CN102140633A - Method for preparing nano silver film with wide plasma-adsorption wave band at constant temperature - Google Patents
Method for preparing nano silver film with wide plasma-adsorption wave band at constant temperature Download PDFInfo
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- CN102140633A CN102140633A CN 201110006987 CN201110006987A CN102140633A CN 102140633 A CN102140633 A CN 102140633A CN 201110006987 CN201110006987 CN 201110006987 CN 201110006987 A CN201110006987 A CN 201110006987A CN 102140633 A CN102140633 A CN 102140633A
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- constant temperature
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- silver film
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- ultrapure water
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 title 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 6
- 229940038773 trisodium citrate Drugs 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 2
- 241000405217 Viola <butterfly> Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical group COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- MECHNRXZTMCUDQ-RKHKHRCZSA-N vitamin D2 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)/C=C/[C@H](C)C(C)C)=C\C=C1\C[C@@H](O)CCC1=C MECHNRXZTMCUDQ-RKHKHRCZSA-N 0.000 description 1
- 235000001892 vitamin D2 Nutrition 0.000 description 1
- 239000011653 vitamin D2 Substances 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
基于恒温制备具有宽等离子吸收波带的纳米银膜方法，本发明首先配置硝酸银固体颗粒、柠檬酸三纳固体颗粒和超纯水而且其质量比为5～6∶1～2∶20的混合液，其中超纯水的电阻率大于18.0MΩ·cm；然后将载玻片放入体积比为1∶1的浓度为28％双氧水和浓度为30％氨水溶液中浸泡11～13小时后放入装有混合中的密闭容器内，在70～90℃恒温条件下静置2～5h即可制得纳米银膜。本发明具有良好的稳定性、可靠性、重复性，保存时效长、容易制备，成本低廉的优点。Based on the method of constant temperature preparation of nano-silver film with wide plasma absorption band, the present invention first configures silver nitrate solid particles, citrate three-nano solid particles and ultrapure water with a mass ratio of 5 to 6: 1 to 2: 20. liquid, in which the resistivity of ultrapure water is greater than 18.0MΩ·cm; then put the glass slide in a volume ratio of 1:1 concentration of 28% hydrogen peroxide and concentration of 30% ammonia solution for 11 to 13 hours and then put The nano-silver film can be prepared by standing still for 2-5 hours at a constant temperature of 70-90°C in a closed container equipped with a mixing medium. The invention has the advantages of good stability, reliability and repeatability, long storage time, easy preparation and low cost.
Description
Technical field
The invention belongs to nanotechnology and use, especially relate to a kind of efficient detection hyperfluorescence material, the nanometer silver membrane preparation method technical field of organic pesticide and biomacromolecule.
Background technology
Surface enhanced Raman scattering (SERS) is as a kind of easy, and high-sensitive spectroscopic techniques has been widely used in fluorescence molecule, hazardous and noxious substances and the biomacromolecule detection.But the problem of running in above-mentioned three classes detect is: at first, how to obtain signal to noise ratio SERS spectrum preferably for hyperfluorescence small molecules and biomacromolecule under the situation of eliminating fluorescence interference; Secondly, be not that all detection molecules are all had good reinforced effects at the bottom of the SERS active group, and often embody molecule or part molecule are had good SERS activity.Three, the repeatability of substrate, stability and persistent problem.At present, realize the active detection of SERS with regard to the comparatively common solution of the problems referred to above for the replacing excitation light source and by the spacing that changes nano particle shape, size and adjusting nano particle.But, if selected excitation light source wavelength is during away from the plasma absorption band of substrate then can reduce surface enhanced Raman scattering spectrographic quality.Therefore, preparing the nanometer silver structure that wide plasma absorbs wavestrip has great significance.With regard to the stability of substrate, at the bottom of the colloidal SERS active group often preservation condition height and time short.The nanometer silverskin is then preserved conveniently, and working lipe is long and activity is constant substantially.
Summary of the invention
The objective of the invention is to overcome the weak point that exists at the bottom of the above-mentioned SERS active group, a kind of preparation method that wide plasma body absorbs wavestrip and hyperfluorescence small molecules, biomacromolecule and poisonous and harmful organic molecule had the silver-colored film substrate of the active nanostructure of good SERS that has is provided.Its preparation principle is the nano-Ag particles that utilizes the chemical reduction legal system of Lee, and the nano-Ag particles of different-grain diameter is adsorbed on densely under the glass surface electrostatic interaction on the substrate and forms the nanometer silverskin.The gap that forms shape and vary in size between nano particle, owing to can produce huge local electric field between intensive nano-Ag particles, so the gap between this nano-Ag particles becomes SERS " focus ".The nanometer silverskin that adopts this method to prepare is owing to the gap length molecule that embodies different size that differs all has SERS activity preferably.
The objective of the invention is to realize by following technical solution.
Preparation has the nanometer silver membrane method that wide plasma absorbs wavestrip based on constant temperature, preparation method of the present invention is: at first disposing Silver Nitrate solid particulate, citrate three sodium solid particulate and ultrapure water and its mass ratio is 5～6: 1～2: 20 mixed solution, and wherein ultrapure resistivity of water is greater than 18.0M Ω cm; The concentration of then slide glass being put into volume ratio and being 1: 1 is that 28% hydrogen peroxide and concentration are that 30% ammonia soln soaks after 11～13 hours and puts into the encloses container that mixing is housed, and leaves standstill 2～5h and can make the nanometer silverskin under 70～90 ℃ of constant temperatures.Encloses container of the present invention is airtight square plastic container, and its optimal volume is 8 * 5 * 3.5cm
3
The nanometer silverskin principal character of the inventive method preparation has: 1. nano surface silver particle size distribution is comparatively extensive, and median size is 91.7 ± 37.8nm; 2. the plasma absorption band that broad is arranged between 400～850nm; 3. under excitation wavelength 785nm near-infrared laser, show good SERS activity.
The invention has the beneficial effects as follows good reinforced effects is all arranged for hyperfluorescence molecule, hazardous and noxious substances and biomacromolecule.Under near-infrared excitation light, all obtained the higher surface enhanced Raman scattering spectrum of quality as Viola crystallina, parathion-methyl and healthy human serum etc.In order to detect the stability of this nanometer silverskin, to same silverskin difference and testing and statistical study by the surface enhanced Raman spectroscopy of the silverskin of the different batches of Same Way preparation.The result shows that the plastisied dispersion of the SERS spectrum peak position basically identical of specimen and spectrum peak area ratio is also very little, illustrates that this film has good repeatability.The present invention detects by the UV, visible light photothermal spectroscopic analyzer, and the UV-vis absorption spectrum shows that the nanometer silverskin has the plasma absorption band of a broad in 400～850nm interval; Find that by scanning electron microscopic observation the median size of nano-Ag particles on this nanometer silverskin surface is at 91.7 ± 37.8nm simultaneously, wherein size distribution is at 18～100nm, nano particle between 100～160nm and the 160～200nm accounts for 64.9%, 28.9% and 6.1% respectively.At room temperature, the nanometer silverskin for preparing is kept in the airtight vacuum container, can makes things convenient for use at any time, and the working lipe of preservation silverskin is more than 240 days.In addition, this nanometer silver membrane prepare condition is simple, with low cost, has popularizing value widely.
Embodiment
Embodiment one
Mixed solution (Silver Nitrate solid particulate, citrate three sodium solid particulate and ultrapure water mass ratio: 5: 1: 20) is respectively charged into airtight square plastic container (8 * 5 * 3.5cm
3) in.Slide glass put into respectively put into the vitriol oil and the heating of hydrogen peroxide (volume ratio 7: 3) mixed solution and stir 20min after dehydrated alcohol, acetone and deionized water for ultrasonic are cleaned 20min.Putting into hydrogen peroxide and ammoniacal liquor (volume ratio 1: 1) after drying in air soaked 12 hours.At last the sheet glass after the above-mentioned processing vertically is close to the wall of container insertion Silver Nitrate is housed, in the square plastic container of the mixed aqueous solution of trisodium citrate and deionized water, again it is left standstill 5h under constant temperature water area condition (70 ℃) and promptly make the nanometer silverskin.The UP water (resistivity 〉=18.0M Ω cm) of wherein testing institute's water and being, Silver Nitrate solid particulate (〉=99.8%), trisodium citrate solid particulate (〉=99%).
Embodiment two
Mixed solution (Silver Nitrate solid particulate, citrate three sodium solid particulate and ultrapure water mass ratio: 5: 1.5: 20) is respectively charged into airtight square plastic container (8 * 5 * 3.5cm
3) in.Slide glass put into respectively put into the vitriol oil and the heating of hydrogen peroxide (volume ratio 7: 3) mixed solution and stir 20min after dehydrated alcohol, acetone and deionized water for ultrasonic are cleaned 20min.Putting into hydrogen peroxide and ammoniacal liquor (volume ratio 1: 1) after drying in air soaked 12 hours.At last the sheet glass after the above-mentioned processing vertically is close to the wall of container insertion Silver Nitrate is housed, in the square plastic container of the mixed aqueous solution of trisodium citrate and deionized water, again it is left standstill 2.5h under constant temperature water area condition (80 ℃) and promptly make the nanometer silverskin.The UP water (resistivity 〉=18.0M Ω cm) of wherein testing institute's water and being, Silver Nitrate solid particulate (〉=99.8%), trisodium citrate solid particulate (〉=99%).
Embodiment three
Mixed solution (Silver Nitrate solid particulate, citrate three sodium solid particulate and ultrapure water mass ratio: 6: 2: 20) is respectively charged into airtight square plastic container (8 * 5 * 3.5cm
3) in.Slide glass put into respectively put into the vitriol oil and the heating of hydrogen peroxide (volume ratio 7: 3) mixed solution and stir 20min after dehydrated alcohol, acetone and deionized water for ultrasonic are cleaned 20min.Putting into hydrogen peroxide and ammoniacal liquor (volume ratio 1: 1) after drying in air soaked 12 hours.At last the sheet glass after the above-mentioned processing vertically is close to the wall of container insertion Silver Nitrate is housed, in the square plastic container of the mixed aqueous solution of trisodium citrate and deionized water, again it is left standstill 2h under constant temperature water area condition (90 ℃) and promptly make the nanometer silverskin.The UP water (resistivity 〉=18.0M Ω cm) of wherein testing institute's water and being, Silver Nitrate solid particulate (〉=99.8%), trisodium citrate solid particulate (〉=99%).
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110006987 CN102140633A (en) | 2011-01-14 | 2011-01-14 | Method for preparing nano silver film with wide plasma-adsorption wave band at constant temperature |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110006987 CN102140633A (en) | 2011-01-14 | 2011-01-14 | Method for preparing nano silver film with wide plasma-adsorption wave band at constant temperature |
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| CN102140633A true CN102140633A (en) | 2011-08-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102313730A (en) * | 2011-08-11 | 2012-01-11 | 江南大学 | Surface enhanced Raman scattering rapid screening method for methamidophos in vegetable |
| CN103308506A (en) * | 2013-05-21 | 2013-09-18 | 楚雄师范学院 | Method for preparing gold nanoparticle island film with near-infrared surface-enhanced Raman scattering substrate through thermostatic water bath |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025202A (en) * | 1995-02-09 | 2000-02-15 | The Penn State Research Foundation | Self-assembled metal colloid monolayers and detection methods therewith |
| CN101294904A (en) * | 2008-06-05 | 2008-10-29 | 华东理工大学 | A kind of preparation method of surface-enhanced Raman scattering substrate |
| CN101676711A (en) * | 2008-09-21 | 2010-03-24 | 西北师范大学 | Substrate with surface-enhanced Raman scattering activity and preparation method thereof |
-
2011
- 2011-01-14 CN CN 201110006987 patent/CN102140633A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025202A (en) * | 1995-02-09 | 2000-02-15 | The Penn State Research Foundation | Self-assembled metal colloid monolayers and detection methods therewith |
| CN101294904A (en) * | 2008-06-05 | 2008-10-29 | 华东理工大学 | A kind of preparation method of surface-enhanced Raman scattering substrate |
| CN101676711A (en) * | 2008-09-21 | 2010-03-24 | 西北师范大学 | Substrate with surface-enhanced Raman scattering activity and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《中国激光》 20091031 刘仁明，等 "二维纳米结构银膜表面增强拉曼散射基底的制备与研究" 2658 1-2 第36卷, 第10期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102313730A (en) * | 2011-08-11 | 2012-01-11 | 江南大学 | Surface enhanced Raman scattering rapid screening method for methamidophos in vegetable |
| CN103308506A (en) * | 2013-05-21 | 2013-09-18 | 楚雄师范学院 | Method for preparing gold nanoparticle island film with near-infrared surface-enhanced Raman scattering substrate through thermostatic water bath |
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Application publication date: 20110803 |