CN104316509A - Method for detecting 2-MIB (2-methylisoborneol) in water by utilizing graphene nano silver complex enhanced Raman scattering - Google Patents
Method for detecting 2-MIB (2-methylisoborneol) in water by utilizing graphene nano silver complex enhanced Raman scattering Download PDFInfo
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- CN104316509A CN104316509A CN201410564722.XA CN201410564722A CN104316509A CN 104316509 A CN104316509 A CN 104316509A CN 201410564722 A CN201410564722 A CN 201410564722A CN 104316509 A CN104316509 A CN 104316509A
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Abstract
The invention relates to a method for detecting 2-MIB (2-methylisoborneol) in water by utilizing graphene nano silver complex enhanced Raman scattering, belonging to the technical field of environmental detection. According to the method, a graphene composite nano silver stable complex is prepared through a one-step process to serve as a surface-enhanced Raman scattering (SERS) substrate, and 2-MIB of mu g/L concentration level in the water is detected; a quartz cuvette which has the light path of 1mm and is sealed by using a sealing film is taken as a closed determination carrier, so that volatilization of 2-MIB is effectively avoided; and a surface-enhanced Raman scattering correction algorithm is provided, and the peak area of a G/D peak of the graphene Raman spectrum serves as a correction internal standard, and the detection stability is improved. The method disclosed by the invention has the characteristics that a novel carbon material graphene nano silver composite material serves as the surface-enhanced Raman scattering substrate, and the trace detection of 2-MIB is rapid and reliable. Compared with the conventional chromatographic detection method, the method for detecting the 2-MIB in the water disclosed by the invention has the advantages that sample pretreatment is not needed, the detection time consumption is low, and nondestructive testing can be realized. Moreover, the method is conveniently combined with the other pretreatment methods, is a method for detecting the 2-MIB in the water and is easy and convenient to operate, high-efficiency and environmentally friendly.
Description
Technical field
The present invention relates to and utilize graphene nano silver composite Surface enhanced raman spectroscopy to detect the method for 2-methyl isoborneol (2-MIB) in water, belong to technical field of environmental detection.
Background technology
Drinking water safety problem is the major issue that people very pay close attention to, and the taste problem of smelling wherein in potable water also becomes study hotspot in the last few years.Taste compound is mainly smelt in the generation of smelling taste problem, as class organic compounds such as 2-methyl isoborneol, ground depth cause.This compounds has volatility more, content is low, and how detecting these trace materialss is fast difficult point and study hotspot.
The detection of tradition 2-MIB uses liquid chromatography-mass spectrometer, maybe needs to carry out loaded down with trivial details sample pre-treatments, or needs accurate expensive chromatographic apparatus, and sample is longer from collecting minute interval.Raman spectrum is used to a kind of spectrographic technique studying molecular vibration, different material molecule is because their chemical compositions shown Raman spectrum characteristic different from structure is different, researchist obtains the information of molecule by Raman spectrum, carries out and differentiates and detect different material.Raman spectroscopy measurement is simple, quick, accurate, reliable; Sample preparation is simple, generally must not destroy sample, can carry out Non-Destructive Testing; The interference of water to spectrum is little, can directly in the measurement of aqueous solution; The wavelength etc. of exciting light can be changed easily.
The present invention adopts graphene nano silver composite as surface enhanced Raman substrate, without the need to sample pre-treatments, utilizes surface-enhanced Raman to detect 2-MIB in water.Compound substance has merged the advantage of 2 kinds of materials.Graphene nano material has simple two-dimensional structure, specific surface area is large, adsorption site is many, be conducive to the reunion that the deposition of nano metal on its surface also effectively prevents nano particle, and Graphene carbon structure rich surface is containing large π key, to Organic substance in water, there is good suction-operated, serve the effect of enrichment.And homodisperse Nano Silver has surface-enhanced Raman effects, the Raman signal of binding molecule is strengthened greatly compared to its normal Raman signal, to improve the accuracy of detection.It is easy to detect, simple that this method detects 2-MIB, is applicable to the exploitation of field detecting device, is with a wide range of applications.
Summary of the invention
The object of the present invention is to provide new method to detect underwater trace material 2-MIB fast, supplementing prior art detecting the deficiency existed in 2-MIB, to meet the application demand of express-analysis and field monitoring.
The method utilizing graphene nano silver composite material Surface enhanced raman spectroscopy to detect 2-MIB in water provided by the invention, with new carbon Graphene, loading nano silvery forms stability of composite materials, as surface enhanced Raman scattering substrate, quick and precisely detects 2-MIB in water easily.A kind of method utilizing graphene nano silver composite to strengthen 2-MIB in Raman scattering detection water of the present invention, its essential characteristic is following process and step:
A. prepare surface enhanced Raman scattering substrate material: adopt in-situ chemical synthetic method, in aqueous, with graphene oxide and silver nitrate for raw material, the mass percent shared by graphene oxide is 35%-50%; Take sodium borohydride as reductive agent, concentration is 100mM-150mM, adds 150 μ L-200 μ L in 5s-30s; Take polyvinylpyrrolidone as stabilizing agent, lucifuge, next step reaction of normal temperature 30-60min, namely obtains stable graphene nano silver composite surface enhanced and draws Raman scattering substrate material; This material graphene nano silver composite is dispersed in ultrapure water, in suspension, is designated as rGO-Ag.
B. after the 2-MIB solution of the variable concentrations of configuration being mixed with volume ratio 1:1 in brown sample bottle with rGO-Ag liquid substrate material respectively, load in the quartz colorimetric utensil of 1mm light path, with sealed membrane sealing, detect under being placed in confocal Raman microscopy and obtain Raman spectrum.
C adopts a kind of internal calibrations computing method of new Surface enhanced raman spectroscopy: adopt Raman spectrum 1500 cm
-1place represents the peak area correcting determination value at the G peak of D peak and the in plane vibration vibrated between graphene layer, and utilizes the standard concentration curve figure of 2-MIB to calculate its concentration.
The graphene nano silver composite Surface enhanced raman spectroscopy that utilizes provided by the invention detects 2-MIB in water, be carrier loaded Nano Silver with functionalization graphene, prepare and there is synergistic graphene nano silver composite, the organic Raman signal being adsorbed on graphenic surface, to organic enriched character, is significantly strengthened by Nano Silver by the Raman enhancing characteristic of coupled nanosecond silver and Graphene.Substrate is prepared by a stage reduction method, its characteristic is by optimizing sodium borohydride concentration, dosage and add speed, prepares the deposition of silver particle of nano shape, have employed the stabilizing agent that polyvinylpyrrolidone does dispersion of materials, effectively avoid the spontaneous reunion of Nano Silver; Adopt 1mm light path and with sealed membrane sealing quartz colorimetric utensil as closed mensuration loading, effectively avoid the volatilization of 2-MIB; Provide a kind of correcting algorithm of surface-enhanced Raman innovatively, improve the linear of detection.This method is to the detection of 2-MIB in water without the need to carrying out sample detection pre-treatment, and the practicable harmless 2-MIB accurately detecting μ g/L concentration level, and easily combining with other detection means method is that one is easy and simple to handle, the method for 2-MIB in the detection water of high-efficiency environment friendly.
Accompanying drawing explanation
Fig. 1 is the graphene oxide of non-loading nano silvery and the uv-visible absorption spectroscopy figure of graphene nano silver composite.
Fig. 2 is the graphene oxide of non-loading nano silvery and the Raman spectrogram of graphene nano silver composite.
Fig. 3 is 2-MIB titer, ultrapure water Surface enhanced raman spectroscopy figure.
Fig. 4 is that (figure a is canonical plotting without internal calibrations for the canonical plotting of 2-MIB; Figure b is the canonical plotting after internal calibrations).
Embodiment
After now specific embodiments of the invention being described in.Detecting step in the present embodiment is as follows:
A. graphene nano silver composite material is prepared: adopt in-situ chemical synthetic method, in aqueous, with graphene oxide and silver nitrate for raw material, synchronously complete the reduction of metallic reducing, deposition and graphenic surface, mass percent wherein shared by graphene oxide is 48%, take sodium borohydride as reductive agent, concentration is 130mM, 180 μ L are added in 15s, take polyvinylpyrrolidone as stabilizing agent, lucifuge, at normal temperatures single step reaction 30min, namely obtain stable graphene nano silver surface and strengthen base material.
B. after the aqueous solution of variable concentrations 2-MIB being mixed with volume ratio 1:1 with rGO-Ag fluent material respectively in brown sample bottle, be loaded in the quartz colorimetric utensil of 1mm light path, with sealed membrane sealing, detect under being placed in confocal elliptical waveguide, obtain Raman spectrum.
C. according to the Raman spectrum of graphene oxide at 1500cm
-1the two bimodal areas in place as " interior mark ", by 2-MIB at 3000cm
-1peak area revise divided by " interior mark " area, Linear Quasi is right reaches 0.9993.
every test for the present invention
Test example 1
The experiment that graphene nano silver composite has surface enhanced Raman scattering effect as the substrate of surface-enhanced Raman is carried out according to the following steps: under the condition that lucifuge stirs, to through ultrasonic disperse evenly and concentration is the AgNO adding 100mL1mM in the graphene oxide dispersion of 160mg/L
3solution, in 10s, fast and stable dropwise adds the NaBH of 180 μ L130mM
4solution, the polyvinylpyrrolidonesolution solution of 1.6mL4mg/mL, ultrasonic 10min, makes to mix, and can obtain stable silver/graphite alkene nano-complex.Graphene nano silver composite and the graphene oxide dispersion of non-plus nano silver are carried out full wavelength scanner respectively at UV-Vis spectrometer, obtains spectrogram as Fig. 1; By in the quartz colorimetric utensil of the graphene oxide dispersion of graphene nano silver composite and non-plus nano silver respectively at 1mm light path, with sealed membrane sealing, detect under being placed in confocal elliptical waveguide, obtain Raman spectrum and the results are shown in Figure 2.
Test example 2
The experiment that the standard reserving solution of 2-MIB detects is carried out according to the following steps: get 2-MIB standard solution that concentration is 100mg/L and rGO-Ag fluent material forms mixed solution with 1:1 volume ratio, with same ratio, rGO-Ag fluent material and deionized water solution being formed mixed solution is blank simultaneously, be placed in the quartz colorimetric utensil of 1mm light path, seal with sealed membrane, detect under being placed in confocal elliptical waveguide, obtain Raman spectrum and the results are shown in Figure 3.
Test example 3
Utilize Graphene to carry Argent grain nano-complex Surface enhanced raman spectroscopy to detect the experiment that 2-MIB in water obtains typical curve and carry out according to the following steps: the concentration of configuration 2-MIB is 1ppb, 5ppb, 50ppb, 100ppb and 250ppb, obtains the 3000cm that 2-MIB variable concentrations is corresponding
-1and 1500cm
-1the area at place and the mean value of height, make the logarithm value of 2-MIB concentration and the linear relationship chart of peak area, see Fig. 4 a; With Raman collection of illustrative plates 1500cm
-1the bimodal area of graphene oxide as " interior mark ", by 2-MIB at 3000cm
-1peak area revise divided by " interior mark " area after, make the logarithm value of 2-MIB concentration and the linear relationship chart of peak area ratio, see Fig. 4 b.
the interpretation of result of each test gained accompanying drawing
1, accompanying drawing 1 interpretation of result
Can find out in accompanying drawing 1 that graphene oxide has the absorption peak of C=C key at 226nm place, at the absorption peak of 300nm place C=O key; When Ag is carried on GO surface, having obvious acromion at 400nm place, is the surface plasmon absorption peak of typical Ag nano particle.Result shows, Ag nano particle is successfully carried on graphenic surface.
2, accompanying drawing 2 interpretation of result
In fig 2, graphene oxide is at 1500cm
-1the bimodal position of left and right is not clearly, and its intensity level is less than 100, and graphene nano silver composite is at 1500cm
-1the bimodal obvious enhancing of left and right.Visible graphene nano silver composite has surface-enhanced Raman effects, therefore can be used as the enhancing substrate that surface Raman detects 2-MIB.
3, accompanying drawing 3 interpretation of result
Contrasted by 2-MIB and ultrapure water Raman spectrum from accompanying drawing 3, can find to add in the sample of 2-MIB at 3000cm
-1the Raman shift of left and right, have obvious bimodal appearance, ultrapure water is at 3000 cm
-1left and right does not occur bimodal, can get rid of the impact that ultrapure water measures 2-MIB Raman, judge that the peak position that of the Raman spectrum of 2-MIB is positioned at 3000cm simultaneously
-1place, and be bimodal, this conforms to the peak position that goes out of the theoretical Raman collection of illustrative plates of 2-MIB, and explanation graphene nano silver composite has feasibility as the base material survey 2-MIB of Surface enhanced raman spectroscopy scattering.
4, accompanying drawing 4 interpretation of result
In figure 4, after " interior mark " area is revised, 2-MIB log concentration value and peak area ratio are good linear dependence, Linear Quasi is right reaches 0.9993, the fluctuation of the surface enhanced effect caused because a difference got by microscope when effectively can overcome test sample, thus the fiduciary level promoting measurement result.
Claims (1)
1. utilize graphene nano silver composite Surface enhanced raman spectroscopy to detect a method of 2-MIB in water, it is characterized in that there is following process and step:
A. prepare surface enhanced Raman scattering substrate material: adopt in-situ chemical synthetic method, in aqueous, with graphene oxide and silver nitrate for raw material, the mass percent shared by graphene oxide is 35%-50%; Take sodium borohydride as reductive agent, concentration is 100mM-150mM, adds 150 μ L-200 μ L in 5s-30s; Take polyvinylpyrrolidone as stabilizing agent, lucifuge, next step reaction of normal temperature 30-60min, namely obtains stable graphene nano silver composite surface enhanced and draws Raman scattering substrate material; This material graphene nano silver composite is dispersed in ultrapure water, in suspension, is designated as rGO-Ag;
B. after the 2-MIB solution of the variable concentrations of configuration being mixed with volume ratio 1:1 in brown sample bottle with rGO-Ag liquid substrate material respectively, load in the quartz colorimetric utensil of 1mm light path, with sealed membrane sealing, detect under being placed in confocal Raman microscopy and obtain Raman spectrum;
C adopts a kind of internal calibrations computing method of new Surface enhanced raman spectroscopy: adopt Raman spectrum 1500 cm
-1place represents the peak area correcting determination value at the G peak of D peak and the in plane vibration vibrated between graphene layer, and utilizes the standard concentration curve figure of 2-MIB to calculate its concentration.
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Cited By (5)
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| CN106353299A (en) * | 2016-10-11 | 2017-01-25 | 合肥国轩高科动力能源有限公司 | Quantitative analysis method for graphene compound conductive paste |
| CN107233803A (en) * | 2017-06-02 | 2017-10-10 | 青岛大学 | A kind of graphene/Argent grain combined filtration film and its preparation and application |
| CN110389232A (en) * | 2019-07-18 | 2019-10-29 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Protein Detection film and preparation method and based on aptamer-graphite Raman frequency displacement method of protein detection |
| CN110857914A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof |
| CN111610176A (en) * | 2020-05-15 | 2020-09-01 | 清华大学 | Unsymmetrical dimethylhydrazine detection method based on surface enhanced Raman scattering |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107233803A (en) * | 2017-06-02 | 2017-10-10 | 青岛大学 | A kind of graphene/Argent grain combined filtration film and its preparation and application |
| CN107233803B (en) * | 2017-06-02 | 2020-05-19 | 青岛大学 | Graphene/silver particle composite filter film and preparation and application thereof |
| CN110857914A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof |
| CN110389232A (en) * | 2019-07-18 | 2019-10-29 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Protein Detection film and preparation method and based on aptamer-graphite Raman frequency displacement method of protein detection |
| CN110389232B (en) * | 2019-07-18 | 2023-05-02 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Protein detection membrane, preparation method and protein detection method based on aptamer-graphene Raman frequency shift |
| CN111610176A (en) * | 2020-05-15 | 2020-09-01 | 清华大学 | Unsymmetrical dimethylhydrazine detection method based on surface enhanced Raman scattering |
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