CN104308169A - Manufacturing method of concave silver nanoparticles with high-index crystal face - Google Patents
Manufacturing method of concave silver nanoparticles with high-index crystal face Download PDFInfo
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- CN104308169A CN104308169A CN201410554040.0A CN201410554040A CN104308169A CN 104308169 A CN104308169 A CN 104308169A CN 201410554040 A CN201410554040 A CN 201410554040A CN 104308169 A CN104308169 A CN 104308169A
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Abstract
The invention discloses a manufacturing method of concave silver nanoparticles with a high-index crystal face. The method comprises the steps of respectively preparing a polyvinylpyrrolidone ethanol solution and a silver nanoparticle ethanol suspension liquid; adding the prepared polyvinylpyrrolidone ethanol solution and the silver nanoparticle ethanol suspension liquid into a polytetrafluoroethylene high temperature reactor; reacting for a certain time under sealing and constant temperature conditions; cooling the reactants fast and centrifuging the reactants to obtain sediments which are the concave silver nanoparticles with the high-index crystal face. The manufacturing method is simple and high in repeatability, can be used for manufacturing various shapes of the concave silver nanoparticles with the high-index crystal face, and can be used for large-scale production. The concave silver nanoparticles with the high-index crystal face manufactured by the method is uniform in size, good in dispersity, controllable in concave curvature and high in yield.
Description
Technical field
The present invention relates to a kind of preparation method of silver nano-grain, be specifically related to a kind of preparation method with the concave surface silver nano-grain of high miller index surface.
Background technology
Silver nano material all shows very excellent character in fields such as optics, electronics, catalysis, biological diagnosis mark and anti-inflammations.Up to now, a large amount of methods has been had can to synthesize the silver nano material of different-shape, size and structure accurately.But these silver nano materials overwhelming majority is convex surface (convex surface) silver nano-grain of low index crystal plane.And concave surface (concave surface) silver nano-grain that the synthesis that recent years initiates has a high miller index surface is proved and shows the character more efficient or more special than the convex surface silver nano-grain of low index crystal plane in fields such as optics, catalysis, electronics.But theoretical and experiment proves that the concave surface silver nano-grain of high miller index surface has higher surface chemistry energy, is not thermodynamically stable nano material, therefore needs just to synthesize the concave surface silver nano-grain obtaining high miller index surface under special synthesis condition.Current report still cans be counted on one's fingers for the preparation of the method for the concave surface silver nano-grain of high miller index surface.Peidong Yang and his partner report the method (J.Am.Chem.Soc.2010,132,268-274) that the concave surface silver nano-grain of high miller index surface is prepared in the corrosion of a kind of combinatorial chemistry.Younan Xia and his partner report a kind of concave surface silver nanoparticle octahedron (octahedrons) preparing high miller index surface of dynamics Controlling and the outgrowth method (Angew.Chem.2011 of concave surface silver tetrahexahedron (trisoctahedrons), 123,12750-12754).They also find that the concave surface silver nano-grain of the high miller index surface prepared has extraordinary spectrum characteristic simultaneously.Therefore, study the method preparing the concave surface silver nano-grain of high miller index surface to have great importance.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of technique simple, use less, convenient source, and a kind of preparation method preparing the concave surface silver nano-grain with high miller index surface of large-scale production can be carried out, the silver nano-grain prepared has the controlled inner concave of dispersiveness highly, topography uniformity and curvature; The concave surface silver nano-grain of the high miller index surface of difformity and structure can be prepared; The concave surface silver nano-grain productive rate of the single batch of high miller index surface prepared is high, can reach ~ the productive rate of 99%.
The present invention proposes a kind of preparation method of concave surface silver nano-grain of high miller index surface, be dissolved in by polyvinylpyrrolidone in ethanol, preparation obtains polyvinylpyrrolidone ethanolic solution; Preparation silver nano-grain alcohol suspension; The polyvinylpyrrolidone ethanolic solution of aforementioned preparation and silver nano-grain alcohol suspension are joined in polytetrafluoroethylene (PTFE) pyroreaction still and seals, certain hour is reacted under constant temperature, after quick cooling, through the concave surface silver nano-grain being precipitated as described high miller index surface that centrifugation obtains.
In the present invention, described polyvinylpyrrolidone mean molecule quantity is 10000Da ~ 55000Da.Preferably, described polyvinylpyrrolidone mean molecule quantity is 29000Da.It is 29000Da that described polyvinylpyrrolidone is not limited to mean molecule quantity; Can also be the polyvinylpyrrolidone of other mean molecule quantities, such as 10000Da and 55000Da.
In the present invention, the concentration of described polyvinylpyrrolidone ethanolic solution is 0.1 ~ 10 mM/l.Preferably, the concentration of described polyvinylpyrrolidone ethanolic solution is 1 mM/l.
In the present invention, the concentration of the silver nano-grain in described silver nano-grain alcohol suspension is 1.0 × 10
11~ 1.0 × 10
15particle/liter.Preferably, the concentration of described silver nano-grain is 2.2 × 10
13particle/liter.
In the present invention, the silver nano-grain added in described reaction, namely the silver nano-grain added in silver nano-grain alcohol suspension is prepared, comprise the silver nano-grain of various shape, comprise silver nanoparticle ball (Ag nanosphere), silver nanocubes (Ag nanocube), silver nanoparticle octahedron (Ag nano-octahedron), silver nanoparticle bicone (Ag nano-right-bipyramid), Silver nanorod (Ag nanorod), silver nanoparticle bar (Ag nanobar), nano silver wire (Ag nanowire), silver nanoparticle hexahedron nano silver wire, silver nanoparticle decahedron (Ag nano-decahedron), silver nanoparticle tetrahexahedron (Ag nano-isosahedron), silver nanoparticle cuboctahedron (Ag nano-cuboctahedron), also comprise the concave surface silver nano-grain of various shape, also comprise the silver nano-grain of other patterns, also comprise the alloy nanoparticle containing silver of various shape.
In the present invention, the described reaction time is 0.5 ~ 24 hour.
In the present invention, described reaction temperature is 60 ~ 300 DEG C.
In the present invention, described reaction is carried out under high-temperature high-pressure reaction kettle device or constant-pressure and high-temperature back flow reaction device.
In the present invention, the volume of described reactor is 1 ~ 10
6milliliter.Preferably, the volume of described reactor is 25 milliliters.
In the present invention, the speed of described centrifugation precipitation is 1000-55000 revolutions per minute.Preferably, described centrifugation speed is 15000 revolutions per minute.
In a specific embodiment, in preparation method of the present invention, the silver nano-grain alcohol suspension with low index crystal plane obtained by other synthetic methods is joined in the polyvinylpyrrolidone ethanolic solution of 10 milliliters, then reaction solution is transferred in polytetrafluoroethylene (PTFE) autoclave, 80 DEG C of reactions 6 hours, then reactor is placed in room temperature tank to cool fast, obtains the concave surface silver nano-grain with high miller index surface.
The present invention also proposes the concave surface silver nano-grain of the high miller index surface prepared by above-mentioned preparation method.
Compared with prior art, advantage of the present invention comprises: preparation technology is simple, and repeatability is high, and raw material uses simply cheap, can be used for the concave surface silver nano-grain of the high miller index surface preparing different morphologies, size and structure, can be applicable to large-scale production.The concave surface silver nano-grain size uniformity of the high miller index surface that the present invention prepares, good dispersion, concave curvature is controlled, and productive rate can reach ~ high yield of 99%, as shown in specific embodiment and Fig. 1 and Fig. 2.
Accompanying drawing explanation
Fig. 1 is TEM figure and the SEM figure of the concave surface silver nano-grain (cube) of the high miller index surface that the inventive method prepares.
Fig. 2 is that the concave surface silver nanocubes SEM of the high miller index surface that the concave curvature obtained by the differential responses time in the present invention is increased gradually schemes.
Fig. 3 is the SEM figure of the concave surface silver nanoparticle cube frame of the high miller index surface that the inventive method prepares.
Fig. 4 is the edge sawtooth shape silver triangular plate of the concave surface silver nano-grain of the high miller index surface that the inventive method prepares and the SEM figure of hexagonal sheet.
Fig. 5 is the SEM figure of the cuboctahedron (cuboctahedrons) of the concave surface silver nano-grain of the high miller index surface that the inventive method prepares.
Detailed description of the invention
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
Embodiment 1, the preparation of the concave surface silver nano-grain of high miller index surface of the present invention
Comprise the following steps:
1. be dissolved in ethanol by polyvinylpyrrolidone (mean molecule quantity is 29000 Da), preparation obtains the ethanolic solution of 1 mM/l of (in units of mean molecule quantity) polyvinylpyrrolidone;
2. the polyvinylpyrrolidone ethanolic solution prepared 10 milliliters joins in the polytetrafluoroethylene (PTFE) pyroreaction still of 25 milliliters of volumes;
3. compound concentration is 2.2 × 10
13particle/liter silver nano-grain alcohol suspension, 0.3 milliliter of this silver nanocubes alcohol suspension is joined in above-mentioned polytetrafluoroethylene (PTFE) pyroreaction still;
4. reactor sealing is tightened, be then placed in the constant temperature oven of 80 DEG C and react 6 hours;
5., during reaction time cut-off, reactor is placed in tank and cools fast;
6. when temperature of reaction kettle drops to room temperature, open reactor, by centrifugal for reaction solution (15000 rotating speeds/minute, 10 minutes) remove supernatant, namely the centrifugal sediment obtained is the concave surface silver nano-grain (cube) of product high miller index surface, as shown in Figure 1, wherein, A represents the TEM figure of the concave surface silver nano-grain (cube) of the high miller index surface obtained, and B represents the SEM figure of the concave surface silver nano-grain (cube) of the high miller index surface obtained.
In the present invention, if the silver nano-grain of the concave surface of other high miller index surfaces will be prepared, only silver nanocubes need be changed into other silver nano-grains of close concentration, then can complete according to above-mentioned steps operation.
The preparation of the concave surface silver nanocubes of the high miller index surface that embodiment 2 concave curvature is different
Other implementation conditions and step are with reference to embodiment 1.In above-described embodiment, the reaction time is 1, and 2,4, within 6 hours, stop reaction, the concave surface silver nanocubes of the high miller index surface of different concave curvature can be obtained, as shown in Figure 2.Wherein, scheme A, B, C, D and be illustrated respectively in the concave surface silver nanocubes that reaction stops the high miller index surface of the different concave curvature obtained for 1,2,4,6 hours.
The preparation of the concave surface silver nanocubes of embodiment 3 high miller index surface
Other implementation conditions and step are with reference to embodiment 1.In above-described embodiment, reaction temperature is brought up to 160 DEG C, namely reaction can obtain the concave surface silver nanocubes of high miller index surface for 1-2 hour, the method can carry out Reaction time shorten by improving reaction temperature, can obtain high-quality concave surface silver nanocubes equally.
The preparation of the concave surface silver nanoparticle cube frame of embodiment 4 high miller index surface
Other implementation conditions and step are with reference to embodiment 1.In above-described embodiment, the reaction time stopped reaction at 8 hours, can obtain the concave surface silver nanoparticle cube frame of high miller index surface, as shown in Figure 3.
The preparation of embodiment 5 edge sawtooth shape silver triangular plate and hexagonal sheet
Other implementation conditions and step are with reference to embodiment 1.In above-described embodiment, the reaction time stopped reaction at 12 hours, can obtain edge sawtooth shape silver triangular plate and hexagonal sheet, as shown in Figure 4.
The preparation of the concave surface silver nanoparticle cuboctahedron of embodiment 6 high miller index surface
Other implementation conditions and step are with reference to embodiment 1.The silver nanocubes added is changed into similar concentration (2.2 × 10 in above-described embodiment
13particle/liter) silver-colored cuboctahedron, namely product can obtain the concave surface silver nanoparticle cuboctahedron of high miller index surface, as shown in Figure 5.
Claims (10)
1. have a preparation method for the concave surface silver nano-grain of high miller index surface, it is characterized in that, be dissolved in by polyvinylpyrrolidone in ethanol, preparation obtains polyvinylpyrrolidone ethanolic solution; Preparation silver nano-grain alcohol suspension; The polyvinylpyrrolidone ethanolic solution of aforementioned preparation and silver nano-grain alcohol suspension are joined in polytetrafluoroethylene (PTFE) pyroreaction still and seals, react under constant temperature, after quick cooling, through the concave surface silver nano-grain being precipitated as described high miller index surface that centrifugation obtains.
2. preparation method as claimed in claim 1, it is characterized in that, described polyvinylpyrrolidone mean molecule quantity is 10000Da ~ 55000Da; The concentration of described polyvinylpyrrolidone ethanolic solution is 0.1 ~ 10 mM/l.
3. preparation method as claimed in claim 1, it is characterized in that, the concentration of described silver nano-grain is 1.0 × 10
11~ 1.0 × 10
16particle/liter.
4. preparation method as claimed in claim 1, it is characterized in that, the silver nano-grain added in described reaction comprises silver nanoparticle ball, silver nanocubes, silver nanoparticle octahedron, silver nanoparticle bicone, Silver nanorod, silver nanoparticle bar, nano silver wire, silver nanoparticle decahedron, silver nanoparticle tetrahexahedron, silver nanoparticle cuboctahedron, concave surface silver nano-grain or the alloy nanoparticle containing silver.
5. preparation method as claimed in claim 1, it is characterized in that, the described reaction time is 0.5 ~ 24 hour; Described reaction temperature is 60 ~ 300 DEG C.
6. preparation method as claimed in claim 1, it is characterized in that, described reaction is carried out under high-temperature high-pressure reaction kettle device or constant-pressure and high-temperature back flow reaction device.
7. preparation method as claimed in claim 1, it is characterized in that, the volume of described reactor is 1 ~ 10
6milliliter.
8. preparation method as claimed in claim 1, is characterized in that, the rotating speed of described centrifugation precipitation is 1000-55000 revolutions per minute.
9. preparation method as claimed in claim 1, it is characterized in that, the productive rate that described preparation method obtains the concave surface silver nano-grain of high miller index surface reaches 99%.
10. the concave surface silver nano-grain with high miller index surface prepared by claim 1 preparation method.
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Cited By (8)
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| CN105127446A (en) * | 2015-09-18 | 2015-12-09 | 温州大学 | Precious-metal nanometer bipyramid and preparing method thereof |
| CN105458293A (en) * | 2016-01-08 | 2016-04-06 | 苏州大学 | Bipyramid structure gold nanoparticle and preparation method thereof |
| CN105833865A (en) * | 2016-04-11 | 2016-08-10 | 河南科技学院 | A preparing method of a graphene-loaded Ag photocatalyst having a cubic morphology |
| CN106179315A (en) * | 2016-07-10 | 2016-12-07 | 王映朴 | A kind of preparation method of the graphene-supported Bi photocatalyst with 40 shape of octahedron |
| CN106268803A (en) * | 2016-07-20 | 2017-01-04 | 武夷学院 | A kind of preparation method of the graphene-supported Ag Bi photocatalyst with 40 shape of octahedron |
| CN107008258A (en) * | 2017-04-20 | 2017-08-04 | 河南科技学院 | TiO2Application of the nanometer Ag photochemical catalyst of load in degradation of phenol |
| CN107029709A (en) * | 2017-04-20 | 2017-08-11 | 河南科技学院 | A kind of TiO2The preparation method of the tetrahexahedron pattern nanometer Ag photochemical catalyst of the high miller index surface of load |
| CN108031858A (en) * | 2017-11-28 | 2018-05-15 | 苏州大学 | A kind of controllable octahedral preparation method of palladium nano cubic of surface topography |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105127446A (en) * | 2015-09-18 | 2015-12-09 | 温州大学 | Precious-metal nanometer bipyramid and preparing method thereof |
| CN105458293A (en) * | 2016-01-08 | 2016-04-06 | 苏州大学 | Bipyramid structure gold nanoparticle and preparation method thereof |
| CN105458293B (en) * | 2016-01-08 | 2017-11-03 | 苏州大学 | A kind of double cone structure golden nanometer particle and preparation method thereof |
| CN105833865A (en) * | 2016-04-11 | 2016-08-10 | 河南科技学院 | A preparing method of a graphene-loaded Ag photocatalyst having a cubic morphology |
| CN105833865B (en) * | 2016-04-11 | 2017-12-26 | 河南科技学院 | A kind of preparation method of the graphene-supported Ag photochemical catalysts with concave surface cube pattern |
| CN106179315A (en) * | 2016-07-10 | 2016-12-07 | 王映朴 | A kind of preparation method of the graphene-supported Bi photocatalyst with 40 shape of octahedron |
| CN106268803A (en) * | 2016-07-20 | 2017-01-04 | 武夷学院 | A kind of preparation method of the graphene-supported Ag Bi photocatalyst with 40 shape of octahedron |
| CN107008258A (en) * | 2017-04-20 | 2017-08-04 | 河南科技学院 | TiO2Application of the nanometer Ag photochemical catalyst of load in degradation of phenol |
| CN107029709A (en) * | 2017-04-20 | 2017-08-11 | 河南科技学院 | A kind of TiO2The preparation method of the tetrahexahedron pattern nanometer Ag photochemical catalyst of the high miller index surface of load |
| CN107008258B (en) * | 2017-04-20 | 2019-07-05 | 河南科技学院 | TiO2Application of the nanometer Ag photochemical catalyst of load in degradation of phenol |
| CN108031858A (en) * | 2017-11-28 | 2018-05-15 | 苏州大学 | A kind of controllable octahedral preparation method of palladium nano cubic of surface topography |
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