CN114965418B - Method for rapidly detecting mercury by surface enhanced Raman scattering - Google Patents
Method for rapidly detecting mercury by surface enhanced Raman scattering Download PDFInfo
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 28
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 39
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 239000003623 enhancer Substances 0.000 claims abstract description 24
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012086 standard solution Substances 0.000 claims description 15
- 238000001237 Raman spectrum Methods 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- PUMZXCBVHLCWQG-UHFFFAOYSA-N 1-(4-Hydroxyphenyl)-2-aminoethanol hydrochloride Chemical compound [Cl-].[NH3+]CC(O)C1=CC=C(O)C=C1 PUMZXCBVHLCWQG-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229940046937 octopamine hydrochloride Drugs 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052737 gold Inorganic materials 0.000 abstract description 9
- 239000010931 gold Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
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- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 25
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 23
- 150000002343 gold Chemical class 0.000 description 17
- QHGUCRYDKWKLMG-MRVPVSSYSA-N Octopamine Natural products NC[C@@H](O)C1=CC=C(O)C=C1 QHGUCRYDKWKLMG-MRVPVSSYSA-N 0.000 description 8
- 229960001576 octopamine Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QHGUCRYDKWKLMG-QMMMGPOBSA-N (R)-octopamine Chemical compound NC[C@H](O)C1=CC=C(O)C=C1 QHGUCRYDKWKLMG-QMMMGPOBSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000002689 soil Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 238000012417 linear regression Methods 0.000 description 4
- 238000000120 microwave digestion Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 241000238557 Decapoda Species 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 235000013372 meat Nutrition 0.000 description 3
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- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
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- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
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Abstract
The invention discloses a method for rapidly detecting mercury by surface enhanced Raman scattering, which comprises the steps of preparing a Chapteramine carbon point, preparing a Chapteramine carbon point gold nanometer Raman scattering enhancer, determining a SERS characteristic peak of Hg 2+ and measuring Hg 2+ in a sample; according to the method, the reducing property of the carbon dot surface groups such as hydroxyl (-OH) and the prepared carbon dot raw material of the chapter amine is utilized as a reducing agent and a stabilizing agent for preparing gold nanometer, and the prepared chapter amine carbon dot gold nanometer Raman scattering reinforcing agent has obvious Raman reinforcing effect and stability, can strengthen the interaction of Hg 2+ on the gold nanometer surface and the carbon dot, plays a double role of electromagnetic enhancement and chemical enhancement, realizes high-sensitivity detection of Hg 2+, and has the detection limit of 0.1 mu g/L.
Description
Technical Field
The invention relates to the technical field of chemical analysis and detection, in particular to a method for rapidly detecting mercury by surface enhanced Raman scattering.
Background
Mercury and most of its compounds are widely present in water and soil. Excessive emissions of plant sewage, combustion of fossil fuels, and incineration of waste have led to an increase in mercury in the environment. Mercury is easily enriched in water and easily absorbed by skin, respiratory tract and digestive tract, and damages central nervous system of human body and causes brain death. Therefore, the detection work of mercury in water and environment is very important to human health.
The detection method of Hg 2+ is mainly divided into instrument analysis detection and sensing analysis detection. Conventional instrumental analysis and detection methods mainly include Atomic Absorption Spectrometry (AAS), atomic Fluorescence Spectrometry (AFS), inductively coupled plasma mass spectrometry (ICP-MS), and the like. The instrumental analysis detection method has great advantages in detection sensitivity and accuracy, but cannot be used for on-site and rapid detection of Hg 2+ due to the limitation of expensive equipment requirements, complex sample pretreatment process, long detection period and other factors. The Surface Enhanced Raman Spectrum (SERS) greatly enhances the Raman signal of a target substance through noble metal materials such as gold, silver and the like, realizes the detection of trace substances, has the advantages of simple sample pretreatment, high detection speed, few required samples and the like besides the fingerprint spectrum characteristics, and further has a unique position in the field of food safety detection. However, the existing preparation method of the Raman enhancer is not more, so that the target capable of generating Raman signals is limited, and the preparation of the Raman enhancer is also a bottleneck for restricting SERS application.
Disclosure of Invention
Therefore, the invention provides a method for rapidly detecting mercury by surface enhanced Raman scattering, which utilizes the reducibility of a group carried on the surface of a carbon dot, such as hydroxyl (-OH), and the prepared carbon dot raw material, namely, the octopamine, and the prepared gold nano has obvious Raman enhancement effect and stability, has dual effects of electromagnetic enhancement and chemical enhancement on SERS of Hg 2+, and has a linear relation between Hg 2+ and the peak area of a characteristic peak in a certain concentration range, and the detection limit reaches 1 mu g/L. The limit of mercury in the food is 1-100 mug/L, the method completely meets the detection requirement of the related limit, has specificity, does not interfere with the detection of related coexists, and can realize SERS high-sensitivity detection of Hg 2+.
In order to achieve the above object, the present invention provides the following technical solutions:
preparing a modified gold nano Raman scattering enhancer by taking a Chapter amine carbon point as a reducing agent and a stabilizing agent;
Mixing Hg 2+ standard solution with a modified gold nano Raman scattering enhancer of a kavalamine carbon point; carrying out Raman spectrum detection on the mixture by using a portable Raman instrument, determining a characteristic peak at 1335 cm -1 according to the molecular structure and Raman peak position attribution of the modified gold nanometer of the amine carbon point, wherein the characteristic peak can be used as a judging basis for detecting Hg 2+ by using a surface enhanced Raman scattering spectrum, and determining a linear relation between Hg 2+ concentration and peak area of the characteristic peak;
mixing a sample liquid to be detected with a modified gold nano Raman scattering enhancer of a chapter amine carbon point; carrying out Raman spectrum detection on the mixture to be detected by using a portable Raman instrument, and calculating the Hg 2+ concentration in the sample to be detected according to the peak area of the characteristic peak.
Further, the chapter amine carbon point modified gold Mi Laman scattering enhancer is prepared as follows:
(1) Synthesis of the amine carbon point: 1.0-2.0g of octopamine hydrochloride, 0.5-1.0g of citric acid and 0.5-1.0g of ethylenediamine are weighed and dissolved in 20mL of ultrapure water, the mixture is evenly mixed by ultrasonic, the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle, the mixture is heated for 8-10 hours at the constant temperature of 180-200 ℃, and the mixture is naturally cooled to room temperature after the reaction is completed, so as to obtain brown solution; removing large-particle impurities from the brown solution by using a 0.22 mu m filter membrane, centrifuging at a high speed, and vacuum drying supernatant to obtain a chapter amine carbon point;
(2) Dissolving 12-15mg of the kavalamine carbon point and 20-25mg of sodium citrate in 40mL of ultrapure water, heating the mixture to 100 ℃ in an oil bath, adding HAuCl 4,HAuCl4, stirring the mixture for 60 minutes in a dark place, cooling the mixture to room temperature, and centrifuging the mixture at a high speed, wherein the supernatant is the modified gold nano Raman scattering enhancer for the kavalamine carbon point.
The sample liquid to be detected is liquid to be detected which is prepared by preprocessing a mercury-containing sample according to a conventional method.
Further, the concentration of the Hg 2+ standard solution is 0.1-1000 mug/L; the addition amount of the modified gold nano Raman scattering enhancer of the amine carbon dots is 50-100 mu L.
Further, the raman spectrum detection shows that the surface enhanced raman scattering spectrum peaks of the Hg 2+ standard solution have 1189, cm -1、1335 cm-1 and 1607 and cm -1 peaks under the conditions of 785 nm excitation light, 500mW laser power and 10s scanning time.
Further, the detection concentration of the Hg 2+ standard solution reaches 0.1 mug/L.
The invention has the following advantages:
1. according to the method for rapidly detecting mercury by surface-enhanced Raman scattering, the reducing property of the carbon dot surface-carried groups such as hydroxyl (-OH) and the prepared carbon dot raw material of the chapter amine is utilized as a reducing agent and a stabilizing agent for preparing gold nano-particles, and the prepared gold nano-particles have remarkable Raman enhancement effect and stability;
2. According to the method for rapidly detecting mercury by surface enhanced Raman scattering, disclosed by the invention, the carbon point raw material, namely the octopamine modified gold nanomaterial, is used as a Raman scattering enhancer, so that the interaction of Hg 2+ on the gold nano surface and a carbon point can be enhanced, the dual effects of electromagnetic enhancement and chemical enhancement are achieved, the high-sensitivity detection of Hg 2+ is realized, and the detection limit is 1 mug/L;
3. the method for rapidly detecting mercury by surface enhanced Raman scattering is used for detecting mercury in an actual sample, and the coexisting materials do not interfere with measurement, and has the characteristics of strong specificity, simplicity and rapidness in operation and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those skilled in the art from this disclosure that the drawings described below are merely exemplary and that other implementations drawings can be obtained from the extensions of the drawings provided without inventive effort;
FIG. 1 is a SERS spectrum of Hg 2+ standard and AuNPs at different concentrations in example 1 of the present invention;
FIG. 2 is a graph showing the linear relationship between Hg 2+ at various concentrations and the characteristic peak intensities in example 1 of the present invention;
FIG. 3 is a schematic diagram showing the results of interference experiments of different metals on the detection system of the present invention in example 1 of the present invention.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: rapid detection of mercury in rice by surface enhanced Raman scattering
(1) 1.0G of octopamine hydrochloride, 0.5g of citric acid and 0.5g of ethylenediamine are weighed and dissolved in 20mL of ultrapure water, the mixture is evenly mixed by ultrasonic, the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle, the mixture is heated for 10 hours at the constant temperature of 180 ℃, and the mixture is naturally cooled to room temperature after the reaction is completed, so as to obtain brown solution; removing large-particle impurities from the brown solution by using a 0.22 mu m filter membrane, centrifuging at 8000r/min, and vacuum drying the supernatant at 60 ℃ to obtain a chapter amine carbon dot;
(2) Dissolving 12mg of the octopamine carbon point and 20mg of sodium citrate in 40mL of ultrapure water, heating an oil bath to 100 ℃, adding HAuCl 4,HAuCl4 to the concentration of 10mg/mL in the mixed solution, stirring for 60min in a dark place, cooling to room temperature, centrifuging at 8000r/min, and obtaining a supernatant as the octopamine carbon point modified gold nano Raman scattering enhancer;
(3) SERS detection of Hg 2+ standard solution: mixing 200 mu L of Hg 2+ standard solution (the concentration range is 0.1-1000 mu g/L) with 100 mu L of the modified gold nano Raman scattering enhancer of the amine carbon point, scanning for 10s under the conditions of 785nm excitation light and 500mW of laser power, and carrying out Raman spectrum detection on the mixture by using a portable Raman instrument;
(4) SERS spectrum detection wavenumber determination of Hg 2+ and SERS analysis of standard: as shown in fig. 1, SERS characteristic peaks are observed at 1189cm -1、1335cm-1 and 1607cm -1 peaks in the SERS spectrum of Hg 2+, and according to the correlation characteristics of the concentration change of Hg 2+ and the SERS peak, the characteristic peak at 1335cm -1 is determined as the basis for judging Hg 2+ detected by the SERS spectrum; the characteristic peak intensity in the SERS spectrum of Hg 2+ varies with the standard solution concentration (0.1-1000 μg/L), and as shown in fig. 2, the linear regression equation of Hg 2+ concentration and characteristic peak area is: y= 1815.11x-5043.56, r 2 = 0.9801, and all have obvious raman spectrum peaks at concentrations as low as 1 μg/L; therefore, the detection concentration of the Hg 2+ standard solution reaches 1 mug/L;
(5) SERS determination of mercury in rice reference sample (GBW 10045 a)
(51) Pretreatment of rice samples: accurately weighing 0.3g (0.001 g accurate) of a rice reference sample, placing the sample in a microwave digestion tank, adding 6.0mL of nitric acid, digesting in a microwave digestion instrument, and performing microwave digestion according to a microwave digestion program shown in Table 1; after digestion is finished and cooling is carried out, deionized water is used for fixing the volume to 20mL, and a sample measuring solution is obtained;
(52) Mixing 200 mu L of sample liquid to be detected with 100 mu L of a modified gold nano Raman scattering enhancer of a chapter amine carbon point, carrying out Raman spectrum detection on an object to be detected by using a portable Raman instrument, and calculating that the mercury content in the sample to be detected is 3.3 mu g/kg according to the peak area of a characteristic peak, wherein the detection result is in an error range compared with a reference value of 3.5 mu g/kg;
Table 1 microwave digestion procedure
；
(6) Interference experiment of different metal ions on the detection system of the embodiment
The replacement of 20 mug/kg of Hg 2+ with 200 mug/kg of other metal ions （Ar3+、Mg2+、Zn2+、Cu2+、Ca2+、Sn2+、Cd2+、Ag2+、Pb2+、Fe2+） is used for verifying the specificity of the detection system, and the result in FIG. 3 shows that the detection system has better selectivity to Hg 2+.
Example 2: surface enhanced Raman scattering rapid detection of mercury in soil
(1) 1.5G of octopamine hydrochloride, 0.7g of citric acid and 0.7g of ethylenediamine are weighed and dissolved in 20mL of ultrapure water, the mixture is evenly mixed by ultrasonic, the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle, the mixture is heated for 8 hours at the constant temperature of 200 ℃, and the mixture is naturally cooled to room temperature after the reaction is completed, so as to obtain brown solution; removing large-particle impurities from the brown solution by using a 0.22 mu m filter membrane, centrifuging at 8000r/min, and vacuum drying the supernatant at 60 ℃ to obtain a chapter amine carbon dot;
(2) Dissolving 15mg of the octopamine carbon point and 20mg of sodium citrate in 40mL of ultrapure water, heating an oil bath to 100 ℃, adding HAuCl 4,HAuCl4 to the concentration of 12mg/mL in the mixed solution, stirring for 60min in a dark place, cooling to room temperature, centrifuging at 8000r/min, and obtaining a supernatant as the octopamine carbon point modified gold nano Raman scattering enhancer;
(3) SERS detection and linear regression equation of Hg 2+ standard solution are the same as those of example 1;
(4) SERS determination of mercury in soil
(41) Pretreatment of soil samples: the soil is a national standard substance GBW07447, 0.3g (accurate to 0.001 g) of a sample is accurately weighed, the sample is poured into a 50mL colorimetric tube with a plug, a small amount of purified water is used for wetting the sample, 10mL of concentrated hydrochloric acid and aqua regia with the volume ratio of concentrated nitric acid of 1:1 are added, the mixture is uniformly shaken after the plugging is added, the mixture is put into a boiling water bath for digestion for 2 hours, the mixture is taken out and cooled, and then 10mg/L of L-cysteine (which is a stabilizer and is used for preventing mercury from volatilizing and adsorbing on the inner wall of glass) is added to a fixed volume to a scale; shaking, standing, and collecting supernatant to obtain sample measurement solution;
(42) 200 mu L of sample liquid to be detected is mixed with 100 mu L of modified gold nano Raman scattering enhancer of the amine carbon point, raman spectrum detection is carried out on the object to be detected by using a portable Raman instrument, the mercury content in the sample to be detected is calculated to be 18 mu g/kg according to the peak area of the characteristic peak, the certificate reference value is 0.015+/-0.003 mg/kg, the measuring result is in an error range, and the measuring method has accuracy.
Example 3: quick detection of mercury in shrimp meat by surface enhanced Raman scattering
(1) 2.0G of octopamine hydrochloride, 1.0g of citric acid and 0.9g of ethylenediamine are weighed and dissolved in 20mL of ultrapure water, the mixture is evenly mixed by ultrasonic, the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle, the mixture is heated for 9 hours at the constant temperature of 190 ℃, and the mixture is naturally cooled to room temperature after the reaction is completed, so as to obtain brown solution; removing large-particle impurities from the brown solution by using a 0.22 mu m filter membrane, centrifuging at 8000r/min, and vacuum drying the supernatant at 60 ℃ to obtain a chapter amine carbon dot;
(2) Dissolving 13mg of octopamine carbon point and 23mg of sodium citrate in 40mL of ultrapure water, heating an oil bath to 100 ℃, adding HAuCl 4,HAuCl4 to the concentration of 15mg/mL in the mixed solution, stirring for 60min in a dark place, cooling to room temperature, centrifuging at 8000r/min, and obtaining a supernatant as the octopamine carbon point modified gold nanometer;
(3) SERS detection and linear regression equation of Hg 2+ standard solution are the same as those of example 1;
(4) SERS determination of mercury in shrimp meat
(41) Pretreatment of shrimp meat samples: removing the shell and head, weighing 1.0g (accurate to 0.0001 g) of the sample, placing the sample in a 15mL plastic centrifuge tube, adding 10mL hydrochloric acid solution (5 mol/L), performing ultrasonic treatment at 25 ℃ for 30min and standing overnight; extracting with ultrasonic water bath at 25deg.C for 60min, and shaking for several times; centrifuging at 8000r/min for 5min at 4deg.C, collecting supernatant, and filtering with 0.45 μm filter membrane to obtain sample solution;
(42) Mixing 200 mu L of sample liquid to be detected with 100 mu L of the modified gold nano Raman scattering enhancer of the amine carbon point, carrying out Raman spectrum detection on an object to be detected by using a portable Raman instrument, and calculating the mercury content of 25 mu g/kg in the sample to be detected according to the peak area of the characteristic peak.
Example 4: surface-enhanced Raman scattering rapid detection of mercury in drinking water
(1) Synthesis of the amine carbon point: as in example 1;
(2) Preparing the modified gold nano-particles with the amine carbon dots: as in example 1;
(3) SERS detection and linear regression equation of Hg 2+ standard solution are the same as those of example 1;
(4) SERS determination of mercury in drinking water
(41) Pretreatment of drinking water samples: 10.0mL of water sample is added with 0.20mL of concentrated nitric acid and is left for 20min to obtain a measuring solution;
(42) Mixing 200 mu L of sample liquid to be detected with 100 mu L of a modified gold nano Raman scattering enhancer of a kavalamine carbon point, and carrying out Raman spectrum detection on an object to be detected by using a portable Raman instrument, wherein the object to be detected is not detected; because the concentration of Hg 2+ in the sample liquid to be detected is lower than 1 mu g/L;
The detection method provided by the invention has good experimental reproduction, and is verified by a sample labeling recovery rate and precision test, and the detection method is concretely as follows: different Hg 2+ standard solutions are added into blank sample liquid to be detected, samples with Hg 2+ concentration of 5, 10 and 15 mug/L are prepared, SERS detection is carried out, experimental reproduction is good, RSD is less than 3.0%, and detection rate is more than 90%.
The method for rapidly detecting Hg 2+ by surface enhanced Raman scattering, which is established by the invention, uses the modified gold nanometer of the amine carbon point of the chapter as a Raman scattering enhancer to detect the SERS of Hg 2+, and has the characteristics of high sensitivity, specificity, rapidness, simple and convenient operation and the like.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (3)
1. The method for rapidly detecting mercury by surface enhanced Raman scattering is characterized by comprising the following steps of:
preparing a modified gold nano Raman scattering enhancer by taking a Chapter amine carbon point as a reducing agent and a stabilizing agent;
Mixing Hg 2+ standard solution with a modified gold nano Raman scattering enhancer of a kavalamine carbon point; carrying out Raman spectrum detection on the mixture by using a portable Raman instrument, determining a characteristic peak at 1335cm -1 according to the molecular structure and Raman peak position attribution of the modified gold nanometer of the amine carbon point, wherein the characteristic peak can be used as a judging basis for detecting Hg 2+ by using a surface enhanced Raman scattering spectrum, and determining the linear relation between the concentration of Hg 2+ and the peak area of the characteristic peak;
Mixing a sample liquid to be detected with a modified gold nano Raman scattering enhancer of a chapter amine carbon point; carrying out Raman spectrum detection on the mixture to be detected by using a portable Raman instrument, and calculating Hg 2+ concentration in the sample to be detected according to the peak area of the characteristic peak;
The chapter amine carbon point modified gold Mi Laman scattering enhancer is prepared as follows:
(1) 1.0-2.0g of octopamine hydrochloride, 0.5-1.0g of citric acid and 0.5-1.0g of ethylenediamine are weighed and dissolved in 20mL of ultrapure water, the mixture is evenly mixed by ultrasonic, the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle, the mixture is heated for 8-10 hours at the constant temperature of 180-200 ℃, and the mixture is naturally cooled to room temperature after the reaction is completed, so as to obtain brown solution; removing large-particle impurities from the brown solution by using a 0.22 mu m filter membrane, centrifuging at a high speed, and vacuum drying supernatant to obtain a chapter amine carbon point;
(2) Dissolving 12-15mg of kavaline carbon point and 20-25mg of sodium citrate in 40mL of ultrapure water, heating an oil bath to 100 ℃, adding HAuCl 4,HAuCl4 to the mixed solution with the concentration of 10-15mg/mL, stirring for 60min in a dark place, cooling to room temperature, centrifuging at a high speed, and obtaining a supernatant as the kavaline carbon point modified gold nano Raman scattering enhancer.
2. The method according to claim 1, characterized in that: the concentration of Hg 2+ standard solution is 0.1-1000 mug/L; the addition amount of the modified gold nano Raman scattering enhancer of the amine carbon dots is 50-100 mu L.
3. The method according to claim 1, characterized in that: raman spectrum detection under the conditions of 785nm excitation light, 500mW laser power and 10s scanning time, the surface enhanced Raman scattering spectrum peaks of Hg 2+ standard solution have 1189 cm -1、1335 cm-1 and 1607 cm -1 peaks.
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