CN112161969A - Method and system for detecting content of metal ions in different forms - Google Patents
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
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Abstract
The invention discloses a method and a system for detecting the content of metal ions in different forms, which are characterized in that metal ions in different forms are selectively separated and enriched by an electrochemical method, and the enriched content of the metal ions is detected by a laser-induced breakdown spectroscopy method. The invention combines the selective electric field separation and the laser-induced breakdown spectroscopy method, thereby being capable of detecting the contents of heavy metal ions in different forms in the water body in situ, simply, conveniently and quickly. Therefore, the method solves the problem that the content of the heavy metal ions in different forms cannot be detected by the traditional laser-induced breakdown spectroscopy, and realizes high-sensitivity detection of the content of the heavy metal ions.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to a method and a system for detecting the content of metal ions in different forms.
Background
At present, the water environment pollution problem is increasingly prominent, especially heavy metal pollution. The trace concentration of the compound can generate toxic effect and has the functions of sustainability, accumulation and amplification, so that the ecological environment and the life health of human beings are seriously threatened. Monitoring is the basis for prevention and management. Therefore, the method has important scientific significance for accurately analyzing the content of the heavy metal pollutants in the water environment.
It should be noted that different forms of the same heavy metal element have different harms to human and environment. For example, cr (iii) is considered to be a trace element necessary for the normal operation of living organisms, while cr (vi) is toxic to biological systems. Inhalation of cr (vi) causes an increase in the incidence of diseases such as asthma, bronchitis, pneumonia, inflammation of the throat and liver, and contact of cr (vi) compounds with the skin may cause skin allergy, dermatitis, and the like. In view of these significant toxicological differences, it is important to analyze not only the total Cr concentration in water, but also to quantify its "morphology".
Laser Induced Breakdown Spectroscopy (LIBS) is a promising technology. LIBS is widely used for analysis of heavy metals due to its unique advantages, such as multi-element analysis, fast response, easy operation, no need for sample processing, and less sample damage. However, LIBS can only analyze the total amount of heavy metal elements in water, and cannot distinguish the forms of heavy metal pollutants.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method and a system for detecting the contents of metal ions in different forms, which can detect the contents of the metal ions in different forms in a water body in situ, simply, conveniently and quickly.
The invention provides a method for detecting the content of metal ions in different forms, which comprises the following steps: selectively separating and enriching metal ions with different forms, and detecting the content of the enriched metal ions.
Preferably, the selective separation and enrichment of metal ions in different forms is achieved by electrochemical methods;
preferably: the metal ions with different forms exist in the form of anions and cations in the electrolyte solution respectively, and are enriched on the anode electrode and the cathode electrode respectively under the action of electric field force.
Preferably, the "different forms of metal ions are present in the form of anions and cations, respectively, in the electrolyte solution" is achieved by adjusting the pH of the electrolyte solution;
preferably: the buffer solution is adopted to enable metal ions with different forms in the electrolyte solution to exist in the forms of anions and cations respectively.
Preferably, the anode electrode or the cathode electrode is a titanium sheet, a copper sheet or a glassy carbon sheet;
preferably, the surface of the anode electrode or the cathode electrode is further coated with an anion adsorption material or a cation adsorption material;
further preferably, the anion-adsorbing material is amino-modified graphene, and the cation-adsorbing material is carboxyl-modified graphene or graphene oxide.
Preferably, the step of detecting the enriched metal ion content is realized by a laser-induced breakdown spectroscopy method;
preferably: and carrying out in-situ determination on the metal ions enriched in the anode electrode and the cathode electrode respectively by using a laser-induced breakdown spectroscopy technology.
The invention also provides a system for detecting the content of metal ions in different forms, which comprises: electrochemical systems and laser-induced breakdown spectroscopy systems;
the electrochemical system comprises a first electrode (4), a second electrode (5), an electrochemical cell (12) and an electrochemical power source (7);
the electrochemical cell (12) is used for containing electrolyte, and the electrolyte contains metal ions with different forms in the forms of anions and cations;
the electrochemical power supply (7) is used for applying an electric field between the first electrode (4) and the second electrode (5) so as to enable metal ions with different forms existing in the form of anions and cations in the electrolyte to be enriched on the first electrode (4) and the second electrode (5) respectively;
the laser induced breakdown spectroscopy system comprises a laser (1), a spectrometer (11) and a detector (10);
the laser (1) is used for outputting laser to the first electrode (4) or the second electrode (5) so as to excite different forms of metal ions enriched on the first electrode (4) or the second electrode (5) to generate plasma light;
the spectrometer (11) is used for analyzing the plasma light and outputting a spectrum signal;
the detector (10) is used for detecting the spectrum signal and transmitting the spectrum signal to processing equipment for data analysis, and the content of metal ions in different forms is obtained.
Preferably, the first electrode (4) and the second electrode (5) are titanium sheets, copper sheets or glassy carbon sheets;
preferably, the surface of the first electrode (4) or the second electrode (5) is further coated with an anion adsorbing material or a cation adsorbing material;
further preferably, the anion-adsorbing material is amino-modified graphene, and the cation-adsorbing material is carboxyl-modified graphene or graphene oxide.
Preferably, the laser (1) is a Q-switched Nd: YAG laser or CO2The laser and the electrochemical power supply (7) are electrochemical work stations.
Preferably, the laser induced breakdown spectroscopy system further comprises a reflector (2), a focusing lens (3), a light receiver (8) and an optical fiber (9);
the reflector (2) is used for reflecting the laser output by the laser (1);
the focusing lens (3) is used for focusing the laser reflected by the reflector (2) and outputting the laser to the first electrode (4) and the second electrode (5);
the light receiver (8) is used for receiving the plasma light and guiding the plasma light into the spectrometer (11) through the optical fiber (9).
Preferably, the focusing lens (3) is a quartz convex mirror or a germanium convex mirror; the detector (10) is a charge coupled device CCD or an enhanced charge coupled device ICCD.
The invention provides a method and a system for detecting the content of metal ions in different forms. In the electrochemical enrichment stage, heavy metal cations in the actual water environment are fixed on the second electrode, the heavy metal cations existing in the form of anions are fixed on the first electrode, at the moment, a laser in the laser-induced breakdown spectroscopy system outputs laser, the laser is focused on the first electrode and the second electrode through a focusing lens and ablates the heavy metal ions of which the surfaces are fixed, the heavy metal ions are excited and release specific emission spectra, and therefore the content of the heavy metal ions in corresponding forms can be determined according to peaks in the spectra.
Therefore, the method combines the selective electric field separation and the laser-induced breakdown spectroscopy method, so that the content of heavy metal ions in different forms in the water body can be detected in situ, simply, conveniently and quickly. Therefore, the method solves the problem that the content of the heavy metal ions in different forms cannot be detected by the traditional laser-induced breakdown spectroscopy, and realizes high-sensitivity detection of the content of the heavy metal ions.
Drawings
FIG. 1 is a schematic structural diagram of a system for detecting contents of metal ions of different forms according to the present invention;
FIG. 2 is a schematic structural diagram of an electrochemical system in a system for detecting contents of metal ions with different forms according to the present invention;
FIG. 3 is a diagram of detection signals of Cr (III) and Cr (VI) in a water sample to be detected according to embodiment 1 of the present invention;
fig. 4 is a diagram of detection signals of cr (iii) and cr (vi) in a water sample to be detected according to embodiment 2 of the present invention.
Detailed Description
Referring to fig. 1, the system for detecting the content of metal ions in different forms, provided by the invention, specifically enriches heavy metal ions in different forms on two electrodes respectively by an electrochemical system through a selective electric field separation method, and then measures the content of heavy metal ion pollutants in situ by using a laser-induced breakdown spectroscopy system.
Referring to fig. 1, the laser induced breakdown spectroscopy system includes a laser 1, a reflector 2, a focusing lens 3, an optical receiver 8, an optical fiber 9, a detector 10 and a spectrometer 11;
referring to fig. 1 and 2, the electrochemical system comprises a two-electrode system consisting of a first electrode 4 and a second electrode 5, and both are connected with an electrochemical power supply 7 (electrochemical workstation).
The method for detecting the content of the metal ions in different forms is further explained by combining specific components of an electrochemical system and a laser-induced laser spectroscopy system, and specifically comprises the following steps:
s1, taking solutions containing heavy metal ions to be detected in different forms as solutions to be detected; specifically, an actual water environment is used as a solution to be detected, or actual water samples containing heavy metal ions to be detected in different forms are added into a buffer solution to be used as the solution to be detected;
s2, immersing the first electrode 4 and the second electrode 5 in the solution to be detected, applying a preset positive potential to the first electrode 4 for a preset time, transferring heavy metal anions in the solution to be detected to the surface of the first electrode 4 and transferring heavy metal cations in the solution to be detected to the surface of the second electrode 5 under the action of an electric field force; specifically, a voltage threshold of a preset positive potential is set according to the oxidation-reduction potential of the heavy metal ions to be detected, and both the preset voltage threshold and a time value need to be optimized;
s3, outputting laser through the laser 1, reflecting the laser to the focusing lens 3 through the reflector 2, focusing the laser on the first electrode 4 or the second electrode 5 through the focusing lens 3, and forming plasma by ablating the heavy metal ions to be detected enriched on the surface of the first electrode 4 or the second electrode 5; specifically, the laser 1 adopts a Q-switched Nd: YAG laser or CO2A laser, wherein a focusing lens 3 adopts a quartz convex lens or a germanium convex lens;
s4, the optical receiver 8 absorbs the optical signal emitted in the plasma cooling process and transmits the optical signal into the spectrometer 11 through the optical fiber 9, the detector 10 detects the spectral signal analyzed by the spectrometer 11 and transmits the spectral signal to the preset processing equipment for data analysis, and the content of the heavy metal ions to be detected in the solution to be detected is obtained.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A method for selectively detecting the contents of Cr (VI) and Cr (III) in water specifically comprises the following steps:
(1) adding a water body containing Cr (VI) and Cr (III) into a buffer solution of HAc-NaAc to obtain a water sample to be detected, adjusting the pH of the water sample to be detected to be 5.0, wherein the water sample to be detected contains 200ppb Cr (VI) and 200ppb Cr (III), and the Cr (VI) is mainly HCrO4 -Form (III) of Cr (OH)2+The form exists;
selecting two glassy carbon sheets with the thickness of 3mm and the size of 30mm multiplied by 10mm, sucking 30 mu L of turbid liquid containing 10mg/mL amino-modified graphene by using a liquid transfer gun, uniformly dripping the turbid liquid onto one glassy carbon sheet, and taking the glassy carbon sheet as a first electrode 4 (the amino-modified graphene can be added to HCrO4 -Adsorbing), then using a pipette to suck 30 μ L of suspension containing 10mg/mL of carboxyl-modified graphene, and uniformly dropping the suspension onto another glass carbon sheet to serve as a second electrode 5 (the carboxyl-modified graphene can be added to Cr (OH)2+Adsorption of (d);
the amino modified graphene is prepared by adopting the following process: dispersing 20mg of graphene oxide in 30mL of absolute ethyl alcohol, adding 2mL of deionized water, 2mL of ammonia water (25%) and 200 muL of 3-Aminopropyltrimethoxysilane (APTMS), carrying out ultrasonic treatment for 8h at normal temperature, washing with deionized water after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ for later use, thus obtaining the amino modified graphene;
the carboxyl modified graphene is prepared by adopting the following process: dispersing 20mg of graphene oxide in 30mL of absolute ethyl alcohol, adding 2mL of deionized water and 0.2g of Ethylene Diamine Tetraacetic Acid (EDTA), performing ultrasonic treatment for 8 hours at normal temperature, washing with methanol and deionized water in sequence after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ for later use to obtain the carboxyl modified graphene;
in the preparation process of both amino-modified graphene and carboxyl-modified graphene, the graphene oxide is prepared by a Hummers method, which refers to Hummers, w.s.; offeman, R.E.preparation of graphical Oxide [ J ]. J.am.chem.Soc.,1958,80(6):1339-1339.
(2) Adding the solution to be detected into an electrochemical cell 12 as an electrolyte solution, placing a magnetic stirrer 6 into the electrochemical cell 12, placing the magnetic stirrer on a magnetic stirrer, fixing a first electrode 4 and a second electrode 5, inserting the bottom end of the first electrode 4 and the bottom end of the second electrode 5 into the electrochemical cell 12, respectively connecting the first electrode 4 and the second electrode 5 to an electrochemical power supply 7 (an electrochemical workstation CHI 660D), and applying a positive voltage of 1.0V to the first electrode 4 for 600s to drive HCrO4 -Transfer from solution to the surface of the first electrode 4 while driving Cr (OH)2+Transfer from solution to the surface of the second electrode 5, during which time the magnetic stirrer is turned on and more HCrO is made available by stirring4 -、Cr(OH)2+Realizing the transfer;
(3) YAG laser (Brilliant, Quantel)1 is used as an incident light source, laser with the output wavelength of 1064nm, the repetition frequency of 1Hz, the maximum energy of a single pulse of 100mJ and the pulse width of 5ns is output, the laser is respectively gathered on a first electrode 4 and a second electrode 5 through a focusing convex mirror with the focal length of 100mm, and HCrO enriched on the first electrode 4 and the second electrode 5 is respectively ablated4 -Anion and Cr (OH)2+The positive ions form plasma, plasma light with specific wavelength is emitted in the cooling process of the plasma, after being received by the light receiver 8, the plasma light is conducted into the spectrometer 11 through the optical fiber 9, the ICCD detector 10 detects spectral signals analyzed by the spectrometer 11, data analysis is carried out by computer software, and the content of 197 +/-1.52 ppb Cr (VI) and 198 +/-2.08 ppb Cr (III) in a water sample to be detected is finally detected, wherein the specific detection map is shown in fig. 3. Therefore, the method of the embodiment realizes the Cr (III) and the Cr (III) in the waterVI) trace detection.
Example 2
A method for selectively detecting the contents of Cr (VI) and Cr (III) in water specifically comprises the following steps:
(1) adding a water body containing Cr (VI) and Cr (III) into a buffer solution of HAc-NaAc to obtain a water sample to be detected, adjusting the pH of the water sample to be detected to be 5.0, wherein the water sample to be detected contains 500ppb Cr (VI) and 200ppb Cr (III), and the Cr (VI) is mainly HCrO4 -Form (III) of Cr (OH)2+The form exists;
selecting two titanium sheets with the thickness of 3mm and the size of 30mm multiplied by 10mm, ultrasonically cleaning in acetone, selecting one titanium sheet to be immersed in a solution of amino modified graphene, taking out the titanium sheet to be used as a first electrode 4 (the amino modified graphene can increase the p-HCrO)4 -Adsorption), another piece of titanium sheet is selected to be immersed into the graphene oxide solution, and the titanium sheet is taken out to be used as a second electrode 5 (the surface of the graphene oxide contains carboxyl and hydroxyl, and the ratio of the carboxyl to the hydroxyl can be increased, namely Cr (OH)2+Adsorption of (d);
the amino modified graphene is prepared by adopting the following process: dispersing 20mg of graphene oxide in 30mL of absolute ethyl alcohol, adding 2mL of deionized water, 2mL of ammonia water (25%) and 200 muL of 3-Aminopropyltrimethoxysilane (APTMS), carrying out ultrasonic treatment for 8h at normal temperature, washing with deionized water after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ for later use, thus obtaining the amino modified graphene;
the graphene oxide is prepared by a Hummers method, which is specifically referred to Hummers, W.S.; offeman, R.E.preparation of graphical Oxide [ J ]. J.am.chem.Soc.,1958,80(6):1339-1339.
(2) Adding the solution to be detected into an electrochemical cell 12 as an electrolyte solution, placing a magnetic stirrer 6 into the electrochemical cell 12, placing the magnetic stirrer on the magnetic stirrer, fixing a first electrode 4 and a second electrode 5, inserting the bottom end of the fixed first electrode into the electrochemical cell 12, connecting the first electrode 4 and the second electrode 5 to an electrochemical power supply 7 (an electrochemical workstation CHI 660D), respectively, applying a positive voltage of 1.5V to the first electrode 4 for 600s,to drive HCrO4 -Transfer from solution to the surface of the first electrode 4 while driving Cr (OH)2+Transfer from solution to the surface of the second electrode 5, during which time the magnetic stirrer is turned on and more HCrO is made available by stirring4 -、Cr(OH)2+Realizing the transfer;
(3) YAG laser (Brilliant, Quantel)1 is used as an incident light source, laser with the output wavelength of 1064nm, the repetition frequency of 1Hz, the maximum energy of a single pulse of 100mJ and the pulse width of 5ns is output, the laser is respectively gathered on a first electrode 4 and a second electrode 5 through a focusing convex mirror with the focal length of 100mm, and HCrO enriched on the first electrode 4 and the second electrode 5 is respectively ablated4 -Anion and Cr (OH)2+The positive ions form plasma, plasma light with specific wavelength is emitted in the cooling process of the plasma, the plasma light is transmitted into a spectrometer 11 through an optical fiber 9 after being received by a light receiver 8, a spectrum signal analyzed by the spectrometer 11 is detected by an ICCD detector 10, data analysis is carried out by computer software, and the contents of 498 +/-2.65 ppb Cr (VI) and 198 +/-2.52 ppb Cr (III) in a water sample to be detected are finally detected, wherein the specific detection map is shown in figure 4. Therefore, the method in the embodiment also realizes trace detection of Cr (III) and Cr (VI) in water.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications thereof should be included in the technical scope of the present invention.
Claims (10)
1. A method for detecting the content of metal ions with different forms is characterized by comprising the following steps: selectively separating and enriching metal ions with different forms, and detecting the content of the enriched metal ions.
2. The method for detecting the content of the metal ions with different forms is characterized in that the selective separation and enrichment of the metal ions with different forms is realized by an electrochemical method;
preferably: the metal ions with different forms exist in the form of anions and cations in the electrolyte solution respectively, and are enriched on the anode electrode and the cathode electrode respectively under the action of electric field force.
3. The method for detecting the content of different forms of metal ions according to claim 2, wherein the step of "allowing different forms of metal ions to exist in the form of anions and cations in the electrolyte solution" is realized by adjusting the pH of the electrolyte solution;
preferably: the buffer solution is adopted to enable metal ions with different forms in the electrolyte solution to exist in the forms of anions and cations respectively.
4. The method for detecting the content of different-form metal ions according to claim 2 or 3, wherein the anode electrode or the cathode electrode is a titanium sheet, a copper sheet or a glassy carbon sheet;
preferably, the surface of the anode electrode or the cathode electrode is further coated with an anion adsorption material or a cation adsorption material;
further preferably, the anion-adsorbing material is amino-modified graphene, and the cation-adsorbing material is carboxyl-modified graphene or graphene oxide.
5. The method for detecting the content of different forms of metal ions according to any one of claims 1 to 4, wherein the step of detecting the content of the enriched metal ions is realized by a laser-induced breakdown spectroscopy method;
preferably: and carrying out in-situ determination on the metal ions enriched in the anode electrode and the cathode electrode respectively by using a laser-induced breakdown spectroscopy technology.
6. A system for detecting the content of different forms of metal ions, comprising: electrochemical systems and laser-induced breakdown spectroscopy systems;
the electrochemical system comprises a first electrode (4), a second electrode (5), an electrochemical cell (12) and an electrochemical power source (7);
the electrochemical cell (12) is used for containing electrolyte, and the electrolyte contains metal ions with different forms in the forms of anions and cations;
the electrochemical power supply (7) is used for applying an electric field between the first electrode (4) and the second electrode (5) so as to enable metal ions with different forms existing in the form of anions and cations in the electrolyte to be enriched on the first electrode (4) and the second electrode (5) respectively;
the laser induced breakdown spectroscopy system comprises a laser (1), a spectrometer (11) and a detector (10);
the laser (1) is used for outputting laser to the first electrode (4) or the second electrode (5) so as to excite different forms of metal ions enriched on the first electrode (4) or the second electrode (5) to generate plasma light;
the spectrometer (11) is used for analyzing the plasma light and outputting a spectrum signal;
the detector (10) is used for detecting the spectrum signal and transmitting the spectrum signal to processing equipment for data analysis, and the content of metal ions in different forms is obtained.
7. The system for detecting the content of different-form metal ions is characterized in that the first electrode (4) and the second electrode (5) are titanium sheets, copper sheets or glassy carbon sheets;
preferably, the surface of the first electrode (4) or the second electrode (5) is further coated with an anion adsorbing material or a cation adsorbing material;
further preferably, the anion-adsorbing material is amino-modified graphene, and the cation-adsorbing material is carboxyl-modified graphene or graphene oxide.
8. System for detecting content of metal ions with different forms according to claim 6 or 7, characterized in that the laser (1) is a Q-switched Nd: YAG laser or CO2The laser and the electrochemical power supply (7) are electrochemical work stations.
9. The system for detecting the content of different-form metal ions according to any one of claims 6 to 8, wherein the laser induced breakdown spectroscopy system further comprises a reflector (2), a focusing lens (3), an optical receiver (8) and an optical fiber (9);
the reflector (2) is used for reflecting the laser output by the laser (1);
the focusing lens (3) is used for focusing the laser reflected by the reflector (2) and outputting the laser to the first electrode (4) and the second electrode (5);
the light receiver (8) is used for receiving the plasma light and guiding the plasma light into the spectrometer (11) through the optical fiber (9).
10. The system for detecting the content of different-form metal ions according to claim 9, wherein the focusing lens (3) is a quartz convex lens or a germanium convex lens; the detector (10) is a charge coupled device CCD or an enhanced charge coupled device ICCD.
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