CN101049574A - Photocatalysis material possessing hud structure of photoluminescent property, and preparation method - Google Patents
Photocatalysis material possessing hud structure of photoluminescent property, and preparation method Download PDFInfo
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- CN101049574A CN101049574A CN 200710103141 CN200710103141A CN101049574A CN 101049574 A CN101049574 A CN 101049574A CN 200710103141 CN200710103141 CN 200710103141 CN 200710103141 A CN200710103141 A CN 200710103141A CN 101049574 A CN101049574 A CN 101049574A
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- sio
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Abstract
A photocatalyst with fluorescent core-shell nano-structure has an expression formula: SiO2@AxMy:RB, where x=0-2, y=0-3, A is chosen from Ti, Fe, Zn, Pb and Ag, M is chosen from O and S, and RB is rhodamine used as both fluorescent marker and surfactant. Its preparing process features that the spherical SiO2 particles with controllable diameter is used as core, and the dye rhodamine is embedded in the core-shell nano-structure.
Description
Technical field:
The invention belongs to preparation method with photoluminescent property nucleocapsid structure catalysis material
Background technology:
As the inoganic solids functional material, catalysis material has been widely used in the degraded of catalysis pollutant, the preparation of fine chemistry reagent and the every field such as comprehensive utilization of the energy, plays irreplaceable effect in national economy and daily life.Development along with society, people have higher requirement to the aspects such as catalytic activity, selectivity and manufacturing cost of catalysis material, because core-shell material has that specific area is big, shape is regular, scantling is controlled, stable performance and product are easy to plurality of advantages such as recycling, thereby has broad application prospects at catalytic field.And rhodamine class dyestuff is widely used on laser, the fluorescence labeling owing to having stronger photoluminescent property, but organic dyestuff normally photo-labile and also the photobleaching phenomenon takes place easily.By the particle of preparation nucleocapsid structure, wherein making the dyestuff embedding outside have one deck shell to coat is a kind of good protected mode.At present, laboratory and industrial extensive employing hydro-thermal method, micro emulsion method and sol-gel process prepare this class material, it is simple that these class methods have equipment, raw material obtains easily, advantages such as purity height, good uniformity, chemical composition precise control, but the cost of hydro-thermal method and sol-gel process is higher, and the reunion of resultant material is also relatively more serious.The micro emulsion method can be wrapped up the layer of surface active agent molecule at particle surface, the difficult reunion.But this method need consume a lot of surfactants and organic solvent.So as a whole, these methods can't satisfy the demand of industrial production to catalysis material merely.
Summary of the invention:
An object of the present invention is to provide and have photoluminescent property nucleocapsid structure catalysis material; Another purpose provides the method that a kind of preparation has photoluminescent property nucleocapsid structure catalysis material
Expression formula with photoluminescent property nucleocapsid structure catalysis material of the present invention is: SiO
2@A
xM
y: RB wherein: 0＜x≤2,0＜y≤3, A=Ti, Fe, Zn, Pb, Ag; M=O, S, RB are rhodamine
Raw materials of compound used in the present invention is 99.99% TiCl
4, K
4Fe (CN)
6, Zn (CH
3COO)
2, Pb (CH
3COO)
2, Ag (CH
3COO)
2, Zn (CH
3COO)
2Solvent is water and ethanol; Hydrochloric acid is used to dissolve above-mentioned metallic compound, and rhodamine is pure for analyzing; Analytically pure ethyl orthosilicate is used to prepare different big or small monodispersed SiO with ammoniacal liquor
2Microballoon.
Preparation method and condition with photoluminescent property nucleocapsid structure catalysis material are as follows:
(1) preparation SiO
2Microballoon
Absolute ethyl alcohol, ammoniacal liquor and water are added to together and stir, the mixed liquor that in the mixed solution that forms, adds ethyl orthosilicate and ethanol, wherein the volume ratio of water, ammoniacal liquor, absolute ethyl alcohol and ethyl orthosilicate is 1～3: 2～4: 8～15: 0.8～1.6, magnetic agitation 4-8 hour continuously, then the reactant liquor centrifugation, wash centrifugation again with aquae destillata, repeatable operation three times, remove supernatant liquor at last, 50 ℃ of following vacuum drying 24 hours, resulting white powder is monodispersed SiO
2Particle.
(2) preparation has photoluminescent property nucleocapsid structure catalysis material
Under room temperature or heating condition, above-mentioned a kind of metallic compound is dissolved with certain density HCl, the SiO of step (1) preparation
2Powder is ultrasonic to be distributed in the certain density rhodamine ethanolic solution, keeps SiO
2The mol ratio of microballoon and metal ion is 0.1～20: 1, the mixed liquor room temperature or add thermal agitation or hydrothermal treatment consists 4-18 hour.Centrifugation, the distilled water washing, repeated centrifugation is separated, the washing several, and product obtains having photoluminescent property nucleocapsid structure catalysis material room temperature to 50 ℃ following vacuum drying 24 hours.
That the present invention selects is cheap, preparation and size-controllable spherical SiO easily
2Microballoon is examined, select cheap metal inorganic salt as primary raw material, select rhodamine both to can be used as the surfactant that prevents that microballoon from reuniting, and have stronger photoluminescent property, make particle can be good at being coated on template surface as stabilizing agent again.The material particle size that the present invention obtains is even, and single the dispersion, (560-900nm) is controlled for particle size, and has stronger photoluminescent property, is convenient to detect, and process equipment is simple.
The specific embodiment:
Embodiment 1
TiO
2: the preparation of RB nucleocapsid structure catalysis material
Earlier absolute ethyl alcohol, 12mL ammoniacal liquor and the 5mL distilled water of 20mL is joined in the reaction bulb of 100mL and stir, mixed liquor with the absolute ethyl alcohol of the ethyl orthosilicate of 4.02mL and 30mL adds wherein again, continue to stir 8 hours, then the reactant liquor centrifugation, incline and wash centrifugation again with aquae destillata after supernatant, triplicate, product obtain needed single SiO of dispersion 50 ℃ of following vacuum drying 24 hours
2Microballoon.Under the room temperature, will singly disperse SiO
2Microballoon 0.5g is ultrasonic to be distributed in the RB ethanolic solution of 0.005mol/L, adds HCl and TiCl that 30ml contains 2mol/L
4The aqueous solution.Stir water-bath heating down 5 hours.The washing of centrifugation, distilled water repeats for several times, and 50 ℃ of following vacuum drying 24 hours can obtain SiO
2@TiO
2: RB nucleocapsid structure catalysis material.This material particle is uniformly dispersed average grain diameter 560nm.Light degradation K
2Cr
2O
7The experiment of solution shows that this material has extraordinary photocatalysis property.
Embodiment 2
Fe
2O
3: the preparation of RB nucleocapsid structure catalysis material
Stir in absolute ethyl alcohol, 12mL ammoniacal liquor and the 10mL distilled water adding reaction bulb with 20mL earlier, mixed liquor with the absolute ethyl alcohol of the ethyl orthosilicate of 4.02mL and 30mL adds wherein again, continue to stir 8 hours, then the reactant liquor centrifugation, incline and wash centrifugation again with aquae destillata after supernatant, triplicate, product obtain needed single SiO of dispersion 50 ℃ of following vacuum drying 24 hours
2Microballoon.Under the room temperature, will singly disperse SiO
2Microballoon 0.5g is ultrasonic to be distributed to 1 * 10
-3In the RB aqueous solution of mol/L, add 0.42g K again
4Fe (CN)
6, (the NH of 0.78g
4)
2S
2O
8NaH with 0.22g
2PO
4, stir.Solution is sealed in the reactor of polytetrafluoroethylene (PTFE) subsequently, hydrothermal treatment consists 8h in the time of 180 ℃, and post-processing filtering obtains wine-colored Fe
2O
3, washing repeatedly with deionized water and ethanol, vacuum drying 24h under the room temperature can obtain SiO
2@Fe
2O
3: RB nucleocapsid structure catalysis material.This material particle is uniformly dispersed average grain diameter 420nm.The experiment of light degradation salicylic acid solution shows that this material has extraordinary photocatalysis performance.
Embodiment 3
The preparation of ZnO:RB nucleocapsid structure catalysis material
Stir in absolute ethyl alcohol, 15mL ammoniacal liquor and the 10mL distilled water adding reaction bulb with 28mL earlier, mixed liquor with the absolute ethyl alcohol of the ethyl orthosilicate of 4.02mL and 30mL adds wherein again, continue to stir 6 hours, then the reactant liquor centrifugation, incline and wash centrifugation again with aquae destillata after supernatant, triplicate, product obtain needed single SiO of dispersion 50 ℃ of following vacuum drying 24 hours
2Microballoon.Under the room temperature, will singly disperse SiO
2Microballoon 0.25g is ultrasonic to be distributed to 2 * 10
-3In the RB aqueous solution of mol/L, add 0.55g Zn (CH again
3COO)
22H
2O and 0.334mL ethylenediamine are after continuing to stir, at 160 ℃ of following hydrothermal treatment consists 12h, with the reactant liquor cool to room temperature.Product is collected and use repeatedly distilled water and absolute ethanol washing, and vacuum drying at room temperature then obtains the faint yellow solid powder at last, can obtain SiO
2@ZnO:RB nucleocapsid structure catalysis material.This material particle is uniformly dispersed average grain diameter 720nm.The experiment of light degradation salicylic acid solution shows that this material has extraordinary photocatalysis performance.
Embodiment 4
The preparation of ZnS:RB nucleocapsid structure catalysis material
Stir in absolute ethyl alcohol, 20mL ammoniacal liquor and the 15mL distilled water adding reaction bulb with 35mL earlier, mixed liquor with the absolute ethyl alcohol of the ethyl orthosilicate of 5.84mL and 40mL adds wherein again, continue to stir 8 hours, then the reactant liquor centrifugation, incline and wash centrifugation again with aquae destillata after supernatant, triplicate, product obtain needed single SiO of dispersion 50 ℃ of following vacuum drying 24 hours
2Microballoon.Under the room temperature, will singly disperse SiO
2Microballoon 0.5g is ultrasonic to be distributed to 1 * 10
-3In the RB aqueous solution of mol/L, add 10mL 0.15molL again
-1The aqueous solution of ethylenediamine adds 0.4mLCS then
2With 5mL 0.1molL
-1Zinc acetate solution, continue to stir 4h, product is through centrifugation, distilled water, absolute ethanol washing, vacuum drying at room temperature is a powder, can obtain SiO
2@ZnS:RB nucleocapsid structure catalysis material.This material particle is uniformly dispersed average grain diameter 900nm.The experiment of light degradation methyl orange solution shows that this material has extraordinary photocatalysis performance.
Embodiment 5
The preparation of AgS:RB nucleocapsid structure catalysis material
Stir in absolute ethyl alcohol, 15mL ammoniacal liquor and the 15mL distilled water adding reaction bulb with 30mL earlier, mixed liquor with the absolute ethyl alcohol of the ethyl orthosilicate of 4.02mL and 30mL adds wherein again, continue to stir 6 hours, then the reactant liquor centrifugation, incline and wash centrifugation again with aquae destillata after supernatant, triplicate, product obtain needed single SiO of dispersion 50 ℃ of following vacuum drying 24 hours
2Microballoon.Under the room temperature, will singly disperse SiO
2Microballoon 0.5g is ultrasonic to be distributed to 2 * 10
-3In the RB aqueous solution of mol/L, stir the silver acetate of adding 5mL 0.14mol/L down, and then slowly add the thioacetamide of 5mL0.60mol/L, mixture at room temperature stirs 18h, and color shows the generation of AgS gradually by the colourless brownish black that becomes.End product is by centrifugation, and deionized water washing back several times can obtain SiO at 40 ℃ of following vacuum drying 12h
2@AgS:RB nucleocapsid structure catalysis material.This material particle is uniformly dispersed average grain diameter 650nm.The experiment of light degradation methyl orange solution shows that this material has extraordinary photocatalysis performance.
Embodiment 6
The preparation of PbS:RB nucleocapsid structure catalysis material
Stir in absolute ethyl alcohol, 10mL ammoniacal liquor and the 5mL distilled water adding reaction bulb with 20mL earlier, mixed liquor with the absolute ethyl alcohol of the ethyl orthosilicate of 3.84mL and 20mL adds wherein again, continue to stir 4 hours, then the reactant liquor centrifugation, incline and wash centrifugation again with aquae destillata after supernatant, triplicate, product obtain needed single SiO of dispersion 50 ℃ of following vacuum drying 24 hours
2Microballoon.Under the room temperature, will singly disperse SiO
2Microballoon 0.5g is ultrasonic to be distributed to 3 * 10
-3In the RB aqueous solution of mol/L, stir the lead acetate of adding 5mL 0.16mol/L down, and then slowly add the thioacetamide of 5mL0.64mol/L, mixture at room temperature stirs 18h, and color shows the generation of PbS gradually by the colourless brownish black that becomes.End product is by centrifugation, and deionized water washing back several times can obtain SiO at 40 ℃ of following vacuum drying 12h
2@PbS:RB nucleocapsid structure catalysis material.This material particle is uniformly dispersed average grain diameter 650nm.The experiment of light degradation methyl orange solution shows that this material has extraordinary photocatalysis performance.
Claims (2)
1, has photoluminescent property nucleocapsid structure catalysis material, it is characterized in that expression formula is: SiO
2@A
xM
y: RB wherein: 0＜x≤2,0＜y≤3, A=Ti, Fe, Zn, Pb, Ag; M=O, S, RB are rhodamine.
2, the preparation method who has photoluminescent property nucleocapsid structure catalysis material is characterized in that employed raw materials of compound is 99.99% TiCl
4, K
4Fe (CN)
6, Zn (CH
3COO)
2, Pb (CH
3COO)
2, Ag (CH
3COO)
2, Zn (CH
3COO)
2Solvent is water and ethanol; Hydrochloric acid is used to dissolve above-mentioned metallic compound, and rhodamine is pure for analyzing; Analytically pure ethyl orthosilicate is used to prepare different big or small monodispersed SiO with ammoniacal liquor
2Microballoon.
Its method step and condition are as follows:
(1) preparation SiO
2Microballoon
Absolute ethyl alcohol, ammoniacal liquor and water are added to together and stir, the mixed liquor that in the mixed solution that forms, adds ethyl orthosilicate and ethanol, wherein the volume ratio of water, ammoniacal liquor, absolute ethyl alcohol and ethyl orthosilicate is 1～3: 2～4: 8～15: 0.8～1.6, magnetic agitation 4-8 hour continuously, then the reactant liquor centrifugation, wash centrifugation again with aquae destillata, repeatable operation three times, remove supernatant liquor at last, 50 ℃ of following vacuum drying 24 hours, resulting white powder is monodispersed SiO
2Particle; (2) preparation has photoluminescent property nucleocapsid structure catalysis material
Under room temperature or heating condition, the TiCl with 99.99%
4, K
4Fe (CN)
6, Zn (CH
3COO)
2, Pb (CH
3COO)
2, Ag (CH
3COO)
2, Zn (CH
3COO)
2In a kind of metallic compound dissolve with certain density HCl, with the SiO of step (1) preparation
2Powder is ultrasonic to be distributed in the certain density rhodamine ethanolic solution, keeps SiO
2The mol ratio of microballoon and metal ion is 0.1～20: 1, the mixed liquor room temperature or add thermal agitation or hydrothermal treatment consists 4-18 hour, centrifugation, the distilled water washing, repeated centrifugation is separated, the washing several, product obtains having photoluminescent property nucleocapsid structure catalysis material room temperature to 50 ℃ following vacuum drying 24 hours.
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|---|---|---|---|
| CN 200710103141 CN101049574A (en) | 2007-04-26 | 2007-04-26 | Photocatalysis material possessing hud structure of photoluminescent property, and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710103141 CN101049574A (en) | 2007-04-26 | 2007-04-26 | Photocatalysis material possessing hud structure of photoluminescent property, and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN101049574A true CN101049574A (en) | 2007-10-10 |
Family
ID=38781295
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071016A (en) * | 2011-01-11 | 2011-05-25 | 湖南信多利新材料有限公司 | Aluminate blue fluorescent powder and preparation method thereof |
| CN102988058A (en) * | 2011-09-16 | 2013-03-27 | 国家纳米科学中心 | Color silica nano-particle used for displaying latent fingerprints and preparation method thereof |
| CN104004511A (en) * | 2014-04-30 | 2014-08-27 | 南方医科大学 | Rhodamine fluorescent nanocomposite particles, and preparation method and application thereof |
| CN104946236A (en) * | 2015-04-28 | 2015-09-30 | 上海大学 | Silver/graphene-coated silicon dioxide composite upconversion nanocrystal and preparation method thereof |
| CN111468139A (en) * | 2020-06-10 | 2020-07-31 | 中南大学 | Core-shell structure nanosphere photocatalytic material and preparation method and application thereof |
| CN112121853A (en) * | 2020-09-08 | 2020-12-25 | 重庆邮电大学 | Mesoporous hollow silica nanosphere loaded with prolinol catalyst and preparation method and application thereof |
-
2007
- 2007-04-26 CN CN 200710103141 patent/CN101049574A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071016A (en) * | 2011-01-11 | 2011-05-25 | 湖南信多利新材料有限公司 | Aluminate blue fluorescent powder and preparation method thereof |
| CN102988058A (en) * | 2011-09-16 | 2013-03-27 | 国家纳米科学中心 | Color silica nano-particle used for displaying latent fingerprints and preparation method thereof |
| CN102988058B (en) * | 2011-09-16 | 2015-05-13 | 国家纳米科学中心 | Color silica nano-particle used for displaying latent fingerprints and preparation method thereof |
| CN104004511A (en) * | 2014-04-30 | 2014-08-27 | 南方医科大学 | Rhodamine fluorescent nanocomposite particles, and preparation method and application thereof |
| CN104004511B (en) * | 2014-04-30 | 2016-01-20 | 南方医科大学 | A kind of rhodamine fluorescent nanometer composite particle and its preparation method and application |
| CN104946236A (en) * | 2015-04-28 | 2015-09-30 | 上海大学 | Silver/graphene-coated silicon dioxide composite upconversion nanocrystal and preparation method thereof |
| CN111468139A (en) * | 2020-06-10 | 2020-07-31 | 中南大学 | Core-shell structure nanosphere photocatalytic material and preparation method and application thereof |
| CN111468139B (en) * | 2020-06-10 | 2021-08-24 | 中南大学 | Core-shell structure nanosphere photocatalytic material and preparation method and application thereof |
| CN112121853A (en) * | 2020-09-08 | 2020-12-25 | 重庆邮电大学 | Mesoporous hollow silica nanosphere loaded with prolinol catalyst and preparation method and application thereof |
| CN112121853B (en) * | 2020-09-08 | 2023-03-28 | 重庆邮电大学 | Mesoporous hollow silica nanosphere loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silica nanosphere |
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