CN104174865A - Carbon-wrapped polyhedron silver nano-particle and controllable self-assembly preparation method thereof - Google Patents
Carbon-wrapped polyhedron silver nano-particle and controllable self-assembly preparation method thereof Download PDFInfo
- Publication number
- CN104174865A CN104174865A CN201310190322.2A CN201310190322A CN104174865A CN 104174865 A CN104174865 A CN 104174865A CN 201310190322 A CN201310190322 A CN 201310190322A CN 104174865 A CN104174865 A CN 104174865A
- Authority
- CN
- China
- Prior art keywords
- carbon
- nano
- polyhedron
- pvp
- preparation
- 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.)
- Granted
Links
- 238000001338 self-assembly Methods 0.000 title claims abstract description 35
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 8
- 239000004332 silver Substances 0.000 title claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 51
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 51
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 17
- 239000008103 glucose Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011246 composite particle Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000000877 morphologic effect Effects 0.000 abstract 1
- 239000010944 silver (metal) Substances 0.000 description 25
- 239000002082 metal nanoparticle Substances 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002107 nanodisc Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon-wrapped polyhedron silver nano-particle and a controllable self-assembly preparation method thereof. A one-step water heating technology is adopted, glucose serves as a reducing agent and a carbon source, and polyvinylpyrrolidone (PVP) serves as a morphological control agent for metallic silver growth and triggers self-assembly of composite particles. The method for preparing the carbon-wrapped polyhedron silver nano-particle comprises the following steps: sequentially dissolving 1.0-2.0g of glucose, 0.25-2.80g of PVP and 0.02-0.04g of silver nitrate in 100ml of deionized water, and ultrasonically dissolving a solid for 20 minutes until the solid is completely dissolved; transferring 40ml of mixed solution into a 50ml reaction kettle, performing constant-temperature reaction for 6 hours at a certain temperature of 160-200 DEG C, and cleaning and drying a product. According to the self-assembly of the composite nano-particles, other conditions are unchanged, the concentration of the PVP is increased to reach a certain value, and the suspension liquid of the cleaned product is directly added to the surface of a carbon film, a silicon chip or other carriers dropwise. The method has a simple process, is low in cost and easy to industrialize, and can be popularized to preparation and industrialized production of other core-shell structure nano-particles and self-assembly structures.
Description
Technical field
The present invention relates to be applied to the noble metal nano particles pattern control in the fields such as minitype optical device, waveguide and biological detection and the preparation method of self assembly thereof, especially one-step synthesis carbon wraps up the nuclear shell structure nano compound particle of polyhedron Ag, or synchronously realizes the self assembly of this Ag/C compound particle; By regulating surfactant concentration, self assembly form is regulated and controled.
Background technology
Noble metal nano particles, owing to showing the character such as many optical, electrical, magnetic, catalysis and sensings that are different from bulk, has boundless application prospect.These character depend on pattern and the size of particle strongly, so the control of the pattern of metal nanoparticle has become one of current study hotspot.The preparation that realizes specific morphology (as polyhedron) noble metal nano particles is the key of optimization and controlled material performance.Yet due to small-size effect and high surface energy, exposed metal nanoparticle is oxidizable inefficacy in application process.In order to address this problem, at the coated oxidation resistant material of particle surface, become one of effective way.Because material with carbon element has excellent chemical stability, biocompatibility and electric conductivity etc., carbon nano-encapsulated has incomparable advantage.Obtain the evenly polyhedron metal nanoparticle of parcel of carbon, often all must realize by multistep reaction, first preparation has single dispersion polyhedron metal nanoparticle of specific morphology, and then by solwution method, it is carried out to surface carbon parcel.Such process steps is loaded down with trivial details, and condition is harsh, and cost is higher, and product heterogeneity (surface of many metal nanoparticles can not be wrapped, and the thickness of different particle clads is also difficult to evenly) often, is difficult for being converted into large-scale production.
The self assembly of metal nanoparticle is one of important channel of realizing device.And the ordered structure that particle assembling forms tends to show many peculiar properties.Particularly, the light cooperative effect that interaction in ordered structure between particle, between particle and substrate causes, greatly enriched the optical property of metal nanoparticle, made it at aspects such as molecular recognition, molecular device, microsensor, thin-film optical filters, the separated detection of high sensitivity and surface is against corrosion, catalysis, electronics transmission, there is more wide application prospect.Yet due to the requirement of self assembly to nano particle pattern, at present the report of metal self-assembly mainly concentrates on and have specific morphology the particle of (as bar-shaped and spherical etc.), the self assembly of polyhedron nano particle still rarely has report.Especially, the pattern that a step realizes metal nanoparticle is controlled, surface carbon nano-encapsulated and synchronous controlled self assembly thereof are still the difficult problem that material science workers face.
In recent years, hydro-thermal method has developed into efficient, easy, fabrication technology cheaply.By regulating the temperature, reaction time, pH etc. of hydro-thermal reaction, can control the pattern of product, size and composition.So far, the existing report that is prepared with organic polymer parcel nano silver wire about one step hydro thermal method, organic coating layer can be protected nano silver wire kernel well, prevents its oxidation, but does not affect electric conductivity.The present invention will develop a kind of new preparation method based on hydrothermal technique, realize the nano-complex particle of one-step synthesis carbon parcel polyhedron Ag, or one-step synthesis be by the different dimensions self-assembled material of this Ag/C core-shell structure nanometer particle structure.The method has very important significance to the device of the development of nanometer technology, metal nanoparticle and application industry.
Summary of the invention
Object of the present invention: propose a kind of simple, quick, economic and applicable preparation method, by regulating the parameters such as reaction solution concentration, realize the nuclear shell structure nano compound particle of one-step synthesis carbon parcel polyhedron Ag, or synchronously realize the controlled self assembly (self assembly of different dimensions) of this Ag/C compound particle.The method has overcome that the pattern that a step realizes Nano silver grain is controlled, the technical barrier of surface carbon parcel and controlled self assembly.
Technical scheme of the present invention: the preparation method of carbon parcel polyhedron Nano silver grain and self-assembled structures thereof, it is characterized in that, the glucose of usining is not only as reducing agent but also as carbon source, and polyvinylpyrrolidone (PVP) is not only as the pattern controlling agent of argent growth but also cause compound particle self assembly.By changing PVP concentration, the list that can obtain carbon parcel disperses, has Ag nano particle/carbon nucleocapsid structure composite nanoparticle of specific polyhedron pattern, or synchronously realizes the self assembly of this particle and the control of assembling form thereof.And the thickness of carbon nano-encapsulated layer can regulate and control.
The step of preparing carbon parcel polyhedron Nano silver grain is: successively 1.0-2.0g glucose, 0.25-0.75gPVP and 0.02-0.04g silver nitrate are dissolved in 100mL deionized water, solid and PVP were dissolved completely in ultrasonic 20 minutes.Get 40mL mixed solution and be transferred in 50mL reactor, at a certain temperature within the scope of 160-200 ℃, isothermal reaction is 6 hours.Reactor is naturally cooled to room temperature, and product, through centrifugal, cleaning repeatedly, is finally dried in 50 ± 10 ℃ of baking ovens under vacuum or N2 protective atmosphere.Product is that the polyhedron Ag nano particle (core) and the carbon layer on surface (shell) that by the length of side, are about 40-60nm are formed.
The self assembly of Ag/C core-shell nano: other reaction condition is constant, increases to certain value by PVP concentration, and the product suspension after cleaning is directly added drop-wise to carbon film, silicon chip or other carrier surface.When PVP concentration reaches 0.07M, polyhedron Ag/C self-assembly becomes 1-dimention nano chain structure; PVP concentration increases to 0.11M, and Ag/C self-assembly forms banded structure, the about 300nm of its width left and right; When PVP concentration further reaches 0.22M, Ag/C nano particle is assembled into arranges orderly two-dimensional circle plate-like nanostructured.
Silver nitrate, glucose, PVP are dissolved in and in deionized water, prepare reactant mixed solution.Room temperature or a little more than all can obtain solution under room temperature condition.For solid and PVP are dissolved completely, mixed solution needs ultrasonic 20 minutes.
Described hydro-thermal method, reaction time and reaction temperature all can be carried out in programme controlled isothermal reaction system.Hydro-thermal reaction liquor capacity is 40mL, and filling rate is 80%, and optimal reaction temperature is 160-200 ℃, and optimum reacting time is 6h.
The raw material that the preparation method of carbon parcel polyhedron Nano silver grain adopts is cheap glucose and silver nitrate reagent, obtain the optimum condition of monodisperse particle: concentration of glucose is 0.056-0.12M, silver nitrate concentration is 1.18-2.35mM, PVP concentration 0.02-0.06M.Product is through centrifugal, cleaning repeatedly, at vacuum or N
250 ± 10 ℃ of oven dry under atmosphere, be more than 6 hours drying time.
Other reaction condition is constant, when PVP concentration meets and exceeds 0.07M, can realize the self assembly of Ag/C nano particle.At carbon film, silicon chip or other carrier surface, all can obtain.
Hydro-thermal method of the present invention is without any need for template, and step is simple, and a step realizes the preparation of Ag/C core-shell structure nanometer particle and self-assembled structures, has overcome the shortcoming that template (as electrochemical deposition, chemical vapour deposition (CVD)) and multistep processes are complicated, cost is high.Product is consisted of the about 40-60nm polyhedron of length of side Ag particle (core) and carbon layer on surface (shell).Being coated with of carbon is beneficial to oxidation, the corrosion that prevents nanometer galactic nucleus, thereby improves its chemical reactivity and heat endurance.In addition, self-assembled structures shows excellent optical property, at aspects such as molecular device, microsensor, thin-film optical filters, the separated detection of high sensitivity and surface is against corrosion, catalysis, electronics transmission, has broad prospect of application.The method experimental provision is simple, easy and simple to handle, controllability is good, easily accomplish scale production, and especially has very strong applicability, extends to other metal system.
Beneficial effect of the present invention:
(1) to can be used to prepare crystallite dimension be nano level Ag/C nucleocapsid structure compound particle to method disclosed by the invention, and galactic nucleus is polyhedron, and the length of side is about 40-60nm, even size distribution; And synchronously realize the self assembly of different dimensions;
(2) adopting cheap glucose, silver nitrate and PVP is raw material, and step is simple, and cost is lower;
(3) the invention discloses a kind of simple, fast, economical and can be applicable to the syntheti c route of the nucleocapsid structure compound particle self-assembled material of different dimensions; Overcome traditional preparation method's complicated operation, the shortcoming that complex steps and cost are high.
(4) other preparation method (as sol-gal process) compares, the feature of hydro-thermal method:
1. experimental provision, experiment condition and preparation process are simple, easily operation, and the productive rate of material is high;
2. controllability is good, can control the feature of product by regulator solution concentration, heat treatment temperature and time;
3. with low cost, easily realize, there is good industrial applications prospect;
4. applicability is strong, extends to other metal.
(5) compare the distinct advantages that the product of this patent of invention has with fine silver nano particle:
1. coated reunion, oxidation and the corrosion that can prevent nano metal of carbon, thus its chemical reactivity and heat endurance improved;
2. the ordered structure of self assembly shows excellent optical property, can apply to microdevice and novel light absorbing material etc.
Accompanying drawing explanation:
Fig. 1 is SEM figure (A) and the XRD collection of illustrative plates (B) of the prepared product of representative experiment (glucose 0.07M, PVP concentration 0.04M, silver nitrate 0.25mM, 180 ℃, reaction 6h).
Fig. 2 is the TEM figure (A) of product shown in Fig. 1, the TEM of single representative Ag/C core-shell particles (B) and HRTEM figure (illustration).
Fig. 3 is that other condition is constant, and the reaction time is respectively 1h, 2h, 3h, the digital photograph (A) of 4h and product that 5h obtains and corresponding uv-visible absorption spectra figure (B).
Fig. 4 is that reaction condition is identical with representative experiment, and PVP concentration is respectively the TEM figure of prepared product under 0.07M (A), 0.11M (B) and 0.22M (C) condition; D is the further amplification of C figure.
Fig. 5 is the digital photograph (A) of product shown in Fig. 4 and corresponding uv-visible absorption spectrum figure (B), and wherein the PVP concentration of a, b, c is 0.07M, 0.11M and 0.22M.
The specific embodiment
In the present invention, to prepare the specific embodiment of carbon parcel polyhedron Nano silver grain and self-assembled structures thereof as follows for hydro-thermal method:
Embodiment 1
The preparation of Ag/C nucleocapsid structure compound particle: successively 1.25g glucose, 0.50gPVP and 0.028g silver nitrate are dissolved in successively in 100ml deionized water and obtain reaction mixture, solid and PVP were dissolved completely in ultrasonic 20 minutes.The concentration of solution glucose in solutions, PVP and silver nitrate is respectively 0.07M, 0.04M and 0.25mM.Get 40ml mixed solution and be transferred in 50ml reactor, under 180 ℃ of constant temperatures, react 6 hours.Reactor is naturally cooled to room temperature, and product is through centrifugal, cleaning repeatedly, finally at vacuum or N
2under protective atmosphere, in 50 ± 10 ℃ of baking ovens, dry.
Fig. 1 (A) is the SEM figure of embodiment 1 prepared product, can see, a large amount of mono-dispersed nano particles form.SEM illustration by high-amplification-factor can find out, nano particle presents uniform polyhedron pattern, and the length of side is about 40-60nm.The XRD collection of illustrative plates that Fig. 1 (B) is this product, stronger diffraction maximum shows that product has good crystallinity, the diffraction maximum of the position of diffraction maximum and face-centred cubic structure silver is in full accord.22 ° (2 θ) locate the amorphous characteristic peak that wider faint diffraction maximum belongs to carbon encapsulating layer.XRD result shows that product is the polyhedron Nano silver grain that carbon parcel has high crystalline.
Fig. 2 (A) is the TEM picture of product shown in Fig. 1, can see, nano particle is polyhedron pattern, has good homogeneity and monodispersity, and this is consistent with the SEM result of Fig. 1.Fig. 2 (B) is the TEM figure of single representative composite particle, and significantly contrast shows that kernel is metal A g, and top layer is carbon.The polygonal length of side is on average about 45nm, and the about 5-10nm of carbon integument thickness has further confirmed the nucleocapsid structure of Ag/C compound particle.The nano-particles size numerical value of being measured by TEM is consistent with the result that SEM characterizes.Meanwhile, the multiple twin structure showing in illustration HRTEM has also shown the polyhedral structure feature of silver-colored kernel nano particle.
Embodiment 2
Reaction time changes 1 hour into.Other conditions are with embodiment 1.
Embodiment 3
Reaction time changes 2 hours into.Other conditions are with embodiment 1.
Embodiment 4
Reaction time changes 4 hours into.Other conditions are with embodiment 1.
Embodiment 5
Reaction time changes 5 hours into.Other conditions are with embodiment 1.
Fig. 3 (A) is that reaction mixture concentration is constant, and reaction is 180.Hydro-thermal reaction 1h at ℃, 2h, 4h, 5h obtains the photo of product aqueous suspension.Can find, the color of product water solution with the increase in reaction time by milky to dark brown alternation gradually.Fig. 3 (B) is corresponding uv-visible absorption spectrum figure, and the absworption peak position of reaction time 1-4h is about 284nm, and obviously skew does not occur in absworption peak position; Reaction time is that the absworption peak position of 5h is 279nm, to shortwave skew, is 5nm.Can infer thus, when reaction proceeds to 5h, the corner angle of particle surface are more outstanding, caused the variation of characteristic absorption peak position.
Embodiment 6
In reaction mixture, PVP content is 0.02M, and other conditions are with embodiment 1.
Embodiment 7
In reaction mixture, PVP content is 0.06M, and other conditions are with embodiment 1.
Embodiment 8
In reaction mixture, PVP content is 0.07M, and other conditions are with embodiment 1.
Embodiment 9
In reaction mixture, PVP content is 0.11M, and other conditions are with embodiment 1.
Embodiment 10
In reaction mixture, PVP content is 0.18M, and other conditions are with embodiment 1.
Embodiment 11
In reaction mixture, PVP content is 0.22M, and other conditions are with embodiment 1.
Fig. 4 is Ag and concentration of glucose when constant in reaction mixture, and PVP concentration is respectively the TEM figure of product prepared by 0.07M (embodiment 8), 0.11M (embodiment 9), next step hydro-thermal method of 0.22M (embodiment 11).Can see, when PVP concentration and 0.04M increase to 0.07M, product is become the package assembly (Fig. 4 A) of 1-dimention nano chain by monodispersed polyhedron Ag/C nano particle (Fig. 1 and Fig. 2).Further increase PVP concentration to 0.11M (embodiment 9), the one dimension banded structure consisting of Ag/C self-assembly generates, and the width of nanobelt reaches 300nm left and right, as shown in Fig. 4 (B).When PVP concentration reaches 0.22M (embodiment 11), Ag/C nano particle is assembled into arranges orderly two-dimensional nano disc structure (Fig. 4 C).Along with the increase of PVP content, the ordering degree of nanobelt can further improve.Therefore, PVP has played key effect to Ag/C core-shell nano in assembling in varying degrees.
Fig. 5 (A) is for obtaining the digital photograph of product aqueous suspension under the different PVP concentration shown in Fig. 4.Can see, solution colour with the increase of PVP concentration by yellow to bottle green alternation, this is the form different (seeing Fig. 4) due to the self assembly of the Ag/C nano particle of PVP initiation, the very near nano-sized silver particle surface phasmon leaning on each other interacts, and this makes different assembling forms produce different collective effects.Fig. 5 (B) is corresponding uv-visible absorption spectrum figure, and absworption peak mainly concentrates on visible region.Along with the increase gradually of PVP concentration, maximum absorption band is respectively in 548nm, 511nm and the appearance of 452nm place, and peak position occurs obviously mobile to short-wave band.
Claims (8)
1. the carbon parcel polyhedron Nano silver grain that the present invention proposes and the preparation method of controlled self assembly thereof, it is characterized in that, glucose is not only as reducing agent but also as carbon source, and polyvinylpyrrolidone (PVP) is not only as the pattern controlling agent of argent growth but also cause compound particle self assembly.The step of preparing single dispersed carbon parcel polyhedron Nano silver grain is: successively 1.0-2.0g glucose, 0.25-0.75gPVP and 0.02-0.04g silver nitrate are dissolved in 100mL deionized water, solid and PVP were dissolved completely in ultrasonic 20 minutes.Get 40mL mixed solution and be transferred in 50mL reactor, at a certain temperature within the scope of 160-200 ℃, isothermal reaction is 6 hours.Reactor is naturally cooled to room temperature, and product is through centrifugal, cleaning repeatedly, finally at vacuum or N
2under protective atmosphere, in 50 ± 10 ℃ of baking ovens, dry.The preparation of Ag/C core-shell nano self-assembled structures: other reaction condition is constant, increases to certain value by PVP concentration, and the product suspension after cleaning is directly added drop-wise to carbon film, silicon chip or other carrier surface.
2. according to the preparation method described in claims 1, it is characterized in that, the mixed solution of glucose, PVP and silver nitrate of take is reaction solution, and preparation method is one step hydro thermal method.Glucose is not only as reducing agent but also as carbon source, and PVP is not only as the pattern controlling agent of argent growth but also cause compound particle self assembly.By changing PVP concentration, can make the ordered arrangement that monodispersed Ag/C core-shell nano or their self assemblies build.
3. according to the preparation method described in claims 1, for solid and PVP are dissolved completely, need ultrasonic 20 minutes.Hydro-thermal reaction liquor capacity is 40mL, and filling rate is 80%, and optimal reaction temperature is 160-200 ℃, and optimum reacting time is 6h.
4. according to the carbon parcel polyhedron method for preparing silver nano-particles described in claims 1, product is through centrifugal, cleaning repeatedly, finally at vacuum or N
2under protective atmosphere, in 50 ± 10 ℃ of baking ovens, dry, be more than 6 hours drying time.
5. according to the preparation method of the carbon parcel polyhedron Nano silver grain described in claims 1, concentration of glucose is 0.056-0.12M, and silver nitrate concentration is 1.18-2.35mM, PVP concentration 0.02-0.06M.
6. according to the preparation method of the carbon parcel polyhedron Nano silver grain described in claims 1, prepared Ag/C core-shell nano is to be about 40-60nm polyhedron Ag nano particle (core) and carbon layer on surface (shell) is formed by the length of side.Kernel silver particles has specific polyhedron pattern, and carbon nano-encapsulated layer is as shell, and the thickness of carbon-coating can regulate and control.
7. according to the preparation method of the controlled self assembly of carbon parcel polyhedron Nano silver grain described in claims 1, PVP concentration in mixed reaction solution is increased to over 0.07M, and the product suspension after cleaning is directly added drop-wise to carbon film, silicon chip or other carrier surface.
8. according to the preparation method of the controlled self assembly of carbon parcel polyhedron Nano silver grain described in claims 1, when PVP concentration reaches 0.07M, polyhedron Ag/C self-assembly becomes 1-dimention nano chain structure; PVP concentration increases to 0.11M, and Ag/C self-assembly forms banded structure, the about 300nm of its width left and right; When PVP concentration further reaches 0.22M, Ag/C nano particle is assembled into arranges orderly two-dimensional circle plate-like nanostructured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310190322.2A CN104174865B (en) | 2013-05-22 | 2013-05-22 | Carbon parcel polyhedron Nano silver grain and the preparation method of controlled self assembly thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310190322.2A CN104174865B (en) | 2013-05-22 | 2013-05-22 | Carbon parcel polyhedron Nano silver grain and the preparation method of controlled self assembly thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104174865A true CN104174865A (en) | 2014-12-03 |
| CN104174865B CN104174865B (en) | 2016-12-28 |
Family
ID=51956368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310190322.2A Active CN104174865B (en) | 2013-05-22 | 2013-05-22 | Carbon parcel polyhedron Nano silver grain and the preparation method of controlled self assembly thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104174865B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105717091A (en) * | 2016-01-29 | 2016-06-29 | 南京理工大学 | Durable and efficient SERS substrate and preparation method thereof |
| CN105798289A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of carbon shell isolated noble metal nanoparticles |
| CN106475022A (en) * | 2015-09-02 | 2017-03-08 | 南京理工大学 | A kind of active antibacterial microballoon and preparation method thereof |
| CN108264016A (en) * | 2017-12-26 | 2018-07-10 | 中国科学院合肥物质科学研究院 | A kind of diverse nano structure composite array and preparation method thereof |
| CN108568519A (en) * | 2018-05-21 | 2018-09-25 | 江汉大学 | A kind of preparation method and application of argentum nano composite material |
| CN109909493A (en) * | 2019-02-25 | 2019-06-21 | 华中科技大学 | A kind of method that electron beam irradiation improves metal material stability |
| CN113698828A (en) * | 2021-08-24 | 2021-11-26 | 南京大学 | Preparation method of anti-corrosion coating material based on carbon-coated silver nanospheres |
| CN113909486A (en) * | 2021-07-23 | 2022-01-11 | 徐州工程学院 | Preparation method of ferroferric oxide loaded carbon-based thin-film gold nano composite particles |
| CN114160806A (en) * | 2021-12-02 | 2022-03-11 | 深圳市华科创智技术有限公司 | Core-shell structure silver nanoparticles prepared by biomass reduction and preparation method thereof |
| CN114713813A (en) * | 2022-03-24 | 2022-07-08 | 厦门大学 | Carbon-coated gold/silver nano-particle for photovoltaic power generation and synthesis method thereof |
| CN115055672A (en) * | 2022-06-15 | 2022-09-16 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396025A (en) * | 2002-07-02 | 2003-02-12 | 华东师范大学 | Process for preparing electric silver/graphite contact material by nano technique |
| JP2004043892A (en) * | 2002-07-11 | 2004-02-12 | Sumitomo Electric Ind Ltd | Fine particle of noble metal and manufacturing method therefor |
| CN1676244A (en) * | 2005-01-17 | 2005-10-05 | 武汉科技大学 | Carbon-clad metal nano particle and its preparing method |
| CN1870186A (en) * | 2004-05-26 | 2006-11-29 | 索尼株式会社 | Group of metal magnetic nanoparticles and method for producing the same |
| CN101506994A (en) * | 2006-06-30 | 2009-08-12 | 三菱麻铁里亚尔株式会社 | Composition for forming electrode in solar cell, method of forming the electrode, and solar cell employing electrode obtained by the formation method |
| CN102672169A (en) * | 2012-06-07 | 2012-09-19 | 北京科技大学 | Method for preparing gold/titanium dioxide core-shell nanoparticle |
-
2013
- 2013-05-22 CN CN201310190322.2A patent/CN104174865B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396025A (en) * | 2002-07-02 | 2003-02-12 | 华东师范大学 | Process for preparing electric silver/graphite contact material by nano technique |
| JP2004043892A (en) * | 2002-07-11 | 2004-02-12 | Sumitomo Electric Ind Ltd | Fine particle of noble metal and manufacturing method therefor |
| CN1870186A (en) * | 2004-05-26 | 2006-11-29 | 索尼株式会社 | Group of metal magnetic nanoparticles and method for producing the same |
| CN1676244A (en) * | 2005-01-17 | 2005-10-05 | 武汉科技大学 | Carbon-clad metal nano particle and its preparing method |
| CN101506994A (en) * | 2006-06-30 | 2009-08-12 | 三菱麻铁里亚尔株式会社 | Composition for forming electrode in solar cell, method of forming the electrode, and solar cell employing electrode obtained by the formation method |
| CN102672169A (en) * | 2012-06-07 | 2012-09-19 | 北京科技大学 | Method for preparing gold/titanium dioxide core-shell nanoparticle |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105798289A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of carbon shell isolated noble metal nanoparticles |
| CN105798289B (en) * | 2014-12-31 | 2019-02-19 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method and applications for the noble metal nano particles that carbon is shell isolated |
| CN106475022A (en) * | 2015-09-02 | 2017-03-08 | 南京理工大学 | A kind of active antibacterial microballoon and preparation method thereof |
| CN105717091B (en) * | 2016-01-29 | 2019-01-18 | 南京理工大学 | Durable and efficient SERS substrate and preparation method thereof |
| CN105717091A (en) * | 2016-01-29 | 2016-06-29 | 南京理工大学 | Durable and efficient SERS substrate and preparation method thereof |
| CN108264016A (en) * | 2017-12-26 | 2018-07-10 | 中国科学院合肥物质科学研究院 | A kind of diverse nano structure composite array and preparation method thereof |
| CN108568519A (en) * | 2018-05-21 | 2018-09-25 | 江汉大学 | A kind of preparation method and application of argentum nano composite material |
| CN109909493A (en) * | 2019-02-25 | 2019-06-21 | 华中科技大学 | A kind of method that electron beam irradiation improves metal material stability |
| CN113909486B (en) * | 2021-07-23 | 2024-02-23 | 徐州工程学院 | Preparation method of ferroferric oxide loaded carbon-based thin film gold nanocomposite particles |
| CN113909486A (en) * | 2021-07-23 | 2022-01-11 | 徐州工程学院 | Preparation method of ferroferric oxide loaded carbon-based thin-film gold nano composite particles |
| CN113698828A (en) * | 2021-08-24 | 2021-11-26 | 南京大学 | Preparation method of anti-corrosion coating material based on carbon-coated silver nanospheres |
| CN114160806A (en) * | 2021-12-02 | 2022-03-11 | 深圳市华科创智技术有限公司 | Core-shell structure silver nanoparticles prepared by biomass reduction and preparation method thereof |
| CN114713813A (en) * | 2022-03-24 | 2022-07-08 | 厦门大学 | Carbon-coated gold/silver nano-particle for photovoltaic power generation and synthesis method thereof |
| CN114713813B (en) * | 2022-03-24 | 2023-03-10 | 厦门大学 | Carbon-coated gold/silver nano particle for photovoltaic power generation and synthesis method thereof |
| CN115055672A (en) * | 2022-06-15 | 2022-09-16 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
| CN115055672B (en) * | 2022-06-15 | 2023-10-24 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104174865B (en) | 2016-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104174865A (en) | Carbon-wrapped polyhedron silver nano-particle and controllable self-assembly preparation method thereof | |
| Wang et al. | Ultraselective acetone-gas sensor based ZnO flowers functionalized by Au nanoparticle loading on certain facet | |
| Thiagarajan et al. | Facile methodology of sol-gel synthesis for metal oxide nanostructures | |
| Yu et al. | Integrating plasmonic Au nanorods with dendritic like α-Bi2O3/Bi2O2CO3 heterostructures for superior visible-light-driven photocatalysis | |
| CN108502918B (en) | Synthesis method of inorganic perovskite nanowire | |
| Sun et al. | Investigating the multiple roles of polyvinylpyrrolidone for a general methodology of oxide encapsulation | |
| Wang et al. | Investigation of optical and photocatalytic properties of bismuth nanospheres prepared by a facile thermolysis method | |
| Habibi et al. | Preparation and characterization of nanocomposite ZnO–Ag thin film containing nano-sized Ag particles: influence of preheating, annealing temperature and silver content on characteristics | |
| CN100560504C (en) | The preparation method of the ZnO nano-powder of sheet porous structural | |
| CN104162681A (en) | Preparation method for silver-zinc oxide nano-composite structure | |
| Tseng et al. | Synthesis of 1D, 2D, and 3D ZnO Polycrystalline Nanostructures Using the Sol‐Gel Method | |
| Chang et al. | Ionic liquid/surfactant-hydrothermal synthesis of dendritic PbS@ CuS core-shell photocatalysts with improved photocatalytic performance | |
| CN109530718B (en) | Preparation method of flower-shaped gold nanowire composite nanoparticles | |
| Selvi et al. | Interfacial effect on the structural and optical properties of pure SnO2 and dual shells (ZnO; SiO2) coated SnO2 core-shell nanospheres for optoelectronic applications | |
| Ouyang et al. | Shape controlled synthesis and optical properties of Cu2O micro-spheres and octahedrons | |
| Tsuji et al. | Toward to branched platinum nanoparticles by polyol reduction: a role of poly (vinylpyrrolidone) molecules | |
| WO2007124445A2 (en) | Organosilane-stabilized nanoparticles of si or ge in an oxide matrix | |
| Ahmad et al. | Superior atomic layer deposition of conformal ZnO shell on spherical SiO2 particles for enhanced photocatalytic activity | |
| CN101362947A (en) | Method for synthesizing near-infrared light argentic sulfide nanocrystalline coated by ligand | |
| CN101613078B (en) | Silicon dioxide/tin oxide composite nanoparticle with nuclear shell structure and preparation method thereof | |
| Chen et al. | Influence of cleaning treatment on structure, optical and electrical properties of Ag/ZnSe microspheres prepared by silver mirror reaction | |
| Shan et al. | The effect of PVP on the formation and optical properties ZnO/Ag nanocomposites | |
| Bangi et al. | Effects of successive additions of two capping ligands on the structural properties of PbO nanoparticles | |
| CN103128305B (en) | Method for preparing Ag/Co magnetic nano composites | |
| CN103073053B (en) | Method for directly synthesizing lead sulfide cube nano particle film |
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 |