CN102173865B - Method for fixing noble metal nano particles on single-crystal silicon surface polymer brush - Google Patents
Method for fixing noble metal nano particles on single-crystal silicon surface polymer brush Download PDFInfo
- Publication number
- CN102173865B CN102173865B CN201110003737A CN201110003737A CN102173865B CN 102173865 B CN102173865 B CN 102173865B CN 201110003737 A CN201110003737 A CN 201110003737A CN 201110003737 A CN201110003737 A CN 201110003737A CN 102173865 B CN102173865 B CN 102173865B
- Authority
- CN
- China
- Prior art keywords
- polymer brush
- noble metal
- nano particles
- metal nano
- silicon chip
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Silicon Polymers (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a method for fixing noble metal nano particles on a single-crystal silicon surface polymer brush, which comprises the following steps: soaking a single-crystal silicon wafer in a hydrofluoric acid solution to obtain a silicon wafer A; dropwisely adding 4-vinylbenzyl chloride onto the surface, radiating, rinsing with acetone, drying, and adding into a monomer-containing solvent; adding copper bromide or copper chloride, cuprous bromide or cuprous chloride and ligand into the solvent to carry out surface-initiated atom transfer and free radical polymerization, thus obtaining a silicon wafer C; putting the silicon wafer C in a dichloromethane solution of trifluoroacetic acid, and stirring to obtain a carboxyl-containing polymer brush; and sufficiently soaking the polymer brush in a solution containing noble metal ions, then taking out, and finally reacting in a sodium borohydride solution, thus fixing the noble metal nano particles on the single-crystal silicon surface polymer brush. The invention achieves the following technical effects: the activity is controllable in the polymerization process, the graft polymerization density is high; the polymer chain is prevented from falling off the substrate; and the controllable fixation of the noble metal nano particles is effectively implemented.
Description
Technical field
The present invention relates to a kind of noble metal nano particles is fixed on the method on the monocrystalline silicon surface polymer brush, belong to technical field of micro nano material preparation.
Background technology
Because quantum effect and great specific surface area, metal nanoparticle has unique character.They have had tempting application prospect in fields such as photoelectric device, transmitter, catalysis and medical science.Therefore, the structure of metal nanoparticle has become one of core research contents of nano science.Modal problem is the high surface energy owing to nanoparticle in metal nanoparticle preparation and application, and their are very easy to reunite.In order to reduce or to stop gathering, metal nanoparticle must be stable is dispersed in solution, matrix, macro surface or interface.Discover; The matrix material of nano polymer/metal particle had both kept the unique photoelectric properties of metal nanoparticle, and guaranteed that through the host-guest interaction between controlling polymers and the metal nanoparticle metal nanoparticle better space is dispersed.
Polymer brush is a kind ofly can control metal nanoparticle accumulative effective ways on macro surface.Polymer brush is generally through surface grafting (grafting to) or the preparation of surperficial initiated polymerization methods such as (grafting from).The former makes polymer chain be fixed on substrate surface through reactive group on the polymer chain and the group generation chemical reaction on the macro surface, but its shortcoming is that grafting density is low, and grafting is inhomogeneous, is difficult to obtain the polymer brush of controllable thickness.The latter is the initiating group through substrate surface, realizes the polymer brush that links to each other with substrate surface with chemical bond.ATRP is a kind of controlled living polymerization.Adopt the surface to cause ATRP, the mode that can pass through grafting from obtains the polymer brush of highdensity controllable thickness in macroscopical substrate like material surfaces such as silicon, simple glass, conductive glass, mf, polymeric films.
Summary of the invention
Problem to be solved by this invention is that propose to above-mentioned existing deficiency a kind of is fixed on the method on the monocrystalline silicon surface polymer brush with noble metal nano particles, obtains the polymer brush of controllable thickness, effectively realizes the controlled fixing of noble metal nano particles.
The present invention by the problem of the above-mentioned proposition of solution the employing solution be: a kind of noble metal nano particles is fixed on the method on the monocrystalline silicon surface polymer brush, it is characterized in that including following steps:
1) places the hydrofluoric acid solution of 10 vol% to soak 2-5 minute monocrystalline silicon piece,, obtain the silicon chip A of surface hydriding to remove the silica oxides layer of monocrystalline silicon sheet surface;
2) 4-vinyl benzene methyl chloride is dripped on silicon chip A surface, radiation with acetone rinsing, oven dry, obtained the silicon chip B that atom transfer free radical polymerization initiating group is contained on the surface after 3 minutes under UV-light;
3) silicon chip B is joined contain in the monomeric solvent, remove oxygen, add cupric bromide or cupric chloride, cuprous bromide or cuprous chloride and part carry out surface initiation ATRP, and temperature of reaction is 50-70
oC, the reaction times is 12-48 hour, obtains the silicon chip C that polymer brush is contained on the surface;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid, trifluoroacetic acid and monomeric mol ratio are 4:1-6:1, stir 24-36 hour under the room temperature, obtain containing the polymer brush of carboxyl at monocrystalline silicon surface;
5) polymer brush that step 4) is obtained fully soaked into 1-2 hour in containing precious metal ion solution, took out the back and in sodium borohydride solution, reacted, and the reaction times is 0.5-4 hour, thereby noble metal nano particles is fixed on the monocrystalline silicon surface polymer brush.
Press such scheme, described monomer is Bing Xisuandingzhi or NSC 20956;
Press such scheme, described part is bipyridine or five methyl diethylentriamine;
Press such scheme, described solvent is acetone, THF or octane;
Press such scheme, described noble metal nano particles is silver, nickel or platinum.
Reaction mechanism of the present invention is: earlier the initiating group of ATRP is introduced silicon chip surface; The trigger monomer polymkeric substance obtains being grown in the polymer brush of monocrystalline silicon surface; Obtain containing the polymer brush of carboxyl again through acidolysis; Through the hydrogen ion on the polymer brush carboxyl and the IX of precious metal cation, on-the-spot reduction is fixed on noble metal nano particles on the polymer brush at last.
Compared with present technology, the technique effect that reached of the present invention:
1) will be bonded on the carrier of the polymer brush of monocrystalline silicon surface through carbon-carbon bond as a kind of fixedly noble metal nano particles;
2) used polymerization method is a living control polymerization, and graft polymerization density is high, and the polymerization degree that can the controlling polymers brush, thickness etc.;
3) polymer brush firmly is connected monocrystalline silicon surface through carbon-carbon bond, avoids ester group when the acidic conditions hydrolysis generates carboxyl, and self comes off polymer chain from substrate;
4), effectively realize the controlled fixing of noble metal nano particles through the hydrogen ion on the polymer brush carboxyl and the IX of precious metal cation.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention not only is confined to following embodiment below in conjunction with embodiment.
Embodiment 1:
1) monocrystalline silicon piece is placed the hydrofluoric acid solution 2 minutes of 10vol%,, obtain the silicon chip A of surface hydriding to remove the silica oxides layer of monocrystalline silicon sheet surface;
2) 4-vinyl benzene methyl chloride is dripped on silicon chip A surface, radiation with acetone rinsing, oven dry, obtained the silicon chip B that atom transfer free radical polymerization initiating group is contained on the surface after 3 minutes under UV-light;
3) silicon chip B adding is contained among the acetone 15mL of Bing Xisuandingzhi 50mmol, remove oxygen, add cupric bromide 0.01mmol, cuprous bromide 0.5mmol and bipyridine 1mmol carry out the surface and cause ATRP, and temperature of reaction is 50
oC, the reaction times is 12 hours, obtains the silicon chip C that the butyl polyacrylate brush is contained on the surface;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid, the mol ratio of trifluoroacetic acid and Bing Xisuandingzhi is 4:1, stirs 24 hours under the room temperature, obtains polyacrylic polymer brush at monocrystalline silicon surface, and polymer brush thickness is 12nm;
5) will go up the polymer brush that goes on foot acquisition and in the 0.005mol/L silver nitrate solution, soak into 1 hour, and take out the back and in the 0.1mol/L sodium borohydride solution, react, the reaction times is 0.5 hour, thereby Nano silver grain is fixed on the monocrystalline silicon surface polymer brush.
Embodiment 2:
1) with the step 1 of embodiment 1;
2) with the step 2 of embodiment 1;
3) silicon chip B adding is contained among the THF 12mL of Bing Xisuandingzhi 40mmol; Remove oxygen, add cupric bromide 0.01mmol, cuprous bromide 0.5mmol and five methyl diethylentriamine 1mmol; Carry out the surface and cause ATRP, temperature of reaction is 60
oC, the reaction times is 24 hours, obtains the silicon chip C that the butyl polyacrylate brush is contained on the surface;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid, the mol ratio of trifluoroacetic acid and Bing Xisuandingzhi is 4:1, stirs 24 hours under the room temperature, obtains polyacrylic polymer brush at monocrystalline silicon surface, and polymer brush thickness is 18nm;
5) will go up the polymer brush that goes on foot acquisition and in the 0.006mol/L nickel chloride solution, soak into 1 hour, and take out the back and in the 0.1mol/L sodium borohydride solution, react, the reaction times is 1 hour, thereby nickel nano particle is fixed on the monocrystalline silicon surface polymer brush.
Embodiment 3:
1) with the step 1 of embodiment 1;
2) with the step 2 of embodiment 1;
3) silicon chip B adding is contained among the acetone 14mL of NSC 20956 45mmol; Remove oxygen, add cupric chloride 0.0096mmol, cuprous chloride 0.48mmol and five methyl diethylentriamine 0.96mmol; Carry out the surface and cause ATRP, temperature of reaction is 60
oC, the reaction times is 36 hours, obtains the silicon chip C that the poly-n-butyl methacrylate brush is contained on the surface;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid; The mol ratio of trifluoroacetic acid and NSC 20956 is 4:1; Stirred under the room temperature 36 hours, and obtained the polymer brush of polymethyl acrylic acid at monocrystalline silicon surface, polymer brush thickness is 21nm;
5) will go up the polymer brush that goes on foot acquisition and in the 0.005mol/L silver nitrate solution, soak into 1 hour, and take out the back and in the 0.1mol/L sodium borohydride solution, react, the reaction times is 2 hours, thereby Nano silver grain is fixed on the monocrystalline silicon surface polymer brush.
Embodiment 4:
1) with the step 1 of embodiment 1;
2) with the step 2 of embodiment 1;
3) silicon chip B adding is contained among the octane 20mL of NSC 20956 90mmol, remove oxygen, add cupric chloride 0.2mmol, cuprous chloride 1mmol and bipyridine 1.92mmol carry out the surface and cause ATRP, and temperature of reaction is 70
oC, the reaction times is 40 hours, obtains the silicon chip C that the poly-n-butyl methacrylate brush is contained on the surface;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid; The mol ratio of trifluoroacetic acid and NSC 20956 is 6:1; Stirred under the room temperature 36 hours, and obtained the polymer brush of polymethyl acrylic acid at monocrystalline silicon surface, polymer brush thickness is 31nm;
5) will go up the polymer brush that goes on foot acquisition and in 0.005mol/L platinum chloride solution, soak into 1 hour, and take out the back and in the 0.1mol/L sodium borohydride solution, react, the reaction times is 1 hour, thereby nano platinum particle is fixed on the monocrystalline silicon surface polymer brush.
Embodiment 5:
1) with the step 1 of embodiment 1;
2) with the step 2 of embodiment 1;
3) silicon chip B adding is contained among the acetone 16mL of Bing Xisuandingzhi 116mmol, remove oxygen, add cupric bromide 0.3mmol, cuprous bromide 0.05mmol and bipyridine 0.45mmol carry out the surface and cause ATRP, and temperature of reaction is 60
oC, the reaction times is 48 hours, obtains the silicon chip C that the butyl polyacrylate brush is contained on the surface;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid, the mol ratio of trifluoroacetic acid and Bing Xisuandingzhi is 5:1, stirs 24 hours under the room temperature, obtains polyacrylic polymer brush at monocrystalline silicon surface, and polymer brush thickness is 35nm;
5) will go up the polymer brush that goes on foot acquisition and in the 0.005mol/L silver nitrate solution, soak into one hour, and take out the back and in the 0.1mol/L sodium borohydride solution, react, the reaction times is 2 hours, thereby Nano silver grain is fixed on the monocrystalline silicon surface polymer brush.
Embodiment 6:
1) with the step 1 of embodiment 1;
2) with the step 2 of embodiment 1;
3) silicon chip B adding is contained among the acetone 16mL of NSC 20956 50mmol; Remove oxygen, add cupric bromide 0.4mmol, cuprous bromide 0.02mmol and five methyl diethylentriamine 0.6mmol; Carry out the surface and cause ATRP, temperature of reaction is 65
oC, the reaction times is 48 hours, obtains the silicon chip C that the poly-n-butyl methacrylate brush is contained on the surface;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid, the mol ratio of trifluoroacetic acid and Bing Xisuandingzhi is 4:1, stirs under the room temperature 36 hours, obtains the polymer brush of polymethyl acrylic acid at monocrystalline silicon surface, and polymer brush thickness is 24nm;
5) will go up the polymer brush that goes on foot acquisition and in the 0.005mol/L nickel chloride solution, soak into one hour, and take out the back and in the 0.1mol/L sodium borohydride solution, react, the reaction times is 0.5 hour, thereby nickel nano particle is fixed on the monocrystalline silicon surface polymer brush.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (like temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (2)
1. one kind is fixed on the method on the monocrystalline silicon surface polymer brush with noble metal nano particles, it is characterized in that including following steps:
1) places the hydrofluoric acid solution of 10 vol% to soak 2-5 minute monocrystalline silicon piece,, obtain the silicon chip A of surface hydriding to remove the silica oxides layer of monocrystalline silicon sheet surface;
2) 4-vinyl benzene methyl chloride is dripped on silicon chip A surface, radiation with acetone rinsing, oven dry, obtained the silicon chip B that atom transfer free radical polymerization initiating group is contained on the surface after 3 minutes under UV-light;
3) silicon chip B is joined contain in the monomeric solvent, remove oxygen, add cupric bromide or cupric chloride, cuprous bromide or cuprous chloride and part carry out surface initiation ATRP, and temperature of reaction is 50-70
oC, the reaction times is 12-48 hour, obtains the silicon chip C that polymer brush is contained on the surface; Described monomer is Bing Xisuandingzhi or NSC 20956; Described part is bipyridine or five methyl diethylentriamine;
4) silicon chip C is placed the dichloromethane solution that contains the 10vol% trifluoroacetic acid, trifluoroacetic acid and monomeric mol ratio are 4:1-6:1, stir 24-36 hour under the room temperature, obtain containing the polymer brush of carboxyl at monocrystalline silicon surface;
5) polymer brush that step 4) is obtained fully soaked into 1-2 hour in containing precious metal ion solution; Described noble metal nano particles is silver, nickel or platinum; Taking out the back reacts in sodium borohydride solution; Reaction times is 0.5-4 hour, thereby noble metal nano particles is fixed on the monocrystalline silicon surface polymer brush.
2. by claim 1 is described noble metal nano particles is fixed on the method on the monocrystalline silicon surface polymer brush, it is characterized in that described solvent is acetone, THF or octane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110003737A CN102173865B (en) | 2011-01-10 | 2011-01-10 | Method for fixing noble metal nano particles on single-crystal silicon surface polymer brush |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110003737A CN102173865B (en) | 2011-01-10 | 2011-01-10 | Method for fixing noble metal nano particles on single-crystal silicon surface polymer brush |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102173865A CN102173865A (en) | 2011-09-07 |
| CN102173865B true CN102173865B (en) | 2012-10-10 |
Family
ID=44517163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110003737A Expired - Fee Related CN102173865B (en) | 2011-01-10 | 2011-01-10 | Method for fixing noble metal nano particles on single-crystal silicon surface polymer brush |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102173865B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833749B (en) * | 2016-01-22 | 2019-03-29 | 国家海洋局天津海水淡化与综合利用研究所 | A kind of polyamide reverse osmosis composite film of stable against biological contamination and preparation method thereof |
| CN111876757B (en) * | 2020-06-28 | 2021-09-21 | 华南理工大学 | Preparation method of inorganic two-dimensional nano material based on plane patterning polymer brush |
| CN114854139A (en) * | 2022-04-06 | 2022-08-05 | 万华化学（宁波）有限公司 | Conductive polymer composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7351782B2 (en) * | 2002-10-02 | 2008-04-01 | Kaneka Corporation | One-part curable composition |
| CN100497401C (en) * | 2005-09-30 | 2009-06-10 | 中国科学院长春应用化学研究所 | Fixation of ionic liquid using polymer |
-
2011
- 2011-01-10 CN CN201110003737A patent/CN102173865B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Martina K.N. Hirayama et al..Strongly attached ultrathin polymer layers on metal surfaces obtained by activation of Si-H bonds.《Applied Surface Science》.1999,第143卷第256-264页. * |
| 苏旭等.单晶硅表面贵金属晶粒层的制备.《化学学报》.2008,第66卷(第10期),第1215-1220页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102173865A (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kamat | Semiconductor surface chemistry as holy grail in photocatalysis and photovoltaics | |
| CN106252676B (en) | A kind of preparation of quantum dot modified metal organic backbone insertion carbon nano-tube material | |
| CN101913600B (en) | Method for preparing graphene/semiconductor quantum dot composite material | |
| CN102173865B (en) | Method for fixing noble metal nano particles on single-crystal silicon surface polymer brush | |
| CN105399080A (en) | Method for preparing graphene-quantum dot composite material | |
| CN101559918B (en) | Preparation method of graphene/cadmium sulfide quantum dot composite material applied to photoelectric conversion | |
| Li et al. | Hollow mesoporous SiO2–BiOBr nanophotocatalyst: Synthesis, characterization and application in photodegradation of organic dyes under visible-light irradiation | |
| CN101214932A (en) | Method for preparing nanometer tin selenide | |
| CN103738938B (en) | Methods for preparing fullerene and nitrogen-doped fullerene by using cubic cuprous oxide as template | |
| JP6415223B2 (en) | Organic inorganic composite thin film solar cell | |
| CN112958150B (en) | Preparation of ethylenediamine-coated cadmium telluride nano-belt photocatalyst and separation method of uranium in radioactive wastewater | |
| CN102790178A (en) | Preparation of photoelectric device based on surface functionalized semiconductor nanocrystal | |
| CN111007055A (en) | Ti3C2TxPreparation process of/Ag nano composite material and application of Ag nano composite material as Raman substrate material | |
| CN106571460B (en) | A kind of binder free, selenium positive electrode of self supporting structure and preparation method thereof | |
| CN104128180A (en) | Method for synthesis of cuprous oxide/graphene photocatalytic composite nanomaterial by electron beam irradiation | |
| CN105226242B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| Qin et al. | Rational Design of a Core–Shell Structured Plasmonic Au@ MIL-100 (Fe) Nanocomposite for Efficient Photocatalysis | |
| CN104263643B (en) | Based on enzymatic-photocatalysis cooperative effect bioreactor and preparation method thereof and the application in degradating organic dye | |
| CN102101639B (en) | Preparation method of silicon nanowires with controlled surface-modified silver particles as single-molecule SERS (surface enhanced Raman scattering) detection substrate | |
| CN113797749A (en) | Method for degrading nitrogen oxide by manganese-loaded bronze ore titanium dioxide under photo-thermal synergistic condition | |
| CN109939740B (en) | Preparation method and application of gold nanoparticle-loaded two-dimensional nanosheet | |
| CN113083239A (en) | TEMPO pretreated nano-cellulose-cuprous oxide/silver micro-nano structure composite material and preparation method and application thereof | |
| CN104817282A (en) | Preparation method of green photonic crystal structure color thin film with photo-catalytic effect | |
| Nagakawa et al. | Facet-Selective Photoelectrochemical Reactions on Wurtzite CdS Photocatalysts | |
| CN110743578A (en) | Tourmaline-loaded BiOI photocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121010 Termination date: 20160110 |