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CN114166817A - Method for rapidly, qualitatively and quantitatively analyzing trace chloride ions - Google Patents

Method for rapidly, qualitatively and quantitatively analyzing trace chloride ions Download PDF

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Publication number
CN114166817A
CN114166817A CN202111387032.8A CN202111387032A CN114166817A CN 114166817 A CN114166817 A CN 114166817A CN 202111387032 A CN202111387032 A CN 202111387032A CN 114166817 A CN114166817 A CN 114166817A
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chloride ions
solution
silver nanoparticle
detected
nanoparticle sol
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刘强
江世雄
翁孙贤
熊晨汝
顾家镭
王维礼
田中群
刘国坤
吴水平
陈国伟
王重卿
张建勋
涂承谦
吴文庚
车艳红
李熙
张波
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Xiamen University
Electric Power Research Institute of State Grid Fujian Electric Power Co Ltd
State Grid Fujian Electric Power Co Ltd
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Xiamen University
Electric Power Research Institute of State Grid Fujian Electric Power Co Ltd
State Grid Fujian Electric Power Co Ltd
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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Abstract

The invention discloses a method for rapidly detecting and analyzing trace chloride ions, which specifically comprises the following steps: (1) preparing silver nanoparticle sol by using silver nitrate solution to form an SERS enhanced substrate; (2) putting the silver nanoparticle sol prepared in the step (1) into a 96-well plate, adding a solution to be detected and containing chloride ions, and adding high-concentration inorganic salt to induce the silver nanoparticle sol to agglomerate to form a solution to be detected; (3) performing Raman spectrum detection on the solution to be detected to be positioned at 242cm‑1Taking the characteristic Raman peaks of the Ag-Cl on the left and the right as references, recording the intensity and the position of the characteristic peaks, and carrying out qualitative and quantitative detection on chloride ions in a sample to be detected; the method provided by the invention can realize qualitative and quantitative detection of trace chloride ions in the water body, and has the advantages of simplicity, convenience, rapidness, low cost, high stability and the like.

Description

Method for rapidly, qualitatively and quantitatively analyzing trace chloride ions
Technical Field
The invention belongs to the technical field of detection methods of non-metal ions in aqueous solution, and particularly relates to a method for rapidly, qualitatively and quantitatively analyzing trace chloride ions.
Background
Chloride ions widely exist in natural water and cannot cause harm to human under normal conditions. The liquid chlorine method, the sodium hypochlorite method and the chlorine dioxide method are commonly used for disinfection in urban drinking water treatment plants, chlorinated disinfection byproducts such as chlorinated organic matters such as trichloromethane, chloroacetic acid and the like are generated in the process, and the byproducts have carcinogenicity and genetic toxicity to human bodies. The chlorate limit value is 0.7mg/L, the chloride limit value is 250mg/L, and the concentration limit values of the disinfection byproducts of the trichloromethane and the chlorite (when using chlorine dioxide for disinfection) are 0.06mg/L and 0.7mg/L respectively according to the sanitary standard of domestic drinking water issued in China (GB 5749-2006). In order to control the water quality at the tail end of the pipe network, the drinking water standard simultaneously stipulates the residual amount of water at the tail end of the pipe network, wherein the minimum values of free chlorine, total chlorine and chlorine dioxide are respectively 0.05mg/L, 0.05mg/L and 0.02 mg/L. Too high residual chlorine brings odor to water, and too low residual chlorine causes water to lose the capability of maintaining sterilization, thereby reducing the sanitary safety of water supply. Therefore, the method has important practical significance for ensuring the water quality safety by sensitively and efficiently detecting the content of chloride ions in the drinking water treatment process and at the tail end of a pipe network.
At present, common methods for detecting chloride ions include an atomic fluorescence method, an atomic absorption spectrometry method, an inductively coupled plasma mass spectrometry method and the like, but the methods have the defects of large and expensive equipment volume, long detection time, complex operation, incapability of on-line monitoring and the like, and limit the wide application of the methods. Therefore, the search for a chloride ion detection method which is simple, fast, economical, efficient and capable of on-line monitoring has become one of the important research directions in the fields of food, sanitation, environmental analysis and the like at present.
The Surface Enhanced Raman Spectroscopy (SERS) method has the advantages of simplicity and convenience in operation, low detection cost, high sensitivity, high analysis speed and the like, and has great application potential in various fields such as environmental monitoring, biological detection, food science and the like. At present, Ag and Au-based nano materials are the most commonly used SERS enhanced substrates, and a patent with the application number of CN202110123684.4 discloses a method for quickly, qualitatively and quantitatively analyzing trace bromide ions, and particularly discloses a method for preparing gold nanoparticle sol by using chloroauric acid solution to form an SERS enhanced substrate; so that the bromide ions are strongly adsorbed on the surface of the gold nanoparticle sol by forming Au-Br bonds, and qualitative and quantitative detection is carried out on the bromide ions in the sample to be detected. The bromide ions and the chloride ions are halogen elements, and can be used for qualitative and quantitative detection of the halide ions in the water body by using an SERS method, but compared with strong adsorption of the bromide ions and the iodide ions, the chloride ions are relatively weak in adsorption on the surfaces of Au and Ag of a common SERS substrate, so that the difficulty in detecting the chloride ions by using the SERS method is caused; meanwhile, some currently disclosed SERS methods for detecting chloride ions in water mainly focus on qualitative detection of chloride ions in water, lack of exploration on sensitivity detection of chloride ions, and restrict application and popularization of the SERS method for detecting trace chloride ions.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for quickly, qualitatively and quantitatively analyzing trace chloride ions, which can realize convenient, quick, low-cost, high-sensitivity and high-stability detection of chloride ions in the environment.
The technical scheme of the invention is as follows:
a method for rapidly detecting and analyzing trace chloride ions specifically comprises the following steps:
(1) preparing silver nanoparticle sol by using silver nitrate solution to form an SERS enhanced substrate;
(2) putting the silver nanoparticle sol prepared in the step (1) into a 96-well plate, adding a solution to be detected and containing chloride ions, and adding high-concentration inorganic salt to induce the silver nanoparticle sol to agglomerate to form a solution to be detected;
(3) performing Raman spectrum detection on the solution to be detected to be positioned at 242cm-1And taking the left and right Ag-Cl characteristic Raman peaks as references, recording the intensities and positions of the characteristic peaks, and simultaneously constructing a linear relation between the concentration of the chloride ions and the Ag-Cl characteristic Raman peak intensity so as to qualitatively and quantitatively detect the chloride ions in the sample to be detected.
Further, the particle size of the silver nano-ions in the silver nano-particle sol in the step (1) is 15-150 nm.
Further, the high-concentration inorganic salt in the step (3) is an inorganic salt solution with a concentration of 0.1-1M and capable of weakly adsorbing anions such as fluorine ions, perchlorate ions and nitrate ions.
Further, the solution containing chloride ions and the silver nanoparticle sol are added according to the volume ratio of 10: 1; the high-concentration inorganic salt and the silver nanoparticle sol are added according to the volume ratio of 1: 1.
The invention has the beneficial effects that:
(1) the SERS method for rapidly detecting and analyzing the trace chloride ions, provided by the invention, simultaneously researches the detection sensitivity of the trace chloride ions, and the lowest detectable concentration is 10-6And M can be used for quantitative and qualitative detection of trace chloride ions in the water body.
(2) The SERS method provided by the invention has the advantages of simplicity, convenience, rapidness, low cost, high stability and the like for detecting trace chloride ions in water, and meanwhile, the portable Raman spectrometer is convenient for on-line monitoring and has potential market value.
(3) According to the SERS method for rapidly detecting and analyzing the trace chloride ions, provided by the invention, the silver nanoparticle sol prepared from the silver nitrate solution without chloride ions is used for forming the SERS enhanced substrate, and the inorganic salt with weak adsorption anions is used as an aggregating agent, so that the adsorption of the chloride ions is not interfered while a high-activity SERS hot spot is created, and the detection of the trace chloride ions is realized.
Drawings
Fig. 1 is a raman spectrum corresponding to chloride ions of different concentrations in a chloride ion detection method established in embodiment 1 of the present invention;
FIG. 2 is a graph of the intensity of the SERS signal of chloride ions as a function of concentration, as established in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific examples, which are given by way of illustration only and are not to be construed as limiting the invention; unless otherwise specified, the reagent raw materials used in the following examples are biochemical reagent raw materials which are conventionally commercially available or commercially available, and the laboratory instruments used are laboratory conventional instruments, and unless otherwise specified, the methods and apparatuses used in the following examples are those conventionally used in the art.
(1) Preparation of reagents: sodium chloride (analytically pure) and aluminum sulfate (analytically pure) are all produced by chemical reagents of the national drug group, ltd; polystyrene 96 well plates for detection (Corning, usa);
(2) preparing an instrument:
Figure BDA0003367449380000041
a raman spectrometer (budatake opto-electronics technologies, ltd);
example 1
A method for rapidly detecting and analyzing trace chloride ions specifically comprises the following steps:
(1) preparing silver nanoparticle sol by using silver nitrate solution to form an SERS enhanced substrate, wherein the particle size of silver nanoparticles in the silver nanoparticle sol is within the range of 15-150 nm;
(2) putting the silver nanoparticle sol prepared in the step (1) into a 96-well plate, adding a solution to be detected and containing chloride ions, and adding high-concentration inorganic salt to induce the silver nanoparticle sol to agglomerate to form a solution to be detected;
the working principle that chloride ions are adsorbed on the surface of the silver nanoparticle sol and high-concentration inorganic salt is added in the step (3) to promote agglomeration to finally form a solution to be detected for SERS detection is as follows:
Figure BDA0003367449380000042
(3) performing Raman spectrum detection on the solution to be detected to be positioned at 242cm-1Recording the intensity and position of the characteristic peak by taking the left and right Ag-Cl characteristic Raman peaks as a reference, and simultaneously constructing a linear relation between the concentration of the chloride ions and the Ag-Cl characteristic Raman peak intensity so as to qualitatively and quantitatively detect the chloride ions in the sample to be detected;
therein, at 10-7M-10-2In the range of M concentration, the linear relation curve of the chloride ion concentration and the characteristic Raman peak intensity of Ag-Cl is that y is 11.308+1.162lnx, x is the chloride ion concentration, and y is positioned at 242cm-1Characteristic raman peak intensity of Ag-Cl.
Further, the preparation method of the silver nanoparticle sol in the step (1) comprises the following steps: putting 5mL of 53mmol/L silver nitrate solution and 40mL of ultrapure water into a 100mL double-mouth round-bottom flask, continuously stirring the solution at the rotating speed of 1500r/min, heating the solution to boiling for 3-5min, quickly adding 5mL of 1% (m/v) trisodium citrate solution, changing the solution from colorless to golden yellow, finally changing the solution to grey green, keeping boiling for 30min, stopping heating, stirring and cooling the solution to room temperature to prepare silver nanoparticle sol, transferring the silver nanoparticle sol into a 50mL centrifuge tube, and storing the silver nanoparticle sol in a refrigerator at 4 ℃ for later use;
further, the high-concentration inorganic salt and the silver nanoparticle sol are added according to the volume ratio of 1: 1; adding a solution containing chloride ions and silver nanoparticle sol according to a volume ratio of 10:1, wherein the high-concentration inorganic salt is an inorganic salt solution with weak anion adsorption, such as fluorine ions, perchlorate ions and nitrate ions with the concentration of 0.1-1M
Example 2 chloride ion detection sensitivity test
First, the concentrations were 1M and 10M, respectively-1M、10-2M、10-3M、10-4M、10-5M、10-6M、10-7M、10-8M、10-9M sodium chloride solutions with different concentration gradients are shaken by hand and uniformly mixed;
secondly, preparing silver nanoparticle sol according to the method in example 1 to form an SERS enhancing substrate;
then, adding 20 mu L of silver nanoparticle sol into a 96-well plate, respectively adding 200 mu L of sodium chloride solutions with different concentrations as detection samples into the 96-well plate, and finally adding 20 mu L of aluminum sulfate solution (or other inorganic salt solution taking sodium, potassium, magnesium or aluminum ions as cations) selected as high-concentration inorganic salt into the 96-well plate to form a mixed solution to be detected;
finally, the mixed solution to be measured is placed in a Raman spectrometer to obtain a Raman spectrogram shown in figure 1, wherein the Raman spectrogram is 242cm-1Is a characteristic Raman peak of chloride ions with a lowest detectable concentration of 10-6And M, performing qualitative and quantitative analysis on the chloride ions in the sample to be detected.
Referring to the attached figure 2, it can be known that when the concentration of the chloride ions in the water body is 0.1M, the intensity of the SERS signal of the chloride ions is strongest, and the detection effect is most obvious.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (4)

1. A method for rapidly detecting and analyzing trace chloride ions specifically comprises the following steps:
(1) preparing silver nanoparticle sol by using silver nitrate solution to form an SERS enhanced substrate;
(2) putting the silver nanoparticle sol prepared in the step (1) into a 96-well plate, adding a solution to be detected and containing chloride ions, and adding high-concentration inorganic salt to induce the silver nanoparticle sol to agglomerate to form a solution to be detected;
(3) performing Raman spectrum detection on the solution to be detected to be positioned at 242cm-1And taking the left and right Ag-Cl characteristic Raman peaks as references, recording the intensities and positions of the characteristic peaks, and simultaneously constructing a linear relation between the concentration of the chloride ions and the Ag-Cl characteristic Raman peak intensity so as to qualitatively and quantitatively detect the chloride ions in the sample to be detected.
2. The method for rapidly detecting and analyzing the trace chloride ions according to claim 1, wherein the method comprises the following steps: the particle size of the silver nanoparticles in the silver nanoparticle sol in the step (1) is 15-150 nm.
3. The method for rapidly detecting and analyzing the trace chloride ions according to claim 2, wherein the method comprises the following steps: the high-concentration inorganic salt in the step (3) is an inorganic salt solution with a concentration of 0.1-1M and weakly adsorbing anions such as fluorine ions, perchlorate ions and nitrate ions.
4. The method for rapidly detecting and analyzing the trace chloride ions according to claim 3, wherein the method comprises the following steps: the solution containing the chloride ions and the silver nanoparticle sol are added according to the volume ratio of 10: 1; the high-concentration inorganic salt solution and the silver nanoparticle sol are added according to the volume ratio of 1: 1.
CN202111387032.8A 2021-11-22 2021-11-22 Method for rapidly, qualitatively and quantitatively analyzing trace chloride ions Pending CN114166817A (en)

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CN115219479A (en) * 2022-09-21 2022-10-21 中国科学院烟台海岸带研究所 A kind of method for detecting Ag+ in high concentration Cl- environment
CN117070211A (en) * 2022-05-09 2023-11-17 深圳大学 Composite material, preparation method and application thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117070211A (en) * 2022-05-09 2023-11-17 深圳大学 Composite material, preparation method and application thereof
CN115219479A (en) * 2022-09-21 2022-10-21 中国科学院烟台海岸带研究所 A kind of method for detecting Ag+ in high concentration Cl- environment

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Application publication date: 20220311