CN101544805B - Method for preparing noble metal/polymer nanometer hybrid particles - Google Patents
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- CN101544805B CN101544805B CN2009100315890A CN200910031589A CN101544805B CN 101544805 B CN101544805 B CN 101544805B CN 2009100315890 A CN2009100315890 A CN 2009100315890A CN 200910031589 A CN200910031589 A CN 200910031589A CN 101544805 B CN101544805 B CN 101544805B
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Abstract
The invention discloses a method for preparing noble metal/polymer nanometer hybrid particles, comprising the following steps: (1) preparing nanometer silicon dioxide particles enwrapped by a 4-vinylpyridine layer by taking the nanometer silicon dioxide particles as nucleus; and (2) loading noble metal on the 4-vinylpyridine layer to obtain the noble metal/polymer nanometer hybrid particles by taking the 4-vinylpyridine layer loading the noble metal as a shell layer and taking the nanometer silicon dioxide as the nucleus. For the nanometer particles with the nucleus shell structure by taking the 4-vinylpyridine layer loading the noble metal as the shell layer and taking the nanometer silicon dioxide as the nucleus, both the thickness of the 4-vinylpyridine layer and the grain diameter of the nanometer silicon dioxide can be adjusted, thereby the specific surface of the final noble metal/polymer nanometer hybrid particles is adjustable; and meanwhile, the 4-vinylpyridine is enwrapped on the surface of the nanometer silicon dioxide particles and can sufficiently load the noble metal so that the utility ratio of the 4-vinylpyridine is improved.
Description
Technical field
The present invention relates to the preparation field of the polymer nanometer hybrid particles of carried noble metal.
Background technology
Gold and Nano silver grain become the focus of research in recent years owing to its characteristic at aspects such as light, electricity, catalysis, surface-enhanced Ramans.The characteristic of nanoparticle depends on size, dispersion of particles and the stability of particle.In recent years, utilize functionalized polymer microsphere to come load and stable metal particle to become important effective means.
In the prior art, be used for the polymer microballoon of carried noble metal normally by letex polymerization, methods such as seeded emulsion polymerization are prepared from, for example utilize vinylbenzene and vinyl pyridine emulsion copolymerization to form latex particle, supported precious metal nano-particle then, the formation noble metal/polymer nanometer hybrid particles (referring to: 1.WenF., Zhang W.Q.; Zheng P.W.; Zhang X.; Yang X.L.; Wang Y.; Jiang X.W.; Wei G.W., ShiL.Q.Journal of Polymer Science:Part A:Polymer Chemistry, 2008,46,1192-1202.; 2. warm minor benefit, poplar Mu, Ding Hangjun, Wang Ge. the chemistry circular, 2008,3,205-210); In the described prior art, because the latex particle of copolymerization method synthetic vinylbenzene and vinyl pyridine, the part vinyl pyridine is in the inside of latex particle, can't carried noble metal, thereby the utilization ratio of vinyl pyridine is not high, secondly as the polymkeric substance shell of functionalization, its controllability is subjected to certain restriction.
Summary of the invention
The object of the invention provides a kind of method for preparing noble metal/polymer nanometer hybrid particles, can regulate and control the surface-area and the thickness of vinyl pyridine on the one hand, improves the utilization ratio of vinyl pyridine simultaneously; Can regulate and control the size of the nuclear and the shell of nano-hybrid particle on the other hand, thereby regulate the specific surface of noble metal/polymer nanometer hybrid particles.
For achieving the above object, the concrete technical scheme of the present invention is that a kind of method for preparing noble metal/polymer nanometer hybrid particles may further comprise the steps:
(1) with the nano-silicon dioxide particle is nuclear, the nano-silicon dioxide particle of preparation poly 4 vinyl pyridine layer parcel;
(2) carried noble metal on the poly 4 vinyl pyridine layer, obtaining with poly-4-vinylpyridine carried noble metal is shell, nanometer SiO
2Particle is the nuclear case structure hybridization nanoparticle of nuclear, i.e. noble metal/polymer nanometer hybrid particles;
In the technique scheme, the preparation method of described nano-silicon dioxide particle is a prior art, and the particle diameter of nano-silicon dioxide particle can be regulated in the prior art, in actual applications, can decide the particle diameter of nano-silicon dioxide particle according to end-use, for example: in order to improve the specific surface of noble metal/polymer nanometer hybrid particles, the particle diameter of nano-silicon dioxide particle is 20～80nm; The recovery of noble metal/polymer nanometer hybrid particles for convenience, the particle diameter of nano-silicon dioxide particle is 120～200nm.The particle diameter of nano-silicon dioxide particle is 20～300nm, and in the optimized technical scheme, the particle diameter of nano-silicon dioxide particle is 70～140nm;
In the technique scheme, the method of the nano-silicon dioxide particle of preparation poly 4 vinyl pyridine layer parcel is: by reversible addition-chain transfer free radical (RAFT) polymerization graft copolymerized 4-vinyl pyridine, form the nano-silicon dioxide particle that the poly 4 vinyl pyridine layer wraps up on the surface of nano-silicon dioxide particle; Specifically may further comprise the steps:
(1) with nano-silicon dioxide particle and the reaction of chloromethylation silane coupling agent,, obtains the chloromethylation nano-silicon dioxide particle by the silane coupler modified nano-silicon dioxide particle of chloromethylation;
In the above-mentioned reaction, the alcoxyl silylation effect in the hydroxyl of silica sphere and the chloromethylation silane coupling agent; The usage ratio aspect is 100 parts with the quality of nano-silicon dioxide particle, is benchmark with the mass parts; Get 5～10 mass parts chloromethylation silane coupling agents;
The general formula of described chloromethylation silane coupling agent is:
(2) with carbazole, dithiocarbonic anhydride and the reaction of chloromethylation nano-silicon dioxide particle, benzyl cl radical and carbazole by chloromethylation nano-silicon dioxide particle surface, the interaction of dithiocarbonic anhydride reagent loads to silica particle surface with dithio carbazole benzyl formate;
In the above-mentioned reaction,, add dithiocarbonic anhydride and generate corresponding dithio salt, obtain load dithio carbazole benzyl formate silicon dioxide granule with the effect of benzyl cl radical by the diamine groups and the highly basic effect of carbazole; The amount of the dithio carbazole benzyl formate of load is controlled to be: in the silicon dioxide granule of every gram load dithio carbazole benzyl formate, the content of dithio carbazole benzyl formate is 0.1～0.5mmol; Described reaction process is as follows:
(3) the dithio carbazole benzyl formate with the silicon dioxide granule load is a RAFT reagent, at the particle surface graft copolymerized 4-vinyl pyridine, obtains the nano-silicon dioxide particle (SiO of poly 4 vinyl pyridine layer parcel by RAFT polymerization (R functional group method)
2-g-P4VP);
In the technique scheme, RAFT polymerization (R group polymerization) is this area Essential Terms, and in general, the structure of RAFT reagent is as follows:
, also as the part of R group, so be called the R functional group method, the advantage of R functional group method is to obtain the polymkeric substance of higher grafting density to silicon dioxide granule among the present invention;
Because the RAFT polymerization has controllability, can regulate the thickness of the poly 4 vinyl pyridine layer that is wrapped on the nano-silicon dioxide particle by controlling reaction time; In the practical application, the thickness of poly 4 vinyl pyridine layer can be regulated by those skilled in the art as required;
In the technique scheme, described precious metal is selected from: a kind of in gold or the silver; With noble metal support to the poly 4 vinyl pyridine layer belong to prior art (referring to 1. Chen Qing moral, Shen Xinghai, Gao Hongcheng. polymer journal, 2006,5,722-726; 2.Wen, F.; Zhang, W.Q.; Wei, G.W.; Wang, Y.; Zhang, J.Z.; Zhang, M.C.; Shi, L.Q.Chem.Mater.2008,20,2144-2150), general method is: precious metal ion is loaded to the poly 4 vinyl pyridine layer, through the reductive agent reduction, obtain the poly 4 vinyl pyridine layer of carried noble metal; Wherein, precious metal ion is generally corresponding metal salts solution state, as HAuCl
4Or AgNO
3Solution; Reductive agent is selected from: sodium borohydride, carbon monoxide or hydrazine hydrate etc.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. be shell owing to the present invention obtains with poly-4-vinylpyridine carried noble metal, nanometer SiO
2Particle is the nuclear case structure hybridization nanoparticle of nuclear, the wherein thickness and the nanometer SiO of poly-4-vinylpyridine layer
2The particle diameter of particle can be regulated, and therefore, the specific surface of final noble metal/polymer nanometer hybrid particles has controllability;
2. because poly-4-vinylpyridine is wrapped in nanometer SiO
2The surface of particle, therefore abundant carried noble metal has improved the utilization ratio of poly-4-vinylpyridine.
Description of drawings
Transmission electron microscope (TEM) image of nano-silicon dioxide particle among Fig. 1 a. embodiment one;
Chloromethylation SiO among Fig. 1 b. embodiment one
2The transmission electron microscope of nanoparticle (TEM) image;
SiO among Fig. 1 c. embodiment one
2The transmission electron microscope of-BCBD nanoparticle (TEM) image;
Fig. 2. SiO among the embodiment one
2, SiO
2-Cl, SiO
2The uv-absorbing spectrogram of-BCBD and BCBD;
Fig. 3. transmission electron microscope (TEM) image of the nanoparticle that RAFT polymerization different time obtains among the embodiment one;
Fig. 4. SiO among the embodiment one
2The infrared spectrum of-g-P4VP;
Fig. 5. SiO among the embodiment one
2(a), SiO
2-Cl (b), SiO
2-BCBD (c) and SiO
2The thermogravimetric analysis figure of-g-P4VP (d);
SiO among Fig. 6 a. embodiment one
2The transmission electron microscope of-g-P4VP/Au nano-hybrid particle (TEM) image;
SiO among Fig. 6 b. embodiment one
2The transmission electron microscope of-g-P4VP/Ag nano-hybrid particle (TEM) image;
Fig. 7 a. embodiment one gained SiO
2The size distribution figure of Au in the-g-P4VP/Au nano-hybrid particle;
Fig. 7 b. embodiment one gained SiO
2The size distribution figure of Ag in the-g-P4VP/Ag nano-hybrid particle;
Fig. 8. embodiment one gained SiO
2-g-P4VP (a), SiO
2-g-P4VP/Au nano-hybrid particle (b) and SiO
2The X-ray powder diffraction figure of-g-P4VP/Ag nano-hybrid particle (c).
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one
(1) the synthetic and sign of dithio carbazole benzyl formate (BCBD)
In the 100mL three-necked flask, add solvent DMSO (20mL), stir the KOH (0.24g) that adds porphyrize down, add carbazole (0.71g) subsequently, stirring reaction is 2 hours under the room temperature, drip dithiocarbonic anhydride (0.38g) then, get red-purple liquid, continue reaction 5 hours, add cylite (0.86g), reacted about 24 hours, and slowly joined in the 150mL water under reaction solution is stirred, obtain yellow solid.Crude product obtains yellow crystals by ethyl alcohol recrystallization twice, and lucifuge refrigeration is stand-by.
The instrumental analysis data:
1H NMR (CDCl
3): δ 4.73 (s, 2H), 7.32-7.47 (m, 9H), 8.00,7.98 (d, 2H), 8.44,8.46 (d, 2H) .EA.C
20H
15NS
2, calculated:C 72.03, and H 4.53, and N 4.20, and S 19.23, and found:C 72.15, and H 4.53, and N 4.18, S 19.14.HPLC.99%.
(2) SiO
2Synthesizing of nanoparticle
Utilize
The synthetic diameter of method is the SiO of 100 ± 5nm
2Particle (is seen Fig. 1 a).Add 15mL ammoniacal liquor (28wt%) in the 500mL three-necked bottle, the 250mL dehydrated alcohol, powerful stirring drips 10mLTEOS down, obtains white emulsion behind the reaction 24h down at 30 ℃.Obtain white SiO after centrifugal
2Nanoparticle cleans in ethanol, disperses, and is centrifugal again, is able to purifying.The SiO that finally obtains
2Nanoparticle is dried in vacuum drying oven, and is standby.
(3) SiO
2Synthetic (the SiO of area load RAFT reagent BCBD
2-BCBD)
With the above-mentioned SiO that obtains
2Nanoparticle (2.5g) is dispersed in the 30mL toluene, and logical argon gas 30min adds chloromethylation silane coupling agent (0.30g), is warming up to 95 ℃ of reaction 2.5h.After being cooled to room temperature, the centrifugal solid that gets cleans with toluene/ether, disperses, and is centrifugal again, is able to purifying.The chloromethylation SiO that finally obtains
2Nanoparticle (SiO
2-Cl) (see Fig. 1 b) in vacuum drying oven, to dry, standby.
Similar to step (1), in the 100mL three-necked flask, add solvent DMSO (20mL), stir the KOH (0.24g) that adds porphyrize down, add carbazole (0.71g) subsequently, stirring reaction is 2 hours under the room temperature, drip dithiocarbonic anhydride (0.38g) then, get red-purple liquid, continue reaction 5 hours, above-mentioned chloromethylation SiO
2Nanoparticle joins in the solution, continues reaction 36h.Obtain solids SiO by centrifugation
2-BCBD (seeing Fig. 1 c).Clean with DMSO/ Virahol/ether successively, disperse, centrifugal again, be able to purifying.Dry, standby in the flaxen nanoparticle vacuum drying oven that finally obtains.Its sulphur content of ultimate analysis is 1.20%, is equivalent to that RAFT reagent content is 0.188mmol/g in the load.
SiO
2RAFT reagent BCBD is confirmed by ultra-violet absorption spectrum in the particle surface load.Fig. 2 is SiO
2, SiO
2-Cl, SiO
2The uv-absorbing spectrogram of-BCBD and BCBD.BCBD is at 240nm, the uv-absorbing ownership of 285nm and 312nm and phenyl ring and carbazole group, and the uv-absorbing of 365nm belongs to the thiocarbonyl group group.SiO
2The uv-absorbing figure of-BCBD as can be seen, at 240nm, 285nm, 312nm the absorption peak similar to BCBD, SiO have occurred with 365nm
2And SiO
2-Cl does not have the feature ultraviolet absorption peak.The result of ultimate analysis shows, SiO
2-BCBD contains 1.2% element sulphur (being equivalent to the BCBD charge capacity is 0.188mmol/g).These results show that all RAFT reagent BCBD successfully is grafted to SiO
2Particle surface.
Investigated the weightless situation of nanoparticle with thermogravimetric analysis, Fig. 5 shows, the SiO behind the polymerization 24h
2The nanoparticle of-g-P4VP weightlessness in the time of 500 ℃ reaches 26%, only have an appointment 10% weightlessness of other sample, and the description weight loss derives from and is grafted on SiO
2The polyvinylpyridine of particle surface.
(4) SiO
2Surface RAFT method graft copolymerized 4-vinyl pyridine (SiO
2-g-P4VP)
In the ampere bottle by predefined ratio adding 4-VP (1.0mL, 9.3mmol), AIBN (0.1mL, concentration is 0.02mol/L DMF solution), BCBD (0.006g, 0.0188mmol), SiO
2-BCBD (0.1g, 0.0188mmol).Add 4mL DMF as solvent, behind the ultra-sonic dispersion solids, logical argon gas bubbling deoxygenation 15min, fusion tube sealing then.React with being placed in 60 ℃ of oil baths.After polyreaction finishes, by the centrifugal solids that obtain, clean with DMF then, disperse, centrifugal again, repeated multiple times is able to purifying.The SiO of the grafting P4VP that finally obtains
2Dry, standby in the nanoparticle vacuum drying oven.
Simultaneously, investigated the influence (table 1) of polymerization time for grafting thickness, the form of the nanoparticle of the nucleocapsid structure that different polymerization times obtain is observed (Fig. 3 a-3d) by TEM.The result shows that along with the increase (6h-24h) of polymerization time, the thickness of shell also progressively increases (10nm-18nm), has embodied the controlled characteristics of polymerization.SiO
2In the infrared spectrum of-g-P4VP, at 1603cm
-1And 823cm
-1Locate the absorption peak of appearance, belong to the charateristic avsorption band (Fig. 4) of pyridine ring.Investigated the weightless situation of nanoparticle in the experiment with thermogravimetric analysis, Fig. 5 shows, the SiO behind the polymerization 24h
2The nanoparticle of-g-P4VP weightlessness in the time of 500 ℃ reaches 26%, only have an appointment 10% weightlessness of other sample, and the description weight loss derives from and is grafted on SiO
2The polyvinylpyridine of particle surface.
The thickness of table 1 poly 4 vinyl pyridine layer and the relation of RAFT polymerization time
Polymerization time (h) poly 4 vinyl pyridine layer thickness (nm)
1 6 10
2 9 13
3 18 16
4 24 18
The poly 4 vinyl pyridine layer thickness is recorded by the result of TEM.
(5) hybrid particle (SiO of shell carrying metal particles
2-g-P4VP/metal nanoparticles) preparation
The HAuCl that adds the 5.0mmol/L of 10mL in the single neck bottle of 25mL
4Solution stirs adding 0.1g SiO down subsequently
2Stir 30min under the-g-P4VP particle, room temperature.The centrifugal xanchromatic solid that obtains cleans repeatedly with deionized water, is able to purifying.Particle behind the purifying is dispersed in the deionized water once more, adds excessive N aBH
4The aqueous solution, stirring reaction 1h in 50 ℃ of oil baths.Be cooled to room temperature, the centrifugal solids that obtain clean repeatedly with deionized water, are able to purifying.The sorrel product S iO that finally obtains
2Standby after the-g-P4VP/Au vacuum-drying.
Black product S iO
2The preparation method of-g-P4VP/Ag is to above-mentioned similar: with the SiO that obtains
2-g-P4VP nanoparticle is at first at AgNO
3Activate in the solution, use NaBH subsequently
4Reduction obtains SiO
2-g-P4VP/Au or SiO
2-g-P4VP/Ag hybrid material.
With gained SiO
2-g-P4VP/Au nano-hybrid particle and SiO
2-g-P4VP/Ag nano-hybrid particle carries out TEM and detects, and the results are shown in Figure 6a-b;
The mean diameter of the Au nanoparticle in the resulting shell is 2.5 ± 1.0nm, shown in Fig. 7 a; The mean diameter of the Ag nanoparticle in the resulting shell is 7.8 ± 2.5nm, shown in Fig. 7 b.
SiO
2-g-P4VP/Au or SiO
2The crystal formation of metallics is investigated by XRD in the-g-P4VP/Ag hybrid material, as shown in Figure 8, angle of diffraction 2 θ are 38.1 °, 44.3 °, 64.6 ° with 77.5 ° (Fig. 8 b) corresponding to (111) of gold cube mutually, (200), (220) and (311) crystal face indexes, angle of diffraction 2 θ are 38.1 °, 44.4 °, 64.4 ° with 77.6 ° (Fig. 8 c) corresponding to (111) of silver cube mutually, (200), (220) and (311) crystal face indexes, these show in the shell that formed Au and Ag nanoparticle are that crystallization phases is cube mutually.The data of surveying and XRD standard powder card (JCPDS card) match (File NO.:PDF#00-002-1095) and (File No.:PDF#00-001-1164).Do not find the peak of metal oxide in the diffraction peak, show at Au and Ag to have formed the corresponding metal particle at the P4VP shell.
Claims (2)
1. method for preparing noble metal/polymer nanometer hybrid particles is characterized in that: may further comprise the steps:
(1) with the nano-silicon dioxide particle is nuclear, the nano-silicon dioxide particle of preparation poly 4 vinyl pyridine layer parcel;
(2) carried noble metal on the poly 4 vinyl pyridine layer, obtaining with poly-4-vinylpyridine carried noble metal is shell, nanometer SiO
2Particle is the nuclear noble metal/polymer nanometer hybrid particles;
Described precious metal is selected from a kind of in gold or the silver;
The method of the nano-silicon dioxide particle of preparation poly 4 vinyl pyridine layer parcel specifically may further comprise the steps in the step (1):
(1) by the silane coupler modified nano-silicon dioxide particle of chloromethylation, obtains the chloromethylation nano-silicon dioxide particle;
(2) with carbazole, dithiocarbonic anhydride and the reaction of chloromethylation nano-silicon dioxide particle, dithio carbazole benzyl formate is loaded to silica particle surface;
(3) the dithio carbazole benzyl formate with the silicon dioxide granule load is a RAFT reagent, at the particle surface graft copolymerized 4-vinyl pyridine, obtains the nano-silicon dioxide particle of poly 4 vinyl pyridine layer parcel by the RAFT polymerization.
2. noble metal/polymer nanometer hybrid particles, it is characterized in that: the nuclear of described noble metal/polymer nanometer hybrid particles is nano-silicon dioxide particle, and the shell of described noble metal/polymer nanometer hybrid particles is the poly-4-vinylpyridine layer of carried noble metal; Described precious metal is selected from a kind of in gold or the silver; Adopt the method for claim 1 to prepare.
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| CN102603948B (en) * | 2012-03-15 | 2014-09-17 | 苏州大学 | Polyvinyl pyridine preparing method |
| ITUA20163432A1 (en) * | 2016-05-13 | 2017-11-13 | Fondazione St Italiano Tecnologia | PROCESS FOR THE PREPARATION OF NANOPARTICELLE CAVE WITH A METALLIC CORE |
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| CN1417249A (en) * | 2002-12-13 | 2003-05-14 | 清华大学 | Composite polyolefin/sio2 nano particle and its prepn |
| CN1884329A (en) * | 2006-05-29 | 2006-12-27 | 扬州大学 | SiO2 core-polymer shell hybrid nanometer material preparation method |
| KR100785890B1 (en) * | 2006-09-25 | 2007-12-17 | 주식회사 코틱스 | Hybrid nano particle containing metal oxide and carbon, and its preparation thereof |
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| CN1417249A (en) * | 2002-12-13 | 2003-05-14 | 清华大学 | Composite polyolefin/sio2 nano particle and its prepn |
| CN1884329A (en) * | 2006-05-29 | 2006-12-27 | 扬州大学 | SiO2 core-polymer shell hybrid nanometer material preparation method |
| KR100785890B1 (en) * | 2006-09-25 | 2007-12-17 | 주식회사 코틱스 | Hybrid nano particle containing metal oxide and carbon, and its preparation thereof |
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