CN101143337A - Method for preparing a metal heteroatom phosphate aluminium molecular sieve high-efficient visible-light photocatalyst - Google Patents
Method for preparing a metal heteroatom phosphate aluminium molecular sieve high-efficient visible-light photocatalyst Download PDFInfo
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- CN101143337A CN101143337A CNA2007100096841A CN200710009684A CN101143337A CN 101143337 A CN101143337 A CN 101143337A CN A2007100096841 A CNA2007100096841 A CN A2007100096841A CN 200710009684 A CN200710009684 A CN 200710009684A CN 101143337 A CN101143337 A CN 101143337A
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Abstract
The invention relates to a high efficiency visible light photocatalyst preparation method of highly dispersed and isolated doped metal phosphorus and aluminum zeolite MeAPO-5. The invention is characterized in that phosphoric acid, pseudo-boehmite, metal salt, triethylamine and distilled water are mixed according to the weight ratio 20:10:1.5 to 3.5:8 to 10:50 and is stirred evenly; then the liquid is poured into stainless steel high pressure reaction vessel with polytetrafluoroethylene lining, and the reaction is placed in a muffle furnace to perform temperature subsection crystallization reaction; the liquid is further cooled to room temperature, washed and dried before semi-conductive visible light photocatalyst with AlPO4<-5> zeolite framework structure is prepared. The metal salt refers to magnesium sulfate, zinc acetate, ferric nitrate, nickel sulfate or manganese sulfate. In the process of temperature subsection crystallization reaction, the temperature is first raised to 60 to 95 degrees centigrade at a rate of 1 degree centigrade per minute; maintained at the level for 1 to 3 hours, the temperature is raised to 170 to 190 degrees centigrade at a rate of 1 degree centigrade per minute and is maintained for 20 to 40 hours. Tests show that MeAPO-5 has the framework structure of AlPO4<-5> zeolite. When used for dye solution visible light photodegradation, the material has good light catalytic performance.
Description
Technical field
The present invention relates to a kind of metal-doped non-semiconductor visible light photocatalyst material, particularly relate to a kind of preparation method with high dispersive, isolated metal-doped phosphate aluminium molecular sieve MeAPO-5 high-efficient visible-light photocatalyst.
Background technology
The photochemistry principle is thought: photocatalysis is the crosspoint of photochemistry and catalytic science, is meant the photochemical reaction under catalyst participates in; Intramolecule not standard " electron-hole pair " the high energy excitation state of the transfer of the specific charge between homoatomic formation can cause chemical reaction to take place equally.
Current, the exploitation of non-semiconductor photochemical catalyst has become the focus of photocatalysis research.People such as Anpo have proposed the metal oxide of high degree of dispersion under action of ultraviolet light based on the photochemistry principle, can make electronics from O
2 - (1)Transfer to M
N+ (1)Form the viewpoint that corresponding charge shifts excitation state.People such as Anpo by the synthetic hetero-atom molecular-sieve catalyst that makes of ion-exchange and hydro-thermal to NO
xAnd CO
2The steam photo catalytic reduction have good active and selectivity.Their work shows that the Y zeolite and the MCM-41 mesopore molecular sieve that contain transition metal can form isolated metal-oxygen species charge-transfer excitation attitude in skeleton: [Me
(n-1)+-O
-]
*, this excitation state is similar to the right effect in semi-conductive light induced electron-hole, has very strong photocatalytic activity.People such as A.G.Panov find, organic visible light photocatalysis oxidation has very high selectivity to hydro carbons through the zeolite (as NaX, NaY, KY, BaY and CaY etc.) of alkali metal and alkaline-earth metal ions exchange.
Zeolite starts from recent years with the research of photocatalyst, Kato etc. have reported that HZSM-5 and modenite have photocatalytic activity to the methane anaerobic coupling reaction, think that the existence of Al-O unit is the active sites that HZSM-5 and modenite produce photocatalytic activity in the molecular sieve.A.Moissette during load biphenyl (BP), finds that light induced electron-hole is to (BP/H on the Al-ZSM-5 of acidity zeolite
nZSM-5
+) life-span with overlength, wherein counterion H
+Important effect is arranged.The photocatalysis performance of ZSM-5 zeolite to ethene and methyl orange studied by Fu XianZhi professor seminar of Photocatalysis Inst., Fuzhou Univ, finds that the iron content in photocatalysis performance and the sample has good corresponding relation.The result of literature survey shows, research to the effect of heteroatom phosphate aluminium molecular sieve visible light photocatalysis is still rarely reported, and metal ion generally has variable valence state, has the catalytic oxidation-reduction activity, can realize heterogeneousization of metal ion catalysis selective oxidation reaction, this is very noticeable research topic in the current catalytic field.
The appearance of heteroatom phosphate aluminium molecular sieve is the new leap of in the molecular sieve development history, it has novel crystal structure and peculiar property, particularly, greatly improved the ion-exchange performance and the catalytic activity of heteroatom phosphate aluminium series molecular sieve because hetero atom is incorporated on the skeleton of phosphate aluminium molecular sieve.Literature survey is found, though the research work of relevant heteroatom phosphate aluminium molecular sieve catalyst is active, can be applicable in the conversion reaction of many hydro carbons, as: cracking, hydrogenation etc., but the application at the photocatalysis this respect is less relatively, only see the relevant report that FeAPO-5 can be used for photochemical catalytic oxidation synthesizing glycol etc., do not appear in the newspapers as yet in the application aspect the photocatalytically degradating organic dye for method for preparing metal heteroatom phosphate aluminium molecular sieve high-efficient visible-light photocatalyst and heteroatom phosphate aluminium molecular sieve.
Summary of the invention
Purpose of the present invention just is to prepare metal heteroatom phosphate aluminium molecular sieve (MeAPO-5) high-efficient visible-light photocatalyst.
As follows for realizing the technical scheme that purpose of the present invention adopts:
Material phosphoric acid, boehmite, slaine, triethylamine, distilled water.
Proportioning by weight (gram) than for phosphoric acid: boehmite: slaine: triethylamine: the ratio of distilled water=20: 10: 1.5～3.5: 8～10: 50.
Preparation is got phosphoric acid respectively, boehmite (AlOOH) by above proportioning, slaine, triethylamine is after the distilled water mixing and stirring, pour into and have in the teflon-lined stainless steel autoclave, and place Muffle furnace, carry out the temperature-gradient method crystallization.Earlier the speed with 1 ℃/min is warming up to 60～95 ℃, keep constant temperature 1～3h after, the speed with 1 ℃/min is warming up to 170～190 ℃ again, keeps constant temperature 20～40h.Naturally cool to room temperature subsequently, take out sample spend deionised water to pH be 6～7, in 100～120 ℃ of baking ovens, dry, promptly get the former powder of molecular sieve MeAPO-5 high-efficient visible-light photocatalyst.Through X-ray diffraction analysis, determine that MeAPO-5 has AlPO
4-5 framework of molecular sieve structures, and have good degree of crystallinity and purity, crystal is a hexagonal prism.
Slaine of the present invention is meant magnesium sulfate, zinc acetate, ferric nitrate, nickelous sulfate or manganese sulfate.
To prepare the catalyst fines sample, the photocatalytic activity of evaluate catalysts in batch (-type) visible light photocatalysis reactor, the result shows, with the halogen tungsten lamp of 500W as light source, 10ppm methylene blue with 80mL is the target degradation product, catalyst amount is 0.1g, after the adsorption-desorption balance, and the irradiation of turning on light.Reaction time is 5h, and percent of decolourization can reach 92.5%; Mineralization rate with dyestuff methylene blue in the volumetric precipitation method indirect determination photocatalytic degradation process is 23.7%, and behind the illumination 24h, mineralization rate can reach 82.6%.Metal heteroatom phosphate aluminium molecular sieve MeAPO-5 may become the novel visible-light photocatalyst of a class, has good photocatalysis performance.
Accompanying drawing and description of drawings
Fig. 1 is AlPO
4-5 X-ray diffractogram.
Fig. 2 is the X-ray diffractogram of MgAPO-5.
Fig. 3 is the electromicroscopic photograph figure of MgAPO-5.
We record five metal heteroatom phosphate aluminium molecular sieves and all have AlPO
4-The structure of 5 molecular sieves, and have good degree of crystallinity and purity, crystal is a hexagonal prism.
The specific embodiment
Embodiment 1
Material phosphoric acid, boehmite, magnesium sulfate, triethylamine, distilled water.
The phosphoric acid of 100 grams is got in preparation respectively, 50 gram boehmites, 15 gram magnesium sulfate, the distilled water of 50 gram triethylamines, 250 grams mixes, after stirring, pouring 500mL into has in the teflon-lined stainless steel autoclave, and placing Muffle furnace, the speed with 1 ℃/min is warming up to 80 ℃ earlier, keeps 80 ℃ of 1h, speed with 1 ℃/min is warming up to 190 ℃ again, keeps constant temperature 40h and carries out crystallization.Naturally cool to 26 ℃ subsequently, take out sample spend deionised water to pH be 6.5, in 100 ℃ of baking ovens, dry, promptly get the former powder of molecular sieve MgAPO-5 high-efficient visible-light photocatalyst.Through X-ray diffraction analysis, determine that MgAPO-5 has AlPO
4-5 framework of molecular sieve structures, and have good degree of crystallinity and purity, crystal is a hexagonal prism.
Embodiment 2
Material phosphoric acid, boehmite, zinc acetate, triethylamine, distilled water.
The phosphoric acid of 10.0 grams is got in preparation respectively, 5.0 the gram boehmite, 1.0 gram zinc acetates, the distilled water of 4.0 gram triethylamines, 25.0 grams mixes, after stirring, pour 100mL into and have in the teflon-lined stainless steel autoclave, and place Muffle furnace, the speed with 1 ℃/min is warming up to 65 ℃ earlier, keep 65 ℃ of 3h, speed with 1 ℃/min is warming up to 170 ℃ again, keeps constant temperature 20h, carries out crystallization.Naturally cool to 24 ℃ subsequently, take out sample spend deionised water to pH be 7.0, in 120 ℃ of baking ovens, dry, promptly get the former powder of molecular sieve ZnAPO-5 high-efficient visible-light photocatalyst.Through X-ray diffraction analysis, determine that ZnAPO-5 has AlPO
4-5 framework of molecular sieve structures, and have good degree of crystallinity and purity, crystal is a hexagonal prism.
Material phosphoric acid, boehmite, manganese sulfate, triethylamine, distilled water.
The phosphoric acid of 10.0 grams is got in preparation respectively, 5.0 the gram boehmite, 1.5 manganese sulfates, the distilled water of 4.4 gram triethylamines, 25.0 grams mixes, after stirring, pour 100mL into and have in the teflon-lined stainless steel autoclave, and place Muffle furnace, the speed with 1 ℃/min is warming up to 75 ℃ earlier, keep 75 ℃ of 2h, speed with 1 ℃/min is warming up to 180 ℃ again, keeps constant temperature 30h, carries out crystallization.Naturally cool to 25 ℃ subsequently, take out sample spend deionised water to pH be 6.0, in 110 ℃ of baking ovens, dry, promptly get the former powder of molecular sieve MnAPO-5 high-efficient visible-light photocatalyst.Through X-ray diffraction analysis, determine that MnAPO-5 has AlPO
4-5 framework of molecular sieve structures, and have good degree of crystallinity and purity, crystal is a hexagonal prism.
Embodiment 4
Material phosphoric acid, boehmite, ferric nitrate, triethylamine, distilled water.
The phosphoric acid of 10.0 grams is got in preparation respectively, 5.0 the gram boehmite, 0.8 gram ferric nitrate, the distilled water of 4.0 gram triethylamines, 25.0 grams mixes, after stirring, pour 100mL into and have in the teflon-lined stainless steel autoclave, and place Muffle furnace, the speed with 1 ℃/min is warming up to 75 ℃ earlier, keep 75 ℃ of 1.5h, speed with 1 ℃/min is warming up to 175 ℃ again, keeps constant temperature 25h, carries out crystallization.Naturally cool to 23 ℃ subsequently, take out sample spend deionised water to pH be 6.5, in 120 ℃ of baking ovens, dry, promptly get the former powder of molecular sieve FeAPO-5 high-efficient visible-light photocatalyst.Through X-ray diffraction analysis, determine that FeAPO-5 has AlPO
4-5 framework of molecular sieve structures, and have good degree of crystallinity and purity, crystal is a hexagonal prism.
Embodiment 5
Material phosphoric acid, boehmite, nickelous sulfate, triethylamine, distilled water.
The phosphoric acid of 10.0 grams is got in preparation respectively, 5.0 the gram boehmite, 1.7 gram nickelous sulfates, the distilled water of 4.4 gram triethylamines, 25.0 grams mixes, after stirring, pour 100mL into and have in the teflon-lined stainless steel autoclave, and place Muffle furnace, the speed with 1 ℃/min is warming up to 85 ℃ earlier, keep 85 ℃ of lh, speed with 1 ℃/min is warming up to 185 ℃ again, keeps constant temperature 35h, carries out crystallization.Naturally cool to 27 ℃ subsequently, take out sample spend deionised water to pH be 6.5, in 115 ℃ of baking ovens, dry, promptly get the former powder of molecular sieve NiAPO-5 high-efficient visible-light photocatalyst.Through X-ray diffraction analysis, determine that NiAPO-5 has AlPO
4-5 framework of molecular sieve structures, and have good degree of crystallinity and purity, crystal is a hexagonal prism.
Claims (4)
1. metal heteroatom phosphate aluminium molecular sieve high-efficient visible-light photocatalyst is characterized in that:
Material and weight ratio
Phosphoric acid: boehmite: slaine: triethylamine: distilled water=20: 10: 1.5～3.5: 8～10: 50;
Preparation
By above proportioning, get phosphoric acid respectively, boehmite, slaine, triethylamine after the distilled water mixing and stirring, is poured into and is had in the teflon-lined stainless steel autoclave, and places Muffle furnace, carry out the temperature-gradient method crystallization, be cooled to room temperature after, wash, dry.
2. metal heteroatom phosphate aluminium molecular sieve high-efficient visible-light photocatalyst according to claim 1 is characterized in that described slaine is meant magnesium sulfate, zinc acetate, ferric nitrate, nickelous sulfate or manganese sulfate.
3. metal heteroatom phosphate aluminium molecular sieve high-efficient visible-light photocatalyst according to claim 1, when it is characterized in that described temperature-gradient method crystallization, speed with 1 ℃/min is warming up to 60～95 ℃ earlier, after keeping constant temperature 1～3h, speed with 1 ℃/min is warming up to 170～190 ℃ again, keeps constant temperature 20～40h.
4. metal heteroatom phosphate aluminium molecular sieve high-efficient visible-light photocatalyst according to claim 1, it is characterized in that described crystallization is lowered the temperature fully, naturally after, spend deionised water to pH be 6～7, in 100～120 ℃ of baking ovens, dry.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102069006A (en) * | 2010-12-08 | 2011-05-25 | 上海交通大学 | Photocatalytic metal-molecular sieve composite catalyst and preparation method thereof |
| CN104556144A (en) * | 2014-12-31 | 2015-04-29 | 中国石油天然气股份有限公司 | MeAPO-17 molecular sieve containing transition metal, and synthetic method and application thereof |
| CN109692705A (en) * | 2019-01-11 | 2019-04-30 | 中国石油大学(华东) | A kind of method of solid reaction process synthesis MeAPO-5 molecular sieve |
| CN113289633A (en) * | 2021-06-23 | 2021-08-24 | 兰州交通大学 | MnCo2Method for synthesizing bimetallic non-semiconductor photocatalysis nano composite material |
| CN117101714A (en) * | 2023-07-30 | 2023-11-24 | 南京工业大学 | Magnesium modified NiAPO-11 molecular sieve catalyst and application thereof |
-
2007
- 2007-10-22 CN CNA2007100096841A patent/CN101143337A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102069006A (en) * | 2010-12-08 | 2011-05-25 | 上海交通大学 | Photocatalytic metal-molecular sieve composite catalyst and preparation method thereof |
| CN102069006B (en) * | 2010-12-08 | 2012-08-22 | 上海交通大学 | Photocatalytic metal-molecular sieve composite catalyst and preparation method thereof |
| CN104556144A (en) * | 2014-12-31 | 2015-04-29 | 中国石油天然气股份有限公司 | MeAPO-17 molecular sieve containing transition metal, and synthetic method and application thereof |
| CN109692705A (en) * | 2019-01-11 | 2019-04-30 | 中国石油大学(华东) | A kind of method of solid reaction process synthesis MeAPO-5 molecular sieve |
| CN113289633A (en) * | 2021-06-23 | 2021-08-24 | 兰州交通大学 | MnCo2Method for synthesizing bimetallic non-semiconductor photocatalysis nano composite material |
| CN117101714A (en) * | 2023-07-30 | 2023-11-24 | 南京工业大学 | Magnesium modified NiAPO-11 molecular sieve catalyst and application thereof |
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