CN103100414A - Molecular sieve with photocatalysis function, and preparation method thereof - Google Patents
Molecular sieve with photocatalysis function, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a molecular sieve with a photocatalysis function, and a preparation method of the molecular sieve. The molecular sieve comprises an HZSM-5 molecular sieve, and is characterized in that strontium titanate photocatalyst is compounded on the modified HZSM-5 molecular sieve by a sol-gel method; electron-hole pairs are generated by the photocatalyst particles which are loaded in pore channels and surface of the molecular sieve and are irradiated by ultraviolet light; the interiors of the pore channels of the molecular sieve have very strong electric field intensity, and electrons are gathered on the surface of the molecular sieve, so that the electron-hole pairs are prevented from being compounded, and free active groups are very easily obtained by the organic matter absorbed by the molecular sieve; and therefore, the photocatalytic activity of the photocatalyst can be improved.
Description
Technical field
The invention belongs to the water quality purification function Material Field, be specifically related to a kind of molecular sieve with photo-catalysis function and preparation method thereof.
Background technology
The technique for fixing of catalyst and the selection of carrier have become a very crucial problem of photocatalysis technology.Traditional light-catalyzed reaction study general carries out in outstanding slurry attitude light-catalyzed reaction system, photocatalyst granular is less and proportion is low, filtration, flocculation, precipitation and traditional separation method such as centrifugal be difficult to photochemical catalyst separate, recovery and regeneration, thereby can not realize continued operation.And the photocatalyst granular of suspended state on Optical Absorption stop can affect the irradiation degree of depth of light source, therefore outstandingly at present starch the commercial Application that attitude photochemical catalyst photocatalytic system is difficult to carry out scale, be mainly used in the research in laboratory.The immobilization of photochemical catalyst can solve catalyst separation, recovery, regeneration hard problem effectively.The load of photochemical catalyst comprises two broad aspect: the firstth, forming the photocatalyst film material on reactor wall or on the tabular carrier; The secondth, at graininess, fibrous, stratiform, flexible material and have fixed photocatalyst on the carriers such as material of pore passage structure.The characteristics of carrier are: absorption property is good, specific area is large, free settling or easily floating; The Main Function of carrier of photocatalyst has: (1) in carrier surface, can avoid the reunion of particle in suspended phase with photocatalyst, increases the specific area of photochemical catalyst, improves the utilization rate of photochemical catalyst; (2) with carrier, photochemical catalyst is fixed, can be prevented from the loss of photocatalyst powder particle and be easy to recycling; (3) some carrier has good absorption property, can increase the absorption to reactant and intermediate product, and some carrier can become the trapping centre of electronics, is conducive to the separation of electron hole pair, thereby improves the photocatalytic activity of photochemical catalyst; (4) with carrier, catalyst is fixed, be convenient to catalyst is carried out finishing and makes the reactor of various shapes;
Up to the present, the report of also not studying about molecular sieve carried strontium titanates photochemical catalyst.
Summary of the invention
Purpose of the present invention is to provide a kind of molecular sieve with photo-catalysis function, and this molecular sieve is to adopt acid treatment to carry out modification to the HZSM-5 molecular sieve, effectively improves the photocatalysis performance of photochemical catalyst.
Another object of the present invention is to provide a kind of molecular sieve with photo-catalysis function and preparation method thereof.
The technical scheme that adopts is:
A kind of molecular sieve with photo-catalysis function comprises the HZSM-5 molecular sieve, it is characterized in that: adopt sol-gel process composite titanic acid strontium photochemical catalyst on the HZSM-5 of modification molecular sieve;
A kind of molecular sieve with photo-catalysis function and preparation method thereof comprises following processing step:
(1) the sour modification of HZSM-5 molecular sieve
With 50 g NaZSM-5(Catalyst Factory, Nankai Univs, Si/Al=50) He 800 mL acid solutions are placed in the 1L there-necked flask, stir four hours under 92 ℃-95 ℃; The solution suction filtration is cleaned with distilled water simultaneously, then with molecular sieve dry 12 h in 110 ℃ of baking ovens, be placed in again Muffle furnace after grinding in 550 ℃ of calcining 4 h, obtain HZSM-5, standby;
(2) the synthetic support type metatitanic acid strontium photochemical catalyst of sol-gel process
At first 10 mL glacial acetic acid are dissolved in 10 mL deionized waters, uniform stirring obtains solution A, and is standby; Separately get 1.7 mL tetra-n-butyl titanates and be added in absolute ethyl alcohol, wherein the volume ratio of tetra-n-butyl titanate and absolute ethyl alcohol is 1:4, obtains yellow solution B after stirring 10 min, and is standby; Add HZSM-5 molecular sieve 3 g that obtain in strontium nitrate and step (1) in solution A, wherein strontium titanium atom mol ratio
n(Sr):
n(Ti) be 1:1, then solution B dropwise joined in the solution A of high-speed stirred, splash into 0.5 mL ethylene glycol and make stabilizing agent; Along with solvent constantly evaporates, the solution thickness that becomes gradually forms thick colloidal sol at last, and after at room temperature ageing 24 h, dry 8 h under 110 ℃, become gel in drying box, at 800 ℃ of calcining 3 h, and get final product.
Light-catalyzed reaction experiment one:
Estimate the performance of prepared strontium titanate material by the variation of methyl orange solution degradation rate.The light source of photocatalysis experiment is 20 W ultraviolet germicidals (dominant wavelength is 253.7 nm).Add methyl orange solution and photochemical catalyst in the quartz beaker of 60 mL.The initial concentration of methyl orange is 5 mgL
-1, photochemical catalyst concentration is 500 mgL
-1, the volume of reaction solution is 30 mL, with the maximum absorption wavelength 468 nm place mensuration absorbances of 721E type visible spectrophotometer in methyl orange.At first on magnetic stirring apparatus, lucifuge stirs 30 min, and after balance upon adsorption, sampling 5 mL, be the micro-filtrate membrane filtration of 0.45 μ m with the aperture, then measures its absorbance.Calculate methyl orange solution concentration according to Lambert-Beer's law, and calculate photochemical catalyst to the adsorption rate of dyestuff.Then reaction solution is placed under the uviol lamp of unlatching, liquid level is apart from high 5 cm of lamp, and intensity of illumination is 2200 μ Wcm
-2(UV-B type ultraviolet radiation meter mensuration).Use micro-filtrate membrane filtration after the illumination certain hour, again measure its absorbance, calculate photochemical catalyst to the photocatalytic activity of dyestuff.
Detect the photocatalysis performance of the HZSM-5 load strontium titanates that is synthesized according to above-mentioned light-catalyzed reaction experimental technique, during 30 min, the photocatalytic activity of methyl orange is 65%, and is 35% without the photocatalytic activity of the pure strontium titanates of load.
Light-catalyzed reaction experiment two:
Estimate the performance of prepared strontium titanate material by the variation of methyl orange solution degradation rate.The light source of photocatalysis experiment is 20 W ultraviolet germicidals (dominant wavelength is 253.7 nm).Add methyl orange solution and photochemical catalyst in the quartz beaker of 60 mL.The initial concentration of methyl orange is 5 mgL
-1, photochemical catalyst concentration is 500 mgL
-1, the volume of reaction solution is 30 mL, with the maximum absorption wavelength 468 nm place mensuration absorbances of 721E type visible spectrophotometer in methyl orange.At first on magnetic stirring apparatus, lucifuge stirs 30 min, and after balance upon adsorption, sampling 5 mL, be the micro-filtrate membrane filtration of 0.45 μ m with the aperture, then measures its absorbance.Calculate methyl orange solution concentration according to Lambert-Beer's law, and calculate photochemical catalyst to the adsorption rate of dyestuff.Then reaction solution is placed under the uviol lamp of unlatching, liquid level is apart from high 5 cm of lamp, and intensity of illumination is 2200 μ Wcm
-2(UV-B type ultraviolet radiation meter mensuration).Use micro-filtrate membrane filtration after the illumination certain hour, again measure its absorbance, calculate photochemical catalyst to the photocatalytic activity of dyestuff.
Detect the photocatalysis performance of the HZSM-5 load strontium titanates that is synthesized according to above-mentioned light-catalyzed reaction experimental technique, during 30 min, the photocatalytic activity of methyl orange is 70%, and is 35% without the photocatalytic activity of the pure strontium titanates of load.
Light-catalyzed reaction experiment three:
Estimate the performance of prepared strontium titanate material by the variation of methyl orange solution degradation rate.The light source of photocatalysis experiment is 20 W ultraviolet germicidals (dominant wavelength is 253.7 nm).Add methyl orange solution and photochemical catalyst in the quartz beaker of 60 mL.The initial concentration of methyl orange is 5 mgL
-1, photochemical catalyst concentration is 500 mgL
-1, the volume of reaction solution is 30 mL, with the maximum absorption wavelength 468 nm place mensuration absorbances of 721E type visible spectrophotometer in methyl orange.At first on magnetic stirring apparatus, lucifuge stirs 30 min, and after balance upon adsorption, sampling 5 mL, be the micro-filtrate membrane filtration of 0.45 μ m with the aperture, then measures its absorbance.Calculate methyl orange solution concentration according to Lambert-Beer's law, and calculate photochemical catalyst to the adsorption rate of dyestuff.Then reaction solution is placed under the uviol lamp of unlatching, liquid level is apart from high 5 cm of lamp, and intensity of illumination is 2200 μ Wcm
-2(UV-B type ultraviolet radiation meter mensuration).Use micro-filtrate membrane filtration after the illumination certain hour, again measure its absorbance, calculate photochemical catalyst to the photocatalytic activity of dyestuff.
Detect the photocatalysis performance of the HZSM-5 load strontium titanates that is synthesized according to above-mentioned light-catalyzed reaction experimental technique, during 30 min, the photocatalytic activity of methyl orange is 66%, and is 35% without the photocatalytic activity of the pure strontium titanates of load.
By above-mentioned light-catalyzed reaction experimental result, the photocatalysis performance that proves HZSM-5 load strontium titanates exceeds one times nearly more than the photocatalytic activity of the pure strontium titanates of load not.
The invention has the advantages that:
In the present invention, the compound of photochemical catalyst and molecular sieve can obviously strengthen photocatalytic activity, molecular sieve can provide sufficient absorption surface for reactant, the molecular sieve acid site can strengthen photocatalysis efficiency, Al in framework of molecular sieve catches trap for light induced electron provides shallow gesture simultaneously, can extend carrier lifetime.Molecular sieve just in time has good absorption property due to its loose structure and large specific area.Both combine, thereby produce cooperative effect, can effectively improve the photocatalysis performance of photochemical catalyst.Load in molecular sieve pore passage and produce electron-hole pair with lip-deep photocatalyst particles under the irradiation of ultraviolet light, because have very strong electric-field intensity in molecular sieve pore passage, also there is the electronics enrichment on its surface, can play the compound effect of electron-hole pair that suppresses, the active group thereby the organic matter that makes molecular sieve adsorption can gain freedom easily, thereby the photocatalytic activity of raising photochemical catalyst.
The specific embodiment
Embodiment 1
A kind of molecular sieve with photo-catalysis function comprises the HZSM-5 molecular sieve, it is characterized in that: adopt sol-gel process composite titanic acid strontium photochemical catalyst on the HZSM-5 of modification molecular sieve;
A kind of molecular sieve with photo-catalysis function and preparation method thereof comprises following processing step:
(1) the sour modification of ZSM-5 molecular sieve
With 50 g NaZSM-5(Catalyst Factory, Nankai Univs, Si/Al=50) He 0.3 mol/L hydrochloric acid solution 800 mL are placed in the 1L there-necked flask, stir four hours under 92 ℃-95 ℃; The solution suction filtration is cleaned with distilled water simultaneously, then with molecular sieve dry 12 h in 110 ℃ of baking ovens, be placed in again Muffle furnace after grinding in 550 ℃ of calcining 4 h, obtain HZSM-5, standby;
(2) the synthetic support type metatitanic acid strontium photochemical catalyst of sol-gel process
At first 10 mL glacial acetic acid are dissolved in 10 mL deionized waters, uniform stirring obtains solution A, and is standby; Separately get 1.7 mL tetra-n-butyl titanates and be added in absolute ethyl alcohol, wherein the volume ratio of tetra-n-butyl titanate and absolute ethyl alcohol is 1:4, obtains yellow solution B after stirring 10 min, and is standby; Add HZSM-5 molecular sieve 3 g that obtain in strontium nitrate and step (1) in solution A, wherein strontium titanium atom mol ratio
n(Sr):
n(Ti) be 1:1, then solution B dropwise joined in the solution A of high-speed stirred, splash into 0.5 mL ethylene glycol and make stabilizing agent; Along with solvent constantly evaporates, the solution thickness that becomes gradually forms thick colloidal sol at last, and after at room temperature ageing 24 h, dry 8 h under 110 ℃, become gel in drying box, at 800 ℃ of calcining 3 h, and get final product.
Embodiment 2
A kind of molecular sieve with photo-catalysis function comprises the HZSM-5 molecular sieve, it is characterized in that: adopt sol-gel process composite titanic acid strontium photochemical catalyst on the HZSM-5 of modification molecular sieve;
A kind of molecular sieve with photo-catalysis function and preparation method thereof comprises following processing step:
(1) the sour modification of ZSM-5 molecular sieve
With 50 g NaZSM-5(Catalyst Factory, Nankai Univs, Si/Al=50) He 0.5 mol/L phosphoric acid solution 800 mL are placed in the 1L there-necked flask, stir four hours under 92 ℃-95 ℃; The solution suction filtration is cleaned with distilled water simultaneously, then with molecular sieve dry 12 h in 110 ℃ of baking ovens, be placed in again Muffle furnace after grinding in 550 ℃ of calcining 4 h, obtain HZSM-5, standby;
(2) the synthetic support type metatitanic acid strontium photochemical catalyst of sol-gel process
At first 10 mL glacial acetic acid are dissolved in 10 mL deionized waters, uniform stirring obtains solution A, and is standby; Separately get 1.7 mL tetra-n-butyl titanates and be added in absolute ethyl alcohol, wherein the volume ratio of tetra-n-butyl titanate and absolute ethyl alcohol is 1:4, obtains yellow solution B after stirring 10 min, and is standby; Add HZSM-5 molecular sieve 3 g that obtain in strontium nitrate and step (1) in solution A, wherein strontium titanium atom mol ratio
n(Sr):
n(Ti) be 1:1, then solution B dropwise joined in the solution A of high-speed stirred, splash into 0.5 mL ethylene glycol and make stabilizing agent; Along with solvent constantly evaporates, the solution thickness that becomes gradually forms thick colloidal sol at last, and after at room temperature ageing 24 h, dry 8 h under 110 ℃, become gel in drying box, at 800 ℃ of calcining 3 h, and get final product.
Embodiment 3
A kind of molecular sieve with photo-catalysis function comprises the HZSM-5 molecular sieve, it is characterized in that: adopt sol-gel process composite titanic acid strontium photochemical catalyst on the HZSM-5 of modification molecular sieve;
A kind of molecular sieve with photo-catalysis function and preparation method thereof comprises following processing step:
(1) the sour modification of ZSM-5 molecular sieve
With 50 g NaZSM-5(Catalyst Factory, Nankai Univs, Si/Al=50) He 3 mol/L oxalic acid solution 800 mL are placed in the 1L there-necked flask, stir four hours under 92 ℃-95 ℃; The solution suction filtration is cleaned with distilled water simultaneously, then with molecular sieve dry 12 h in 110 ℃ of baking ovens, be placed in again Muffle furnace after grinding in 550 ℃ of calcining 4 h, obtain HZSM-5, standby;
(2) the synthetic support type metatitanic acid strontium photochemical catalyst of sol-gel process
At first 10 mL glacial acetic acid are dissolved in 10 mL deionized waters, uniform stirring obtains solution A, and is standby; Separately get 1.7 mL tetra-n-butyl titanates and be added in absolute ethyl alcohol, wherein the volume ratio of tetra-n-butyl titanate and absolute ethyl alcohol is 1:4, obtains yellow solution B after stirring 10 min, and is standby; Add HZSM-5 molecular sieve 3 g that obtain in strontium nitrate and step (1) in solution A, wherein strontium titanium atom mol ratio
n(Sr):
n(Ti) be 1:1, then solution B dropwise joined in the solution A of high-speed stirred, splash into 0.5 mL ethylene glycol and make stabilizing agent; Along with solvent constantly evaporates, the solution thickness that becomes gradually forms thick colloidal sol at last, and after at room temperature ageing 24 h, dry 8 h under 110 ℃, become gel in drying box, at 800 ℃ of calcining 3 h, and get final product.
Claims (2)
1. the molecular sieve with photo-catalysis function, comprise the HZSM-5 molecular sieve, it is characterized in that: adopt sol-gel process composite titanic acid strontium photochemical catalyst on the HZSM-5 of modification molecular sieve.
2. a kind of molecular sieve with photo-catalysis function according to claim 1 and preparation method thereof, is characterized in that, comprises following processing step:
(1) the sour modification of HZSM-5 molecular sieve
With 50 g NaZSM-5(Catalyst Factory, Nankai Univs, Si/Al=50) He 800 mL acid solutions are placed in the 1L there-necked flask, stir four hours under 92 ℃-95 ℃; The solution suction filtration is cleaned with distilled water simultaneously, then with molecular sieve dry 12 h in 110 ℃ of baking ovens, be placed in again Muffle furnace after grinding in 550 ℃ of calcining 4 h, obtain HZSM-5, standby;
(2) the synthetic support type metatitanic acid strontium photochemical catalyst of sol-gel process
At first 10 mL glacial acetic acid are dissolved in 10 mL deionized waters, uniform stirring obtains solution A, and is standby; Separately get 1.7 mL tetra-n-butyl titanates and be added in absolute ethyl alcohol, wherein the volume ratio of tetra-n-butyl titanate and absolute ethyl alcohol is 1:4, obtains yellow solution B after stirring 10 min, and is standby; Add HZSM-5 molecular sieve 3 g that obtain in strontium nitrate and step (1) in solution A, wherein strontium titanium atom mol ratio
n(Sr):
n(Ti) be 1:1, then solution B dropwise joined in the solution A of high-speed stirred, splash into 0.5 mL ethylene glycol and make stabilizing agent; Along with solvent constantly evaporates, the solution thickness that becomes gradually forms thick colloidal sol at last, and after at room temperature ageing 24 h, dry 8 h under 110 ℃, become gel in drying box, at 800 ℃ of calcining 3 h, and get final product.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307563A (en) * | 2014-10-14 | 2015-01-28 | 沈阳理工大学 | Molecular sieve material loaded with bismuth titanate photocatalyst and preparation method of molecular sieve material |
| CN105854928A (en) * | 2016-04-01 | 2016-08-17 | 盐城工业职业技术学院 | Preparation method of molecular sieve loaded metal modified TiO2 photocatalyst |
| CN106040225A (en) * | 2016-05-24 | 2016-10-26 | 沈阳理工大学 | Thin-layered bismuth titanate material and preparation method thereof |
| CN106179303A (en) * | 2016-07-21 | 2016-12-07 | 沈阳理工大学 | A kind of method preparing netted metatitanic acid gadolinium material |
| CN106824255A (en) * | 2017-03-28 | 2017-06-13 | 沈阳理工大学 | A kind of preparation method of the molecular sieve with photo-catalysis function |
| CN107961776A (en) * | 2017-12-15 | 2018-04-27 | 沈阳理工大学 | A kind of preparation method of the structure mesoporous material of three-dimensional Ti-Sr oxide frameworks |
| CN108435129A (en) * | 2018-03-16 | 2018-08-24 | 沈阳理工大学 | A method of preparing Sr-Ti-In ternary oxide molecular sieves |
| CN109529919A (en) * | 2018-12-26 | 2019-03-29 | 桂林理工大学 | A kind of preparation method of the dedicated modified molecular sieve of ceramic ink |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307563A (en) * | 2014-10-14 | 2015-01-28 | 沈阳理工大学 | Molecular sieve material loaded with bismuth titanate photocatalyst and preparation method of molecular sieve material |
| CN105854928A (en) * | 2016-04-01 | 2016-08-17 | 盐城工业职业技术学院 | Preparation method of molecular sieve loaded metal modified TiO2 photocatalyst |
| CN106040225A (en) * | 2016-05-24 | 2016-10-26 | 沈阳理工大学 | Thin-layered bismuth titanate material and preparation method thereof |
| CN106179303A (en) * | 2016-07-21 | 2016-12-07 | 沈阳理工大学 | A kind of method preparing netted metatitanic acid gadolinium material |
| CN106824255A (en) * | 2017-03-28 | 2017-06-13 | 沈阳理工大学 | A kind of preparation method of the molecular sieve with photo-catalysis function |
| CN107961776A (en) * | 2017-12-15 | 2018-04-27 | 沈阳理工大学 | A kind of preparation method of the structure mesoporous material of three-dimensional Ti-Sr oxide frameworks |
| CN108435129A (en) * | 2018-03-16 | 2018-08-24 | 沈阳理工大学 | A method of preparing Sr-Ti-In ternary oxide molecular sieves |
| CN108435129B (en) * | 2018-03-16 | 2020-09-04 | 沈阳理工大学 | Method for preparing Sr-Ti-In ternary oxide molecular sieve |
| CN109529919A (en) * | 2018-12-26 | 2019-03-29 | 桂林理工大学 | A kind of preparation method of the dedicated modified molecular sieve of ceramic ink |
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Application publication date: 20130515 |