CN100386364C - Method of preparing metallic sulfide nano-particle and mesopore film composite material - Google Patents
Method of preparing metallic sulfide nano-particle and mesopore film composite material Download PDFInfo
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- CN100386364C CN100386364C CNB2006100181197A CN200610018119A CN100386364C CN 100386364 C CN100386364 C CN 100386364C CN B2006100181197 A CNB2006100181197 A CN B2006100181197A CN 200610018119 A CN200610018119 A CN 200610018119A CN 100386364 C CN100386364 C CN 100386364C
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Abstract
The present invention provides a method of preparing a composite material of metallic sulfide nano particles and a mesopore film by the assembly of metallic ions via an immersion method by using an organic / inorganic hybrid mesopore film as a base body. Compared with the prior art, the present invention is characterized in that an organic / inorganic hybrid film is prepared in one step by a copolycondensation method, and sulfhydryl groups are uniformly distributed on the inner surface of a mesopore channel; metallic ions are assembled by the organic / inorganic hybrid film; the composite material of the metallic sulfide nano particles and a mesopore film is obtained by one-step calcining. Controllable sulfhydryl groups are mixed in the hybrid film, and metallic ions can be dispersed and anchored under coordination to solve the problem that the prepared metallic sulfide nano particles block the opening of a mesopore pipe; in addition, the sulfhydryl groups can also be used as a potential sulphur source, and therefore, only metallic elements need leading when sulfide is prepared. The technological process is simple and uses less time; the size and the distribution of nano particles can be effectively controlled by a hole diameter of a mesopore material; the prepared composite body of metallic sulfide nano particles and a mesopore film has favorable optical and electrical properties.
Description
Technical field
The invention belongs to chemistry and inorganic functional material technical field, relate to a kind of in the hybrid mesopore film assembling metal ion prepare the method for metallic sulfide nano-particle and mesopore film composite material.
Background technology
Metallic sulfide is the semiconductor material that is subjected to extensive concern.Semi-conductor nano particles is also referred to as quantum dot, with the photoelectric properties of its homogeneous, has wide practical use at aspects such as photodiode (LED), single-electronic transistor, field-effect thin film transistors.Therefore the character of semi-conductor nano particles depends on its size to a great extent, controls its size and distribution of sizes is crucial.Ordered mesoporous material is the excellent carrier of nanoparticle.Synthesizing nano-particle in mesoporous material can make nanoparticle confinement growth in the duct, thereby can control the particle diameter of nanoparticle well.In addition, mesoporous material and nanoparticle compound can produce novel physics, chemical phenomenon, is the functional materials that a class has wide application prospect.
In recent years, have the report of synthetic metallic sulfide nano-particle in mesoporous material.Its preparation method can be divided into two classes.One class is by mesoporous material dipping adsorbing metal ions, again with H
2Obtain metallic sulfide after the S sulfidizing.Another kind of is to introduce the sulphur source by the mesoporous material that synthesizes is carried out modification with the silylating reagent that contains sulfydryl, floods adsorbing metal ions again in solution.
Summary of the invention
Having the purpose of this invention is to provide a kind of is matrix with the hybrid mesopore film, prepares the method for metallic sulfide nano-particle and mesopore film composite material by pickling process assembling metal ion.Be with the difference of prior art: go on foot by copolycondensation method one and prepare at mesopore orbit internal surface uniform distribution sulfydryl (hybrid film SH), with this assembling metal ion, and can obtain the matrix material of metallic sulfide nano-particle and mesopore film by roasting one step.The controlled sulfydryl of volume not only can disperse and the anchoring metal ion by coordination in the hybrid film, solve the blockage problem of preparation metallic sulfide nano-particle at the mesoporous mouth of pipe, can also make the preparation binary sulfide only need introduce metallic element as potential sulphur source.Simple, the consuming time weak point of this technological process can be controlled the size and the distribution thereof of metallic sulfide nano-particle effectively by the aperture of mesoporous material, and metallic sulfide nano-particle that makes and mesopore film composite material have excellent optics and electrology characteristic.
A kind of method for preparing metallic sulfide nano-particle and mesopore film composite material of the present invention adopts hybrid mesopore film assembling metal ion preparation method, and preparation is carried out in two steps,
The 1st step, preparation hybrid film,
Under the effect of tensio-active agent alkyl polyoxyethylene ether or cetyl trimethylammonium bromide template, tetraethoxy and mercaptopropyl trimethoxysilane copolycondensation prepare parent colloidal sol, this parent colloidal sol is applied to prepares mesopore film on the substrate, remove mesoporous template tensio-active agent with etoh solvent or Virahol extraction, obtain the hybrid mesopore film;
The 2nd step, preparation metallic sulfide nano-particle and mesopore film composite material,
Adopt the method for dipping absorption in the duct of the hybrid mesopore film of step 1 preparation, to introduce Pb
2+, Cd
2+, Ag
+, Zn
2+Or Hg
+Metal ion is at N
2Roasting under the protection of atmosphere, make metal ion in the duct with hybrid mesoporous film duct in sulfydryl reaction generate metallic sulfide nano-particle, promptly make metallic sulfide nano-particle and mesopore film composite material.
The preparation process of the hybrid film described in the present invention is:
1st, tetraethoxy, dehydrated alcohol, distilled water and dilute hydrochloric acid or rare nitric acid are mixed in proportion, stir, wherein the mol ratio of tetraethoxy and dehydrated alcohol is 1: 3-4, and the pH value of mixture is 2 ± 0.5; At 60-90 ℃ of backflow 60-120 minute; Be cooled to and replenish that to add entry be 0.05-0.15molL with the concentration identical with above-mentioned acid after the room temperature
-1Diluted acid, add the ethanolic soln of tensio-active agent alkyl polyoxyethylene ether (trade(brand)name Brij56) or cetyl trimethylammonium bromide then, add mercaptopropyl trimethoxysilane at last, the molar ratio of end reaction thing is Si: dehydrated alcohol: H
2O: H
+: tensio-active agent=1: 11-65: 3-12: 0.002-0.06: 0.03-0.15, its Si source comprises tetraethoxy and mercaptopropyl trimethoxysilane, the molar fraction of mercaptopropyl trimethoxysilane is 0.05-0.15 in the Si source, gets reaction mixture;
2nd, the reaction mixture that step 1 is obtained stirs ageing 2-5 days under 10-30 ℃ of room temperature, obtains colloidal sol;
3rd, adopt dip coating or spin-coating method on slide glass that cleans or silicon chip substrate, to be coated with step 2 and obtain colloidal sol, in temperature is 25 ± 1 ℃, become film under the condition of relative humidity 20%-70%, the gained film is removed seasoning in the air behind tensio-active agent and the repetitive scrubbing with the extraction of ethanol or Virahol, promptly gets the hybrid film.
The described pull rate that dip coating is coated with colloidal sol on substrate is the 7.6-51 cm per minute.The described rotating speed that spin-coating method is coated with colloidal sol on substrate is 2000-8000 rev/min.
The preparation of metallic sulfide nano-particle described in the present invention and mesopore film composite material is: removing tensio-active agent with the extraction of ethanol or Virahol and wash dried hybrid film above-mentioned, is 0.02-0.1molL in concentration
-1The aqueous solution of metal ion or ethanolic soln in dipping 12-48 hour, take out hybrid film, repeatedly water or washing with alcohol and at air drying, at N
2Under the protection of atmosphere,, promptly obtain the matrix material of metallic sulfide nano-particle and mesopore film in 250-350 ℃ of roasting 1-2 hour.
The advantage of the inventive method is: 1, prepare the hybrid film by the method for copolycondensation, sulfydryl is evenly distributed on the internal surface of mesopore orbit, and can accurately control the volume of sulfydryl by the add-on that changes organosilane.2, can make the preparation of film have good circulation ratio by control to filming condition.3, by the extraction of organic solvent, can remove mesoporous template tensio-active agent effectively, keep the mercapto propyl group of mesoporous internal surface.4, the sulfydryl of passing hole channel internal surface can form coordinate bond with metal ion, effectively the metal ion in the adsorbent solution.5, roasting under nitrogen atmosphere, metal ion and sulfydryl reaction generate metallic sulfide.
Embodiment
Embodiment 1
The preparation of cadmium sulfide nano-particles and mesopore film composite material.Preparation process is:
1, the 10.4g tetraethoxy being dissolved in 8.74g dehydrated alcohol, 0.9g distilled water and 0.025mL concentration is 0.1molL
-1The mixing solutions of rare HCl in, 60 ℃ of following stirring and refluxing 90 minutes; Under agitation replenishing adding distilled water and concentration after the cooling is 0.1molL
-1Rare HCl solution, add the ethanolic soln of alkyl polyoxyethylene ether then, add mercaptopropyl trimethoxysilane at last, the molar ratio that makes each several part in the final solution is 0.9 tetraethoxy: 0.1 mercaptopropyl trimethoxysilane: 22 ethanol: 5H
2O: the 0.004HCl:0.050 alkyl polyoxyethylene ether, colloidal sol stirs ageing 3 days down at 20 ± 5 ℃;
2, at 25 ± 1 ℃, relative humidity is 43% the interior film forming of coating device, after the slide glass of cleaning immerses colloidal sol, with the speed pull-up of 20 cm per minute, after in coating device, keeping making Stability Analysis of Structures in 10 minutes, removed in 3 hours 150 ℃ of dryings and to desolvate, the tensio-active agent alkyl polyoxyethylene ether was removed in extraction in 12 hours in hot ethanol, take out the back with washing with alcohol 3 times, seasoning in the air promptly makes hybrid film on slide glass;
3, will wash, dried hybrid film in mass concentration is 1% Cd (Ac)
22H
2Dipping is 24 hours in the ethanol solution of O, takes out the back with washing with alcohol 3 times, seasoning in the air, and the following 300 ℃ of roastings of nitrogen atmosphere 1 hour promptly obtain the matrix material of cadmium sulfide nano-particles and mesopore film.
Embodiment 2
The preparation of the matrix material of Zinc sulfide nano-particle and mesopore film.Preparation process is:
1, the 56.9g tetraethoxy being dissolved in 48.1g dehydrated alcohol, 4.4g distilled water and 0.51mg concentration is 0.07molL
- 1Rare HNO
3Mixing solutions in, 80 ℃ of following stirring and refluxing 60 minutes.Under agitation replenishing adding distilled water and concentration after the cooling is 0.07molL
-1Rare HNO
3Solution adds the ethanolic soln liquid of cetyl trimethylammonium bromide then, adds mercaptopropyl trimethoxysilane at last, and the molar ratio that makes each several part in the final solution is 0.95 tetraethoxy: 0.05 mercaptopropyl trimethoxysilane: 22 ethanol: 5H
2O: the 0.004HCl:0.096 cetyl trimethylammonium bromide, colloidal sol stirs ageing 3 days down at 20 ± 5 ℃;
2, at 25 ± 1 ℃, relative humidity is in 60% the coating device, with the silicon chip of cleaning with 5000 rev/mins rotating speed spin-coating film, after in coating device, keeping making Stability Analysis of Structures in 10 minutes, remove in 150 ℃ of dryings 3 hours and to desolvate, the tensio-active agent cetyl trimethylammonium bromide was removed in extraction in 12 hours in hot ethanol, took out the back with washing with alcohol 3 times, seasoning in the air promptly makes hybrid film on silicon chip;
3, the hybrid film after will extracting is 0.0gmolL in concentration
-1ZnCl
2Ethanol solution in soaked 24 hours, take out the back repeatedly with washing with alcohol, seasoning in the air, the following 300 ℃ of roastings of nitrogen atmosphere 1 hour promptly obtain the matrix material of Zinc sulfide nano-particle and mesopore film.
Embodiment 3
The preparation of silver sulfide nanoparticle and mesopore film composite material.Preparation process is:
1, the 10.4g tetraethoxy being dissolved in 8.74g dehydrated alcohol, 0.9g distilled water and 0.025mL concentration is 0.1molL
-1Rare HNO
3Mixing solutions in, 60 ℃ of following stirring and refluxing 90 minutes; Under agitation replenishing adding distilled water and concentration after the cooling is 0.1molL
-1Rare HNO
3Solution adds the ethanolic soln of alkyl polyoxyethylene ether then, adds mercaptopropyl trimethoxysilane at last, and the molar ratio that makes each several part in the final solution is 0.95 tetraethoxy: 0.05 mercaptopropyl trimethoxysilane: 22 ethanol: 5H
2O: 0.004HNO
3: 0.050 alkyl polyoxyethylene ether, colloidal sol stirs ageing 3 days down at 20 ± 5 ℃;
2, at 25 ± 1 ℃, relative humidity is in 60% the coating device, with the silicon chip of cleaning with 5000 rev/mins rotating speed spin-coating film, after in coating device, keeping making Stability Analysis of Structures in 10 minutes, remove in 150 ℃ of dryings 3 hours and to desolvate, the tensio-active agent alkyl polyoxyethylene ether was removed in extraction in 12 hours in hot ethanol, took out the back with washing with alcohol 3 times, seasoning in the air promptly makes hybrid film on silicon chip;
3, the hybrid film after will extracting is 0.1molL in concentration
-1AgNO
3The aqueous solution in soaked 12 hours, take out the back repeatedly with water washing, seasoning in the air, the following 300 ℃ of roastings of nitrogen atmosphere 1 hour promptly obtain the matrix material of silver sulfide nanoparticle and mesopore film.
Embodiment 4
The preparation of the matrix material of lead sulfide nanoparticle and mesopore film.Preparation process is:
1, the 56.9g tetraethoxy being dissolved in 48.1g dehydrated alcohol, 4.4g distilled water and 0.51mg concentration is 0.07molL
-1The mixing solutions of rare HCl in, 80 ℃ of following stirring and refluxing 60 minutes.Under agitation replenishing adding distilled water and concentration after the cooling is 0.07molL
-1Rare HCl solution, add the ethanolic soln liquid of cetyl trimethylammonium bromide then, add mercaptopropyl trimethoxysilane at last, the molar ratio that makes each several part in the final solution is 0.9 tetraethoxy: 0.1 mercaptopropyl trimethoxysilane: 22 ethanol: 5H
2O: the 0.004HCl:0.096 cetyl trimethylammonium bromide, colloidal sol stirs ageing 3 days down at 20 ± 5 ℃;
2, at 25 ± 1 ℃, relative humidity is 43% the interior film forming of coating device, after the slide glass of cleaning immerses colloidal sol, with the speed pull-up of 20 cm per minute, after in coating device, keeping making Stability Analysis of Structures in 10 minutes, removed in 3 hours 150 ℃ of dryings and to desolvate, the tensio-active agent cetyl trimethylammonium bromide was removed in extraction in 12 hours in hot ethanol, take out the back with washing with alcohol repeatedly, seasoning in the air promptly makes hybrid film on slide glass:
3, will wash, dried hybrid film is at 0.1molL
-1Pb (Ac)
2The aqueous solution in dipping 40 hours, take out the back repeatedly with water washing, seasoning in the air, the following 300 ℃ of roastings of nitrogen atmosphere 1 hour promptly obtain the matrix material of lead sulfide nanoparticle and mesopore film.
Claims (4)
1. a method for preparing metallic sulfide nano-particle and mesopore film composite material is characterized in that, is hybrid mesopore film assembling metal ion preparation method, and preparation is carried out in two steps:
The 1st step, preparation hybrid film,
The preparation method is:
1), tetraethoxy, dehydrated alcohol, distilled water and dilute hydrochloric acid or rare nitric acid are mixed in proportion, stir, wherein the mol ratio of tetraethoxy and dehydrated alcohol is 1: 3-4, and the pH value of mixture is 2 ± 0.5; At 60-90 ℃ of backflow 60-120 minute; Be cooled to and replenish that to add entry be 0.05-0.15molL with the concentration identical with above-mentioned acid after the room temperature
-1Diluted acid, add the ethanolic soln of tensio-active agent alkyl polyoxyethylene ether or cetyl trimethylammonium bromide then, add mercaptopropyl trimethoxysilane at last, the molar ratio of end reaction thing is Si: dehydrated alcohol: H
2O: H
+: tensio-active agent=1: 22: 5: 0.004: 0.05～0.096, its Si source comprises tetraethoxy and mercaptopropyl trimethoxysilane, the molar fraction of mercaptopropyl trimethoxysilane is 0.05-0.15 in the Si source, gets reaction mixture;
2), reaction mixture that step 1) is obtained stirs ageing 3 days under 10-30 ℃ of room temperature, obtain colloidal sol;
3), adopt dip coating or spin-coating method on the slide glass of cleaning or silicon chip substrate, to be coated with step 2) obtain colloidal sol, in temperature is 25 ± 1 ℃, become film under the condition of relative humidity 20%-70%, the gained film is removed seasoning in the air behind tensio-active agent and the repetitive scrubbing with the extraction of ethanol or Virahol, promptly obtains the hybrid film;
The 2nd step, preparation metallic sulfide nano-particle and mesopore film composite material,
Adopt the method for dipping absorption in the duct of the hybrid mesopore film of the 1st step preparation, to introduce Pb
2+, Cd
2+, Ag
+, Zn
2+Or Hg
+Metal ion is at N
2Roasting under the protection of atmosphere, make metal ion in the duct with hybrid mesoporous film duct in sulfydryl reaction generate metallic sulfide nano-particle, promptly make metallic sulfide nano-particle and mesopore film composite material.
2. the method for preparing metallic sulfide nano-particle and mesopore film composite material as claimed in claim 1, it is characterized in that, in the preparation process of described hybrid film, dip coating is coated with molten wrist on substrate pull rate is the 7.6-51 cm per minute.
3. the method for preparing metallic sulfide nano-particle and mesopore film composite material as claimed in claim 1, it is characterized in that, in the preparation process of described hybrid film, spin-coating method is coated with colloidal sol on substrate rotating speed is 2000-8000 rev/min.
4. the method for preparing metallic sulfide nano-particle and mesopore film composite material as claimed in claim 1, it is characterized in that, the preparation of metallic sulfide nano-particle and mesopore film composite material is: will remove tensio-active agent with ethanol or Virahol extraction and wash dried hybrid film, be 0.02-0.1molL in concentration
-1The aqueous solution of metal ion or ethanolic soln in dipping 12-48 hour, take out its hybrid film, water or washing with alcohol and seasoning in air repeatedly is at N
2Under the protection of atmosphere,, promptly obtain metallic sulfide nano-particle and mesopore film composite material in 250-350 ℃ of roasting 1-2 hour.
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Citations (4)
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|---|---|---|---|---|
| CN1184699A (en) * | 1997-09-29 | 1998-06-17 | 天津大学 | Mesopore molecular sieve inorganic composite film used for water purification |
| WO2001081487A1 (en) * | 2000-04-21 | 2001-11-01 | Science & Technology Corporation @ Unm | Prototyping of patterned functional nanostructures |
| US20050221087A1 (en) * | 2004-02-13 | 2005-10-06 | James Economy | Nanoporous chelating fibers |
| CN1683067A (en) * | 2005-02-13 | 2005-10-19 | 复旦大学 | Method for preparing metal sulfide hollow micro capsule |
-
2006
- 2006-01-09 CN CNB2006100181197A patent/CN100386364C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184699A (en) * | 1997-09-29 | 1998-06-17 | 天津大学 | Mesopore molecular sieve inorganic composite film used for water purification |
| WO2001081487A1 (en) * | 2000-04-21 | 2001-11-01 | Science & Technology Corporation @ Unm | Prototyping of patterned functional nanostructures |
| US20050221087A1 (en) * | 2004-02-13 | 2005-10-06 | James Economy | Nanoporous chelating fibers |
| CN1683067A (en) * | 2005-02-13 | 2005-10-19 | 复旦大学 | Method for preparing metal sulfide hollow micro capsule |
Non-Patent Citations (6)
| Title |
|---|
| A general one-pot process leading to highly functionalisedordered mesoporous silica films. F.Cagnol, D.Grosso, C.Sanchez.Chem.Commun.. 2004 |
| A general one-pot process leading to highly functionalisedordered mesoporous silica films. F.Cagnol, D.Grosso, C.Sanchez.Chem.Commun.. 2004 * |
| Periodic Mesoporous Silica-Based Organic-InorganicNanocomposite Materials. Abdelhamid Sayari, Safia Hamoudi.Chem.Mater,Vol.13 No.10. 2001 |
| Periodic Mesoporous Silica-Based Organic-InorganicNanocomposite Materials. Abdelhamid Sayari, Safia Hamoudi.Chem.Mater,Vol.13 No.10. 2001 * |
| Rapid prototyping of patterned functional nanostructures. Hongyou Fan, Yunfeng Lu, Aaron Stump et al.Nature,Vol.405 . 2000 |
| Rapid prototyping of patterned functional nanostructures. Hongyou Fan, Yunfeng Lu, Aaron Stump et al.Nature,Vol.405 . 2000 * |
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