CN107436301A - A kind of 2,6 chlorophenesic acid trace sensors based on surface enhanced Raman technique and its production and use - Google Patents
A kind of 2,6 chlorophenesic acid trace sensors based on surface enhanced Raman technique and its production and use Download PDFInfo
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Abstract
The invention belongs to functional material preparing technical field, there is provided a kind of 2,6 chlorophenesic acid trace sensors based on surface enhanced Raman technique and its production and use.Step is as follows：The preparation of step 1, Ag balls；The preparation of step 2, Ag/CdTe；The preparation of step 3, Ag/CdTe/APTES；The preparation of step 4, Ag/CdTe/MIPs sensors.The present invention is combined Raman detection technology with molecular imprinting technology so that product has the selectivity of sensitive detection property and height；In the present invention, Ag/CdTe substrates are combined with molecular imprinting technology, wherein CdTe is outstanding semiconductor, possesses the optical characteristics of uniqueness, can be applied to the detection to 2,6 chlorophenesic acids.The SERS materials of high-sensitivity metal semiconductor heterostructure have stronger, more sensitive surface-enhanced Raman signals.In the present invention, special structure causes invention product to become more competitive sensor, and has widened the application of SERS.
Description
Technical field
The invention belongs to functional material preparing technical field, is related to a kind of high-performance compound of detection 2,6- chlorophenesic acids
SERS trace sensor and preparation method and purposes.
Background technology
In recent years, serious threat has arrived our living environment for organic contamination.Organic pollution refers to carbon aquation
Natural organic substance existing for the forms such as compound, protein, amino acid and fat and some other are biodegradable artificial
The pollutant of synthesis of organic substance matter composition.With economic fast development, chemical industry generates substantial amounts of poisonous chemical contamination
Emission, chlorophenol are one of them.This kind of compound has low biological degradability, high toxicity and persistence, can have a strong impact on life
Thing denitrification process, or even serious influence can be caused to the internal system of people.Therefore, the detection of parachlorphenol class compound is ten
Divide important.
At present, the determination method of parachlorphenol includes ultraviolet spectrophotometry, high performance liquid chromatography, gas chromatography
With electrochemical method etc..However, these conventional methods have many shortcomings, such as:Operation sequence is complicated, and testing cost is higher, and
Skilled skill is needed mostly.Therefore, we, which are badly in need of exploring a kind of effective method, comes to micro in surroundings
Chlorophenol carries out quick, sensitive detection.
In recent years, SERS (SERS) technology is because with cost is low, preparation technology is simple and operation is simple
Just premium properties is waited, is received much concern in analysis detection field.SERS can be detected to object, identified and quantified.Typically
For, SERS scattering enhancing factor is divided into two aspects:Electromagnetism (EM) mechanism and electric charge transfer (CT) mechanism.Work as target molecule
Absorption stromal surface or it is close when, Raman signal will be greatly enlarged.When purchasing SERS matrix, scientific research personnel is mostly by mesh
Light concentrates on noble metal nano particles (such as gold, silver), because noble metal nano particles can provide excellent optics, electro
Matter, and have strong characteristic absorption in visibility region.Especially as the silver of noble metal, more stable SERS can be showed
Detection performance.It is higher in view of traditional SERS matrix cost, and in order to further promote and expand SERS application, we
Need to develop lower-cost, reusable, the controllable SERS matrix of appearance structure.Recently, high-sensitivity metal-half
Conductor heterojunction structure matrix attracts attention, and this is a kind of compound SERS bases for being combined noble metal nanometer material with semiconductor
Material.For example, Ko is prepared for three-dimensional aluminum oxide film load Au nano particles (Au NPs) with partner, its SERS is strengthened
Property is studied, it was demonstrated that it can detect TNT and HMTD on a molecular scale.Although SERS technologies detect in microchemistry
Aspect has developed rapidly, but current SERS researchs are principally dedicated to the modification of backing material, ignore traditional matrices material
The shortcomings that:Lack specific selectivity to target molecule.Therefore, a kind of method is explored as early as possible to promote traditional SERS substrates material
The selectivity of material, it will be enlarged by the application of SERS detections.
The content of the invention
In order to improve the selectivity of traditional SERS matrix, the present invention examines molecular imprinting technology (MIT) and traditional SERS
Survey technology is combined.It is well known that multiple action site can be formed when template molecule contacts with polymer monomer in MIT, pass through
Polymerization process memorizes this action site, and after template molecule removes, being formed in polymer can be with template point
The hole with multiple action point that subspace configuration matches, such hole will have specific selectivity to template molecule.
Traditional SERS technologies can be improved to the utmost and lack the shortcomings that selective.
The present invention is combined SERS technologies with surface molecule print technology, using Ag/CdTe as SERS matrix, 2,6- dichloros
Phenol (2,6-DCP) is template molecule, and it is compound to be prepared for a kind of high-performance by atom transfer radical polymerisation technique (ATRP)
Type SERS traces sensor (Ag/CdTe/MIPs).Meanwhile to its specific adsorption ability, detection sensitivity, selective enumeration method
Studied.Finally our performances to 2,6-DCP of sensor detection have carried out actual sample detection, find the compound SERS
Trace sensor has shown outstanding detection performance in terms of detection 2,6-DCP pollutants.
The technical solution adopted by the present invention is as follows:
A kind of preparation method of 2, the 6- chlorophenesic acid trace sensors based on surface enhanced Raman technique, step are as follows:
The preparation of step 1, Ag nanospheres
By AgNO3Solution, mandelic acid solution are dispersed in water, and several minutes of ultrasound, are stirred under condition of ice bath several minutes,
VC solution is rapidly added, continues to stir, after reacting 15min, the product of synthesis is centrifuged, drying is washed, obtains Ag nanometers
Ball；It is stand-by；
The preparation of step 2, Ag/CdTe
By silver nanoparticle ball made from step 1, CdCl2, TGA is distributed in water, and pH value is adjusted to 10-12 with NaOH solution,
Obtain mixed solution A；
Meanwhile by Te powder, NaBH4It is mixed in a small amount of water in centrifuge tube, sealing ultrasound, excessive gas is excluded with syringe needle,
Until solution colour becomes colorless；Presoma is made；
Presoma is injected into mixed solution A rapidly, maintaining nitrogen purge, temperature is increased to 90-110 DEG C, back flow reaction
After 23-25h, the product of synthesis is centrifuged, drying is washed, obtains Ag/CdTe；It is stand-by；
The preparation of step 3, Ag/CdTe/APTES
Ag/CdTe made from step 2 is dispersed in toluene solution, adds APTES, temperature is increased to 80-100 DEG C of reaction
23-25h, after completion of the reaction, the product of synthesis is centrifuged, washed, vacuum drying, obtains Ag/CdTe/APTES；It is stand-by；
The preparation of step 4, Ag/CdTe/MIPs sensors
Product Ag/CdTe/APTES made from step 3 is distributed in the mixed solution of TEA and tetrahydrofuran (THF), led to
N2After several minutes, THF and 2-BIB mixed solutions is added dropwise, whole process leads to nitrogen and ice bath, continues logical nitrogen number after completion of dropwise addition
Minute, seal, after ice bath 1.0-3.0h, continue to react at room temperature 23-25h；Reaction separates synthetic product centrifuge washing after terminating,
It is dried for standby, is designated as product A；
Product A and MAA, AM and EGDMA are distributed in acetonitrile, after room temperature is slowly stirred 2.0-4.0h, leads to nitrogen, adds
The CuBr and bipyridyl cleaned, whole process persistently lead to nitrogen, seal, and then temperature is increased to 60-80 DEG C, react 23-25h,
Ag/CdTe/MIPs sensors are obtained, are then washed repeatedly with acetonitrile, second alcohol and water, are centrifuged, drying.
In step 1, the AgNO3Solution, mandelic acid solution, the amount ratio of water and VC solution are 1.0mL：40-60 μ
L：5.0-15mL：0.5-1.5mL；
The AgNO3The concentration of solution is 1.0mol L-1, the concentration of mandelic acid solution is 0.25mol L-1, VC solution
Concentration be 1.0mol L-1, temperature is subzero.
In step 2, the silver nanoparticle ball, CdCl2, TGA, Te powder and NaBH4Usage ratio be 50mg：300-400 mg：
300-400mg：50-55mg：70-90mg；
The concentration of the NaOH solution is 1.0molL-1。
In step 3, the Ag/CdTe, toluene and APTES amount ratio are 500mg:45-55mL:1.0-2.0mL.
In step 4, when preparing product A,
The amount ratio of each material is in Ag/CdTe/APTES, TEA and THF mixed solution：Ag/CdTe/APTES, TEA and
THF amount ratios are 500mg：2.0-4.0mL：20-40mL；
The amount ratio of each material is in Ag/CdTe/APTES, THF and 2-BIB mixed solution：Ag/CdTe/APTES、 THF
It is 500mg with 2-BIB amount ratios：10-20mL：2.0-4.0mL；
In step 4, when preparing Ag/CdTe/MIPs sensors, product A, MAA, AM, EGDMA, acetonitrile, CuBr, bipyridyl
Amount ratio be 500mg：2.0-4.0mmol：3.0-5.0mmol：5.0-15mmol：70-90mL：0.3-0.4 mmol：2.2-
2.3mmol。
Described washing, it is that ethanol washs 3 times in step 1-4.
Described Ag/CdTe sensors are used for selective absorption 2,6-DCP.
The preparation method of non-imprinted polymer corresponding to the present invention as above, but is not added with 2,6-DCP similar to synthetic method, product
It is designated as Ag/CdTe/NIPs.
The technological merit of the present invention:
The present invention is combined Raman detection technology with molecular imprinting technology so that product has sensitive detection property and height
Selectivity；In the present invention, Ag/CdTe substrates being combined with molecular imprinting technology, wherein CdTe is outstanding semiconductor,
Possess the optical characteristics of uniqueness.The SERS materials of high-sensitivity metal-semiconductor heterostructure have stronger, more sensitive table
Face strengthens Raman signal.In the present invention, special structure causes invention product to become more competitive sensor, and
And the application of SERS is widened.
Brief description of the drawings
Fig. 1:Ag nano-particles (a), Ag/CdTe composites (b), Ag/CdTe composites scanning mapping figures (c),
Ag/CdTe/MIPs (d) scanning electron microscope (SEM) photograph (upper right corner figure is Ag/CdTe/MIPs transmission electron microscope pictures in d figures) (scanning electron microscope (SEM) photograph
1 μm of transmission electron microscope picture size 50nm of size)；
Fig. 2:Ag/CdTe/MIPs (a) and Ag/CdTe/NIPs (b) infrared spectrogram；
Fig. 3:Ag nano-particles (a), Ag/CdTe composites (b), Ag/CdTe/MIPs (c) and Ag/CdTe/NIPs (d)
X ray diffraction spectrums；
Fig. 4:Ag/CdTe/MIPs and Ag/CdTe/NIPs shows figure to the absorption property of different target thing；
Fig. 5:Ag/CdTe/MIPs is for the various concentrations 2,6-DCP Raman spectrograms (a) detected and 1596cm-1When,
Ag/CdTe/MIPs raman scattering intensity and the detection linear relationship chart (b) of 2,6-DCP change in concentration；
Fig. 6:Ag/CdTe/MIPs is being 10 to concentration-5mol L-12,6-DCP (a), 2,5-DCP (b) and hydroquinones
(c) selective enumeration method figure.
Embodiment
With reference to Figure of description and specific implementation example, the present invention will be further described.
Embodiment 1:
(1) synthesis of Ag balls
In 25mL flasks, by 1.0mL AgNO3Solution, 40 μ L mandelic acid solution are dispersed in 5.0mL water, ultrasonic number
Minute, stirred under condition of ice bath several minutes, be rapidly added 0.5mL VC, continue to stir, after reacting 15min, by the production of synthesis
Thing centrifuges, and washs repeatedly for several times, and vacuum drying is stand-by.
(2) Ag/CdTe synthesis
In 150mL flasks, by 50mgAg balls, 300mgCdCl2, 300mg TGA are distributed in 100mL water, are used
1.0mol L-1NaOH adjusts pH value to 10, adds presoma:By 50mg Te powder, 70mg NaBH4Centrifugation is mixed in a small amount of water
Guan Zhong, sealing ultrasound, excessive gas is excluded with syringe needle, until solution colour becomes colorless.Presoma is injected into rapidly above-mentioned
In solution, maintaining nitrogen purge, temperature is increased to 90-110 DEG C, back flow reaction 23-25h, then, by the product centrifugation point of synthesis
From, wash for several times repeatedly, then be dried in vacuo, it is stand-by.
(3) Ag/CdTe/APTES synthesis
In 150mL single-necked flasks, 500mg Ag/CdTe are dispersed in 45mL toluene solutions, add 1.0mL
APTES, temperature are increased to 90 DEG C of reaction 24h.Then, the product of synthesis is centrifuged, washed repeatedly with ethanol three times, vacuum
Dried for standby.
(4) preparation of Ag/CdTe/MIPs molecularly imprinted polymers
In 150mL single-necked flasks, 500mg Ag/CdTe/APTES are distributed to the mixed of 2.0mL TEA and 20mL THF
Close in solution, lead to nitrogen, 10mL THF and 2.0mL 2-BIB mixed solution is added dropwise, 2.0h is reacted under condition of ice bath, then
24h is reacted at ambient temperature.Synthetic product is centrifuged, ethanol washs three times, and vacuum drying is stand-by.
In 150mL single-necked flasks, above-mentioned product is distributed to 2.0mmol MAA, 3.0mmol AM, 5.0mmol
In EGDMA and 70mL acetonitriles, after room temperature is slowly stirred 3.0h, lead to nitrogen 15min, add cleaning the mmol of CuBr 0.3 and
2.2mmol bipyridyls, whole process persistently lead to nitrogen, sealing.Temperature is increased to 70 DEG C of reaction 24h, obtains Ag/CdTe/MIPs biographies
Sensor, then washed, centrifuged repeatedly with acetonitrile, second alcohol and water, drying.
Wherein, in the reaction system described in step (1), mandelic acid, water and VC amount ratio are 40 μ L:5.0mL:0.5
mL.Washing described in step, washed 3 times for ethanol.
In reaction system described in step (2), CdCl2, TGA, Te powder and NaBH4Amount ratio be 300mg:300mg:50
mg:70mg.Washing described in step, washed 3 times for ethanol.
In reaction system described in step (3), toluene and APTES amount ratio are 45mL:1.0mL.Described in step
Washing, washed 3 times for ethanol.
In reaction system described in step (4), TEA and THF amount ratios are 2.0mL:20mL；THF and 2-BIB amount ratios are
10mL:2.0mL；MAA, AM, EGDMA, acetonitrile, CuBr, the amount ratio of bipyridyl are 2.0mmol:3.0 mmol:5.0mmol:
70mL:0.3mmol:2.2mmol.Washing described in step, washed respectively 3 times for ethanol and water.
The preparation method of non-imprinted polymer corresponding to the present invention as above, but is not added with 2,6-DCP similar to synthetic method.
Embodiment 2:
(1) synthesis of Ag balls
In 25mL flasks, by 1.0mL AgNO3Solution, 50 μ L mandelic acid solution are dispersed in 10mL water, ultrasonic number
Minute, stirred under condition of ice bath several minutes, be rapidly added 1.0mL VC, continue to stir, after reacting 15min, by the production of synthesis
Thing centrifuges, and washs repeatedly for several times, and vacuum drying is stand-by.
(2) Ag/CdTe synthesis
In 150mL flasks, by 50mg silver, 365mgCdCl2, 360mg TGA are distributed in 100mL water, use
1.0mol L-1NaOH adjusts pH value to 11, adds presoma:By 51mg Te powder, 80mg NaBH4Centrifugation is mixed in a small amount of water
Guan Zhong, sealing ultrasound, excessive gas is excluded with syringe needle, until solution colour becomes colorless.Presoma is injected into rapidly above-mentioned
In solution, whole process maintaining nitrogen purge, and temperature is increased to 90-110 DEG C, after back flow reaction 23-25 h, by the production of synthesis
Thing centrifuges, and washs repeatedly for several times, and vacuum drying is stand-by.
(3) Ag/CdTe/APTES synthesis
In 150mL single-necked flasks, 500mg Ag/CdTe are dispersed in 50mL toluene solutions, add 1.5mL
APTES, temperature are increased to 90 DEG C of reaction 24h.Then, the product of synthesis is centrifuged, washed repeatedly with ethanol three times, vacuum
Dried for standby.
(4) preparation of Ag/CdTe/MIPs molecularly imprinted polymers
In 150mL single-necked flasks, 500mg Ag/CdTe/APTES are distributed to the mixed of 3.0mL TEA and 30mL THF
Close in solution, lead to nitrogen, 15mL THF and 3.0mL 2-BIB mixed solution is added dropwise, react 2.0h under condition of ice bath, then
24h is reacted under room temperature condition.Synthetic product is centrifuged, ethanol washs three times, and vacuum drying is stand-by.
In 150mL single-necked flasks, above-mentioned product is distributed to 3.0mmol MAA, 4.0mmol AM, 10mmol EGDMA
In 80mL acetonitriles, after room temperature is slowly stirred 3.0h, lead to nitrogen 15min, add cleaning the mmol of CuBr 0.38 and
2.28mmol bipyridyls, whole process persistently lead to nitrogen, sealing.Temperature is increased to 70 DEG C of reaction 24h, obtains Ag/CdTe/MIPs
Sensor, then washed, centrifuged repeatedly with acetonitrile, second alcohol and water, drying.
Wherein, in the reaction system described in step (1), mandelic acid, water and VC amount ratio are 50 μ L:10mL:1.0
mL.Washing described in step, washed 3 times for ethanol.
In reaction system described in step (2), CdCl2, TGA, Te powder and NaBH4Amount ratio be 365mg:360mg:51
mg:80mg.Washing described in step, it is that ethanol washs 3 times.
In reaction system described in step (3), toluene and APTES amount ratio are 50mL:1.5mL.
In reaction system described in step (4), TEA and THF amount ratios are 3.0mL:30mL；THF and 2-BIB amount ratios are
15mL:3.0mL；MAA, AM, EGDMA, acetonitrile, CuBr, the amount ratio of bipyridyl are 3.0mmol:4.0 mmol:10mmol:
80mL:0.38mmol:2.28mmol.Washing described in step, it is that ethanol and water wash 3 times respectively.
The preparation method of non-imprinted polymer corresponding to the present invention as above, but is not added with 2,6-DCP similar to synthetic method.
Embodiment 3:
(1) synthesis of Ag balls
In 25mL flasks, by 1.0mL AgNO3Solution, 60 μ L mandelic acid solution are dispersed in 15mL water, ultrasonic number
Minute, stirred under condition of ice bath several minutes, be rapidly added 1.5mL VC, continue to stir, after reacting 15min, by the production of synthesis
Thing centrifuges, and washs repeatedly for several times, and vacuum drying is stand-by.
(2) Ag/CdTe synthesis
In 150mL flasks, by 50mg silver, 400mgCdCl2, 400mg TGA are distributed in 100mL water, use 1.0mol
L-1NaOH adjusts pH value to 12, adds presoma:By 55mg Te powder, 90mg NaBH4It is mixed in a small amount of water in centrifuge tube, it is close
Envelope ultrasound, excessive gas is excluded with syringe needle, until solution colour becomes colorless.Presoma is injected into rapidly in above-mentioned solution,
Maintaining nitrogen purge, temperature are increased to 90-110 DEG C, after back flow reaction 23-25h, the product of synthesis are centrifuged, washed repeatedly
For several times, it is dried in vacuo stand-by.
(3) Ag/CdTe/APTES synthesis
In 150mL single-necked flasks, 500mg Ag/CdTe are dispersed in 55mL toluene solutions, add 2.0mL
APTES, temperature are increased to 90 DEG C of reaction 24h.Then, the product of synthesis is centrifuged, washed repeatedly with ethanol three times, vacuum
Dried for standby.
(4) preparation of Ag/CdTe/MIPs molecularly imprinted polymers
In 150mL single-necked flasks, 500mg Ag/CdTe/APTES are distributed to the mixed of 4.0mL TEA and 40mL THF
Close in solution, lead to nitrogen, 20mL THF and 4.0mL 2-BIB mixed solution is added dropwise, 2.0h is reacted under condition of ice bath, then
24h is reacted at ambient temperature.Synthetic product is centrifuged, ethanol washs three times, and vacuum drying is stand-by.
In 150mL single-necked flasks, above-mentioned product is distributed to 4.0mmol MAA, 5.0mmol AM, 15mmol EGDMA
In 90mL acetonitriles, after room temperature is slowly stirred 3.0h, lead to nitrogen 15min, add the CuBr 0.4mmol and 2.3mmol of cleaning
Bipyridyl, whole process persistently lead to nitrogen, sealing.Temperature is increased to 70 DEG C of reaction 24h, obtains Ag/CdTe/MIPs sensors, so
Acetonitrile is used afterwards, and second alcohol and water washs repeatedly, centrifuges, drying.
Wherein, in the reaction system described in step (1), mandelic acid, water and VC amount ratio are 60 μ L:15mL:1.5
mL.Washing described in step, washed 3 times for ethanol.
In reaction system described in step (2), CdCl2, TGA, Te powder and NaBH4Amount ratio be 400mg:400mg:55
mg:90mg.Washing described in step, it is that ethanol washs 3 times.
In reaction system described in step (3), toluene and APTES amount ratio are 55mL:2.0mL.
In reaction system described in step (4), TEA and THF amount ratios are 4.0mL:40mL；THF and 2-BIB amount ratios are
20mL:4.0mL；MAA, AM, EGDMA, acetonitrile, CuBr, the amount ratio of bipyridyl are 4.0mmol:5.0 mmol:15mmol:
90mL:0.4mmol:2.3mmol.Washing described in step, it is that ethanol and water wash 3 times respectively.
The preparation method of non-imprinted polymer corresponding to the present invention as above, but is not added with 2,6-DCP similar to synthetic method.
Specific Raman detection of the invention is carried out by the following method:In this experiment, all Raman detection conditions are equal
Unanimously:The a length of 633nm of excitation light wave.The spectral collection of each sample and time for exposure are 10s, and the power of incident laser is
0.25 mW.SERS spectrograms are collected with 50 × nikon lens.All SERS substrates are placed on slide, are used for after natural drying
The detection of SERS.
Test example 1:As shown in Fig. 5 (a), 2,6-DCP as template molecule, have detected Ag/CdTe/MIPS's by us
SERS activity, and test limit is determined.The chart is bright, in 1596cm-1The SERS intensity at place is most strong.From number
In as can be seen that as 2,6-DCP concentration is from 10-5mol L-1To 10-9mol L-1, SERS intensity also changes therewith.When 2,
6-DCP concentration is 10-10mol L-1, Raman signal almost disappears.In addition, as shown in Fig. 5 (b), the change of feature peak intensity and 2,
The change of 6-DCP concentration is linear.2,6-DCP concentration is 10-5mol L-1To 10-9mol L-1Between when (R2) detection
Coefficient is 0.96.
Test example 2:In order to study specific selectivities of the Ag/CdTe/MIPS to 2,6-DCP, we used with 2,6-DCP
Structure is similar, 2,5-DCP and benzenediol studied come further.As shown in fig. 6, adsorbed respectively with Ag/CdTe/MIPS dense
Spend for 10-5mol L-12,6-DCP, 2,5-DCP and benzenediol, due to 2,5-DCP and benzenediol molecular structure and 2,6-DCP
It is different, it is impossible to by Ag/CdTe/MIPS selective absorptions, so faint SERS intensity can only be observed.
Fig. 1 is Ag nano-particles (a), and Ag/CdTe composites (b), Ag/CdTe composites, which scan mapping, schemes
(c), Ag/CdTe/MIPs (d) scanning electron microscope (SEM) photograph, from figure 1 it appears that the scantling prepared is homogeneous, show good
Good dispersiveness；
Fig. 2 is Ag/CdTe/MIPs (a) and Ag/CdTe/NIPs (b) infrared spectrogram, is as can be seen from Figure 2 polymerize
React and successfully trigger；
Fig. 3 is Ag nano-particles (a), Ag/CdTe composites (b), Ag/CdTe/MIPs (c) and Ag/CdTe/NIPs
(d) X-ray diffraction spectra figure, as can be seen from Figure 3 Ag nano-particles are successfully prepared, and success load C dTe；
Fig. 4 is that Ag/CdTe/MIPs and Ag/CdTe/NIPs shows figure to the absorption property of different target thing, can from Fig. 4
To find out that Ag/CdTe/MIPs has shown more excellent selective absorption performance than Ag/CdTe/NIPs.
Claims (10)
- A kind of 1. preparation method of 2, the 6- chlorophenesic acid trace sensors based on surface enhanced Raman technique, it is characterised in that Comprise the following steps：Step 1, Ag nanospheres are prepared, it is standby；The preparation of step 2, Ag/CdTe：By silver nanoparticle ball made from step 1, CdCl2, TGA is distributed in water, is adjusted pH value to 10-12 with NaOH solution, must be mixed Solution A；Meanwhile by Te powder, NaBH4It is mixed in a small amount of water in centrifuge tube, sealing ultrasound, excessive gas is excluded with syringe needle, until molten Liquid color becomes colorless；Presoma is made；Presoma is injected into mixed solution A rapidly, maintaining nitrogen purge, temperature is increased to 90-110 DEG C, back flow reaction 23- After 25h, the product of synthesis is centrifuged, drying is washed, obtains Ag/CdTe；It is stand-by；The preparation of step 3, Ag/CdTe/APTES：Ag/CdTe made from step 2 is dispersed in toluene solution, adds APTES, temperature is increased to 80-100 DEG C of reaction 23- 25h, after completion of the reaction, the product of synthesis is centrifuged, washed, vacuum drying, obtains Ag/CdTe/APTES；It is stand-by；The preparation of step 4, Ag/CdTe/MIPs sensors：Product Ag/CdTe/APTES made from step 3 is distributed in the mixed solution of TEA and tetrahydrofuran (THF), leads to N2Number After minute, THF and 2-BIB mixed solutions is added dropwise, whole process leads to nitrogen and ice bath, continues logical nitrogen number point after completion of dropwise addition Clock, seal, after ice bath 1.0-3.0h, continue to react at room temperature 23-25h；Reaction separates synthetic product centrifuge washing after terminating, and dries It is dry standby, it is designated as product A；Product A and MAA, AM and EGDMA are distributed in acetonitrile, after room temperature is slowly stirred 2.0-4.0h, leads to nitrogen, adds cleaning The CuBr and bipyridyl crossed, whole process persistently lead to nitrogen, seal, and then temperature is increased to 60-80 DEG C, react 23-25h, obtain Ag/CdTe/MIPs sensors, then washed, centrifuged repeatedly with acetonitrile, second alcohol and water, drying.
- A kind of 2. system of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique according to claim 1 Preparation Method, it is characterised in that in step 1, the method for preparing Ag nanospheres is：By AgNO3Solution, mandelic acid solution are dispersed in In water, several minutes of ultrasound, stirred under condition of ice bath several minutes, be rapidly added VC solution, continue to stir, will after reacting 15min The product of synthesis centrifuges, and washs drying, obtains Ag nanospheres.
- A kind of 3. system of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique according to claim 2 Preparation Method, it is characterised in that the AgNO3Solution, mandelic acid solution, the amount ratio of water and VC solution are 1.0mL：40-60μ L：5.0-15mL：0.5-1.5mL；The AgNO3The concentration of solution is 1.0mol L-1, the concentration of mandelic acid solution is 0.25mol L-1, VC solution it is dense Spend for 1.0mol L-1, temperature is subzero；Described washing is that ethanol washs 3 times.
- A kind of 4. system of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique according to claim 1 Preparation Method, it is characterised in that in step 2, the silver nanoparticle ball, CdCl2, TGA, Te powder and NaBH4Usage ratio be 50mg： 300-400mg：300-400mg：50-55mg：70-90mg；The concentration of the NaOH solution is 1.0molL-1。
- A kind of 5. system of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique according to claim 1 Preparation Method, it is characterised in that in step 3, the Ag/CdTe, toluene and APTES amount ratio are 500mg:45-55mL:1.0- 2.0mL。
- A kind of 6. system of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique according to claim 1 Preparation Method, it is characterised in that in step 4, when preparing product A,The amount ratio of each material is in Ag/CdTe/APTES, TEA and THF mixed solution：Ag/CdTe/APTES, TEA and THF are used It is 500mg to measure ratio：2.0-4.0mL：20-40mL；The amount ratio of each material is in Ag/CdTe/APTES, THF and 2-BIB mixed solution：Ag/CdTe/APTES, THF and 2- BIB amount ratios are 500mg：10-20mL：2.0-4.0mL.
- A kind of 7. system of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique according to claim 1 Preparation Method, it is characterised in that in step 4, when preparing Ag/CdTe/MIPs sensors,Product A, MAA, AM, EGDMA, acetonitrile, CuBr, the amount ratio of bipyridyl are 500mg：2.0-4.0mmol：3.0- 5.0mmol：5.0-15mmol：70-90mL：0.3-0.4mmol：2.2-2.3mmol.
- A kind of 8. system of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique according to claim 1 Preparation Method, it is characterised in that described washing, be that ethanol washs 3 times in step 2-4.
- 9. a kind of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique are characterized in that, wanted by right Ask made from 1~8 preparation method.
- 10. a kind of 2,6- chlorophenesic acid trace sensors based on surface enhanced Raman technique described in claim 9 are used for Selective absorption 2,6-DCP purposes.
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