CN105088231B - A kind of simple method for preparing of surface enhanced Raman scattering substrate - Google Patents
A kind of simple method for preparing of surface enhanced Raman scattering substrate Download PDFInfo
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- CN105088231B CN105088231B CN201510527905.9A CN201510527905A CN105088231B CN 105088231 B CN105088231 B CN 105088231B CN 201510527905 A CN201510527905 A CN 201510527905A CN 105088231 B CN105088231 B CN 105088231B
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- peroxide
- enhanced raman
- raman scattering
- free radical
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Abstract
The present invention relates to a kind of simple method for preparing of surface enhanced Raman scattering substrate, it, which is related to (1) and prepares a kind of liquid reagent containing peroxide, prepares free radical generating agent；(2) surface mechanical polishing processing is carried out to metal foil film；(3) metal foil film by step (2) processing is placed in the free radical generating agent of step (1) configuration；(4) surface enhanced Raman scattering substrate with certain surface roughness and particular surface chemical species is formed after the processing such as circulation immersion, illumination or ultrasound.Preparation that can be simple, quick, controllable using the method for the invention has the repeatable base material utilized of stronger surface-enhanced raman scattering enhancing effect, base material is avoided that the cross pollution in detection process, and it is easy to carry and preserves, base material, up to 3 μ g/L, and can realize the quantitative analysis to inorganic arsenic ion to the Monitoring lower-cut of inorganic arsenic ion in water.
Description
Technical field
The present invention relates to the fields such as nano material chemistry, analytical chemistry, life chemistry, and in particular to a kind of surface enhanced is drawn
Graceful scattering substrate and preparation method thereof.
Background technology
With developing rapidly for the fields such as biology, medical science, environment, the even monomolecular detection of extremely low concentration compound is needed
Ask and increasingly highlight.SERS (SERS) because of the features such as it is easy, quick, cheap, precision is good, response is high, into
To study the focus with industry development.Indiana, USA in 1997 founds university Nie etc. and reported based on Ag nano particles
Unimolecule surface-enhanced Raman detection technique (Science 1997,275,1102-1106).Northwestern Univ USA in 2002
Mirkin groups report the cancer markers such as DNA, RNA detection technique in the active somatic cell based on SERS (Science 2002,
297,1536-1540)。
The patent of invention that Intel rate first to file in 2003 is prepared on commercial surface enhancing Raman substrate.
Its core is to prepare multicrystalline silicon substrate by etch, there is provided surface roughness, and have being deposited thereon by cathodic electromigration method
There is the metallic (CN03813551, PCT/US2003/015277) of Raman activity.Shanghai ray machine institute of Chinese Academy of Sciences Zhou Zenghui etc.
Surface etch is carried out to the silica glass of doped precious metal using pulsed laser beam, then obtained through liquid-phase reduction in situ with homogeneous
The noble metal overlay film SERS substrates (CN200710042776.X) of roughness.Hefei Institute Of Intelligent Machines Chinese Academy Of Sciences Zhao likes force etc.
Perfect similar strategy, it is proposed that the silicon base controllable preparation based on ultraviolet photolithographic technology or plasma dry etch technology
Strategy, and using the tree metal battle array of nanoassemble and the hydrothermal technique orderly periodic structure of deposition three-dimensional on a silicon substrate
Arrange (CN200810100562.8).Physics and chemistry institute of Chinese Academy of Sciences Shi Wensheng etc. then devises silicon nanowire array and netted silver nanoparticle film
Compound structure (CN200910079487.6).Harbin Institute of Technology's Xu's equality has developed macromolecule-nanogold-Nano Silver three
Tie up the preparation method (200910072176.7) of compound SERS substrates.Capital Normal University Ge Yue etc. proposes a kind of multilayer and answered
Close the SERS underlying structures (CN201310286834.9) of nanofiber.These preparation technologies combine complicated length of schooling of coming to the surface more
Standby technology or technical process, strategy being prepared using laser ablation or layering plated film etc., preparation substrate precision is high, controllability is good, but
It is complex process, control requirement height, it is difficult to realize prepared by large-scale low-cost.
Theoretical research shows, with nano-particle enhancing effects such as certain roughness or one end sharp Ag, Au, Cu, Pd
Most preferably, multiple nano particle ordered arrangements can cause effective superposition of the electromagnetic field in local space, so as to form stronger local
Focus, cause Raman enhancer further raising (Appl.Phys.Rev.2003,82,3095-3097；
ChemPhysChem 2003,4,1001-1005；J.Am.Chem.Soc.2008,130,10472–10473；
J.Am.Chem.Soc.2014,136,10299-10307).The thus SERS bases using nano-metal particle controllable preparation as core
It is also relatively conventional that bottom, which prepares thinking,.Southeast China University king in 2007 writes member etc. and describes one kind based on liquid phase solvent chemical reaction
Ultra paramagnetic particle preparation method, gained particle is tested available for SERS, but but does not propose how to be assembled into business
Device (CN200710024583.1).Univ California-Berkeley Yang in 2008 etc. is reported based on controllable self assembly
Nano-grain array be used for trace inorganic heavy metal ion Examined effect, except rough surface is outside one's consideration grain structure also in enhancing
The factor is closely related (Angew.Chieme.Int.Ed.2008,47,6456-6460).SERS relies on the polarization of local electromagnetic field
Enhancing, causes the Raman signal of extremely low concentration molecule to be detected to strengthen.Tanaka group seminar of Xiamen University is prepared for having within 2010
Have the nano-particle of shell isolation structure, can be achieved to organic molecule the inspection of unimolecule high sensitivity (Nature 2010,
464,392-395；CN201010044867.9).Shanghai Normal University's poplar seapeak etc. is proposed with coated in indium oxide tin glass
On phytic acid micelle be branch support group SERS preparation technologies.It can realize that SERS lives in the Ji Zhishang monolayer organizations nano gold sol
The controllable preparation (CN201010247520.4) of property substrate.Hefei material research institute of Chinese Academy of Sciences bambusa textile woods etc. proposes in-situ deposition
In the preparation method (CN200910184976.8) of the gold nano stick array of golden film.Changchun Institute of Applied Chemistry of Chinese Academy of Sciences Sun Yu waits quietly proposing
In the uv induction Nano Silver growth in situ strategy of metallic nickel foam surface, high sensitivity, high reappearance SERS inspections are realized
Survey.Chinese Academy of Sciences's Suzhou research in nanotechnology Wang Xin and Zou Nan then propose with noble metal nano rod adsorb Raman signal molecule, then
" trans " SERS inspection policies of silica or polyelectrolyte nano particle of the assembling with the sandwich Rotating fields of noble metal
(CN201210050801.X).Liu Xiong armies of University of Science ＆ Technology, Beijing use Ag-Mg-Ca amorphous alloy thins as base material, with electrolysis
Erosion removal Mg, Ca element therein prepares the nanoporous Argent grain with excellent SERS activity
(CN201310187669.1).Hefei material science research institute of nearest Chinese Academy of Sciences Tanghai guest etc. discloses a kind of compound half of gold and silver
The preparation method of spherical nanoparticle array, method be related to substrate surface process, expanding treatment, layering plated film, selective etch,
The multi-step process such as ion sputtering (CN201310415653.1).It is molten that pattern and composition regulation and control to metallic often relate to liquid phase
Agent chemistry, surface chemistry, control accuracy is high, and need to additionally carry out self assembly, controllable deposition or the Film forming operations to particle, technique
Step is complicated, requires high to state modulator.
Thus this area, which is needed badly, proposes a kind of convenience, easy and be suitable for the technology prepared on a large scale.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of simple method for preparing of surface enhanced Raman scattering substrate,
Its core is to prepare the free radical generating agent with stabilized radical generating ability using liquid phase peroxide, by commercial metal paper tinsel
Film is immersed, and is increased by lasting free-radical chemistry etching preparation surface roughness and surface chemistry species are controllable with surface
The SERS substrates of strong Raman scattering active.
The present invention is achieved by the following technical solutions：
A kind of simple method for preparing of surface enhanced Raman scattering substrate, it is characterised in that methods described includes following step
Suddenly：
(1) prepare a kind of liquid reagent containing peroxide and prepare free radical generating agent：
Peroxide, peroxide decomposition catalyst, pH adjusting agent, ionic strength adjustor is added in a solvent to be made certainly
By base propellant, wherein peroxide, the content of peroxide decomposition catalyst is respectively the 0.01wt% of free radical generating agent
~100wt% and 0.00005wt%~10wt%；PH adjusting agent, 0 that the content of ionic strength adjustor is free radical generating agent
~15wt%；
Wherein, described solvent be selected from water, methanol, ethanol, acetonitrile, n-hexane, normal octane, benzene,toluene,xylene,
The mixture of one or more of compositions in two sulphur sulfoxides,
Described peroxide is selected from hydrogen peroxide (H2O2), TBHP (TBHP), tertiary amyl hydrogen peroxide
(TAHP), di-tert-butyl hydrogen peroxide (DTBHP), cyclohexyl hydroperoxide (CHHP), isopropyl benzene hydroperoxide (CHP), two different
Cumene hydroperoxide (DBHP), p-menthane hydroperoxide (PMHP), cumyl peroxide (DCP), azodiisobutyronitrile (AIBN),
One or more in cyclohexanone peroxide (CYP), ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, Potassium peroxysulfate form mixed
Compound,
Described peroxide decomposition catalyst is selected from Fe2+、Fe3+、Cu+、Cu2+、Co2+、Co3+、Cr3+、Cr6+、Mn2+、Mn4 +、Ag+In one or more of compositions mixtures,
Described pH adjusting agent is selected from HCl, HNO3、H2SO4、HClO4、H2C2O4、NaOH、KOH、NH4One kind or several in OH
The mixture of kind composition,
Described ionic strength adjustor is selected from NaCl, NaNO3、Na2SO4、NaClO4、Na2C2O4、KCl、KNO3、K2SO4、
KClO4、K2C2O4、NH4Cl、NH4NO3、(NH4)2SO4、NH4ClO4、(NH4)2C2O4In one or more of compositions mixtures；
(2) metal foil film is surface-treated；
Wherein, metal foil film contains the alloy of one or more of compositions in Ag, Au, Pd, Pt, Cu, Ni, Cr；
(3) metal foil film by step (2) processing is placed in the free radical generating agent of step (1) configuration：
Metal foil film is placed in free radical generating agent, for temperature range at 5~180 DEG C, pressure is normal pressure to 30bar, is put down
The atmosphere that weighs is air or pure oxygen；
(4) under fill-in light photograph or assisting ultrasonic, surface enhanced Raman scattering substrate is formed through continuous or circulation immersion.
In step 4)：
Described continuous dipping or the soak time of circulation immersion are 1~3600s, and cycle-index is 1~100 time.
Described illumination is：170~1240nm of illumination wavelength, 1~3000W of light source power, 1~3600s of irradiation time.
The Ultrasound Instrument power that described supersound process uses is 1~2500W, 1~3600s of ultrasonic time.
The surface enhanced Raman substrate surface roughness of described preparation in 50~200nm, can excitation wavelength be 325~
1100nm。
Brief description of the drawings
Accompanying drawing 1.SERS substrate preparation flow schematic diagrames
The surface enhanced Raman spectrums of accompanying drawing 2.10mg/L melamines
The surface enhanced Raman spectrums of accompanying drawing 3.0.2uM arsenic acid radical ions
The afm image of 4. embodiment of accompanying drawing, 3 made SERS substrates
The surface enhanced Raman spectrums of accompanying drawing 5.3~300ppb arsenite ions
The relation of the arsenic ion concentration of accompanying drawing 6. and scattering peak intensity
Embodiment
According to following embodiments, the present invention may be better understood, however, as it will be easily appreciated by one skilled in the art that real
Apply the content described by example and be merely to illustrate the present invention, without limitation on protection of the invention described in detail in claims
Scope.
Embodiment 1：
Prepare (the CAS of Potassium peroxysulfate containing 14mM:7727-21-1, be purchased from Acros) the aqueous solution, add 2mM Co
(NO3)2, add NaOH to adjust pH value to 12.Add the commercial silver foil (CAS ground through 800 mesh sand paper 15 minutes:7440-22-4, purchase
In Alfa Aesar), under the irradiation of ultraviolet light (Beijing NewBide, 250W mercury lamps), 30min is soaked, takes out, spends ultra-pure water
Clean, air blow drying is standby (schematic diagram is as shown in Figure 1).
Melamine (the CAS for being 10mg/L with ultra-pure water compound concentration:108-78-1, purity are more than>98%, it is purchased from ladder
Uncommon love) solution, the solution is added dropwise to substrate, is placed under Raman spectrum (Horiba LabRAM), light collection is excited using 514nm
The Raman spectrum such as Fig. 2 of surface plasma body resonant vibration enhancing.
Embodiment 2：
In 14mM TBHPs (CAS:75-91-2, be purchased from Acros) the aqueous solution, add 2mM CuNO3, add
Ammoniacal liquor adjusts pH value to 10.Add the commercial silver foil (CAS ground through 1200 mesh sand paper 30 minutes:7440-22-4, it is purchased from Alfa
Aesar), 30s is soaked under ultrasonication, paper tinsel film taking-up is cleaned with ultra-pure water, air blow drying is standby.Repeat solution prepare and
Immersion, totally 10 times.
Natrium arsenicum (the CAS for being 0.2uM with ultra-pure water compound concentration:13510-46-8, chemistry is pure, is purchased from Chinese medicines group
Learn reagent Co., Ltd) solution, the solution substrate is added dropwise, is placed under Raman spectrum (Horiba LabRAM), using 514nm
The Raman spectrum such as Fig. 3 of exciting light collection surface plasma resonance enhancing.
Embodiment 3：
In 200mg/L hydrogen peroxide (CAS:7722-84-1, purity>30wt%, it is limited to be purchased from Chinese medicines group chemical reagent
Company) the aqueous solution, add 2mM Fe (NO3)2, add HNO3Adjust pH value to<1.0.Add commercial silver foil (CAS:7440-22-
4, it is purchased from Alfa Aesar), 30s is soaked under ultrasonication, paper tinsel film taking-up is cleaned with ultra-pure water, air blow drying is standby.Weight
Compounding makes fresh free radical generation solution and prepares and soak, totally 35 times.The AFM of gained Ag-SERS substrates
(AFM) shown in photo below figure (Fig. 4).
With ultra-pure water respectively compound concentration be 3ppb, 30ppb, 60ppb, 300ppb natrium arsenicum (CAS:7784-46-5,
Chemistry is pure, is purchased from Chemical Reagent Co., Ltd., Sinopharm Group) solution, solution 10uL is added dropwise to substrate surface, is placed in Raman light
Compose under (Horiba LabRAM), using 633nm exciting lights (outlet intensity 20mW), 50 times of telephoto lenses, confocal pinhole size
10um.The Raman spectrum below figures (Fig. 5) of collection surface plasma resonance enhancing.According to 790cm-1As-OH is flexible at wave number shakes
The intensity and solution concentration at dynamic peak carry out linear regression, and the invariance curve that can obtain scattering peak and solution concentration is as shown in Figure 6.Should
The linear regression coeffficient of curve can be established to arsenic ion pH adjusting agent, ionic strength adjustor qualitative analysis up to 0.9996
Method.
Claims (5)
1. a kind of simple method for preparing of surface enhanced Raman scattering substrate, it is characterised in that the described method comprises the following steps：
(1) prepare a kind of liquid reagent containing peroxide and prepare free radical generating agent：
Peroxide, peroxide decomposition catalyst, pH adjusting agent, ionic strength adjustor are added in a solvent, and free radical is made
Propellant, wherein peroxide, the content of peroxide decomposition catalyst be respectively free radical generating agent 0.01wt%~
100wt% and 0.00005wt%~10wt%；PH adjusting agent, the content of ionic strength adjustor for free radical generating agent 0~
15wt%；
Wherein, described solvent is selected from water, methanol, ethanol, acetonitrile, n-hexane, normal octane, benzene,toluene,xylene, two sulphur
The mixture of one or more of compositions in sulfoxide,
Described peroxide is selected from hydrogen peroxide, TBHP, tertiary amyl hydrogen peroxide, di-tert-butyl peroxide
Hydrogen, cyclohexyl hydroperoxide, isopropyl benzene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, peroxidating diisopropyl
One kind in benzene, azodiisobutyronitrile, cyclohexanone peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, Potassium peroxysulfate or
The mixture of several compositions,
Described peroxide decomposition catalyst is selected from Fe2+、Fe3+、Cu+、Cu2+、Co2+、Co3+、Cr3+、Cr6+、Mn2+、Mn4+、Ag+
In one or more of compositions mixtures,
Described pH adjusting agent is selected from HCl, HNO3、H2SO4、HClO4、H2C2O4、NaOH、KOH、NH4One or more of groups in OH
Into mixture,
Described ionic strength adjustor is selected from NaCl, NaNO3、Na2SO4、NaClO4、Na2C2O4、KCl、KNO3、K2SO4、
KClO4、K2C2O4、NH4Cl、NH4NO3、(NH4)2SO4、NH4ClO4、(NH4)2C2O4In one or more of compositions mixtures；
(2) metal foil film is surface-treated；
Wherein, metal foil film contains the alloy of one or more of compositions in Ag, Au, Pd, Pt, Cu, Ni, Cr；
(3) metal foil film by step (2) processing is placed in the free radical generating agent of step (1) preparation：
Metal foil film is placed in free radical generating agent, for temperature range at 5~180 DEG C, pressure is normal pressure to 30bar, Balance Air
Atmosphere is air or pure oxygen；
(4) in the case where fill-in light is shone or assisting ultrasonic is handled, surface enhanced Raman scattering substrate is formed through continuous or circulation immersion.
2. the simple method for preparing of surface enhanced Raman scattering substrate as claimed in claim 1, it is characterised in that described company
The soak time of continuous immersion or circulation immersion is 1~3600s, and cycle-index is 1~100 time.
3. the simple method for preparing of surface enhanced Raman scattering substrate as claimed in claim 1, it is characterised in that described is auxiliary
The illumination is helped to be：170~1240nm of illumination wavelength, 1~3000W of light source power, 1~3600s of irradiation time.
4. the simple method for preparing of surface enhanced Raman scattering substrate as claimed in claim 1, it is characterised in that described is auxiliary
Help and be ultrasonically treated the Ultrasound Instrument power used as 1~2500W, 1~3600s of ultrasonic time.
5. the simple method for preparing of surface enhanced Raman scattering substrate as claimed in claim 1, it is characterised in that described table
The roughness on face enhancing Raman substrate surface is 50~200nm, can excitation wavelength be 325~1100nm.
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| CN105728945A (en) * | 2016-03-07 | 2016-07-06 | 北京理工大学 | Method for preparing surface-enhanced Raman substrate through femtosecond laser double pulses with one-step method |
| CN109440156A (en) * | 2018-11-27 | 2019-03-08 | 广州三孚新材料科技股份有限公司 | Chromium-free roughening solution for ABS (acrylonitrile butadiene styrene) plastics and using method thereof |
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| CN101089615A (en) * | 2007-06-22 | 2007-12-19 | 东南大学 | Preparation method of magnetic surface strength laman scattering mark |
| CN101450798A (en) * | 2007-11-29 | 2009-06-10 | 索尼株式会社 | Method for processing carbon nanotube, carbon nanotube and carbon nanotube element |
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| CN101089615A (en) * | 2007-06-22 | 2007-12-19 | 东南大学 | Preparation method of magnetic surface strength laman scattering mark |
| CN101450798A (en) * | 2007-11-29 | 2009-06-10 | 索尼株式会社 | Method for processing carbon nanotube, carbon nanotube and carbon nanotube element |
Non-Patent Citations (3)
| Title |
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| "Nanoparticle-Functionalized Porous Polymer Monolith Detection Elements for Surface-Enhanced Raman Scattering";Jikun Liu et al.;《Analytical Chemistry》;20110315;第83卷(第6期);2119-2114 * |
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