum dryings 36 hours, promptly obtains the catalyst of load.
Embodiment 4
Styrene/divinylbenzene of getting selected particle diameter and being 0.05～0.45 micron is reinforcing yin essence ion exchange resin (the Amberlite IRA of the U.S. Aldrich reagent company 900 types) 1.0g of the band quaternary amines of EVA, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 100 milliliter 3 * 10 -3Silicotungstic sodium (the Na of M 4SiW 12O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till the silico-tungstic acid radical ion with rinsed with deionized water, centrifugation then 50 ℃ of low-temperature vacuum dryings 36 hours, promptly obtains the catalyst of load.
Embodiment 5
Get selected particle diameter and be reinforcing yin essence ion exchange resin (Chemical Plant of Nankai Univ. of band quaternary amines of 0.5～1.8 micron polystyrene type, the D201 type) 1.0g, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 32.6 milliliter 8 * 10 -4Sodium phosphomolybdate (the Na of M 3PMo 12O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till the phosphomolybdic acid radical ion with rinsed with deionized water, centrifugation then 40 ℃ of low-temperature vacuum dryings 30 hours, promptly obtains the catalyst of load.
Embodiment 6
Styrene/divinylbenzene of getting selected particle diameter and being 0.05～0.45 micron is reinforcing yin essence ion exchange resin (the Amberlite IRA of the U.S. Aldrich reagent company 900 types) 1.0g of the band quaternary amines of EVA, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 20 milliliter 1 * 10 -2Phosphotungstic acid (the H of M 3PW 12O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till the phosphotungstic acid radical ion with rinsed with deionized water, centrifugation then 30 ℃ of low-temperature vacuum dryings 36 hours, promptly obtains the catalyst of load.
Embodiment 7
Styrene/divinylbenzene of getting selected particle diameter and being 30～200 microns is band amino group weak anion exchange resin (the Anhui Samsung of EVA, the D301 type) 1.0g, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 60 milliliter 2 * 10 -3Phosphomolybdic acid lithium (the Li of M 3PMo 12O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till the phosphotungstic acid radical ion with rinsed with deionized water, centrifugation then 50 ℃ of low-temperature vacuum dryings 30 hours, promptly obtains the catalyst of load.
Embodiment 8
Get selected particle diameter and be weak anion exchange resin (Chemical Plant of Nankai Univ. of band amino group of 0.5～1.8 micron polystyrene type, the D301R type) 1.0g, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 100 milliliter 4 * 10 -3Many sodium molybdate (Na of M 2Mo 6O 19) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till many molybdenum acid ions with rinsed with deionized water, centrifugation then 50 ℃ of low-temperature vacuum dryings 30 hours, promptly obtains the catalyst of load.
Embodiment 9
Styrene/divinylbenzene of getting selected particle diameter and being 30～200 microns is band amino group weak anion exchange resin (the Anhui Samsung of EVA, the D301 type) 1.0g, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 50 milliliter 6 * 10 -3Many sodium tungstate (Na of M 4W 10O 32) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till many tungstate ions with rinsed with deionized water, centrifugation then 50 ℃ of low-temperature vacuum dryings 30 hours, promptly obtains the catalyst of load.
Embodiment 10
Styrene/divinylbenzene of getting selected particle diameter and being 0.05～0.45 micron is reinforcing yin essence ion exchange resin (the Amberlite IRA of the U.S. Aldrich reagent company 900 types) 1.0g of the band quaternary amines of EVA, electromagnetic agitation is 30 minutes in the HCl of the 50 milliliters of 0.5M aqueous solution, after the filtration, electromagnetic agitation is 30 minutes in the NaOH of the 50 milliliters of 0.5M aqueous solution, washs with 500 ml deionized water.Filter out the resin of handling well, join in the glass container, add 20 ml deionized water, slowly add 25 milliliter 1 * 10 -2A kind of ternary heteropoly acid (molecular formula H of M 3PW 6Mo 6O 40) aqueous solution, and with the HClO of 0.1M 4Transfer to pH 4.60, under the electromagnetic agitation, carry out the load bonding.Stirred 48 hours, and stopped to stir.Detect to the solution less than till this ternary heteropoly acid radical ion with rinsed with deionized water, centrifugation then 50 ℃ of low-temperature vacuum dryings 36 hours, promptly obtains the catalyst of load.

Claims (9)

1. solid-phase photocatalyst that utilizes visible light, by polymer support and with it the oxo transistion metal compound of bonding form, it is characterized in that: the polymer support of this solid-phase photocatalyst is an anion exchange resin, and the mass ratio of described oxo transistion metal compound and polymer support is 0.01～1.5: 1;
Described anion exchange resin is selected from a kind of in the reinforcing yin essence ion exchange resin, band amino group weak anion exchange resin that styrene/divinylbenzene is EVA of reinforcing yin essence ion exchange resin, band quaternary amines that styrene/divinylbenzene is EVA of band quaternary amines of weak anion exchange resin, polystyrene type of the band amino group of polystyrene type;
Described oxo transistion metal compound is for having photoactive isopolyacid, heteropoly acid or ternary heteropoly acid.
2. solid-phase photocatalyst according to claim 1 is characterized in that: the particle diameter of described anion exchange resin is 0.05～200 micron.
3. solid-phase photocatalyst according to claim 1 is characterized in that: described isopolyacid is selected from H 2Mo 6O 19, H 4W 10O 32, Li 2Mo 6O 19, Li 4W 10O 32, Na 2Mo 6O 19, Na 4W 10O 32In a kind of.
4. solid-phase photocatalyst according to claim 1 is characterized in that: described heteropoly acid is selected from H 3PMo 12O 40, H 3PW 12O 40, H 4SiW 12O 40, Li 3PMo 12O 40, Li 3PW 12O 40, Li 3SiW 12O 40, Na 3PMo 12O 40, Na 3PW 12O 40, Na 4SiW 12O 40In a kind of.
5. solid-phase photocatalyst according to claim 1 is characterized in that: it is H that described ternary heteropoly acid is selected from general formula 3(PW xMo 12-xO 40) a kind of in the acid, wherein x=1～6.
6. the preparation method according to each described solid-phase photocatalyst of claim 1～5 is characterized in that, this method may further comprise the steps:
(1) pre-treatment of anion exchange resin
After anion exchange resin carried out pickling and alkali cleaning, to neutral, after the vacuum drying, grind to form particle diameter and be 0.05～200 micron single-size, place drier standby with deionized water drip washing;
(2) configuration of oxo transistion metal compound storing solution
Configuration 1 * 10 -4～1 * 10 -2The oxo transistion metal compound storing solution of M, standby; (3) loading process of oxo transistion metal compound on resin
In the container of agitating device is housed, put into the resin that step (1) was handled, add the oxo transistion metal compound of step (2) preparation, wherein, the mass ratio of oxo transistion metal compound and resin is 0.01～1.5: 1; Use HClO 4Transfer to pH3.90～4.60, stir under the room temperature, supernatant liquor is removed in centrifugation, the deionized water washing, and centrifugation again, the deionized water washing, repetitive operation detects in supernatant liquor less than oxo transistion metal compound; Vacuum drying under 10～50 ℃ of low temperature then;
Described anion exchange resin is selected from a kind of in the reinforcing yin essence ion exchange resin, band amino group weak anion exchange resin that styrene/divinylbenzene is EVA of reinforcing yin essence ion exchange resin, band quaternary amines that styrene/divinylbenzene is EVA of band quaternary amines of weak anion exchange resin, polystyrene type of the band amino group of polystyrene type;
Described oxo transistion metal compound is for having photoactive isopolyacid, heteropoly acid or ternary heteropoly acid.
7. method according to claim 6 is characterized in that: described isopolyacid is selected from H 2Mo 6O 19, H 4W 10O 32, Li 2Mo 6O 19, Li 4W 10O 32, Na 2Mo 6O 19, Na 4W 10O 32In a kind of.
8. method according to claim 6 is characterized in that: described heteropoly acid is selected from H 3PMo 12O 40, H 3PW 12O 40, H 4SiW 12O 40, Li 3PMo 12O 40, Li 3PW 12O 40, Li 3SiW 12O 40, Na 3PMo 12O 40, Na 3PW 12O 40, Na 4SiW 12O 40In a kind of.
9. method according to claim 6 is characterized in that: it is H that described ternary heteropoly acid is selected from general formula 3(PW xMo 12-xO 40) a kind of in the acid, wherein x=1～6.
CNA2005100112883A 2005-01-31 2005-01-31 Solid-phase photocatalyst utilizing visible light and its preparing method Pending CN1814348A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100493713C (en) * 2006-09-25 2009-06-03 中国科学院化学研究所 Visible light photocatalyst for constructing non-nitrogen and iron complex with hydrogen-like quinone and uses of the same
CN103191719A (en) * 2013-04-01 2013-07-10 桂林理工大学 Visible-light-responded photocatalyst Li4M5O17 and preparation method thereof
CN101869848B (en) * 2009-04-24 2013-08-14 中国科学院福建物质结构研究所 Semiconductor metallic oxide photocatalyst and preparation method and application thereof
CN103288739A (en) * 2013-06-19 2013-09-11 陕西师范大学 Complex of heteropoly tungstic acid anions and alkyl imidazolium cations and preparation method
CN104229927A (en) * 2014-09-17 2014-12-24 湖北师范学院 Method for degrading methyl orange through photocatalysis of H3PW6Mo6O40/ZrO2-SiO2 treated by H2O2
CN106179498A (en) * 2016-07-12 2016-12-07 天津工业大学 Polystyrene catalysis bead and slurry photocatalytic reactor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100493713C (en) * 2006-09-25 2009-06-03 中国科学院化学研究所 Visible light photocatalyst for constructing non-nitrogen and iron complex with hydrogen-like quinone and uses of the same
CN101869848B (en) * 2009-04-24 2013-08-14 中国科学院福建物质结构研究所 Semiconductor metallic oxide photocatalyst and preparation method and application thereof
CN103191719A (en) * 2013-04-01 2013-07-10 桂林理工大学 Visible-light-responded photocatalyst Li4M5O17 and preparation method thereof
CN103288739A (en) * 2013-06-19 2013-09-11 陕西师范大学 Complex of heteropoly tungstic acid anions and alkyl imidazolium cations and preparation method
CN104229927A (en) * 2014-09-17 2014-12-24 湖北师范学院 Method for degrading methyl orange through photocatalysis of H3PW6Mo6O40/ZrO2-SiO2 treated by H2O2
CN106179498A (en) * 2016-07-12 2016-12-07 天津工业大学 Polystyrene catalysis bead and slurry photocatalytic reactor

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